United States         Office of Water and    ' /, SW-646
Environmental Protection     Waste Management      ..QQQ
Agency           Washington, DC 20460


Solid Waste



Test Methods    ^ -



for Evaluating Solid Waste







Physical/Chemical Methods

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                                      SW846
    TEST METHODS FOR EVALUATING  SOLID WASTE
          PHYSICAL/CHEMICAL  METHODS
         WASTE CHARACTERIZATION  BRANCH
             OFFICE OF SOLID  WASTE
U.S.  ENVIRONMENTAL PROTECTION AGENCY  / MAY 1980

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                            ABSTRACT









This manual provides test procedures which may be used to




evaluate those properties of a solid waste which determine




whether the waste is a hazardous waste within the definition




of Section 3001 of the Resource Conservation and Recovery




Act (PL 94-580).  These methods are approved for obtaining




data to satisfy the requirement of 40 CFR Part 261, Identifica-




tion and Listing of Hazardous Waste.  This manual encompasses




methods for collecting representative samples of solid wastes,




and for determining the reactivity, corrosivity, ignitability,




and composition of the waste and the mobility of toxic species




present in the waste.

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                         ACKNOWLEDGEMENT
     The Office of Solid Waste would like to especially thank

the following individuals and groups for the help and advice

they gave us during the preparation of this manual:

    Dr.  Gregory Diachenko,  Food & Drug Administration,
        Division of Chemical Technology, Washington, B.C.

    Dr.  Wayne Garrison, Environmental Research Laboratory,
        Athens, GA

    Dr.  Donald Gurka,  Environmental Monitoring and Systems
        Laboratory, Las Vegas, NV

    Drs. Dean Neptune  and Mike Carter, Effluent Guidelines
        Division, Washington, DC

    Quality Assurance  Division, Environmental Monitoring &
        Systems Laboratory, Las Vegas, NV

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oEPA
            United StatM
            Environmental Protection
            Agency
        Office of Weter end
        Wette Management
        Washington, DC 20460
SW-846
Revision B
July 1981
            Solid Waste
Test Methods
for Evaluating Solid Waste

Physical/Chemical Methods
                Technical
                   U pdate

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           TEST METHODS FOR EVALUATING SOLID WASTE

                  PHYSICAL/CHEMICAL METHODS

                       Technical Update
This manual (SW-846B) updates the Test Methods for Evaluating
  Splid Waste (SW-846), and was written by the Hazardous and
   Industrial Waste Division of the Office of Solid Waste.
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                          July 1981

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   This publication (SW-846B) is the second revision to Test Methods for
Evaluating Solid Waste (SW-846).  Any mention of commercial products in
the manual or this revision does not constitute endorsement by the U.S.
Government.  Editing and technical content were the responsibilities of
the Hazardous and Industrial Waste Division, Office of Solid Waste.

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                                          Revision B   4/15/81
                        Table of Contents
Section
          Introduction
  1.0     Evaluation Plan Design
  2.0     Chain of Custody Considerations
  3.0     Sampling Methodology
            3.1  Sampling Plan Design [Reserved]
            3.2  Sampling Equipment
            3.3  Sample Containers
            3.4  Sample Handling & Preservation [Reserved]
  4.0     Ignitability  (40 CFR 261.21)
  5.0     Corrosivity   (40 CFR 261.22)
  6.0     Reactivity    (40 CFR 261.23)
  7.0     Extraction Procedure Toxicity  (40 CFR 261.24)
            7.1  Regulations
            7.2  Separation Procedure
            7.3  Sample Size Reduction  [Reserved]
            7.4  Structural Integrity Procedure
            7.5  Extractors
  8.0     Analytical Methodology
          Gas  Chromatographic Methods
            8.01   Volatile organics,  general
            8.02   Volatile aromatics, selected ketones  &  ethers
            8.03   Acrolein, Acrylonitrile and  Acetonitrile
            8.04   Phenols
            8.06   Semi-volatile organics,  not  otherwise  specified
            8.08   Organochlorine pesticides and PCBs

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                                    Revision B   4/15/81
 8.09  Nitroaromatics
 8.10  Polynuclear Aromatic Hydrocarbons
 8.11  Haloethers [Reserved]
 8.12  Semi-volatile chlorinated hydrocarbons, Not Otherwise
       Specified
 8.13  Chlorinated Dibenzo-p-dioxins [Reserved]
 8.22  Organophosphorus pesticides
 8.40  Chlorophenoxy acid pesticides
 Gas Chromatographic/Mass Spectroscopy Methods
 8.24  Volatile organics
 8.25  Semi-volatile organics
 8.27  Capillary Column GC/MS Metod for the Analysis of Wastes
 High Performance Liquid Chromatographic Methods
"8.30  Polynuclear Aromatic Hydrocarbons  [See method 8.10]
~8.32  Carbamates [Reserved]
 Atomic Absorption Spectrographic Methods
 8.49  General Requirements
 8.50  Antimony
 8.51  Arsenic
 8.52  Barium
 8.53  Cadmium
 8.54  Chromium
 ^8.55  Cyanide
 8.56  Lead
 8.57  Mercury
 8.58  Nickel
 8.59  Selenium
 8.60  Silver

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                                         Revision B   4/15/81
      Other Measurement Methods

        8.55  Titrimetric Method for Cyanide

        8.56  Microcoulometric Method for Total Organic Halide

        8.57  Titrimetric Method for Sulfides

      Sample Preparation/Introduction Techniques

        8.80  Direct Injection

        8.82  Headspace

        8.83  Purge and Trap

        8.84  Shake Out

        8.85  Sonication

        8.86  Soxhlet Extraction

 9.0  Interference Removal Procedures

        9.01  Liquid - Liquid Extraction

10.0  Quality Control/Quality Assurance

11.0  Suppliers

 Appendices

   I  "Samplers and Sampling Procedures for Hazardous Waste
      Streams", EPA-600/2-80-018

  II  Selected sections of "Methods for Chemical Analysis
      of Water and Wastes",  EPA-600/4-79-020.

 Ill  "Methods for Benzidine/ Chlorinated Organic
      Compounds,  Pentachlorophenol and  Pesticides in Water and
      Wastewater"


  IV  Selected sections from the Federal Register,  "Guidelines
      Establishing Test Procedures for  the Analysis of Pollutants;
      Proposed Regulations", 44 FR 69464-69567.

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                        INTRODUCTION
     This first edition of  "Test  Methods  for  Evaluating Solid




Waste" contains the procedures  that may be  used  by the regulated




community or others in order  to determine whether  a waste is a




hazardous waste as defined  by regulations promulated under




Section 3001 of the Resource  Conservation and Recovery Act




(RCRA), PL 94-580 (40 CFR Part  261).   The manual provides




methodology for collecting  representative samples  of the




waste, and for determining  the  ignitability ,  corrosivity,




reactivity, Extraction Procedure  (EP)  Toxicity and composition




of the waste.




     This document has been developed  to:




     a.  provide methods which  will be acceptable  to the




         Agency when used by  the  regulated  community to




         support waste evaluations and listing and




         delisting petitions, and




     b.  describe the methods that will be  used  by the




         Agency in conducting investigations  under




         Sections 3001, 3007, and 3008.




     The practice of evaluating solid  wastes  for environmental




and human health hazards is new.  Experience  has only recently




accumulated in analyzing wastes for inorganic and  organic




species, and for intrinsic  properties  such  as pH,  flash point,




reactivity and leachability .  This manual will serve as a

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compilation of state-of-the-art methodology for conducting




such tests.  It is meant to be a dynamic document.  The




methodology descriptions will be frequently updated and




expanded in order to keep pace with the developments being




achieved by EPA, the regulated community, and others.




    Standardized approved methods must be available so that




the regulated community can be certain that the data it  pro-




vides will be acceptable to the Agency.  This manual thus




makes available to the regulated community and others, those




methods that the Agency considers suitable.




    Many of the methods presented in this manual  have not been




fully evaluated by the Agency using materials characteristic  of




the wastes regulated under RCRA.  Such evaluations are underway.




However, until such time as the methods in this manual are




superseded, the Agency will accept data obtained  by the  test




methods presented in this manual.  Only those data that  are




obtained when Quality Control and Quality Assurance procedures




are followed by the testing organization will be  accepted by




the Agency.




    This manual will eventually include a second  part comprised




of biological methods for determining toxic properties of




RCRA wastes.  Such toxic properties may include carcinogenicity,




mutagenicity, teratogenicity, aquatic toxicity, phytotoxicity,




and mammalian toxicity.  The Agency anticipates that these




methods will not be available before the later part of 1981.
                              ii

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     Methods will be  provided  in  this  present  volume for the




following specific areas:




    a-  design of sampling  and  evaluation  plans;




    b.  collection of samples  from  various  types  of  environments




        (e.g., pipes, drums, pits,  ponds,  piles,  tanks);




    c.  transportation and  storage  of  samples;




    d.  chain-of-custody considerations  to  insure defensibility




        of data;




    e.  determination of the pH,  corrosivity  to  steel,  flash point,




        and explosivity;




    f.  conduct of the Extraction Procedure;




    g.  analysis of wastes  and  extracts  for organic  and  inorganic




        constituents;




    h.  safety in solid waste  sampling and  testing,  and




    i.  quality control and quality assurance.






     The analytical and sampling  methods presented  in this




manual have been derived from  a number of published  sources,




chiefly:




    a.  "Methods for  the Evaluation of Water  and  Wastewater,"




        EPA-600/4-79-020, U. S. EPA, Environmental  Monitoring




        and Support Laboratory, Cincinnati, OH 45268,




    b.  "Methods  for Benzidine, Chlorinated Organic  Compounds,




        Pentachlorophenol and  Pesticides in Water  and Wastewater,"




        U.S. EPA, Environmental Monitoring and Support




        Laboratory, Cincinnati, OH 45268, September  1978,
                             iii

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    c.  Guidelines Establishing Test Procedures for  the




        Analysis of Pollutants; Proposed Regulations;




        44 FR 69464-69575, and




    d.  "Samplers and Sampling Procedures for Hazardous  Waste




        Streams," EPA-600/2-80-018, U.S. EPA, Municipal  Environ-




        mental Research Laboratory, Cincinnati, OH 45268.




    In addition, work conducted by and the assistance  of




scientists of the Environmental Monitoring Systems Laboratory




at Las Vegas, NV, the Environmental Research Laboratory  at




Athens, GA, and  the National Enforcement Investigations  Center




at Denver, CO, is gratefully acknowledgd and appreciated.




    For the convenience of those using this manual,  the  above




publications have been appended to this manual.   Users are




encouraged to review these additional sources of  information




prior to initiating laboratory work.




    Although a sincere effort  has been made to  select  methods




that are applicable to the widest range of expected  wastes,




significant interferences, or  other problems, may be encountered




with certain samples.  In these situations, the analyst  is




advised to contact the Manager, Waste Analysis  Program (WH-565),




Waste Characterization Branch, Office of Solid  Waste,  Washington,




D.C. 20460 (202-755-9187) for  assistance.  The  manual  is intended




to serve all those with a need to evaluate solid  waste.   Your




comments, corrections, suggestion, and questions  concerning  any




material contained in, or omitted from, this manual  will be




gratefully appreciated.   Please direct your comments to  the




above address .
                               iv

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                                                             1.0-1
                 1.0  Evaluation Plan Design




Purpose




     40 CFR Part 262.11 requires generators to evaluate




their waste in order to determine whether it meets the defini-




tion of a hazardous waste.  On the basis of engineering




evaluations of processes and their raw materials, many genera-




tors will elect to declare their waste hazardous without




testing it.  Other generators, who believe that their waste




is not hazardous, will elect to test their waste in order to




so demonstrate.




     This section of the manual has two purposes.  The first




is to discuss relevant factors which generators should




consider in developing a sampling and testing plan that




provides maximum information at minimum cost.  The second




purpose is to outline for the regulated community standards




of proof the Agency considers sufficient to demonstrate whether




a waste does or does not possess a given property.  Such




demonstrations are necessary when generators petition the




Agency under 40 CFR 260.20 and 260.22 to delist a waste.



Such demonstrations are also crucial when the Agency determines




that a waste meets the definition of a hazardous waste and




the generator elects to challenge that determination.  In such




cases, conclusions regarding a waste's nature that are obtained




using the procedures and standards of proof described in this




manual will be accepted by the Agency as evidence that the




determinations were made in good faith.

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                                                                  1.0-2
Why is there a need for such guidance?




     The Agency has defined hazardous waste in terms of  a




waste's chemical and physical properties.  If all wastes were




perfectly homogeneous and if properties could be measured




with 100% accuracy, there would be no need for this manual.




In the real world, however, waste testing is far from simple




or ideal.  Errors can occur:




     a.  during the process of collecting a representative




         sample of the waste, unanticipated non-uniformity  in




         the process generating the waste (i.e., due to




         changes in the waste's composition over time) or to




         the fact that the contaminants of concern in the




         waste are not uniformly distributed throughout  the




         particular sample of waste (i.e., non-homogeneity),




         and




     h.  in analyzing the sample for the property of concern.




The discussion in this section of the manual pertains to how:




     a.  to design a sampling plan which yields a




         statistically representative sample of a waste,




     b.  to maximize the accuracy of an evaluation while




         minimizing the costs, and




     c.  to determine when a given waste has been adequately




         characterized.




     Other sections of this manual will address the mechanics  of




collecting samples of a given batch or lot of waste, and of




performing the laboratory procedures required to determine




its physical or chemical properties.

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                                                                 1.0-3
     The decision criteria presented in this section can be
used by generators to determine if the evaluation of the
waste is adequate to demonstrate that the true value for a
specific property falls below the particular regulatory
threshold value for that property.
Statistical Calculations
     A statistic is a number that describes a certain aspect
of a sample.  The arithmetic mean (average) and standard
deviation (s) are all statistics computed from a part of a
populaton or universe (i.e., a sample).
     The most useful statistics, and the ones to be used in
determining the adequacy of the characterization, are the arith-
metic mean of the sample (x) and the standard deviation (s),
which is a measure of the variability of the data obtained.
These terms are defined as:
                                      r»
                                      n
                                          n - i
     Based on these statistical measures, a confidence interval
can be developed within which the true value for the parameter
being determined can be said to lie with a high degree of
confidence.  Thus if the upper bound of this interval (Upper
Confidence Level (UCL)) is below the applicable threshold

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then it can confidently be concluded to be non-hazardous.   If, on




the other hand, the UCL is above the threshold, then even though




the values obtained for the samples tested fall below the




threshold, one cannot confidently conclude the waste is not a




a hazardous waste.




     As will be discussed later, in developing a sampling




plan and in collecting samples of a waste, it is important  to




insure that all portions of the waste have an equal chance




of being represented. If representative samples are collected,




the data obtained from testing will follow a normal distribution.




In such cases, for purposes of waste characterization, the




UCL can be calculated using the formula:






                 UCL =  "x + (k' )(s)  where
                             'n






k' is given in Table 1-1 and is a function of the number of




samples tested .




     Example:




          A waste has a true concentration of cadmium  of 10  mg/kg.




The total waste was divided into 5 portions and each portion




was analyzed to yield the following concentration values:




                      Xli;  5mg/kg




                      X2 = 15mg/kg




                      X3 . 15 mg/kg




                      X4 =  8mg/kg




                      X5 =  7mg/kg

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                                                                    1.0-5
     If the first and second portions had been selected as




the random samples to test, the arithmetic mean would be




identical to the population mean:




                 IF = (xj_+ x2)/2  = (5 +15)/2 = 10




If however, portions 4 and 5 had been selected, the




arithmetic mean would be significantly different from the




population mean:




                 H  - (X4 + X5/2 = (8 + 7)/2 = 7.5




Had portions 4 and 5 been selected, the UCL would still




be reasonably close to the true value (e.g., within 10%).




                 x = 7.5




                 n - 2




                 s - Aj[(8.0 - 7.5)* + (7.0 - 7.5)^]/l




                   - 0.7






               UCL = 7.5 + k'(0.7)/ -




                   = 7.5 + (3.078)(0.7)/1.4




                   =  9.04

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                                                                     1.0-6
                          Table  1-1
n-1
1
2
3
4 . . .
5 . . .
6
7
8 . . .
9
10 . . .
11
12 . . .
13
14
15
16 . . .
17
18 . . .
19
20
21
22 . . .
23 . . .
24
25 . . .
26
27 . . .
28 . . .
29
00 . . .
k'
. . . 3.078
. . . 1 .886
. . . 1.638
. . . 1.533
. . . 1 .476
. . . 1 .440
. . . 1 .415
. . . 1.397
. . . 1 .383
. . . 1.372
. . . 1 .363
. . . 1.356
. . . 1.350
. . . 1.345
. . . 1 .337
. . . 1.341
. . . 1 .333
. . . 1.330
. . . 1 .328
. . . 1.325
. . . 1 .323
. . . 1.321
. . . 1.319
. . . 1.318
. . . 1.316
. . . 1.315
. . . 1 .314
. . . 1.313
. . . 1 .311
. . . 1.282
n = Number of samples tested

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                                                                1.0-7
Sampling Cons1deration s




     The physical characteristics of a waste determine  the




method of collecting samples as well as the number  of samples




that should be collected and tested before calculating  an




initial UCL.  In evaluating wastes, it is impossible to have




complete population data since only a very small  fraction of




the waste will be subjected to laboratory study.  The objective




of sampling, therefore, is to select a portion of the waste




which is representative of the whole.  In order to  use  the




acceptance criteria described in this section, each component




of the waste must have an equal chance of being sampled and




tested.  Therefore, before a sampling plan can be designed,




the type of contamination distribution should be  determined




by an engineering analysis of the process generating the




waste.  The purpose of this analysis is to determine the




appropriate sampling plan for obtaining a representative




sample of the waste in question.




     Wastes can be classified into six types depending on the




uniformity of the process generating the waste and  the homo-




geneity of the contaminant distribution within the waste.




These categories determine the approach that should be used




in conducting the sampling and the number of samples that




should .be tested initially.  The six types of waste are:




          I.  Uniformly homogeneous




         II.  Non-uniformly homogeneous




        III.  Uniformly, randomly heterogeneous




         IV.  Non-uniformly, randomly heterogeneous

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                                                               1.0-8
          V.  Uniformly, non-randomly heterogeneous




         VI.  Non-uniformly,  non-randomly heterogeneous




In these classifications uniformity is defined as constancy




of waste composition over a period of time.  Homogeneity




refers to the degree to which the components of the waste are




uniformly distributed throughout the mass of waste (i.e., in a




homogeneous sample all possible subsamples have an Identical




composition).




     A Type I waste (uniformly homogeneous) is the one whose




overall composition does not  vary with time and for which




the constituent of concern is evenly and randomly distributed




throughout the waste (i.e., any single subsample of the




whole would be expected to contain the same proportion of a




given constituent as would any other subsample).  Examples of




wastes are liquid waste products disposed of on a regular




basis (e.g., waste pesticide  formulations remaining in




holding tanks at the conclusion of a production run) and




wastes generated from a well  controlled manufacturing process




(e.g., spent semiconductor etching solutions).




     In Type II wastes, while any given unit quantity of the




waste would be homogeneous, the nature of the process generating




the waste is such that the overall composition changes with




time.  Such a situation might occur at a facility that uses




batch processes to make a variety of similar products and




which generates a well mixed, single phase liquid waste.




While any portion of the waste generated from a given production

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                                                                1.0-9
run would be equivalent, wastes from different runs would have




different properties.




     Types III through VI wastes are much more complex.




Types III and V, deal with the cases where the composition




of the waste as a whole remains the same, but the components




are not uniformly distributed throughout the waste.  In a




randomly heterogeneous waste (Types III and IV) the likelihood




is the same that any given sampling point will contain a




specific type of contaminant.  An example of a Type III




waste is that generated by a batch plating operation that




involves a number of plating processes, where all wastes




feed into a single treatment facility, and where the sludge




is stored in a tank that holds several weeks' worth of sludge.




While the concentration of a given metal would not be uniform




thoughout the tank, no one region within the tank is more




likely to contain high concentrations of any one metal more




than any other.



     With Type V waste, placement of the waste is not random




because of the nature of the storage or disposal process.




For example, when a waste is discharged into a pond or lagoon,




the heavier particles settle out first; thus, stratification




occurs on a continuous basis.  Samples of waste selected




near the entrance point in the holding tank would always




the more dense material.  This is the reverse of the Type IV




waste, in which no one type of waste is more likely than any

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                                                                   1.0-10
other to be found at a given point.

     With Types I and III wastes, a simple random  sample  and  a

randomly prepared composite sample, respectively,  will  suffice

as representative samples.  With Type V wastes  which  may  be

stratified, the waste would have to be divided  into a number

of strata;  each stratum would then have the properties  of

either a Type I or Type III waste.  A random  sample of  each

stratum would then be used to form a composite  sample.  The

number of random subsamples collected from each stratum would

then be a function of the relative proportion of that particular

stratum in the waste as a whole.  If, for example, dense

particles comprised 50% of the waste and 10 subsamples  were

to be used in forming a composite, then 5 of  those subsamples

should be randomly collected from the dense particle  substratum.

     At this point, it should be mentioned that when  the

waste is non-uniform (i.e., Types II, IV, and VI), the  generator

would have to sample the waste over time. The techniques

described herein for uniform wastes should be used in order

to determine the significance of the changes  with  respect to

the property of concern.

     A major consideration in solid waste evaluation  is the

number of samples that should be tested.  The sample  size is

determined by:

     a.  the degree of accuracy desired,

     b.  the cost of collecting and testing the samples,
         and

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                                                                   1.0-11
     c.  the variability  of  the  population from which
         the samples are  being  taken  (e.g.,  Type I wastes
         are exceedingly  uniform  and  thus  fewer samples
         would have to be  tested  whereas Type  IV wastes are
         very variable and more  samples  would  have to be
         tested) .

As the number of samples  tested  increases,  the confidence

interval gets smaller (UCL approaches  the  mean) and the

accuracy of the determination increases.   At least 2  samples

(the recommended minimum  is  3 samples) must  be collected and

tested prior to calculating  an  initial average and upper

confidence limit.

Testing Considerations

     An additional aspect  of waste  testing  that must  be

considered relates to the  precision of the  test methods

used to measure the parameter of  concern.   The standard

deviation of the values obtained  when  testing  wastes  is a

function of both the sampling variability  and  the  measurement

variability, i.e.,:

                 So " flss + f2sa


where
                 So = overall standard deviation

                 Ss = standard deviation attributable to
                      sampling error

                 Sa = standard deviation attributable to
                      analytical  error

                  f = complex function

     In evaluating solid wastes,  a number  of testing  procedures

are used to determine if the waste is a hazardous  waste.

The precision of these methods varies not  only as  a function

of thet method used, but also as a function of  the  waste

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                                                                   1.0-12
matrix and the level of the property of interest  (e.g.,




concentration of toxic species).




     Where prior information is available that indicates  the




portion of the total testing error attributable to the measurement




phase, the generator can use this information to  determine




the best (i.e., most cost effective) means of reducing the




UCL.  When Sa is high, then replicated measurements on the




sample would tend to be more efficient than collecting and




testing a larger number of samples.  On the other hand,




when Sa is low and Ss is high, larger numbers of  samples




should be evaluated.  When Sa is unknown or cannot be




estimated in advance, generators may find it cost effective




to determine Sa during the initial experiments that are con-




ducted to calculate UCL.




     Once initial testing has been concluded and  the UCL




calculated, the decision on whether further testing is warranted




depends upon several factors.  Among these are:




     a.  relation of x and UCL to the threshold value,




     b.  cost of testing, and




     c.  relative cost of disposal as hazardous waste.




For example, if x is greater than the threshold value and




(UCL x) is small, there is a statistically small  probability




that the waste is not a hazardous waste, and thus there is




little to be gained by further testing.   If the  UCL is less




than the threshold value, the Agency will accept  the conclusion




drawn from such data and again there is little to be gained




from futher testing.  However, this acceptance by the Agency

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                                                                   1.0-13
is conditional on the generator's having used a sample




collection plan that yields a sample that Is representative




of the whole, (as was discussed previously in this section).




When the testing costs are low and the disposal costs are




high, generators may want to do additional testing in order




to increase the accuracy of the evaluation.  One should keep




in mind that the standard error is inversely proportional to




the square root of the number of samples tested (e.g., increas-




ing the number of samples tested from 4 to 16 reduces the




standard error by 50%) .




     The Agency believes that, after taking these factors into




account, each generator  must make his own decisions as to the




size of the testing program required to adequately evaluate




a particular waste.  The Agency will continue to expand




material in this manual  as new information develops in order




to offer the regulated community further guidance and assistance.

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                                                                     2.0-1
                          Section 2.0




                CHAIN OF CUSTODY CONSIDERATIONS









     Chain of custody establishes the documentation  and  control




necessary to identify and trace a sample  from  sample collection




to final analysis.  Such documentation  includes  labeling to




prevent mix up, container seals to  prevent  unauthorized  tampering




with contents of the sample containers, secure custody,  and




the necessary records to support potential  litigation.




Sample Labels




     Sample labels (Figure 2.0-1) are necessary  to  prevent mis-




identification of samples.  Gummed  paper  labels  or  tags  are




adequate.  The label must include at least  the following




information:




          Name of collector.




          Date and time of collection.




          Place of collection.




          Collector's sample number, which  uniquely  identifies




            the sample.

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                                                                        2.0-2
Collector 	 Collector's  Sample  No




Place of Collection
Date Sampled 	 Time Sampled




Field Information
                          Figure 2 .0-1




                   EXAMPLE  OF SAMPLE LABEL

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                                                                      2.0-3
Sample Seals
     Sample seals are used to preserve the integrity of the
sample from the time it is collected until it is opened in the
laboratory.  Gummed paper seals may be used for this purpose.
The paper seal must include, at least, the following information:
          Collector's name.
          Date and time of sampling.
          Collector's sample number.  (This number must be
            identical with the number on the sample label.)
     The seal must be attached in such a way that it is necessary
to break it in order to open the sample container.  An example
of a sample seal is shown in Figure 2.0-2.

-------
                                                                      2.0-4
     NAME AND ADDRESS  OF  ORGANIZATION COLLECTING  SAMPLES


Person                                        Collectors
Collecting Sample 	 Sample  No.
                          (Signature)

Date Collected 	  Time Collected  	

Place Collected
                          Figure 2.0-2

               EXAMPLE  OF  OFFICIAL SAMPLE SEAL

-------
                                                                      2.0-5
Field Log Book

     All information pertinent  to  a  field  survey  and/or sampling

must be recorded in a log book.  This must  be  a bound  book,

preferably with consecutively numbered  pages  that are  21.6 by

27.9 cm (8 1/2 by 11 in.).  Entries  in  the  log book must include

at least, the following:

          Purpose of sampling (e.g.,  surveillance,  contract
            number)

          Location of sampling  point.

          Name and address of field  contact.

          Producer of waste and  address if  different than location.

          Type of process (if known)  producing waste.

          Type of waste  (e.g.,  sludge,  wastewater)

          Suspected waste composition including concentrations.

          Number and volume of  sample taken.

          Description of  sampling  point and sampling methodology.

          Date and time  of collection.

          Collector's sample  identification number(s).

          Sample distribution and  how transported (e.g.,
            name of laboratory,  UPS,  Fedeal Express)

          References such as maps  or photographs  of the
            s ampling site.

          Field observations.

          Any field measurements made (e.g.,  pH,  flammability,
            explositivity).

     Sampling situations  vary widely.   No  general rule can be

given as to the extent of information that  must be entered in

the log book.  A good rule, however,  is to  record sufficient

information so that someone can  reconstruct the sampling

without reliance on the  collector's  memory.

-------
                                                                      2.0-6
     The log book must be protected and kept in a safe place.

Chain of Custody Record

     To establish the documentation necessary to trace sample

possession from the time of collection, a chain of custody record

must be filled out and accompany every sample.  This record

becomes especially important when the sample is to be intro-

duced as evidence in a court litigation.  An example of a

chain of custody record is illustrated in Figure 2.0-3.

     The record must contain the following minimum information:

          Collector's sample number.

          Signature of collector.

          Date and time of collection.

          Place and address of collection.

          Waste type.

          Signatures of persons involved in the chain of
            pos session.

          Inclusive dates of possession.

-------
                                                                               2.0-7

                                     Collector's Sample No. 	
                      CHAIN OF CUSTODY RECORD
 Location  of  Sampling: 	Producer   	 Hauler    	 Disposal Site

                      	 Other: 	
                               Sample
 Shipper Name: 	
 Address:
       number     street           city       state        zip

 Collector's Name	Telephone: (   )
                             signature

 Date  Sampled 	Time Sampled 	hours

 Type  of  Process Producing Waste 	

 Field Information
 Sample Receiver:

 1.
         name and  address of organization receiving sample

 2.
 3.
 Chain of  Possession:

.1. 	  	   	
      signature                  title               inclusive dates

 2.
      signature                  title               inclusive dates

 3.
      signature                 title               inclusive dates

                             Figure 2.0-3

                EXAMPLE OF CHAIN OF CUSTODY RECORD

-------
                                                                                     2.0-8
                       EXAMPLE OF CHAIN OF CUSTODY RECORD








Sample Analysis Request Sheet




     The sample analysis request sheet (Figure 2.0-4) is intended




to accompany the sample on delivery to the laboratory.  The field




portion of this form must be completed by the person collecting




the sample and should include most of the pertinent information




noted in the log book.  The laboratory portion of this form is




intended to be completed by laboratory personnel and to include at




a minimum:




          Name of person receiving the sample.




          Laboratory sample number.




          Date of sample receipt.




          Sample allocation.




          Analyses to be performed.

-------
PART I:  FIELD SECTION
                             SAMPLE ANALYSIS REQUEST
                                                                                       2.0-9
Collector
Affiliation of Sampler

Address
                   Date Sampled
            number

Telephone (	)
LABORATORY
  SAMPLE
  NUMBER
COLLECTOR'S
SAMPLE NO.
         street           city

        	  Company Contact
TYPE OF
SAMPLE*
                          Time
                       hours
                          state
                      zip
FIELD INFORMATION**
Analysis Requested
Special Handling and/or Storage
PART II:  LABORATORY SECTION**
Received by
Analysis Required
                         Title
                                   Date
*   Indicate whether sample is soil, sludge, etc.
**  Use back of page for additional information relative to sample location

                                  Figure 2.0-4

               EXAMPLE OF HAZARDOUS WASTE SAMPLE ANALYSIS REQUEST SHEET

-------
                                                                     2.0-10
Sample delivery to the laboratory




     Preferably, the sample must be delivered in person to the




laboratory for analysis as soon as practicable—usually within




1 or 2 days after sampling.  The sample must be accompanied by




the chain of custody record (Figure 2.0-3) and by a sample anal-




ysis request sheet (Figure 2.0-4).  The sample must be delivered




to the person in the laboratory authorized to receive samples




(often referred to as the sample custodian).






Shipping of Samples




     A material identified in the DOT Hazardous Material Table




(49 CFR 172.101)               must be transported as prescribed




in the table.  All other hazardous waste samples must be trans-




ported as follows:




1.  Collect sample in an appropriately sized glass or poly-




    ethylene container with non-metallic teflon lined screw




    cap.  Allow sufficient ullage (approximately 10% by




    volume) so container is not liquid full at 54°C Celsius




    (130°).  If sampling for volatile organic analysis, fill



    container to septum but use closed cap with space to




    provide an air space within the container.  Large quantities,




    up to 3.785 liters (1 gallon), may be collected if the




    sample's flash point is >^ 23°C (73°F).  In this case,




    the flash point must be marked on the outside container




    (e.g., carton, cooler).

-------
                                                                    2.0-11
2.  Seal sample and place in a 4 ml thick polyethylene bag,

    one sample per bag.

Liquids

3.  Place sealed bag inside a metal can with noncombustible,

    absorbent, cushioning material (e.g., vermiculite or

    earth) to prevent breakage, one bag per can.  Pressure-

    close the can and use clips, tape or other positive

    means to hold the lid securely.

A.  Mark the can with:

         Name

         Address

         "Flammable Liquid N.O.S."

         (or "Flammable Solid N.O.S.")

Note;  Using "Flammable" does not convey the certain knowledge

that a sample is flammable but is intended to prescribe the

class of packing needed to comply with DOT regulations.

5.  Place one or more metal cans in a strong outside container

    such as a picnic cooler or fiberboard box.  Ice or dry

    ice may be used between the metal cans and the outside

    container and must be contained to avoid water leakage

    during transport.  No other preservatives are allowed.

6.  Complete carrier's certification form as shown in Figure 2.0-5

7.  Samples may be transported by rented or common carrier

    truck, bus, railroad, and entities such as Federal Express*

    but not by normal common carrier air transport even on a

    "cargo only" aircraft.
*These procedures are designed to enable shipment by entities
 like Federal Express; however, they should not be construed
 as an endorsement by EPA of a particular commercial carrier.

-------
                                                                    2.0-12
Solids

3.  Place sealed bag inside cushioned overpack.  If sample

    is expected to undergo change during shipment cool using

    dry or wet ice.  Overpack must be designed to prevent

    water leakage during transport.  No other preservatives

    are allowed.

4.  Complete carrier's certification form as shown in Figure

    2.0-5.

5.  Samples may be transported by rented or common carrier

    truck, bus, railroad, and entities such as Federal Express* but

    not by normal common carrier air transport even on a "cargo
    6
    only" aircraft.

Receipt and Logging of Sample

     In the laboratory, a sample custodian should be assigned

to receive the samples.  Upon receipt of a sample, the custodian

should inspect the condition of the sample and the sample seal,

reconcile the information on the sample label and seal against

that on the chain of custody record, assign a laboratory number,

log in the sample in the laboratory log book, and store the

sample in a secured sample storage room or cabinet until

assigned to an analyst for analysis.

     The sample custodian should inspect the sample for any

leakage from the container.  A leaky container containing

multiphase sample should not be accepted for analysis.  This

sample will no longer be a representative sample. If the

sample is contained in a plastic bottle and the walls show
*These procedures are designed to enable shipment by entities
 like Federal Express; however, they should not be construed
 as,an endorsement by EPA of a particular commercial carrier.

-------
                                                                2.0-13
the sample is under pressure or releasing gases, respectively,




it should be treated with caution.   The sample can be explosive




or release extremely poisonous gses.  The custodian should




examine whether the sample seal is  intact or broken, since a




broken seal may mean sample tampering and would make analysis




results inadmissible in court as evidence.  Discrepancies




between the information on the sample label and seal and




that on the chain of custody record and the sample analysis




request sheet should be resolved before the sample is assigned




for analysis.  This effort might require communication with




the sample collector.  Results of the inspection should be




noted on the sample analysis request sheet and on the laboratory




sample log book.




     Incoming samples usually carry the inspector's or collec-




tor's identification numbers.  To further identify these




samples, the laboratory should assign its own identification




numbers, which normally are given consecutively.  Each sample




should be marked with the assigned  laboratory number.  This




number is correspondingly recorded  on a laboratory sample log




book along with the information describing the sample.  The




sample information is copied from the sample analysis request




sheet and cross-checked against that on the sample label.






Assignment of Sample for Analysis




     In most cases, the laboratory  supervisor assigns the




sample for analysis.  The supervisor should review the infor-




mation on the sample analysis request sheet, which now includes

-------
                                                                     2.0-14
inspection notes recorded by the laboratory sample custodian.




The supervisor should then decide what analyses are to be




performed.  The sample may have to be split with other labora-




tories to obtain the necessary information about the sample.




The supervisor should decide on the sample location and




delineate the types of analyses to be performed on each allo-




cation.  In his own laboratory, the supervisor should assign




the sample analysis to at least one analyst, who is to be




responsible for the care and custody of the sample once it is




received.  He should be prepared to testify that the sample




was in his possession or secured in the laboratory at all




times from the moment it  was received from the custodian




until the analyses were performed.




     The receiving analyst should record in the laboratory




notebook the identifying information about the sample, the




date of receipt, and other pertinent information. This record




should also include the subsequent testing data and calcu-




lations .

-------
                                                                     3.0-1
                         Section 3.0




                     SAMPLING METHODOLOGY






Introduction






    This section describes the equipment and procedures which




the Agency has determined are suitable for use in obtaining




a representative sample of a solid waste.




    Because the types of solid waste regulated under RCRA




cover a very broad range of physical and chemical types, the




information in this section will of necessity be general in




nature.  It is incumbent upon those persons conducting sampling




programs to exercise caution when using the methods described




herein.

-------
                                                                     3.2-1
                         Sub-Section 3.2




                        SAMPLING EQUIPMENT




Introduction






    Sampling the diverse types of RCRA regulated wastes requires




a variety of different types of samplers.   A number of such




sampling devices are described in this section.  While some of




these samplers are commercially available, others will have to be




fabricated by the user.  Table 3.2-1 is a general guide to the types




of waste that can be sampled by each of the samplers described.

-------
                                                                   3.2-2
                 Table  3.2-1




SAMPLING EQUIPMENT FOR  PARTICULAR WASTE TYPES
Sampling
I Point

| Waste
llype
Free
(Flowing
I Liquid s
land
Slurries
Sludges
Moist
Powders
or
Granules
Dry
Powders
or
Granules
Sand or
Packed
Powders
and
Granules
Large
Grained
Solids


Drum




Coli-
wasa

Trier

Trier



Thief




Auger


arge
Trier


Sacks
and
Bags



N/A


N/A

Trier



Thief




Auger


Large
Trier


Open
Bed
Truck



N/A


Trier

Trier



Thief




Auger


Large
Trier


Closed
Bed
Truck



Coli-
wasa

Trier

Trier



Thief




Auger


Large
Trier


Storage
Tanks
or Bins



Weighted
Bottle

Trier

Trier



Thief







Large
Trier



Waste
Piles



N/A


N/A

Trier



Thief







Large
Trier


Ponds,
Lagoons
& Pits



Dipper




Trier



Thief







Large
Trier


Con-
veyor
Belt



N/A
1

N/A

Shovel



Shovel




N/A


'Large
'Trier



Pipe




Dip-
per

N/A

















-------
                                                                     3.2-3
       3.2.1  Composite Liquid Waste Sampler (Coliwasa)






Scope and Purpose^




    The Coliwasa is a device employed to sample free  flowing




liquids and slurries contained in drums, shallow open  top




tanks, pits and similar containers.  It is especially  useful




in sampling wastes which consist of a number of immiscible




liquid phases.




    The Coliwasa consists of a glass, plastic, or metal  tube




equipped with an end closure which can be opened and  closed




while the tube is submerged in the material to be sampled.




    The Coliwasa was developed by the California Department




of Health under a grant from the U.S. EPA and their report,




"Samplers and Sampling Procedures for Hazardous Waste  Streams"




[Appendix I of this manual] should be consulted.




General Comments and Precautions




1.  Do not use a plastic Coliswasa to sample wastes containing




    organic materials.




2.  Do not use a glass Coliwasa  to sample liquids that contain




    hydrofluoric acid.




3.  If significant amounts of solid material are present




    within 2  inches of the bottom of the container  to  be sampled,




    special procedures will be necessary to obtain  a  representative




    sample of this solid phase.

-------
Apparatus




    Coliwasas are not available commercially and must be




fabricated to conform to the specifications detailed in




Figure 3.2-1.  Table 3.2-2 lists the parts required to fabricate




a plastic or glass Coliwasa.




                        Table 3.2-2




             PARTS FOR CONSTRUCTING A COLIWASA
Quantity
1
1
1
1
1
1
1
1
Item
Sample tube, translucent
PVC plastic, 4.13 cm
I.D. x 1.52 m long
x 0.4 cm wall thickness
Sample tube, borosilicate
glass, 4.13 cm I.D. x
1.52 m long
Stopper, neoprene rubber #9
Stopper rod, PVC, 0.95 cm
O.D. x 1.67 m long
Stopper rod, teflon,
0.95 cm O.D. x 1.67 m long
Locking block, PVC, 3.8 cm
O.D. x 10.2 cm long with
0.56 cm hole in center
Locking block sleeve, PVC
4.13 cm I.D. x 6.35 cm
long
T-handle, aluminum, 18 cm
long x 2.86 cm wide with
1.27 cm wide channnel
Comments
Plastic
Coliwasa
only
Glass
Coliwasa
only

Plastic
Coliwasa
only
Glass or
Plastic
Coliwasa
Fabricate by
drilling
0.56 cm hole
through
center
Fabricate
from stock
4.13 cm PVC
pipe
Fabricate
from aluminum
bar stock
Supplier
Plastic
supply
houses
Corning
Glass Works
#72-1602
Laboratory
supply house
Plastic
supply
houses
Plastic
supply
houses
Plastic
supply
houses
Plastic
supply
houses
Hardware
stores

-------
3.2-5
Quantity
1
1
1
1
1
1
1
1
Item
Swivel, aluminum bar
1.27 cm square x 5.08 cm
long with 3/8" NC inside
thread to attach stopper
rod
Nut, PVC, 3/8" NC
Washer, PVC, 3/8" NC
Nut, stainless steel,
3/8" NC
Washer, stainless steel,
3/8"
Bolt, 3.12 cm long x
3/16" NC
Nut, 3/16" NC
Washer, lock 3/16"
Comments
Fabricate
from aluminum
bar stock







Supplier
hardware
stores
Plastic
supplier
Plastic
supplier
Hardware
stores
Hardware
stores
Hardware
stores
Hardware
stores
Hardware
stores

-------
                                                                     3.2-6
Assembly






Assemble sampler as follows:




1.  Attach swivel to the T-handle with the 3.12cm long bolt




    and secure with the 3/16" NC washer and lock nut.




2.  Shape stopper into a cone by boring a 0.95 cm hole through




    the center of the stopper.  Insert a short piece of 0.95




    cm O.D. handle through the hole until the end of the handle




    is flush against the bottom (smaller diameter) surface




    of the stopper.  Carefully and uniformly turn the stopper




    into a cone against a grinding wheel.  This is done by turning




    the stopper with the handle and grinding it down conically




    from about 0.5 cm of the  top (larger diameter) surface to




    the edge of the 0.95 cm hole on the bottom surface.  Attach




    neoprene stopper to one end of the stopper rod and secure




    with the 3/8" NC washer and lock nut.




3.  Install the stopper and stopper rod assembly in the




    sampling tube.




4.  Secure locking block sleeve on the block with glue




    or screws.




5.  Position the locking block on top of the sampling tube




    so that the sleeveless portion of the block fits inside




    the tube, the sleeve sits against the top end of the tube,




    and the upper end of the  stopper rod slips through the center




    hole of the block.




6.  Attach the upper end of the stopper to the swivel of




    the T-handle.

-------
                                                                     3.2-7
7.  Place the sampler In the closed position and adjust the




    tension on the stopper by screwing the T-handle in or out.




8.  Test the tension by filling the Coliwasa with water to




    insure it is leak free.




Procedure




1.  Clean Coliwasa.




2.  Adjust sampler's locking mechanism to insure that the




    stopper provides a tight closure.  Open sampler by placing




    stopper rod handle in the T-position and pushing the rod down




    until the handle sits against the sampler's locking block.




3.  Slowly lower the sampler into the waste at a rate which




    permits the level of liquid inside and outside the sampler




    to remain the same.   If the level of waste in the sampler




    tube is lower inside than outside, the sampling rate is




    too fast and will produce a non-representative sample.




4.  When the sampler hits the bottom of the waste container,




    push sampler tube down to close and lock the stopper by turning




    the T-handle until it is upright and one end rests on the




    locking block.




5.  Withdraw Coliwasa from waste and wipe the outside




    with a disposable cloth or rag.




6.  Place sample tube at mouth of a container and discharge




    sample by slowly opening the sampler.

-------
                                                    2.86c«U-l/a»)
j

^





1
1

1
1
1





Capered
\~ ^
} 6
T
1



1
I



- Locking r
.35c«(2-l/2") block > j
1

i
i




1.52ui(5'-0")
1
1
1
1


1
1
1
1
1 1








stopper *7[lV «-
T^
I7.0cm(7")
\4"
I1-1-
1
1

€
1
1


--





I
i



1
J <
P*
                                                           Stopper  rod,  PVC
                                                           0.95cm(3/8")O.D.
                                                           Pipe. PVC,  4.13cM(l-5/8")l.D.
                                                           4.26cm(l~7/a")O.D.
                                                            Stopper, neoprene, #9 with
                                                            3/8"  S.S. or PVG nut and washer
SAMPLING POSITION
CLOSE POSITION
                                    Figure 3.2-1
                       COMPOSITE LIQUID WASTE SAMPLER  (COLIWASA)

-------
                                                                     3.2-9
                    3.2.2  Weighted Bottle






Scope and Application




     The sampler consists of a glass or plastic bottle, sinker,




stopper and a line which is used to lower and raise the bottle




and to open the bottle.  A weighted bottle samples liquids




and free flowing slurries.




General Comments and Precautions




1.  Do not use a plastic bottle to sample wastes containing




    organic materials.




2.  Do not use a glass bottle to sample wastes that contain




    hydrofluoric acid.




3.  Before sampling insure that the waste will not corrode




    the sinker, bottle holder or line.




Apparatus




    A weighted bottle with line is built to the specifications in




ASTM Methods D 270 and E 300 (Figure 3,2).




procedure




1.  Clean bottle.



2*  Assemble weighted bottle sampler.




3.  Lower the sampler to directed depth and pull out the




    bottle stopper by jerking the line.




4.  Allow bottle to fill completely as evidenced by cessation




    of air bubbles.




5.  Raise sampler, cap and wipe off with a disposable  cloth.




    The bottle can serve as a sample container.

-------
                                                       3.2-10
                           Washer
                          Pin
                             Nut
       Figure 3.2
WEIGHTED BOTTLE SAMPLER

-------
                                                                     3.2-11
                        3.2.3  Dipper


Scope and Application

    The dipper consists of a glass or plastic beaker clamped

to the end of a 2 or 3 piece telescoping aluminum or fiberglass

pole which serves as the handle.  A dipper samples liquids

and free flowing slurries.

General Comments and Precautions

1.  Do not use a plastic beaker to sample wastes containing

    organic materials.

2.  Do not USQ a glass beaker to sample wastes of high pH or

    which contain hydrofluoric acid.

3.  Paint aluminum pole and clamp with a 2 part epoxy or

    other chemical resistant paint when sampling either alkaline

    or acidic wastes.

Apparatus

     Dippers are not available commercially and must be fabri-

cated to confrom to the specifications detailed in Figure 3.2-3«

Table 3.2-3 lists the parts required to fabricate a dipper.

                         Table 3.2-3
               PARTS FOR CONSTRUCTING A DIPPER
1
Quantity I Item
1
I Adjustable clamp, 6.4 to 8.9 cm
1 | (2 1/2 to 3 1/2") for 250 to
I 600 ml beakers. Heavy duty
I aluminum.
1
I Tube 2.5 to 4.5 meters long with
1 | joint cam locking mechanism.
1 Diameter 2.54 cm ID and 3.18
) cm ID.
Supplier
Laboratory
supply
houses
Swimming
pool supply
houses

-------
                                                                    3.2-12
Quantity
1
4
4
Item
Polypropylene or glass beaker,
250 ml to 600 ml.
Bolts 2 1/4" x 1/4", NC
Nuts, 1/4", NC
Supplier
Laboratory
supply
houses
Hardware
stores
Hardware
stores
Procedure




1.  Clean beaker,  clamp, and handle.




2.  Assemble dipper by bolting adjustable clamp to the pole.




    Place beaker in clamp and fasten shut.




3.  Turn dipper so the mouth of the beaker faces down and




    insert into waste material.  Turn beaker right side up when




    dipper is at desired depth.  Allow beaker to fill completely




    as shown by the cessation of air bubbles.




4.  Raise dipper and transfer sample to container.

-------
                                                                                         3.2-13
        Varigrip clamp
    Beaker

250 to 600 ml
                                     Telescoping aluminum pole

                                   2.5 to 4.5 meters  (8 to  f5 ft)
                                      Figure  3.2-3
                                         DIPPER

-------
                                                                    3.2-14
                         3.2.4  Thief






Scope and Appication



    A thief consists of two slotted concentric tubes usually made




of stainless steel or brass.  The outer tube has a conical




pointed tip which permits the sampler to penetrate the material




being sampled.  The inner tube is rotated to open and close




the sampler.  A thief is used to sample dry granules or




powdered wastes whose particle diameter is less than 1/3 the




width of the slots.




Apparatus




    A thief is available at laboratory supply stores.  (Figure 3.2-4)




Procedure




1.  Clean sampler.




2.  Insert closed thief into waste material.  Rotate inner




    tube to open thief.  Wiggle the unit to encourage material




    to flow into thief.  Close thief and withdraw.  Place sampler




    thief in a horizontal position with the slots facing upward.



    Remove inner tube from thief and transfer sample to a container.

-------
                                                     3.2-15
60-100 cm    —>
          JL  V
             -HK-
           1.27-2.54 cm
            Figure 3.2-4
           THIEF SAMPLER

-------
                                                                    3.2-16
                         3.2.5  Trier






Scope and Application




     A trier consists of a tube cut in half lengthwise with a




sharpened tip that allows the sampler to cut into sticky




solids and loosen soil.  A trier samples moist or sticky solids




with a particle diameter less than 1/2 the diameter of the trier.




Apparatus




1.  Triers 61 to 100 cm long and 1.27 to 2.54 cm in




    diameter are available at laboratory supply stores.




2.  A large trier can be fabricated to confrom to the specifications




    in Figure 3-5.  A metal or polyvinyl chloride pipe 1.52




    m (51) long x 3.2 cm (1.4") I.D. with a 0.32 cm (1 1/8")




    wall thickness is needed.  The pipe should be sawed length-




    wise, about 60-40 split, to form a trough stretching from one




    end to 10 cm away from the other end.  The edges of the slot




    and the tip of the pipe are sharpened to permit the sampler




    to cut into the waste material being sampled.  The unsplit




    length of the pipe serves as the handle.




Procedure



1.  Clean trier.




2.  Insert trier into waste material 0 to 45° from horizontal.




    Rotate trier to cut a core of the waste.  Remove trier




    with concave side up and transfer sample to container.

-------
                                                                        3.2-1?
C
                     122-183 cm
                      (48-72")
                                                    1
5.08-7.62 cm
                 \
         60-100 cm
                   /
                   \
                       c/
                         k-
                  1.27-2.54 cm
                   Figure 3.2-5
                 SAMPUNG TKEERS

-------
                                                                    3.2-18
                         3.2.6  Auger




Scope and Application



     An auger consists of sharpened spiral blades attached to




a hard metal central shaft.  An auger samples hard or packed




solid wastes or soil.




Apparatus




     Augers are available at hardware and laboratory supply stores




Procedures



1.  Clean sampler.




2.  Bore a hole through the middle of an aluminum pie pan




    large enough to allow the blade of the auger to pass




    through.  The pan will be used to catch the sample brought to




    the surface by the auger.




3.  Place pan against the sampling point.  Auger through the




    hole in the pan until the desired sampling depth is




    reached.  Back off the auger and transfer the sample in the




    pan and adhering to the auger to a container.  Spoon out the



    rest of the loosened sample with a sample trier.

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                                                                     3.2-19
                   3.2.7  Scoop and Shovel






Scope and Application




     Scoops and shovels are used to sample granular or powdered




material In bins, shallow containers and conveyor belts.




Apparatus




     Scoops are available at laboratory supply houses.  Flat




nosed shovels are available at hardware stores.




procedure




1.  Clean sampler.




2.  Obtain a full cross section of the waste material with




    the scoop or shovel large enough to contain the waste




    collected in one cross section sweep.

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                                                                     3.3-1
                       Sub-Section 3.3




                      SAMPLE CONTAINERS




Containers




     The most important factors to consider when choosing




containers for hazardous waste samples are compatibility




with the waste, cost, resistance to breakage, and volume.




Containers must not distort, rupture, or leak as a result of




chemical reactions with constituents of waste samples.  Thus,




it is important to have some idea of the properties and




composition of the waste.  The containers must have adequate




wall thickness to withstand handling during sample collection




and transport to the laboratory.  Containers with wide mouths




are desirable to facilitate transfer of samples from samplers




to containers.  Also, the containers must be large enough to




contain the required volume of sample or the entire volume




of a sample contained in samplers.




     Plastic and glass containers are generally used for




collecting and storing of hazardous waste samples.  Commonly




available plastic containers are made of high-density or




linear polyethylene  (LPE), conventional polyethylene, poly-




propylene, polycarbonate, teflon FEP (flourinated ethylene




propylene), polyvinyl chloride (PVC), or polymethylpentene.




Teflon FEP is almost universally usuable due to its chemical




inertness and resistance to breakage.  However, its high cost




severely limits its use.  LPE, on the other hand, offers the



best combination of chemical resistance and low cost when




inorganic wastes are involved.

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                                                                     3.3-2
     Glass containers are relatively inert to most chemicals




and can be used to collect and store almost all hazardous waste




samples except those that contain strong alkali and hydro-




flouric acid.  Soda glass bottles are suggested due to their




low cost and ready availability.  Borosilicate glass containers,




such as Pyrex and Corex, have advantages relative to Inertness




and resistance to breakage respectively but are expensive and




not always readily available.  Glass containers are generally




more fragile and much heavier than plastic containers.  Glass




or FEP containers must be used for waste samples that will be




analyzed for organic compounds.




     The containers must have tight, screw-type lids.  Plastic




bottles are usually provided with screw caps made of the same




material as the bottles.  Buttress threads are recommended.




Cap liners are not usually required for plastic containers.




Teflon cap liners should be used with glass containers supplied




with rigid plastic screw caps.  These caps are usually provided




with waxed paper liners.  Other liners that may be suitable




are polyethylene, polypropylene, neoprene, and teflon FEP




plastics.  Teflon liners may be purchased from plastic specialty




supply houses (e.g., Scientific Specialties Service, Inc.,




P.O. Box 352, Randallstown, Maryland  21133).

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                                                                     4.0-1
                           Section 4




                         IGNITABILITY




Introduction




     The objective of the Ignitability characteristic is to




identify wastes which present fire hazards due to being




ignitable under routine storage, disposal, and transportation




and wastes capable of severely exacerbating a fire once




started.

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                         Sub-Section 4.1

          CHARACTERISTIC OF IGNITABILITY REGULATION

    A solid waste exhibits the characteristic of

ignitability if a representative sample of the waste has any

of the following properties:

1.  It is a liquid, other than an aqueous solution  con-

    taining less than 24 percent alcohol by volume, and has

    a flash point less than 60°C (140°F), as determined

    by a Pensky-Martens Closed Cup Tester, using the test

    method specified in ASTM Standard D-93-79, or a Setaflash

    Closed Cup Tester, using the test method specified in ASTM

    standard D-3278-78, or as determined by an equivalent test

    method approved by the Administrator under the procedures

    set forth in §§260.20 and 260.21.*

2.  It is not a liquid and is capable, under standard

    temperature and pressure, of causing fire through fric-

    tion, absorption of moisture or spontaneous chemical

    changes and, when ignited, burns so vigorously and per-

    sistently that it creates a hazard.

3.  It is an ignitable compressed gas as defined in 49 CFR

    173.300 an-* as determined by the test methods described

    in that regulation or equivalent test methods approved

    by the Administrator under §§260.20 and 260.21.

4.  It is an oxidizer as defined in 49 CFR  173.151.
* ASTM Standards are available from ASTM, 1916 Race Street,
 Philadelphia, PA  19103.

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                                                                      4.1-2
     A solid waste that exhibits the characteristic of




ignitabillty,  but is not listed as a hazardous waste in




Subpart D, has the EPA Hazardous Waste Number of D001.

-------
                       Sub-Section 4.4




                   IGNITABLE COMPRESSED GAS




     For the purpose of this regulation the following terminol-




ogy is defined:




     1.  Compressed gas.  The term "compressed gas" shall




         designate any material or mixture having in the




         container an absolute pressure exceeding 40 p.s.i. at




         70°F or, regardless of the pressure at 70°F, having an




         absolute pressure exceeding 104 p.s.l. at 130°F, or




         any liquid flammable material having a vapor pressure




         exceeding 40 p.s.i. absolute at 100°F as determined by




         ASTM Test D-323.




     2.  Ignitable compressed gas.  Any compressed gas as




         defined in paragraph (a)  of this section shall be




         classed as an "ignitable  compressed gas" if any one




         of the following  occurs:




         a.  Either a mixture of 13 percent or less




             (by volume) with air  forms a flammable mixture




             or the flammable range with air is wider than




             12 percent regardless of the lower limit.  These




             limits shall  be determined at atmospheric




             temperature and pressure.   The method of sampling




             and test procedure shall be acceptable to the




             Bureau of Explosives.




         b.  Using the Bureau of Explosives' Flame




             Projection Apparatus  (see  Note 1), the flame




             projects more than 18 inches beyond the ignition

-------
                                                           4.4-2
    source with valve opened fully,  or, the flame

    flashes back and burns at the valve with any

    degree of valve opening.

c.  Using the Bureau of Explosives'  Open Drum

    Apparatus (see Note 1), there is any significant

    propagation of flame away from the ignition source.

d.  Using the Bureau of Explosives'  Closed Drum

    Apparatus (see Note 1), there is any explosion

    of the vapor-air mixture in the  drum.

NOTE 1:  A description of the Bureau of
Explosives' Flame Projection Apparatus,
Open Drum Apparatus, Closed Drum Appa-
ratus, and method of tests may be
procured from the Bureau of Explosives.

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                                                                    4.5-1
                        Sub-Section 4.5



                           OXIDIZER



     An oxidizer for the purpose of this regulation is any



material that yields oxygen readily to stimulate the



combustion of organic matter (e.g., chlorate, permanganate,



peroxide, nitro carbo nitrate, inorganic nitrate).

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                                                                    5.(XL
                          Section 5




                         CORROSIVITY




Introduction




     The corrosivity characteristic, as defined in 40 CFR




261*22, is designed to identify wastes which might pose a




hazard to human health or the environment due to their ability




to:



     a.  Mobilize toxic metals if discharged into a landfill




         environment•




     b.  Require handling, storage, tranportation and management




         equipment to be fabricated of specially selected mater-




         ials of construction, and




     c.  Destroy human or animal tissue in the event of inadver-




         tant contact.




     In order to identify such potentially hazardous materials,




the Agency has selected several properties upon which to base




the definition of a corrosive waste.  These properties are




pH and corrosivity toward Type SAE 1020 steel.  The following




section presents methodology for measuring the pH of aqueous



wastes and for determining whether the waste is corrosive to




steel.

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                                                                    5.1-1
                       Sub-Section 5.1

           CHARACTERISTIC OF CORROSIVITY REGULATION


1.  A solid waste exhibits the characteristic of corrosivity

    if a representative sample of the waste has either of

    the following properties:

    a.  It is aqueous and has a pH less than or equal to 2

        or greater than or equal to 12.5, as determined by a

        pH meter using either the test method specified in the

        "Test Methods for the Evaluation of Solid Waste, Physical/

        Chemical Methods"* (also described in "Methods for Analysis

        of Water and Wastes" EPA 600/4-79-020, March 1979), or

        an equivalent test method approved by the Administrator

        under the procedures set forth in §§260.20 and 260.21.

    b.  It is a liquid and corrodes steel (SAE 1020) at a

        rate greater than 6.35 mm (0.250 inch) per year at a

        test temperature of 55°C (130°F) as determined by the

        test method specified in NACE (National Association of

        Corrosion Engineers) Standard TM-01-69** as standardized

        in "Te^t Methods for the Evaluation of Solid Waste,

        Physical/Chemical Methods," or an equivalent test

        method approved by the Administrator under the proce-

        dures set forth in §§260.20 and 260.21.

2.  A solid waste that exhibits the characteristic of corrosivity,

    but is not listed as a hazardous waste in Subpart D, has

    the EPA Hazardous Waste Number of D002.
*This document is available from Solid Waste Information, U.S.
 Environmental Protection Agency, 26 W. St. Clair Street,
 Cincinnati, Ohio 45268
**The NACE Standard is available from the National Association of
  Corrosion Engineers, P.O. Box 986, Katy, Texas 77450

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                                                                    5.2-1
                          Method 5.2

                        pH MEASUREMENT


Scope and Application

     This method* is applicable to aqueous wastes and those

multiphasic wastes where the aqueous phase comprises at least

20% of the total volume of the waste.

Summary

     The pH of the sample is determined electrometrically

using either a glass electrode in combination with a reference

potential or a combination  electrode.  The measuring device

is calibrated using a series of solutions of known pH.

Interferences

1.  The glass electrode, in general, is not subject to solution

    interferences from color, turbidity, colloidal matter,

    oxidants, reductants or high salinity.

2.  Sodium error at pH levels greater than 10 can be reduced

    or eliminated by using a "low sodium error" electrode.

3.  Coatings of oily material or particulate matter can

    impair electrode response.  These coating can usually be

    removed by gentle wiping or detergent washing, followed by

    distilled water rinsing.  An additional treatment with

    hydrochloric acid (1 + 9) may be necessary to remove any

    remaining film.
*This method has been adapted from Method 150.1 of "Methods
for the Analysis of Water and Wastewater", EPA-6000/4-79-020,
U.S. EPA, EMSL, Cincinnati, OH  45268

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                                                                5.2-2
4.  Temperature effects on the electrometric determination




    of pH arise from two sources.  The first is caused by the




    change In electrode output at various temperatures.  This




    interference can be controlled with instruments having




    temperature compensation or by calibrating the electrode-




    instrument system at the temperature of the samples.  The




    second source is the change of pH inherent in the sample at




    various temperatures.  This error Is sample dependent




    and cannot be controlled; It should, therefore, be noted




    by reporting both the pH and temperature at the time of




    analysis.




Apparatus




1.  pH Meter-laboratory or field model.  A wide variety of




    instruments are commercially available with various




    specifications and optional equipment.




2.  Glass electrode.




3.  Reference electrode - a silver-silver chloride or other




    reference electrode of constant potential may be used.




    NOTE:  Combination electrodes incorporating both measuring




    and referenced functions are convenient to use and are




    available with solid, gel type filling materials that require




    minimal maintenance.




 4.  Magnetic stirrer and Teflon-coated stirring bar.




 5.  Thermometer or temperature sensor for automatic compensation.




Reagents




1.  Primary standard buffer salts are available from the




    National Bureau of Standards and should be used in situations

-------
                                                                    5.2-3




    where extreme accuracy is necessary.  Preparation of




    reference solutions from these salts requires some special




    precautions and handling(l) such as low conductivity




    dilution water, drying ovens, and carbon dioxide free




    purge gas*  These solutions should be replaced at least




    once each month.




2.  Secondary standard buffers may be prepared from NBS




    salts or purchased as a solution from commercial vendors.




    Use of these commercially available solutions, that have




    been validated by comparison to NBS standards, are recom-




    mended for routine use.




Calibration




1.  Because of the wide variety of pH meters and accessories,




    detailed operation procedures cannot be incorporated




    into this method.  Each analyst must be acquainted with




    the operation of each system and familiar with all instru-




    ment functions.  Special attention to care of the electrodes




    is recommended.




2.  Each instrument/electrode system must be calibrated




    at a minimum of two points that bracket the expected pH



    of the samples and are approximately three pH units or




    more apart.  Various instrument designs may involve use




    of a "balance" or "standardize" dial and/or slope adjust-




    ment as outlined in the manufacturer's instructions.




    Repeat adjustments on successive portions of the two




    buffer solutions as outlined in procedure 8.2 until
   National Bureau of Standards Special Publication 260.

-------
     readings are within 0.05 pH units of the buffer solution




     value.




 Procedure




 1.  Standardize the meter and electrode system as outlined




     in Section 7.



 2.  Place the sample or buffer solution in a clean glass




     beaker using a sufficient volume to cover the sensing




     elements of the electrodes and to give adequate clearance




     for the magnetic stirring bar.  If field measurements




     are being made the electrodes may be immersed directly




     in the sample stream to an adequate depth and moved in a




     manner to insure sufficient sample movement across the




     electrode sensing element as indicated by drift free




     «0.1 pH) readings.




• 3.  If the sample temperature differs by more than 2° C




     from the buffer solution, the measured pH values must be




     corrected.  Instruments are equipped with automatic or




     manual compensators that electronically adjust for tempera-




     ture differences.  Refer to manufacturer's instructions.




 4.  After rinsing and gently wiping the electrodes, if




     necessary, immerse them into the sample beaker or sample




     stream and stir at a constant rate to provide homogeneity




     and suspension of solids.  Rate of stirring should minimize




     the air transfer rate at the air water interface of the




     sample.  Note and record sample pH and temperature.




     Repeat measurement on successive volumes of sample until




     values differ by less than 0.1 pH units.  Two or three




     volume changes are usually sufficent.

-------
                                                                    5.2-5

                         Bibliography

1.  Standard Methods for the Examination of Water and Wastevater,
    14th Edition,  p. 460, (1975).

2.  Annual Book of ASTM Standards,  Part 31, "Water", Standard
    D1293-65, p. 178, (1976).

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                                                                   5.3-1
                          Method 5.3

                   CORROSIVITY TOWARD STEEL


Introduction

     This methodt is applicable to either aqueous or non aqueous

liquid wastes.

Summary of the Method

     This test exposes coupons of SAE Type 1020 steel to the

liquid waste to be evaluated and, by measuring the degree to

which the coupon has been dissolved, determines the corrosivity

of the waste.

Precautions and Comments

1.  In laboratory tests, such as this one, corrosion of

    duplicate coupons is usually reproducible to within + 10%.

    Occasional exceptions, in which large differences are

    observed, can occur under conditions where the metal

    surfaces become passivated.  Therefore, at least dupli-

    cate determinations of corrosion rate should be made.

2.  A circular specimen of about 3.75 cm (1.5 inch) diameter

   is a convenient shape for laboratory use.   With a thick-

   ness of approximately 0.32 cm (0.125 inch) and a 0.80 cm

   (0.4 inch) diameter hold for mounting, these specimens

   will readily pass through a 45/50 ground glass joint of a

   distillation kettle.  The total surface area of a circular

   specimen is given by the following equation:
  tThis method is based on NACE Standard TM-01-69(1972 Revision),
   "Laboratory Corrosion Testing of Metals for the Process Industries",
   National Association of Corrosion Engineers, 3400 West Loop South,
   Houston, TX  77027

-------
                                                                    5.3-2




     A - 3.14/2(D2-d2)+(t)(3.14)(D)+(t)(3.14)(d)




where t * thickness, D - diameter of the specimen, and




d - diameter of the mounting hole. If the hole is completely




covered by the mounting support, the last term [(t) (3 .14)(d) ]




in the equation is omitted.




3.  All coupons should be measured carefully to permit




    accurate calculation of the exposed areas.  An area cal-




    culation accurate to 4^ 1% is usually adequate.




4.  More uniform results may be expected if a substantial




    layer of metal is removed from the coupons prior to testing




    the corrosivity of the wste.  This can be accomplished




    either by chemical treatment (pickling), electrolytic




    removal, or by grinding with a coarse abrasive.  At




    least 0.000254 cm (0.0001 inch ) or 2 to 3 mg/cm2 should




    be removed.  Final surface treatment should include




    finishing with #120 abrasive paper or cloth.  Final




    cleaning consists of scrubbing with bleachfree scouring




    powder,  followed by rinsing in distilled water, then



    acetone  or methanol, and finally air drying.  After




    final cleaning the coupon should be stored in a desic-



    cator until used.




5.  The minimum ratio of volume of waste to area of the




    metal coupon to be used in this test is 40 ml/cm2.




Equipment




1.  A versatile and convenient apparatus should be used, con-




    sisting  of a kettle or flask of suitable size (usually 500




    to 5000  millilieters), a reflex condenser with atmospheric

-------
                                                                    5.3-3
    seal, a thermowell and temperature regulating device, a




    heating device (mantle, hot plate, or bath), and a specimen




    support system.  A typical resin flask set up for this type




    test is shown in figure 1.




2.  The supporting device and container should not he




    affected by or cause contamination of the waste under test.




3.  The method of supporting the coupons will vary with




    the apparatus used for conducting the test but should be




    designed  to insulate the coupons from each other physically




    and electrically and to insulate the coupons from any metallic




    container or other device used in the test.  Some common




    support materials include:  glass, fluorocarbon or coated metal.




4.  The shape and form of the coupon support should assure free




    contact with the waste.




Test Procedure




1.  Assemble the test apparatus as described the "Equipment"




    section above.




2.  Fill the container with the appropriate amount of waste.




    (See #5 under the "Precautions and Comments" section.)




3.  Begin agitation at a rate sufficient to insure that




    the liquid is kept well mixed and homogeneous.




4.  Using the heating device bring the temperature of




    the waste to 55° C (130° F).




5.  If the anticipated corrosion rate is moderate (i.e.,




    <635 mmpy),  the test should be run for at leat 200 hours to




    insure adequate weight loss to permit accurate results to be




    obtained.  If the corrosion rate is low (i.e., >100 mmpy),

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                                                                       5.3-4
       then the  test  duration  should  be  on  the  order  of  2000  hours.



       in cases  where the  anticipated corrosion rate  is  completely




       unknown,  initial  testing  should be  performed using a 200




       hour duration.




   6.   In order  to  accurately  determine  the amount of material




       lost to  corrosion,  the  coupons have  to be cleaned after




       immersion and  prior to  weighing.   The cleaning procedure




       should  remove  all products  of  corrosion while  removing a




       minimum  of sound  metal.  Cleaning methods can  be  divided




       into three general  categories:  mechanical, chemical and




       electrolytic.




        Mechanical  cleaning includes  scrubbing, scraping, brushing




   and ultrasonic procedures.   Scrubbing with a bristle  brush




   and mild abrasive  is  the most popular of these methods; the




   others are  used  in cases of heavy  corrosion as a first step




   in  removing  heavily encrusted corrosion products prior to




   scrubbing.   Care should be  taken to avoid removing sound metal.




        Chemical cleaning implies  the removal of material from




   the surface  of the coupon by dissolution in an appropriate




   solvent.  Solvents such as  acetone, dichloromethane,  and




   alcohol are  used to remove  oil, grease  or resinous materials,




   and are used  prior to immersion to remove the products of corrosion.




   Solutions suitable for removing corrosion from the steel




   coupon are:




           Solution                     Soaking Time       Temperature




   20% NaOH +  200g/l  zinc dust             5 min            Bailing




           or




Cone.  HC1 + 50g/l SnCl2  + 20g/l SB-^    Until clean            Cold

-------
                                                                    5.3-5
     Electrolytic cleaning should be preceeded by scrubbing




to remove loosely adhering corrosion products.  One method of




electrolytic cleaning that can be employed is:
     Solution




     Anode




     Cathode




     Cathode current density




     Inhibitor




     Temperature




     Exposure Period
50 g/1 H2S04




Carbon or lead




Steel coupon




20 amp/cm2 (129 amp/in2)




2 cc organic inhibitor/liter




74°C (165°F)




3 minutes
Note; Precautions must be taken to insure good electrical




contact with the coupon, to avoid contamination of the cleaning




solution with easily reducible metal ions, and to insure




that inhibitor decomposition has not occurred.  Instead of




using a proprietary inhibitor, 0.5 g/1 or either diorthotolyl




thiourea or quinolin ethiodide can be used.




     Whatever treatment is employed to clean the coupons, its




effect in removing sound metal should be determined using a




blank (i.e., a coupon that has not been exposed to the waste).




The blank should be cleaned along with the test coupon and




its waste loss subtracted from that calculated for the test




coupons.




7.  After corroded specimens have been cleaned and dried,




    they are reweighed.  The weight loss is employed as the




    principal measure of corrosion.  Use of weight loss as a

-------
                                                                5.3-6
measure of corrosion required making the assumption that

all weight loss has been due to generalized corrosion

and not localized pitting.  In order to determine the

corrosion rate for purpose of this requlation, the following

formula is used:

      Corrosion Rate (mmpy) =» (weight loss) (0.268)
                                (area) (time)

      where weight loss is in milligrams, area in square

      centimeters, time in hours, and corrosion rate in

      millimters  per year (mmpy).

-------
f!J] technical practices committsss
NACE Standard TM-01-89
   (1972 Revision)
                     Test Method
    Laboratory  Corrosion  Testing  of Metais
             for the Process Industries
                        Approved March, 1969
                        Revised August, 1972
                  National Association of Corrosion Engineers
                        2400 Wert Loop Sooth
                        Houston, Texas 77027
                          713/622-8980

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                                                                                                                 5.3-6
The National Association of Corrosion Engineers issues this
Standard  in conformity to  the best current technology
regarding  the specific subject.  This Standard represents
minimum requirements  and should in  no way be  inter-
preted as a restriction on the use of better procedures or
materials. Neither is this  Standard intended to apply in any
and all cases  relating  to the subject. Numerous external
factors may  negate the usefulness  of  this  Standard in
specific instances.

This Standard may be used in whole or in part by any party
 without prejudice if recognition of the source is included.
 The National Association of Corrosion Engineers  assumes
 no responsibility  for  the  interpretation or  use  of  this
 Standard-

 Nothing contained in  this Standard of the National Asso-
 ciation  of  Corrosion  Engineers is  to  be construed as-
 granting any right, by implication or otherwise, for manu-
 facture, sale, or  use  in  connection  with any  method,
 apparatus, or product  covered by Letters Patent, nor as
 indemnifying or  protecting anyone  against  liability for
 infringement of Letters Patent.
                                                    Foreword
Unit Committee T-5A ("Corrosion in Chemical Processes")
of the National Association of Corrosion Engineers issues
this Standard with a dual purpose.

The  first  purpose is to standardize, as much' as possible,
simple immersion corrosion studies.  In  this sense,  this
Standard  is  reasonable and effective  without  imposing
inflexible  requirements as  to  apparatus, conditions, or
techniques. The actual conditions of test will be determined
by the problem at hand and limited only by the  ingenuity
of the individual investigator.

The  second purpose of this Standard is to present to the
user  a consensus on the best current technology in this fieJd
of laboratory  corrosion testing.  As  such,  this  Standard
enumerates and discusses the many factors which must be
considered, controlled,  and reported  in order to aid in
correlation or reproducibility of such studies.

The techniques described permit the investigator to repro-
duce to a considerable  extent  in the laboratory,  through
judicious experimental design, the process conditions which
govern  corrosion  mechanisms.  The tests  are  not to  be
construed  as "accelerated"  tests,  which  are generally
unreliable. The methods described are also applicable to
materials qualification tests for quality control. However,
the  latter  require more  rigid definition,  of apparatus,
conditions, and technique.

The ultimate purpose is  better correlation of results in the
future and  the reduction of conflicting reports through a
more detailed  recording of meaningful factors and con
ditions.

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                          TEST METHOD
              Laboratory Corrosion Testing of Metals
                     for the Process Industries
                            CONTENT*

  1. Genera]    	2

  2. Specimen Preparation	2

  3. Equipment and Apparatus   	3

  4. Test Conditions   	4

  5. Methods of Cleaning Specimens
     After the Test	7

  6. Evaluation of Results   	8

  7. Calculating Corrosion Rates	9

  8. Reporting the Data	10

  References    	10
Additional copies of this NACE Standard are available at 52 per copy from
NACE Headquarters, 2400 West Loop South, Houston, Texas 77027.

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                                                   1. General
 1.1  This  Standard describes the  factors which influence
 laboratory tests.  These factors include specimen prepara-
 tion,  apparatus,  test  conditions  (solution  composition,
 temperature,  velocity,  aeration,  volume,  method  of
 supporting  specimens,  duration  of  test),  methods  of
 cleaning specimens, evaluation of results, and calculation of
 corrosion  rates. This Standard also emphasizes the impor-
 tance of recording  all pertinent data and provides a check
 list for reporting test data.

 1.2  Experience has shown that all metals and alloys do
not  respond  alike  to  the many factors that  control
corrosion and that  "accelerated", corrosion  tests- give
indicative results only. Consequently, it is impractical to
propose an inflexible standard laboratory corrosion testing
procedure for general use except for material qualification
tests, where standardization is obviously required,

1.3  In designing any corrosion test, consideration must be
given to  the various factors discussed in this test method
because these factors have been found to affect greatly the
results obtained.
,5*3
                                            2. Specimen Preparation
2.1   In  laboratory tests,  corrosion  rates  of duplicate
specimens  are  usually  within ± 10% under the same test
conditions.  Occasional  exceptions, in which a large dif-
ference is observed, can occur under conditions of border-
line  passivity of metals or alloys 'that depend on a passive
film for their  resistance to corrosion. Therefore,  at least
duplicate specimens should be exposed in each test.

2.2   If the effects of  corrosion are to be determined by
changes  in  mechanica]  properties,  untested  duplicate
specimens should oe preserved in a non-corrosive environ-
n.^.ii for  comparison  with the corroded specimens. The
mechanical property commonly used for comparison is the
tensile strength. The*procedure for determining this value is
shown in detail in ASTM Standard E-8- latest edition.

2.3   The size and the shape of specimens will vary with the
purpose of the  test, nature of the materials, and apparatus
used. A large surface-to-mass ratio and a small ratio of edge
area  to total area are desirable. These ratios can be achieved
through the  use  of rectangular or circular specimens of
minimum  thickness. Circular  specimens  should  be cut
preferably from sheet  and not bar  stock  to minimize the
exposed end grain.

     2.3.1   A  circular  specimen  of about  1 1/2-thch
     diameter is a  convenient shape for laboratory corro-
     sion tests. With a  thickness of approximately 1/8 inch
     and a 5/16 or 7/16-inch diameter hole for mounting,
     these  specimens  will readily  pass through a  45/50
     ground  glass joint of a distillation kettle. The total
     surface  area  of a circular  specimen is given  by the
     following equation:
               A= -
     where t = thickness, D = diameter of the specimen,
     and d = diameter of the mounting hole. If the hole is
     completely covered by the mounting support, the last
     term (t~d) in the equation is omitted.
      2.3.2   Strip coupons fof about 4 square inches) may
      be preferred as corrosion specimens, particularly if
      interface or liquid line effects are to be studied by the
      laboratory test, but such effects are beyond the scope
      of this Standard.

      2.3.3   All specimens should be measured carefuuy to
      permit  accurate calculation of the exposed areas.- An
      area calculation  accurate to  plus or  minus 1% is
      usually adequate.

2.4   More uniform results may be expected if a substantia7
layer of metal is removed from the specimens to eliminate
variations in  condition of the original metallic surface. This
can  be  done either by  chemical treatment  (pickling),
electrolytic removal, or by grinding with a coarse abrasive
paper or  cloth,  such as No. 50, using caie not to work
harden  the surface (see Section 2.7). At least 0.0001 inch
or 10 to 15 milligrams per square inch should be removed.
If clad  alloy specimens are to be used, special attention
must be given to insure that excessive metal is not removed-
After  final  preparation   of the  specimen  surface-trie
specimens should be stored in a desiccator until exposure if
they are not used immediately.

2.5   Exposure of sheared edges should be avoided unless
the purpose of the test is to study effects of the shearing
operation. It may be desirable to test a surface representa-
tive  of  the  material and metallurgical  condition used in
practice.

2.6   The specimen can be  stamped with an appropriate
identifying mark.

      2.6.1   The stamp, besides identifying the specimen,
     introduces  stresses and cold  work in the specimen,
      that could  be  responsible  for  localized  corrosion
     and/or stress corrosion cracking.

     2.6.2   Stress  corrosion cracking  at the identifying
     mark is a positive  indication of susceptibility to such

-------
      corrosion;  however, "the  absence of cracking should
      not be interpreted as indicating resistance. Additional
      tests should be run to study specifically the effects of
      stress.

 2.7  Final surface  treatment  of  the  specimens  should
 include  finishing with No.  120 abrasive paper or cloth, or
 the equivalent, unless the surface  is to be  used in  the
 mill-finished condition.  This resurfacing may cause some
 surface work-hardening to an extent which will be deter-
 mined by  the  vigor of the  surfacing operation but is  not
 ordinarily significant.

      2.7.1   Coupons  of   different  alloy   compositions
      should never be ground on the same cloth.

      2.7.2   Wet grinding should be used on alloys which
      work harden quickly, such as the  austenitic stainless
      steels,

 2.S  The specimens  should be finally degreased by scrub-
 bing  with  bleach-free  scouring powder,  followed  by
 thorough rinsing in water and in a suitable solvent (such as
 acetone, methanol, or a mixture of 50%methanol and ,50%
 ether) and  air dried. For  relatively soft metals  such as
 aluminum, magnesium, and copper, scrubbing with abrasive
        is not always needed and can mar the surface of the-
 specimen. Trie  use of towels for drying may introduce an
 error through contamination of the specimens with grease
 or lint.

 2.9   The  dried  specimens  should be  weighed  on  an
 analytical balance  to an accuracy  of plus  or minus  0.5
 milligram.
2 10 The  method  of  specimen  preparation  should be
described when reporting tests results to facilitate interpre-
tation of data by other persons.

     2.10.1 Reports   should  include   trade   name  or
     composition of specimens in the following order of
     preference: (a) chemical composition determined by
     analysis,  (b)   approximate  or  nominal  chemical
     composition,  and  (c)  trade  name  or  grade  and
     specification (if bought to MIL, ASTM, etc.)

     2.10.2 Metallurgical  condition of  the  specimens
     including the degree of hot or cold working arid heat
     treatment,  should  be  described as  completely as
     possible.

2.11 The use  of  welded  specimens  is  often  desirable
because some welds may be cathodic or anodic to the base
metal and may affect the corrosion.

     2.11.1 The heat-affected zone is also of importance
     but should be studied  separately  because wtlds on
     coupons do not  faithfully reproduce heat input or
     size effects of full-size vessels.

     2.11.2 Corrosion of a welded coupon is best reported
     by  description 'and  thickness  measurements  rather
     than  a mils-per-year  rate  because  the  attack is
     normally localized and not  representative of  the
     entire surface.

     2.11.3 A complete discussion of corrosion testing of
     welded  coupons or the effect of heat treatment on
     the corrosion resistance of a metal is not within the
     scope of this Standard.
                                                                                                                    5.3-n
                                         3.  Equipment and Apparatus
3.1  A versatile and convenient apparatus should be used,
consisting of a kettle or flask of suitable size (usually 500
to 5000 mJMiters), a reflux condenser with atmospheric
seal, a  sparger for  controlling  atmosphere or aeration, a
thermowell  and temperature regulating device,  a  heating
device  (mantle, hot plate, or bath), and a specimen support
system. If  agrfation  is required, the  apparatus  can be
modified to accept  a suitable stirring mechanism such as a
magnetic stirrer. A  typical  resin flask set up for this type
test is shown in Figure 1.

3.2  These  suggested components can be modified, simpli-
-fied or made more  sophisticated to  fit  the needs of a
particular  investigation. The suggested apparatus is basic,
and the apparatus  is limited only by the judgment and
ingenuity of the investigator.
     3.2.1   A  glass reaction  kettle  can be used wnere
     configuration and size of specimens will permit entry
     through the narrow kettle neck.

     3.2.2   In some  cases, a  wide  mouth  jar with  a
     suitable closure is sufficient when simple immersion
     tests at ambient temperatures aie to be investigated.

     3.2.3   Open beaker tests should not be used because
     of evaporation and contamination.

     3.2.4   In  more complex  tests,  provisions might be
     needed for continuous flow or replenishment of the
     corrosive liquid while  simultaneously maintaining a
     controlled atmosphere.

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                                                4.  Test Conditions
4.1   Selection of the conditions for a laboratory corrosion
test will be determined by the purpose of the test.

      4.1.1   If the test is to be a guide for the selection of
      a  material  for  a particular purpose, the limits of
      controlling  factors in  service  must be determined.
      These factors include oxygen concentration, tempera-
      ture, rate of flow, pH value,  and other important
      characteristics of the solution.

4.2   An  effort should  be  made to duplicate  all service
conditions in the corrosion test.

4.3   It is important  that  test  conditions be  controlled
throughout, the test in order  to ensure reproducible results.

4.4   The spread  in  corrosion  rate  values for  duplicate
specimens in a-given test probably should not exceed ± 105o
of the average when the attack is uniform.

4.5   Composition of soJution-

      4.5.1   Test  solutions should be prepared accurately
      from chemicals conforming to  the Standards of the
      Committee  on Analytical Reagents  of the  American
      Chemical Society,1 and  distilled  water,  except in
      these  cases  where naturally occurring  solutions or
      these  tzken directly from some plant,process are
      used.

      4.5.2   The composition of the test solution should
      be controlled to the fullest extent possible and should
      be described as  completely  and as accurately as
     possible when the results are reported.

             4.5.2.1 Minor  constituents  should not  be
            overlooked because they often affect corro—
            sion rates-

             4.5.2.2 Chemical content should be reported
            zs  percentage  by  weight  of the  solution.
            Molarity  and normality are  also  helpful in
             defining the concentration of chemicals in the
             test solution.

     4.5.3   The composition of the test solution should
     be checked  by analysis  at the end  of the  test to
     determine the extent of change in composition, such
     as might result from evaporation.

     4.5.4   Evaporation losses  should  be controlled by a
     constant level device  or by  frequent additions of
     appropriate  solution to maintain the'orieinal volume
     within ± \%.

      4.5.5   In some cases,  composition of the test solu-
      tion may change as a result  of catalytic  decompo-
       1 - Typical resin flask that can b% useo as a versat'ri* »»d
 convenient apparatus to conduct simple immersion tuts. Con-
 figuration of the flask top it such th*t more  sophisticated
 apparatus can be added as required by the specific test b«tng
 conducted. A * thermowell. B • resin flask. C* specimens hong
 on supporting device,  D - a*t inlet. E  " heating mentlev F -
 liquid interface, G - opening in flash for additional apparatus
 that may be required, and H ™ reflux condenser.

     sition  or by reaction  with the- test coupon  These
     changes should be  determined .if possible.  Where
     required, the exhausted constituents should be added
     or a fresh solution provided, during the course of the
     test.

     4.5.6   When possible, only one type of metal should
     be exposed in a given test. If several different metals
     are  exposed  in  the same solution,  the corrosion
     products from one metal may affect the rate of attack
     on another metal. For example,  copper corrosion
     products can reduce corrosion of stainless steel and
     titanium but can accelerate corrosion of aluminum,

4.6  Temperature of solution.

     4.6.1   Temperature of the corroding solution should
     be  controlled  within  ±IC (± l.S F)  and  must be
     stated in the report of test results.

-------
      4.6.2   If no specific temperature, such as boiling, is
      required or if a temperature range is to be investi-
      gated, the selected temperatures used in the test must
      be reported.

      4.6.3   For tests at  ambient temperatures, the tests
      should  be conducted  at  the  highest temperature
      anticipated for  stagnant storage in summer months.
      This temperature may be as high as 40 to 45 C (104
      to 113  F) in some areas. The variation in temperature
      should be reported also (e.g., 40 C ± 2 C).

 4.7  Aeration of solution.

      4.7.1    Unless specified, the solution should not be
      aerated. Most  tests  related to process  equipment
      should be run with the natural atmosphere Inherent in
      the process, such as the vapors of the boiling liquid.

      4.7.2   If aeration is used, the specimens  should not
      be located  in the direct air stream from the sparger.
      Extraneous effects can be encountered  if  the  air
      stream impinges on the specimens.

      4.73   If complete exclusion of dissolved oxygen is
      necessary, specific techniques are required such,as
      prior  heating of the  solution and  sparging with an
      inert gas (usually nitrogen). A liquid atmospheric seal
      is required  on  the  test vessel  to prevent  further
      contamination.

      4.7.4  _1£ oxygen saturation  of  the  test  solution is
      desired, this can best  be achieved by sparging.  For
      other  degrees  of aeration, the  solution  should  be
      sparged  with synthetic mixtures of air or oxygen with
      an inert gas.

4.8   Solution velocity

      4.8.1  The effect of velocity is not usually deter-
      mined in normal laboratory  tests  although  specific
      tests have been designed for this purpose. However,
      for the sake of reproducibility, some velocity control
      is  desirable.

      4.8.2  Tests at the boiling point should be  conducted
      with minimum possible heat input, and boiling chips
      should  be used  to  avoid excessive turbulence and
      bubble impingement.

      4.8.3  In tests  conducted  below the boiling point,
      thermal  convection generally is  the  only source of
      liquid velocity.

        .4  In test solutions with high viscosities, supple-
      mental  controlled stirring is recommended.
4.9  Volume of test solution.
      4.9.1   me volume of  the  test solution should b«
      large enough to avoid any sppf-reiabie change in its
      corrosiveness either through exhaustion of corrosive
      constituents or accumulation  of corrosion products
      that might affect further corrosion.

      4.9.2 The preferred minimum volume-to-area ratio is
      250 rnillititers of solution per square inch of specimen
      surface as stipulated jn ASTM  Standard A-279-63 on
      "Total Immersion Corrosion Test of Stainless Steels,"
     4.9.3  When the test objective is to determine the
     effect of a metal or a21oy on the characteristics of the
     test solution (for example, to determine the effects of
     rsetals on dyes), it is  desirable to reproduce the ratio
     of solution volume   to  exposed metal  surface that
     exists Li practice. The actual time of ^contact  of the
     metal with the solution also  must be  taken into
     account. Any necessary distortion  of  the test con-
     ditions  must be  considered when  interpreting the
     results.
4.10 Method of supporting specimens.

     4.10.1 The  supporting device and container should
     nor be affected by or cause contamination of the test
     solution.

     4.10.2 The  method cf supporting specimens w31 vary
     with  the apparatus used for conducting the test but
     should be designed  to insulate the specimens from
     each  other physically and electrically and to insulate
     the specimens from any metallic container or support-
     ing device used with the apparatus.

     4.10.3 Shape and  form of  the  specimen support
     should assure free contact of the specimen with the
     corroding solution, the liquid  line, or the vapor phase
     as .shown in Figure  1. If clad alloys are exposed,
     special procedures will be required to insure that only
     the cladding is  exposed unless the purpose is to test
     the ability of the cladding to protect cut edges in the
     test solution.

     4.10.4 Some common  supports are glass or ceramic
     rods,  glass saddles, glass hooks, fluorocarbon plastic
     strings,  and various  insulated or coated  metallic
     supports.
4.11 Duration of test.

     4.11.1 Although  duration of any test  will be deter-
     mined by  the nature  and purpose  of the test» an

-------
 excellent procedure for evaluating the effect of time
 on  corrosion of the metal and also on the corrosive-
 ness of the environment in laboratory tests has been
 presented by Wachter and Treseder.2 This technique
 is calied the "Planned Interval Test," and the proce-
 dure and evaluation of  results are given in Table  1.
 Other  procedures that  require  the removal of solid
 corrosion products between exposure periods will not
 measure accurately the  normal  changes of corrosion
 with time.

 4.1J.2 Materials  which  experience severe  corrosion
 generally do not need lengthy tests to obtain accurate
 corrosion rates. Although this assumption is valid  in
 many cases, there  are cases where it is not valid. For
 example, lead exposed to sulfuric acid corrodes at an
 extremely high rate at first whiJe building a protective
 film,  then  the rates decrease considerably so that
 further corrosion  is negligible. Tne phenomenon of
 forming  a  protective  film  is observed  with many
 corrosion resistant materials, and therefore short tests
 on such materials would indicate a high corrosion rate
 and woiJd be completely misleading.

 4.113 Short  time  tests also can give  misleading
 results  on  alloys  that  form passive  films, such  as
 stainless steels. With borderline  conditions,  a pro-
 longed test  may be  needed to permit breakdown  of
 the  passive film and subsequently more  rapid attack.
 Consequently,  tests run for long  periods  are con-
 siderably  more -realistic than those conducted for
 short durations. This.statement must be qualified by
 stating that  corrosion should notproceed'to the point
 where  the original specimen size  or the exposed area
 is drastically reduced or  where  the metal is per-
 forated.

 4.11.4  If anticipated corrosion rates are moderate or
 low  the following equation2 gives a suggested test
 duration:

                                   2000
              TABl_£ 1 - =M»nned IntervM
    Duration of test (hr)-   COITOsion rate (mpy)
Examples: Where the corrosion rate is 10 mpy, the
test  should run for at least 200 hours. If the rate is 1
mpy, the duration should be at least 2000 hours.

        4.11.4.1  This  method  of  estimating  test
        duration is useful  only as an aid in deciding,
        after a test has been made, whether or not it is
        desirable to repeat the test for a longer period.
        Tne most common testing periods are  48 to
        168 hours (2 to 7 days).

4.11.5  In  some cases,  it may be necessary to know
the degree of contamination caused by the products
of corrosion; this can be accomplished by analysis of
(Reprinted by permission from "Chemical Engineering Progress.*"
                       June, 1947.)
                                                            '5.3-4*

•u
8 A,
oo " "
- 1 I
H 0 1
A,

Time

B

t H
Identical specimens-all placed in the same corrosive Quid. Impend
conditions of the test kept constant for entire time t •+• 1. Letters,
AI, At, AJ+J, B, represent corrosion damage experienced by each
test specimen. A; is calculated by subtracting At from Al+ j.
  Occurrences During Corrosion Test
   Liquid corrosiveness
   Metal corrodibility
                                             Criteria
unchanged
decreased
increased
unchanged
decreased
increased
A,=B
B B
AI A2

-------
      The  solution after corrosion has occurred. The corro-
      sion rate can be calculated from the concentration of
      the matrix metal found in the solution, and it can be
      compared to that determined from the weight loss of
                        the  specimens.  However,  scrr.s of  the corrosion
                        products usually adhere to ihe specimen as a. scale,
                        and  the  corrosion  rate calculated  from the metal
                        content in the solution is not always correct.
                                                   5.3-15
                               5. Methods of Cleaning Specimens After the Test

S.I  Before specimens are cleaned, their appearance should     5.2   Cleaning specimens after the test is a vital step.in the
be observed and recorded. Location of deposits, variations     corrosion test procedure  and, if not done  properly, can
in types of deposits, or variations in corrosion products are     cause misleading results.
extremely important in evaluating localized corrosion, such
as pitting and concentration cell attack.                             5.2.1  Generally, the  cleaning  procedure  should.

                      TABLE 2—Method*for Chemical Cleaning of Corrosion Test Specimens After Exposjre
                    Material
Chemical
                                                           Time
Tempera-
  ture
                                            Remarks
Aluminum and
Aluminum Alloys
Copper and
Copper ADoys
Lead and
Lead Alloys
Iron and Steel
Magnesium and
Magaesium ADoys
Nickel and
Nickel Alloys
Stainless Steel
Tin and Tin AlJoys
Zinc
70% HSO3
2r»Cr03>5%H3P04, Sob.
15-20% KC1
5-10%H2S04.
1% acetic acid
5% ammonium acetate
80g/lNaOH,
50 g/1 majuiitol,
0.62 g/1 hydrazine sulfate
20% NaOH, 200 g/1 zinc dast
cone. HO, 50 g/1.
Snd2 + 20 g/1 SbCl3
15%CrO3, !%AgCrO4 Spin.
15-20% HC1
10%H2SO4
10%HNO3
lS#Na3PO«
10%NH4a
followed by
5%CrO3. 1% AgN03 Sob.
Saturated amnionium
acetate
lOOj/lNaCN
2-3 mia
lOrr.b
2-3 nib
2-3 min
10 min
5 min
30 rr.in, or
until clem
5 mia
LJntfl ctean
15 min
Unu! cl:an
Until clsLi
UntD ck£n
10 -in
5 min
20 we
Untfl clean
15 nib
Room
175-185 F
(79-S5 Q
Room
Room
Boiling
Hot
Boiling
Bofling
Cold
Boiling
Room
Room
140 F
(60Q
Boiling
Room
Boiling
Room
Room
FoDow by light scrub.
Used when oxide film
resists HNO3 treat- •
ment. Follow by 70S.
HNO3 treatment pre-
viously described.
Follow by light scrub.
•
Follov by light scrub.
Follow by light scrub.
Removes PbO.
FoUow by light scrub.
Removes PbO and/or
PbSO«.
Follow by light scrub.
...
—
—
...
...
Avoid contamination
with chlorides
Follow by scrubbing.
Follow by light
scrubbing.
Follow by light scrub.
• • •

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      remove all corrosion products from specimens with a
      minimum removal of sound metal.

      5.2.2   Set  rules  cannot  be applied  to specimen
      cleaning because procedures  will vary depending on
      the type of metal being cleaned and on the degree of
      adherence of corrosion products.

5.3   Cleaning methods can be divided  into three general
categories: mechanical, chemical, and electrolytic.

      5.3.1   Mechanical   cleaning  includes   scrubbing,
      scraping,  brushing, mechanical  shocking,  and ultra-
      sonic procedures. Scrubbing with a bristle brush and
      mild abrasive is the most popular  of these methods;
      the  others are  used principally  as a supplement to
      remove heavily encmsted corrosion products before
      scrubbing.  Care  should be used  to  avoid the removal
      of sound metal.

      5.3.2   Chemical  cleaning  implies the  removal of
      material from the surfs ce of the specimen  by dissolu-
      tion in  an appropriate  chemical  solution. Solvents
      such as acetone, carbon tetrachlorice, and alcohol.-^re
      used to remove oil.-grease, or resin and are usually
      applied prior to other methods of cleaning. Chemicals
      are chosen for application to a specific material. Some
      of  these  treatments in general  use are outlined  in
      Tabie 2.

      5.3.3   Electrolytic cleaning  should be  preceded by
      scrubbing  to   remove  loosely  adhering corrosion
      products. One  method  of electrolytic cleaning that
     has been found  to ^>e useful  for many metals and
     alloys is as followr
        Solution  	5% (by weight) H, SO4
        Anode	Carbon or lead
        Cathode	Test specimen.
        Cathode CD	20 amp/dm3
                             (129amp/sqin)
        Inhibitor	2 cc organic inhibitor
                             per liter
        Temperature	74 C (165 F)
        Exposure period... 3 minutes

            53.3.1 Precautions must be taken to insure
            good electrical contact with the  specimen, to
            avoid contamination  of  the solution with
            easily reducible metal  ions, and to insure that
            inhibitor decomposition  has not  occurred.
            Instead of using~2 milliiiters of any proprie-
            tary inhibitor, 0.5 gram per liter of inhibitors
            such as  dionhotolyl  thiourea or  quinoline
            ethiodide can be used.

5.4  Whatever treatment is used to clean specimens after a
corrosion  test, its  effect  in  removing metal  should be
determined, and  the  weight  loss  should be  corrected
accordingly: A  "blank"  specimen  should  be  weighed
before and after  exposure to  the cleaning procedure to
establish this weight loss.

     5.4.1  Following removal of all scale,  the specimen
     should be treated as discussed in Section 2.8.

     5.4.2  A description of the cleaning method should
     be included with the data reported.
5.3-1
                                           6.  Evaluation of Results
6.1  After corroded specimens  have been cleaned,  they
should be reweighed with  an accuracy corresponding to
that  of the original weighing. The weight loss during the
test  period  can  be used  as the  principal  measure  of
corrosion.

6.2  After the specimens have been reweighed, they should
be examined carefully for the presence of pits. If there are
pits,  the average  and maximum depths of pits are deter-
mined  after measurement with a pit gauge or a calibrated
microscope which can be  focused first on the edge and then
on the bottom of the pit. An excellent discussion of pitting
corrosion has been published.3

     6.2.1   Pit depths should be reported in millimeters
     or thousandths of an inch for the test period and not
     interpolated or extrapolated to millimeters per year
     or thousandths of  an  inch per  year or  any other
     arbitrary period because rarely, if ever, is the rate of
     initiation or propagation of pits uniform.
     6.2.2  The  size,  shape, and distribution  of pits
     should  be noted.  A  distinction should  be  made
     between those  occurring underneath the supporting
     devices (concentration cells) and those on  surfaces
     that were freely exposed to the test solution..

6.3  If the  material being tested is  suspected of being
subject  to dealloying forms of corrosion such as dezincifi-
cation,  or to intergranular  attack, a cross section of the
specimen  should be microscopically examined to determine
the type and depth of such attack.

6.4  The specimen  may  be subjected to simple bending
tests to  determine whether any embrittlement has occurred.

6.5  It may be desirable to make quantitative mechanical
tests to compare  the exposed specimens  with uncorroded
specimens reserved for the purpose, as described in Section
2.2.

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                                           7. Calculating Corrosion Rates
  7.1  The calculation  of corrosion rates requires  several
 pieces of information and several assumptions.

      7.1.1   The  use of corrosion rates implies  that  all
      weight  loss has been due to general corrosion and not
      to  localized corrosion,  such as pitting or sensitized
      areas on  welded  coupons.  Localized corrosion is
      reported separately.

      7.1.2   The use of corrosion rates also implies that
      the material has not been internally attacked  as by
      dezincification or intereranular corrosion.

      7.1.3   Internal attack can be expressed as a corrosion
      rate if desired. However, the calculations must not be
      based on  weight loss, which is usually small, but on
      rnicrosections which show depth of attack.

 7.2   Assuming that localized or internal corrosion is not
            present or  are recorded separately  in  the  report,  the
            corrosion  rate expressed as mils penetration per year (rr.py)
            or millimeters per year (rnmpy) can be calculated by  thu
            equations:
                                    wt loss x 534
                    mpy  =  (area) (time) (metal density)
                                   wtlossx 13.56
                             (area) (time) (metal density)


            where weight loss is in milligrams, area is square inches of
            metal surface exposed, and time is hours exposed.

            Metal density of many common alloys (expressed in grams
            per  cubic centimeter) is  listed in  Table 3. The density for
            new  or unlisted  alloys can be obtained from the producer
            or from various metal handbooks.
                                                                                                                          5.3-1?
                          TABLE 3 — Density of Common Metals for Use in Corrosion Rate Calculations9
 Alloy
Density,
 &/cc
 Aluminum
  99.0 + A1  .   ,   	   2.71
  AU-2Mn   	.	2,73
  AU.OMg.O.«-Si;0.25&   	   2.70

 Brass
  85 Cu. 15 Zn   	   8.75
  71 Cu, 28 Zn, I Sn	  .   8.53
  65 Cu, 35 Zn   	   8.47
  60Cu,39.25Zn,0.75Sn	8.41

Bronze
  95 CU, 5Sn	   8.86
  90 Cu, 10 Sn    	8.78
  85Cu..SSn, 5Zn,SPb -    	8.80
  94.8 Cu, 3 Si   ,	   8.53
  95Cu,SAJ	   8J7
  85-90 Cu, 10 Al   	   7.58
Copper
  99.90 Cu. 0.01 P
  8.91
Cu pro-Nickel
  90 Cu, 10 Ni    	   8.93
  70 Cu, 30 Ni    	   8.94

Iron
  94 Fe, 3.5 C, 2.5 Si	7.00
  96 Fe, 3.0 C	   7.60
  99 ~ Fe, 0.025 S, 0.017 Mn, 0.012 C, 0.005 P   ....   7.86
  J       14.5 Si, 0.35 Mn, 0.85 C    	   7.00
Alloy
Dsnsitv
 g/cc
            Lead
             99.90 + Pb   	11.34

            Nickel
             99.4Ni + Co    	8.89-
             67Ni,30Cu    	8.84
             62 Ni, 30 Mo, 5 Fe	9.24
             58 Ni, 17 Mo, 15Cr,5W, 5 Fft	£.94
             80 Ni, 14 Cx, 6 Fe	   8.51
           Steel
             0.20C,Mn,P,S
                                                      7.85
Stainless Steel
  ll.50-13.50Cr, 0.15 C   	_ .  .   7.75
  14.00-18.00 Cr, 0.12 C   	7.70
  18.00-20.00 Ci, 8.00-12.00 Ni, 0.08 C	7.93
  16.00-18.00 Ci, 10.00-14.00 Ni,
   2.00-3.00 Mo, 0.08 C   	7.98
  17.00-19.00 Cr, 9.00-12.00 Ni, 0.08 C'Ti   	8.02
  17.00-19.00 Cr, 9.00-12.00 Ni, 0.08 C, Co	8^
  19.00-21.00 Cr, 24.00-30.00 Ni, ZOO-3.00 Mo,
   3.00-4.00 Cu	8.02.
           Tantalum
                                                    16.60
           Tin	730

           Titanium	   4.54

           Zirconium	   6.53

-------
                                                S. Reporting the Data
  8.1   The importance of reporting all data as completely as
  possible cannot be overemphasized.

  S.2   Expansion of the  testing  program in  the future or
  correlating  the  results with tests of other investigators will
  be possible  only if all  pertinent  information is properly
  recorded.

  8.3   The following checklist is  a  recommended guide for
  reporting all important information and data:

       8.3.1   Corrosive media and concentration (changes
       during test).

       8.3.2  Volume of test solution.

       8.3.3   Temperature (maximum, minimum, average).

       8.3.4  Aeration (describe  conditions or technique).

       8.3.5   Agitation (describe conditions or technique).

       8.3.6   Type of apparatus used for test.

       8.3.7   Duration of each test.

       8.3.8   Chemical composition  or  trade name  of
       metals tested.

       8.3.9   Form and  metallurgical  conditions  of speci-
       mens.
      83.10  Exact size, shape, and aita of specimens.

      8.3.11  Treatment used to prepare specimens for test-

      8.3.12  Number of specimens of each material tested,
      and whether  specimens were  tested  separately  or
      which specimens were tested in the same container.

      8.3.13  Method used to clean specimens after expo-
      sure and the extent of  any error expected by this
      treatment.

      8.3.14  Actual weight losses for each specimen..

      8.3.15  Evaluation of attack  if other  than genera],
      such as crevice corrosion under support rod, pit depdi
      and distribution, and results of microscopic examina-
      tion or bend tests.

      8.3.16  Corrosion  rates for each specimen expressed
      as mils per year.

 8.4   Minor occurrences or deviations from  the  proposed
 test  program  often can have significant  effects and should
 be reported if known.

 8.5   Statistics  can be  a valuable  tool  for analyzing tie
 results  from test programs designed to  generate  adequate
 data  and  should  be  used wherever possible. Exteilent
 references for the  use of  statistics  in corrosion studies
 induce References  4 through 8.
                                                                                                                         5.3-1*
                                                      References
 1. Joseph Rosin. Reagent Chemicals and Standard*, Fifth Edition.
   D. Van Nostrand Co., Inc., 120 Alexander St., Princeton, N. J.,
   1966.
 2. A. Vv'achter and R. S. Trtseoer. Corrosion Testing Evaluation of
   Metals for Process  Equipment. Chemical Engineering Progress.
   43, 315-326(1947) June.
 3. N. D. Greene and M« G. Fontana. A i_nucaJ Analysis of Pining
   Corrosion. Corrosion. IS, 25t (1959) January.
 4. Harold S. MieWey,  Thomas K. Sherwood, and Charles E. Reed
   (editors). Applied Mathematics in Chemical Engineering, (second
   edition). McGraw-Hill, New York, N. Y... 1957.
 5. D. M. Douglas, Are You Using or Abusing Data? Paper presented
   at the Northeast-North Central Region  Conference, National
 J . B. Ajots
 W. G. Ashbaugh
 R. L Becker
 G. L. Bedford
 J.M. Bialosky
 J. F. Bosich
 F. C. Brauuean
 B. Brod\vin
 W. B. Brooks
 A. A, Brouwe*
 T. V. Bruno
 H. G. Burbidge
W. H. Burton"
J. W. Cangi
R. F. Catlett

A. S. Couper
T. F. Degnan
H. L. Dickey
C. P. Dillon
L E. Drake, Ji.
G. B. Elder
J. L. English
O. H. Fenner
A. O.'Fisher
M. G. Fontana
J. M. Ford
R. E. Gackenbach
P. J. Gegner
L. V>'. Gieekman
D. L. Graver
Membership of Unit
J. J. HaJbig
F. B. Hamel
A. C. Hamstead
P. R. Handt
F. A. Kencershot
D. R. Hise
T. L. Hoffman
P. R. Hoffmann
R. L. Horst.Jr.
E. C. Hoxie
J. R. Jeter
R. L. Kane
J. M. Keyes
R. W.Kirch ncr
G. Kobrin
Committee T-5A
A. S.Krisher
K. F.Krysiak
J. C. Kuli
E. V. Kunkel
J. Q. Lackey
P. T. Lahi
R. P. Lee
R. B. Leonard
W. A. Luce
R. McFailand
S. W. McHrath
J. M. MaDory
D. S. Neill
G. T. Paul
J. H. Peacock

A. J. Pietrzak
H. D. Rice
L. M, Rogers
J. W. Rollins
G. A. Saltzman
R, C. Scarberry
L- R. Scharfstein
J. H. Schemel
J. R. Schiey
N. B. Schmidt
S. W. Shepaid
O. W. Siebcrt
G. L. Snair
S. S. Spate:
J. M. Stammeft
   Association of Corrosion Engineers, October 4-6,  1965, Pitts-
   burgh, Pa.
6. W. J.  You den. Experimentation  and Measurement. National
   Science Teachers Association, Washington, D. C, 1962.
7. F. F. Booth  and G. E. G. Tucker. Statistical Distribution of
   Endurance in  Electrochemical Stress-Corrosion Tests. Corrosion,
   21,173 (1965) May.
8. Compilation  of Examples  of Applying Statistics to Corrosion
   Problems. ASTM Standard G-16, ASTM, 1916 Race St., Phila-
   delphia, Pa.

9. Metals Handbook,  American  Society for Metals, Metals Park,
   Novelry, Ohio, Sth Edition, Volume 1,1961.
                                       L. S. Surteej
                                       H. C. Templeton
                                       A. Tesmen
                                       R. L. Thompwn
                                       A. P. C. Thomson
                                       E. A. Tice
                                       J. W. Tracht
                                       R. S. Treseder
                                       J. M. A. Van dei Horst
                                       A. Wachter
                                       W. W. Wheeler
                                       H. Wijsman
                                       C. P. Williams
                                       C. A. Zimmerman

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                                                                      6.0-1
                         Section 6.0




                          REACTIVITY






Introduction.



     The regulation (40 CFR 261.23) defines reactive wastes




to include wastes which (1) readily undergo violent chemical




change; (2) react violently or form potentially explosive




mixtures with water; (3) generate toxic fumes when mixed




with water or, in the case of cyanide or sulfide bearing




wastes, when exposed to mild acidic or basic conditions; (4)




explode when subjected to a strong initiating force; (5)




explode at normal temperatures and pressures; or (6) fit




within the Department of Transportation's forbidden explosives,




Class A explosives, or Class B explosives classifications.




     This definition is intended to identify wastes which,




because of their extreme instability and tendency to react




violently or explode, pose a problem at all stages of the




waste management process.  The definition is to a large extent




a paraphrase of the narrative definition employed by the




National Fire Protection Association.  The Agency chose to




rely on a descriptive, prose definition of reactivity because




the available tests for measuring the variegated class of




effects embraced by the reactivity definition suffer from a




number of deficiencies.

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                                                                     6.1-1
                       Sub-Section 6.1




           CHARACTERISTIC OF REACTIVITY REGULATION




     A solid waste exhibits the characteristic of reactivity




If a representative sample of the waste has any of the following




properties:




     1.   It  is normally unstable and readily undergoes




         violent change without detonating.




     2.   It  reacts violently with water.




     3.   It  forms potentially explosive mixtures with water.




     4.   When mixed with water, it generates toxic gases,




         vapors or fumes in a quantity  sufficient to present a




         danger to human health or the  environment.




     5.   It  is a cyanide or sulfide bearing waste which,




         when exposed to pH conditions  between 2 and 12.5,




         can generate toxic gases, vapors or fumes in a




         quantity sufficient to present a. danger to human




         health or the environment.




     6.   It  is capable of detonation or explosive reaction




         if  it is subjected to a strong initiating source or




         if  heated under confinement.




     7.   It  is readily capable of detonation or explosive




         decomposition or reaction at standard temperature




         and pressure.




     8.   It  is a forbidden explosive as defined in 49 CFR




         173.51, or a Class A explosive as defined in 49 CFR




         173.53 or a Class B explosive  as defined in 49 CFR 173.88.

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                                                                     6.1-2
     A solid waste that exhibits the characteristic of




reactivity, but is not listed as a hazardous waste in Subpart D,




has the EPA Hazardous Waste Number of D003.

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                                                                     6.2-1
                       Sub-Section 6.2

              DEFINITION OF EXPLOSIVE MATERIALS

     For purposes of this regulation a waste which is a

reactive waste by reason of explosivity is  one which meets

one or more of the following descriptions:

     1.  Is explosive and ignites  spontaneously or undergoes
         marked decomposition when subjected for 48 consecutive
         hours to a temperature of 75°C (167°F).

     2.  Firecrackers,  flash crackers, salutes, or similar
         commercial devices which  produce or are intended to
         produce an audible effect,  the explosive content of
         which exceeds  12 grains each in weight, and pest control
         bombs, the explosive content of which exceeds 18 grains
         each in weight; and any such devices, without respect
         to explosive content, which on functioning are liable
         to project or  disperse metal, glass or brittle plastic
         fragments.

     3.  Fireworks that combine an explosive and a detonator
         or blasting cap.

     4.  Fireworks containing an ammonium salt and a chlorate.

     5.  Fireworks containing yellow or white phosphorus.

     6.  Fireworks or fireworks compositions that ignite
         spontaneously  or undergo  marked decomposition when
         subjected for  48 consecutive hours to a temperature of
         75°C (167°F).

     7.  Toy torpedoes, the maximum outside dimension of
         which exceeds  7/8 inch, or toy torpedoes containing a
         mixture of potassium chlorate, black antimony and sulfur
         with an average weight of explosive composition in each
         torpedo exceeding four grains.

     8.  Toy torpedoes  containing  a cap composed of a mixture
         of red phosphorus and potassium chlorate exceeding an
         average of one-half (0.5) grain per cap.

     9.  Fireworks containing copper sulfate and a chlorate.

    10.  Solid materials which can be caused to deflagrate
         by contact with sparks or flame such as produced by safety
         fuse or an electric squib,  but cannot be detonated (see Note
         1) by means of a No. 8 test blasting cap (see Note 2).
         Example: Black powder and low explosives.

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                                                                  6.2-2
11.  Solid materials which contain a liquid ingredient,
     and which, when unconfined (see Note 3), can be detonated
     by means of a No. 8 test blasting cap (see Note 2); or
     which can be exploded in at least 50 percent of the
     trials in the Bureau of Explosives' Impact Apparatus
     (see Note 4) under a drop of 4 inches or more, but cannot
     be exploded in more than 50 percent of the trials under
     a drop of less than 4 inches Example: High explosives,
     commercial dynamite containing a liquid explosive ingredient

12.  Solid materials which contain no liquid ingredient
     and which can be detonated, when unconfined (see Note 3),
     by means of No. 8 test blasting cap (see Note 2); or
     which can be exploded in at least 50 percent of the
     trials in the Bureau of Explosives' Impact Apparatus
     (see Note 4) under a drop of 4 inches or more, but cannot
     be exploded in more than 50 percent of the trials under
     a drop of less than 4 inches.  Example: High explosives,
     commercial dynamite containing no liquid explosive ingre-
     dient, trinitrotoluene, amatol, tetryl, picric acid,
     ureanitrate, pentolite, commercial boosters.

13.  Solid materials which can be caused to detonate
     when unconfined (see Note 3), by contact with sparks or
     flame such as produced by safety fuse or an electric
     squib; or which can be exploded in the Bureau of Explosives'
     Impact Apparatus (see Note 4), in more than 50 percent
     of the trials under a drop of less than 4 inches.  Example:
     Initiating and priming explosives, lead azide, fulminate
     of mercury, high explosives.

14.  Liquids which may be detonated separately or when
     absorbed in sterile absorbent cotton, by a No. 8 test
     blasting cap (see Note 2); but which cannot be exploded
     in the Bureau of Explosives' Impact Apparatus (see Note
     4), by a drop of less than 10 inches.  The liquid must
     not be significantly more volatile than nitroglycerine
     and must not freeze at temperatures above minus 10°F.
     Example: High explosives, desensitized nitroglycerine.

15.  Liquids that can be exploded in the Bureau of
     Explosives' Impact Apparatus (see Note 4) under a drop
     of less than 10 inches.  Example: Nitroglycerine.

16.  Blasting caps.  These are small tubes, usually
     made of an alloy of either copper or aluminum, or of
     molded plastic closed at one end and loaded with a charge
     of initiating or priming explosives.  Blasting caps (see
     Note 5) which have been provided with a means for firing
     by an electric current, and sealed, are known as electric
     blasting caps.

-------
                                                                 6.2-3
17.   Detonating primers which contain a detonator and an
     additional charge of explosives, all assembled in a suit-
     able envelope.

18.   Detonating fuses, which are used in the military
     service to detonate the high explosive bursting charges
     of projectiles, mines,  bombs, torpedoes, and grenades.
     In addition to a powerful detonator, they may contain
     several ounces of a high explosive, such as tetryl or
     dry nitrocellulose, all assembled in a heavy steel enve-
     lope.  They may also contain a small amount of radioactive
     component.  Those that  will not cause functioning of
     other fuses, explosives, or explosive devices in the
     same or adjacent containers are classed as class C explo-
     sives and are not reactive waste.

19.   A shaped charge, consisting of a plastic, paper, or
     other suitable container comprising a charge of not to
     exceed 8 ounces of a high explosive containing no liquid
     explosive ingredient and with a hollowed-out portion
     (cavity) lined with a rigid material.

20.   Ammunition or explosive projectiles, either fixed,
     semi-fixed or separate  components which are made for use
     in cannon, mortar, howitzer, recoilless rifle, rocket,
     or other launching device with a caliber of 20 mm or
     larger.

21.   Grenades.  Grenades, hand or rifle, are small metal
     or other containers designed to be thrown by hand or pro-
     jected from a rifle.  They are filled with an explosive
     or a liquid, gas, or solid material such as a tear gas
     or an incendiary or smoke producing material and a bursting
     charge.

22.   Explosive bombs.  Explosive bombs are metal or
     other containers filled with explosives.  They are used in
     warfare and include airplane bombs and depth bombs.

23.   Explosive mines.  Explosive mines are metal or compo-
     sition containers filled with a high explosive.

24.   Explosive torpedoes.  Explosive torpedoes,  such  as
     those used in warfare, are metal  devices containing a means
     of propulsion and a quantity of high explosives.

25.  Rocket ammunition.  Rocket ammunition  (including
     guided missiles)  is ammunition  designed for launching from
     a  tube, launcher,  rails, trough,  or other  launching device,
     in which  the  propellant material  is a  solid propellent
     explosive.  It  consists of an igniter,  rocket motor,  and
     projectile  (warhead) either  fused  or unfused, containing
     high explosives  or  chemicals.

-------
                                                                  6.2-4
26.  Chemical ammunition.  Chemical ammunition used in
     warfare is all kinds of explosive chemical projectiles,
     shells, bombs, grenades, etc., loaded with tear, or
     other gas, smoke or incendiary agent, also such miscel-
     laneous apparatus as cloud-gas cylinders, smoke generators,
     etc., that may by utilized to project chemicals.

27.  Boosters, bursters, and supplementary charges.
     Boosters and supplementary charges consist of a casing
     containing a high explosive and are used to increase the
     intensity of explosion of the detonator of a detonating fuse
     Bursters consist of a casing containing a high explosive and
     are used to rupture a projectile or bomb to permit release
     of its contents.

28.  Jet thrust units or other rocket motors containing a
     mixture of chemicals capable of burning rapidly and produc-
     ing considerable pressure.

29.  Propellant mixtures (i.e, and chemical mixtures
     which are designed to function by rapid combustion with
     little or no smoke).

 Note 1;  The detonation test is performed by placing the
 sample in an open-end fiber tube which is set on the end
 of a lead block approximately 1 1/2 inches in diameter
 and 4 Inches high which, in turn, is placed on a solid
 base.  A steel plate may be placed between the fiber
 tube and the lead block.

 Note 2;  A No. 8 test blasting cap is one containing two
 grams of a mixture of 80 percent mercury fulminate and 20
 percent potassium chlorate, or a cap of equivalent strength.

 Note 3;  "Unconfined" as used in this section does not
 exclude the use of a paper or soft fiber tube wrapping to
 facilitate tests.

 jjo t e 4;  The Bureau of Explosives' Impact Apparatus is a
 testing device designed so that a guided 8-pound weight
 may be dropped from predetermined heights so as to impact
 specific quantities of liquid or solid materials under
 fixed conditions.  Detailed prints may be obtained from
 the Bureau of Explosives, 2 Pennsylvania Plaza, New York,
 New York, 10001.

 Note 5;  Blasting caps, blasting caps with safety fuse,
 or electric blasting caps in quantities of 1,000 or
 less are classified as class 0 explosives and not subject
 to regulation as a reactive waste.

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                                                                     7.0-1
                         Section 7.0




                EXTRACTION PROCEDURE TOXICITY




Introduction^




     The Extraction Procedure (EP) is designed to simulate




the leaching a waste will undergo if disposed of in an




improperly designed sanitary landfill.  It is a laboratory




teat in which a representative sample of a waste is extracted




with distilled water maintained at pH » 5 using acetic acid.




The extract obtained from the EP (the "EP Extract") is then




analyzed to determine if any of the thresholds established




for the 8 elements (i.e., arsenic, barium, cadmium, chromium,




lead, mercury, selenium, silver), four pesticides (i.e.,




Endrin, Lindane,  Methoxychlor, Toxaphene), and two herbicides




(i.e., 2,4,5-Trichlorophenoxypropionic acid, 2,4-Dichloro-




phenoxyacetic acid) have been exceeded.  If the EP Extract




contains any one of the above substances in an amount equal




to or exceeding the levels specified in 40 CFR 261.24, the




waste possesses the characteristic of Extraction Procedure




Toxicity and is a hazardous waste.




     The Extraction Procedure consists of 5 steps:




1.  Separation Procedure




         A waste containing unbound liquid is filtered and if




the solid phase is less than 0.5% of the waste, the solid




phase is discarded and the filtrate analyzed for trace




elements, pesticides, and herbicides (step 5).  If the waste




contains more than 0.5% solids, the solid phase is extracted




and the liquid phase stored for later use.

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                                                            7.0-2
2.  Structural Integrity Procedure/Particle Size Reduction

          Prior to extraction, the solid material must

either pass through a 9.5 mm (0.375 in) standard sieve,

have a surface area per gram of waste of 3.1 cm^ , or if it

consists of a single piece, be subjected to the Structural

Integrity Procedure.  The Structural Integrity Procedure Is

used to demonstrate the ability of the waste to remain intact

after disposal.  If the waste does not meet one of these

conditions it must be ground to pass the 9.5 mm sieve.

3.  Extraction of Solid Material

         The solid material from step 2 is extracted for

24 hours in an aqueous medium whose pH is maintained at or

below 5, using 0.5 N acetic acid.  The pH is maintained

either automaticlly or manually.  Acidification to ph 5

is subject to a specification as to total amount of acid

to be added to the system.

4.  Final Separation of the Extraction from the Remaining
         Solid

         After extraction, the liquid: solid ratio is adjusted

to 20:1 and the mixture of solid and extraction liquid are

separated by filtration, the solid discarded and the liquid

combined with the filtrate obtained in step I.  This is the

EP Extract that is subjected to the evaluation requirements

in 40 CFR 261.24.

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                                                                     7.0-3
     5•   Testing (Analysis) of EP Extract




         Inorganic and organic species are identified and




quantified using the appropriate methods in Section 8 of




this manual.

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                      Figure  7.G
           EXTRACTION PROCEDURE FLOWCHART
                                                                 7.0-4
Wet Waste Sample
contains < 0.5% ^
non-filterable
solids
Liquid Solid
Separation
V
Representative
Waste Sample
> 100 grams
Dry Wasi
— ^Solld
Discard
/ >
:e Sample
 0.5%
^ non-filterable
solids
1
Liquid Solid
Separation
\
                    Particle size
Liquid
          > 9.5 mm
                                  < 9.5 mm    monolithic
                                                                .quid
Sample Size

 Reduction
                                                      Structural

                                                      Integrity

                                                      Procedure
              Extraction of Solid Waste
 Solid {	
                                                                         Store at

                                                                        4° C and/or

                                                                         at pH = 2
                          Liquid Solid Separation
Discard
                        Liquid
                     EP Extract
                         1
                  Analysis  Methods

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                                                                     7.1-1
                       Sub-Section 7.1




           CHARACTERISTIC OF EP TOXICITY REGULATION






    A solid waste exhibits the characteristic of EP




toxicity if, using the test methods described in Appendix II




of 40 CFR Part 261 or equivalent methods approved by the




Administrator  under the procedures set forth in 40 CFR 260.20 and




260.21, the extract from a representative sample of the waste




contains any of the contaminants listed in Table 7.1-1 at a concen-




tration equal to or greater than the respective value given in




that Table.  Where the waste contains less than 0.5 percent filter-




able solids, the waste itself, after filtering, is considered




to be the extract for the purposes of this section.




    A solid waste that exhibits the characteristic of




EP toxicity, but is not listed as a hazardous waste in




Subpart D, has the EPA Hazardous Waste Number specified in




Table 7.1-1 which corresponds to the toxic contaminant




causing it to be hazardous.

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                                                                        7.1-2
                           Table 7.1-1

             MAXIMUM CONCENTRATION OF CONTAMINANTS
                FOR CHARACTERISTIC OF EP TOXICITY
     EPA
Hazardous Waste
   Number	

   D004

   D005

   D006

   D007

   D008

   D009

   D010

   D011


   D012
   D013



   D014


   D015



   D016


   D017
Contaminant
       Maximum
    Concentration
(milligrams per liter)
Arsenic 	    5.0

Barium 	  100.0

Cadmium	    1.0

Chromium	    5.0

Lead	    5.0

Mercury	    0.2

Selenium......	    1.0

Silver	    5.0


Endrin (1,2,3,4,10,10-Hexachloro-l
  7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-1
  4-endo, endo-5,8-dimethanonaph-
  thalene	    0.02

Lindane (1,2,3,4,5,6-
  Hexachlorocyclohexane, gamma
  isomer	   0-4

Methoxychlor  (1,1, l-Trichloro-2,2-bis
  [p-methoxyphenyl]ethane).            10.0

Toxaphene (C^QHiQCl3, Technical
  chlorinated camphene, 67-69
  percent chlorine)....	  0.5

2,4-D (2,4-Dichlorophenoxyacetic
  acid)	 10.0

2,4,5-TP    [Silvex]    (2,4,5-
  Trichlorophenoxypropionic acid)	  1.0

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                                                                     7.1-3
                         APPENDIX II
                               «
                       EP TOXICITY TEST


Procedure

1.  A representative sample of the waste to be tested

    (minimum size 100 grams) should be obtained using the

    methods specified in Appendix I of 40 CFR 261 or any

    other method capable of yielding a representative sample

    within the meaning of 40 CFR 260.

2.  The sample should be  separated into its component

    liquid and solid phases using the method described in

    "Separation Procedure" below.  If the dry weight of

    the solid residue* obtained using this method totals

    less than 0.5% of the original wet weight of the waste,

    the residue can be discarded and the operator should

    treat the liquid phase as the extract and proceed immedi-

    ately to Step 8.

3.  The solid material obtained from the Separation

    Procedure should be evaluated for its particle size.  If

    the solid material has a surface area per gram of material

    equal to, or greater than, 3.1 cm^ or passes through a

    9.5 mm (0.375 inch) standard sieve, the operator should

    proceed to Step 4.  If the surface area is smaller or the
*The percent solids is determined by drying the filter pad at
 80°C until it reaches constant weight and then calculating
 the percent solids using the following equation:

 (weight of pad + solid) - (tare weight of pad) X 100 - % solids
           initial wet weight of sample

-------
                                                                     7-1-4



    particle size larger than specified above, the solid



    material would be prepared for extraction by crushing,



    cutting or grinding the material so that it passes through



    a 9.5 mm (0.375 inch) sieve or, if the material is in a



    single piece, by subjecting the material to the "Structural



    Integrity Procedure" described below.



4.  The solid material obtained in Step 3 should be weighed



    immediately and placed in an extractor with 16 times its



    weight of deionized water.  Do not allow the material



    to dry prior to weighing.  For purposes of this test, an



    acceptable extractor is one which will impart sufficient



    agitati'on to the mixture to not only prevent stratification



    of the sample and extraction fluid but also insure that
                                     •


    all sample surfaces are continuously brought into contact



    with well mixed extraction fluid.



5.  After the solid material and deionized water are placed



    in the extractor, the operator should begin agitation



    and measure the pH of the solution in the extractor.



    If the pH is greater than 5.0, the pH of the solution



    should be decreased to 5.0 + 0.2 by adding 0.5 N acetic



    acid.  If the pH is equal to or less than 5.0, no acetic



    acid should be added.  The pH of the solution should be



    monitored, as described below, during the course of the



    extraction and if the pH rises above 5.2, 0.5N acetic



    acid should be added to bring the pH down to 5.0 +0.2.



    However, in no event shall the aggregate amount of acid

-------
                                                                 7.1-5
added to the solution exceed 4 ml of acid per gram of

solid.  The mixture should be agitated for 24 hours and

maintained at 20°-40°C (68° 104°F) during this time.  It

is recommended that the operator monitor and adjust the

pH during the course of the extraction with a device

such as the Type 45-A pH Controller manufactured by

Chemtrix, Inc., Hillsboro, Oregon 97123 or its equivalent,

in conjunction with a metering pump and reservoir of 0.5N

acetic acid.  If such a system is not available, the

following manual procedure shall be employed:

a.  A pH meter should be calibrated in accordance
    with the manufacturer's specifications.
                                                     »

b.  The pH of the solution should be checked and,
    if necessary, 0.5N acetic acid should be
    manually added to the extractor until the
    pH reaches 5.0 ± 0.2.  The pH of the solution
    should be adjusted at 15, 30, and 60 minute
    intervals, moving to the next longer interval
    if the pH does not have to be adjusted more
    than 0.5 pH units.

c.  The adjustment procedure should be continued
    for at least 6 hours.

d.  If at the end of the 24-hour extraction period,
    the pH of the solution is not below 5.2 and
    the maximum amount of acid (4 ml per gram of
    solids) has not been added, the pH should be
    adjusted to 5.0 +_ 0.2 and the extraction
    continued for an additional four hours, during
    which the pH should be adjusted at one hour
    intervals.

At the end of the 24 hour extraction period, deionized

water should be added to the extractor in an amount

determined by the following equation:

-------
                                                               7.1-6
          V- (20)(W) - 16(W) - A




          V- ml delonlzed water to be added




          W» weight in grams of solid charged to extractor




          A= ml of 0.5N acetic acid added during extraction




7.  The material in the extractor should be separated




    into its component liquid and solid phases as described




    under "Separation Procedure."




8.  The liquids resulting from Steps 2 and 7 should be combined.




    This combined liquid (or the waste Itself if it has less




    than 0.5% solids, as noted in step 2) is the extract and




    should be analyzed for the presence of any of the contami-




    nants specified in Table I of 40 CFR 261.24 using the




    Analytical Procedures designated below.




                     Separation Procedure




Apparatus




    A filter holder, designed for filtration media having a




nominal pore size of 0.45 micrometer and capable of applying




a 5.3 kg/cm^ (75 psig) hydrostatic pressure to the solution




being filtered shall be used.  For mixtures containing non-




absorptive solids, where separation can be effected without




imposing a 5.3 kg/cm^ pressure differential, vacuum filters




employing a 0.45 micrometer filter media can be used.

-------
                                                                    7.1-7
Procedure*

1.  Following manufacturer's directions,  the filter unit

    should be assembled with a filter bed consisting of

    a 0.45 micrometer filter membrane.  For difficult

    or slow to filter mixtures a prefilter bed consisting

    of the following prefilters in increasing pore size

    (0.65 micrometer membrane, fine glass fiber prefilter,

    and coarse glass fiber prefilter) can be used.

2.  The waste should be poured into the filtration unit.

3.  The reservoir should be slowly pressurized until liquid

    begins to flow from the filtrate outlet at which point

    the pressure in the filter should be immediately lowered

    to 10-15 psig.  Filtration should be continued until

    liquid flow ceases.

4.  The pressure should be increased stepwise in 10 psig

    increments to 75 psig and filtration continued until

    flow ceases or the pressurizing gas begins to exit from

    the filtrate outlet.
*This procedure is intended to result in separation of the "free"
 liquid portion of the waste from any solid matter having a
 particle size >0.45um.  If the sample will not filter, various
 other separation techniques can be used to aid in the filtration.
 As described above, pressure filtration is employed to speed up
 the filtration process.  This does not alter the nature of the
 separation.  If liquid does not separate during filtration, the
 waste can be centrifuged.  If separation occurs during centrifuga-
 tion, the liquid portion (centrifugate) is filtered through the
 0.45um filter prior to becoming mixed with the liquid portion of
 the waste obtained from the initial filtration.  Any material
 that will not pass through the filter after centrifugation is
 considered a solid and is extracted.

-------
                                                                     7.1-8
5.  The filter unit should be depressurized, the  solid material




    removed and weighed and then transferred to the  extraction




    apparatus, or, in the case of final filtration prior  to




    analysis, discarded.  If the solid is to be extracted do




    not allow the material retained on the  filter pad to  dry




    prior to weighing.




6.  The liquid phase should be stored at 4°C for  subsequent




    use in Step 8.




                Structural Integrity Procedure




Apparatus




     A Structural Integrity Tester having a 3.18  cm  (1.25




in.) diameter hammer weighing 0.33 kg (0.73 Ibs.) and having




a free fall of 15.24 cm (6 in.) shall be used.  This device




is available from Associated Design and Manufacturing




Company, Alexandria, VA., 22314, as Part No. 125, or it may




be fabricated to meet the specifications shown in Figure 7-2.




Procedure




1.  The sample holder should be filled with the material




    to be tested.  If the sample of waste is a large mono-




    lithic block, a portion should be cut from the block




    having the dimensions of a 3.3 cm (1.3  in.) diameter x




    7.1 cm (2.8 in.) long cylinder.  For a  fixated waste,




    samples may be cast in the form of a 3.3 cm (1.3 in.)




    diameter x 7.1 cm (2.8 in.) cylinder for purposes of




    conducting this test.  In such cases, the waste may be




    allowed to cure for 30 days prior to further  testing.

-------
                                                                7.1-9
2.  The sample should be placed  into the  Structural  Integrity




    Tester,  then the hammer should be raised to its  maximum




    height and dropped.   This  should be  repeated fifteen




    times.




3.  The material should  be removed from  the sample




    holder,  weighed, and transferred to  the extraction




    apparatus for extraction.




Procedures for Analyzing Extract




     The test methods for analyzing the  extract are  as




follows:




1.  For arsenic, barium, cadmium,  chromium, lead, mercury,




    selenium or silver:   "Methods  for Analysis of Water and




    Wastes," Environmental Monitoring and Support Laboratory,




    Office of Research and Development,  U.S. Environmental




    Protection Agency, Cincinnati, Ohio  45268 (EPA-600/4-79-020,




    March 1979).




2.  For Endrin; Lindane; Methoxychlor; Toxaphene; 2,4-D;




    2,4,5-TP (Silvex): in "Methods for Benzidine, Chlorinated




    Organic Compounds, Pentachlorophenol and Pesticides in




    Water and Wastewater," September 1978, U.S. Environmental




    Protection Agency, Environmental Monitoring and  Support




    Laboratory, Cincinnati, Ohio 45268.




    as standardized in "Test Methods for the Evaluation of




    Solid Waste, Physical/Chemical Methods."




     For all analyses, the method  of standard addition shall




be used for the quantification of  species concentration.

-------
                                                                     7.1-10




This method is described in "Test  Methods  for  the  Evaluation



of Solid Waste." (It is also described  in  "Methods  for  Analysis



of Water and Wastes.")

-------
                            o
                        7.1-11
                            t
                            15.25cm
                             (6")
V -. /:
                            3.3cm
                            (1.3")
                            9.4cm
                            (3.7")
                                        COMBINED
                                        WEIGHT
                                        33Kg
                                        (.73lb|
       (3.15cm)
       (1.25")
                                     SAMPLE
                                        ELASTOMERIC*
                                        SAMPLE HOLDER
                                        7.1cm
                                        (2.8")

                                         I
^ELASTOMERIC SAMPLE HOLDER FABRICATED OF
 MATERIAL FIRM ENOUGH TO SUPPORT THE SAMPLE
              Figure  7-2.
    COMPACTION TESTER

-------
                                                                 7.2-1
                             Method 7.2




                        SEPARATION PROCEDURE




Scope and Application




     This procedure is used to separate a waste into its liquid and




solid phases both prior to and after extraction.




Summary of Method




     The Separation Procedure involves vacuum or pressure filtration




of a waste or extraction mixture.  To minimize filtration time,




pressure, settling, centrifugation and prefilters may be employed as




an adjunct to filtration.  Pressure filtration is required when vacuum




filtration is inadequate for complete separation.




Apparatus




1.  Filter holder:   A filter holder capable of supporting a 0.45




    urn filter membrane and able to withstand the pressure needed




    to accomplish separation.  Suitable filter holders range from




    simple vacuum units to relatively complex systems that can




    exert up to 5.3 kg/cm^ (75 psi) of pressure.  The type of




    filter holder used depends upon the properties of the mixture




    to be filtered.  Filter holders known to the Agency and deemed




    suitable for use are listed in Table 7.2-1




2.  Filter membrane: Filter membrane suitable for conducting the




    required filtration shall be fabricated from a material which:




    a.  is not physically changed by the waste material to




        be filtered.




    b.  does not absorb or leach the chemical species for




        which a waste's EP Extract will be analyzed.

-------
                                                                    7.2-2
    Table 7.2-2 lists filter media known to the Agency and generally




    found to be suitable for solid waste testing.




3.  In cases of doubt contact the filter manufacturer to determine




    if either membrane or prefilter are adversely affected by the




    particular waste.  If no information is available, submerge




    the filter in the waste's liquid phase.  After 48 hours a




    filter that undergoes visible physical change (i.e. curls,




    dissolves, shrinks, or swells) is unsuitable for use.




          Use the following procedure to establish if a filter




    membrane will leach or adsorb chemical species.




     a.  Prepare a standard solution of the chemical species of




         interest.




     b.  Analyze the standard for its concentration of the chemical




         species.




     c.  Filter the standard and re-analyze.  If the concentration




         of the filtrate differs from the original standard, the




         filter membrane leaches or absorbs one or more of the




         chemical species.




General Procedure




1.  Weigh filter membrane and prefilter to + 0.01 gram.  Handle




    membrane and prefilters with blunt curved tip forceps or




    vacuum tweezers, or by applying suction with a pipette.




2.  Assemble filter holder, membranes, and prefilters following




    the manufacturer's instructions.  Place the 0.45 urn membrane




    on the support screen and add prefilters in ascending order of




    pore size.  Do not pre-wet filter membrane.

-------
                                                                     7.2-3
3.  Allow slurries to stand to permit the solid phase to settle.




    Slow to settle wastes may be centrifuged prior to filtra-




    tion.




4.  Wet the filter with a small portion of the waste's or extraction




    mixture's liquid phase.  Transfer the remaining material to the




    filter holder and apply vacuum or gentle pressure (10-15 psi)




    until all liquid passes through the filter.  Stop filtration when




    air or pressurizing gas moves through the membrane. If this point




    is not reached under vacuum or gentle pressure slowly increase the




    pressure in 10 psi increments to 75 psi.  Halt filtration when




    liquid flow stops.






5.  Remove solid phase and filter media and weigh to +_ 0.01 gram.




    Discard solid if it comprises less than 0.5% of the mixture




    (see below).  If the sample contains >0.5% solids use the wet




    weight of the solid phase obtained in this separation for




    purposes of calculating amount of liquid and acid to employ




    for extraction using the following equation:




                     W = Wf - Wt




    W  =  wet weight in grams of solid to be charged to extractor



    Wf -  wet weight in grams of filtered solids and filter media




    Wt =  weight in grams of tared filters.




Procedure for Determining Percent Solids of a Waste




1.  Determine percent solids of a waste sample by:




    a.  separately weighing the waste sample and filters.




    b.  filtering the waste material.




    c.  drying the solid and filters at 80°C until two




        successive weighings yield the same value.   Cal-

-------
                                                                            7-2-4
               culate the percent solids using the following

               equation:
weight of filtered solid and filters -  tared weight of filters x 100 = % solids
                   initial weight of waste material

            NOTE;   This procedure is only used to determine if the solid
            must be extracted or if it can be discarded unextracted.  It
            is not used in calculating the amount of water or acid to use
            in the extraction step.  Do not extract solid material that
            has been dried at 80°C.  A new sample will have to be used
            for extraction if a % solids determination is performed.

-------
                                                                        7.2-5
                                Table 7.2-1

                         APPROVED FILTER HOLDERS
Vacuum Filters
Manufacturer
Size
  Model No
  Comments
  Nalgene
500 ml
   Systems

  Millipore
 142 mm
    45-0045


p


Nuclepore
Millipore
ressure Filters
Nuclepore
Micro Filtration
47 mm
4 7 mm

142 mm
142 mm
410400
XX10 047 00

420800
302300
YT30 142 HW
Disposable plastic unit,
includes prefilter and
filter pads, and reservoir
Should only be used when
solution is to be analyzed
for inorganic constituents

-------
                                                                          7.2-6
                                  Table 7.2-2

                           APPROVED FILTRATION  MEDIA
Filter
Type
Supplier
Filter To Be Used
For Aqueous Systems*
Filter To Be Used
For Organic Systems*

Coarse
Pref liter

Medium
Pref liters
Fine
Pref liters
Fine
Filters
(0.45um)



Gelman
Nuclepor e
Millipore
Nuclepore
Millipore
Nuclepore
Millipore
Gelman
Pall
Nuclepore
Millipore
Selas
61653
61669
210907
211707
AP25 042 00
AP25 127 50
21095
211705
AP20 042 00
AP20 124 50
210903
211703
AP25 042 00
AP25 127 50
60173
60177
047NX50
142NX25
111107
112007
HAWP 047 00
HAWP 142 50
83485-02
83486-02
61652
61669
210907
211707
AP25 042 00
AP25 127 00
21095
211705
AP20 042 00
AP20 124 50
210903
211703
AP25 042 00
AP25 127 50
60540
60544

181107
182007
FHLP 047 00
FHLP 142 00
83485-02
83486-02

-------
                                                                     7.4-1
                          Method 7.4




                STRUCTURAL INTEGRITY PROCEDURE




Application



     The Structural Integrity Procedure (SIP) is employed




to approximate the physical degradation a monolithic waste




undergoes in a landfill or when compacted by earthmoving




equipment.




Equipment




1.  Structural Integrity Tester meeting the specifications




    detailed in Figure 7.4-1.




2 .  Sample  holders of elastomeric material firm enough




    to support a cylindrical waste sample 3.3 cm (1.32 in.) in




    diameter and 7.1 cm (2.84 in.) long.




Procedure^




1.  Cut a 3.3 cm in diameter by 7.1 cm long cylinder




    from the waste material.  For wastes which have been treated




    using a fixation process the waste may be cast in the form




    of a cylinder and allowed to cure for 30 days prior to testing.



2.  Place waste into sample holder and assemble the




    tester.  Raise the hammer to its maximum height and drop.



    Repeat  14 times.




3.  Remove  solid material from tester and scrape off




    any particles adhering to sample holder.  Weigh the waste to




    the nearest 0.01 gram and transfer its to the Extractor.

-------
                                                             7.5-1
                        Sub-Section 7.5




                          EXTRACTORS






Introduction




     An acceptable extractor is one which will prevent




stratification of a waste sample and extraction fluid and




will insure that all sample surfaces continuously contact




well mixed extraction fluid.  There are two types of acceptable




extractors: 1) stirrers and 2) tumblers.  Stirrers consist of a




container in which the waste/extraction fluid mixture is




agitated by spinning blades.  Rotators agitate by turning a




sample container end over end through a 360° revolution.



                           Stirrer




Scope and Application




     One such stirrer approved for use in evaluating solid




waste is illustrated in Figure 7.5-1.  It is a container in




which a waste/extraction fluid mixture is agitated by 2




blades spinning at >_ 40 rpm.  This extractor can be used



with either automatic or manual pH adjustment.




Precautions




1.  Large particles (>_ 0.25 in. in diameter) may be




    ground by the spinning blades or abrade the container.




    If metal containers are employed this may result in




    contamination of the EP Extract.




2.  Monolithic wastes should not be extracted in the stirrer




    as they may bend or break the stirring blades.

-------
                                                                     7.5-2
Summary of Operation




     Place waste In extractor, add extraction fluid and




stir for the required period of time.  Adjust pH while stirrer




is in operation by addition of acid through port in cover.




pH may be continuously monitored using port in cover designed




to accept a pH electorde.




Manufactures




     Extractors of this design may be fabricated by the user




or are known to be available commercially from Associated




Design and Manufacturing Co. and Millipore Corporation.



                       Rotary Extractor




Scope and Application




     The rotary extractor consists of a rack or box type




device holding a number of plastic or glass bottles which




rotate at approximately 29 rpm.  Rotary extractors are used




with manual pH adjustment.




Precautions




1.  Use glass or fluorocarbon bottles for wastes whose




    EP Extract will be analyzed for organic compounds.



    For extracts to be analyzed only for metals, poly-




    ethylene bottles may be substituted.




2.  Be careful not to tighten the screws too far and




    shatter the bottle when using the design in Figure




    7.5-2.




3.  Do not use glass bottles for extracting large blocks




    of waste as these may cause the bottles to shatter.

-------
                                                                     7.5-3
4.  It is recommended that the bottles be alternated In




    an opposing manner in the apparatus to minimize torque




    (e.g., when one bottle faces up,  the next bottle faces




    down.)  When extracting an odd number of samples,




    balance the extractor by adding a bottle containing




    an amount of water approximately equal to the volume




    in the other bottles.




Equipment






1.  Rotary extractors approved for use in evaulating the




    EP toxicity of solid wastes are illustrated in Figure




    7.5-2 and 7.5-3.




2.  Plastic or glass bottles sized to fit the particular




    extractor.




3.  The equipment illustrated in Figure 7.5-2 may be




    fabricated by the user or is available commercially




    from Associated Design and Manufacturing Co.




4.  The equipment illustrated in Figure 7.5-3 is available




    from the Acurex Corporation.




Summary of Operation



     Fill plastic or glass bottles with the solid material.




Add distilled deionized water to each bottle and start extractor.




Stop extractor after 1 minute and adjust pH.  Restart extractor




and continue pH adjustment for the first six hours of agitation




as described in the "Manual pH Adjustment Procedure" (Section




7.1).  After 24 hours of agitation stop extractor, check pH as




described and, if within range specified, adjust volume




of fluid and remove for liquid solid separation.

-------
                                                          7.5-4
    NON CLOGGING SUPPORT BUSHING

1 inch BLADE AT 30° TO HORIZONTAL
         Figure 7.5-1
          EXTRACTOR

-------
7.5-5

-------
7.5-6

-------
                                                              8.01-1
                         Method 8.01

                 METHOD FOR VOLATILE ORGANICS



Scope and Application

     The following volatile organic compounds may be determined

by this method:


        Volatile Compound               Detector

        Acrylamide                        FID
        Benzyl Chloride                   HSD
        Bis(2-chloroethoxymethane)         HSD
        Bis(2-Chloroisopropyl) ether      HSD
        Carbon Disulfide                  FID
        Carbon Tetrachloride              HSD
        Chloroacetaldehyde                HSD
        Chlorobenzene                     HSD, FID
        Chloroform                        HSD
        Chloromethane                     HSD '
        Dichlorobenzene                   HSD
        Dibromomethane                    HSD
        Ethyl ether                       FID
        Formaldehyde                      FID
        Methanol                          FID
        Methyl Ethyl Ketone               FID
        Methyl Isobutyl Ketone            FID
        Paraldehyde                       FID
        Tetrachloroethane                 HSD
        Tetrachloroethene                 HSD
        Trichloroethene                   HSD
        Trichlorofluoromethane            HSD
        Trichloropropane                  HSD
        Vinyl Chloride                    HSD
        Vinylidene Chloride               HSD

-------
                                                                    8.01-2
Summary of Method




1.  The volatile compounds are introduced to the gas chromato-




    graph by direct injection (Method 8.80), the Headspace




    Method (Method 8.82), or the Purge and Trap method (Method




    8.83).  A temperature program is used in the gas chromato-




    graph to separate the organic compounds.  Detection is




    achieved by either a halide specific detector (HSD) or a




    flame ionization dectector (FID).  The detector used




    depends on the compound(s) of interest.




2.  If interferences are encountered, the method provides an




    optional gas chromatographic column that may be helpful




    in resolving the compounds of interest from the inter-




    ferences .




Interferences




     Samples can be contaminated by diffusion of volatile




organics (particularly chlorofluorocarbons and methylene




chloride) through the sample container septum during shipment




and storage.  A sample blank carried through sampling and




subsequent storage and handling can serve as a check on such




contamination.




Apparatus




It  Vial with cap - 40 ml capacity screw cap (Pierce #13075 or




    equivalent).   Detergent wash and dry at 105°C before use.




2.  Septum - teflon - forced silicone (Pierce #12722 or




    equivalent).   Detergent wash, rinse with tap and distilled




    deionized water,  and dry at 105°C for one hour before use.

-------
                                                                 8.01-3
 3.   Sample introduction apparatus  (Methods  8.80,  8.82  and  8.83)




 4.   Gas  chromatograph - Analytical system complete with



     programmable gas  chromatograph suitable for  on-column




     injection and all required  accessories, including  HSD  or,




     FID,  column supplies,  recorder and  gasses.   A data system




     for  measuring peak area is  recommended.




 5.   Carbopack B 60/80 mesh coated  with  1% SP-1000 packed




     in an 8 ft. x 0.1 in.  ID stainless  steel or  glass  column



     (Column 1)  or ?orisil-C 100/200 mesh coated  with n-octane




     packed in a 6 ft. x 0.1 in.  ID stainless steel or  glass




     column (Column 2).




 6.   Syringes -  5 ml glass  hypodermic with Luerlok tip  (2  each).




 7.   Micro syringe - 10, 25, 100  ul.




 8.   2-way syringe valve with Luer  ends  (3 each).




 9.   Syringe - 5 ml -  gas tight  with shut-off valve.




10.   Bottle - 15 ml screw-cap, with teflon cap liner.




 Reagents




 1.   Activated carbon  - Filtrosorb  200 (Calspan Corp.)  or




     equivalent.




 2.   Organic-free water generated by passing tap  water  through



     a carbon filter bed containing about 1  Ib.  of activated




     carbon.  A water  purification  system (Millipore Super  -




     Q or  equivalent)  may be used to generate organic-free




     deionized water.   Organic free water may also be prepared




     by boiling  water  for 15 minutes.  Subsequently, while




     maintaining the temperature  at 90°  C, bubble a contaminant-




     free  inert  gas through the  water for one hour.

-------
                                                                   8.0M.
3.  Stock standards - prepare stock standard solutions in




    methyl alcohol using assayed liquids or gas cylinders




    as appropriate.  Because of the toxicity of many of




    the compounds being analyzed,  primary dilutions of these




    materials should be prepared in a hood .  A NIOSH/MESA




    approved toxic gas respirator  should be used when




    the analyst handles high concentrations of such




    materials.




    a.  Place about 9.8 ml of methyl alcohol into a 10 ml




        ground  glass stoppered volumetric flask. Allow




        about 10 minutes or until  all alcohol wetted surfaces




        have dried.  Weigh the flask to the nearest 0.1 mg.




    b.  Add the assayed reference  material:




        i.   Liquids




            Using a 100 ul syringe, immediately add 2 drops




            of  assayed reference material to the flask, then




            reweigh.  Be sure that the 2 drops fall directly




            into the alcohol without contacting the neck of




            the flask.




       ii .  Gases




           To prepare standards from any of the organic




           compounds that  boil below 30°C,  fill a 5 ml valved




           gas-tight syringe with  the reference standard to  the




           5 ml mark.   Lower the needle to  5 mm above the methyl




           alcohol meniscus.  Slowly inject the reference




           standard above  the surface of the liquid (the heavy




           gas  will rapidly dissolve into the methyl alcohol).

-------
                                                                   8.01-5




    c.  Reweigh,  dilute to volume,  stopper,  then mix by




        by inverting the flask several times.   Transfer the




        standard  solution to a 15 ml screw cap bottle with a




        teflon cap liner.




    d.  Calculate the concentration in mg/1  from the net




        gain in weight.




    e.  Store stock standards at 40° C.  Prepare fresh standards




        weekly for the 4 compounds whose BP  <^ 30° C.  All other




        standards must be replaced with fresh standards each




        month.




Calibration




1.  Using stock standards, prepare secondary dilution standards




    in methyl alcohol that contains the compounds of interest,




    either singly or mixed together.




2.  Assemble necessary gas chromatographic apparatus and establish




    operating parameters equivalent to those indicated in the




    Procedure section.  By injecting secondary standards, adjust




    the sensitivity of the analytical system for each compound



    being analyzed so as detect _< 1 ug.




Quality Controls




1.  Before processing any samples,  the analyst should daily




    demonstrate through the analysis of an organic-free water




    or solvent blank that the entire analytical system is




    interference  free.




2.  Standard quality assurance practices should be used with




    this method.   Field replicates  should be collected to




    validate the  precision of the sampling technique.

-------
                                                                   8.01-6
    Laboratory replicates should be analyzed to validate the




    the precision of the analysis.  Fortified samples should




    be analyzed to validate the accuracy of the analyses.




    Where doubt exists over the identification of a peak




    on the gas chromatogam, confirmatory techniques such as




    mass spectroscopy should be used.




3.  The analyst should maintain constant surveillance of




    both the performance of the analytical system and the




    effectiveness of the method in dealing with each sample




    matrix by spiking each sample with known amounts of the




    compounds the waste is being analyzed for.  Using these




    spiked samples,  readjust the sensitivity of the instrument




    such that 1 ug/gm of sample can be readily detected




    (see Quality Control).




Procedure




1.  Assemble gas chromatograph with either Column 1 or 2.




    (See Apparatus section.)




    Column 1:




    a)  Set helium gas flow at 40 ml/min flow rate.




    b)  Set column temperature at 45° C for 3 minutes




        then program a 8° C/minute temperature rise to




        220° C and hold for 15 minutes.




    Column 2:




    a)  Set helium carrier gas flow at 40 ml/minute flow




        rate.




    b)  Set column temperature at 50° C for 3 minutes, then

-------
                                                              8.01-7
        program a 6° C/min temperature rise to 170°  C and




        hold for 4 minutes.




2.  Introduce volatile compounds to the gas chromatograph




    using direct injection, headspace, or purge and  trap.




3.  Table 8.01-1 summarizes the estimated retention  times for




    a number of organic compounds analyzable using this




    method.  An example of the separation achieved by Column 1




    is shown in Figure 8.01-1.




4.  Calibrate the system immediately prior to conducting any




    analysis and recheck as in Quality Control for each type




    of waste.  Calibration should be done no less frequently




    than at the beginning and end of each analyses session.




C aleu1a t i o n s




1.  If a response for the contaminant being analyzed for is greater




    than 2x background, then the waste does not meet




    the criteria for delisting of being fundamentally different




    than the listed waste.  If a response is not noted, then




    prior to concluding that the sample does not contain the




    specific contaminant, the analyst must demonstrate, using




    the spiked samples, that the instrument sensitivity is



    < 1 ug/gm of sample.

-------
                         Table 8.01-1

        ORGANOHALIDES TESTED USING PURGE AND TRAP METHOD
                                                                   8.01-S
Compound

     Acrylamlde

     Bis(2-chloroethoxymethane)

     Bis(2-chlorolsopropyl) ether

     Carbon disulfide

     Carbon tetrachloride

     Chloroacetaldehyde

     Chlorobenzene

     Chloroform

     Chloromethane

 1,3-Dichlorobenzene

 1,2-Dlchlorobenzene

 1,4-Dichlorobenzene

 1,1-Dichloroethane

 1,2-Dichloroethane

     Dichloromethane

     Ethyl ether

     Formaldehyde

     Methanol

     Methyl ether ketone

     Methyl isobutyl ketone

     Paraldehyde (trimer of
       acetaldehyde)
Retention Time (Min)
Col. 1        Col. 2
 13.0
14.4
24.2
10.7
1.50
34.00
34.9
35.4
9.30
11.4
18
12
5
22
12
15
12
15
.8
.1
.28
.4
.6
.4
.6
.4

-------
   Compound


1,1,2,2-Tetrachloroethane

1,2,2,2-Tetrachloroethane

1,1,1,2-Tetrachloroethane

        Tetrachloroethene

  1,1,1-Tetrachloroethane

  1.1,2-Trlchloroethane

        Trichloroethene

        Trichlorofluoromethane

        Trichloropropane

        Vinyl Chloride

        Vinylidene Chloride
                                                                   8.01-9
Retention Time (Mln)
Col. 1        Col. 2
 21.6
21.7
12.6
16.5
15.8
7.18
15.0
13.1
18.7
13.1

 2.67
5.28

-------
                                                                8.01-10
  NS
  oo

1S
O

Ol
             U>
                        BROMOMETHANE



                               CHLORO ETHANE
                                         CHLOROMETHANE
                                      1.1-DJCHLOROETHENL





                                   cis-1.2- DICHLORETHENE






                                 1.1,1- TRICHLOROETHANE



                                   1, 2-OICHLOROPROPANE
                                   i^


                             trans -1, 3-D1CHLOROPROPENE

                            cisi 1, 3-DICHLOROPROPENE

                       1. 2-DIBROMOETHANE


                                     1.1.1.2.TETRACHLOROETH ANt
                             1, 2. 3-TR1CHLOROPROPANE

                             MMHK


                             1.1, 2. 2-TETRACHLOROETHANE
               CHLOROBENZENE

           1-CHLOROHEXANE





          BROMOBENZENE
                                                       O2O
                                                       ggo
                                                         — o
                                                       O
                    2.CHLOROTOLUENE
                      1, 4-DI CHLORO BENZENE
                                            is
                                            §1

-------
                                                                   8.02-1




                         Method 8.02




      METHOD FOR VOLATILE AROMATICS, KETONES AND ETHERS




Scope and Application




     This method covers the determination of certain volatile




aromatics, some methyl ketones, and ethyl ether.  The following




compounds may be determined by this method:




          Benzene




          Chlorobenzene




          Dichlorobenzene




          Ethyl ether




          Methyl ethyl ketone




          Methyl isobutyl ketone




          Toluene




          Xylene




Summary of Method




     The volatile compounds are introduced to the gas chroma-




tograph by direct injection (Method 8.80), the headspace




method (Method 8.82), or the purge and trap technique (Method




8.83).  A temperature program is used in the GC system to



separate the compounds prior to detection with a photoionization




detector (PID) or flame ionization detector (FID).




Interferences




     Samples can be contaminated by diffusion of volatile




organics (particularly chlorofluorcarbons and methylene




chloride) through the sample container septum during shipment




and storage.  A sample blank carried through sampling and




subsequent storage and handling can serve as a check for such




contamination.

-------
                                                                     a.02^2
Apparatus

1.  Gas chromatograph - Analytical  system  complete with

    programmable gas chromatograph  suitable  for  on-column injection

    and all required accessories  including Model PI-51-02 photo-

    ionization detector (P1D),  column  supplies,  recorder and gases.

    A data system for measuring peak areas is  recommended.

2.  Supelcoport 100/200 mesh  coated with 5%  SP-2100 and

    1.75% Bentone 34 packed in  a  6  ft.  x 0.085  inch ID stainless

    steel column.

3.  Syringes - 5 ml glass hypodermic with  Luerlok tip

    (2 each).

4.  Micro syringes - 10, 25,  100  ul .

5.  2-way syringe valve with  Luer ends  (3  each),

6.  Syringe - 5 ml gas-tight  with shut-off valve.

7.  Bottle - 15 ml screw-cap, with  teflon  cap  liner.

Reagents

1.  Activated carbon - Filtrosorb 200  (Calgon  Corp.)

    or equivalent.

2.  Organic-free water generated  by passing  distilled or deionized

    water through a filter bed containing  of activated carbon.

    A water purification system (Millipore Super-Q  or equivalent)

    may be used to generated  organic-free  deionized water.   Organic

    free water may also be prepared by  boiling water  for 15  minutes.

    Subsequently while maintaining  the  temperature  at 90°C,  bubble

    a contaminant-free inert  gas  through the water  for one hour.

-------
                                                                    8.02-3
3.  Stock standards - Prepare stock standard solution in




    methyl alcohol using assayed liquids.   Because of the




    toxicity of many of the compounds being analyzed primary




    diluting of these materials should be  prepared in a




    hood.  A NIOSH/MESA approved toxic gas respirator should




    be used when the analyst handles high  concentrations of




    such materials .




    a.  Place about 9.8 ml of methyl alcohol into a




        10 ml ground glass stoppered volumetric flask.  Allow




        the flask to stand, unstoppered, for about 10 minutes




        or until all alcohol wetted surfaces have dried.  Weigh




        the flask to the nearest 0.1 mg.




     b.   Using a 100 ul syringe, immediately add 2 drops




         of assayed reference material to  the flask, then




         reweigh.  Be sure that the 2 drops fall directly




         into the alcohol without contacting the neck of the



         flask.




     c.   Dilute to volume, stopper, then mix by inverting




         the flask several times.  Transfer the standard solution




         to a 15 ml screw-cap bottle with a teflon cap liner.




     d.   Calculate the concentration in ug/ml from the net




         gain in weight .




     e.   Store stock standards at 4°C•  All standards




         must be replaced with fresh standard each month.

-------
                                                             8.02-4
Calibration



1.  Using stock standards, prepare secondary dilution




    standards in methyl alcohol that contains the compounds




    of interest, either singly or mixed together.




2.  Assemble necessary gas chromatographic apparatus and




    establish operating parameters equivalent to those




    indicated in the Procedure section.  By injecting secondary




    standards adjust the sensitivity limit and the linear




    range of the analytical system for each compound being




    analyzed for to a sensitivity of <_ 1 ug/1 (2 x background).




Quality Control




1.  Before processing any samples the analyst should




    daily demonstrate through the analysis of an organic-




    free water or solvent blank that the entire analytical




    system is interference free.




2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to




    validate the precision of the sampling technique.  Labora-




    tory replicates should be analyzed to validate the precision



    of the analysis.  Fortified samples should be analyzed




    to validate the accuracy and sensitivity of the analysis.




    Where doubt exists over the identification of a peak on




    the gas chromatogram, confirmatory techniques such as




    mass spectroscopy should be used.




3.  The analysis should maintain constant surveillance of




    both the performance of the analytical system and the




    effectiveness of the method in dealing with each sample

-------
                                                                8.02-5
    matrix by spiking each sample with known amounts of the




    compounds the waste is being analyzed for.  Using these




    spiked samples readjust the sensitivity of the instrument




    such that 1 ug/gm of sample can be readily detected.




Procedure




1.  Assemble gas chromatograph with column specified




    in Apparatus section and detector indicated in




    Table 8.02-1.




2.  Set helium carrier gas at 36 ml/min flow rate.




3.  Hold column temperature at 50°C for 2 minutes then




    program a 6°C/minute rise to 90°/C for a final hold of




    40 minutes.




4.  Table 8.02-1 summarizes the estimated retention times for




    a number of organic compounds analyzable using this method.




    An example of the separation achieved by this column is




    shown in Figure 8.02-1.



5.  Calibrate the system immediately prior to conducting




    any analyses and recheck as in Quality Control for each




    type of waste.  Calibration should be done no less frequently



    than at the beginning and end of each analysis session.




Calculations




1.  If a response for the contaminant being analyzed for




    is greater than 2 x background, then the waste




    does not meet the criteria for delisting of being funda-




    mentally different than the listed waste.  If a response




    is not noted, then prior to concluding that the sample

-------
                                                                             8.02-6
       IU
                  Ul
                  (SI
            LU

         UJ  2
         O
         i
         o
-   |2
S   Id
               LU

LU


f«J  u3


LU  Z

S  S
O  03
                               u z
                               5H
                               «r 9
                                     en


                                     O
0   2   4   6   8   10  12  14  16 18  20  22  24  26  28
                  RETBYTIORI TIME-MINUTES
                         Figure  8.02-1

          GAS CHROMATOGRAM OF VOLATILE AROMATICS

-------
                                                                     8.02-7
    does not contain the specific contaminant, the analyst

    must demonstrate, using spiked samples, that the method

    sensitivity is _<_ 1 ug/gm of sample.

2.  When duplicate and

    spiked samples are analyzed, all data obtained 'should be

    reported.

3.  If one desires to determine the actual concentration of

    the compound in the waste, the method of standard addition

    should be  used.


                         Table 8.02-1

                        CHROMATOGRAPHY
Retention Time
Compound (min)*
Benzene 3.33
Chlorobenzene 9.17
1,4 Dichlorobenzene 16.8
1,3 Dichlorobenzene 18.2
1,2 Dichlorobenzene 25.9
Ethyl ether
Methyl ethyl ketone
Methyl isobutyl ketone
Toluene 5.75
Xylene
Detector
Methods
PID
PID
PID
PID
PID
FID
FID
FID
PID
PID
* 6' x 0.085 in. column packed with 1.75% Bentone 34 and 5%
  SP-2100 on Supelcoport 100/200.

-------
                                                             8.03-1
                         Method 8.03

            METHOD FOR ACRYLONITRILE, ACETONITRILE
                         AND ACROLEIN

Scope and Application

     This method is applicable to the determination of

acrylonitrile, acetonitrile and acrolein in waste samples.

Summary of Method

     The compounds are introduced into the gas chromatograph

by either direct injection (Method 8.80), the headspace

technique (Method 8.82) or the purge and trap technique

(Method 8.83).

     A temperature program is used in the gas chromatograph

to separate the organic compounds for detection by a flame

ionization detector (FID).

Interference

     Samples can be contaminated by diffusion of volatile

organics (particularly chlorofluorocarbons and methylene

chloride) through the sample container septum into the sample

during shipment and storage.  A sample blank carried through

sampling and subsequent storage and handling protocols can

serve as a check on such contamination.

Apparatus

1.  Vial, 40 ml capacity screw cap (Pierce #13075

    or equivalent).  Detergent wash and dry at 105°C before

    use.

2.  Septum,  teflon faced silicone (Pierce #12722 or

    equivalent).   Detergent wash, rinse with tap and

-------
                                                                     8.03-2
     distilled deionized water,  and dry at 105°C for one hour




     before use.




 3.   Sample introduction apparatus (see Methods 8.80, 8.82 or




     8.83).




 4.   Gas chromatograph - Analytical system complete with




     programmable gas chromatograph suitable for on-column




     injection and all required  accessories, column supplies,




     recorder and gasses.




     A data system for measuring peak areas is recommended.




 5.   Chromosorb 101 80/100 mesh  packed in a 6' x 1/8" O.D.




     stainless steel or glass column.




 6.   Syringes, 5  ml glass hypodermic with Luerlock tip (2




     each) .




 7.   Micro  syringe, 10, 25, 100  ul.




 8.   2-way  syringe valve with Luer ends (3 each).




 9.   Syringe - 5  ml gas tight -  with shut-off valve.




10.   Vial,  15 ml  screwcap, with  teflon cap liner.




 Reagents




 1.   Activated carbon, Filtrosorb - 200 (Calspan Corp.) or




     eqivalent.




 2.   Organic-free water generated by passing tap water through




     a carbon filter bed containing about 1 Ib of activated




     carbon.  A water purification system (Millipore Super -




     Q or equivalent) may be used to generate organic-free




     deionized water.  Organic free water may also be prepared




     by boiling distilled deionized water for about 15 minutes.




     Subsequently, while maintaining the temperature at 90°C,

-------
                                                                    8.03-3
    bubble a contaminant-free inert gas through the water




    for one hour.




3.  Stock standards - prepare stock standard solutions in




    propanol using assayed liquids or gas cylinder as appro-




    priate.  Because of the toxicity of many of the compounds




    being analyzed, primary dilutions of these materials




    should be prepared in a hood.   A NIOSH/MESA approved




    toxic gas respirator should be used when the analyst




    handles high concentrations of such materials.




    a.   Place about 9.8 ml of propanol into a 10 ml ground




        glass stoppered volumetric flask.  Allow about 10




        minutes or until all alcohol wetted surfaces have




        dried.   Weigh the flask to the nearest 0.1 mg.




    b.   Using a 100 ul syringe, immediately add all 2 drops




        of assayed reference material to the flask, then




        reweigh.  Be sure that the 2 drops fall directly




        into the propanol without  contacting the neck of the




        flask.




    c.   Dilute  to  volume, stopper, then mix by inverting the




        flask several times.  Transfer the standard solution




        to a 15 ml screw-cap bottle with a teflon cap liner.




    d.   Calculate  the concentration in micrograms/liter




        from the net gain in weight.




    e.   Store stock standards at A°C.   All standards must be




        replaced with fresh standard each month.

-------
                                                                    8.03^
Calibration




1.  Using stock standards, prepare secondary dilution standards




    in propanol that contain the compounds of interest,




    either singly or mixed together.




2.  Assemble necessary gas chromatographic apparatus and




    establish operating parameters equivalent to those indicated




    in the Procedure section.  By injecting secondary standards,




    adjust the sensitivity limit and the linear range of the




    analytical system for each compound being analyzed for a




    sensitivity of <_ 1 ug ( 2 x background).




Quality Control




1.  Before processing any samples, the analyst should demon-




    strate through the analysis of an organic-free water or




    solvent blank that the entire analytical system is inter-




    ference free.




2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to




    validate the precision of the sampling technique.  Labora-




    tory replicates should be analyzed to validate the accuracy




    of the analysis.  Where doubt exists over the identification




    of a peak on the gas chromatogram, confirmatory techniques




    should be used.




3.  The analyst should maintain constant surveillance of both




    the performance of the analytical system and the effective-




    ness of this method in dealing with each sample matrix by

-------
                                                                     8.03-5
    spiking each sample with known amounts of the compounds




    the waste is being analyzed for.  Using these spiked




    samples, readjust the sensitivity of the instrument such




    that 1 ug/gm of sample can be readily detected.




Procedure




1.  Assemble gas chromatograph with column specified in




    Apparatus section.




2.  Set helium carrier gas at 45 ml/minute flow rate.




3.  Hold column temperature at 80°C for 5 minutes, then




    program an 8°C/minute rise to 150°C and hold until all




    species have eluted.




4.  Calibrate the system  immediately prior to conducting any




    analyses and recheck  as in Quality Control for each type




    of waste.  Calibration should be done no less frequently




    than at the beginning and end of each analysis session.




    See Figure 8.03-1 for an example of the chromatogram




    to be expected using  these conditions.

-------
                                                                       8.03-6
     COLUMN: CHROMOSORB 101
     PROGRAM: 80'C -5 MINUTES.
              8CC/MINUTE TO 150"C
     DETECTOR: FLAME IONIZAT10N
                                  LU
           2468
              RETENTION TIME-MINUTES
10
                   Figure 8.03-1
GAS CHROMATOGRAM OF ACROLECN AND ACRYLONITRILE

-------
                                                               8.04-1
                         Method 8.04




                           PHENOLS






Scope and Application




     The following compounds may be determined by this




method:




     2-Chlorophenol




     Cresol(s)




     Cresylic acid(s)




     2,4,-Dimethylphenol




     4,6-Dinitro-o-cresol




     4-Nitrophenol




     Pentachlorophenol




     Tetrachlorophenol




     Trichlorophenol(s)




Summary of Method




     The sample or sample extract is injected onto the gas




chromatograph column following appropriate sample preparatioi




procedures:  (Shake out (Method 8.84), Soxhlet extraction




(Method 8.86), or Sonication (Method 8.85)).  A general



clean-up procedure employing liquid-liquid extraction is




described in Method 9.1.  An optional clean-up procedure




specific for this group of compounds is described at the end




of this method, for samples or extracts which may require




further clean-up.  A temperature program is used in the GC




system to separate the compounds before detection with a




Flame lonization Detector (FID) or Halogen Specific Detector




(HSD).

-------
                                                                    8.04-2
     The method also provides for the preparation of penta-




fluorobenzylbromide (PFB) derivatives for electron capture gas




chromatography with additional clean-up procedures to aid the




analyst in the elimination of interferences.




Interferences




1.  Solvents, reagents, glassware, and other sample processing




    hardware may yield discrete artifacts and/or elevated base-




    lines causing misinterpretation of gas chromatograms.  All




    of these materials must be demonstrated to be free from




    interferences under the conditions of the analysis by




    running method blanks.  Specific selection of reagents and




    purification of solvents by distillation in all-glass




    systems may be required.




2.  Interferences coextracted from s-amples will vary considerably




    from source to source depending upon the waste being sampled.




    While general cleanup techniques are provided in Section 9




    and as part of this method, unique samples may require additional




    cleanup.




Apparatus




1.  Vial with cap - 40 ml  capacity screw cap (Pierce #13075




    or equivalent).  Detergent wash and dry at 105°C before use.




2.  Septum, teflon faced silicone (Pierce #12722 or equivalent).




    Detergent wash, rinse with tap and distilled deionized




    water, and dry at 105°C for one hour before.




3.  Sample introduction apparatus (Methods 8.80 or 8.82 or 8.83).

-------
                                                                 8.04-3
 4.  Gas chromatograph - Analytical system complete with




     programmable gas chromatograph suitable for on-column




     injection and all required accessories, including FID or




     HSD, column supplies, recorder and gases.  A data system




     for measuring peak area is recommended.




 5.  Supelcoport 80/100 mesh coated with 1% SP-1240 DA in




     1.8 meter long 2 mm ID glass column (Column 1) or Chromosorb




     W-AWDMCS 80/100 mesh coated with 5% OV-17 packed in a 1.8




     meter long X mm ID glass column (Column 2).




 6.  Syringes - 5 ml glass hypodermic with L-uerlok tip (2each).




 7.  Micro syringe - 10, 25, 100 ul.




 8.  2-way syringe valve with Luer ends (3 each).




 9.  Syringe - 5 ml gas tight with shut-off valve.




10.  Bottle - 15 ml screw-cap,  with teflon cap liner.




11.  Kuderna-Danish apparatus (K-D) [Kontes K-570000 or equivalent]




     with 3 ball Snyder column.




12.  Water bath - heated with concentric ring cover capable




     of temperature control (± 2°C).  The bath should be used




     in a hood.




13.  Chromatographic column - 10mm ID by 100mm  length with




     teflon stopcock.




14.  Reaction vial - 20 ml with teflon - lined cap.




 Reagents




 1.  2  - propanol - pesticide quality or equivalent




 2.  Stock standards - prepare  stock standard solutions at




     a  concentration of 1.0 ug/ul by dissolving 0.100 grams

-------
                                                             8.04-4
of assayed reference material in pesticide quality 2-propanol




and diluting to volume in a 100 ml ground glass stopped




volumetric flask.   The stock solution is transferred to




ground glass stoppered reagent bottles,  stored in a refrigera-




tor, and checked frequently for signs of degradation or




evaporation, especially just prior to preparing working stan-




dards from them.




3.  PFB derivative reagents:




    a.  Hexane and toluene - pesticide quality or equivalent




    b.   Sodium gulfate - (ACS) granular, anhydrous (purified




         by heating at 400°C for 4 hours in a shallow tray).




    c.   Potassium carbonate - (ACS) powdered.




    d.   Silica gel - (ACS) 100/200 mesh, grade 923; activated




         at 130°C and stored in a dessicator.




    e.   Pentafluorobenzyl bromide - 97% minimum purity.




    f.   1,4,7,10,13,16-Hexaoxacylooctadecane (18




          crown 6) - 98% minimum purity.




Calibration




1.  Using stock standards, prepare secondary dilution standards




    in 2-propanol that contain the compounds of interest, either




    singly or mixed together.




2.  Assemble necessary gas chromatographic apparatus and




    establish operating parameters equivalent to those in the




    "procedure section."  By injecting secondary standards




    adjust the sensitivity limit and the linear range of the




    analytical system for each compound being analyzed for to




    a sensitivity of < 1 ug (2X background).

-------
                                                                   8.04-5
Quality Control




1.  Before processing any samples the analyst should demon-




    strate through the analysis of an organic - free water




    or solvent blank that the entire analytical system is




    interference free.




2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to vali-




    date the precision of the sampling technique.  Laboratory




    replicates should be analyzed to validate the accuracy of




    the analysis.  Where doubt exists over the identification




    of a peak on the gas chromatogram confirmatory techniques




    such as mass spectroscopy should be used.




3.  The analyst should maintain constant surveillance of both




    the performance of the analytical system and the effective-




    ness of this method in dealing with each sample matrix by




    spiking each sample with known amounts of the compounds




    the waste is being analyzed for and using these spiked




    samples readjust the sensitivity of the instrument such




    that 1 ug/gm of sample can be readily detected (see Quality




    Control).




          Flame lonization Gas Chromatography Procedure




1.  Assemble gas chromatograph with column 1 and Flame lonization




    Detector (apparatus section).




2.  Set nitrogen carrier gas at 30 ml/min flow rate.




3.  Set column temperature at 80°C at injection and program




    to immediately rise at 8°C/mln to 150°C.

-------
                                                                   S.04-6
 Derivatization and Electron Capture Gas Chromatography Procedure




1.  Pipet a 1.0 ml aliquot of the 2-propanol solution of standard




    or sample extract into a glass reaction vial.  Add 1.0 ml




    derivatization reagent.  This is a sufficient amount of




    reagent to derivatize a solution whose total phenolic




    content does not exceed 0.3 mg/ml.




2.  Add about 3 mg of potassium carbonate to the solution and




    shake gently.




3.  Cap the mixture and heat for 4 hours at 80°C in a hot




    water bath.




4.  Remove the solution from the hot water bath and allow it




    to cool.




5.  Add 10 ml hexane to the reaction vial and shake vigorously




    for one minute.  Add 3.0 ml of distilled deionized water




    to the reaction vial and shake for two minutes.




6.  Decant organic layer into a concentrator tube and cap with




    a glass stopper.




7.  Pack a 10mm ID chromatographic column with 4.0 grams of




    activated silica gel.  After settling the silica gel by




    tapping the column, add about two grams of anhydrous sodium




    sulfate to the top.




8.  Pre-elute the column with 6 ml hexane.  Discard the eluate




    and just prior to exposure of the sulfate layer to air




    pipet onto the column 2.0 ml of the hexane solution that




    contains the derivatized sample or standard.  Elute the




    column with 10.0 ml of hexane (Fraction 1) and discard

-------
                                                                    8.04-7
     this fraction.  Elute the column, in order with 10.0 ml




     15% toluene in hexane (Fraction 2), 10.0 ml 40% toluene




     in hexane (Fraction 3), 10.0 ml 75% toluene in hexane




     (Fraction 4), and 10.0 ml 15% 2-propanol in toluene (Fraction




     5).  Elution patterns for the phenolic derivatives are




     shown in Table 8.04-2 Fractions may be combined as desired




     depending upon the specific phenols of interest or level




     of interferences.  Collect the fractions in appropriate




     sized K-D apparatus and concentrate each fraction to 10 ml.




 9.  Assemble gas chromatograph with column 2 and HSD (apparatus




     section).




10.  Using 5% methane/95% argon as the carrier gas adjust flow to




     30 ml/min.




11.  Set column  temperature at 200°C.




12.  Inject 2-5ml of the appropriate fraction using the solvent -




     flush technique.   Smaller (1.0 ml) volumes can be injected




     if automatic devices are employed.  Record volume injected




     to the nearest 0.05 ml and the resulting peak size in area




     units.  If  the peak area exceeds  the linear range of the



     system dilute the extract and reanalyze.




      Calibrate  the system immediately prior to conducting any



 analyses and recheck  as in Quality Control for each type of




 waste.  Calibration should be done no less frequently than at




 the beginning and end of each session.

-------
Calculations




1.  If a response for the contaminant being analyzed for is




    greater than 2X background is noted, then the waste does




    not meet the criteria for delisting of being fundamentally




    different than the listed waste.   If a response is not noted,




    then prior to concluding that the sample does not contain




    the specific contaminant, the analyst must demonstrate, using




    spiked samples, that the instrument sensitivity is _<_ 1 ug/gm.




2.  When duplicate and spiked samples are analyzed, all data




    obtained should be reported.




3.  If one desires to determine the actual concentration of




    the compound in the waste, the method of standard addition




    should be used.

-------
                                                                                 8.04-9
          CO
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          SO
                                                                2-CHIOROPHENOL
                                                PHENOL
                       2-NITROPHENOL
                              2.4-DIMETHYLPHENOL
            2.4-DICHLOROPHENOL
2. 4. 6-TRICHLOROPHENOL
  4-CHLORO-3-METHYLPHENOL      § § p
 2. 4-DINITROPHENOL             3 § i
    2-METHYL-4, 6-DINITROPHENOL  g 3 fr
                     PENTACHLORCPHENOL
                                                                   «»
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                                 35

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                                                                 2. 4-DIMETHYLPHENOL
                                       4-NITROPHENOL
                           2-CHLOROPHENOL
                  4-CHLORO-3-METHYLPHENOL
               2. 4.-DICHLOROPHENOL
               2. 4. 6-TRICHLOROPHENOL

           2-NITROPHENOL
                                                                    o
                                  iBl
                                  s-|a
                                  s'g<
                                  _| O .
                                   PENTACHLOROPHENOL
                                                                      o -»
                                                                    o
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                                                                        s
                                                                        99
                                                                        I

-------
                                                      8.04-10
                  Table  8.04-1

 FLAME  IONIZATION  GAS  CHROMATOGRAPHY  OF  PHENOLS


                                      Retention Time*
	Compounds	(minutes)

     2-Chlorophenol                        1.70

     Cresol(s)

     Cresylic  acid

     2,4-Dimethylphenol                   4.03

     4 ,6-Ditvitro-O-cresol

     4-Nitrophenol                        24.25

     Pentachlorophenol                    12.42

     Phenol                                3.01

     Tetrachlorophenol

     2,4,6-Trichlorophenol                 6.05



  *Column  1

-------
                                                             8.04-11
                          Table 8.04-2

     ELECTRON CAPTURE GAS CHROMATOGRAPHY OF PFB DERIVATIVES

                     Retention   Recovery percent by fraction
Parent compound        time
                     (minutes)*




2 , 4 , 6— T ri chlor opheno 1 ...




I
3.3 	
1.8 	
2.9 	
7.0 	
28.8 	
. 14.0 	


2345
	 90 >1 	
	 90 10 	
	 95 7 	
50 50 	
75 20 	
	 >1 90


Retention times included for qualitative information only.
The lack of accuracy and precision of the derivatization
reaction precludes the use of this approach for quantitative
purposes.

*Column 2

-------
                                                                    8.06-1
                           Method 8.06

                GAS CHROMATOGRAPHY GENERAL  METHOD
                     FOR EXTRACTABLE ORGANICS

Scope and Application

     This is a general gas chromatographic  method  suitable  for

the determination of the presence of the  following  compounds  in

RCRA materials:

          Formic acid

          Heptachlor

          Hexachlorethane

          Hexachloracyclopentadiene

          Maleic anhydride

          Naphthoquinone

          Phosphorodithioic acid esters

          Phthalic anhydride

          2-Picoline

          Pyridine

          Toluene Diisocyanate(s)

     Prior to using this method waste samples  should  be

prepared for chromatography (if necessary)  using  the  appropriate

sample preparation method (e.g., shake out,  soxhlet extraction,

sonication).

Summary of Method

     Chromatographic conditions are described  which allow

for the measurement of the presence of the  compounds  in the

extract at levels sufficient to determine the  presence of the

compounds in the original waste at a concentration  of 1 ug/gram.

-------
                                                              8.06-2
     If interferences are encountered during chromatography




the method provides a general purpose cleanup procedure to aid




the analyst.




Precaution




     Solvents, reagents, glassware, and other sample process-




ing hardware may yield discrete artifacts and/or elevated baseline




causing misinterpretation of gas chromatograms.   All of these




materials should be demonstrated to be free from interferences




under the conditions of the analysis by running  method blanks in




order to prevent difficulties during the analysis.  Specific




selection of reagents and purification of solvents by distillation




in all-glass systems may be required to eliminate interferences.




     Interfering substances coextracted from the sample will




vary considerably from source to source, depending upon the




diversity of the waste being sampled.  While general cleanup




techniques are provided as part of this method,  unique samples




may require additional cleanup approaches to achieve the




sensitivities required.




     Phthalate esters contaminate many types of  products



commonly found in the laboratory.  The analyst should demonstrate




that no phthalate residues contaminate the sample or solvent




extract under the conditions of the analysis before deciding that




the compound being analyzed for is actually present.  Of particular




importance is the avoidance of plactics such as  polyvinyl chloride




because phthalates are commonly used as plasticizers and are




easily extracted.

-------
                                                                8.06-3
 Apparatus

 1.  Vial with cap - 40 ml capacity screw cap  (Pierce #13075 or

     equivalent).   Detergent  wash and dry at  105°C before use.

 2.  Septum - teflon - forced silicone (Pierce #12722 or equiva-

     lent).  Detergent wash,  rinse with tap and distil'ed dionized

     water, and dry at 105°C  for one hour before.

     Gas chromatograph - Analytical system complete with program-

     mable gas chromatograph  suitable for on-column injection and

     all required  accessories,  including Halogen Specific or

     Flame lonization Detector,  column supplies, recorder and

     gases.  A data system for  measuring peak  area is recommended.

 3.  Supelcoport 100/120 mesh,  coated with 1.5% SP-2250 + 1.95%

     SP-2401 in a  180 cm long x 4 mm ID glass  column (column 1) or

     Supelcoport,  100/120 mesh,  coated with 3% OV-1 in a 180 cm

     long x 4 mm ID glass column (column 2).

 4.  Syringes - 5  ml glass hypodermic with luerlok tip (2 each).

 5.  Micro syringe - 10, 25,  100 ul.

 6.  2-way syringe valve with Luer ends (3 each).

 7.  Syringe - 5 ml gas-tight with shut-off valve.

 8.  Bottle - 15 ml screw-cap,  with teflon cap liner.

 9.  Drying column - 20 mm ID pyrex chromatograph  column with
                                            •
     coarse frit.

10.  Kuderna-Danish (K-D) Apparatus equipped  with  the appropriate

     Synder columns [Kontes K-570000 or equivalent].

 11.  Boiling chips - solvent  extracted, approximately 10/40 mesh.

-------
12.  Water Bath - heated, with concentrating cover, capable of




     temperature control (2°C).  The bath should be used in a




     hood.




13.  Chromatography column-300 mm long x 10 mm ID with coarse




     fritted disc at bottom and Teflon stopcock. (Kontes K-420540-




     0213 or equivalent).




Reagents




1.  Sodium sulfate - (ACS) Granular, anhydrous (purified by




    heating at 400°C for 4 hours in a shallow tray).




2.  Stock standards - Prepare stock standard solutions at a




    concentration of 1.00 ug/ul by dissolving 0.100 grams of




    assayed reference material in pesticide quality iso-octane




    or other appropriate solvent and diluting to volume in a 100




    ml ground glass stoppered volumetric flask.  The stock




    solution is stored in a refrigerator, and checked frequently




    for signs of degradation or evaporation, especially just




    prior to preparing working standards from them.




3.  Diethyl Ether - Nanograde, redistilled in glass if necessary.




    Must be free of peroxides as indicated by EM Quant test




    strips.  (Test strips are available from EM Laboratories,




    Inc., 500 Executive Boulevard, Elmsford, N.Y. 10523.)




    Procedures recommended for removal of peroxides are provided




    with the test strips.  After cleanup, 20 ml ethyl alcohol




    preservative must be added to each liter of ether.

-------
                                                                    8.06-5
4.  Florisil - PR grade (60/200 mesh);  purchase activated at




    1250°F and store in dark in gl^ss container with ground




    glass stoppers or foil-lined screw caps.




5.  Hexane - Pesticide Quality




Calibration




1.  Prepare calibration standards that contain the compounds of




    interest either singly or mixed together.




2.  Assemble the necessary gas chromatographic apparatus and




    establish operating parameters equivalent  to those Indicated




    in the Gas Chromatography section.   By injecting calibration




    standards, adjust the sensitivity of the detector and the




    analytical system for each compound being  analyzed for so as




    to detect <^ 1 ug of the compound.




3.  Before using any cleanup procedure, the analyst must process




    a series of calibration standards through  the procedure to




    determine elution patterns and the absence of interferences




    from the reagents.



Quality Control




1.  Before processing any samples, the analyst should demonstrate



    through the analysis of a distilled water  method blank, that




    all glassware and reagents are interference free.  Each time




    a set of samples is extracted or there is  a change in




    reagents, a method blank should be processed as a safeguard




    against chronic laboratory contamination.   The blank samples




    should be carried through all stages of the sample preparation




    and measurement steps.

-------
                                                              8.06-6
2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to validate



    the precision of the sampling technque.  Laboratory replicates




    should be analyzed to validate the precision of the analysis.




    Fortified samples should be analyzed to validate the sensi-




    tivity and accuracy of the analysis.  If the fortified samples




    do not indicate sufficient sensitivity to detect jC 1 ug of




    the compound per gm of sample then the sensitivity of the instru-




    ment should be increased or the sample should be subjected to




    additional clean up.  The fortified samples should be carried




    through all stages of the sample preparation and measurement




    steps.  Where doubt exists over the identification of a peak




    on the chromatogram, confirmatory techniques such as mass




    spectroscopy should be used.




Cleanup




1.  If the entire extract is to be cleaned up to remove inter-




    ferences it must first be concentrated to about 2 ml:



 a. To the K-D apparatus, add a clean boiling chip and attach a




    two-ball micro-Snyder column.  Prewet the column by adding




    about 0.5 ml hexane through the top.  Place the K-D apparatus



    on a hot water bath (80°C) so that the concentrator tube is




    partially immersed in the hot water.  Adjust the vertical




    position of the apparatus and the water temperature as required




    to complete the concentration in 5-10 minutes.  At the proper




    rate of distillation the balls of the column will actively




    chatter but the chambers will not flood.  When the volume of

-------
                                                              8.06-7
    liquid reaches about 0.5 ml,  remove the K-D apparatus




    and allow It to drain for at  least 10 minutes while, cooling.




    Remove the micro-Synyder column and rinse its lower joint




    into the concentration tube with 0.2 ml of hexane.




2.   Florisil Column Clean-up




     In order to employ the Florisil column cleanup procedure the




analyst will have to determine using standards the elution pattern




of  each compound to be analyzed for.  Once this has been done the




following procedure can be followed to effect cleanup of the




sample.




    a.  Place 100 g of Florisil into a 500 ml beaker and heat




        for approximately 16 hours at 400°C.  After heating




        transfer to a 500 ml reagent bottle.  Tightly seal and




        cool to room temperature.   When cool add 3 ml of




        distilled water which is  free of phthalates and inter-




        ferences.  Mix thoroughly by shaking or rolling for 10




        minutes and let it stand  for at least 2 hours.  Keep




        the bottle sealed tightly.




    b.  Place lOg of this Florisil preparat-ion into a 10 mm ID




        chromatography column and tap the column to settle the




        Florisil.  Add 1 cm of anhydrous sodium sulfate to the




        top of the Florisil.




    c.  Preelute the column with  40 ml of hexane.  Discard this




        eluate and, just prior to exposure of the sodium sulfate




        layer to the air, transfer the sample onto the column




        using an additional 2 ml  of hexane to complete the transfer.

-------
                                                                    8.06-8
    d.  Just prior to exposure of the sodium sulfate layer to
        the air add 40 ml hexane and continue the elution at
        the rate of 2 ml/minute.  This eluate is Fraction 1.
        Concentrate the fraction by standard K-D technque.  No
        solvent exchange is necessary.  After concentration and
        cooling, transfer the 10 ml volumetric flask, dilute to
        10 ml and analyze by gas chromatography.
    e.  Next elute the Florisil with 100 ml of 5 percent ethyl
        ether/95% hexane (v/v) and concentrate as in step d.
        [Fraction 2] .
    f.  Next, elute with 100 ml of 15% ethyl ether/85% hexane
        (v/v) and concentrate Fraction 3 as in step d.
    g.  Elute with 100 ml of 50% ethyl ether/50% hexane (v/v),
        and concentrate, Fraction A as in step d.
    h.  Finally, elute with 100 ml of ethyl ether, and concen-
        trate,  Fraction 5 as in step d.
Gas Chromatography
1.  Assemble gas chromatograph with either Column 1 or 2 (see
    Apparatus).
Column 1 (Supelcoport 100/120 with 1.5%  SP 2250 + 1.95% SP 2401)
    a.  Set carrier gas at 60 ml/minute  flow rate.
    b.  Column  temperatures will vary from 180°C to 220°C depending
        on the  compound.
Column 2 (Supelcoport 100/120 with 3% OV-1)
    a.  Set carrier gas at 60 ml/min flow rate.
    b.  Column  temperature will vary from 200°C to 220°C depending
        on the  compound.

-------
                                                                    8.06-9
2.  Calibrate the system at the beginning and end of an analytical




    session by spiking allquots of the extract with calibration




    standards.




3.  Inject 2-5 ul of the sample extract or appropriate Florisil




    eluate using the solvent-flush technique.  Smaller (1.0 ul)




    volumes can be injected if automatic devices are employed.




    Record the volume injected to the nearest 0.05 ul, and the




    resulting peak size, in area units.




4.  If a response for the contaminant being analyzed for is greater




    than 2x background,  then the waste does not meet the criteria




    for delisting of being fundamentally different than the




    listed waste.  If a  response is not noted, then prior to




    concluding that the  sample does not contain the specific




    contaminant, the analyst must demonstrate, using the spiked




    samples, that the method sensitivity ±e <_ I \ig of compound




    per gm of sample.




5.  If the peak area measurement is prevented by the presence of




    interferences, further cleanup is required.

-------
                                                                   8.06-10
                  K>
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  DIMETHYL PHTHALATE

   DIETHYL PHTHALATE
                                                    DI-n-OUTYL PHTHALATE
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                                               Dl n OCTVL PHTHALATE
                                                                         m *o
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-------
                                                                    8.08-1
                            Method 8.08




          GC METHOD FOR ORGANOCHLORINE PESTICIDES AND PCB's



Scope and Application




     This method covers the determination of certain organochlorine




pesticides and polychlorinated biphenyls (PCB's).  The following




compounds may be determined by this method:



     Chlordane




     Chlorinated biphenyls




     Endrin




     Heptachlor




     Lindane



     Methoxychlor




     Toxaphene




Summary of Method




     Prior to using this method, the waste samples should be




prepared for chromatography (if necessary) using the appropriate




sample preparation method (i.e. shake out, sonication, or soxhlet



extraction).  This method provides chromatographic conditions




for the detection of _>. 1 n»8/l of the compounds in the extract.




     If interferences are encountered, the method provides a



selected general purpose cleanup procedure to aid the analyst




in their elimination.




Interferences




     Solvents, reagents, glassware, and other sample processing




hardware may yield discrete artifacts and/or elevated baselines




causing misinterpretation of gas chromatograms.  All of these

-------
                                                                    8.08-2
materials must be demonstrated to be free from Interferences


under the conditions of the analysis by running method blanks.


Specific selection of reagents and purification of solvents by


distillation in all-glass systems may be required.


     Interferences coextracted from the samples will vary con-


siderably from source to source, depending upon the diversity of


the waste being sampled.  While a general cleanup technique is


provided as part of this method, unique samples may require


additional cleanup.


     Glassware must be scrupulously clean.  Clean all glassware


as soon as possible after use by rinsing with the last solvent


used.  This should be followed by detergent washing in hot water.


Rinse with tap water, distilled water, acetone and finally


pesticide quality hexane.  Heavily contaminated glassware may

                                            o
require treatment in a muffle furnace at 400 C for 15 to 30


minutes.  Some high boiling materials, such as PCBs, may not be


eliminated by this treatment.  Volumetric ware should not be


heated in a muffle furnace.  Glassware should be sealed/stored


in a clean environment immediately after drying or cooling to


prevent any accumulation of dust or other contaminants.  Store


inverted or capped with aluminum foil.


     Interferences by phthalate esters can pose a major problem


in pesticide analysis.  These materials elute in the 15% and 50%


fractions of the Florisil cleanup.  They usually can be minimized


by avoiding contact with any plastic materials.  The contamination


from phthalate esters can be completely eliminated with the use


of a microcoulometric or electrolytic conductivity detector.

-------
                                                                    8.08-3
Apparatus


1.  Kuderna-Danish (K-D) Apparatus, equipped with a 3 ball


    Snyder column (Kontes K-570000 or equivalent).


2.  Boiling chips—extracted with extraction solvent,


    approximately 10/40 mesh.


3.  Water .bath, heated, with concentric ring cover, capable


    of temperature control (~*"2 C).  The bath should be used in


    a hood.


4.  Gas chromatograph—Analytical system complete with gas


    chromatograph suitable for on-column injection and all


    required acessories including electron capture or halogen


    specific detector, column supplies, recorder, gases, syringes.


    A data system for measuring peak areas is recommended.


5.  Chromatographic column-Pyrex, 400 mm X 25 mm OD, with coarse


    fritted plate and Teflon stopcock (Kontes K-42054-213 or


    equivalent).


R.eagents


1.  Methylene chloride-Pesticide quality or equivalent.


2.  Sodium Sulfate (ACS) Granular anhydrous (purified by heating

          o
    at 400 C for 4 hrs. in a shallow tray).


3.  Stock standards--Prepare stock standard solutions at a


    concentration of 1.0 ug/ul by dissolving 0.100 grams of


    reference material in pesticide quality isooctane or other


    appropriate solvent and diluting to volume in a 100 ml ground


    glass stoppered volumetric flask.  Store the solution in a


    refrigerator.  Check stock solutions frequently for signs

-------
    of degradation or evaporation, especially just prior to


    preparing working standards from them.


4.  Mercury, triple distilled.


5.  Hexane, pesticide residue analysis grade.


6.  Isooctane (2,2,4-trimethyl pentane), pesticide residue


    analysis grade.


7.  Acetone, pesticide residue analysis grade.


8.  Diethyl ether, Nanograde, redistilled in glass if necessary.


    Must be free of peroxides as indcated by EM Quant Test Strips


    (Test strips are available from EM Laboratories, Inc.,


    500 Executive  Blvd,  Elmsford, N.Y., 10523).


9.  Florisil, PR grade (60/100 mesh); purchase activated at

        o
    1250 F and store in glass containers with glass stoppers or


    foil lined screw caps.  Before use activate each batch at


    least 16 hours at 130°C in foil covered glass container.


Calibration


1.  Prepare calibration standards that contain the compounds


    of interest, either singly or mixed together.


2.  Assemble the necessary gas chromatographic apparatus and


    establish operating parameters equivalent to those indicated


    in Table 8.08-1.  By injecting calibration standards, adjust


    the sensitivity of the detector and of the analytical system


    for each compound being analyzed for so as to detect <^ 1 ug.


3.  The cleanup procedure utilizes Florisil chromatography.


    Florisil from  different batches or sources may vary in absorp-


    tion capacity.  To standardize the amount of Florisil which is


    used, the use  of lauric acid value (Mills, 1968) is suggested.

-------
                                                                    8.08-5
    The referenced procedure determines the adsorption from




    hexane solution of lauric acid (mg) per gram Florisil.




    The amount of Florisil to be used for each column is calculated




    by dividing this factor into 110 and multiplying by 20 grams.




4.  Before using any cleanup procedure, the analyst must process




    a series of calibration standards through the procedure to




    validate elution patterns and the absence of interferences




    from the reagents.




Quality Control




1.  Before processing any samples, the analyst should demonstrate




    through the analysis of a distilled water method blank, that




    all glassware and reagents are interference-free.  Each time




    a set of samples is extracted or there is a change in reagents




    a method blank should be processed as a safeguard against




    chronic laboratory contamination.  The blank samples should be




    carried through all stages of the sample preparation and




    measurement steps.




2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to validate




    the precision of the sampling technique.  Laboratory replicates




    should be analyzed to validate the precision of the analysis.




    Fortified samples should be analyzed to validate the sensitivity




    and accuracy of the analysis.  If the fortified samples do not




    indicate sufficient sensitivity to detect _< 1 ug/gm of sample




    then the sensitivity of the instrument should be increased or




    the extract subjected to additional cleanup.  The fortified




    samples should be carried through all stages of the sample

-------
                                                                    8.08-6
    preparation and measurement steps.  Where doubt exists over




    the identification of a peak on the chromatogram, confirmatory




    techniques such as mass spectroscopy should be used.




Cleanup and Separation




     Cleanup procedures are used to extend the sensitivity of a




method by minimizing or eliminating interferences that mask or




otherwise disfigure the gas chromatographic response to the




pesticides and PCB's.   The Florisil column allows for a select




fractionation of the compounds and will eliminate polar materials.




Elemental sulfur interferes with the electron capture gas chro-




matography of certain pesticides but can be removed by the




techniques described below.




Florisil Column Cleanup:




1.  Add a weight of Florisil, (nominally 21g,) predetermined by




    calibration to a chromatographic column.   Settle the Florisil




    by tapping the column.  Add sodium sulfate to the top of the




    Florisil to form a layer 1-2 cm deep.   Add 60 ml of hexane to



    wet and rinse the sodium sulfate and Florisil.  Just prior to




    exposure of the sodium sulfate to air, stop the elution of the




    hexane by closing the stopcock on the chromatography column.




    Discard the eluate.




2.  Adjust the sample extract volume to 10 ml and transfer it from




    the K-D concentrator tube to the Florisil column.  Rinse the




    tube twice with 1-2 ml hexane, adding each rinse to the column.




3.  Place a 500 ml K-D flask and clean concentrator tube under the




    chromatography column.  Drain the column into the flask until




    the sodium sulfate layer is nearly exposed.  Elute the column

-------
                                                                    8.08-7
    with 200 ml of 6% ethyl ether in hexane (Fraction 1) using a




    drip rate of about 5 ml/min.   Remove the K-D flask and set




    aside for later concentration.




4.   Elute the column again, using 200 ml of 15% ethyl ether in




    hexane (Fraction 2), into a second K-D flask.  Perform the




    third elution using 200 ml of 50% ethyl in hexane (Fraction




    3).  The elution patterns for the pesticides and PCB's are




    shown in Table 8.08-2.




5-   Concentrate the eluates by standard K-D techniques, substituting




    hexane for the glassware rinses and using the water bath at




    about 85°C.  Adjust final volume to 10 ml with hexane.  Analyze




    by gas chromatography.




6.   Elemental sulfur will usually elute entirely in Fraction 1.




    To remove sulfur interference from this fraction or the




    original extract, pipet 1.00 ml of the concentrated extract




    into a clean concentrator tube or Teflon-sealed vial.  Add 1-3




    drops of mercury and seal.  Agitate the contents of the vial




    for 15-30 seconds.  Place the vial in an upright position on




    a reciprocal laboratory shaker for 2 hours.  Analyze by gas




    chromatography.




Gas Chromatography




     Table 8.08.1 summarizes some recommended gas chromatographic




column materials, operating conditions for the instrument, and




stifle estimated retention times.  Examples of the separations




achieved by these columns are shown in Figures 8.08-1 through




8.08-10.  Calibrate the system at the beginning and end of an




analytical session by spiking aliquots of the extract with the

-------
                                                                    8.08-8
    compound of Interest in order to insure a sensitivity of




    _<_ 1 ug/gm of original waste tested.




1.  Inject 2-5 ul of the sample extract using the solvent flush




    technique.  Smaller (1.0 ul) volumes can be injected if auto-




    matic devices are employed.  Record the volume injected to the




    nearest 0.05 ul, and the resulting peak size, in area units.




2.  If the peak area exceeds the linear range of the system, dilute




    the extract and reanalyze.  If the peak area measurement is




    prevented by the presence of interferences, further cleanup is




    required.




3.  If detectable amounts of the compounds of interest are detected




    the waste does not meet the criteria for dellsting of being




    fundamentally different from that of the listed waste.




Bibliography




1.   Mills, P.A., "Variation of Florisil Activity:  Simple




     Method for Measuring Absorbent Capacity and Its Use in




     Standardizing Florisil Columns,"  Journal of the Association




     of Official Analytical Chemists, 51,  29(1968).

-------
                                                                    8,08-9
                        Table 8.08.1




            GAS CHROMATOGRAPHY OF PESTICIDES AND PCB's
Compound
Chlordane
Endrin
Lindane
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260

Retention
(min)
Col. I1
(3)
6.55

(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)

zone
Col. 22
(3)
8.10
(3)
(3)
(3)
(3)
(3)
(3)
(3)
(3)
     1.  Supelcoport 100/120 mesh, coated with 1.5% SP-2250/1.95%




SP-2401 packed In a 180 cm long x 4 mm ID glass column with 5%




Methane/95% Argon carrier gas at 60 ml/minute flow rate.  Column




temperature is 200°C.




     2.  Supelcoport 100/120 mesh, coated with 3% OV-1 in a 180 cm




long x 4 mm ID glass column with 5% Methane/95% Argon carrier gas



at 60 ml/minute flow rate.  Column temperature is 200°C.




     3.  Multiple peak response.  See Figures 8.08-2 through 8.08-10,

-------
                                                                8.08-10
                          Table 8.08.2

       DISTRIBUTION AND RECOVERY OF CHLORINATED PESTICIDES
           AND PCBs USING FLORISIL COLUMN CHROMATOGRAPHY
                                            Recovery (percent) by
                                                   fraction
Compound
                               ethyl ether
    15%         50%
ethyl ether  ethyl ether
Chlordane
Endrin
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
100
4 96
96
97
97
95 4
97
103
90
95

-------
                                                            8.08-11
COLUMN: 1.5% SP-2250*
         1.95% SP-2401 ON SUPH.COPORT
TEMPERATURE: 200'C.
DETECTOR: ELECTRON  CAPTURE
      LU
      c
      4        8        12
       RETENTION TIME-MINUTES
16
              Figure  8.08-1
     GAS CHROMATOGRAM OF PESTICIDES

-------
                                                        8.08-12
COLUMN: 1.5K SP-2250*
         1.95% SP-2401 ON SUPELCOPORT
TEMPERATURE: 200'C.
DETECTOR: ELECTRON  CAPTURE
4         8        12
RETENTION TIME-MINUTES
                               16
          Figure 8.08-2
  GAS CHROMATOGRAM OF CHLORDANE

-------
                                                                                                     8.08-13
           IS)
           01
        79
        o
        2
        m
        2
        c
           ro
           at
CD
           Is!
           00

-------
            O>
        3
        m

        &  *
        2
        C
        m
        ts>
           oo
                                                                                          8.08-14
                                                                                     O
CO

-------
                                                                 8.08-15
COLUMN:  1.5% SP-2250 +1.95% SP-2401 ON SUPB.COPORT
TEMPERATURE: 160'C.
DETECTOR: ELECTRON CAPTURE
                  10       14      18
            RETENTION TIME-MINUTES
22
                  Figure 8.08-7
           GAS  CHROMATOGRAM OF PCB-1242

-------
                                                                 8.08-16
COLUMN:  1.5% SP-2250+ 1.95% SP-2401 ON SUPELCOPORT
TEMPERATURE: 160*C.
DETECTOR: ELECTRON CAPTURE
        &       10      14      18
              RETENTION TIME-MINUTES
22
26
                 Figure 8.08-8
          GAS CHROMATOGRAM OF PCB-1248

-------
                                                                      8.08-17
   K)
   O>
i  s
s
m
   oo
   K>
   CD



   C»
m




Is

m
C/I
                                                                   i
                                                                   P





                                                                   1

-------
                                                                    8.09-1
                         Method 8.09

           GC METHOD FOR SEMIVOLATILE AROMATICS AND
                PHOSPHORODITHIOIC ACID ESTERS
Scope and Application

     This method covers the determination of  the  following

compounds:

           Compounds                          Detector

      Dinitrobenzene                            FID

      2,4-Dinitrotoluene                        ECD

      Naphthoquinone                            FID

      Nitrobenzene                              FID

      Phosphorodithioic acid esters             FID

      Phthalic anhydride                        FID

      2-Picoline                                FID

      Pyridine                                  FID

Prior to using this method, the waste samples should be prepared

for chromatography,if necessary, using the appropriate sample

preparation method (i.e. shake out, sonication, or soxhlet

extraction).  This method provides gas chromatographic

techniques for measurement of the compound(s) of  interest.

Flame ionization or electron capture detection may be used,

depending on the compound(s) of interest.

Summary of Method

     If interferences are encountered the method  provides a

general purpose cleanup procedure to aid the analyst in

their elimination.

-------
                                                                    8.09-2
Interferences




     Solvents, reagents, glassware,  and other sample processing




hardware may yield discrete artifacts and/or elevated baselines




causing misinterpretation of gas chromatograms.   All of these




materials must be demonstrated to be free from interferences




under the conditions of the analysis by running method blanks.




Specific selection of reagents and purification of solvents by




distillation in all-glass systems may be required.




     Interferences coextracted from the samples will va~y




considerably from source to source,  depending upon the diversity




of the waste being sampled.  While general cleanup techniques are




provided as part of this method, unique samples may require




additional cleanup.




Apparatus




1.  Kuderna-Danish (K-D) Apparatus including:




    a.  Concentrator tube-lOml. graduated (Kontes K-570050-1025 or




        equivalent).  Calibration must be checked.  Ground glass




        stopper (size 19/22 joint) is used to prevent evaporation




        of extracts.




    b.  Evaporative flask-500 ml (Kontes K-57001-0500 or




        equivalent).  Attach to concentrator tube with springs.




        (Kontes K503000-0121 or equivalent).




    c.  Snyder column-three-ball macro (Kontes K503000-0121 or




        equivalent).




    d.  Snyder column-two ball micro (Kontes K-569001-0219




        or equivalent).

-------
2.  Boiling chips - solvent extracted, approximately




    10/40 mesh.




3.  Water bath - heated, with concentric ring cover, capable




    of temperature control (+2°C).  The bath should be used




    in a hood.




4.  Gas chromatograph - Analytical system complete with gas




    chromatograph suitable for on-column injection and all




    required accessories including both electron capture and




    flame ionization detectors, column supplies, recorder,




    gases, syringes.  A data system for measuring peak




    areas is recommended.




5.  Chromatography column - 400 mm long x 10 mm ID, with coarse.




    fritted plate on bottom and Teflon stopcock.




Reagents




1.  Methylene chloride - Pesticide quality or equivalent.




2.  Sodium sulfate - (ACS) Granular anhydrous (purified by




    heating at 400°C for 4 hrs. in a shallow tray).




3.  Stock standards - prepare stock standard solutions at a




    concentration of 1.0 ug/ul by dissolving 0.100 grams of




    reference material in pesticide quality isooctane




    or other appropriate solvent and diluting to volume in a




    100 ml ground glass stoppered volumetric flask.  The




    stock solution is transferred to ground glass stoppered




    reagent bottles, stored in a refrigerator, and checked




    frequently for signs of degradation or evaporation,




    especially just prior to preparing working standards




    from them.

-------
                                                                   8.09-^
4.  Acetone, hexane, methanol, toluene - pesticide quality or




    equivalent.




5.  Florisil-PR grade (60/100 mesh); purchase activated at




    1250°F and store in glass containers with glass stoppers




    or foil lined screw caps.  Before use, activate each




    batch overnight at 200°C in glass containers loosely




    covered with foil.




Calibration




     Prepare calibration standards that contain the compounds




of interest, either singly or mixed together.




     Assemble the necessary gas chromatographic apparatus




and establish operating parameters equivalent to those indicated




in Table 8.09-1.  By injecting calibration standards adjust




sensitivity of the detector and the analytical system for each




compound being analyzed for so as to detect <_ 1 ug.




     Before using any cleanup procedure, the analyst must




process a series of calibration standards through  the procedure




to validate elution patterns and the absence of interferences




from the reagents.




Quality Control




     Before processing any samples, the analyst should




demonstrate through the analysis of a distilled water method




blank that all glassware and reagents are interference-free.




Each time a set of samples is extracted or there is a change in




reagents, a method blank should be processed as a  safeguard




against chronic laboratory contamination.  The blank samples

-------
                                                                    8.09-5
should be carried through all stages of the sample preparation




and measurement steps.




     Standard quality assurance practices should be used with




this method.  Field replicates should be collected to validate




the precision of the sampling technique.  Laboratory replicates




should be analyzed to validate the precision of the analysis.




Fortified samples should be analyzed to validate the precision




and accuracy of the analysis.  If the fortified samples do




not indicate sufficient sensitivity to detect _< 1 ug/gram of




sample, the sensitivity of the instrument should be increased




or the sample subjected to additional clean up.  The fortified




samples should be carried through all stages of the sample




preparation and measurement steps.  Where doubt exists over




the identification of a peak on the chromatogram, confirmatory




techniques such as mass spectroscopy should be used.




Cleanup and Separation




1.  Prepare a slurry of lOg of activated Florisil in 10%




    methylene chloride in hexane (V/V). Use it to pack a 10 mm




    chromatography column gently tapping the column to settle




    the Florisil.  Add 1 cm anhydrous sodium sulfate to the top




    of the Florisil.




2.  Just prior to exposure of the sodium sulfate layer to




    the air, transfer the 1 ml sample extract onto the column




    using an additional 2 ml of toluene to complete the




    transfer.

-------
                                                                    8.09-6
3.  Just prior to exposure of the sodium sulfate layer




    to the air,  add 30 ml 10% methylene chloride in hexane and




    continue the elution.  Elution should be at a rate of about




    2 ml per minute.   Discard the eluate from this fraction.




4.  Next elute the column with 30 ml of 10% acetone/90%




    methylene chloride (V/V) into a 500 ml K-D flask equipped




    with a 10 ml concentrator tube.  Concentrate the collected




    fraction by the K-D technique described in Method 9.01




    including the solvent exchange into 1 ml toluene.  This




    fraction should contain the compounds of interest.




5.  Analyze by gas chromatography.




Gas Chromatography




1.  Dinitrotoluene is analyzed by a separate injection
                                                          •



    into an electron capture gas chromatograph.  The other




    compounds covered by this method are analyzed by injection of




    a portion of the extract into a gas chromatograph with a flame




    ionization detector.  Table 8.09-1 summarizes some recommended




    chromatographic column materials and operating conditions




    for the instruments.  Included in this table are estimated




    retention times.  Examples of the separations achieved by




    the,primary column are shown in Figures 8.09-1 and 8.09-2.




    Calibrate the system at the beginning and end of an analytical




    session by spiking aliquots of the extract with  each  of  the




    compounds of interest.




2.  Inject 2-5 ul of the sample extract using the solvent




    flush technique.  Smaller  (1.0 ul) volumes can be injected




    if  automatic devices are employed.

-------
                                                                    8.09-7
3.  If a response for the contaminant being analyzed is




    greater than 2X background, then the waste does not meet




    the criteria for delisting of being fundamentally different




    than the-listed waste.  If a response is not noted, then




    prior to concluding that the sample does not contain the




    specific contaminant, the analyst must demonstrate,




    using spiked samples, that the instrument sensitivity




    is <1 ug/gm of sample.

-------
                                                              8.09-8
                         Table 8.09-1

              GAS CHROMATOGRAPHY RETENTION TIMES
                                        Retention time
                                             (min)
            Compound                    	
                                        Column  Column
                                           A       B
Nitrobenzene
2,4
2,6
-Dinitrotoluene
-Dinitrotoluene

3
5
3

.31
.35
.52
4
6
4
.31
.54
.75
A.   Gas-Chrom Q, 80/100 mesh, coated with 1.95% OF-1/1.5%

OV-17 packed in a 4'  x 1/4" OD. glass column.  FID analysis

requires nitrogen gas at 44 ml/minute and 85°C column temper-

ature.  EDC analysis  requires 10% Methane/90% argon carrier

gas at 44 ml/minute flow rate and 145°C column temperature.

B.  Gas-Chrom Q, 80/100 mesh, coated with 3% OV-101 packed in

a 10' x 1/4" OD glass column.  FID analysis requires nitrogen

carrier gas at 44 ml/minute flow rate and 100°C column temper-

ature.  BCD analysis  requires 10% methane/90% argon carrier

gas at 44 ml/minute flow rate and 150°C column temperature.

-------
        COLUMN:  1.5X OV-17+ 1.95% QF-1 ON GAS CHROM Q
        TEMPERATURE:  85*C.
        DETECTOR: FLAME IONIZAT10N
COLUMN:  1.5% OV-17* 1.95% QF-1 ON GAS CHROM 0
TEMPERATURE:  145*C.
DETECTOR: ELECTRON CAPTURE
      Ul
      s

      i
        2468

     RETENTION TIME-MINUTES
                  Figure 8.09-1

GAS CHRQMATOGRAM OF NITROBENZENE AND ISOPROPANE
                                                                      2    46    8   10

                                                                    RETENTION TIME-MfNUTES
                                                                               Figure 8.09-2
                                                                   GAS CHROMATOGRAM OF DINITROTOLUENES

-------
                                                                     8.10-1
                           Method 8.10

               GC AND HPLC METHODS FOR POLYNUCLEAR
                      AROMATIC HYDROCARBONS
Scope and Application

     This method covers the determination of certain polynuclear

aromatic hydrocarbons (PAH).  The following compounds may be

determined by this method:

        Benz(a)anthracene

        Benz(b)fluoranthene

        Chrysene

        Creosote (Phenanthrene and Carbazole)

        Naphthalene

     This method contains both liquid and gas chromatographic

approaches, depending upon the needs of the analyst.  However,

the gas chromatographic procedure cannot adequately resolve the

following three pairs of compounds:   Anthracene and phenanthrene;

chrysene and benzo(a)anthracene;  benzo(b)fluoranthene and benzo(k)-

fluoranthene.   If one wishes to resolve these pairs, the liquid

chromatographic approach must be used for these compounds.

Summary of Method

     Prior to  using this method,  the waste samples should be

prepared for chromatography (if necessary) by using the appropriate

sample preparation method (i.e.,  Shake Out, Sonication, or Soxhlet

Extraction).  This method provides chromatograpahic conditions

which allow for the detection of  the compounds in the extract by

-------
                                                                     8.10-2.
either High Performance Liquid Chromatograph (HPLC) or gas




chromatography.




     If interferences are encountered, the method provides a




selected general purpose cleanup procedure to aid the analyst in



their elimination.




Interferences




     Solvents, reagents, glassware, and other sample processing




hardware may yield discrete artifacts and/or elevated baselines




causing misinterpretation of the chromatograms.  All of these




materials should be checked to insure freedom from interferences




under the conditions of the analysis by running method blanks.




Specific selection of reagents and purification of solvents by




distillation in all-glass systems may be required.




     Interferences coextracted from the samples will vary consi-




derably from source to source, depending upon the diversity of




the waste sample.   While a general clean-up technique is provided




as part of this method, unique samples may require additional




clean-up.  The extent of interferences that may be encountered




using liquid chromatographic techniques has not been fully assessed.



Apparatus




1.  Kuderna-Danish (K-D) Apparatus equipped with the appropriate




    •Snyder columns [Kontes K-570000 or equivalent]



2.  Boiling chips  - solvent extracted, approximately 10/40 mesh.




3.  Water bath - Heated, with concentric ring cover, capable




    of temperature control (+2° G).  The bath should be used




    in a hood.




4.  HPLC Apparatus:

-------
                                                               8.10-3
    a.  Gradient pumping system,  constant flow.




    b.  Reverse phase column,  5 micron HC-ODS Sil-X,




        250 mm x 26 mm ID (Perkin Elmer No. 809-0716  or




        equivalent).




    c.  Fluorescence  detector,  for excitation at 280  nm




        and emission  at 389 nm.




    d.  UV detector,  254 nm, coupled to fluorescence  detector.




    e.  Strip chart recorder compatible with detectors.




        (A data system for measuring peak areas is recommended).




5.  Gas chromatograph - Analytical system complete with gas




    chromatograph suitable for  on-column injection and all




    required accessories including dual flame ionization detectors,




    column supplies,  recorder,  gases, syringes.  A data system




    for measuring peak areas is recommended.




6.  Chromatographic column - 250 mm long x 10 mm ID with




    coarse fritted disc at bottom and Teflon stopcock.




Reagents



1.  Methylene chloride, pentane,  cyclohexane, high purity water -




    HPLC quality, distilled in  glass.




2.  Sodium sulfate -  (ACS) Granular, anhydrous (purified by



    heating at 400° C for 4 hrs,  in a shallow tray).




3.  Stock standards - Prepare  stock standard solutions at a




    concentration of  1.0 mg/ml  by dissolving 0.100 grams of




    assayed reference material  in pesticide quality isooctane




    or other appropriate solvent and diluting to volume in a




    100 ml ground glass stoppered volumetric flask.  The stock




    solution should be stored  in a refrigerator, and  checked

-------
                                                                     8.10-4
    frequently for signs of degradation or evaporation, especially




    just prior to preparing working standards from them.




4.  Acetonitrile - Spectral quality.




5.  Silica gel - 100/200 mesh desiccant (Davison Chemical




    grade 923 or equivalent).  Before use, activate for at




    least 16 hours at 130° C in a foil covered glass container.




Calibration




     Prepar'e calibration standards that Contain the compounds of




interest, either singly or mixed together.




     Assemble the necessary HPLC or gas chromatographic apparatus




and establish operating parameters equivalent to those indicated




in Table 8.10-1 or 8.10-2.  By injecting calibration standards




adjust the sensitivity of the detectors and the analytical systems




for each compound being analyzed for so as to detect ^1 ug.




     Before using any cleanup procedure, the analyst must process




a series of calibration standards through the procedure to validate




elution patterns and the absence of interferences from the




reagents.




Quality Control




     Before processing any samples, the analyst should demonstrate




through the analysis of a distilled water method blank, that all




glassware and reagents are interference-free.  Each time a set




of samples is extracted or there is a change in reagents, a




method blank should be processed as a safeguard against laboratory




contamination.   The blank samples should be carried through all




stages of the sample preparation and measurement steps.




     Standard quality assurance practices should be used with

-------
                                                                     8.10-5
this method.  Field replicates should be collected to validate




the precision of the sampling technique.  Laboratory replicates




should be analyzed to validate the precision of the analysis.




Fortified samples should be analyzed to validate the sensitivity




and accuracy of the analysis.  If the fortified samples do not




indicate sufficient sensitivity to detect _<_ 1 ug of contaminant/




gm of sample then the sensitivity of the instrument should be




increased or the sample subjected to additional clean up.  The




fortified samples should be carried through all stages of the




sample preparation and measurement steps.




Cleanup and Separation




     (If the sample does not require cleanup, this section may




be omitted.)  Before the silica gel cleanup technique can be




utilized, the extract solvent must be exchanged to cyclohexane.




1.  Add a 1-10 ml aliquot' of sample extract (in methylene




    chloride) and a boiling chip to a clean K-D concentrator




    tube.



2.  Add 4 ml cyclohexane and attach a micro-Snyder column.




    Prewet the micro Snyder column by adding 0.5-ml raethylene




    chloride to the top.




3.  Place the micro-K-D apparatus on a boiling (100° C) water




    bath so that the concentrator tube is partially immersed in




    the hot water.  Adjust the vertical position of the apparatus




    and the water temperature as required to complete concentration




    in 5-10 minutes.  At the proper rate of distillation the




    balls of the column will actively chatter but the chambers




    will not flood.

-------
                                                              8.10-6
4.  When the apparent volume of the- liquid reaches 0.5 ml, remove




    K-D apparatus and allow it to drain for at least 10 minutes




    while cooling.




5.  Remove the micro-Snyder column and rinse its lower joint




    into the concentrator tube with a minimum of cyclohexane.




6.  Adjust the extract volume to about 2 ml.




Silica Gel Column Cleanup for PAHs




1.  Prepare a slurry of lOg activated silica gel in methy-




    lene chloride and place this in a 10 mm ID chromatography




    column.  Gently tap the column to settle the silica gel and




    elute the methylene chloride.  Add 1-2 cm of anhydrous




    sodium sulfate to the top of the silica gel.




2.  Preelute the column with 40-ml pentane.  Discard the




    eluate and just prior to exposure of the sodium sulfate




    layer to the air, transfer the 2 ml cyclohexane sample




    extract onto the column, using an additional 2 ml of cyclo-




    hexane to complete the transfer.




3.  Just prior to exposure of the sodium sulfate layer to



    the air, add 25 ml pentane and continue elution of the




    column.  Discard the pentane eluate.




4.  Elute the column with 25 ml of 40% methylene chloride/60%




    pentane (v/v) and collect the eluate in a 500 ml K-D flask equipped




    with a 10 ml concentrator tube.  Elute the column at a rate




    of about 2 ml/minute.




5.  Concentrate the collected fraction to less than 10 ml




    by K-D techniques, using pentane to rinse the walls of the




    glassware.  Proceed with HPLC or gas chromatographic analysis.

-------
                                                                     8.10-7
High Performance Liquid Chromatography (HPLC)




1.  To the extract in the concentrator tube, add 4 ml aceto-




    nitrile and a new boiling chip,  then attach a micro-Snyder




    column.  Increase the temperature of the hot water bath to




    95-100° C.  Concentrate the solvent to less than 0.5 ml.




    After cooling, remove the micro-Snyder column and rinse its




    lower joint into the concentrator tube with about 0.2 ml




    acetonitrile.  Adjust the extract volume to 1.0 ml.




2.  Calibrate the system at the beginning and end of an




    analytical session by spiking aliquots of the extract with




    the compound of interest in order to insure a sensitivity




    of ^ 1 ug.  Table 8.10-1 summarizes the recommended HPLC




    column materials and instrument  operating conditions.  Included




    in this table are estimated retention times.  An example of




    the separation achieved by this  column is shown in Figure




    8.10-1.




3.  Inject 2-4 ml of the sample extract with a high pressure




    syringe or sample injection loop.  Record the volume injected




    to the nearest 0.05 ml, and the  resulting peak size, in




    area units.




4.  If the peak area exceeds the linear range of the system,




    dilute the extract and reanalyze.




5.  If measurement of the peak area  measurement is prevented




    by the presence of interfering species, further cleanup is




    required.




6.  The UV detector is recommended for the determination of




    napthalene and the fluorescence  detector is recommended for

-------
                                                                     8.10-8
    the remaining PAHs.




Gas Chromatography




     The gas chromatographic procedure will not resolve certain




isomeric pairs as was previously indicated.  The liquid chroma-



tographic procedure must be used for these materials.




1.  To achieve maximum sensitivity with this method, the




    extract must be concentrated to 1.0 ml.  Add a clean boiling




    chip to the methylene chloride extract in the concentrator




    tube.  Attach a two-ball micro-Snyder column.  Prewet the




    micro-Snyder column by adding about 0.5 ml of methylene




    chloride to the top.  Place this micro-K-D apparatus on a




    hot water bath (60-65° C) so that the concentrator tube is




    partially Immersed in the hot water.  Adjust the vertical




    position of the apparatus and water temperature as required




    to complete the concentration in 5 to 10 minutes.  At the




    proper rate of distillation the balls will actively chatter



    but the chambers will not flood.  When the apparent volume




    of liquid reaches 0.5 ml, remove the K-D apparatus and allow




    it to drain for at least 10 minutes while cooling.  Remove



    the micro-Snyder column and rinse its lower Joint into the




    concentrator tube with a small volume of methylene chloride.




    Adjust the final volume to 1.0 ml and stopper the concentrator



    tube.




2.  Table 8.10-2 describes the recommended gas chromatographic




    column material and operating conditions for the instrument.




    Included in this table are some estimated retention times

-------
                                                                    8.10-9
    that should be achieved by this method.   Table 8ilO-3 indicates




    the appropriate chromatographic detectors.   Calibrate the




    gas chromatographic system at the beginning and end of an




    analytical session by spiking aliquots of the extract with




    the compound of interest in order to insure a sensitivity of




    < 1 ug.




3.  Inject 2-5 ml of the sample extract using the solvent-




    flush technique.  Smaller (1.0 ml) volumes  can be injected




    if automatic devices are employed.  Record  the volume injected




    to the nearest 0.05 ml, and the resulting peak size, in area




    units.




4.  If the peak area measurement is prevented by the presence




    of interferences, further cleanup is required.  If a response




    for the  contaminant being analyzed for is greater than 2x




    background is noted; then the waste does not meet the




    criteria for delisting of being fundamentally different




    than the listed waste.  If a response is not noted, then




    prior to concluding that the sample does not contain the




    specific contaminant, the analyst must demonstrate, using




    the spiked samples, that the method sensitivity is




    < 1 ug of contaminant/gm of sample.

-------
                                                                8.10-10
                           Table 8.10-1
       HIGH PERFORMANCE LIQUID CHROMATOGRAPHY OF PAH'S
                 Compound                      Retention time
                                                   (min)	


      Naphthalene	       16.17

      Phenanthrene	       22.32

      Benzo(a)anthracene	       29.26

      Benzo(b)fluoranthene	       32.44

      Chrysene	       30 .14




Chromatographlc conditions:

    Reverse phase HC-ODS Sil-X 2.6 x 250 mm Perkin-Elmer column;

isocratic elution for 5 minute using 40% acetonitrile/60% water,

then linear gradient elution to 100% acetonitrile over 25 minutes;

flow rate is 0.5 ml/minute.

-------
                                                               8.10-11
                           Table 8.10-2
                  GAS CHROMATOGRAPHY OF PAH'S
                 Compound                         Retention time
                                                       (min)
          Nephthalene	         4.5

          Phenanthrene	        15.9

          Benzo(a)anthracene	        20.6

          Benzo(b)fluoranthene	        28.0

          Chrysene . .	        24.7



Chromatographic conditions:

     Chromosorb W-AW-DCMs 100/120 mesh coated with 3% OV-17 ,

packed in a 6'  x 2 mm ID glass column, with nitrogen carrier  gas

at 40 ml/minute flow  rate.   Column temperature was held at  100°

C for 4 minutes, then programmed at 8°/minute to  a final hold at

280° C.

-------
                                                    8.10-12
              Table 8.10-3
 APPROPRIATE GAS CHROMATOGRAPHIC DETECTORS
    Compound                  Detector






Benz(a)anthracene                FID




Benz(b)fluoranthene              FID




Carbazole                        ECD




Chrysene                         FID




Phenanthrene                     ECD




Naphthalene                      FID

-------
COLUMN: HC-ODS SIL-X
MOBILE PHASE: 40* TO 100% ACETONITRILE IN WATER
DETECTO& FLUORESCENCE
                                              1!
                                              Ol S"
      A
          !.._.!_
                                                                    8.10-13
                              i 	L
8   12    16   20   24
                                 28
36
40
                   RETENTION TIME-MINUTES
                  Figure 8.10-1

     LIQUID CHROMATOGRAPHI OF POLYNUCLEAR AROMATICS

-------
                                                                   8.12-1
                         Method 8.12




            GC METHOD FOR CHLORINATED HYDROCARBONS






Scope and Application




     This method covers the determination of certain chlorinated




hydrocarbons.  The following compounds may be determined by




this method.




            Benzotrichloride




            Benzyl Chloride




            Dichlorobenzene




            Dichloropropanol




            Hexachlorobutadiene




            Tetrachlorobenzene




Summary of Method




     Prior to using this method, the waste samples are prepared




for chromatography (if necessary) using the appropriate




sample preparation method (i.e. shake out, sonication, or




soxhlet extraction).   This method describes chromatographic




conditions which allow the accurate measurement of the compounds




using electron capture detection.




     If interferences are encountered or expected, the method




provides a selected general purpose cleanup procedure to aid




the analyst in their elimination.




Interferences




     Solvents, reagents, glassware, and other sample processing




hardware may yield discrete artifacts and/or elevated baselines




causing misinterpretation of gas chromatograms.  All of these




materials must be demonstrated to be free from interferences

-------
                                                                   3.12-2
under the conditions of the analysis by running method blanks.


Specific selection of reagents and purification of solvents


by distillation in all glass systems may be required.


     Interferences coextracted from the samples will vary


considerably from source to source, depending upon the diversity


of the waste being sampled.  While general cleanup techniques


are provided, unique samples may require additional cleanup.


Apparatus


1.  Kuderna-Danish (K-D) Apparatus (Kontes K-570000 or


    equivalent).


    a.  Snyder column-three-ball macro (Kontes K503000-0121


         or eqivalent).


    b.  Snyder column-two-ball micro (Kontes K503000-0219


        or eqivalent).


2.  Boiling chips-solvent extracted, approximately 10/40 mesh.


3.  Water bath -heated, with concentric ring cover, capable


    of temperature control (+2°C).  The bath should be used in


    a hood.


4.  Gas chromatograph-Analytical system complete with gas


    chromatograph suitable for on-column injection and all
                                                          %

    required accessories including electron capture detector


    column supplies, recorder, gases, syringes.  A data


    system for measuring peak areas is recommended.


5.  Chromatography column-300 mm long x 10 mm ID with coarse


    fritted disc  at bot'tom and Teflon stopcock.

-------
                                                               8.12-3
Reagents




1.  Methylene chloride, hexane isooctane and petroleum




    ether (boiling range 30-60°C)-pesticide quality or




    equivalent.




2.  Sodium sulfate (ACS) granular, anhydrous (purified by




    heating at 400°C for A hours in a shallow tray).




3.  Stock standards - Prepare stock standard solutions at




    a concentration of 10 ug/ul by dissolving 0.100 grams of




    assayed reference material in pesticide quality isooctane




    or other appropriate solvent and diluting to volume in




    a 100 ml ground glass stoppered volumetric flask.  The




    stock solution is stored in a refrigerator, and checked




    frequently for signs of degradation or evaporation,




    especially just prior to preparing working standards from




    them.




4.  Florisil-PR  grade (60/100 mesh); purchase activated at




    1250°F and store in the dark in glass containers with




    glass stoppers or foil lined screw caps.  Before use,




    activate each batch at 130°C in covered glass containers




    loosely covered with foil.




Calibration




1.  Prepare calibration standards that contain the compounds




    of interest,  either singly or mixed together.




2.  Assemble the  necessary gas chromatographic apparatus




    and establish operating parameters equivalent to those




    indicated in  Table 8.12-1.  By injecting calibration

-------
                                                                     8.12-4
    standards adjust the sensitivity of the detector and




    the analytical system for each compound being analyzed




    for to detect £ 1 ug.




3.  The cleanup procedure utilizes "Florisil chromatography.




    Florisil from different batches or sources may vary in




    adsorption capacity.  To standardize the amount of




    Elorisil which is used, the use of lauric acid value




    (Mills, 1968) is suggested.   The referenced procedure




    determines the adsorption from hexane solution of lauric




    acid (mg) per gram Florisil.  The amount of Florisil to




    be used for each column is calculated by dividing this




    ratio by 110 and multiplying by 20 grams.




4.  Before using any cleanup procedure, the analyst must




    process a series of calibration standards through the




    procedure to validate elution patterns and the absence of




    interferences from the reagents.




Quality Control




1.  Before processing any samples, the analyst should demonstrate



    through the analysis of a distilled water method blank, that




    all glassware and reagents are interference-free.  Each




    time a set of samples is extracted or there is a change




    in reagents, a method blank should be processed as a




    safeguard against chronic laboratory contamination.




    The blank samples should be carried through all stages




    of the sample preparation and measurement steps.

-------
                                                                    8.12-5
2.  Standard quality assurance practices should be used




    with this method.  Field replicates should be collected




    to validate the precision of the sampling technique.




    Laboratory replicates should be analyzed to validate the




    precision of the analysis.  Fortified samples should be




    analyzed to validate the sensitivity and accuracy of




    the analysis.  If the fortified samples do not indicate




    sufficient sensitivity to detect _< 1 ug/gm of the sample




    then the sensitivity of the instrument should be increased




    or the sample subjected to additional cleanup.  The




    fortified samples should be carried through all stages




    of the sample preparation and measurement steps.  Where




    doubt exists over the identification of a peak on the




    chromatogram, confirmatory techniques such as mass




    spectroscopy should be used.




Cleanup and Separation




     Unless the sample is known to require cleanup omit this




section and proceed to analysis by gas chromatography.




1.  Adjust the sample extract to 10 ml.



2.  Place a 12 gram charge of activated Florisil in a 10 mm




    ID chromatography column.  After settling the Florisil




    by tapping the column add a l-2cm layer of anhydrous




    granular sodium sulfate to the top.




3.  Pre-elute the column, after cooling, with 100 ml of




    petroleum ether.  Discard the eluate and just prior to

-------
                                                                    8.12-6
    exposure of the sulfate layer to air,  quantitatively




    transfer the sample extract into the column by decantatlon




    and subsequent petroleum ether washings.   Just prior to




    exposure of the sodium sulfate layer to the air,  begin




    eluting the column with 200 ml petroleum ether and




    collect the eluate in a 500 ml K-D flask equipped with




    a 10 ml concentrator tube.   This fraction should  contain




    all of the chlorinated hydrocarbons.




4.  Add 1-2 clean boiling chips to the flask and attach a




    three-ball Snyder column.  Prewet the Snyder column




    by adding about 1 ml hexane to the top.  Place the K-D




    apparatus on a hot water bath (60-65°C) so that the




    concentrator tube is partially immersed in the hot




    water, and the entire lower rounded surface of the flask




    is bathed in vapor.  Adjust the vertical position of the




    apparatus and the water temperature as required to complete




    the concentration in 15-20  minutes.  At the proper rate




    of distillation the balls of the column will actively



    chatter but the chambers will not flood.  When the apparent




    volume of liquid reaches l-2ml, remove the K-D apparatus




    and allow it to drain for at least 10 minutes while cooling.




    Note; The dichlorobenzenes  have a sufficiently high




    volatility that significant losses may occur in concen-




    tration steps if care is not exercised.  It is important




    to maintain a constant gentle evaporation rate and not




    to allow the liquid volume  to fall below l-2ml before

-------
                                                             8.12-7
    removing the K-D from the hot water bath.  When the




    apparatus is cool, remove the Snyder column and rinse




    the flask and its lower joint into the concentrator




    tube with 1-2 ml hexane.




5.  Transfer to a 10 ml volumetric flask and dilute to




    volume.




Gas Chromatography




1.  Table 8.12-1 lists the recommended gas chromatographic




    column materials and operating conditions for the instrument.




    Included in this table are some estimated retention times.




    Examples of the separations achieved by this column are




    shown in Figures 1 and 2.  Calibrate the system at the




    beginning and end of an analytical session by spiking




    aliquots of the sample being analyzed with the compound




    of interest in order to insure a sensitivity of (1




    ug/gm) of original waste or extract tested.




2.  Inject 2-5 ul of the sample extract using the solvent flush




    technique.  Smaller (1.0 ul) volumes can be injected if




    automatic devices are employed.




3.  If the peak area exceeds the linear range of the system




    the extract can be diluted and reanalyzed.




4.  If peak  detection is prevented by the presence of inter-




    ferences, further cleanup is required.  If detectable




    amounts  of the compounds of interest are detected the




    waste does not meet the criteria for delisting of being




    fundamentally different from that of the listed waste.

-------
                                                                    8.12-8
Calculations




1.   If a response for the contaminant being analyzed for




     greater than 2x background is noted, then the waste does




     not meet the criteria for delisting of being fundamentally




     different than the listed waste.  If a response is not




     noted, then prior to concluding that the sample does not




     contain the specific contaminant, the analyst must




     demonstrate, using the spiked samples, that the instrument




     sensitivity is <_ 1 ug/gm of sample.






Bibliography




1.   Mills, P.A., "Variation of Florisil Activity:  Simple




     Method for Measuring Absorbent Capacity and Its Use in




     Standardizing Florisil Columns," Journal of the Association




     of Official Analytical Chemists, 51,29 (1968).

-------
                                                              8.12-9
                          Table 8.12-1
         RETENTION TIMES FOR SOME CHLORINATED HYDROCARBONS
               Compound




         1, 3 dichlorobenzene




         1, 4 dichlorobenzene




         1, 2 dichlorobenzene




         Hexachlorobutadiene




         Benzotrichloride




         Benzyl chloride




         Dichloropropanol




         Tetrachlorobenzene(s)
Retention time (min)*




        4.0




        4.3




        5.3




       11.6
(1)   Gas chrom Q,  80/100 mesh,  coated with 1.5% OV-1/1.5%




     OV-225  packed in a 1.8 m long x 2 mm ID glass column




     with 5% methane/95% Argon  carrier gas at 30 ml/min




     flow rate.   Column temperature is 75°C.  Under these




     conditions  Retention Time  of Aldrin is 18.8 min at




     160°C.

-------
                                                                               8.12-10
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-------
                                                                    8.22-1




                         Method 8.22




                           PHORATE






Scope and Application




     This method covers the determination of the presence of




phorate in RCRA materials.




     Prior to using this method,  the waste samples should be




prepared for chromatography (if necessary) using the appropriate




sample preparation method (i.e.,  shake out, sonication, or




soxhlet extration).




Summary of Method




     This method provides chromatographic conditions which




allow for the detection of the compounds in the extract.




     The detector of choice is the flame photometric detector




operated in the phosphorus mode.  A thermionic detector




operated in the phosphorus-nitrogen mode may also be used.




     If interferences are encountered, it may be necessary to




apply cleanup procedures.




Interferences




     Solvents, reagents, glassware, and other sample processing




hardware may yield discrete artifacts and/or elevated baselines




causing misinterpretation of gas  chromatograms .  All of these




materials must be demonstrated to be free from interferences




under the conditions of the analysis by running method blanks.




Specific selection of reagents and purification of solvents




by distillation in all-glass systems may be required.




     Interferences coextracted from the samples will vary




considerably from source to source, depending upon the

-------
                                                             8.22-2
diversity of the waste sample.   Unique samples may require




clean-up to achieve the required sensitivity in which case




the analyst must devise appropriate cleanup procedures.




     Elemental sulfur may interfere with the determination of




organophosphorus pesticides by  flame photometric gas




chromatography.




Apparatus




1.  Gas chromatograph-Analytical system complete with gas




    chromatograph suitable for  on-column injection and programmed




    temperature  operation.  Required accessories include:  A




    flame photometric or phosphorous-nitrogen detector, column




    supplies, recorder, gases,  and syringes.  A data system for




    measuring peak areas Is recommended.  A 6 foot long x 4mm




    ID glass column packed with 5% SP-2401 on 100/120 mesh




    Supelcoport  shall be used.




Reagents




1.  Hexane, isooctane, methylene chloride - pesticide quality




    or equivalent.




2.  Stock standards - Prepare stock standard solutions at a




    concentration of 1.00 ug/ul by dissolving 0.0100 grams of




    assayed reference material  in pesticide quality Isooctane




    or other appropriate solvent and diluting to volume In a




    10.0 ml ground glass stoppered volumetric flask.  Transfer




    the stock solution to a small glass vial and seal with a




    Teflon lined screw cap and  store in a refrigerator.




    Check frequently for signs  of degradation or evaporation,




    especially just prior to preparing working standards from




    them.

-------
                                                                    8.22-3






Calibration




1.  Prepare calibration standards that contain the compounds




    of interest, either singly or mixed together.  The




    secondary standards should be prepared at concentrations




    that will bracket the working range of the chromatographic




    sys tern.




2.  Establish operating parameters equivalent to those




    indicated on Figure 8.22-1.  By injecting calibration




    standards, adjust the limit of the detection so as to




    detect < 1 ug of phorate.




Quality Control




1.  Before processing any samples, the analyst should




    demonstrate through the analysis of a distilled water




    method blank, that all glassware and reagents are




    interference free.  Each time a set of samples is extracted




    or there is a change in reagents, a method blank should




    be processed as a safeguard against chronic laboratory




    contamination.




2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected to vali-




    date the precision of the sampling technique.  Laboratory




    replicates should be analyzed to validate the precision




    of the analysis.  Fortified samples of waste should be




    analyzed to validate the accuracy of the analysis.




    Where doubt exists over the identification of a peak on




    the chromatogram, confirmatory techniques such as mass




    spectrometry should be used.

-------
                                                              8.22-4
Procedure




1.  The recommended gas chromatographic column materials and




    operating conditions for the instrument are described under




    "Apparatus" and on Figure 8.22-1.  The retention time for




    phorate using this column is 1.43 min.  An example chroma-




    togram for phorate and other organophosphorus pesticides




    is shown in Figure 8.22-1.  Calibrate the system at the




    beginning and end of an analytical session by spiking aliquots




    of the extract with phorate in order to insure an analytical




    sensitivity of ^ 1 ug/gm of original waste tested.




2.  Inject 2 to 5 ul of the sample extract using the solvent-




    flush technique.  Smaller (1.0 ul) volumes can be




    injected if automatic devices are employed.  Record the




    volume injected to the nearest 0.05 ul, and the resulting




    peak size, in area units.




3.  If the peak area exceeds the linear range of the system,




    dilute the extract and reanalyze.




4.  If peak detection is prevented by the presence of



    interferences, further cleanup is required.




Results




     If a response for the contaminant being analyzed for is




greater than 2x background is noted;  then the waste does not




meet the criteria for delisting of being fundamentally differ-




ent than the listed waste.  If a response is not noted, then




prior to concluding that the sample does not contain the




specific contaminant, the analyst must demonstrate, using




the spiked samples, that the method sensitivity is _< 1 ug of



phorate/gm of sample.

-------
  N9
                                                            8.22-5
                                  DISULFOTON
PHORATE


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                                               -FENTHION
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-------
                                                                     8.40-1
                         Method 8.40

         METHOD FOR CHLOROPHENOXY ACID HERBICIDES


Scope and Application

     This method can be used for the determination of various

chlorinated phenoxy acid herbicides in EP extracts and other

RCRA materials.

     The following pesticides may be determined individually

by this method:

        Compound                               Detector

Dichlorophenoxy acetic acid                      HSD

2,4,5-TP (Silvex) [2,4,5-Trichlorophenoxy        HSD
   proponic acid]

Summary of Method

     Prior to using this method, the waste samples should be

prepared for chromatography, if necessary, using the appropriate

sample preparation method (i.e., Sonication or Soxhlet extraction)

The esters are hydrolyzed to acids and extraneous organic

material is removed by a solvent wash.  The acids are converted

to methyl esters which are extracted from the aqueous phase.

The extract is cleaned by passing it through a micro-adsorption

column.  Identification of the esters is made by selective

gas chromatographic separations and may be corroborated

through the use of two or more unlike columns.  Detection and

measurement is accomplished by electron capture, microulometric

or electrolytic conductivity gas chromatography.  Results

are reported in micrograms per liter.

-------
                                                              8.40-2
Interferences




     Solvents, reagents, glassware and other sample processing




hardware may yield discrete artifacts and/or elevated baselines




causing misinterpretation of gas chromatograms.  All of these




materials should be checked to insure freedom from interferences




under the conditions of the analysis.  Specific selection of




reagents and purification of solvents by distillation in all-




glass systems may be required.




     The interferences in extracts of solid waste are often




high and varied and may pose great difficulty in obtaining




accurate and precise measurement of chlorinated phenoxy acid




herbicides.  Sample cleanup procudures are generally required




and may result In loss of certain of these herbicides.  It




is not possible to describe procedures for overcoming all of




the interferences that may be encountered in solid waste




samples.




     Organic acids, especially chlorinated acids, cause the




most direct interferences with the determination.  Phenols




including chlorophenols will also interfere with this procedure.




     The herbicides, being strong organic acids, react readily




with alkaline substances and may be lost during analysis.




Glassware and glass wool should be acid-rinsed and sodium




sulfate should be acidified with sulfuric acid to avoid this




possiblity.




Apparatus




1.  Gas Chromatograph - Equipped with glass lined injection port.




2.  Detector Options:

-------
                                                             8.40-3
     a.  Electron Capture - Radioactive (Tritium or Nickel-63)




     b.  Microcoulometric Titration




     c.  Electrolytic Conductivity




 3.  Recorder - Potentiometric strip chart (10 in.) compatible




     with the detector.




 4.  Gas Chromatographic Column Materials




     a.  Tubing - pyrex  (180 cm long x 4 mm ID)




     b.  Glass Wool - Silanized




     c.  Solid Support - Gas-Chrom-Q (100-120 mesh)




     d.  Liquid Phase -  Expressed as weight percent coated on




         solid support.




         i.  OV-210,5%




        ii.  OV-17, 1.5% plus QF-1 or OV-210, 1.95%




 5.  Kuderna-Danish (K-D) Glassware




     a.  Snyder Column - three-ball (macro) and  two-ball




         (micro)




     b.  Evaporative Flasks - 250 ml




     c.  Receiver Ampules - 10 ml, graduated




     d.  Ampule Stoppers




 6.  Blender - High speed,  glass or stainless steel cup.




 7.  Graduated cylinders -  100 ml and 250 ml.




 8.  Erlenmeyer flasks - 125 ml, 250 ml ground glass 24/40




 9.  Microsyringes - 10, 25, 50 and 100 1.




10.  Pipets - Pasteur, glass disposable (140 mm  long x 5 mm ID).




11.  Separatory Funnels  - 60 ml and 2000 ml with Teflon stopcock.




12.  Glass wool - Filtering grade, acid washed.

-------
                                                               8.40-4
13.  Diazald Kit - Recommended for the generation of diazomethane




     (available from Aldrich Chemical Co., Cat. #210,025-2)




 Reagents




 1.  Boron Trifluoride-methanol-esterification-reagent,  14 percent




     boron trifluoride by weight.




 2.  N-Methyl-N-nitroso-p-toluenesulfonamide (Diazald) - High




     purity, melting point range 60-62°C.  Precursor for the




     generation of diazomethane (see Appendix IV).




 3.  Potassium Hydroxide Solution - A 37 percent aqueous solution




     prepared from reagent grade potassium hydroxide pellets and




     reagent water.




 4.  Sodium Chloride - (ACS) Saturated solution (pre-rinse NaCl




     with hexane)  in distilled water.




 5.  Sodium Hydroxide - (ACS) 10 N in distilled water.




 6.  Sodium Sulfate, Acidified - (ACS) granular sodium sulfate,




     treated as follows:   Add 0.1 ml of concentrated sulfuric




     acid to lOOg  of sodium sulfate slurried with enough ethyl




     ether to just cover the solids.  Remove the ether with the




     vacuum.  Mix  1 g of the resulting solid with 5 ml of




     reagent water and ensure the mixture has a pH below 4.




     Store at 130°C.




 7.  Sulfuric Acid - (ACS) concentrated, Sp. Gr. 184




 8.  Florisil - PR grade (600-100 mesh) purchased activated




     at 1250°F and stored at 130°C.




 9.  Carbitol (diethylene glycol monoethyl ether).




10.  Diethyl Ether - Nanograde, redistilled in glass,  if necessary.




     a.  Must be free of peroxides as indicated by EM Quant

-------
                                                               8.40-5
         test strips.   (Test  strips  are  available from EM




         Laboratories,  Inc.   500 Executive  Blvd., Elmsford,




         N.Y.  10523.)   Procedures  recommended for removal




         of peroxides  are provided  with  the test strips.




11.   Benzene, hexane -  Nanograde, redistilled in glass, if




     necessary.




12.   Pesticide Standards - Acids and methyl esters,  reference




     grade.




     a.   Stock standard solutions - Dissolve 100 mg  of each




         herbicide in 60 ml ethyl ether; then make to




         100 ml  with redistilled hexane. Solution contains




         1 mg/ml.




     b.   Working standard - Pipet 1.0 ml of each stock




         solution  into  a single 100 ml volumetric flask.




         Make to volume with a mixture of ethyl ether and




         hexane  (1:1).   Solution contains 10 ug/ml of each




         standard.




     c.   Standards for  Chromatography (Diazomethane  Procedure) -




         Pipet 1.0 ml of the working standard into a glass stoppered




         test tube and  evaporate the solvent using a steam bath.




         Add 2 ml  diazomethane to the residue.  Let  stand 10




         minutes with occasional shaking, then allow the




         solvent to evaporate spontaneously.  Dissolve the




         residue in 200 ul of hexane for gas Chromatography.




     d.   Standard  for Chromatography (Boron Trifluoride




         Procedure) - Pipet 1.0 ml of the working standard




         into a  glass stoppered test tube.   Add 0.5  ml

-------
                                                                     8.40-6
        of benzene and evaporate to 0.4 ml using a two-ball




        Snyder microcolumn and a steam bath.  Proceed as in




        the Esterificatlon section (3)(a).  Esters are then




        ready for gas chromatogrphy.




Calibration




1.  By injecting secondary standards, adjust the sensitivity




    limit and the linear range of the analytical system for




    each compound being analyzed for to a sensitivity of




    jC 1 ug (2 x background).




2.  Standards, prepared from methyl esters of phenoxy acid




    herbicides calculated as the acid equivalent are injected




    frequently as a check on the stability of operating




    conditions.  Gas chromatograms of several chlorophenoxys




    are shown in Figure 8.40-1.




3.  The elution order and retention ratios of methyl esters




     of chlorinated phenoxy acid herbicides are provided in




     Table 8.40-1, as a guide.




Quality Control




1.  Duplicate and spiked sample analyses are recommended as




    quality control checks.  Quality control check samples




    and performance evaluation samples should be analyzed on




    a regular basis.




2.  Each time a set of samples is extracted, a method blank is




    determined on a volume of distilled water equivalent to that




    used to dilute the sample.




Hydrolysis




1.  Add 15 ml of distilled water and a small boiling stone to

-------
                                                                    8.40-7
    the flask containing the ether extract (prepared by




    approriate sample preparation method) and fit the flask




    with a three-ball Snyder column.  Evaporate the ether in a




    steam bath and continue heating for a total of 60 minutes.




2.  Transfer the concentrate to a 60-ml separatory funnel.




3.  Acidify the contents of the separatory funnel by adding




    2 ml of cold (4°C) 25 percent sulfuric acid.  Extract




    the herbicides once with 20 ml of ether and twice with 10 ml




    of ether.  Collect the extracts in a 125 ml Erlenmeyer




    flask containing about 0.5 g of acidified anydrous sodium




    sulfate.  Allow the extract to remain in contact with




    the sodium sulfate for approximately two hours.




Easter if ication




1.  Transfer the ether extract through a funnel plugged with




    glass wool into a Kuderna-Danish flask equipped with a




    10 ml graduated ampule.  Use liberal washings of ether.




    Using a glass rod crush any caked sodium sulfate during



    the transfer.




    a.  If esterification is to be done with diazomethane,




        evaporate to approximately 4 ml on a steam bath (do




        not immerse the ampule in water) and proceed as directed




        under "Diazomethane Esterification".  Prepare diazo-




        methane as directed in manufacturer's instructions.




    b.  If esterification is to be done with boron trifluoride,




        add 0.5 ml benzene and evaporate to about 5 ml on a




        steam bath.  Remove the ampule from the flask and




        further concentrate the extract to 0.4 ml using a

-------
                                                                    8.40-8
        two-ball Snyder microcolumn and proceed as directed


        under "Boron Trifluoride Esterification.


2.  Diazomethane Esterification:


    a.  Disconnect the ampule from the K-D flask  and place
                                             •

        in a hood away from steam bath.  Adjust volume to


        4 ml with ether, add 2 ml diazomethane, and let stand


        10 minutes with occasional swirling.


    b.  Rinse inside wall of ampule with several  hundred


        microliters of ethyl ether.  Take sample  to


        approximately 2 ml to remove excess diazomethane


        by allowing solvent to evaporate spontaneously


        (room temperature).


    c.  Dissolve residue in 5 ml of hexane.  Analyze by


        gas chromatography.


    d.  If further cleanup of the sample is required, proceed


        as in 3(c), substituting hexane for benzene.


3.  Boron Trifluoride Ester ification:


    a.  After the benzene solution in  the ampule  has cooled,


        add 0.5 ml of borontrifluoride-methanol reagent.


        Use the two-ball Snyder microcolumn as an air-cooled


        condenser and hold the contents of the ampule at 50°C


        for 30 minutes on the steam bath.


    b.  Cool and add about 4.5 ml of a neutral 5  percent


        aqueous sodium sulfate solution so that the benzene-


        water interface is in the neck of the Kuderna-Danish


        ampule.  Seal the flask with a ground glass stopper


        and shake vigorously for about one minute.  Allow

-------
                                                             8.40-9
        to stand for three minutes for phase separation.




    c.   Pipet the solvent layer from the ampule to the top




        of a small column prepared by plugging a disposable




        Pasteur pfpet with glass wool and packing with 2.0




        cm of sodium sulfate over 1.5 cm of Florisil adsorbent.




        Collect the elute in in a graduated ampule.  Complete




        the transfer by repeatedly rinsing the ampul with




        small quantities of benzene and passing the rinses




        through the column until a final volume of 5.0 ml




        of eluate is obtained.   Analyze by gas chromatography.




Calculation and Results




     In analyzing EP extracts to determine if a waste is  a




hazardous waste by reason of EP toxicity, calculate results




in milligrams per liter as the  acid equivalent after correcting




for recovery data.  When duplicate and spiked samples are




analyzed, all data obtained should be reported.




     In determining if a waste  should be delisted, if a




response for the contaminant being analyzed for greater than




2 x background is noted, then the waste does not meet the




criteria for delisting of being fundamentally different than




the listed waste.  If a response is not noted, then prior to




concluding that the sample does not contain the specific




contaminant, the analyst must demonstrate, using that spiked




samples, that the instrument sensitivity is < lug of contaminant




/gm of sample.

-------
                                                                     8.24-1
                         Method 8.24




              GC/MS METHOD FOR VOLATILE ORGANICS









Scope and Application




     This method is designed to determine volatile organic




compounds.






Summary of Method




     The volatile compounds are introduced to the gas chromato-




graph by direct injection (Method 8.80), the Headspace  Method




(Method 8.82) or the Purge and Trap Method (Method 8.83).  The




components are separated via the gas chromatograph and  detected




using a mass spectrometer which is used to provide both




qualitative and quantitative information.  The chromatographic




conditions as well as typical mass spectrometer operating




parameters are given.




Interferences




     Interferences coextracted from the samples will vary con-




siderably from source to source, depending upon the particular




waste or extract being tested.  The analytical system,  however,




should be checked to insure freedom from interferences  under




the conditions of the analysis by running method blanks.




Method blanks are run by analyzing organic-free water in the




normal manner.  The use of non-TFE plastic tubing, non-TFE




thread sealants, or flow controllers with rubber components




in the purging device should be avoided.




     Samples can be contaminated by diffusion of volatile

-------
                                                             8.24-2
organics (particularly methylene chloride) through the septum




seal into the sample during shipment and storage.  A field




blank prepared from organic-free water and carried through




the sampling and handling protocol can serve as a check on




such contamination.




     Cross contamination can occur whenever high level and




low level samples are sequentially analyzed.  To reduce cross




contamination, it is recommended that the purging device and




sample syringe be rinsed out twice, between samples, with




organic-free water.  Whenever an unusually concentrated sample




is encountered, it should be followed by an analysis of




organic-free water to check for cross-contamination.  For




samples containing large amounts of water soluble materials,




suspended solids, high boiling compounds, or high organohalide




levels, it may be necessary to wash out the purging device




with a soap solution, rinse with distilled water, and then




dry in a 105°C oven between analyses.




Apparatus and Materials




1.   Gas chromatograph—Analytical system complete with a




     temperature programmable gas chromatograph suitable for




     on-column injection and all required accessories including




     an analytical column.




     a.  Column l--An 8 ft. stainless steel column (.125 in.




         OD x 2 mm ID) packed with 1% SP-1000 coated on 60/80




         mesh Carbopack B proceeded by a 1 ft. stainless steel




         column (.125 in. OD x 2mm ID) packed with 1% SP-1000




         coated on 60/80 mesh Chromosorb W.  A glass column .25 i




         x 2mm ID may be substituted for the stainless steel. The

-------
                                                                    8.24-3
         glass precolumn is necessary only during conditioning.



     b.  Column 2—An 8 ft. stainless steel column (.125 in.



         OD x 2 mm ID) packed with 0.2% Carbowax 1500 coated



         on 60/80 mesh Carbopack C preceded by a 1 ft. stainless



         steel column (.125 in. OD x 2 mm ID) packed with 3%



         Carbowax 1500 coated on 60/80 mesh Chromosorb W.  A



         glass column (1/4 in.  OD x 2mm ID) may be substituted



         for the stainless steel.  The precolumn is necessary



         only during conditioning.



2.   Syringes—glass, 5 ml hypodermic with Luer-Lok tip



     (3 each) .



3.   Micro syringes--10,  25, 100 ul .



4.   2-way syringe valve with Luer ends (3 each, Teflon or



     Kel-F) .



5.   Syringe--5 ml gas-tight with shut-off valve.



6.   8-inch, 20 gauge syringe needle—one needle for each



     5-ml syringe.



7.   Mass Spectrometer--capable of scanning from 20-260 a.m.u.



     in six seconds or less at 70 volts (nominal), and producing



     a recognizable mass spectrum at -unit resolution from 50 ng



     of DFTPP when injected through the GC inlet.  The mass



     spectrometer must be interfaced with a gas chromatograph
                         «


     equipped with an all-glass, on-column injector system



     designed for packed column analysis.  All sections of



     the transfer lines must be glass or glass-lined and



     deactivated.  Use Sylon-CT, Supelco, (or equivalent)



     to deactivate.  The GC/MS interface can utilize any

-------
                                                                    8.24-4




     separator that gives recognizable mass spectra (back-




     ground corrected) and acceptable calibration points




     at the limit of detection specified for each compound




     in Table 8.24-1 .




8.   A computer system should be interfaced to the mass




     spectrometer to allow acquisition of continuous mass




     scans for the duration of the chromatographic program.




     The computer system should also be equipped with mass




     storage devices for saving all data from GC-MS runs.




     There must be computer software available to allow




     searching any GC/MS run for specific ions and plotting




     the intensity of the ions with respect to time or




     scan number.  The ability to integrate the area under




     a specific ion plot peak is essential for quantification.




Reagents




1.   Activated carbon--Filtrasorb-200 (Calgon Corp.) or




     equivalent.




2.   Organic-free water.




     a.  Organic-free water is defined as water free of




         interference when employed in the purge and trap




         procedure described herein.  It is generated by




         passing distilled deionized water through a carbon




         filter bed containing activated carbon.




     b.  A water system  (Millipore Super-Q or equivalent) may




         be used to generate organic-free deionized water.




     c.  Organic-free water may also be prepared by boiling




         deionized distilled water 15 minutes.  Subsequently,

-------
                                                                   8.24-5
         while maintaining the temperature at 90°C, bubble a




         contaminant-free inert gas through the water for




         one hour.  While still hot, transfer the water to a




         narrow mouth screw cap bottle equipped with a Teflon




         seal .




3.   Stock standards (2 mg/ml)--Prepare stock standard solutions




     in methanol using assayed liquids or gases as appropriate.




     Because of the toxicity of some of the organohalides,




     primary dilutions of these materials should be prepared




     in a hood.  A NIOSH/MESA approved toxic gas respirator




     should be worn when the analyst handles high concentrations




     of such materials.




     a.  Place about 9.8 ml of methanol into a 10 ml ground




         glass stopped volumetric flask.  Allow the flask to




         stand, unstoppered, for about 10 minutes or until




         all alcohol wetted surfaces have dried.  Tare the




         flask to the nearest 0.1 mg .




     b.  Add the assayed reference material:




         Liquids—using a 100 ul syririge, immediately add




         2 to 3 drops of assayed reference material to the




         flask, then reweigh.  Be sure that the drops fall




         directly into the alcohol without contacting the




         neck of the flask.




         Gases—To prepare standards of bromomethane, chloro-




         ethane, chloromethane, and vinyl chloride, fill a




         5-ml valved gas-tight syringe with the reference




         standard to the 5.0 ml mark.   Lower the needle to




         5 mm above the methyl alcohol menicus .  Slowly inject

-------
                                                               8.24-6
    the reference standard into the neck of the flask




    (the heavy gas will rapidly dissolve into the methyl




    alcohol).




c.  Reweigh the flask, dilute to volume, stopper, then




    mix by inverting the flask several times.  Transfer




    the standard solution to a 15 ml screw-cap bottle




    equipped with a Teflon cap liner.




d.  Calculate  the concentration in mg per ml (equivalent




    to ug per  ul) from the net gain in weight.




e.  Store stock standards at 4°C.  Prepare fresh standards




    every second day for the four gases and 2-chloroethyl-




    vinyl ether.  All other standards must be replaced




    with fresh standards each week.




Surrogate Standard Dosing Solution—From stock standard




solutions prepared as above, add a volume to give 1000 ug




each of bromochloromethane, 2-bromo-l-chloropropane, and




1,4-dichlorobutane to 40 ml of organic-free water contained




in a 50 ml volumetric flask, mix and dilute to volume.




Prepare a fresh surrogate standard dosing solution  weekly.




Dose the surrogate standard mixture into every 5 ml sample




and reference  standard analyzed.

-------
                                                                    8.24-7
Calibration




1.   Using the stock standards, prepare secondary dilution




     standards of the compounds of interest, either singly




     or mixed together in methanol.  The aqueous standards




     must be prepared fresh daily.  Standards should be at




     concentrations such that the aqueous standards to be




     prepared will bracket the working range of the




     chromatographic system.  If the limit of detection




     listed in Table 8.24-1 is 10 ug/1, for example, prepare




     secondary methanolic standards at 100 ug/1, and 500 ug/1,




     so that aqueous standards prepared from the secondary




     calibration standards, and the primary standards will




     define the linearity of the detector in the working




     range.




2.   Assemble the necessary gas chromatographic and mass




     spectrometer apparatus and establish operating parameters




     equivalent to those indicated in Table 8.24-1.  By inject-




     ing secondary dilution standards, adjust the sensitivity




     of the analytical system for each compound to <1 ug.




Quality Control




1.   Before processing any samples, the analyst should daily




     demonstrate through the analysis of an organic-free




     water method blank, that the entire analytical system




     is interference-free.  The blank samples should be carried




     through all stages of the sample preparation and measurement




     steps .

-------
2.   Standard quality assurance as indicated in Section 10 should




     be followed. Field replicates should be collected to validate




     the precision of the sampling technique.  Laboratory




     replicates and fortified samples should be analyzed to




     validate the sensitivity and accuracy of the analysis.




     If the fortified samples do not indicate sufficient




     sensitivity to detect £ 1 ug/gm of sample then the sensitivity




     of the instrument should be increased or the sample




     subjected to additional clean up.  The fortified samples




     should be carried through all stages of the sample




     preparation and measurement steps.




3.   The analyst should maintain constant surveillance of




     both the performance of the analytical system and the




     effectivenesss of the method in dealing with each sample




     matrix •




Gas Chromatography-Mass Spectrometry




1.   Table 8.24-1 summarizes the recommended gas chromatographic




     column materials and operating conditions for the instru-




     ment.  Included in this table are some estimated retention




     times.  An example of the separation achieved by Column 1




     is shown in Figure 8.24-4.




2.   GC-MS Determination--Suggested analytical conditions are




     given below.  Operating conditions vary from one system




     to another, therefore, each analyst must optimize the




     conditions for his particular GC/MS system.

-------
                                                                    8.24-9
3.   Mass Spectrometer Parameters:




        Electron energy—70 volts (nominal).




        Mass, rang.e--20-27, 33-260 amu.




        Scan time—6 seconds or less.




4.   Calibration of the gas chromatography-mass spectrometry




     GC-MS system—Evaluate the system performance each day




     that it is to be used for the analysis of samples or




     blanks by examining the mass specrum of DFTPP or BFB .




     a.  To use DFTPP, remove the analytical column  and




         substitute a column more appropriate to the boiling




         point of the reference compound (e.g. 3% SP-2250 on




         Supelcoport).  Inject a solution containing 50 ng




         DFTPP and check to insure that the performance




         criteria listed in Table 8.24-2 are met.




     b.  To use BFB, inject a solution containing 20 ng BFB




         and check to insure that the performance criteria




         listed in Table 8.24-3 are met.




     c.  If the system performance criteria are not  met for




         either test, the analyst must retune the spectrometer




         and repeat the performance check.  The performance




         criteria must be met before  any samples or  standards




         may be analyzed.




5.   Analyze an internal or external  calibration standard to




     develop response factors for each compound.




Quantitative Determination




1.   To qualitatively identify a compound, obtain an Extracted




     Ion Current Profile (EICP) for the primary ion  and at




     least two other ions (if available) listed in Table

-------
                                                                  8.24-10
     8.24-4.   The criteria below must be met for a quantitative




     identification.




     a.   The  characteristic ions for the compound must be found




         to maximize  in the same or within one spectrum of each




         other.




     b.   The  retention time at the experimental mass spectrum




         must be within 60 seconds of the retention time of the




         authentic compound.




     c.   The  ratios  of the three EICP peak heights must agree




         with +  20%  with the ratios of the relative intensities




         for  these ions in a reference mass spectrum.  The




         reference mass spectrum can be obtained from either a




         standard analyzed through the GC-MS system or from a




         reference library.




     d.   Structural  isomers that have very similar mass spectra




         can  be  explicitly identified only if the resolution




         between the  isomers in a standard mix is acceptable.




         Acceptable  resolution is achieved if the valley height




         between isomers is less than 25% of the sum of the two




         peak heights.  Otherwise structural isomers are




         identified  as isomeric pairs.




2.   The primary ion  listed in Table 8.24-4 is to be used to




     quantify each compound.  If the sample produces an inter-




     ference  for the  primary ion, use a secondary ion to




     quantify.




3.   For low  concentrations, or direct aqueous injection of




     acrylonitrlie and acrolein, the characteristic masses

-------
                                                                  8.24-11
     listed for the compounds in Table 8*24-4 may be used for




     selected ion monitoring (SIM).  SIM is the use of a mas.s




     spectrometer as a substance selective detector by




     measuring the mass spectrometric response at one or several




     characteristic masses in real time.




Results




     If a response for the contaminant being analyzed for




greater than 2 X background is noted; then the waste does not




meet the criteria for delisting of being fundamentally different




than the listed waste.  If a response is not noted, then prior




to concluding that the sample does not contain the specific




contaminant, the analyst must demonstrate, using the spiked




samples, that the instrument sensitivity is < 1 ug/gm of




sample.

-------
                                                                   g.24-12
References




1.   "The Analysis of Halogenated Chemical  Indicators  of




     Industrial Contamination in Water by the Purge  and




     Trap Method," U.S. EPA, Environmental  Monitoring  and




     Support Laboratory, Cincinnati, OH, 45268,  Dec. 1978.




2.   Determining Volatile Organics at  Microgram-per-Liter




     Levels by Gas Chromatography," T.A. Bellar  and  J.J.




     Lichtenberg, Jour. AWWA, 66, 739-744,  Dec.  1974.




3.   ASTM Annual Standards--Water, Part 31,  Method D2908




     "Standard Recommended Practice for Measuring Water  by




     Aqueous-Injection Gas Chromatography."




4.   "Direct Analysis of Water Samples for  Organic Pollutants




     with Gas Chromatography-Mass Spectrometry," Harris,  L.E.,




     Budde, W.L., and Eichelberger, J.W. Anal.  Chem.,  46,  1912




     (1974).




5.   "Sampling and Analysis Procedures for  Screening of




     Industrial Effluents for Priority Pollutants,"  March  1977




     (revised April 1977).  USEPA, Effluent Guidelines Division,




     Washington, D.C. 20460.




6.   "Proceedings:  Seminar on Analytical Methods for  Priority




     Pollutants," Volume 1 - Denver, Colorado,  November  1977;




     Volume 2 - Savannah, Georgia,  May 1978; Volume  3  -  Norfolk,




     Virginia, March 1979; USEPA, Effluent  Guidelines  Division,




     Washington, D.C. 20460.

-------
                                                                  8.24-13
                              Table 8.24-1
                    GAS CHROMATOGRAPHY OF ORGANICS
Compound
                    Retention Time (min)
                  Column 1       Column 2
chlorome thane
vinyl chloride
trichlorofluorom ethane
1,1-dichloroethane
chloroform
1,2-dichloroethane
1 ,1,1-trichloroethane
carbon tetrachlor ide
trichloroethene
1,1,2-trichloroethane
benzene
1,1,2,2-tetrachloroethane
tetrachloroethene
toluene
chlorobenzene
acrolein
acrylonitr lie
1 .50
2 .67
7 .18
9.30
10.68
11 .40
12.60
13 .02
15.80
16.52
	
21,62
21 .67
	
24.18


2.10
2.57
5.14
6.48
7.70
8.29
9.28
9.45
11 .98
12.86
12.95
17.70
17.44
18.53
20.57

*
Column 1 Eight ft. stainless steel column (.125 in OD x 0.1 in.
         ID) packed with 1% SP-1000 coated on 60/80 mesh
         Carbopack B preceded by a 1 ft. stainless steel column
         (.125 in. OD x 0.1 in. ID) packed with 1% SP-1000 coated
         on 60/80 mesh Chromosorb W.  (A glass column (.25 in.
         OD x 2 mm ID) may be substituted).  Carrier gas helium
         at 40 ml/min.  Temperature program:  3 min isothermal
         at 45°C, then 8°/min to 220°, hold at 220° for 15 minutes
Column 2 Eight ft. stainless steel column (.125 in
         ID) packed with 0.2% Carbowax 1500 coated
         Carbopack C preceded by a 1 ft. stainless
         (.125 in. OD x 0.1 in. ID) packed with 3%
                             OD x 0.1 in
                            on 60/80 mesh
                            steel column
                            Carbowax 1500
         coated on 60/80 mesh
         ( .25 in. OD x mm ID)
         helium at 40 ml/min.
         isothermal at
         all compounds
60°C then
elute.
       Chromosorb W.  (A glass column
       may be substituted.  Carrier
        Temperature program:  3 min
8°/min to 160°, hold at 160 until

-------
                                                        8.24-14
                     Table 8.24-2
      DFTPP KEY IONS AND ION ABUNDANCE CRITERIA
Mass                       Ion Abundance Criteria




 51                        30-60% of mass 198




 68                        less than 2% of mass 69




 70                        less than 2% of mass 69




127                        40-60% of mass 198




197                        less than 1% of mass 198




198                        base peak, 100% relative abundance




199                        5-9% of mass 198




275                        10-30% of mass 198




365                        greater than 1% of mass 198




441                        present but less than mass 443




442                        greater than 40% of mass 198




443                        17-23 of mass 442

-------
                                                       8.24-15
                      Table 8.24-3
        BFB KEY IONS AND ION ABUNDANCE CRITERIA
Mass                       Ion Abundance Criteria




 50                        20-40% of mass 95




 75                        50-70% mass 95




 95                        base peak, 100% relative abundance




 96                        5-9% of mass 95




173                        less than 1% of mass 95




174                        70-90% of mass 95




175                        5-9% of mass 95




176                        70-90% of mass 95




177                        5-9% of mass 95

-------
Table 8.24-4
                                 8.24-16
CHARACTERISTIC
Compound
chlorome thane
vinyl chloride
trichlorof lu or ome thane
1 , 1 -d i ch lor o ethane

chloroform
1,2-dichloroethane
1,1,1-trichloroethane
carbon tetrachloride
trichloroethene
1,1,2-trichloroethane

benzene

tetrachloroethene
1,1,2,2-tetrachloroethane

toluene
chlorobenzene
acrolein
acrylonitrile
IONS OF
E
50
62
101
63
85
83
62
97
117
95
83
99
78
252
129
83
166
91
112
26
26
VOLATILE ORGANICS
I Ions
52
64
103
65 83
98 100
85
64 98 100
99 177 199
119 121
97 130 132
85 97
132 134

254 256
131 164 166
85 131 133
168
92
114
27 55 56
51 52 53

Primary Ion
50
62
101
63

83
98

117
130

97
78

164

168
92
112
56
53

-------
                                                                 8.24-17
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                          BROIWOMETHAIME


                                 CHLOROMETHANE
                                          •CHLOROMETHANE
               1.1-DICHLOROETHENE




           cis-1,2-DICHLOROETHANE






           1.1.1- TRICHLOROETHANE



            1. 2-DICHLOROPROPANE
      trans -1. 3-DICHLOROPROPENE

    cis-1. 3-D1CHLOROPROPENE

1. 2-D1BROW10ETHANE

              1.1.1.2-TETRACHLOROETH AWE
      1. 2, 3-TRICHLOROPROPANE


      1. 1. 2. 2-TETRACHLOROETHANE
                           CHLOROBEIMZENE

                       1-CHLOROHEXANE





                      BROiWOBENZENE
                                                             0
                                  •** ss

                                    *
                                                           Is
                                                           tn O
                                                           09>
                                                           Sfi
                                                           O

-------
                                                             8.25-1
                            Method 8.25




                       GC/MS METHOD, GENERAL






Scope and Application




     The following compounds may be determined by this method!




Benzo(a)anthracene




Benzo(a)pyrene




Benzotrichloride




Benzyl chloride




Benzo(b)fluoranthene




Chlordane




Chlorinated dibenzodioxin




Chlorinated biphenyls




2-Chlorophenol




Chrysene




Creosote




Cresol(s)




Cresylic acid(s)




Dichlorobenzene(s)




Dichlorophenoxyacetic acid




Dichloropropanol




2,4-Dimethylphenol




Dinltrobenzene




4,6-Dinitro-o-cresol




2,4-Dinitrotoluene




Endrin




Formic acid




Heptachlor

-------
                                                                    8.25-2
Hexachlorobenzene

Hexachlorobutadiene

Hexachloroethane

Hexachloroeyelopentadiene

Lindane

Maleic anhydride

Methyl ethyl ketone

Methyl isobutyl ketone

Naphthalene

Napthoquinone

Nitrobenzene

Pentachlorophenol

Phenol

Phthalic anhydride

2-Picoline

Pyridine

Tetrachlorobenzene(s)

Toluenediamine

Toluene diisocyanate(s)

Toxaphene

Trichlorophenol(s)

2,4,5-TP(Silvex)

Summary of Method

     prior to using this method, the waste samples should be

prepared for chromatography (if necessary) using the appropriate
                                                •
sample preparation method (i.e., shake out, sonication, or

soxhlet extraction).  If emulsions are a problem, continuous

-------
                                                             8.25-3
extraction techniques should be used.   This method describes




chromatographlc conditions which allow for the separation of




the compounds In the extract.




Interferences




     Solvents, reagents, glassware, and other sample processing




hardware may yield discrete artifacts  and/or elevated baselines




causing misinterpretation of chromatograms.  All of these




materials must be demonstrated to be free from interferences




under the conditions of the analysis by running method blanks.




Specific selection of reagents and purification of solvents




by distillation in all-glass systems may be required.




     Interferences coextracted from the samples will vary




considerably from source to source, depending upon the




diversity of the industrial complex or waste being




sampled.




     The recommended analytical procedure may not have



sufficient resolution to differentiate between certain isomeric




pairs.  These are anthracene and phenanthrene, chrysene,




and benzo(a)anthracene, and benzo(b)fluoranthene and




benzo(k)fluoranthene.  The GC retention time and mass spectral




data are not sufficiently unique to make an unambiguous




distinction between  these compounds.  If identification of




these specific compounds is required Method 8.10 should be




used.




Apparatus




1.  Separatory funnel - 20 mm, with Teflon stopcock (Ace




    Glass 7228-T072  or equivalent).

-------
                                                                    3.25-4
2.  Drying column - 20 mm ID pyrex chromatographic column




    equipped with coarse glass frit or glass wool plug.




3.  Kuderna-Danish (K-D) Apparatus equipped with 3-ball Snyder




    column (Kontes K-570000 or equivalent).




4.  Water bath - Heated with concentric ring cover, capable




    of temperature control (+_ 2°C).  The bath should be used




    in a hood.




5.  Gas chromatograph - Analytical system complete with gas




    chromatograph capable of on-column injection and all




    required accessories including column supplies, gases, etc.




6.  Column 1 - For Base/Neutral and Pesticides a 6-foot glass




    column (1/4 in OD x 2 mm ID) packed with 3% SP-2250 coated




    on 100/120 Supelcoport (or equivalent).




7.  Column 2 - For Acids, a 6-foot glass column (1/4 in OD x




    2mm ID) packed with 1% SP-1240 DA coated on 100/120 mesh




    Supelcoport (or equivalent).




8.  Mass Spectrometer - Capable of scanning from 35 to 450




    a.m.u. every 7 seconds or less at 70 volts (nominal) and




    producing a recognizable mass spectrum at unit resolution




    from 50 ng of DFTPP when the sample is introduced through




    the GC inlet (References 2).  The mass spectrometer must




    be interfaced with a gas chromatograph equipped with an




    injector system designed for splitless injection and




    glass capillary columns or an injector system designed




    for on-column injection with all-glass packed columns.




    All sections of the transfer lines must be glass or

-------
                                                                    8.25-5
     glass-lined  and must  be  deactivated.   (Use  Sylon-CT,


     Supelco,  Inc., or  equivalent  to  deactivate.)
                                                       *

 Note;  -  Systems  utilizing a  jet  separator  for  the  GC  effluent



 are  recommended  since  membrane  separators  may  lose sensitivity



 for  light  molecules and  glass  frit  separators  may  inhibit  the



 elution  of polynuclear aromatics.   Any of  these separators



 may  be used provided  that it gives  recognizable mass  spectra


 and  acceptable calibration points at the  required  limit  of


 detection.



 9.   A computer system  must be  interfaced  to the mass  spectro-



     meter  to allow acquisition of continuous mass  scans  for



     the  duration of  the  chromatographic program.   The computer


     system should also be equipped  with mass storage  devices



     for  saving all data  from GC-MS  runs.   There must  be



     computer software  available to  allow searching any GC-MS



     run  for specific  ions and plotting the intensity  of  the


     ions with respect  to time or scan number.   The ability


     to integrate the  area under any specific ion plot peak



     is essential if  quantification  is to be attempted.


10.   Continuous  liquid-liquid extractors-Teflon or  glass



     connecting  joints  and stopcocks, no lubrication.   (Hershberg-



     Wolf Extractor-Ace Glass Co.,  Vineland, N.J. P/N  6841-10 or


     eqivalent).



 Reagents


 1.   Sodium hydroxide  - (ACS) 6N in  distilled water.



 2.   Sulfuric acid -  (ACS) 6N in distilled water.

-------
                                                                    8.25-6
3.  Sodium sulfate - (ACS) granular anhydrous (rinsed with




    methylene chloride (20 ml/g) and conditioned at 400°C




    for 4 hrs . ) .




4.  Methylene chloride - Pesticide quality or equivalent.




5.  Stock standards - Prepare stock standard solutions at a




    concentration of 1.00 ug/ul.  For example, dissolve 0.100




    grams of assayed reference material in pesticide quality




    isooctane or  other appropriate solvent and dilute to




    volume in a 100 ml ground glass stoppered volumetric




    flask.  The stock solution is transferred to 15 ml Teflon




    lined screw cap vials, stored in a refrigerator, and




    checked frequently for signs of degradation of evaporation,




    especially  just prior to preparing working standards




    from them.   Protect standards from light.




Procedure




1.  Calibrate instrument using the conditions indicated in




    Table 8.25-1, so that a response greater than 2 times




    background  is obtained for 1 ug of each species being




    analyzed for.




2.  Inject the  extract derived from 1 gm of the sample being




    analyzed.  The extract should be diluted and range finding




    studies conducted prior to injection of concentrated extract




    in order to prevent instrument overload.




Results




     If a response for the contaminant being analyzed for is




greater than 2x background is noted; then the waste does not

-------
                                                                    8.25-7
meet the criteria for delisting of being fundamentally




different than the listed waste.  If a response is not noted,




then prior to concluding that the sample does not contain




the specific contaminant, the analyst must demonstrate, using




the spiked samples, that the instrument sensitivity is




_£ 1 ug/gm of sample.




guallty Control



1.  Before processing any samples, demonstrate through the




    analysis of a method blank, that all glassware and




    reagents are interference-free.  Each time a set of




    samples Is extracted or there is a change in reagents,




    a method blank should be processed as a safeguard against




    chronic laboratory contamination.




2.  Standard quality assurance practices should be used with




    this method.  Field replicates should be collected and




    analyzed to determine the precision of the sampling




    technique.  Laboratory replicates should be analyzed to




    determine the precision of the analysis.  Fortified




    samples should be analyzed to determine the accuracy




    of the analysis.  Field blanks should be analyzed to




    check for contamination introduced during sampling




    and transportation.

-------
                                                            8.25-8
                         Table 8.25-1
                  CHROMATOGRAPHIC CONDITIONS
Benz(a)anthracene                BN
Benzo(a)pyrene                   BN
Benzotrichloride                 BN
Benzyl chloride                  BN
Benz(b)fluoanthene               BN
Chlordane                        BN
Chlorinated dibenzodioxin        BN
Chlorinated biphenyls            BN
2-Chlorophenol                   BN
Chrysene                         BN
Creosote                         BN
Cresol(s)                        A
Cresylic acid(s)                 A
Dichlorobenzene(s)               BN
Dichlorophenoxyacetic acid       A
Dichloropropanol                 BN
2,4-Dimethylphenol               A
Dinitrobenzene                   BN
4 ,6-Dinitro-o-cresol             A
2,4-Dinitrotoluene               BN
Endrin                           P
Formic acid                      BN
Heptachlor                       P
Hexachlorobenzene                BN
Hexachlorobutadiene              BN
Hexachloroethane                 BN
Hexachlorocyclopentadiene        BN
Lindane                          P
Maleic anhydride                 BN
Methyl ethyl ketone              A
Methyl isobutyl ketone           A
Naphthalene                      BN
Napthoquinone                    BN
Nitrobenzene                     B
Pentachlorophenol                A
Phenol                           BN
Phthalic anhydride               BN
2-Picoline                       BN
Pyridine                         BN

-------
                                                               8.25-9
                     Table 8.25-1 (Cont.)
Tetrachlorobenzene(s)            BN
Toluenediamine                   BN
Toluene dlisocyanate(s)          BN
Toxaphene                        P
Trichlorophenol(s)               A
2,4,5-TP(Silvex)                 A
 (A)  °8 foot glass column (1/4 in. OD x  2 mm ID) packed with
      1% SP-1240 DA coated on 100/120 mesh Supelcoport.  Carrier
      gas helium at 30 ml per min.  Temperature program:  2 min
      isothermal at 70°, then 8° per min to 200°C.  If desired,
      capillary or SCOT columns may be used.

(BN)  #Six foot glass column (1/4 in. OD x 2 mm ID) packed with
      3% SP-2250 coated on 100/120 mesh Supelcoport.  Carrier gas
      helium at 30 ml per min.  Temperature program:  isothermal
      for 4 minutes at 50°C, then 8° per min to 270°C.  Hold at
      270°C for 30 minutes.  If desired, capillary or SCOT columns
      may be used.

 (P)  °6 foot glass column (1/4 in. OD x 2 mm ID) packed with 3%
      SP-2250 coated on 100/120 mesh Superlcoport.  Carrier gas
      helium at 30 ml per min.  Temperature program:  isothermal
      for 4 minutes at 50°C, then 8° per minute to 270°.  Hold at
      270°C for 30 minutes.  If desired, capillary or SCOT columns
      may be used

-------
                                                                           8.25-10
           ,1,3-DICHLOROBENZENE
             1,4-DICHLOROBENZENE
                   1.2-DICHLOROBENZENE + HEXACHLOROETHANE
           BIS(METHYL-2CHLOROETHYL)ETHER  + BISI2-CHLOBOETHYDETHER
                           .HEXACHLOROBUTADIENE
                           .1.2.4-TRICHLOROBENZENE
                           ISOPHORONE
                         NAPTHALENE
             HEXACHLOROCYCLOPENTADIENE
   C1
  TO
za
rn
                 2-CHLORONAPTHALENE
                                       ACENAPHTHYLENE
                                        ACENAPHTHENE
                                          DIMETHYL PHTHALATE
                                         2,6-DINITROTOLUENE
                                          4-CHLOROPHENYL PHENYL ETHER
                                                IYLPHTHALATE
                                                DIPHENYLHYDRAZINE
                                      	( DIETHYLPHTHALATE
                                      VIEl •»- 1.2-
                      HEXACHLOROBENZENE
                 "4-BROMO PHENYL PHENYL ETHER
                                       PHENANTHRENE  ANTHRACENE
   ro
   «n
m
   CO
v>
                                              d-10 ANTHRACENE
                         DIBUTYL PHTHALATE
                                 FLUORANTHENE
                                PYRENE
                               BENZYL BUTYL PHTHALATE
                                    B1S|2-ETHYLHEXYL)PHTHALATE
                    4,4'-DICHLOROBENZIDtNE
   U)
   W
                          BENZO(b)FLUORANTHENE
                          BENZOdOFLUOfiANTHENE
                                            D1OCTYL PHTHALATE
                                                        O 2 O
                                                        3o£
                  BENZO(a)PYRENE
C
S
•2.
                                                        _ 01
                                                        53
                                                        t» O
                                                           >^ fO
                                                        co    ro
                                                        TJ 3 01
                                                        m ~ o
                                                              i
              JNOENO{1.2.3-cd)PYRENE
              /DIBENZO(ah) ANTHRACENE
                                                        2 oo
   S
              BENZO(ghi)PERYLENE
                                                          3S
                                                           o

-------
                                                            8.25-11
                                            o
                                            m
                                                 o
m

^j

O




IE
m
2 _»
C ro
-H
m
co
  ro
  o
  ro
  ro
                                            oSi
                                            •H J> S

                                            §8"
                                            co O %'

                                            to ro 1.

                                            c/> S Ifa
                                            m =; o

                                            O .  P
                                            §5
                             2-CHLOROPHENOL m 1
                                            m
                                            3D
                              2-NITROPHENOL     ro
                                               o
                                               o

                                               0°
                                       PHENOL -°
                                  2,4-DIMETHYLPHENOL
O
z

co
C
-o

P
O
O
-o
O
so
                                 2,4-DICHLOROPHENOL
                               2,4,6-TRICHLOROPHENOL
                             4-CHLORO-3-METHYLPHENOL
                           2,4-DIWITROPHEWOL
                           2-METHYL-4.6-DINITROPHEWOL



                              PEiMTACHLOROPHEMOL
                              4-NITROPHEIMOL

-------
                                                               8.25-12
m
m
Z
c
  to
  o
                                    /?-BHC & HEPTACHLOR
ro
en
                                              ALDRIN

                      HEPTACHLOR EPOXIDE

               ENDOSULFAN I

               =====— DIELDRIN & 4.4' DDE
                     -4,4'-DDT

             ENDOSULFAN SULFATE
                             ENDOSULFAN E & 4,4'-DDD

-------
                                                                 8.25-13
COLUMN: 3% SP-2250 ON SUPacOPORT
PROGRAM: 50'C, 4 WIN, 8°PER IVIIN TO 270'C
DETECTOR: MASS SPECTROMETER
                                  'PEAKS GIVING THE THREE
                                    CHARACTERISTIC IONS
                RETENTION TIME-MINUTES
                    Figure  8.25-4
            GAS CHROMATOGRAM OF  CHLORDANE

-------
                                                                 8.25-14
COLUMN: 3% SP-2250 DIM SUPELCOPORT
PROGRAM: 50°C. 4 MIN. 8°PER MIN TO 270°C
DETECTOR: MASS SPECTROMETER
         25              30             35
                RETENTION TIME-MINUTES
                  Figure 8.25-5
          GAS CHRQMATOGRAM OF TOXAPHENE

-------
                                                                     8.25-15
COLUMN: 3% SP-2250 ON SUPELCOPORT
PROGRAM: 50°C. 4 MIIM, 8°PER MIN TO 270°C
DETECTOR: MASS SPECTROMETER
                                    A m/e 224 PRESENT
                                    B m/e 260 PRESENT
                                    C m/e 294 PRESENT
           20
   25            30*
RETENTION TIME-MINUTES
35
                     Figure 8.25-6
            GAS  CHROMATOGRAM OF AROCHLOR 1248

-------
                                                                  8.25-16
COLUMN-: 3% SP-2250 ON SUPELCOPERT
PROGRAM: 50°C, 4 MIN, 8° PER MIN TO 270°C
DETECTOR: MASS SPECTROMETER
 A m/e 294 PRESENT
 B m/e 330 PRESENT
 C m/e 362 PRESENT
          20            25            30
               RETENTION TIME-ftflfWUTES
                    Figure  8.25-7
          GAS CHHOMATOGRAM  OF AROCHn5R 1254

-------
                                                                    8.49-1
                           Method 8.49




            GENERAL REQUIREMENTS FOR METALS ANALYSIS






I.  It is essential to prevent contamination of the sample.




    Reagents must be of the highest grade and all laboratory




    equipment must be kept scrupulously clean and protected.




    Pipets with disposable tips are recommended.  Glassware,




    plastic containers, and sample tubes should be subjected




    to the following series of washes in the order given:




    a.  Thoroughly scrub with detergent and water.




    b.  Rinse with a solution of one part concentrated nitric




        acid to one part water.




    c.  Rinse with water.




    d.  Rinse with a solution of one part hydrochloric acid




        and one part water.




    e.  Rinse with water.




    f.  Rinse with deionized distilled water.




    g.  Dry the plastics at 50° C, the glassware at 105° C.




2.  Sample bottles may be of borosilicate glass, polyethylene,




    polypropylene or teflon.  It is recommended that they be




    used one time and discarded.  If this is not feasible,




    they must be subjected to the series of washes listed in




    1.




3.  Deionized distilled water is made by passing distilled




    water through a mixed bed ion exchange resin column.




    All reagents, standards and dilutions shall be prepared




    using this water.

-------
                                        Revision B  4/15/81 /«.*27-l


                         Method 8.27

   Capillary Column GC/MS method for the analysis of Wastes



Scope and Application

     This method may be used to determine the presence and
concentration of the volatile and extractable organic compounds
which are listed in Appendix VIII, 40 CFR 261.33 in wastes.  The
method employs capillary column gas chromatography-mass
spectrometry.  Quantitation can be performed in two ways depending
on the level of information required.

Summary of Method

     The waste is categorized by its physical makeup into one
of the following three classes.

        0 Liquid (either single or multi-phase systems)
        0 Solid
        0 Combination of Liquid and Solid

     Liquids are analyzed in their "as received" form except that
if more than one phase is present the organic and aqueous phases
are separated and the two phases analyzed separately.  The
organic phases are analyzed by direct injection onto the
capillary column using either the split or splitless technique.
Aqueous phases are determined by a combination of the purge
and trap technique for volitiles and a series of extractions
for the base/neutrals and acids.  The extracted fractions
are then combined and analyzed as a single solution using
the splitless technique.
     Solids are analyzed using purge and trap technique for
volatiles and a soxhlet extraction for the extractables.
     Samples containing both liquid and solid phases are first
separated into their component liquid and solid phases
using centrifugation.  The separated phases are then analyzed
as either liquids or solids as described above.
     The components of the sample are quantitated in either
of two ways, depending on the degree of quantitation necessary.
The first way estimates concentration and assigns these
estimated concentrations into ranges.  Since this is not a
rigorous quantitative procedure it may only be used for
order of magnitude type estimates of concentration.  These
ranges are:

        0 Greater than 50%
        0 -Between 10 and 50%
        0 Between 1 and 10%
        0 Between 100 ppm and 1%
        0 Between 1 and 100 ppm

-------
                                        Revision B  4/15/81  8.27-2

For determining the precise concentration of a component in a
sample the method of standard additions is employed.

Procedure
     The analyst must first determine which category  the
sample belongs to.

        0 If the sample is a liquid go to the section labled
          "Liquids" (I) of this procedure.
        0 If the sample is a solid go to the section  labled
          "Solids" (II) of this procedure.
        0 If the sample contains both liquid and solid go to
          the section labled "Mixtures of Liquids and Solids"
          (III) of this procedure.

I.  Liquids

     The analyst should determine if more than one liquid
phase is present in the sample.  If more than one phase is
present the sample should be separated into its organic and
aqueous phases respectively.  This separation can be  achieved
by using either gravity or cenrifugation.  The separated
phases should be weighed.  10.0 gm of well mixed sample
should be used.

   A.  Organic Liquids

       1. Summary
          Organic Liquids are injected directly onto  the
          capillary column using either the split or  splitless
          mode.  The liquid may be diluted if necessary to
          facilitate sample handling or to accomodate the
          linear range of the mass spectrometer.

       2. Apparatus and Materials
          a. Sample Vials - 10 dram vials with teflon lined caps
          b. Gas Chromatograph. - Analytical system capable of
             split and splitless injections and all required
             accessories including column supplies, gases, etc.
          c. Column - 30m SE-30, SE-52, SE-54, or equivalent,
             .2 to .25mm internal diameter with a film thickness
             between .15 to .40u.
          d. Mass Spectrometer - Capable of scanning  from 35 to
             450 daltons every 1 second or less.  The mass-
             spectrometer must be able to operate at  70
             volts for electron ionization and must produce
             a recognizable mass spectrum for 50 ng or less
             of DFTPP when the sample is introduced through
             the GC column.  The GC column should be  directly
             interfaced  (i.e. no separator) to the mass
             spectrometer through either an all glass or all
             glass lined system.  If a fused silica capillary
             column is used, the analyst is required  to
             complete the interface by placing the end of

-------
                                 Revision  B   4/15/81   8.27-3


      the column in the ion source.

   e. Computer System - The computer system interfaced
      to the mass spectrometer should be capable of
      continuously acquiring mass spectra for the duration
      of the gas chromatographic program,  (about 1 hr.)
      All data must be stored either within the data
      system or on line mass storage devices such as
      disk or tape.  The system must have software
      available capable of searching GC/MS runs for
      the following:

         1) selected ion chromatograms
         2) total ion chromatograms
         3) reverse and forward search for any compound
            from the EPA/NIH Mass Spectral Data Base.

3. Reagents
   a. Methylene chloride -  Pesticide quality
   b. Ethyl Ether        -  "
   c. Ethylacetate       -  "               "
   d. Methanol           -  "
   e. Standards - Standards can be made up as necessary
      if appropriate reagents are available.  Naphthalene-dg
      or phenanthrene-dio may be used as internal standards.

4. Calibration
   a. The mass spectrometer is calibrated with either
      PFK or FC-43 ovver the scan range. The mass spec-
      trometer should be scaned from 35 to 450 daltons
      in 2 sec or less.  50ng or less of DFTPP should
      be injected in the splitless mode using the
      conditions given in Table 8.27-1.
   b. The DFTPP spectrum obtained from the top of the
      chromatographic peak (backgroud subtracted)
      should meet the criteria listed in Table 8.24-2.

5. Sample Preparation
   a. If the liquid can be convieniently drawn into a
      10 ul syringe, then no sample preparation is
      necessary.  Weigh 1 gm of the liquid into a
      a pre-tared 10 dram vial.  Add the internal
      standard at a level that would give  50 ng on
      column when injected.  (The amount added will
      vary with split ratio)
   b. If it is necessary to dilute the sample, a weighed
      portion of the organic phase should  be transfered
      to an appropriate volumetric flask and diluted
      to volume with one of the solvents listed in
      the reagent section.  The internal standard is
      added at a level that would give 50  ng on column
      when injected prior to dilution.  Record the
      dilution volume.

-------
                                 Revision B  4/15/81  8.27-4
6. Gas Chromatography/Mass spectrometry
   a. Establish the chromatographic conditions given
      in table 8.27-1.
   b. Set the Gas Chromatograph for either split
      or splitless injection depending on estimated
      concentration.  For example,  an organic liquid
      that can be conveniently drawn up in a syringe
      can be analyzed using the split mode.  An oily
      sample that needs to be diluted to 1:100 might
      best be handled using the splitless mode.  If
      using the split mode, record  the split ratio.
      Record both linear and volume column flow.
   c. Inject sample, start the chromatographic program,
      and acquire data.  Record amount of sample
      injected. (1 to 5 ul when using split mode and
      1 to 2 ul when the splitless  mode is employed).
   d. Inject appropriate standards  and acquire data using
      sample conditions as employed in c.

7. Qualitative and Quantitative Determination
   a. A compound will be judged to  have been identified
      if either three or more characteristic ions of
      the compound maximize within  one scan of the
      apex of the peak and the integrated ion areas
      agree with a library or standard mass spectrum
      within + 20%; or, a reverse search yields a numerical
      value equivalent to the criteria stated above.
   b. Samples can be quantitated in two ways.  The first
      is by the method of standard  additions.  This
      method is always acceptable and must be used
      when the actual concentration is needed.  The
      second method is used when order of
      magnitude estimates of concentration are
      needed.  This is done by comparing the Total
      Ion Chromatogram of the compound in the sample
      with a standard.   For example, if 100 ng of
      benzene gives a total of 10,000 integrated area
      counts then a peak corresponding to toluene
      with 25,000 counts would be expected to correspond
      to about 250 ng.   When using  this method the
      analyst should try to use standards which resemble
      the compounds in question as  closely as possible.
      The internal standard is used as a method check.
      For example, if 50 ng of the  internal standard
      normally gives 5000 integrated area counts,
      this condition should be met  in the sample
      +20%
   c. Example Calculation
      5 ul of a 5 mg/ml solution of benzene was injected
      with a split ratio of 100:1 to produce the

-------
                                Revision B  4/1S/81  C.27-5


      chromatogram in figure 8.27-1.   The integrated
      area of the benzene peak from the total ion
      chromatogram was 7840 counts.   10 gm of an
      organic liquid sample was disolved in methylene
      chloride in a volumetric flask  to a final volume
      of 100 ml.  5 ul of this solution was injected
      with the same split ratio to produce the chromatogram
      in figure 8.27-2.  The integrated area for
      benzene in this sample was 4235 counts.   The
      peak for toluene gave an area of 4827 counts.
      The estimated concentration of  benzene and
      toluene in this sample are:

      Benzene Standard

         5 mg/ml = 5 ug/ul

         5 ug/ul x 5 ul = 25 ug injected

         7840 counts/25 ug = 313.6 counts/ug

      Benzene in Sample

         4235 counts/5 ul injected x  1 ug/ 313.6 counts =

         13.5 ug/5 ul

         13.5 ug/5 ul x 1000 ul/ml -

         2700 ug/ml

         2700 ug/ml x 100 ml/10 gm dilution = 27000 ug/gm

         27000 ug/gm =  27 mg/gm

         27 mg/gm x 1 gm/1000 mg = .027 = 2.7%

         The sample is 2.7% benzene

      Toluene in sample

         By an analogus method the sample is calculated to

         be 3.1% toluene.

8.   Report
   a. Report the results of each analysis giving
      the method used to quantify each comound.
      Report the scan number of each  compound.
   b. Example:

-------
                                      Revision  B   4/15/81   8.27-6


Compound          Quantitation         Scan     Amount    Range
                  Method                 #

Benzene           Estimate/Benzene      500        2%      1-10%
Toluene           Estimate/Benzene      622        3%      1-10%

 B.  Aqueous Liquid

     1. Summary
        Aqueous liquids are analyzed by purge and trap and
        extraction methods given in Methods 8.83 and 8.84.
        After the aqueous sample is purged and traped and
        extracted by Methods 8.83 and 8.84 the traped material
        and the extracts (which have been combined) are
        analyzed by capillary column gas chromatography-mass
        spectrometry.

     2. Apparatus and Materials
        See the appropriate sections in Methods 8.83, 8.84, and
        the apparatus and materials section for organic liquids
        in this method

     3. Reagents
        See the appropriate sections in Methods 8.83, 8.84, and
        the reagents section for organic liquids in this method.

     4. Calibration
        a. The mass spectrometer is calibrated with PFK or
           FC-43 over the scan range of interest.  For the
           volatiles scan over the range 20 to 260 daltons,
           and scan over the range 35 to 450 daltons for
           the base/neutrals and acid extractables.  The
           scan rates should be 2 sec. or less.  50 ng or
           less of bromoflurobenzene or DFTPP should be injected
           for the volitiles and extractables respectively.
           Chromatographic conditions are given in Tables
           8.27-2 and 8.27-3.
        b. The specta obtained from the top of the Chromatographic
           peak (background subtracted) should meet the criteia
           listed in Tables 8.24-2 and 8.24-3.

     5. Sample Preparation
        a. Follow the purge and trap and extraction methods
           given in Methods 8.83 and 8.84 of this manual
           for preparation of the sample.
        b. Base/neutral and acid extractable fractions
           may be combined and analyzed in a single GC/MS
           analysis.

     6. Gas Chromatography/Mass Spectrometry
        a. Establish the chromatographic conditions described
           in Tables 8.27-2 or 8.27-3, whichever is appropriate.
        b. Set gas chromatograph in either the split or

-------
                                Revision B  4/15/81  8.27-7
      splitless mode.   If using the split mode record
      the split ratio.  Record both the linear and
      volume column flow.
   c. When analyzing volatiles it may be necessary to
      adjust desorption time or cool the first few
      cm of the column with a flurocarbon spray
      in order to maintain chromatographic resolution.
   d. Inject sample and acquire data/ recording the amount
      injected. Follow the same procedure for any standards.

7. Quantitative and Qualitative Determination
   a. A compound can be qualitativly identified in either
      of two ways.  At least three characteristic ions  of the
      compound must maximize within one scan of the apex
      of the peak and  the integrated ion areas agree with
      a library or standard mass spectrum within jH 20%;
      or, a reverse search yeilds a numerical value
      equivalent to the criteria stated above.
   b. Samples can be quantitated in two ways.   The first
      is by the method of standard additions.   This
      method is always acceptable and should be used
      when the exact concentration is needed.   The
      second method is to be used only for order of
      magnitude estimates of concentartion.   This is
      done by comparing the Total Ion Chromatogram of
      the compound in  the sample with a standard.   For
      example, if 100  ng of benzene gives a total of
      10,000 integrated area counts then a peak corresponding
      to toluene with  25,000 counts would be expected
      to correspond to about 250 ng.   When using this
      method the analyst should try to use standards
      which resemble the compounds in question as
      closely as possible.  The internal standard is used
      as a method check.  For example, if 50 ng of
      the internal standard normally gives 5000 integrated
      area counts, this condition should be met in
      the sample +20%
   c. Example Calculation
      A 10 gm sample contained 3.5 gm of organic liquid
      with a volume of 3.9 ml.   5 ul of the organic
      liquid was injected with a split ratio of 100
      to 1.  The integrated area of benzene gave 3582
      counts.  Benzene in the organic phase is calculated:

          3582 counts/5 ul x 1 ug/313.6 counts =11.4 ug/5 ul

          11.4 ug/5 ul x 1000 ul/ml = 2280 ug/ml

          the density  is 3.5gm/3.9ml « .9 gm/ml

          2280 ug/ml = 2.28mg/ml

          2.28mg/ml x  Igm/lOOOmg x 1 ml/.9gm « .0025 =  .25%

-------
                                     Revision B  4/15/81  8.27-8

           The purge and trap analysis  of the aqueous phase
           was performed on 6.5 gm of liquid.  Benzene gave
           12562 counts.  The benzene in the aqueous phase
           is:

               12562 counts/6.5 gm x 1  ug/313.6 counts =

               40.0 ug/6.5 gm =  6.2 ppm

               This is insignificant compared to .25%

           The total amount of benzene  in the sample is
           calculated:

               .25% x .35 of total = .0875% or 875  ppm
      8. Report
        a. Report the results of each analysis giving
           each compound identified,  the scan number, the
           quantity of the compound,  and the method used
           to calculate that quantity.
        b. Example

Compound          Quantitation         Scan     Amount    Range
                  Method                 #

Benzene           Estimate/Benzene      687      875ppm  100ppm-l%

-------
                                        Revision B  4/15/81  8.27-9

II.  Solids

     Two samples of well mixed solid should be used in this
analysis.  One sample is used for the purge and trap analysis
of volatiles and one for soxhlet extraction analysis.

   A.  Purge and Trap Determination of Volatiles in Solids

       1. Summary
          An appropriate weight of sample (1-10 gin) is diluted
          with 10 ml of organic-free water.   The diluted
          sample is purged for 12 min. with inert gas  at
          room temperature. The gaseous phase is passed
          through a sorbent trap where the organic compounds
          are concentrated.  The contents of the trap  are
          desorbed into the GC/MS by heating and backflushing
          the trap.

       2. Apparatus and Materials
          a. See the apparatus section of Method 8.83  of this
             manual.
          b. Gas Chromatograph - Analytical system capable of
             split and splitless injections and all required
             accessories including column supplies, gases, etc.
          c. Column - 30m SE-30, SE-52, SE-54, or equivalent,
             .2 to ,25mm internal diameter with a film thickness
             between .15 to .40u.
          d. Mass Spectrometer - Capable of scanning from 20 to
             260 daltons every 1 second or less.  The  MS must
             be able to operate at 70 volts for electron
             ionization and must produce a recognizable mass
             spectrum for 50 ng or less of BFB when the sample
             is introduced through the GC column.  The GC column
             should be directly interfaced (i.e. no separator)
             to the mass spectrometer through an all glass
             or all glass lined system.  If a fused silica
             capillary column is used, the analyst is  required
             to complete the interface by directly connecting
             the end of the column to the ion source.
          e. Computer System - The computer system interfaced
             to the mass spectrometer should be capable of
             continuously acquiring mass spectra for the duration
             of the gas chromatographic program, (about 1 hr.)
             All data must be s,tored either within the data
             system or on line mass storage devices such as
             disk or tape.  The system must have software
             available capable of searching GC/MS runs for
             the following:

                1) selected ion chromatograms
                2) total ion chromatograms

-------
                                 Revision B  4/15/81  8.27-10
         3)  reverse and forward search for any compound
            from the EPA/NIH Mass Spectral Data Base

3. Reagents  - Standards as necessary  (See Methods 8.24,
              8.83, and I-A-3e of this Method)

4. Calibration
   a. The mass spectrometer is calibrated with either
      PFK or FC-43 over the scan range.   50ng or less of
      BFB should be injected in the splitless mode
      using  the conditions given in table 8.27-3.
   b. The spectrum obtained from the top of the chro-
      matographic peak (backgroud subtracted) should
      meet the criteria listed in table 8.24-2.

5. Sample Preparation
   a. Weigh  an appropriate sample into a pretared  10 to
      15 ml  Teflon lined,  screw-capped vial.
   b. Dilute the sample with 10 ml distilled water.
      Disperse the sample  into the water.  Transfer
      the total sample to  the purging device using a
      syringe with an 1/8  in. gauge Teflon needle.
      Seal the sample in the purging device.   Add
      the internal standard and purge with 40
      ml/min (He or N2) for 12 min. at room temperature.

6. Gas Chromatography/Mass spectrometry
   a. Establish the chromatographic conditions given
      in table 8.27-1.
   b. Set up the Gas Chromatograph for either split
      or splitless injection.  If using the split
      mode,  record the split ratio, linear and volume
      column flow.
   c. The first few inches of the column should be
      cooled using flurocarbon spray.  Heat the trap
      to 200°C.  Backflush it for 4 min in the
      desorb mode into the gas chromatograph.

7. Qualitative and Quantitative Determination
   a. A compound can be qualitativly identified in either
      of two ways.  At least three characteristic  ions of the
      compound must maximize within one scan of the apex
      of the peak and the  integrated ion areas agree with
      a library or standard mass spectrum within + 20%;
      or, a  reverse search yeilds a value equivalent to
      the criteria stated  above.
   b. Samples can be quantitated in two ways.  The first
      is by  the method of.  standard additions.  This

-------
                           Revision B  4/15/81  8.27-11

method is always acceptable and should be used
when the exact concentration is needed.
The second method is to be used only for order
of magnitude estimates of concentration as
given on page 1 of this method.  This is done
by comparing the Total Ion Chromatogram of the
compound in the sample with a standard.  For
example, if 100 ng of benzene gives a total of
10,000 integrated area counts then a peak corresponding
to toluene with 25,000 counts would be expected
to correspond to about 250 ng.  When using this
method the analyst should try to use standards
which resemble the compounds in question as
closely as possible.  The internal standard is
used as a method check.  For example, if 50 ng
of the internal standard normally gives 5000
integrated area counts this condition should
be met in the sample jf20%.
Example Calculation
5.0 gm of a solid sample was mixed with 10 ml
water and purged and traped by the procedure
specified.  A splitless injection gave 29,043
integrated area counts for toluene.  1 ul of
a standard solution of Toluene 100 ug/ml gave
16,290 integrated counts.

   16290 counts/ 1 ul x 1000 ul/100 ug = 162900 counts/ug

   29043 counts/5 gm x 1 ug/162900 counts = .18 ug/5 gm

   .18 ug/5 gm = .036 ug/gm = .036 ppm

-------
                                Revision  B   4/15/81   8.27-12
8.  Report
  a.  Report the results of each analysis giving
     each compound identified,  the scan number/ the
     quantity of the compound,  and the method used
     to calculate that quantity.
  b.  Example

     The level of toluene in the sample is very low
     and for the purpose of this analysis is reported
     at less than 1 ppm

-------
                                    Revision B  4/15/81  8.27-13

B. Soxhlet Extraction for Solids

   1.  S umma ry
      The sample is mixed with anhydrous sodium sulfate,
      placed in an extraction thimble or between two
      plugs of glass wool and extracted using methylene
      chloride.  The extract is reserved.  The remaining
      contents of the thimble are mixed with distilled
      water and the pH is adjusted to 2 or less.  This
      aqueous mixture is extracted with ethyl ether.
      The two extracts are dried, combined,  and anaylzed
      in one GC/MS analysis.

   2.  Apparatus and Materials
      a. Soxhlet extractor - 40 mm id, with 500 ml round-
         bottom flask.
      b. Kuderna-Danish Apparatus [Kontes K-570000 or equivalent]
         with 3-ball snyder column
      c. Gas Chromatograph - Analytical system capable of
         split and splitless injections and all required
         accessories including column supplies, gases, etc.
      d. Column - 30m SE-30, SE-52,  SE-54, or equivalent,
         .2 to .25mm internal diameter with a film thickness
         between .15 to .40u.
      e. Mass Spectrometer - Capable of scanning from 35 to
         450 daltons every 1 second  or less.  The MS must
         be able to operate at 70 volts for electron
         ionization and must produce a recognizable mass
         spectrum for 50 ng or less  of DFTPP when the sample
         is introduced through the GC column.  The GC column
         should be directly interfaced (i.e. no separator)
         to the mass spectrometer through an all glass
         or all glass lined system.   If a fused silica
         capillary column is used, the analyst is required
         to complete the interface by directly connecting
         the end of the column to the ion source.
      f. Computer System - The computer system interfaced
         to the mass spectrometer should be capable of
         continuously acquiring mass spectra for the duration
         of the gas chromatographic  program, (about 1 hr.)
         All data must be stored within the data system.
         Mass storage devices such as disk or tape are
         accepable.  The system must have software available
         to allow searching GC/MS runs for the following:
            1) selected ion chromatograms
            2) total ion chromatograms
            3) reverse and forward search for any compound
               from the EPA/NIH Mass Spectral Data Base

   3.  Reagents
      a. Methylene chloride - Pesticide grade
      b. Ethyl Ether - Pesticide grade

-------
                                 Revision  B   4/15/81   8.27-14

   c.  Anhydrous Sodium Sulfate,  ACS  grade, purified
      by heating at 400°C for 4  hr.  in a shallow tray.

4. Calibration
   a.  The mass spectrometer is calibrated  with either
      PFK or FC-43 over the scan range.   50ng or less of
      DFTPP should be injected in the splitless mode
      using the conditions given in  table  8.27-1.
   b.  The DFTPP spectrum obtained from the top of  the
      chromatographic peak (backgroud subtracted)
      should meet the criteria listed in table 8.24-2.

5. Sample Preparation
   a.  Blend 10.0 gm of the solid sample with 10.0  gm
      of anhydrous sodium sulfate.   Weigh  this mixture
      to the nearest 0.1 gm.   Place  in either a paper
      (pre-washed with methylene chloride  and dried)
      or glass extraction thimble.
   b.  Place the thimble in the extractor.   (If any
      problems arise when using  the  thimble, i.e.  if
      the sample clogs the thimble,  an alternative
      would be to place a plug of glass wool in the
      extraction chamber, transfer the sample into
      the chamber, then cover the sample with another
      plug of glass wool.)
   c.  Place 250 ml of methylene  chloride into the  500 ml
      roundbottom flask, add a boiling chip  and attach
      the flask to the extractor.  Extract the sample
      for 16 hours.
   d.  After the extraction is complete,  cool the extract;
      rinse extractor flask and  thimble with fresh
      solvent.  Combine the extract  and rinse.
      Dry the extract by passing it  through  a 4 inch
      column of sodium sulfate that  has been washed
      with solvent.  Collect the dried extract
      in a 500 ml Kuderna-Danish (KD) flask  fitted with
      a 10 ml graduated concentartor tube.
      Empty the contents of the  thimble into a pre-weighed
      250 ml Erlinmeyer flask.  Add  100 ml distilled
      water to the flask.
   e.  Adjust the pH to 2 or less with sulfuric acid
      solution.  Extract three times with  fresh 60 ml
      portions of ethyl ether.  Combine the  three
      extracts and dry by passing through  a  4 inch
      column of sodium sulfate.   Rinse column with
      fresh solvent.  The dried  extract is added to
      the KD.
   f.  Evaporate the aqueous solution in the  erlinmeyer
      flask to dryness; cool the flask and weigh the
      residue.  Determine the weight difference between

-------
                                  Revision B 4/15/81   8.27-15

      the residue in the erlinmeyer flask and the
      original sample.
   g. Concentrate the dried extracts in the KD.  A
      level that would  give a final concentration of
      about 1 mg/ml is  generally appropriate for
      GC/MS.
   h. The concentrated  extract should be placed in a
      volumetric flask  and made up to the appropriate
      volume.

6. Gas Chromatography/Mass spectrometry
   a. Establish the chromatographic conditions given
      in table 8.27-1.
   b. Set the Gas Chromatograph for either split
      or splitless injection.  If using the split
      mode, record the  split ratio.  Record both
      liniar and volume column flow.
   c. Inject sample and acquire data.  Record amount
      of sample injected. (2 to 5 ul for split
      and 1 to 2ul for  splitless)
   d. Inject appropriate standards and acquire data as
      in c.

7. Qualitative and Quantitative Determination
   a. A compound can be qualitativly identified in either
      of two ways.  At  least three characteristic ions of the
      compound must maximize within one scan of the apex
      of the peak and the integrated ion areas agree with
      a library or standard mass spectrum within + 20%;
      or, a reverse search yeilds a value equivalent to
      the criteria stated above.
   b. Samples can be quantitated in two ways.  The first
      is by the method  of standard additions.  This
      method is always  acceptable and should be used
      when the exact concentration is needed.  The
      second method is  to be used only for order of
      magnitude estimates of concentartion.  This is
      done by comparing the Total Ion Chromatogram of
      the compound in the sample with a standard.  For
      example, if 100 ng of benzene gives a total of
      10,000 counts then a peak corresponding to toluene
      with 25,000 counts would be expected to correspond
      to about 250 ng.   When using this method the
      analyst should try to use standards which resemble
      the compounds in  question as closely as possible.
      The internal standard is used as a method check.
      For example, if 50 ng of the internal standard
      normally gives 5000 integrated area counts this
      condition should  be met in the sample +20%.
   c. Example Calculation
      10 gm of solid sample was extracted with methylene
      chloride and ethyl ether as in the procedure. The

-------
                                       Revision B 4/15/81   8.27-16

           sample lost about 4 gm during the extraction.   The
           combined extracts were diluted to 500 ml with
           methylene chloride.  5 ul was injected with a
           split ratio of 100 to 1.   Hexachlorobenzene was
           found in the extract with a total of 7,121
           total area counts.

           Dichlorobenzene was used  as a standard

               5 ul x  1 mg/ml x 1 ml/1000 ul = 5 ug

               Total counts for Dichlorobenzene was 3760

               3760 counts/5 ug = 752 counts/ug

           Hexachlorobenzene in sample

               7121 counts/5 ul x 1  ug/752 counts = 9.47  ug/5 ul

               9.47 ug/5 ul x 1000 ul/1 ml x 500 ml = 947000ug

               947000 ug = .947 gm

               .947 gm/10 gm = .0947 = 9.5% hexachlorobenzene
      8. Report
        a. Report the results of each analysis giving
           each compound identified, the scan number, the
           quantity of the compound, and the method used
           to calculate that quantity.
        b. Example

Compound          Quantitation         Scan     Amount    Range
                  Method                 #

Hexachloro        Estimate/dichloro     693      9.5 %    1-10%
benzene               benzene

-------
                                        Revision B  4/15/81  8.27-17

III.   Mixtures of Liquids and Solids
     A 10 to 20 gm sample of well mixed waste is used.   The sample
is divided into its component phases and the procedures oulined
in sections I and II of this Method are employed for analysis.

   A.   Separation Procedure for Liquids and Solids

       1. Summary
          A 10 to 20 gnv sample of the waste is separated into
          its component phases by centrifugation.  The  Liquid
          Phases are either decanted or pipeted for analysis
          using section I and the solid residue is analyzed
          using section II.

       2. Apparatus and Materials
          a. Centrifuge tubes - 10-20 ml pyrex glass or equivalent
             with ground glass stopper.
          b. Centrifuge -  Capable of 2400 RPM

       3. Reagents - Reserved

       4. Calibration - See calibration sections in parts
          I and II of this method

       5. Sample Preparation
          a. Alliquot a 10 to 20 gm sample of well mixed waste
             into a pre weighed cenrifuge tube.  Weigh.
          b. Place tube into centrifuge and spin at 2400 RPM
             for 15 min. or until the solids and liquid phases
             are separated.
          c. Pour off liquid phase and weigh.  Proceed  to section
             I of this method.
          d. Weigh remaining solids and proceed to section II of
             this method.  The purge and trap method for the
             determination of volatiles in solids may be
             omitted since the volatiles are determined in the
             liquid phase of the sample.

   B.   Report

       1. Report the results as a weighted average of the
          liquid phases and solid phase.
       2. Example calculation
          See sections I and II

-------
                                        Revision B  4/15/81  8.27-18
                    Table 8.27-1 (Liquids)

Column:   SE-30, SE-52, SE-54      (30 m)
Linear Flow Rate:   50 cm/sec H2 or 30 cm/sec He
Temperature Program:   Inject at 25°C then 50°C
                      Program 50° to 280° C at 8°/min
                      Hold at 280°C for 15 min.
                 Table 8.27-2  (Extractables)

Column:  SE-30, SE-52, SE-54    (30 m)
Linear Flow Rate:   50 cm/sec H2 or 30 cm/sec He
Temperature Program:   Inject at 50°C hold 2 min.
                      Program to 280°C at 8°C/min
                      Hold at 280°C for 15 min
                  Table 8.27-3  (Volatiles)

Column:  Same as 8.27-2
Linear Flow Rate:  Same as 8.27-2
Temperature Program:   Inject at 25°C (cool head of column with
                      flurocarbon spray) then to 50°C
                      Program 50°C to 200°C at 4°C/mir
                      Hold at 200°C for 10 min

-------
                                                      Revision  B  4/15/81  8.27-19
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-------
                                                              8.49-2
4.  Acids must be Spectrograde.   If metals are found to be




    present the acid they should be diluted 1:1 with distilled




    water and redistilled in a hood.




5.  An Atomic Absorption Spectrophotometer provides the




    simplest and most accurate means  of determining metal




    concentrations in the low ranges  required.  In principle,




    a prepared solution is vaporized  in a flame.   Metal




    atoms in the flame are capable of absorbing light of a




    particular and characteristic wavelength.   When a light




    beam, which emanates from the pure metal in a cathode




    lamp, is passed through a flame,  the absorption is propor-




    tional to the concentration.  Through various detecting




    devices, this absorption may be read directly or be re-




    corded as a peak on a strip  chart recorder.




         Most metals may be determined in an air  plus acetylene




    flame.  However, some metals require more  energy in




    order to dissociate and a nitrous oxide -  acetylene




    flame must be used.  Additionally, when the fuel itself




    absorbs a particular wavelength,  then the  fuel may be




    changed to a non-interfering one.




         The most common type of burner is known  as a "premix"




    in which the spray is mixed  with  air or oxidant.  It may




    be fitted with a conventional head (4 inch single slot),




    a 3 slot "Boling" head for air-acetylene fuel, or a 2




    inch short slot for use with nitrous oxide-acetylene




    fuel.  These various heads influence the burning rate,




    carbon build-up and sensitivity.   The instrument manual

-------
                                                                   8.49-3
    will list the head that has been found to work best for




    a given element.




         A graphite furnace is especially useful for measuring




    low levels.   In this device the sample is evaporated in




    a graphite tube,  charred and vaporized in a confined and




    inert atmosphere.   However, this method is susceptible




    to interference from chlorides and other dissolved solids.




    If the samples smoke, light scattering can occur which




    causes erroneously high results.  A deuterium background




    corrector should  be employed to correct for non-specific




    interference.




         The spectrophotometer chosen should have a wavelength




    range of 190 to 800 nanometers, and use an output device




    with high sensitivity and fast response time.  The instru-




    ment may provide  direct readout or use a 10 millivolt




    strip chart  recorder.  The use of a recorder will furnish




    a permanent  record of the analysis and the operating




    condit ions.




         Single  element hollow cathode lamps are preferred.




    Electrodeless discharge lamps may also be used when




    available.




Venting




    A vent must  be installed 6 to 12 inches above the burner




to remove toxic  fumes and vapors.  The slight vacuum insures




a constant air flow which tends to stabilize the flame.  A




variable speed blower is an advantage in that the air flow




may be adjusted  to prevent disturbance of the flame.

-------
7.  Instrument Operation .




    Procedures vary with the particular model and manufacturers'




    instructions should be followed.  In general, the following




    should be carried out:




    a.  Install the selected cathode lamp.




    b.  Install the proper burner head.




    c.  Set the wavelength dial and align the lamp.




    d.  Set the slit width.




    e.  Turn on the instrument and apply correct current.




    f.  Allow the instrument to warm up.  This time varies




        but is usually around 20 minutes.




    g.  Turn on the air and adjust flow rate.




    h.  Turn on the acetylene, adjust flow rate and ignite




        flame.  Note that it may be necessary to reduce the




        fuel flow if the sample fluid acts as as a fuel.




    i.  Atomize deionized distilled water acidified with 1.5




        ml concentrated nitric acid per liter, and check the




        aspiration rate.  Adjust the rate to between 3 and 5




        ml per minute.  Zero the instrument.




    j.  Atomize a solution containing a known amount of test




        element and adjust the burner up, down or sideways




        to get maximum response.




    k.  When analyses are finished, turn off the acetylene




        first and then the air.




Optimum Concentration Range




    The most accurate results may be obtained in this range

-------
                                                                   8.49-5
and it varies for different elements and for different instru-




ments.  It may be necessary to dilute a sample of higher con-




centration in order to keep it in this range, in which case




the value obtained must be doubled, tripled, etc. accordingly.




     In the case of lower concentrations it may be sufficient




to show that the sample is below the required limit and




therefore non-hazardous.  When the generator wishes to know




the exact level, it may be possible to concentrate a sample




to bring it into the optimum range.




     It is necessary to correct for background absorption




for precise work.  A double beam instrument or dual double




beam system permits a wider range of selectivity and precision




A background corrector is frequently useful to minimize




background absorption.




Calibration




    The concentration of metal in the sample is determined




by comparing its absorbance to that of solutions of known




concentration.  The samples are preserved at a pH of less




than 2 with nitric acid, and calibration is performed with




distilled deionized water acidified in the same way.




Quantification




     When analyzing industrial wastes  or the Toxicant Ex-




traction Procedure extract, where unknown dissolved materials




may interfere with the determination, the Method of Standard




Additions must be used:

-------
                                                                 8.49-6
Method  of  Standard Additions


     In  this  method, equal volumes  of  sample are added


to a deionized  distilled water blank and  to three stan-


dards containing different known  amounts  of the test


element.   The final volume of the blank and of the stan-


dards must  be the same so that the  interfering substance


is present  in the same amount.  The absorbance of each


solution is determined and then plotted on  the vertical


axis of a  graph  with the concentrations of  the standard


plotted on  the  horizontal axis.   When  the resulting line


is extrapolated  back to zero absorbance,  the point of


interception  of  the abscissa is the concentration of the


unknown.  The abscissa on the left  of  the ordinate is


scaled the  same  as on right side, but  in  the opposite


direction from  the ordinate.   An  example  of a plot so


obtained is shown below:
                                                    Concentration
  I Cone, of
  Sample
Addn 0
No Addn
Addn I
Addn of 50%
of Expected
Amount
Addn 2     Addn 3
Addn of 100% Addn of 150%
of Expected  of Expected
Amount     Amount
                       Figure 8.49-1
            PLOT OF METHOD OF STANDARD ADDITIONS

-------
                                                                    8.49-7
Note;  For this method to be valid, the plot must be linear.




The slope of this line should not differ by more than 20%




from the slope of the standard solutions.  The effect of the




assumed interference must not change as the proportion of




sample to standard changes.




Solids, Sludges and Slurries




     Solids, sludges and slurries may be analyzed by these




methods by weighing out suitable portions and digesting as




described for each metal.  The material is then filtered




through a 0.45 micron filter while washing down the sides of




the beaker and rinsing the filter with distilled deionized




water.  The filtrate is then made up to a suitable volume




and analyzed in the ususal manner.  Results can be related




back to the original sample weight and reported as mg/kg.




Conclusion




     The details of the following approved methods are examples




of acceptable techniques.  Dilutions and concentrations may




have to be varied to suit the instrument being used.  It is




important not to overwhelm the instrument with very high




concentrations above the optimum recommended range.  Contami-




nation can result which is difficult to remove.  At the same




time, many dilutions introduce error which can be avoided by




some knowledge of the waste beforehand.  If nothing is known,




caution is advised.




     For additional information the applicable sections of




"Methods for Chemical Analysis of Water and Wastes", EPA




600/4-79-020 (Appendix II of this manual) may be consulted.

-------
                                                                   8.50-1
                          Method 8.50




                            ANTIMONY






Scope and Application




     The following atomic absorption procedures are approved




methods for determining the concentration of antimony in a




waste or Extraction Procedure Extract




Summary of Method




     A sample is digested using nitric acid and the concentra-




tion of antimony measured using either a flame or graphite




furnace equipped atomic absorption spectrometer.  The flame




method is most accurate when employed with solutions containing




1-40 mg/liter antimony while the graphite furnace procedure




is best suited for solutions containing 20 - 300 ug/liter.




Apparatus




     Atomic absorption spectrometer equipped with either a




graphite furnace or flame burner head as described in




Section 8.49.




Reagents




1.  When using the flame procedure air and acetylene are




    required.  Air should be cleaned and dried through a




    suitable filter to remove oil, water, and other foreign




    substances.  The source may be a compressor or a cylinder




    of industrial grade compressed air.  High purity acetylene




    should be used.  Acetone which is always present in




    acetylene cylinders, can be prevented from entering and




    damaging the burner head by replacing a cylinder when




    its pressure has fallen to 7 kg/era-^ (100 psig) acetylene.

-------
                                                                    3.50-2
2.  Nitric Acid, J.T.  Baker Ultrex Grade or equivalent.




3.  Antimony potassuim tartrate,  analytical reagent grade.




4.  Hydrochloric Acid  Solution,  J.T.  Baker Ultrex Grade or




    equivalent diluted 1:1 with  distilled deionized water.




Procedure




Standard Solutions




1.  Prepare Antimony Standard Stock Solution by dissolving




    2.7426 g antimony  potassium  tartrate, analytical reagent




    grade, in distilled deionized water containing 1.5 ml




    HN03/liter and bringing to volume in a 1 liter volumetric




    flask (1 ml - 1 mg Sb).




2.  Prepare working standards from stock solution.  If it is




    desired to work in the optimum concentration range, using




    the flame technique,  the following is suggested:




    a.  Transfer 0, 0.1,  1.0, 2.0, 3.0, and 4.0 ml of stock




        solution to separate 100  ml volumetric flasks.  Bring




        t*o volume with distilled  deionized water containing




        2 ml HN03/liter.   The concentrations of these working




        standards are  0,  1, 10,  20, 30 and 40 mg Sb/liter.




3.  When using the graphite furnace procedure working standards




    should be prepared to cover  the range 20 to 300 ug Sb/liter




    by preparing dilutions of the above working standards.




Sample Preparation




1.  Transfer 100 ml of well-mixed sample to a 250 ml beaker.




    Add 3 ml cone. HN03.   Place  the beaker on a hot plate




    and evaporate to near dryness, cautiously, so that the




    sample does not boil.  Cool,  and  add another 3 ml cone.

-------
                                                                   8.50-3
    HN03.  Cover the beaker with a watch glass and return




    to the hot plate.  Heat so as to produce a gentle




    refluxing.  Continue adding 3 ml portions of HNOg until




    the  sample is light in color and no longer changes in




    color.  Evaporate to near dryness and cool.  Add 1 ml




    of 1:1 HC1 and warm the beaker in order to dissolve any




    precipitates.  Cool the beaker.  Transfer to a 100 ml




    volumetric flask and bring to volume using distilled




    deionized water containing 2 ml HN03/liter.  Note that




    hydrochloric acid is used to aid in dissolving of antimony




    residues .




2.  If particulates such as silicate remain in the sample, it




    must be centrifuged and the supernatant sampled.




Standard Addition




a.  Take the 50, 75, and 100 ug standards and pipet 5 ml from




    each into separate 10 ml volumetric flasks.  Add to each




    2 ml of the prepared sample.  Bring to volume with




    distilled deionized water.




b.  Add 2 ml of prepared sample to a 10 ml volumetric flask.



    Bring to volume with distilled deionized water.  This is




    the blank.




Note;  The absorbance from the blank will be 1/5 that




produced by the prepared sample.  The absorbance from the




spiked standards will be 1/2 that produced by the standard




plus the contribution from 1/5 of the prepared sample.




Keeping these in mind the correct dilutions to produce  optimum




absorbance can be judged.

-------
                                                                    8.50-4
Instrument Operation

     Wavelength:   217.6 nanometers
          Note:   The presence of lead in the waste may
          interfere since lead absorbs at this
          wavelength.  In this case, use the 231.1
          nanometer antimony line.

     Optimum Concentration Range:   1-40 ing/liter

     Lower Detectable limit: 0.2 mg/liter

     Fuel:  Acetylene

     Oxidant:  Air

     Type of Flame: Lean

     A general outline for instrument operation is given in

Section 8.49.  Follow the manufacturer's instructions for

the Spectrophotometer being used.

                   Graphite Furnace Method

Wavelength:  217.6 nanometers

Optimum Concentration Range:  20-300 ug/liter

Lower Detection Limit:  3 ug/liter

Purge gas:  Argon or nitrogen

Drying time and temperature:  30 sec at 215° C

Ashing time and temperature:  30 sec at 800° C

Atomizing time and temperature:   10 sec at 2700° C

     The conditions listed above are based on a 20 ul injection;

continuous flow purge gas and non-pyrolytic graphite on a

Perkin Elmer model HGA 2100 furnace.  Other equipment will

have different requirements.  Follow the manufacturer's manual.

Note:  If the chloride presents  a matrix problem, add an excess

of 5 mg ammonium nitrate to the  furnace and ash using a ramp

-------
                                                                    8.50-5
accessory; or with incremental steps, until ashing temperature




is reached.




Quantification




     The absorbances of spiked samples and blank vs. the




concentrations are plotted according to the Method of Standard




Additions as described in Section 8.49.  The extrapolated




value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line, a non-




linear interference is present.  This can sometimes be over-




come by dilution, or addition of other reagents if there is




some knowledge about the waste.

-------
                                                                   8.51-1
                         Method 8.51




                           ARSENIC






Scope and Application




     The following atomic absorption procedures are approved




for determining the concentration of arsenic in a waste or




Extraction Procedure Extract.  Both methods are generally




acceptable for RCRA type samples.  However, the graphite




furnace method is sensitive to the presence of chlorides and




dissolved solids in the sample, while the hydride method requires




greater preparation and is sensitive to high concentrations




of chromuim, copper, mercury, silver, cobalt, and molybdenum.




Summary of Methods




     In the furnace method the sample is digested using nitric




acid and hydrogen peroxide.  The method is most accurate for




solutions containing 5 - 100 ug Arsenic/liter.



     In the gaseous hydride method the sample is digested




using nitric and sulfuric acids.  The arsenic is then reduced




to the trivalent form with stannous chloride, and converted




to arsine, AsH3, using zinc metal.  The hydride is swept into




an argon entrained hydrogen flame for analysis.  It is most




accurate when employed for solutions containing 2 - 20 ug




As/liter.  However, mercury, silver, cobalt and molybdenum




can interfere in the analysis.




     Preoxidation (digestion) is required in both methods in




order to convert organic forms of arsenic to the inorganic




form, and to remove organic interferences.

-------
                                                                   8.51^2





Precaution




     Severe poisoning can result from ingestion of as little




as 100 mg Arsenic.  Chronic effects can appear with constant




Intake of lower levels.  Exercise care in the handling and




cleanup of the materials and work area.






                   Graphite Furnace Method






Apparatus




1.  Atomic absorbtion spectrometer equipped with a non-pyrolytic



    graphite furnace.




Reagents




1.  Standard Stock Solution




    Stock solution may be purchased, or prepared as follows:




    a.  Dissolve 4g NaOH in 100 ml distilled deionized water.




        Dissolve 1.3203 g of analytical reagent grade arsenic




        trioxide (AS203) in the solution.




    b.  Acidify this solution with 20 ml concentrated HN03.




    c.  Transfer to a 1 liter volumetric flask with careful




        rinsing, and bring to volume with distilled deionized




        water.  The concentration of this solution is 1000




        mg arsenic/liter (1 ml^l mg As).



2.  Nickel Nitrate Solution, 5%




    Dissolve 24.780 g of ACS Reagent Grade Ni(N03>2•6H20




    in distilled deionized water and make up to 100 ml.




3.  Nickel Nitrate Solution, 1%




    Dilute 20 ml of the 5% solution to 100 ml with distilled




    deionized water.

-------
                                                                   8.51-3
4.  30% Hydrogen Peroxide,  ACS Reagent Grade




5.  Sodium Hydroxide,  ACS Reagent Grade




6.  Concentrated Nitric Acid,  J.T. Baker Chemical Co. Ultrex




    Grade or equivalent.




Procedure




1.  Transfer 100 gm (or in the case of EP Extract analysis 100




    ml) of well mixed  sample to a 250 ml beaker and add 2 ml




    of 30% H202 and 1  ml of concentrated HN03.   Heat on




    a hot plate for 1  hour at  95°C or until the volume is




    less than 50 ml.   It may be necessary to repeat this




    operation to digest all of the material present.




2.  Cool, transfer to  50 ml volumetric flask and bring to




    volume with distilled deionized water.




3.  If particulate matter remains, after oxidation, it




    must be removed by centrifugation and only the supernatant




    used.




4.  Pipet 25 ml of this solution into a 50 ml volumetric




    flask.  Add 5 ml of 1% nickel nitrate solution and bring




    to 50 ml with distilled deionized water.  The sample is




    ready for injection.




5.  Prepare standards  from stock solution.  The following




    provides standards covering the optimium working range:




6.  Pipet 1 ml stock solution into a 1 liter volumetric




    flask.  Bring to volume with distilled deionized water




    containing 1.5 ml  cone. HN03 per liter.  The concentration




    of this solution is 1 mg As/liter (1 ml=l ug As).




7.  Prepare 6 working  standards by transferring 0, 1.0.

-------
    2.5, 5, 7.5, and 10 ml from (a) into 100 ml volumetric




    flasks.  Add to each flask 1 ml concentrated HN03, 2




    ml 30% H202 and 2 ml 5% nickel nitrate solution, bring




    to volume with distilled deionized water.  The concen-




    trations of these working standards are 0, 25, 50, 75,




    and 100 ug As/liter.  They are ready for injection.




8.  Take the 50, 75, and 100 ug/liter standards and pipet 5 ml




    from each into separate 10 ml volumetric flasks.  Add to




    each 2 ml of the prepared sample.  Add 0.3 ml of 1% of




    nickel nitrate solution, and 0.3 ml H202 solution.




    Bring to volume with distilled deionized water.




9.  Add 2 ml of prepared sample to a 10 ml volumetric




    flask.  Add 0.8 ml nickel nitrate solution and 0.8 ml




    H202 solution.  Bring to volume with distilled deionized




    water.  This is the blank.




Note;   The absorbance from the blank, will be 1/5 that




produced by the prepared sample.  The absorbance from the




spiked standards will be 1/2 that produced by the standards




plus the contribution from 1/5 of the prepared sample.




Keeping these in mind the correct dilutions to produce optiraium




absorbance can be judged.




Instrument Operation:




     Wavelength:  193.7 nanometer




     Optimum Concentration Range:   5-100 ug/liter




     Lower Detection Limit:  1 ug/liter




     Drying time and temperature:   30 sec at 125°C




     Ashing time and temperature:   30 sec at 1100°C




     Atomizing time and temperature:   10 sec at 2700°C

-------
                                                                   8.51-5
     Purge gas:   Argon




     These conditions are based on a 20 ul injection; con-




tinuous flow purge gas and non-pyrolytic graphite on a Perkln




Elmer Model HGA 2100 furnace.   Other equipment will have




different operating requirements.   For specific information,




the manufacturer of the instrument should be consulted.




Quantification




     The absorbances of spiked samples and blank vs. the con-




centrations are plotted according  to the Method of Standard




Additions as described in Section  8.49.  The extrapolated




value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line a non-linear




interference is present.  This can sometimes be overcome by




dilution, or addition of other reagents if there is some




knowledge about the waste.






                    Gaseous Hydride Method




Reagents




1.  Potassium iodide solution:  Dissolve 20 g KI in 100 ml




    deionized distilled water.




2.  Stannous chloride solution:  Dissolve 100 g SnCl2 in




    100 ml cone HC1.




3.  Zinc slurry:  Add 50 g zinc metal dust (200 mesh) to 100




    ml deionized distilled water.




4.  Diluent:  Add 100 ml 18N H2S04 and 400 ml concentrated




    HC1 to 400 ml deionized distilled water in a 1-liter




    volumetric flask and bring to  volume with deionized




    distilled water.

-------
                                                                   8.51-6
5.  Arsenic Solutions:




    a.  Stock arsenic solution, (1000 mg/liter):




        Dissolve 1.3203 g arsenic trioxide, AS203, in 100 ml




        distilled water containing 4 g NaOH.  Acidify with




        20 ml concentrated HN03 and dilute to 1000 ml with




        deionized distilled water (1 ml = 1 mg As).




    b.  Intermediate arsenic solution:  Pipet 1 ml stock




        arsenic solution into a 100-ml volumetric flask and




        bring to volume with deionized distilled water con-




        taining 1.5 ml concentrated HN03/1 ("1 ml = 10 "8 As).



    c.  Standard arsenic solution:  Pipet 10 ml inter-




        mediate arsenic solution into a 100-ml volumetric




        flask and bring to volume with deionized distilled




        water containing 1.5 ml concentrated HN03/1 (1 ml »




        1 ug (As).




6.  Concentrated nitric acid, J.T. Baker Chemical Co. Ultrex




    grade or equivalent.




7.  Concentrated sulfuric acid, J.T. Baker Chemical Co. Ultrex




    grade or equivalent.




Apparatus




1.  Atomic Absorption Spectrophotometer with Boling burner.




2.  Flow meter, capable of measuring 1 liter/minute,  such




    as that used for auxiliary argon.1




3.  Medicine dropper, capable of delivering 1.5 ml, fitted




    into a size "0" rubber stopper.




4.  Reaction flask, a pear-shaped vessel with side arm and




    50 ml capacity, both arms having 14/20 joint.1




5.  Special gas inlet-outlet tube, constructed from a micro
^Gilmont No. 12 or equivalent

-------
                                                                    8.51-7
    cold finger condenser^ by cutting off  the  portion  below


    the 14/20 ground glass joint.


6.  Magnetic stirrer, strong enough  to homogenize  the  zinc


    slurry.


7.  Drying tube, 10 cm polyethylene  tube filled  with  glass


    wool to keep particulate matter  out of  the burner.
Apparatus Set-Up
                       Argon
                    Flow
          JM-3325
 Medicine
Dropper in
 Size "0"
 Rubber
 Stopper
                                      (Auxiliary Air)

                                         Argon
                                      - (Nebulizer
                                          Air)
                          • JM-5835
1.  Assemble the apparatus as  shown  above.


2.  Connect the outlet of the  reaction  vessel  to the auxiliary


    oxidant input of the burner with tygon  tubing.


3.  Connect the inlet of the reaction vessel  to the outlet


    side of the auxiliary oxidant  (Argon  supply) control


    valve of the instrument.


Procedure


1.  To a 50 gm sample (or in the case of  analysis of EP extracts


    50 ml) of the material to  be analyzed in  a 100  ml beaker


    add 10 ml concentrated HN03 and  12  ml 18  N H2S04.


    Evaporate the sample in the hood on an  electric hot
^Scientific Glass JM-5835  or  equivalent.

2Scientific Glass JM-3325  or  equivalent.

-------
    plate until white 803 fumes are observed (a volume of




    about 20 ml).  Do not let the sample char.  If charring




    occurs, immediately turn off the heat, cool, and add an




    additional 3 ml of HNC>3 .  Continue to add additional HN03




    in order to maintain an excess (as evidenced by the forma-




    tion of brown fumes).  Do not let the solution darken




    because arsenic may be reduced and lost.  When the sample




    remains colorless or straw yellow during evolution of




    SOg fumes the digestion is complete.  Cool the sample,




    add about 25 ml distilled deionized water and again




    evaporate until 803 fumes are produced in order to




    expel oxides of nitrogen.  Cool.  Transfer the digested




    sample to a 100 ml volumetric flask.  Add 40 ml of concen-




    trated HC1 and bring to a volume with distilled deionized




    water.




2.  Prepare working standards from the standard Arsenic




    solution under Reagents (5c).  Transfer 0, 0.5, 1.0,  1.5,




    2.0, and 2.5 ml standard to 100 ml volumetric flasks and




    bring to volume with diluent.  These concentrations will be




    0, 5, 10, 15, 20 and 25 ug As/liter.




3.  Take the 15, 20, and 25 rag/liter standards and transfer




    quantitatively 25 ml from each into separate 50 ml




    volumetric flasks.  Add to each 10 ml of the prepared




    sample.  Bring to volume with distilled deionized




    water containing 1.5 ml HN03/liter.




4.  Add 10 ml of prepared sample to a 50 ml volumetric




    flask.  Bring to volume with distilled deionized water

-------
                                                                   8.51-9
    containing 1.5 ml HN03 per liter.  This is the blank.


Note;   The absorbance from the blank, will be 1/5 that


produced by the prepared sample.  The absorbance from the


spiked standards will be 1/2 that produced by the standards


plus the contribution from 1/5 of the prepared sample.


Keeping these in mind the correct dilutions to produce optimum


absorbance can be judged.


5.  Transfer a 25-ml portion of the digested sample or


    standard to the reaction vesse-1, and add 1 ml potassium


    iodide solution.  Add 0.5 ml SnCl2 solution.  Allow at


    least 10 min for the metal to be reduced to its lowest


    oxidation state.  Attach the reaction vessel to the


    special gas inlet-outlet glassware.  Fill the medicine


    dropper with 1.50 ml zinc slurry that has been kept in


    suspension with the magnetic stirrer.  Firmly insert the


    stopper containing the medicine dropper into the side
                                   »

    neck of the reaction vessel.  Squeeze the bulb to introduce


    the zinc slurry into the sample or standard solution.  The


    metal hydride will produce a peak almost immediately.  After


    the recorder pen begins to return to the base line, the


    reaction vessel can be removed.  Caution: Arsine is very


    toxic.  Caution must be taken to avoid inhaling arsine gas.


Instrument Operation


     Fuel:  Argon-hydrogen flame


     Wavelength: 193.7 nanometer


     Optimium Concentration Range:  2-20 ug As/liter


     Lower Detection Limit: 2 ug/liter

-------
                                                                   8.51-10
     1. Turn on the Argon and adjust the flow rate to about



8 liters/minute, with an auxiliary Argon flow of 1 liter/minute




     2. Turn on the hydrogen, adjust flow rate to about 7




liters/minute and ignite.  The flame is colorless.  The hand




may be passed 1 ft above the burner to detect heat, in order




to insure ignition.




     Follow the instructions given with the Atomic Absorption




Spectrophotometer.




Quantification




     The absorbances of spiked samples and blank vs. the con-



centrations are plotted according to the Method of Standard




Additions as described in Section 8.49.  The extrapolated




value will be 1/10 the concentration of the original sample.




     If the plot does not result in a straight line a non-




linear interference is present.   This can sometimes be overcome




by dilution, or addition of other reagents if there is some




knowledge about the waste.

-------
                                                                    8.52-1
                         Method 8.52




                            BARIUM






Scope and Application




     The following atomic absorption procedures are approved




methods for determining the concentration of Barium in a waste




or an Extraction Procedure Extract.




Summary of Method




     The sample is digested using nitric and/or hydrochloric




acids and the concentration of Barium measured using either a




flame or graphite furnace equipped atomic absorption spectro-




photometer.  The flame method is most accurate when employed




with solutions containing 1-20 mg Ba/liter while the graphite




furnace procedure is best suited for solutions containing 10-




200 ug Ba/liter.




Precaution




     Barium affects the heart muscle.  A dose of 550 to 600




mg is considered fatal to man.  Afflictions resulting from




ingestion, inhalation or absorption involve the heart, blood




vessels and nerves.




Interferences




     If a nitrous oxide-acetylene flame is used with Direct




Aspiration chemical interferences are virtually eliminated.




In this method Potassium (1000 mg/1) is added to prevent




ionlzation of barium in this flame.  If the air-acetylene




flame must be used then the presence of phosphate, silicon




and aluminum will lower the barium absorbance.  This may be




overcome by addition of lanthanum.

-------
                                                                   8.52-2
     The graphite furnace method Is sensitive to the presence




of chlorides and dissolved solids.






                  Direct Aspiration Method






Reagents




1.  Air, cleaned and dried through a suitable filter to remove




    oil, water, and other foreign substances.  The source may




    be a compressor or a cylinder of industrial grade compressed




    air.




2.  Acetylene, should be of high purity.  Acetone, which is




    always present in acetylene cylinders, can be prevented




    from entering and damaging the burner head by replacing




    the cylinder when its pressure has fallen to 100 psig.




3.  Deionized distilled water: Use deionized distilled water




    for the preparation of all reagents and calibration




    standards, and as dilution water.




4.  Hydrochloric acid, HC1, concentrated, Ultrex grade.




5.  Nitric acid, HN03, concentrated, Ultrex grade.




6.  Nitrous oxide, commercially available cylinders.




7.  Potassium Chloride solution: Dissolve 95 g KC1 in



    distilled deionized water and bring to volume in a 1




    liter volumetric flask.




8.  Lanthanum Chloride solution if needed.  Dissolve 25 g,




    reagent grade, La203 slowly in 250 ml concentrated.




    HC1.  (Reaction is violent.) Dilute to 500 ml with distilled




    deionized water.



9.  Barium Standard Stock Solution

-------
                                                                   8.52-3
    1000 mg/liter solution may be purchased or prepared as




    follows: Dissolve 1.7787 g barium chloride dihydrate,




    (BaCl2 • 2H20), analytical,  reagent grade,  in about




    200 ml distilled deionized water.  Add 1.5 ml cone.




    HN03«  Add to 1 liter volumetric flask and bring to




    volume.   1 ml » 1 mg Ba.




Apparatus




1.  Atomic Absorption Spectrophotometer with nitrous oxide




    burner head with 2" slot.   Note: A razor blade is required




    to dislodge, about every 20 minutes, the carbon crust




    that forms along the slot  surface.




2.  T-junction valve for rapidly changing from nitrous oxide




    to air,  so the flame can be turned on or off with air as




    oxidant  to prevent flashbacks.




Procedure




1.  Sample preparation




    a.  Transfer 100 ml of sample to a 250 ml beaker and add




        3 ml concentrated  HN03.  Place it on a hot plate and




        evaporate to near dryness, slowly, so that the sample




        does not boil.  Cool the beaker and add another 3 ml




        HN03.   Cover with a watch glass and return to the




        hot  plate.  Continue heating gently,  and add acid as




        necessary until the material is light in color.




        Evaporate to near dryness and cool.  Add 2 ml of 1:1




        HC1  and warm the beaker to dissolve any precipitate.




        Wash down the beaker and watch glass with distilled

-------
                                                                  8.52-^
        deionized water and transfer quantitatively to a 100




        ml volumetric flask, add 2 ml Potassium Chloride




        solution and bring to volume with distilled deionized



        water containing 1.5 ml HN03/liter.




   Notet If air-acetylene is being used add  4.7 ml lanthamum




   chloride solution before bringing to volume.




   b.  If insoluble silicates or other material is present




       the sample must be filtered or centrifuged and the




       supernatant sampled.




2.   Prepare working standards from the Standard Stock Solution.




     If it is desired to bracket the optimum concentration




     range the following is suggested:




     a.  Transfer 0, 0.1, 0.5, 1.0, 1.5, and 2 ml of




         Standard Stock Solution to 100 ml volumetric




         flasks.  Add 2 ml potassium chloride solution.




         If lanthanum chloride was added to  the sample,  4.7




         ml must be added to the standards.   Bring to volume




         with distilled deionized water containing 1.5 ml




         concentrated HN(>3/liter.  The concentrations of these




         standards will be 0, 1, 5, 10, 15 and 20 mg Ba/liter.




Standard Addition




1.   a.  Take the 5, 10, and 15 mg standards and pipet 5 ml




         from each into separate 10 ml volumetric flasks.  Add to




         each 2 ml of the prepared sample and 0.06 ml KC1




         solution.  Bring to volume with distilled deionized




         water containing 1.5 ml HN03/liter.

-------
                                                                  8.52-5
    b.   Add 2 ml of prepared sample to a 10 ml volumetric




        flask.  Add 0.16 ml KC1 solution and bring to




        volume with distilled deionized water containing




        1.5 ml HN03 per liter.   This is the blank.




    Note;   The graph peak from the blank will be 1/5




that produced by the prepared sample.   The peaks from the




spiked  standards will be 1/2 that produced by the standards




plus the contribution from 1/5 of the  prepared sample.




Keeping these in mind the correct dilutions to produce optimum




absorbance can be judged.




Instrument Operation




    Wavelength: 553.6 nanometers




    Fuel:  acetylene




    Oxidant: Nitrous Oxide




    Type of flame: Fuel rich




    Optimum Concentration Range: 1-20  mg/liter Lower




    Detection Limit: 0.1 mg/liter






Follow  the instructions given with the Atomic Absorption




Spectrophotometer.  The following is included as a guide:




    a.   Install a nitrous oxide burner head.




    b.   Turn on the acetylene (without igniting the




        flame), and adjust the flow rate to the value specified




        by the manufacturer for a nitrous oxide-acetylene flame.




    c.   Turn off the acetylene.




    d.   With both air and nitrous oxide supplies turned on,




        set the T junction valve to nitrous oxide and adjust

-------
                                                                   3.52-6
        the flow rate according to the specifications of the




        manufacturer.




    e.  Turn the switching valve to the air position and




        verify that the flow rate is the same.




    f.  Turn the acetylene on and ignite to a bright yellow




        flame.




    g.  With a rapid motion, turn the switching valve to




        nitrous oxide.  The flame should become rose-red; if




        it does not, adjust fuel flow to obtain a red cone in



        flame.




    h.  Atomize deionized distilled water containing 1.5 ml




        cone. HN03/1 and check the aspiration rate.  Adjust




        if necessary to a rate between 3 and 5 ml/min.




    i.  Atomize a 1-mg/l standard of the metal and adjust the




        burner (both sideways and vertically) in the light



        path until maximum response is obtained.




    j.  The instrument is now ready to run standards and




        samples•




    k.  To extinguish the flame, turn the switching valve




        from nitrous oxide to air, and turn off the acetylene.




        This procedure eliminates the danger of flashback




        that may occur on direct ignition or shutdown of




        nitrous oxide and acetylene.




Quantification




     The absorbance of spiked samples and blank vs. concentrations




are plotted according to the Method of Standard Additions




defined in Section 8.49.  The extrapolated value will be 1/5

-------
                                                                   8.52-7
the concentration of the original sample.   If the plot does




not result in a straight line a non-linear interference is




present.  This can sometimes be overcome by dilution, or




addition of other reagents if there is some knowledge about




the waste.




                      Graphite Furnace




Reagents




1.  Barium Standard Stock Solution 1000 mg/liter solution may




    be purchased or prepared as follows: Dissolve 1.7787 g




    barium chloride dihydrate, BaCl2»2H20 analytical reagent




    grade, in about 200 ml distilled deionized water.  Add




    1.5 ml concentrated HN03 and bring to volume in a 1 liter




    volumetric flask.  1 ml = 1 mg Ba.




2.  Concentrated Nitric Acid




Procedure




Sample Preparation




(Note: All chloride and hydrochloric acid is avoided.)




1.  a.  Transfer 100 ml of sample to a 250 ml beaker and




        add 3 ml concentrated HN03.  Place it on a hot plate and



        evaporate to near dryness, slowly, so that the sample




        does not boil.  Cool the beaker and add another 3 ml




        HN03.  Cover with a watch glass and return to the hot




        plate.  Continue heating gently, and add acid as




        necessary until the material is light in color.




        Evaporate to near dryness and cool.  Add a small quantity




        of 1:1 HN03 and warm the beaker to dissolve any




        precipitate.

-------
                                                                  8.52-8
            Wash down the beaker and watch glass with distilled




        deionized water and transfer quantitatively to a 100




        ml volumetric flask.  Bring to volume with distilled



        deionized water containing 1.5 ml HN03/liter.




    b.  If insoluble silicates or other material is present




        the sample must be filtered or centrifuged and the




        supernatant sampled.




2.  a.  Prepare working standards from the Standard Stock Solution.




        If it is desired to bracket the optimum concentration




        range the following is suggested:




    b.  Transfer 1 ml stock solution to a 1 liter volumetric




        flask.  Bring to volume with distilled deionized




        water acidified with 1.5 ml cone. HN03/liter.




        Concentration:  1000 ug Ba/liter.




    c.  Transfer 0, 5,  10, 15, and 20 ml from a) to separate




        100 ml volumetric flasks and bring to volume with




        distilled deionized water acidified with 1.5 ml concentrated




        HN03/liter.  The concentrations of these working



        standards will  be 0, 50, 100, 150, and 200 ug Ba/liter.




Standard Addition




1.  a.  Take the 100, 150, and 200 ug standards and pipet 5




        ml from each into separate 10 ml volumetric flasks.




        Add to each 2 ml of the prepared sample.  Bring to




        volume with distilled deionized water containing 1.5




        ml HN03/liter.




    b.  Add 2 ml of prepared sample to a 10 ml volumetric

-------
                                                                   8.52-9
        flask.   Bring to volume with distilled deionlzed




        water containing 1.5 ml HNC>3 per liter.  This is




        the blank.




     Note;  The absorbance of the blank will be 1/5 that




produced by the prepared sample.  The absorbance of the




spiked standards will be 1/2 that produced by the standards




plus the contribution from 1/5 of the prepared sample.




Keeping these in mind the correct dilutions to produce optimum




absorbance can be judged.




Instrument Operation




     Wavelength: 553.6 nanometers




     Optimum Concentration range: 10 - 200 ug/liter Lower




     Detection limit: 2 ug/liter




     Drying time and temperature: 30 seconds at 125°C




     Ashing time and temperature: 30 seconds at 1200°C




     Atomizing time and temperature: 10 seconds at 2800°C




     Purge gas: Argon.  Do not use nitrogen.




These conditions are based on a 20 ul injection, continuous



flow purge gas and non-pyrolytic graphite on a Perkin Elmer




model HGA 2100 furnace.  Other equipment will have different




requirements.  Follow the manufacturer's manual.




Quantification




     The absorbance of spiked samples and blank vs. the




concentrations are plotted according to the Method of Standard




Additions as defined in Section 8.49.  The extrapolated




value will be the concentration of the original sample.




     If the plot does not result in a straight line a non-

-------
                                                                  8.52-10
linear interference is present.  This can sometimes  be  overcome




by dilution, or addition of other reagents if  there  is  some




knowledge about the waste.

-------
                                                                   S.53-1
                          Method 8.53




                            CADMIUM






Scope and Application




     The following procedures are approved methods for




determining the concentration of Cadmium in a waste or Extraction




Procedure Extract.




Precaution




     Cadmium is highly toxic.  Minute quantities are suspected




of causing adverse changes in human kidneys.




     Cadmium is particularly susceptible to contamination of




the work area.  Special care should be taken in the handling




of the material.




Comments




    Two Atomic Absorption methods are described.




1.  Direct Aspiration




    This method is suitable for higher concentrations (0.05-2




    ug/liter optimum).



2.  Graphite Furnace



    This method is suitable for lower levels (0.5-10 ug/liter




    optimum).




                    Direct Aspiration




Reagents




1.  Air free of oil, water, and other foreign substances.  The




    source may be purified air from a compressor or a cylinder




    of industrial grade compressed air.

-------
                                                                    S.53-2
2.  Acetylene, standard commercial grade.  Acetone, which is



    always present in acetylene cylinders, can be prevented




    from entering and damaging the burner head by replacing




    a cylinder when its pressure has fallen to 7 kg/cm^




    (100 psig) acetylene.




3.  Nitric Acid, concentrated, ACS.




A.  Cadmium Standard Stock Solution (1000 mg/liter):




    Carefully weigh 3.1368 g Cadmium Sulfate Octahydrate




    (Cd SO^.S H20), analytical reagent grade, and dissolve




    in distilled delonized water containing 1.5 ml HN03/liter.




    Transfer quantitatively to a 1 liter volumetric flask




    and bring to volume with the same water.  1 ml - 1 mg Cd.




5*  Hydrochloric acid solution: Dilute concentrated HC1 (ACS)




    1:1 with distilled deionized water.




Procedure




Sample Preparation




1.  Transfer 100 gm of well-mixed sample (use 100 ml when analyzing




    an EP extract) to a 250 ml beaker.  Add 3 ml concentrated




    HNf>3.  Place the beaker on a hot plate and evaporate



    to near dryness, cautiously, so that the sample does not




    boil.  Cool, and add another 3 ml concentrated HN03-




    Cover the beaker with a watch glass and return to the




    hot plate.  Heat so as to produce a gentle refluxing.




    Continue adding 3 ml portions of HN03 until the sample




    is light in color and no longer changes in color.  Evaporate




    to near dryness and cool.  Add 5 ml of 1:1 HC1 and warm




    the beaker just to dissolve any precipitates.

-------
                                                                   8.53-3
    b.   Cool and bring  to  100  ml  with distilled  deionized




        water.




2.  If  particulates such as silicates remain in  the sample




    it  must be  centrifuged and the  supernatant aspirated.




3.  Prepare working standards  from  stock solution.   If it



    is  desired  to work  in  the  optimum concentration range




    the following is suggested:




    a.   Transfer 10 ml  stock solution to a 100 ml volumetric




        flask.   Bring to volume  with distilled deionized




        water containing 1.5 ml  concentrated HN03/  liter.




        Concentration:  100 mg/liter.




    b.   Transfer 0, 0.1, 0.5,  1.0,  1.5,  and 2.0  ml  solution




        from a) to separate 100  ml  volumetric flasks.   Bring




        to volume with  distilled  deionized water containing




        1.5 ml  HN03/liter.  The  concentrations of these




        standards will  be  0, 0.1, 0.5, 1.0, 1.5, and 2.0 mg




        Cd/liter.




Standard Addition




    a.   Take the 1.0, 1.5, and 2.0  mg/liter standards  and pipet 5 ml




        from each into  separate  10  ml volumetric flasks.  Add




        to each 2 ml of the prepared sample.  Bring to volume




        with distilled  deionized  water containing 1.5  ml




        HN03/liter.




    b.   Add 2 ml of prepared sample to a 10 ml volumetric




        flask.   Bring to volume  with distilled deionized




        water containg  1.5 ml HN03  per liter.  This is the



        blank.

-------
    Note!   The absorbance from the blank will be 1/5 that




    produced by the prepared sample.  The absorbance from




    the spiked standards will be 1/2 that produced by the




    standards plus the contribution from 1/5 of the prepared




    sample.  Keeping these In mind the correct dilutions to




    produce optimum absorbance can be judged.




  Instrument Operation




       Wavelength: 228.8 nanometers




       Optimum Concentration Range: 0.05 - 2 mg/liter




       Lower Detection Limit: 0.005 mg/liter




       Fuel: Acetylene




       Oxidant: air




       Type of flame:  oxidizing.




A general  outline for  instrument operation is given in Section




8.49.  Follow the manufacturer's instructions for the Spectro-




photometer being used.




Quantification




     The absorbance of spiked samples and blank vs. the




concentrations are plotted according to the Method of Standard



Additions  as defined in Section 8.49.  The extrapolated




value will be 1/5 the  concentration of the original sample.




     If the plot does  not result in a straight line a non-



linear interference is present.  This can sometimes be




overcome by dilution,  or addition of other reagents if




there is some knowledge about the waste.

-------
                                                                    8.53-5
                        Graphite Furnace




Reagents




1.  Cadmium Standard Stock Solution (1000 mg/liter).  Carefully




    weigh 3.1368 g Cadmium Sulfate Octahydrate (Cd SO^.S H2<>),




    analytical reagent grade, and dissolve in distilled




    deionized water containing 5 ml concentrated HN03/liter.




    Transfer quantitatively to a 1 liter volumetric flask




    and bring to volume with the same water.  1 ml « 1 mg Cd.




2.  Concentrated Hfl(>3 (ACS)




3.  Concentrated HN03 diluted 1:1 with distilled deionized




    water.




4.  Ammonium phosphate solution (40%) Dissolve 40 grams




    Ammonium mono hydrogen phosphate, (NH4)2HP04, analytical




    reagent grade, in distilled deionized water and bring




    to 100 ml.




Procedure




1.  Sample Preparation




    a.   Transfer 100 gm of well-mixed sample (or when analyzing




         an EP extract 100 ml) to a 250 ml beaker.  Add 3 ml




         concentrated HN03.  Place the beaker on a hot




         plate and evaporate to near dryness, cautiously, so




         that the sample does not boil.  Cool, and add another




         3 ml concentrated HN03.  Cover the beaker with a




         watch glass, and return to the hot plate.  Heat so




         as to produce a gentle refluxing.  Continue adding




         3 ml portions of concentrated HN03 until the

-------
                                                                   8.53-6
        sample is light in color and no longer changes in




        color.  Evaporate to near dryness and cool.  Add 1




        ml of 1:1 HN(>3 and warm the beaker just to dissolve




        any precipitates.  Cool the beaker.




    b.  Add 2 ml Ammonium phosphate solution and bring to




        100 ml with distilled deionized water.




2.  If particulates such as silicates remain in the sample




    it must be centrifuged and the supernatant sampled.




3.  Prepare working standards from the stock solution.  If




    it is desired to work in the optimum concentration range




    the following is suggested:




    a.  Transfer 1 ml stock solution to a 1 liter volumetric




        flask.  Bring to volume with distilled deionized




        water containing 5 ml concentrated HN03/liter.




        Concentration: 1000 ug/liter.




    b.  Transfer 10 ml from a) to a 100 ml volumetric flask




        and bring to volume with distilled deionized water




        containing 5 ml HN03/liter.  Concentration: 100



        ug/liter.




    c.  Transfer 0, 0.5, 1.0, 2.5, 5.0, and 10 ml from b)




        to 100 ml volumetric flasks.  Add 2 ml Ammonium




        phosphate solution.  Bring to volume with distilled




        deionized water containing 5 ml HN03/liter.  The




        concentrations of these working standards will be 0,




        0.5,  1.0, 2.5, 5.0, and I'O ug Cd/liter.

-------
                                                                   8.53-7
Standard Addition




1.  a.  Take the 2.5,  5.0 and 10 ug/liter standards and pipet 5 ml




        from each into separate 10 ml volumetric flasks.




        Add to each 2  ml of the prepared sample and 0.06 ml




        ammonium phosphate solution.   Bring to volume with




        distilled deionized water.




    b.  Add 2 ml of prepared sample to a 10 ml volumetric




        flask and add  0.16 ml ammonium phosphate solution.




        Bring to volume with distilled deionized water.




        This is the blank.




Note;   The absorbance  from the blank  will be 1/5 that produced




by the prepared sample.  The absorbance from the spiked




standards will be 1/2  that produced by the standards plus




the contribution from  1/5 of the prepared sample.  Keeping




these in mind the correct dilutions to produce optimium




absorbance can be judged.




Instrument Operation




     Wavelength: 228.8 nanometers




     Optimum Concentration Range: 0.5 - 10 ug/liter




     Lower Detection Limit: 0.1 ug/liter




     Purge Gas: Argon




     Drying time and temperature: 30  sec at 125°C




     Ashlngtime and temperature: 30 sec at 500°C




     Atomizing time and temperature:  10 sec at 1900°C




These conditions are based on a 20 ul injection continuous




flow purge gas and non-pyrolytic graphite on a Perkin Elmer

-------
                                                                   8.53-8
model HGA 2100 furnace.  Other equipment will have different



requirements.  Follow the manufacturer's manual.




(Quantification




     The absorbance of spiked samples and blank vs. the




concentrations are plotted according to the Method of




Standard Additions as defined in Section 4.49.  The extra-




polated value will be 1/5 the concentration of the original




sample.




     If the plot does not result in a straight line a non-




linear interference is present.   This can sometimes be




overcome  by dilution, or addition of other reagents if




there is some knowledge about the waste.

-------
                                                                  8.54-1
                            Method 8.54




                              CHROMIUM






Scope and Application




     The following procedures are approved methods for determining




the concentration of chromium in an Extraction Procedure Extract,




an industrial liquid waste, or landfill liquid component or leachate




Precaution




     Hexavalent chromium is both acutely toxic and carcinogenic




to man.  While the trivalent form is less toxic to humans,




care should be exercised in its handling.




Summary of Method




     The sample is digested using nitric and/or hydrochloric




acids and the concentration of chromium measured using either a




flame or graphite furnace equipped atomic absorption spectre-




photometer.  The flame method is most acurate when employed




with solutions containing 0.5-10 mg Cr/liter while the graphite




furnace procedure is best suited for solutions containing




5-100 ug Cr/liter.




Comments




1.  The direct aspiration method is suitable for a concentration




    range of 0.5-10 mg/1.  The nitrous oxide-acetylene flame is




    recommended bacause, while less sensitive, it eliminates




    interferences from other common metals such as iron and nickel.




    If the air-acetylene flame must be used it should be lean.




    Interference from other ions has reportedly been overcome by




     addition of ammonium biflouride.

-------
                                                                  8.54^2




2.  In the furnace method the presence of calcium  interferes.




    However, since at concentrations above 200 mg/1 its




    effect becomes constant, it is added to insure this




    minimum level.  Hydrogen peroxide is used to bring all




    chromium present in the sample to the +6 state.




                      Direct Aspiration




Reagents




1.  Nitrous oxide, commercially available cylinders




2.  Acetylene should be of high purity standard commercial




    grade •




3.  Concentrated Nitric Acid (HN03)




4.  Chromium Stock Solution (1000 mg/liter):




    Dissolve 1.9231 grams chromium trioxide (Cr03) analytical




    reagent grade, in deionized distilled water.  Add 1.5 ml




    HNO^ and bring to volume in a 1 liter volumetric flask




    with this same water (1 ml = 1 mg Cr).




5.  1% ammonium biflouride solution if needed for air-acetylene




    flame:




    Dissolve 0.2 grams sodium sulfate in distilled deionized




    water.  Add 1 gram ammonium biflouride (NH4HF2).  Bring




    to volume in a 100 ml volumetric flask with distilled




    deionized water.




Apparatus




1.  Atomic Absorption Spectrophotometer with nitrous oxide




    burner head with 2" slot.




2.  T-junction valve for rapidly changing from nitrous oxide




    to air, so the flame can be turned on or off with air as




    oxidant to prevent flashbacks.

-------
                                                                 8.54-3
Procedure




Sample preparation




1.  a.  Transfer 100 ml of well-mixed sample to a 250 ml




        beaker.  Add 3 ml cone HN03.   Place the beaker on a




        hot plate and evaporate to near dryness, cautiously,




        taking care not to let the sample boil.  Cool, and




        add another 3 ml cone HNC>3.  Cover the beaker with




        a watch glass and return to the hot plate.  Heat so




        as to produce a gentle refluxing.  Continue adding




        3 ml portions of HN03 until the sample is light in




        color and no longer changes in color.  Evaporate to




        near dryness and cool.  Add 1 ml HN03 and warm the




        beaker until any precipitates present dissolve.




    b.  Cool and bring to 100 ml with distilled deionized water.




        Note;  If the air-acetylene flame is used add 1 ml




        ammonium biflouride solution just before making up




        to 100 ml volume.




2.  If particulates, such as silicates, remain in the digested




    sample, then centrifuge the digestate and only aspirate the




    supernatant.




3.  Prepare working standards from stock solution.  To bracket




    the optimum concentration range the following is suggested:




    a.  Transfer 0, 0.1, 0.2, 0.5, 0.8, and 1.0 ml stock solution




        to separate 100 ml volumetric flasks.  Bring to volume




        with distilled deionized water containing 1.5 ml HN03/liter




        These working standards will contain 0, 1, 2, 5, 8 and




        10 mg Cr/liter.

-------
        Note;  If the air-Acetylene flame must be used add




        1 ml ammonium biflouride solution just before




        making up to 100 ml volume.




4 .  Standard Addition



    a.  Take the 5,  8,  and 10 mg standards and pipet 5 ml




        from each into  separate 10 ml volumetric flasks.




        Add to each 2 ml of the prepared sample.  Bring to




        volume with distilled deionized water containing 1.5




        ml HN03/liter.




    b.  Add 2 ml of prepared sample to a 10 ml volumetric




        flask.  Bring to volume with distilled deionized




        water containing 1.5 ml HN03 per liter.  This is the




        blank.




        Note;  The absorbance from the blank (b), will be




        1/5 that produced by the prepared sample.  The absorb-




        ance from the spiked standards will be 1/2 that




        produced by the standards plus the contribution from




        1/5 of the prepared sample.  Keeping these in mind




        the correct dilutions to produce optimum absorbance




        can be judged .




Instrument Operation




     Wavelength:  357.9 nanometers




     Optimum concentration range:  0.5-10 mg/liter




     Lower detection limit:  0.05 mg/liter




     Fuel:  Acetylene




     Oxident:  Nitrous  Oxide




     Type of Flame:   Fuel rich

-------
                                                                  8.54-5




Follow the instructions given with the Atomic Absorption




Spectrophotometer.   The following is included as a guide:




    a.  Install a nitrous oxide burner head.




    b.  Turn on the acetylene (without igniting the flame),




        and adjust  the flow rate to the value specified by




        the manufacturer for a nitrous oxide-acetylene flame.




    c.  Turn off the acetylene.




    d.  With both air and nitrous oxide supplies turned on,




        set the T-junction valve to nitrous oxide and adjust




        the flow rate according to the specifications of the




        manufacturer.




    e.  Turn the switching valve to the air position and




        verify that the flow rate is the same.




    f.  Turn the acetylene on and ignite to a bright yellow




        flame.




    g.  With a rapid motion, turn the switching valve to




        nitrous oxide.  The flame should become rose-red; if




        it does not, adjust fuel flow to obtain a red cone




        in flame.




    h.  Atomize deionized distilled water containing 1.5 ml




        conc«HNC>3/l and check the aspiration rate.  Adjust




        if necessary to a rate between 3 and 5 ml/min.




        Atomize a 1 mg/1 standard of the metal and adjust




        the burner (both sideways and vertically) in the




        light path until maximum response is obtained.




        The instrument is now ready to run  standards and




        samples •

-------
                                                                  8.5^-6
    i.  To extinguish the flame, turn the switching valve




        from nitrous oxide to air, and turn off the acetylene.




        This procedure eliminates the danger of flashback




        that may occur on direct ignition or shutdown of




        nitrous oxide and acetylene.




Quantification




     The absorbance of spiked samples and blank vs the concen-




tration are plotted according to the Method of Standard Additions




as defined in General Requirements #11.  The extrapolated




value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line a non-linear




interference is present.   This can sometimes be overcome by




dilution, or addition of  other reagents if there is some




knowledge about the waste.

-------
                                                                  S.54-7
                          Graphite Furnace




Reagents




1.  Chromium Standard Stock Solution (1000 mg/liter):




    a.  Dissolve 1.9231 grams Chromium trioxide (Cr03> analytical




        reagent grade, in deionized distilled water.  Add 5 ml




        HN03 and bring to volume in a 1 liter volumetric flask




        with this same water (1 ml « 1 mg Cr).




2.  Concentrated HN03




3.  Calcium nitrate solution:




    Dissolve 11.8 grams Calcium nitrate tetrahydrate




    (Ca(N03>2.4H20), analytical reagent grade in deionized




    distilled water and dilute to 100 ml (1ml « 20mg Ca).




4.  30% hydrogen peroxide




Procedure




Sample Preparation




1.  a.  Transfer 100 ml of well-mixed sample to a 250 ml




        beaker.  Add 3 ml cone HN03.  Place the beaker on a




        hot plate and evaporate to near dryness, taking care




        not to let the sample boil.  Cool, and add another



        3 ml cone HNC^.  Cover the beaker with a watch glass




        and return to the hot plate.  Heat so as to produce




        a gentle refluxing.  Continue adding 3 ml portions




        of HN03 until the sample is light in color and no




        longer changes in color.  Evaporate to near dryness




        and cool.  Add 1 ml of 1:1 HN03 and warm the beaker




        until any precipitate present dissolves.  Cool the




        beaker .

-------
    b.  Add 1 ml of 30% hydrogen peroxide and 1 ml Calcium




        nitrate solution.  Transfer to a 100 ml flask and




        bring to volume with distilled deionized water.




2.  If any particulates such as silcates remain in the digested




    sample, then centrifuge the digestate and only aspirate




    the supernatant.




3.  Prepare working standards from stock solution:  To bracket




    the optimum working range the following is suggested:




    a.  Transfer 1 ml stock solution to a 1 liter volumetric




        flask.  Bring to volume with distilled deionized




        water containing 5 ml HN03/liter.  Concentration




        lOOOug/liter.




    b.  Transfer 0, 1, 2.5, 5, 7.5 and 10 ml from a) to




        separate 100 ml volumetric flasks.  Add 1 ml 30%




        hydrogen peroxide and 1 ml calcium nitrate solution.




        Bring to volume with distilled deionized water




        containing 5 ml HN03/liter.  The concentrations of




        these working standards are 0, 10, 25, 50, 75, and




        100 ug Cr/Hter.




Standard Addition




1.  a.  Take the 50, 75, and 100 ug standards and pipet 5 ml




        from each into separate 10 ml volumetric flasks.




        Add to each 2 ml of the prepared sample.  Add




        0.03 ml CaN03 solution and 0.03 ml 1^02 solution.




        Bring to volume with distilled deionized water.

-------
                                                                  8.54-9
    b.  Add 2 ml of prepared sample to a 10 ml volumetric




        flask.  Add 0.08 ml CaN03 solution and 0.08 ml




        H202 solution.   Bring to volume with distilled




        deionized water.  This is the blank.




        Note;  The absorbance from the blank (b), will be




        1/5 that produced by the prepared sample.  The absorb-




        ance from the spiked standards will be 1/2 that




        produced by the standards plus the contribution from




        1/5 of the prepared sample.  Keeping these in mind




        the correct dilutions to produce optimum absorbance




        can be judged.




Instrument Operation




     Wavelength:  357.9 nanometers




     Optimum Concentration Range:  5-100 ug/liter




     Lower detection limit:  1 ug/liter




     Purge gas:  Argon




     Drying time and temp.:  30 secs-125°C




     Ashing time and temp.:  30 secs-1000°C




     Atomizing time and temp.:  10 secs-2700°C




The conditions listed above are based on a 20 ul injection;




continuous flow purge gas and non-pyrolytic graphite on a




Perkin Elmer model HGA 2100 furnace.  Other equipment will




have different requirements.  Follow the manufacturer's manual.




Quantification




     The absorbances of spiked samples and blank vs concentra-




tions are plotted according to the Method of Standard Additions




as defined in General Requirements #11.  The extrapolated

-------
                                                                 8.54-10
value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line a non-linear




interference is present.  This can sometimes be overcome by




dilution, or addition of other reagents if there is some know-




ledge about the waste.

-------
                                                               8.56-1
                        Method 8:56




                            LEAD






Scope and Application




     The following atomic absorption procedures are approved




methods for determining the concentration of Lead in a waste




or an Extraction Procedure Extract.




Precaution




     Lead is poisonous and accumulates in the body.  Drinking




water does not usually contain more than 20 ug/liter.  It can




be leached from old lead plumbing by acid water.




Summary of Method




     The sample is digested using nitric and/or hydrochloric




acids and the concentration of lead measured using either a




flame or graphite furnace equipped atomic absorption spectre-




photometer.  The flame method is most accurate when employed




with solutions containing 1-20 mg Pb/liter while the graphite




furnace procedure is best suited for solutions containing




5-100 ug Pb/liter.




Comment s




1.  Two wavelengths are suitable and may be tested for




    best operating conditions.  The 217.0 nm wavelength is




    more sensitive but may produce more background noise.




2.  The Graphite Furnace method is susceptible to sulfate




    interference.  Up to 1500 ppm sulfate can be suppressed




    by addition of Lanthanum.

-------
                                                               8.56-2
3.  Contamination of the working environment is a special




    problem.  All glassware should be cleaned immediately




    prior to use and then covered.




                      Direct Aspiration




Reagents






1.  Air, cleaned and dried through a suitable filter to




    remove oil, water, and other foreign substances.  The




    source may be a compressor or a cylinder of industrial




    grade compressed air.  Breathing quality air can cause




    flashback.




2.  Acetylene should be of high quality grade.   Avoid "purified




    grade" acetylene.   Acetone, which is always present in




    acetylene cylinders, can be prevented from entering and




    damaging the burner head by replacing a cylinder when




    its pressure has fallen to 7 kg/cm^ (100 psig) acetylene.




3.  Nitric Acid cone.




4.  Lead Standard Stock Solution 1000 mg/liter  stock solution




    may be purchased or prepared as follows: Dissolve 1.5985




    g lead nitrate (Pb(N03)2) analytical reagent grade, in



    about 200 ml distilled deionized water.  Acidify with 10




    m 1 cone.  HN03 and bring to volume in a 1  liter volumetric




    flask.  (1 ml = 1  mg Pb.)




5.  Hydrochloric acid  solution: Dilute cone. HC1 1:1 with




    distilled deionized water.

-------
                                                                   8.56-3
Procedure




Sample Preparation




1.  a.  Transfer 100 ml of well-mixed sample to a 250 ml




        beaker.  Add 3 ml cone. HN03.  Place the beaker on




        a hot plate and evaporate to near dryness, cautiously,




        in order to keep the sample from boiling.  Cool,




        and add another 3 ml cone.  HN03.  Cover the beaker




        with a watch glass and return to the hot plate.




        Heat so as to produce a gentle refluxing.  Continue




        adding 3 ml portions of HN03 until the sample is




        light in color and no longer changes In color.




        Evaporate to near dryness and cool.  Add 5 ml of 1:1




        HC1 and warm the beaker just to dissolve any precipi-




        tates .




    b.  Cool and bring to 100 ml with distilled deionized




        water .




2.  If particulates such as silicates remain in the sample




    it must be centrifuged and the supernatant aspirated.




3.  Prepare working standards from stock solution.  If it is




    desired to work in the optimum concentration range




    the following is suggested:




    a.  Transfer 0, 0.1, 0.5, 1.0, 1.5, and 2.0 ml of




        stock solution to separate 100 ml volumetric




        flasks.  Bring to volume with distilled deionized




        water containing 1.5 ml HN03/liter.  The concentrations




        of these working standards are 0, 1, 5, 10, 15, and




        20 mg Pb/liter.

-------
                                                                  8.56-4
Standard Addition

1.  a.  Take the 10, 15, and 20 mg standards and pipet 5

        ml from each into separate 10 ml volumetric flasks.

        Add to each 2 ml of the prepared sample.  Bring to

        volume with distilled deionized water containing 1.5

        ml HN03/liter.

    b.  Add 2 ml of prepared sample to a 10 ml volumetric

        flask.  Bring to volume with distilled deionized

        water containing 1.5 ml HN03 per liter.  This is

        the blank.

        Note;  The  absorbance from the blank (b), will be 1/5

        that produced by the prepared sample.  The absorbance

        from the spiked standards will be 1/2 that produced by

        the standards plus the contribution from 1/5 of the

        prepared sample.  Keeping these in mind the correct

        dilutions to produce optimum absorbance can be judged.

Instrument Operation

     Wavelength:  283.3 nanometers
                 217.0 nanometers (more sensitive)

     Optimum Concentration Range: 1-20 mg/liter

     Lower Detectable limit: 0.1 mg/liter Fuel: Acetylene

     Oxidant: Air

     Type of flame: Oxidizing

     This method is especially sensitive to turbulance in the

     flame.  Special care should be taken to position the

     burner so that the light beam passes through the most

-------
                                                                  8.56-5
     stable center portion of the flame.  The absorbance




     should be maximized with a lead standard.




     A general outline for instrument operation is given in




Section 8.49.  Follow the manufacturer's instructions for




the Spectrophotometer being used.




Quantification




     The absorbances of spiked samples and blank vs.  the




concentrations are plotted according to the Method of




Standard Additions as defined in Section 8.49.  The extrapo-




lated value will be 1/5 the concentration of the original




sample.




     If the plot does not result in a straight line a




nonlinear interference is present.  This can sometimes be




overcome by dilution, or addition of other reagents if there




is some knowledge about the waste.

-------
                                                                   8.56-6
                      Graphite Furnace




Reagents




1.  Lead Standard Stock Solution 1000 mg/llter stock solution




    may be purchased or prepared as follows:  Dissolve 1.5985 g




    lead nitrate (Pb(N03>2) analytical reagent grade, in




    about 200 ml distilled deionized water.  Acidify with 10




    ml cone HN03 and bring to volume in a 1 liter volumetric




    flask.  1 ml - 1 mg Pb.




2.  Concentrated HNC-3




3.  Lanthanum Nitrate Solution: Dissolve 58.64 g analytical




    reagent grade Lanthanum oxide (La2 03) in 100 ml cone.




    HN03 and dilute to 1000 ml with distilled deionized




    water. 1 ml - 50 mg La.




Procedure




Sample Preparation




1.  a.  Transfer 100 ml of well-mixed sample to a 250 ml




        beaker.  Add 3 ml cone. HNC>3.  Place the beaker on




        a hot plate and evaporate to near dryness, cautiously,




        so that the sample does not boil.  Cool, and add



        another 3 ml cone. HN03-  Cover the beaker with a




        watch glass, and return to the hot plate.  Heat so




        as to produce a gentle refluxing.  Continue adding 3




        ml portions of HN03 until the sample is light in




        color and no longer changes in color.  Evaporate to




        near dryness and cool.  Add 1 ml of 1:1 HN03 and




        warm the beaker just to dissolve any precipitates.




        Cool the beaker.  Add 10 ml of Lanthanum nitrate

-------
                                                                   8.56-7
        solution and bring to volume in a 100 ml volumetric




        flask using distilled deionized water.




2.  If particulates such as silicates remain in the sample




    it must be centrifuged and the supernatant sampled.




3.  Prepare working standards from the Stock solution.  If




    it is desired to work in the optimum concentration range




    the following is suggested:




    a.  Transfer 1 ml stock solution to a 1 liter volumetric




        flask.  Bring to volume with distilled deionized




        water containing 5 ml cone. HN03/liter.  Concentra-




        tion: 1000 ug/liter.




    b.  Transfer 0, 0.5, 2.5, 5.0, 7.5, and 10 ml from




        (a)  to separate 100 ml volumetric flasks.  Add 10




             ml Lanthanum Nitrate solution and bring to volume




             using distilled deionized water.  The concentra-




             tions will be 0, 5, 25, 50, 75, and 100 ug/liter.




Standard Addition




1.  a.  Take the 50, 75, and 100 ug standards and pipet




        5 ml from each into separate 10 ml volumetric




        flasks.  Add to each 2 ml of the prepared sample.




        Add 0.8 ml lanthanum nitrate solution and bring to




        volume with distilled deionized water.




    b.  Add 2 ml of prepared sample to a 10 ml volumetric




        flask.  Add 0.8 ml lanthanum nitrate solution and




        bring to volume with distilled deionized water.




        This is the blank.

-------
                                                                  8.56-8
    Note;  The absorbance from the blank (b), will be 1/5

    that produced by the prepared sample.  The absorbance

    from the spiked standards will be 1/2 that produced by

    the standards plus the contribution from 1/5 of the

    prepared sample.  Keeping these in mind the correct

    dilutions to produce optimium absorbance can be judged.

Instrument Operation

     Wavelength: 283.3 nanometers
                 217.0 nanometers

     Optimum concentration range: 5-100 ug/liter

     Lower detection limit: 1 ug/liter.

     Purge gas:  Argon

     Drying time and temp: 30 sec - 125°C

     Ashing time and temp: 30 sec - 500°C

     Atomizing time and temp: 10 sec - 2700°C

          The 217.0 nanometer wavelength is more sensitive.

     The electrodeless discharge lamp has been reported

     helpful at  this wavelength.  The sample may also be

     successfully atomized at a lower temperature. (2400°C)

          The conditions listed above are based on a 20 ul

     injection;  continuous flow purge gas and non-pyrolytic

     graphite on a Perkin Elmer model HGA 2100 furnace.  Other

     equipment will have different requirements.  Follow the

     manufacturer's manual.

Quantification

     The absorbances of spiked samples and blank vs.  the

concentrations are plotted according to the Method of Standard

-------
                                                                  8.56-9
Additions as defined in Section 8.49.  The extrapolated




value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line a nonlinear




interference is present.   This can sometimes be overcome




by dilution, or addition of other reagents if there is




some knowledge about the waste.

-------
                                                                8.57-1
                         Method 8.57






                           MERCURY






Scope and Application




     The flameless, cold vapor, atomic absorption procedure




is approved for use in determining the concentration of




mercury in an Extraction Procedure Extract, a RCRA waste, or




landfill leachate.




Precaution




     The extreme toxiclty of mercury is well known.  Care




should be taken in the handling of materials and to avoid




breathing any vapors.  A trap should be constructed to receive




the exhaust gas.




Summary of Method




    The sample is pretreated to break down organic mercury




compounds, and the mercury is then reduced to the zero oxi-:




dation state.  In this form it is swept from the solution by




a purge gas and enters a glass or plastic absorption cell.




This cell has been aligned with the light beam from the




mercury hollow cathode lamp in the atomic absorption spectro-




photometer, and the mercury absorption is proportional to




the concentration.




Comments




1.  The method is subject to interference from sulfide above




    20 mg/1.  Oxidation with potassium permanganate can be




    used to remove this interference.

-------
                                                                    8.57-2
2.  Chloride containing wastes require excess permanganate




    for removal.   Chlorine gas is generated and must be




    purged from the sample before analysis.




3.  Copper may also interfere.  It is expected that the




    Method of Standard Addition will compensate for this.




4.  In this method it is possible that some organic substance




    will not be oxidized and will absorb at the given wavelength.




    In this case,  a second sample can be prepared and analyzed




    without adding any stannous sulfate to reduce the mercury.




    The true mercury value can then be found from the difference.




5.  Disposal of residues:




    The wastes from mercury analyses can be saved and treated




    to recover the mercury.  (See "Disposal".)  The contaminated




    mercury may be returned to the manufacturer for recycling.




Apparatus



1.  An atomic absorption spectrophotometer with an open




    presentation area so that the cold vapor cell may be




    attached to it.



2.  Absorption cell 10 cm. long and about 1" diameter; composed




    of glass or plexiglass and having quartz end windows.




3.  Air pump capable of delivering 2 liters of air/minute




    with rotameter for monitoring air flow.




4.  Tygon aeration tubing and glass tube with fritted end




    (coarse porosity glass).




5.  Drying tube 6" x 3/4" dia. containing 20 grams magnesium




    perchlorate.

-------
                                                               8.57-3
 60 W light bulb positioned to shine on the  absorption


 cell so that the temperature is maintained  10°C  above


 ambient.  This prevents condensation by moisture.   If


 the drying tube is used this may not be necessary.


 Scrubber bottle containing a glass frit immersed in


 absorbing solution:


 a.  1 part 0.1 molar potassium permanganate to 1 part


     10% sulfuric acid.  or


 b.  3% potassium iodide solution containing 0.25% iodine




I


c
n t
u t
AIR PUMP
r f 	 t
r I 	 ^
1 DESICCANT ,, ,';
! 1
ABSORPTION
3 •* -BUBBLER CELL


\
/








T


c




•


3




T
^^N

-4
SAMPLE SOLUTION
IN BOD BOTTLE
                       Figure 8.57-1
               PLAMELESS MERCURY A.A. SET-UP
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA

-------
                                                                  8.57-4
Procedure






1.  Assemble equipment as in the diagram.




2.  Set the wavelength at 253.7 nanometer.




3.  Install the absorption cell and align  it in the light




    beam using 2 cards, each having a 1" diameter hole.




    These are placed over the ends of the  cell for ease in




    centering the beam.




4.  Turn on the air and adjust flow rate to 1 liter/minute.




    and allow the air to flow continuously.




5.  Follow manufacturer's instructions for  instrument warm




    up and operation.




6.  Prepare working standards from stock solution:




    To bracket the optimum concentration range (0.2-10




    ug/liter) the following is suggested:




    a.  Transfer 1 ml of stock solution to  a 1 liter




        volumetric flask and bring to volume with distilled




        deionized water containing 1.5 ml  HN03/liter.  Con-




        centration: 1000 ug/liter.  (1 ml  - 1 ug Hg)




    b.  Transfer 0, 1, 2, 5, 8, and 10 ml  from a. to separate




        100 ml volumetric flasks and bring  to volume with




        distilled deionized water containing 1.5 ml HN03/




        liter.  The concentrations of these working standards




        will be 0, 10, 20, 50, 80 and 100  ug Hg/liter.  (10




        ml aliquots transferred for analysis will contain




        0, 0.1, 0.2, 0.5, 0.8, and 1.0 ug  Hg.)

-------
                                                                    8.57-5
Reagents




1.  Sulfurlc acid solution (0.5N):




    Dilute 14 ml concentrated H2S04 to 1 liter with distilled




    deionized water.




2.  Nitric Acid, concentrated




3.  Stannous Sulfate solution:




    Add 25 grams SnSO^ to 250 ml sulfuric acid solution




    (0.5N).  This mixture should be stirred continuously




    during analysis.




4.  Sodium chloride - Hydroxylamine sulfate solution:




    Dissolve 12 grams NaCl and 12 grams hydroxylamine sulfate




    in distilled deionized water and dilute to 100 ml.




5.  Potassium Permanganate solution: (5% w/v)




    Dissolve 5g KMn(>4 in 100 ml distilled deionized water.




6.  Potassium Persulfate solution: (5% w/v) Dissolve 5g




    K2S2°8 in 10° ml distilled deionized water.



7.  Mercury stock solution (1000 mg/liter):




    Dissolve 0.1354 grams mercuric chloride (HgCl2) in




    distilled deionized water containing 1.5 ml concentrated




    HN03/liter.  Bring to volume in a 100 ml volumetric




    flask. (1 ml - 1 mg Hg.)

-------
                                                                    8.57-6
7.  Standard Addition




    a.  Take the 50,  80 and 100 ug standards and transfer




        quantitatively 25 ml from each into separate 50 ml




        volumetric flasks.  Add to each 10 ml of the sample.




        Bring to volume with distilled deionized water con-




        taining 1.5 ml HN03/liter.




    b.  Add 10 ml of  sample to a 50 ml volumetric flask.




        Bring to volume with distilled deionized water con-




        taining 1.5 ml HN03/liter.  This is the blank.




Note;  The absorbance from the blank will be 1/5 that




produced by the prepared sample.  The absorbance from the




spiked standards will be 1/2 that produced by the standards




plus the contribution from 1/5 of the prepared sample.




Keeping these in mind the correct dilutions to produce optimium




absorbance can be judged.




8.  Treatment of sample and standards:




    a.  Transfer a 10 ml aliquot to a 300 ml BOD bottle.




        Add distilled deionized water to make 100 ml.  Add 5




        ml sulfuric acid solution and 2.5 ml concentrated




        HN03.  After mixing add 15 ml potassium permanganate




        solution.  Additional permanganate may be required




        for some wastes.  Shake and add enough so that the




        purple color persists for at least 15 minutes.  Then




        add 8 ml potassium persulfate solution and heat for




        2 hours in a water bath at 95°C.  Cool.  The sample




        is now fully oxidized.

-------
                                                                    8.57-7
    b.  During oxidation chlorides, if present, are converted




        to free chlorine which interferes in the analysis*




        Additionally any excess permanganate must be destroyed,




        Add 25 ml hydroxylamine sulfate solution and allow to




        stand for at least 30 seconds.




    c.  Purge the dead air space in the upper portion of the




        BOD bottle, add 5 ml well-mixed stannous sulfate




        solution, and immediately attach the bottle to the




        bubbler apparatus as in the diagram, thus forming a




        closed system.  The pumps must run continuously.




        The absorbance will increase and reach a maximum




        within 30 seconds.




    d.  After about 1 minute, when measurement is complete,




        open the bypass valve and allow the gas to flow




        through the mercury trap.  When absorbance returns




        to baseline remove the sample bottle and replace




        it with a BOD bottle containing distilled deionized




        water.  Flush the system for a few minutes.  Close




        the valve and run the next sample or standard.






Quantification




     The absorbances of spiked samples and blank vs. the




number of micrograms mercury are plotted according to the




Method of Standard Addition as defined in Section 8.49.  If




the additions were made as suggested in the method, the extra-




polated value will be the number of micrograms contained

-------
                                                                   8.57-8
in 2 ml of the sample.  From this the concentration in the




original sample can be calculated.




     If the plot does not result in a straight line, a non-




linear interference is present.  This can sometimes be overcome



by dilution.

-------
                                                                   8.57-9
                           APPENDIX

            DISPOSAL OF IONIC MERCURY IN SOLUTION


1.  Bring the pH of the solution to neutral or basic by

    adding sodium carbonate.  Sodium hydroxide may have to

    be added if neutralization cannot be achieved with sodium

    carbonate.

2.  Add granular zinc or magnesium as follows: For every

    100 grams of either mercurous or mercuric chloride

    present in  the solution, add 110 grams zinc or 40 grams

    magnesium.   This achieves a 4 molar excess.

3.  Stir the solution for 24 hours in a hood.  CAUTION:

    Hydrogen gas will be released during this process.

4.  After 24 hours the solid material (mercury amalgam)

    will have separated.  Decant and discard the supernatant
                      *

    liquid to the sewer.

5.  Quantitatively transfer the solid material to a

    convenient  container and allow to dry.

    The following companies are among those that have

recycled mercury in the past:

    These companies may be able to supply a steel flask of

76 Ibs.  capacity which can be used for storage and shipment

of contaminated metal.

           1) Bethlehem Apparatus Co., Inc.
              Front and Depot Sts.
              Hellertown, PA 18055     Tel: (215) 838-7034

-------
                                                        8.57-10
2) Goldsmith Division,  National Lead Co.
   Ill North Wabash
   Chicago,  111.  60602       Tel:  (312) 726-0232

3) Wood Ridge Chemical  Corp.
   Park Place East
   Wood Ridge, N.J. 07075   Tel: (201) 939-4600

4) Quicksilver Products, Inc.
   350 Brannon Street
   San Francisco, Cal.  94107  Tel:  (415) 781-1988

-------
                                                                   8.58-1




                         Method 8.58




                            NICKEL




Scope and Application




     The following atomic absorption procedures are approved




methods for determining the concentration of nickel in a waste




or Extraction Procedure Extract.




Summary of Methods




     A sample is digested using nitric acid and the concen-




tration of nickel is measured using either a flame or graphite




furnace equipped atomic absorption spectrophotometer .  The




flame method is most accurate when employed with solutions




containing 0.3-5 mg Ni/liter, while the graphite furnace




procedure is best suited for solutions containing 5-100 mg/Ni




liter.

-------
                                                                   8.58-2





                      Direct Aspiration




Reagents




1.  Air, cleaned and dried through a suitable filter to




    remove oil, water and other foreign substances.  The




    source may be a compressor or a cylinder of industrial




    grade compressed air.




2.  Acetylene should be of high purity.  Acetone, which is




    always present in acetylene cylinders, can be prevented




    from entering and damaging the burner head by replacing




    a cylinder when its pressure has fallen to 7 kg/cm^ (100




    psig) acetylene.




3.  Nitric acid, concentrated




4.  Nickel Standard Stock solution, (1000 mg/liter):




    Dissolve 4.9532 g nickel nitrate hexahydrate (Ni(NO.;j)  *




    6H20), analytical reagent grade, in distilled deionized




    water containing 1.5 ml concentrated HN3/liter.  Bring  to




    volume in a 1 liter volumetric flask using the same




    water.  (1 ml * 1 mg Ni)



Procedure



Sample Preparation




1.   a.  Transfer 100 gms (or in the case of EP extracts  and




         100 ml) of well-mixed sample  to a 250 ml beaker .




         Add 3 ml concentrated HN03.   Place the beaker  on




         a hot plate and evaporate to  near dryness,  cautiously,




         so that the sample does not boil.  Cool, and  add




         another 3 ml concentrated HN03.  Cover the  beaker  with  a




         watch glass and return to the  hot plate.  Heat so  as

-------
                                                                   8.58-3
         to produce a gentle refluxing.  Continue adding  3  ml




         portions of HN03 until the sample is light  in  color




         and no longer changes in color.  Evaporate  to  near




         dryness and cool.  Add 5 ml of 1:1 HNC>3 and warm




         the beaker in order to dissolve any precipitates.




     b.  Cool and bring to 100 ml with distilled deionized




         water .




2.  If particulates such as silicates remain in  the  sample,




    it must be centrifuged and the supernatant aspirated.




3.  Prepare working standards from stock solution.   If  it




    is desired to work in the optimum concentration  range,  the




    following is suggested:




    a.  Transfer 10 ml stock solution to a 100 ml volu-




        metric flask.  Bring to volume with distilled




        deionized water containing 1.5 ml concentrated  HN03/liter




        Concentration: 100 mg/liter.




    b.  Transfer 0, 0.5, 1.0, 2.0, 4.0, and 5.0  ml




        solution from a) to separate 100 ml volumetric




        flasks.  Bring to volume with distilled  deionized




        water containing 5 ml HNOg/liter.  The concentrations




        of these standards will be 0, 0.5, 1, 2, 4 and




        5 mg Ni/liter .




Standard Addition




1.  a.  Take the 2, 4 and 5 mg/liter standards and pipet  5  ml




        from each into separate 10 ml volumetric flasks.




        Add to each 2 ml of the prepared sample.  Bring




        to volume with distilled deionized water containing

-------
                                                                   8.58-4
         5 ml HN03 per liter.




     b.  Add 2 ml of prepared sample to a 10 ml volumetric




         flask.  Bring to volume with distilled deionlzed




         water containing 5 ml HN03/liter.  This is the




         blank.




Note:  The absorbance from the blank will be 1/5 that produced




by the prepared sample.  The absorbance from the spiked




standard will be 1/2 that produced by the standard plus the




contribution from 1/5 of the prepared sample.  Keeping these




in mind, the correct dilutions to produce optimum absorbance




can be judged.




Instrument Operation




     Wavelength:  232.0 nanometers (352.4 nm may be used.  It is




             less susceptible to interference, but is somewhat




             less sensitive.)




     Optimum Concentration Range:  0.3-5 mg/liter




     Lower Detection Limit:  0.04 mg/liter




     Fuel:  Acetylene




     Oxidant:  Air




     Type of Flame:  Oxidizing



     A general outline for instrument operation is given  in




     section 8.49.  Follow the manufacturer's instructions




     for the Spectrophotometer being used.




Quantification




     The absorbance of spiked samples and blank vs. the




concentrations are plotted accordng to the  Method of Standard

-------
                                                                  8.58-5
Additions as defined in section 8.49.   The extrapolated




value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line, a non-




linear interference is present.  This can sometimes be over-




come by dilution, or addition of other reagents, if there is




some knowledge about the waste.

-------
                                                                   8.58-6





                       Graphite Furnace




Reagents




     Prepare working standards and  blank  to  bracket  the range




5-100 mg Ni/liter by making appropriate dilutions  of  the




standards described in the direct aspiration method.




Procedure




     The Sample is digested, standard  additions  are  prepared,




and the analysis conducted as described under  the  direct




aspiration method.




Instrument Operation




     Wave length:  232.0 nanometers




     Optimum Concentration Range:   5-100  ug/liter




     Lower Detection Limit:  1.0 ug/liter




     Purge Gas:  Argon or nitrogen




     Drying Time and Temp:  30 sec  at  125° C




     Ashing Time and Temp:  30 sec  at  900° C




     Atomizing Time and Temp:  10 sec  at  2700° C




     These conditions are based on  a 20 ul injection,  con-




     tinuous flow purge gas, and non-pyrolytic graphite on a




     Perkin Elmer model HGA 2100 furnace.  Other equipment




     will have different requirements.  Follow the manufacturer's




     manual.

-------
                                                                   8.59-1
                         Method 8.59




                           SELENIUM




Scope and Application




      The following atomic absorption procedures are approved




methods for determining the concentration of selenium in a




waste or an Extraction Procedure Extract.  While both methods




are generally aceptable for RCRA type samples, the graphite




furnace method is simpler to use than the hydride.  However




it is sensitive to chloride interference when the concentration




is greater than 800 mg/liter.  The presence of sulfate in




concentrations greater than 200 mg/liter will also interfere.




If it does not exceed 2000 mg/liter the sulfate can be suppressed.




The hydride method requires greater preparation and is sensitive




to high concentrations of chromium, copper, mercury, silver




cobalt and molybdenum.




Summary of Methods




      In the furnace method the sample is digested using




nitric acid and hydrogen peroxide.  The method is most




accurate for solutions containing 5 - 100 ug Selenium/liter.




      In the gaseous hydride method the sample is digested




using nitric and sulfuric acids.  The selenium is then reduced




from the +4 to the +2 oxidation state with stannous chloride,




and converted to the hydride SeHg, using zinc metal.  The




hydride is swept into an argon entrained hydrogen flame for




analysis.

-------
                                                                   8.59-2
It is most accurate when employed for solutions containing




2 - 20 ug Selenium/liter.  However high concentrations of




chromium, copper, mercury, silver, cobalt and molybdenum can




interfere in the analysis.






                   Graphite Furnace Method




Reagents




1.  Standard Stock Solution




    1000 ug/liter solution may be purchased, or prepared




    as follows:




    Dissolve 0.3453g of selenous acid (assay 94.6% ^8003)




    in distilled deionized water.  Add to a 200 ml volumetric




    flask and bring to volume (1 ml » 1 mg Se).




2.  Nickel Nitrate Solution, 5%




    Dissolve 24.780g of ACS reagent grade Ni(N03)2 * 6H20




    in distilled deionized water and make up to 100 ml.




3.  Nickel Nitrate Solution, 1%




    Dilute 20 ml of the 5% solution to 100 ml with distilled




    deionized water.




4.  30% Hydrogen Peroxide




5.  Sodium Hydroxide




6.  Concentrated Nitric Acid




Procedure




1.  Sample Preparation




    a.  Transfer 100 gms(or in the case of EP extracts




        100 ml) of well-mixed sample to a 250 ml beaker

-------
                                                                   8.59-3
        and add 2 ml of 30% H202 and 1 ml of concentrated

        HNOj.  Heat on a hot plate for 1 hour at 95°C or

        until the volume is less than 50 ml.

    b.  If particulate material remains in the sample after oxida-

        tion, add additional HN03 and 1^02 and digest until no

        changes are noted in the amount of particulate matter

        remaining.

    c.  At this point cool and bring to 50 ml with distilled

        deionized water.  The mixture should be centrifuged

        and only the supernatant used for the remaining

        steps of the analysis.

    d.  Transfer quantitatively 25 ml of this solution

        into a 50 ml volumetric flask.   Add 5 ml of 1% nickel

        nitrate solution and bring to 50 ml with distilled

        deionized water.

        No_te;  If sulfate is present at concentrations of more
        than 200 mg/1 add 10 ml of 5% nickel nitrate solution
        instead of 5 ml of 1% solution.

2.  Prepare standards from stock solution.  The following

    provides standards in the optimum working range:

    a.  Pipet 1 ml stock solution into a 1 liter volumetric

        flask.  Bring to volume with distilled deionized

        water containing 1.5 ml concentrated HN03 Per

        liter.  The concentration of this solution is 1000

        ug Se/liter (1 ml - 1 ug Se)

    b.  Prepare 6 working standards by transferring 0, 1.0,

        2.5, 5.0, 7.5 and 10.0 ml from a. into 100 ml volumetric

        flasks.  Add 1 ml concentrated HN03, 2 ml 30%

-------
                                                             8.59-4
    and 2 ml 5%  nickel nitrate solution.   Bring to volume

    with distilled deionized water.   The  concentrations

    of these working standards are 0, 10,  25,  50,  75,

    and 100 ug Se/liter.   They are ready  for injection.

    Note! If sulfate is present in the sample  at concen-
    trations of  more than 200 mg/1 add 20  ml of 5% nickel
    nitrate solution instead of 2 ml before bringing to
    volume.

3.  Standard Addition

    a.  Take the 50, 75 and 100 ug/liter  standards and

        pipet 5  ml from each into separate 10  ml volumetric

        flasks.   Add to each 2 ml of the  prepared  sample.

        Add 0.3  ml of 1%  nickel nitrate solution and 0.3

        ml H202  solution.  Bring to volume with distilled

        deionized water.

    b.  Add 2 ml of prepared sample to a  10 ml volumetric

        flask.  Add 0.3 ml of 1% nickel nitrate solution

        and 0.3  ml 1^2®?. solution.  Bring  to volume

        with distilled deionized water.  This  is the

        blank.

        Note; that the absorbance from the blank will

        be 1/5 that producd by the prepared sample.  The

        absorbance from the spiked standards will be 1/2

        that produced by the standards alone plus the

        contribution from 1/5 of the prepared  sample.

        Keeping  these in mind, the correct dilutions to

        produce  optimum absorbance can be judged.

-------
                                                                8.59-5
Instrument Operation




     Wavelength:  196.0 nanometers




     Optimum Concentration Range:  5 - 100 ug/liter




     Lower Detection Limit:  2 ug/liter




     Drying Time and Temperature:  30 seconds at 125°C




     Ashing Time and Temperature:  30 seconds at 1,200°C




     Atomizing Time and Temperature:  10 seconds at 2,700°C




     Pure Gas:  Argon




     These conditions are based on a 20 ul injection,




continuous flow purge gas, and non-pyrolytic graphite in a




Perkin Elmer Model HGA 2100 furnace.  Other equipment will




have different requirements.  Follow the manufacturer's




manual.




Quantification




     The absorbance of spiked samples and blank vs.




the concentrations are plotted according to the Method




of Standard Additions as defined in section 8.49.  The




extrapolated value will be 1/5 the concentration of the



original sample.




     If  the plot does not result in a straight line,




non-linear interference is present.  This can sometimes be




overcome by dilution, or additon of other reagents if there




is some  knowledge about the waste.

-------
                                                                 ^.59-6
                    Gaseous Hydride Method




Reagents




1.  Stannous Chloride Solution:   Dissolve lOOg SnCl2 in




    100 ml concentrated HC1.




2.  Zinc slurry:  Add 50g zinc metal dust (200 mesh)




    to to 100 ml deionized distilled water.




3.  Diluent:  Add 100 ml 18N H2S04 and 400 ml concentrated




    HC1 to 400 ml deionized distilled water In a 1-liter




    volumetric flask and bring to volume with deionized




    distilled water.



4.  Standard Stock Solution:  1000 mg/liter solution may be




    purchased, or prepared as follows: Dissolve 0.3453g of




    selenious acid (assay 94.6% of H2Se03) in distilled




    deionized water.  Add to a 200 ml volumetric flask and




    bring to volume (1 ml » 1 mg Se).




Apparatus




1.  Atomic Absorption Spectrophotometer with Boling Burner.




2.  Flow Meter, capable of measuring 1 1/min, such as that




    used for auxiliary argon.*•



3.  Medicine Dropper, capable of delivering 1.5 ml,




    fitted into a size "0" rubber stopper.




4.  Reaction Flask, a pear-shaped vessel with side arm and




    50 ml capacity, both arms having 1 14/20 joint.2




5.  Special Gas Inlet-Outlet Tube, constructed from a micro




    cold finger condenser-* by cutting off the portion




    below the S 14/20 ground glass joint.
 1 Gilmont No. 12 or equivalent




 2 Scientific Glass JM-5835 or equivalent




 3 Scientific Glass JM-5325 or equivalent

-------
                                                                   8.59-7
6.  Magnetic Stirrer,  strong  enough to homogenize the zinc

    slurry.

7.  Drying Tube, 100-mm-long  polyethylene tube filled with

    glass wool to keep  particulate matter out of the burner

Apparatus Set-Up
          JM-3325
         Medicine
         Dropper in
         Size "0"
          Rubber
          Stopper
                        Argon
                    Flow
                    Meter
•JM-5835
                      (Auxiliary Air)
                        Argon
                       (Nebulizer
                         Air)
      Connect the apparatus with  the burner as shown above.


      Connect the outlet  of the  reaction vessel to the

      auxiliary oxidant input  of  the burner with tygon

      tubing.  Connect the inlet  of  the reaction vessel

      to the outlet side  of the  auxiliary oxident (argon

      supply) control valve of  the  instrument.

-------
                                                                 8.59-8
Procedure




1.  Sample Preparation




    To a 50 gm sample (or in the case of EP extracts a




    50 ml sample) add 10 ml concentrated HN03 and 12




    ml of 18 N 112804.  Evaporate the sample on a hot plate




    until white 803 fumes are observed (a volume of about




    20 ml).  Do not let it char.  If it chars, stop the




    digestion, cool and add additional HNOg.   Maintain an




    excess of HN03 (evidence of brown fumes)  and do not




    let the solution darken, because selenium may be reduced




    and lost.  When the sample remains colorless or straw




    yellow during evolution of 803 fumes, the digestion is




    complete.




    Cool the sample, add about 25 ml distilled deionized




    water and again evaporate to 803 fumes just to expel




    oxides of nitrogen.  Cool.  Add 40 ml of  concentrated




    HCl and bring to a volume of 100 ml with  distilled




    deionized water.




2.  Prepare working standards from the standard stock solution.




    The following provides standards in the optimum working




    range:




    a.  Pipet 1 ml stock solution into a 1 liter volumetric




        flask.  Bring to volume with distilled deionized




        water containing 1.5 ml concentrated  HN03/liter.




        The concentration of this solution is 1 mg Se/liter.




        (1 ml = 1 ug Se)




    b.  Prepare 6 working standards by transferring 0, 0.5,




        1.0, 1.5, 2.0 and 2.5 ml from a.  into 100 ml volumetric

-------
                                                                  8.59-9
        flasks.  Bring to volume with diluent.    The




        concentrations of these working  standards  are  0,  5,




        10, 15, 20 and 25 ug Se/liter.




3.  Standard Additions




    a.  Take the 15, 20, and 25 ug standards  and  transfer




        quantitatively 25 ml from each into separate 50 ml




        volumetric flasks.  Add to each  10 ml of  the prepared




        sample.  Bring to volume with distilled deionized




        water containing 1.5 ml HN03/liter.




    b.  Add 10 ml of prepared sample to  a 50 ml volumetric  flask.




        Bring to volume with distilled deionized  water containing




        1.5 ml HN03 per liter.  This is  the blank.




Instrument Operation




     Fuel:  Argon-hydrogen flame




     Wavelength:  196.0 nanometers




     Optimum Concentration Range:  2-20  ug Se/liter




     Lower Detection Limit:  2 ug/liter




     Turn on the argon and adjust the flow rate to about  8




liters/minute with auxiliary argon flow  at 1 liter/min.




     Turn on the hydrogen, adjust flow rate to about 7 liters/




minute and ignite.  The flame is colorless.  The  hand may be




passed 1 ft. above the burner to detect  heat, in  order to




insure ignition.




     Follow the instructions given with  the atomic absorption




spectrophotometer .

-------
                                                                 8.59-10
Treatment of Samples and Standards




     Transfer a 25-ml portion of the digested sample or




standard to the reaction vessel.  Add 0.5 ml SnCl2 solution.




Allow at least 10 minutes for the metal to be reduced to its




lowest oxidation state.  Attach the reaction vessel to the




special gas inlet-outlet glassware.  Fill the medicine




dropper with 1.50 ml zinc slurry that has been kept in suspension




with the magnetic stirrer.  Firmly insert the stopper containing




the medicine droppper into the side neck of the reaction




vessel.  Squeeze the bulb to introduce the zinc slurry into




the sample or standard solution.  The metal hydride will




produce a peak almost immediately.  When the recorder pen




returns part way to the base line, remove the reaction vessel.




Quantification




     The spiked samples and blank vs. concentrations are




plotted according to the Method of Standard Additions, as




defined in section 8.49.  The extrapolated value will be




1/10 the concentration of the original sample due to a dilution




during preparation.




     If the plot does not result in a straight line, a non-linear




interference is present.  This can sometimes be overcome by




dilution, or addition of other reagents if there is some




knowledge about the waste.

-------
                                                                 8.60-1
                         Method 8.60




                            SILVER




Scope and Application




     The following atomic absorption procedures are approved




methods for determining the concentration of Silver in a




waste or an Extraction Procedure Extract.




Summary of Method




     The sample is digested using nitric and/or hydrochloric




acids and the concentration of silver measured using either a




flame or graphite furnace equipped atomic absorption spectro-




photometer.  The flame method is most accurate when employed with




solutions containing 0.1 - A mg Ag/liter, while the graphite




furnace procedure is best suited for solutions containing 1-25




ug Ag/liter.




Precaution






     Silver in concentrations of 0.4 to 1 mg/liter can cause




damage to liver, kidneys and spleen.  Natural drinking waters




do not generally contain more than 2 ug/liter.




Comments




1.  Silver samples and silver nitrate standards should not




    be stored.  Silver is light-sensitive and has a tendency




    to plate out on the container walls.  Discard solutions




    after use.






2.  The use of hydrochloric acid is avoided to prevent precipi-




    tation of silver chloride.




3.  If plating out or AgCl formation is suspected it can be

-------
                                                                  8.60-2
    redissolved by addition of cyanogen iodide.  However,




    this can only be done after digestion to prevent formation




    of toxic hydrogen cyanide under acid conditions.




                      Direct Aspiration




Reagents




1.  Air, cleaned and dried through a suitable filter to




    remove oil, water, and other foreign substances.  The




    source may be a compressor or a cylinder of industrial




    grade compressed air.




2.  Acetylene should be of high purity.  Acetone, which is




    always present in acetylene cylinders, can be prevented




    from entering and damaging the burner head by replacing




    a cylinder when its pressure has fallen to 7 kg/cm^




    (100 pslg) acetylene.




3.  Concentrated Nitric Acid (HN03>, Ultrex grade.




A.  Concentrated Ammonium hydroxide (NH40H)




5.  Silver Standard Stock Solution; (1000 mg/liter):




    Dissolve 0.7874 g anhydrous silver nitrate (AgN03>




    analytical reagent grade, in deionized distilled water.




    Add 5 ml cone HN03 and bring to volume in a 500 ml




    volumetric flask.  1 ml = 1 mg Ag.




6.  Iodine solution, IN:




    Dissolve 20 grams potassium iodide, (KI), analytical




    reagent grade, in 50 ml distilled deionized water.  Add




    12.7 grams iodine (I2)> analytical reagent grade, and




    dilute to 100 ml.  Place in a brown bottle.

-------
                                                                  8.60-3
7.  Cyanogen Iodide solution:




    To 50 ml deionized distilled water  add 4.0  ml  concentrated




    NH4
-------
                                                                   8.60-4
    c.  Transfer quantitatively to a 100 ml volumetric flask




        and bring to volume with distilled deionized water.




3.  If there are particulates such as silicates remaining in




    the sample it must be centrifuged and only the supernatant




    aspirated.




4.  Prepare working standards from stock solution.  To bracket




    the optimum concentration range the following is suggested:




    a.  Transfer 10 ml stock solution to a 100 ml volumetric




        flask and bring to volume with distilled deionized



        water containing 10 ml HN03/liter.  Concentration:




        100 ing/liter.




    Note:   If, in the sample preparation, it was necessary




    to add cyanogen iodide to insure redissolving of precipi-




    tated  silver, then the standards must be treated in the




    same manner.  Do not add acidified water in step 4. a.




    Transfer 10 ml of stock solution to a small beaker.  Add




    distilled deionized water to make about 80 ml.  Make the




    solution basic (pH above 7) with ammonium hydroxide.




    Rinse  the pH meter electrodes into the solution with




    distilled deionized water.  Add 1 ml cyanogen, iodide and




    allow  to stand 1 hour.  Transfer quantitatively to a 100




    ml volumetric flask and bring to volume with distilled




    deionized water.

-------
                                                               8.60-5
b.  Transfer 0, 0.5, 1.0, 2.0, 3.0 and 4.0 ml from a. to

    separate 100 ml volumetric flasks.  Bring to volume

    with distilled deionized water containing 10 ml

    HN03/liter.  The concentrations of these working

    standards will be 0, 0.5, 1.0, 2.0, 3.0, and 4.0 mg

    Ag/liter.

Note;  If a. was treated with cyanogen iodide these

working standards must be brought to volume with distilled

deionized water made basic with ammonium hydroxide and

containing 10 ml cyanogen iodide/liter.

Standard Addition

a.  Take the 2, 3, and 4 mg standards and pipet 5 ml from

    each into separate 10 ml volumetric flasks.  Add to

    each 2 ml of the prepared sample.  Bring to volume

    with distilled deionized water containing 10 ml

    HN03/liter.

b.  Add 2 ml of prepared sample to a 10 ml volumetric flask.

    Bring to volume with distilled deionized water containing

    10 ml HN03 per liter.  This is the blank.

Note;  For a sample treated with cyanogen iodide these
standard additions are brought to volume with distilled
deionized water made basic with ammonium hydroxide
and containing 10 ml cyanogen iodide/liter.

Note;  The absorbance from the blank b. will be 1/5

that produced by the prepared sample.  The absorption

from the spiked standards will be 1/2 that produced by the

standards plus the contribution from 1/5 of the prepared

-------
                                                                   8.60-6
    sample.  Keeping these in mind the correct dilutions




    to produce optimum absorbance can be judged.




Instrument Operation




     Wavelength: 328.1 nanometers




     Optimum Concentration Range: 0.1-4 mg/liter




     Lower Detection Limit: 0.01 mg/liter




     Fuel: Acetylene




     Oxidant: Air




     Type of flame: oxidizing




     A general outline for instrument operation is given




     in section 8.49.  Follow the manufacturer's instructions




     for the model being used.




Quantification




     The absorbances of spiked samples and blank vs. the con-




centrations are plotted according to the Method of Standard




Additions as defined in section 8.49.  The extrapolated




value will be 1/5 the concentration of the original sample.




     If the plot does not result in a straight line a




nonlinear interference is present.  This can sometimes be




overcome by dilution, or addition of other reagents if there




is some knowledge about the waste.




Records




     It is recommended that recorder outputs chart be retained




as a permanent record of the results and test conditions.

-------
                                                                   8.55-1
                         Method 8.55




                           CYANIDE
Scope and Application




     The following procedure can be used to determine




the concentration of inorganic cyanide in a waste




or leachate.




     Inorganic cyanide may be present as either a simple soluble




salt (e.g., NaCN) or complex radical (e.g., K3(Fe(CN)g)).




These metal complexes have varying tendencies to dissociate




and form toxic hydrogen cyanide in the presence of acids.




It is such soluble cyanides that this method will address.




     This method shall not be used to determine the "reactive"




cyanide content of wastes containing iron-cyanide complexes.




Summary




     The waste is divided into two parts.  One is chlorinated




to destroy susceptible complexes.   Each part is then distilled




to remove interferences and analyzed for cyanide.  The fraction




amenable to chlorination is determined by the difference in




values.




     During the distillation, cyanide is converted to hydrogen




cyanide vapor which is trapped in a scrubber containing sodium




hydroxide solution.  This solution is then titrated with




standard silver nitrate.

-------
                                                                    8.55-
Interferences



1.  Sulfides interfere with the titration.  They may be




    precipitated with cadmium.




2.  Fatty acids form soaps under alkaline titration




    conditions and interfere.   They may be extracted with a




    suitable solvent.




3.  Oxidizing agents may decompose the cyanide.  They




    may be treated with ascorbic acid.




4.  Thiocyanate presence will  interfere by distilling




    over in the procedure.  This can be prevented by addition of




    magnesium chloride.




5.  Aldehydes and ketones may  convert cyanide to




    cyanohydrin under the acid  distillation conditions.






Reagents




1.  Calcium Hypochlorite solution:  Dissolve 5 g of




    hypochlorite (Ca(OCl)2) in  100 ml of distilled water.




2.  Sodium Hydroxide solution  (1.25N):  Dissolve 50 g of



    sodium hydroxide (NaOH) in  distilled water and dilute to 1




    liter.




3.  Ascorbic acid: crystals.




4.  Potassium Iodide-starch paper.




5.  Lead acetate paper




6.  Cadmium carbonate (powdered)




7.  Hexane




8.  Acetic acid solution (1 +  9)

-------
                                                                    8.55-3
 9.  Concentrated H2S04



10.  Silver Nitrate Standard solution (0.0192N):




      Dry 5g AgN(>3 crystals to constant weight at 40°C.




      Weigh out 3.2647 grams and dissolve in distilled




      water.  Dilute 1000ml. (1ml - Img CN)




11.  Rhodanine Indicator solution:




      Dissolve 20mg p-dimethyl-amino-benzalrhodanine in




      100ml acetone.




12.  Magnesium Chloride solution:




         Weigh 510g MgC^.ei^O into a 1 liter volumetric




             flask.  Dissolve and bring to volume with distilled




             water.




 Apparatus;




 1.  Microburet,  5.0 ml, for titration.




 2.  Flasks, condenser, and tubing are needed as shown in




     the diagram.  The boiling flask should be of 1 liter size with




     inlet tube and provision for a condenser.  The gas absorber




     may be a Fisher-Milligan scrubber.  Assemble as shown in the




     diagram.

-------
                                                                   8.55-4
Procedure




1.  Test and treat the sample as follows If It is known




    or suspected that Interferences are present:




    a.  Sulfides:




         If a drop of the distillate on lead acetate test




         paper indicates the presence of sulfides, treat 25 ml more of




         the sample than that required for the cyanide determination




         with powdered cadmium carbonate.   Yellow cadmium sulfide




         precipitates if the sample contains sulfide.  Repeat this




         operation until a drop of the treated sample solution does




         not darken the lead acetate test  paper.   Filter the solution




         through a dry filter paper into a dry beaker, and from the




         filtrate, measure the sample to use for  analysis.  Avoid a




         large excess of cadmium and a long contact time in order to




         minimize  a loss by complexation or occlusion of cyanide on




         the precipitated material.  Sulfides should be removed prior




         to preservation with sodium hydroxide.




    b.  Fatty acids:




        1.   Acidify the sample with acetic acid (1 + 9)



            to pH  6.0 to 7.0.




Caution; This operation must be performed  in the  hood




and the sample left there until it can be  made alkaline




again after the extraction has been performed.

-------
                                                                   8.55-5
2.  Extract with iso-octane, hexane, or chloroform




    (preference in order named) with a solvent volume equal to




    20% of the sample volume.  One extraction is usually adequate




    to reduce the fatty acids below the interference level.




    Avoid multiple extractions or a long contact time at low pH




    in order to keep the loss of HCN at a minimum.  When the




    extraction is completed, immediately raise the pH of the




    sample to above 12 with NaOH solution.




    c.  Oxidizing agents:




        1.  Test a drop of the sample with potassium iodide-




            starch test paper (Kl-starch paper); a blue color indicates




            the need for treatment.  Add ascorbic acid, a few crystals at




            a time, until a drop of sample produces no color on the




            indicator paper.  Then add an additional 0.6 g of ascorbic




            acid for each liter of sample volume.




        2.  Take two sample aliquots.  To one 500.ml aliquot or




            a volume diluted to 500 ml, add calcium hypochlorite solutior




            dropwise while agitating and maintaining the pH between 11




            and 12 with sodium hydroxide solution (1.25N).




Caution:   The initial reaction product of alkaline chlori-




nation is the very toxic gas cyanogen chloride; therefore,




this reaction should be performed in a hood.




For convenience, the sample may be agitated in a 1 liter




beaker by means of a magnetic stirring device.




        3.  Test for residual chlorine with Kl-starch paper and




            maintain this excess for one hour, continuing agitation.  A

-------
                                                                   8.55-6
            distinct blue color on the test paper indicates a sufficient




            chlorine level.   If necessary,  add additional hypochlorite




            solution.




        4.   After one  hour,  add 0.5 g portions of ascorbic acid




            until Kl-starch  paper shows no  residual chlorine.  Add




            an additional 0.5 g of ascorbic acid to insure the presence




            of excess  reducing agent.




            Both the chlorinated and unchlorinated aliquots are now




            separately distilled as follows:




        5.   Place 500  ml of  sample, or an aliquot diluted to 500




            ml in the  1 liter boiling flask.   Add 50 ml of sodium hydrox-




            ide (1.25N) to the absorbing tube and dilute if necessary with




            distilled  water  to obtain an adequate depth of liquid in  the




            absorber.   Connect the boiling  flask, condenser, absorber and




            trap in the train.




        6.   Start a slow stream of air entering the boiling




            flask by adjusting the vacuum source.  Adjust the vacuum so




            that approximately one bubble of air per second enters the




            boiling flask through the air inlet tube.




Caution;  The bubble rate will not remain constant after




the reagents have been added and while heat is being applied




to the flask.  It will be necessary to readjust the air rate




occasionally to prevent the  solution in the boiling flask




from backing up into the air inlet tube.

-------
                                                                   8.55-7
        7.  Slowly add 25 ml cone, sulfuric acid through the air




            inlet tube.  Rinse the tube with distilled water and allow




            the air flow to mix the flask contents for 3 min.  Pour 20ml




            of magnesium chloride solution into the air inlet and wash




            down with a stream of water.




        8.  Heat the solution to boiling, taking care to prevent




            the solution from backing up into and overflowing from the




            air inlet tube.  Reflux for one hour.  Turn off heat and




            continue the airflow for at least 15 minutes.  After cooling




            the boiling flask, disconnect absorber and close off the




            vacuum source.




        9.  Drain the solution from the absorber into a 250 ml




            volumetric flask and bring up to volume with distilled water




            washings from the absorber tube.




       10.  Titration:




            a.  Add the solution or an aliquot diluted to 250 ml




                to a 500 ml erlenmeyer flask.  Add 10-12 drops




                Rhodanine indicator.




     Titrate with standard silver nitrate to the first change




in color from yellow to brownish-pink.  Titrate a distilled




water blank using the same amount of sodium hydroxide and




indicator as in the sample.




     The analyst should familiarize himself with the end




point of the titration and the amount of indicator to be used




before actually titrating the samples.  A 5 or 10 ml mlcroburet

-------
                                                                   8.55-8
may be conveniently used to obtain precise titration.

        b.  Titrate a blank using distilled water.

Calculation;
                       (A - B)l,000    x 	250	
        a.  CN, mg/1 = ml orig. sample   ml of aliquot titrated

                 where:

                 A. = volume of AgNC>3 for titration of sample.


                 B = volume of AgNOg for titration of blank.

        b.   Cyanide amenable to chlorination:

             CN,  mg/1 - A - B

                 A = mg/1 total cyanide in unchlorinated aliquot

                 B = mg/1 total cyanide in chlorinated aliquot

-------
                                                       8.55-9
ALLIHN CONDENSER


AIR INLET
ONE LITER	•
BOILING FLASK
— CONNECTING TUBING
                         GAS ABSORBER
                                              SUCTION
                      Figure 8.55-1
            APPARATUS FOR CYANIDE DISTILLATION

-------
                                                                  8.80-1
                         METHOD 8.80




                       DIRECT INJECTION









     Direct injection is the simplest and most precise technique




for introducing a liquid into a measurement instrument since




transfer losses are eliminated.  Samples are introduced into




the gas chromatograph by injection through the injection port,




into the liquid chromatograph using either the injection port




or sample loop, or into the atomic absorbtion spectrometer




by aspiration into the flame or injection into the graphite




furnace.




     Direct injection should only be used with liquids free of




particulate matter and in the case of the gas chromatograph




also free of non-volatile species (e.g., lipids, polymers)




in order to prevent column degradation.




     When using direct injection of wastes caution must be




exercised to prevent column or detector overload.  To insure




that valid results are obtained the analyst should initially




conduct range finding experiments to insure that the sample




matrix is free enough from interfering species so that the




contaminant of Interest can be determined if present In the




sample at a levl of 1 ug/gm of sample level.  If such sensi-




tivity cannot be obtained, then additional sample cleanup




(e.g., column chromatography, liquid-liquid extraction,




exclusion chromatography) must first be carried out.

-------
                                                  .   .                     o*
                                         (,(,   Revision B   4/15/81   8.56-1
                              Method 8.56
                             TOTAL ORGANIC HALIDE
1.  Scope and Application
    1.1  This method is to be used for the determination of Total  Organic
         Hal ides as Cl" by carbon adsorption, and requires that all
         samples be run in duplicate.  Under conditions of duplicate
         analysis, the reliable limit of sensitivity is 5 ug/L.  Organic
         halides as used in this method are defined as all organic species
         containing chlorine, bromine and iodine that are adsorbed by
         granular activated carbon under the conditions of the method.
         Fluorine containing species are not determined by this method.
    1.2  This is a microcoulometric-titration detection method applicable to
         the determination of the compound class listed above in drinking
         and ground waters, as provided under 40 CFR 265.92.
    1.3  Any modification of this method, beyond those expressly permitted,
         shall be considered as major modifications subject to application
         and approval of alternate test procedures under 40 CFR 260.21.
    1.4  This method is restricted to use by, or under the supervision  of,
         analysts experienced in the operation of a pyrolysis/microcolumeter
         and in the interpretation of the results.
2.  Summary of Method
    2.1  A sample of water that has been protected against the loss  of
         volatiles by the elimination of headspace in the sampling
         container, and is free of undissolved solids, is passed through a
         column containing 40 mg of activated carbon.  The column  is washed

-------
                                                                          f-t
                                               Revision B   4/15/81  8.56-2
         to remove any trapped inorganic halides, .a/id, is then.D.vrolvzed to
         convert the adsorbed organohaTides  to a titratable species that can
         be measured by a microcoulometric detector.
3.   Interferences
    3.1  Method interferences may be caused  by contaminants, reagents,
         glassware, and other sample processing hardware.  All  of these
         materials must be routinely demonstrated to  be free from
         interferences under the conditions  of the analysis by running
         method blanks.
         3.1.1  Glassware must be scrupulously cleaned.  Clean all glassware
                as soon as possible after use by treating with chromate
                cleaning solution.  This should be followed by detergent
                washing in hot water.  Rinse with tap water and distilled
                water, drain dry, and heat in a muffle furnace at 400°C
                for 15 to 30 minutes.  Volumetric ware should not be heated
                in a muffle furnace.  Glassware should be sealed and stored
                in a clean environment after drying and cooling, to prevent
                any accumulation of dust or other contaminants.
         3.1.2  The use of high purity reagents and gases help to minimize
                interference problems.
    3.2  Purity of the activated carbon must be verified t>efore use.  Only
         carbon samples which register less than 1000 ng/40 mg should be
         used.  The stock of activated carbon should be stored in its
         granular form in a glass container with a Teflon seal.  Exposure to
         the air must be minimized, especially during and after milling and
         sieving the activated carbon.  No more than a two-week supply

-------
                                                Revision  B  4/15/81   8.56-3

         should be prepared in advance.  Protect carbon at all times from
         all sources of halogenated organic vapors.   Store prepared carbon
         and packed columns in glass containers with Teflon seals.
    3.3  This method is applicable to samples whose  inorganic-halide
         concentration does not exceed the organic-halide concentration by
         more than 20,000 times.
4.  Safety
    The toxicity or carcinogenicity of each reagent  in this method  has not
    been precisely defined; however, each.chemical compound should  be
    treated as a potential health hazard.  From this viewpoint,  exposure to
    these chemicals must be reduced to the lowest possible level by whatever
    means available.  The laboratory is responsible  for maintaining a
    current-awareness file of OSHA regulations regarding the safe handling
    of the chemicals specified in this method.  A reference file of
    material-handling data sheets should also be made available  to  all
    personnel involved in the chemical analysis.
5.  Apparatus and Materials  (All specifications are suggested.   Catalog
    numbers are included for illustration only).
    5.1  Sampling equipment, for discrete or composite sampling
         5.1.1  Grab-sample bottle - Amber glass, 250-ml, fitted with
                Teflon-lined caps.  Foil may be substituted for  Teflon if
                the sample is not corrosive.  If amber bottles are  not
                available, protect samples from light.  The container must
                be washed and muffled at 400°C before use,  to minimize
                contamination.

-------
                                         Revision  B  4/15/81   8.56-4
5.2  Adsorption System
     5.2.1  Dohrmann Adsorption Module (AD-2),  or equivalent,
            pressurized,  sample and nitrate-wash  reservoirs.
     5.2.2  Adsorption columns - pyrex,  5 cm long X  6-mm  OD X  2-mm ID.
     5.2.3  Granular Activated Carbon (GAC)  - Filtrasorb-400,
            Calgon-APC, or equivalent, ground or  milled,  and screened  to
            a 100/200 mesh range.   Upon  combustion of 40  mg of GAC,  the
            apparent-halide background should be  1000-mg  Cl~
            equivalent or less.
     5.2.4  Cerafelt (available from Johns-Manvilie), or  equivalent -
            Form this material into plugs using a 2-mm ID
            stainless-steel borer  with ejection rod  (available from
            Dohrmann) to  hold 40 mg of GAC in the adsorption columns.
            CAUTION:  Do  not touch this  material  with your fingers.
     5.2.5  Column holders (available from Dohrman).
     5.2.6  Volumetric flasks - 100-mL,  50-mL.
            A general schematic of the adsorption system  is shown in
            Figure 1.
5.3  Dohrmann microcoulometric-titration system (MCTS-20  or DX-20),  or
     equivalent, containing the following components:
     5.3.1  Boat sampler.
     5.3.2  Pyrolysis furnace.
     5.3.3  Microcoulometer with integrator.
     5.3.4  Titration cell.
            A general description  of the analytical  system is  shown in
            Figure 2.
5.4  Strip-Chart Recorder.

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                                                                         ,
                                              Revision B   4/15/81  8.56^5
6.  Reagents
    6.1  Sodium sulfite - 0.1 M, ACS reagent grade (12.6 g/L).
    6.2  Nitric acid - concentrated.
    6.3  Nitrate-Wash Solution (5000 mg NO^/L) - Prepare a  nitrate-wash
         solution by transferring approximately 8.2 gm of potassium nitrate
         into a 1-litre volumetric flask and diluting to volume with reagent
         water.
    6.4  Carbon dioxide - gas, 99.9% purity.
    6.5  Oxygen - 99.955 purity.
    6.6  Nitrogen - prepurified.
    6.7  70/6 Acetic acid in water - Dilute 7 volumes of acetic  acid with  3
         volumes of water.
    6.8  Trichlorophenol solution, stock (1  uL = 10 yg Cl")  - Prepare a
         stock solution by  weighing accurately 1.856 gm of  trichlorophenol
         into a 100-mL volumetric flask.  Dilute to volume  with methanol.
    6.9  Trichlorophenol solution, calibration (1 uL = 500  ng Cl")  -
         Dilute 5 ml of the trichlorophenol  stock solution  to 100 ml with
         methanol.
    6.10 Trichlorophenol standard, instrument-calibration -  First,  nitrate
         wash a single column packed with 40 mg of activated carbon as
         instructed for sample analysis, and then inject the column with
         10 uL of the calibration solution.
    6.11  Trichlorophenol standard, adsorption-efficiency (100 ug C1~/L) -
         Prepare a adsorption-efficiency standard by injecting  10 vl of
         stock solution into 1 liter of reagent water.
    6.12 Reagent water - Reagent water  is defined as a water in which an

-------
                                              Revision B   4/15/81   8.56-6
         interferent is not observed at the method detection limit of each
         parameter of interest.
    6.13 Blank standard - The reagent water used to prepare the calibration
         standard should be used as the blank standard.
7.  Calibration
    7.1  Check the adsorption efficiency of each newly-prepared batch of
         carbon by analyzing 100 mL of the adsorption-efficiency standard,
         in duplicate,  along with duplicates of the blank  standard.  The net
         recovery should be within 5% of the standard value.
    7.2  Nitrate-wash blanks (Method Blanks) - Establish the repeatability
         of the method  background each day by first analyzing several
         nitrate-wash blanks.  Monitor this background by  spacing nitrate-
         wash blanks between each group of eight pyrolysis  determinations.
         7.2.1  The nitrate-wash blank values are obtained  on single columns
                packed  with 40 mg of activated carbon.  Wash with the
                nitrate solution as instructed for sample  analysis, and then
                pyrolyze the carbon.
    7.3  Pyrolyze duplicate instrument-calibration standards and the blank
         standard each  day before beginning sample analysis.  The net
         response to the calibration-standard should be within 3% of the
         calibration-standard value.  Repeat analysis of the
         instrument-calibration standard after each group  of eight pyrolysis
         determinations, and before resuming sample analysis after cleaning
         or reconditioning the titration cell or pyrolysis  system.
8.  Sample Preparation
    8.1  Special care should be taken in the handling of the sample to

-------
                                              Revision  B  4/15/81   8.56-7
         minimize the loss of volatile organohalides.  The adsorption
         procedure should be performed simultaneously on duplicates.
    8.2  Reduce residual chlorine by the addition of sulfite (1 ml of 0.1 M
         per liter of sample).  Addition of sulfite should be done at the
         time of sampling 1f the analysis is meant to determine the TOX
         concentration at the time of sampling.  It shou-ld be recognized
         that TOX may increase on storage of the sample.   Samples should be
         stored at 4°C without headspace.
    8.3  Adjust pH of the sample to approximately 2 with concentrated HN03
         just prior to adding the sample to the reservoir.
9.  Adsorption Procedure
    9.1  Connect two columns in series, each containing 40 mg of
         100/200-mesh activated carbon.
    9.2  Fill the sample reservoir, and pass a metered amount of sample
         through the activated-carbon columns at a rate, of approximately
         3 mL/min.  NOTE:  100 ml of sample is the preferred volume for
         concentrations of TOX between 5 and 500 ug/L; 50 ml for 501 to 1000
         yg/L, and 25 ml for 1001 to 2000 yg/L.
    9.3  Wash the columns-in-series with 2 ml of the 5000-mg/L nitrate
         solution at a rate of approximately 2 mL/min to displace inorganic
         chloride ions.
10.  Pyrolysis Procedure
    10.1 The contents of each column is pyrolyzed separately.   After rinsing
         with the nitrate solution, the columns should be protected from the
         atmosphere and other sources of contamination until ready for
         further analysis.

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                                             Revision  B  4/15/81   8.56-8
    10.2  Pyrolysis  of the  sample  is  accomplished in two  stages.  The
         volatile components  are  pyrolyzed  in a CCL-rich  atmosphere at a
         low  temperature to assure the conversion of brominated
         trihalomethanes to a titratable species.  The less volatile
         components  are then  pyrolyzed at a high temperature  in an (L-rich
         atmosphere.
         NOTE:   The  quartz sampling  boat should have been previously muffled
         at 800°C for at least 2  to  4 minutes as in a previous analysis,
         and  should  be cleaned of any residue by vacuuming.
    10.3  Transfer the contents of each column to the quartz boat for
         individual  analysis.
    10.4  If the  Dohrmann MC-1 is  used for pyrolysis, manual instructions  are
         followed for gas  flow regulation.  If the MCT-20 is  used, the
         information on the diagram  in Figure 3 is used  for gas flow
         regulation.
    10.5  Position the sample  for  2 minutes  in the 200°C  zone  of the
         pyrolysis  tube.   For the MCTS-20,  the boat is positioned just
         outside the furnace  entrance.
    10.6  After 2 minutes,  advance the boat  into the 800°C zone (center) of
         the  pyrolysis furnace.   This second  and final stage  of pyrolysis
         may  require from  6 to  10 minutes to  complete.
11.  Detection
    The effluent gases are directly  analyzed  in the microcoulometric-titra-
    tion  cell.   Carefully  follow  manual  instructions for optimizing cell
    performance.

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                                             Revision B  4/15/81   8.56-9
12.  Breakthrough
    Because the background bias can be of such  an  unpredictable nature,  it
    can be especially difficult to recognize the extent of breakthrough  of
    organohalides from one column to another.  All  second-column
    measurements for a properly operating system should not exceed
    10-percent  of the two-column total measurement.   If the 10-percent
    figure is exceeded, one of three events  can have happened.   Either the
    first column was overloaded and a legitimate measure of breakthrough was
    obtained -  in which case taking a smaller sample may be necessary; or
    channeling  or some other failure occurred - in  which case the sample may
    need to be  rerun; or a high, random,  bias occurred and the  result should
    be rejected and the sample rerun.  Because  knowing which  event has
    occurred may not be possible, a sample analysis should be repeated often
    enough to gain confidence in results.  As a general rule, any analyses
    that is rejected should be repeated whenever sample is available. In
    the event that the second-column measurement is equal  to  or less  than
    the nitrate-wash blank value, the second-column value  should be
    disregarded.
13.  Quality Control
    13.1 Before performing any analyses,  the analyst must  demonstrate the
         ability to generate acceptable accuracy and precision  with this
         procedure by the analysis of appropriate  quality-control check
         samples.
    13.2 The laboratory must develop and  maintain  a statement of method
         accuracy for their laboratory.  The laboratory should  update the
         accuracy statement regularly as  new recovery measurements are made.

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                                              Revision B   4/15/81   8.56-10
    13.3 It is recommended that  the laboratory adopt  additional
         quality-assurance practices  for use  with  this  method.   The  specific
         practices that would be most productive will depend  upon  the needs
         of the laboratory and the  nature of  the samples.   Field duplicates
         may be analyzed to monitor the precision  of  the sampling
         technique.  Whenever possible, the  laboratory  should perform
         analysis of standard reference materials  and participate  in
         relevant performance-evaluation studies.
14.  Calculations
    OX as Cl" is calculated using the following formula:
                    (Cj- c3) * (c2  -  c3 ) u   yg/L  Total Organ1c  Halide
    where:
    C,  = ug Cl" on the first column in  series
    C«  = ug Cl" on the second column in series
    C3  = predetermined, daily, average, method-blank value
           (nitrate-wash blank for a 40-mg carbon column)
    V = the sample volume in L
15. Accuracy and Precision
    These procedures have been applied  to a large number of drinking-water
    samples.  The results of these analysis are summarized in Tables I and
    II.
16. Reference
    Oressman, R., Najar, G., Redzikowski, R., paper presented at the
    Proceedings of the American Water Works Association Water Quality
    Technology Conference, Philadelphia, Dec. 1979.

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                                         Revision B   4/15/81   8.56-11
                                TABLE  I
            PRECISION AND ACCURACY  DATA FOR MODEL COMPOUNDS
Model
Compound
CHCU
0
CHBrCl2
CHBr2Cl
CHBr3
Pentachlorophenol
Dose
ug/L
98
160
155
160
120
Dose
as ug/L Cl
88
106
79
67
80
Average
% Recovery
89
98
86
111
93
Standard
Deviation
14
9
n
8
9
No. of
Replicate;
10
11
13
11
7
                               TABLE II
                 PRECISION DATA ON TAP WATER ANALYSIS
Sample

  A
  B
  C
Avg. halide
 ug Cl/L
     71
     94
    191
Standard
Deviation
 4.3
 7.0
 6.1
  No.  of
Replicates

    8
    6
    4

-------
                                 Revision B  4/15/81  8.56-12
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-------
Revision B  4/15/81  8.56-14

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                                       Revision B   4/15/81   8.57-1
                         Method 8.57

                           Sulfides

1.  Scope and Application
    1.1  This method is applicable to the measurement of total
         and dissolved sulfides in drinking, surface and saline
         waters, domestic and industrial wastes.
    1.2  Acid insoluble sulfides are not measured by this method.
         Copper sulfide is the only common sulfide in this class.
    1.3  This method is suitable for the measurement of sulfide
         in concentrations above 1 mg/1
2.  Summary of Method
    2.1  Excess iodine is added to a sample which may or may
         not have been treated with zinc acetate to produce zinc
         sulfide.  The iodine oxidizes the sulfide to sulfur
         under acidic conditions.   The excess iodine is back
         titrated with sodium thiosulfate or phenylarsine oxide.
3.  Comments
    3.1  Reduced sulfur compounds, such as sulfite, thiosulfate
         and hydrosulfite, which decompose in acid may yield erratic
         results.  Also, volatile iodine-consuming substances
         will give high results.
    3.2  Samples must be taken with a minimum of aeration.
         Sulfide may be volitilized by aeration and any ozygen
         inadvertently added to the sample may convert sulfide
         to an unmeasurable form.
    3.3  If the sample is not preserved with zinc acetate, the
         analysis must start immediately.  Similarly, the
         measurement of dissolved sulfides must also be commenced
         immediately.
4.  Apparatus: Ordinary laboratory glassware
5.  Reagents
    5.1  Hydrochloric acid, HC1, 6N
    5.2  Standard iodine solution, 0.0250 N: Dissolve 20 to 25 g
         KI in a little water in a liter volumetric flask and add
         3.2 g iodine.  Allow to dissolve.  Dilute to 1 liter and
         standardize against 0.0250 N sodium thiosulfate or
         phenylarsine oxide using a starch indicator.
    5.3  Phenylarsine oxide 0.0250 N: commercially available.
    5.4  Starch indicator: commercially available.
    5.5  Procedure for standardization (see Residual Chlorine-
         iodometric titration)
6.  Procedure
    6.1  Unprecipitated sample
         6.1.1  Place a known amount of standard iodine solution
                (5.2) into a 500 ml flask.  The amount should
                be estimated to be in excess of the amount of
                sulfide expected.
         6.1.2  Add distilled water, if necessary, to bring the
                volume to approximately 20 ml.
         6.1.3  Add 2 ml of 6N HC1 (5.1)
         6.1.4  Pipet 200 ml of sample into the flask, keeping
                the tip of the pipet below the surface of the
                sample.
         6.1.5  if the iodine color disappears,  add more iodine

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                                                                 /„ -
                                       Revision B   4/15/81    8.57-2
                until the color remains.  Record the total
                number of milliliters of the standard  iodine  used
                in performing steps 6.1.1 and 6.1.5.
         6.1.6  Titrate with reducing solution  (0.0250 N  sodium
                thiosulfate or 0.0250 N phenylarsine oxide
                solution (5.3)) using the starch indicator  (5.4)
                until the blue color disappears.  Record  the
                number of milliliters used.
    6.2  Precipitated samples
         6.2.1  Add the reagents to the sample  in the  original
                bottle.  Perform steps 6.1.1, 6.1.3, 6.1.5, and
                6.1.6.
    6.3  Dewatered samples
         6.3.1  Return the glass fibre filter paper which con-
                tains the sample to the, original bottle.  Add
                200 ml of distilled water.  Perform steps 6.1.1,
                6.1.3, 6.1.5, and 6.1.6.
         6.3.2  The calculations (7) should be  based on the
                original sample put throug the  filter.
7.   Calculations
    7.1  One ml of 0.0250 N standard iodine solution  (5.2)
         reacts with 0.4 mg of sulfide present  in the  titration
         vessel.
    7.2  Use the formula

         mg/1 sulfide = 400(A-B)/ml sample

         where:
                A=ml of 0.0250 N standard iodine solution (5.2)
                B=ml of 0.0250 N standard reducing sodium
                  thiosulfate or phenylarsine oxide solution  (5.3)

8.   Precision and Accuracy
    8.1  Precision and accuracy for this method have not  been
         determined.
                                            HI.S. GOVERNMENT PRINTING OFFICE: 1981  341-082/248 1-3

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                                                                  8.82-1
                          Method 8.82




                        HEADSPACE METHOD




Scope and Application




     This method provides a procedure for the extraction of




volatile organic compounds in pastes and solids.  The static




headspace technique is a simple method which allows large




numbers of samples to be analyzed in a relatively short period




of time.  Because of the large variability and complicated




matrices of waste samples in the solid and paste forms,




detection limits for this method may vary widely among samples.




The method works best for compounds with boiling points less




than 125°C.  Due to their low solubility, low molecular




weight compounds can only be detected at high concentrations




or at reduced pressure.




     The sensitivity of this method will depend on the equili-




bria of the various compounds between the vapor and dissolved




phases .




                  Static Headspace Technique




Summary of Method




     The waste is collected in sealed glass containers and




allowed to equilibrate at 90°C.  A sample of the headspace




gas is withdrawn with a gas tight syringe for analysis by the




appropriate gas chromatographic method.




Apparatus




1.  Gas-tight syringe - 5-cc.




2.  Head space standard solutions - Prepare two standard solu-




    tions of the compounds being determined at the 50-ng/ul and

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                                                                  8.82-2




    250-ng/ul coneentratioos.   Standard solutions should be prepared




    using methanol,  methane, or other appropriate solvent.  The




    standard solutions should  be stored at less than 0°C, then




    allowed to warm  to room temperature before dosing.  Fresh




    standards should be prepared weekly.  Procedures for preparing




    standards are outlined in  the Purge and Trap Procedure of this




    manual (Method 8.83).




3.  Vials, 125 ml "Hypo-Vials" (Pierce Chemical Co., #12995), or




    equivalent•




4.  Septa, "Tuf-Bond" (Pierce  #12720), or equivalent.




5.  Seals, aluminum, (Pierce #13214), or equivalent.




6.  Crimper, hand, (Pierce #13212), or equivalent.




Procedure




1.  Place 10.0-g each of the well-mixed waste sample into five




    separate 125-ml  septum seal vials.




2.  Dose one sample vial through the septum with 200-ul of the




    50-ng/ul standard methanol solution.  Dose a second vial with




    200-ul of the 250-ng/ul standard.




3.  Place the two dosed sample vials and one non-dosed sample into




    a 90°C water bath for 1 hour.  Store the two remaining samples




    near 4°C for possible future analyses.




4.  While maintaining the sample at 90°C, withdraw 2.0-ml of the




    head gas with a gas tight  syringe and analyze by injecting




    into a GC, operating under the appropriate conditions for




    the GC measurement method  being used.  Analyze all three




    samples in exactly the same manner.  Subtract the peak




    areas of compounds found in the undosed sample from the




    corresponding compounds contained in the dosed samples.

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                                                                   8.82-3
    If a positive response is noted then the waste has not been

    demonstrated to be free of the contaminant of interest and

    is thus not fundamentally different than the listed waste.

    If no response is noted then the required sensitivity

    lug/gm sample) of the procedure must be confirmed using

    spiked samples.

Note;  Standard quality assurance protocols should be employed,

including blanks, duplicates, and dosed samples, as described

in Section 10.


                          Bibliography

1.   "Interim Methods for the Sampling and Analyses of Priority
     Pollutants in Sediments and Fish Tissue," U.S. Environmental
     Protection Agency,  Environmental Monitoring and Support
     Laboratory, Cincinnati, Ohio 45268 [1980].

2.   "Master Scheme for  the Analysis of Organic Compounds in
     Water, Part I:  State-of-the-Art Review of Analytical
     Operations," U.S. Environmental Protection Agency,
     Environmental Research Laboratory, Athens, Georgia 30605.

3.   "An EPA Manual for  Organic Analysis Using Gas Chromatography
     Mass Spectrometry," W.L. Budde and J.W. Eichelberger, U.S.
     Environmental Protection Agency, Environmental Monitoring
     Support Laboratory, Cincinnati, Ohio, 1979, EPA/600/8-79/006,
     Order Number PB-297164.

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                                                                8.83-1
                          Method 8.83




                     PURGE AND TRAP METHOD






Scope and Application




     This method covers a procedure for the extraction of pur-




geable organic compounds from aqueous liquids and free flowing




paste samples prior to gas chromatographic analysis.




     The success of the extraction depends on partitioning




the compounds between the sample phase and gaseous headspace




phases.  This partitioning is a function of temperature,




interfacial area, the volatility of the species being analyzed




for, its solubility in the liquid being purged, and the




volatility of the waste matrix.  For highly volatile matrices,




direct injection preceded by dilution, if necessary, should be




used.  For pastes, dilution of the sample until it becomes free




flowing is used to insure adequate interfacial area.  The




success of this method also depends on the level of interferences




in the sample; results may vary due to the large variability




and complicated matrices of solid waste samples.




Summary of Method




     An inert gas is bubbled through the sample contained in




a specially-designed purging chamber.  This purging transfers




the volatile compounds from the liquid phase to the vapor




phase.  The gaseous effluent is then swept through a short




sorbent tube where the organic compounds are trapped.   After




purging is completed,  the trap is heated and backflushed to

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                                                                8.83-2
desorb the compounds into a gas chromatograph for subsequent




identification and measurement.




Apparatus




1.  Vial, with cap--40 ml capacity screw cap (Pierce #13075




    or equivalent).  Detergent wash and dry vial at 105°C for one




    hour before use.




2.  Septum, Teflon faced silicone (Pierce #12722 or equiva-




    lent).  Detergent wash and dry at 105°C for one hour before




    use.




3.  Purge and Trap Device; The purge and trap equipment




    consists of three separate pieces of apparatus:   a purging




    device, a trap, and a desorber.  The complete device is avail-




    able commercially from several vendors or can be constructed




    in the laboratory according to the specifications of Bellar




    and Lichtenberg (1).  The sorbent trap consists of a 1/8 in.




    O.D. (0.105 in. I.D.) x 25 cm long stainless steel tube




    packed with the appropriate absorbent as described in Table




    8.83-1 (See Figures 8.83-1 through 8.83-4).   10-cm traps may




    be used providing that the recoveries are demonstrated to be




    comparable to the 25-cm traps.



Reagents




1.  Trap Materials, see Table 8.83-1.




2.  Activated carbon Filtrasorb 200 (Calgon Corp.) or equivalent




3.  Organic-free water

-------
                                                                8.83-3
    Organic-free water Is defined as water free of Inter-




    ferences when employed in the purge and trap procedure.




    It is generated by passing distilled or deionized water




    through a carbon filter bed containing activated carbon.




    A water system (Millipore Super-Q or equivalent) may




    be used to generate organic-free deionized water.  Organic-




    free water may also be prepared by boiling deionized distilled




    water for 15 minutes.  Subsequently, while maintaining the




    temperature at 90°C, bubble a contaminant-free inert gas




    through the water for one hour.  While still hot, transfer




    the water to a narrow mouth screw cap bottle equipped




    with a Teflon seal.




Procedures




1.  Assemble the purge and trap device (see Figures 8.83-1




    through 8.83-4).  Purge parameters to be used depend on




    the compounds being analyzed for; see Table 8.83-1.




    Pack the trap as shown in Figure 8.83-2 and condition




    overnight at a nominal 180°C by backflushing with an




    inert gas flow of at least 20 ml/min.  Daily, prior to




    use, condition the traps for 10 minutes by backflushing




    at 180°C.




2.  Remove standards and samples from cold storage (approx-




    imately an hour prior to an analysis) and bring to room




    temperature by placing In a warm water bath at 20-25°C.




3.  Adjust the purge gas (nitrogen or helium) flow rate




    according to Table 8.83-1.

-------
                                                                8.83-4
4.  Attach the trap inlet to the purging device, and

    set the device to the purge mode.  Open the syringe valve

    located on the purging device sample introduction needle.

5.  Remove the plunger from a 5 ml syringe and attach a closed

    syringe valve.  Open the sample bottle (or standard) and

    carefully pour the sample into the syringe barrel until

    it overflows.

    Note;  For pastes it may be necessary to dilute the sample
    by adding a non-volatile solvent to the sample.  In such
    cases  diluting can be performed in the purging device.

6.  Replace the syringe plunger and compress the sample.

    Open the syringe valve and vent any residual air while

    adjusting the sample volume to 5.0 ml.  Since this process

    of taking an aliquot destroys the validity of the sample

    for future analysis, the analyst should fill a second

    syringe at this time to protect against possible loss of

    data.

7.  Add 5.0 ml of the spiking solution through the valve

    bore,  then close the valve.

8.  Attach the syringe-valve assembly to the syringe valve

    on the purging device.  Open the syringe valve and inject

    the sample into the purging chamber.  Close both valves

    and purge the sample for the time specified in Table

    8.83-1.  If method 8.02 will be used for analysis of the

    sample, dry the trap by maintaining a flow rate of 40

    ml/minute dry purge for 6 minutes.

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                                                                 8.83-5
 9.   Attach the  trap  to  the  chromatograph,  and  adjust  the

     device to the  desorb mode.   Introduce  the  trapped materials

     to the GC column by rapidly heating  the  trap to the backflush

     temperature indicated in Table  8.83-1, while backflushing

     the trap with  an inert  carrier  gas  at  20 to 60 ml/minute

     for 4 minutes.   If  rapid heating cannot  be achieved,  the

     gas chromatographic column  must be  used  as a secondary

     trap by cooling  it  to 30°C  (or  subambient, if problems

     persist) instead of the initial program  temperature of 45

     or 50°C.

10.   While the trap is being desorbed into  the  gas chromato-

     graph, clean the purging chamber.   After the purging

     device has  been  emptied, continue  to allow the purge gas

     to vent through  the chamber until  the  frit is dry, and

     ready for the  next  sample.   After  desorbing the sample

     for four minutes, recondition the  trap by  returning the

     purge and trap device to the purge  mode.  Wait 15 seconds

     then close  the syringe  valve on the purging device to

     begin gas flow through  the  trap.  Maintain the trap tempera-

     ture at 180°C.   After approximately seven  minutes, turn

     off the trap heater and open the syringe valve to stop

     the gas flow through the trap.   When cool, the trap is

     ready for the  next  sample.

     Note;  If this bake out step is omitted  when using GC/MS
     as the measurement  technique, the  amount of water entering
     the GC/MS system will progressively increase causing
     deterioration  and potential shut down  of the system.

-------
                                                                8.83-6
11.   The analysis of blanks is most important in the purge




     and trap technique since the purging device and the trap




     can become contaminated by residues from very concentrated




     samples or by vapors in the laboratory.   Prepare blanks by




     filling a sample bottle with organic-free water.  Blanks




     should be sealed,  stored at 4°C,  and analyzed with each




     group of samples.

-------
References




1.  "Determining Volatile Organics at Microgram-per-liter



     Levels by Gas Chromatography," T.A. Bellar and J.J.




     Lichtenberg, Journal. AWWA, 66, 739-744, Dec. 1974.
                                                                 8.83-7

-------
                                                                8.83-8
                               Table 8.83-1

                        PURGE AND TRAP PARAMETERS
Analysis
Method*
Purge Gas
Purge Gas
Flow Rate
(ml/mln)
Purge Time
(minutes )
Purge
Temperature
(°C)
Desorbtlon
Gas Flow
Rate (ml/mln)
Sorbants To
8.01
Nitrogen or
Helium
40
11.0
180°
20
A
8.02 8.03
Nitrogen or Helium
Helium
40 20+1
12.0 30.0
180° 170°
20 20
B C
8.24
Nitrogen or
Helium
40
12.0
180°
20
D
Be Used in
Packing Tube
                            Porous polymer packing, 60/80 mesh,
                            chromatographic grade Tenax GC
                            (2,6-Diphenylene Oxide).

                            Three percent OV-1 on Chromosorb-W,
                            60/80 mesh.

                            Silica gel, 35-60 mesh Davison grade-15
                            or equivalent.

                            Coconut charcoal, 6/10 mesh, Barnaby
                            Chaney C.A. - 580-26 lot # M - 2649
                            or equivalent .	
                 B
Porous polymer packing, 60/80 mesh
chromatographic grade Tenax GC
(2,6-Diphenylene Oxide).

Three percent OV-1 on Chromosorb-W,
60/80 mesh.

Silica gel, 35-60 mesh, Davison grade-15
or equivalent.	
                            Porous polymer packing, 50/80 mesh,
                            chromatographic grade Tenax GC
                            (2,6-Diphenylene Oxide).

-------
                                                               8.83-9
                           Three percent OV-1 on Chromosorb-W,
                           60/80 mesh.

                           Silica gel, 35-60 mesh, Davison grade-15
                           or equivalent.	
                           Porous polymer packing, 60/80 mesh,
                           chromatographic grade Tenax GC
                           (2,6-Diphenylene Oxide).

                           Three percent OV-1 on Chromosorb-W,
                           60/80 mesh.

                           Silica gel, 35-60 mesh, Davison grade-15
                           or equivalent.	
*Measurement method to be employed for identification and
 quantification

-------
                                                                     8.83-10
     OPTIONAL
     FOAM
     TRAP
     0. D.

I—14MM 0. D

 INLET « IN.
     0.0.
  0. D. EXIT
    10WIM GLASS FRIT
    MEDIUM POROSITY
    SAMPLE INLET
    2-WAY SYRINGE VALVE
    •17CM. 20 GAUGE SYRINGE NEEDLE
       . 0. D. RUBBER SEPTUM

      —IQlCia. 0. D.   I/IS IN. O.D.
                  fl/STAIWLESSSTB.
                                        13X MOLECULAR
                                        SIEVE PURGE
                                        GAS FILTER
                                          PURGE GAS
                                          ROW
                                          CONTROL
                       Figure 8.83-1
                      PURGING DEVICE
     PACKING PROCEDURE
    GLASS
    WOOL
GRADE 15
SILICA GEL8CM
 TENAX 15CM
 35i OV-1 1CMJ ^
 GLASS  5MM  &
 WOOL
         CONSTRUCTION
                     COMPRESS10W
                    • FITTWCNL'T
                     AND FERRULES
                     RESISTANCE RTRE
                     WRAPPED SOLID
                      THERMOCOUPLE/
                      CONTROLLER
                      SENSOR
                       ELECTRONIC
                       TEMPERATURE
                       CONTROL
                       AND
                       PYROMETER
                    TUBING 25CU
                    0.105 IN. I.D.
                    0.125 IN. O.D.
                    STAINLESS STE
                   Figure 8.83-2
          TRAP PACKINGS AND CONSTRUCTION
           TO INCLUDE DESORB CAPABILITY

-------
           CARRIER GAS
           FLOW CONTROL  LIQUID INJECTION PORTS
   PRESSURE
     GULATOR
PURGE GAS  ...
FLOW CONTROL]^!,


 13X MOLECULAR ^
 SIEVE FILTER ~
                                            COLUMN OVEN
                                , n n n n_L   CONFIRMATORY COLUMN
                                              DETECTOR
                                             ANALYTICAL COLUMN
     OPTIONAL 4-PORT COLUMN
     SB "CT10N VALVE
6-PORT ThAP INLET
VALVEJ RESISTANCE WIRE

 4w£	THAP {OFF
   ROW3    22°C
                                                   H£ATER
                                   PURGING
                                   DEVICE
                                              Note:
                                              ALL LINES BET.YEEJV
                                              TRAP AND GC
                                              SHOULD BE HEATED
                                              TO BO°C.
                        Figure 8.83-3
         SCHEMATIC OF PURGE AND TRAP DEVICE-PURGE MODE
                                                                            8.83-10
          CARRIER GAS
          FLOW CONTROL
   PRESSURE
   REGULATOR
PURGE GAS
FLOW CONTROL
                       LIQUID INJECTION PORTS
 13X MOLECULAR^
 iiEVE FILTER   p
                             ^OPTIONAL 4-PORT COLUMN
                              SaECTION VALVE
                        6-PORT TRAP INLET
                                          COLUMN OVEN
                               nnnn  I 	CONFIRMATORY COLUMN
                                   iTn_L>TO DETECTOR
                                   ITT ^-ANALYTICAL COLUUM
                                  PURGING
                                  DEVICE
                                                * CONTROL
                                            Note:
                                            ALL LINES
                                            TRAP AND GC
                                            SHOULD BE HEATED
                                            TO 80°C,
                       Figure 8.83-4
      SCHEMATIC  OF PURGE AND TRAP  DEVICE DESORB MODE

-------
                                                                 8.84-1
                           Method 8.84




                       SHAKE OUT PROCEDURE




Introduction




     This procedure provides a method for treating liquid wastes




not soluble in the extraction solvent in order to extract the




organic species prior to measurement by chromatography or, if




necessary, further clean-up.




Summary of Method




     Samples are made acid or alkaline, if necessary, then




extracted three times, with the appropriate solvent using vigo-




rous agitation.  After the combined extracts are dried with




anhydrous sodium sulfate, they are concentrated in a Kuderna-




Danish Apparatus.




Apparatus




1.  Separatory funnel - 250 ml, with Teflon stopcock.




2.  Drying column - 20 mm ID Pyrex chromatographic column




    with coarse frit.




3.  Kuderna-Danish (K-D) Apparatus.  [Kontes K-570000 or




    equivalent.]




4.  Boiling chips - solvent extracted, approximately 10/40




    mesh.




5.  Water bath - Heated, with concentric ring cover, capable




    of temperature control ( + 2° C).   The bath should be used in




    a hood.




Reagents




1.  Sodium hydroxide, (ACS) 10 N in distilled water.

-------
                                                                 8.84-2
2.  Sulfuric acid, (1+1), Mix equal volumes of concentrated




    H2S04 (ACS) with distilled water.




3.  Methylene chloride, acetone, 2-propanol, hexane, toluene-




    Pesticide quality or equivalent.




4.  Sodium sulfate (ACS) Granular, anhydrous (purified by




    heating at 400° C for four hours in a shallow tray).




Procedure




1.  Transfer 50 gms of sample to the separatory funnel.




2.  Adjust the pH of the sample to that indicated in Table




    8.84-1.




3.  Add 50 ml of the appropriate extraction solvent




    (see Table 8.84-1),




4.  Seal and shake the separatory funnel for 60 seconds




    with periodic venting to release vapor pressure.




5.  Allow the phases to separate for a minimum of ten




    minutes.  If the emulsion interface between layers is more




    than one-third the size of the solvent layer, the analyst




    must employ mechanical techniques  to complete the phase




    separation.  The optimum technique depends upon the sample,




    but may include stirring, filtration of the emulsion through




    glass wool, or centrifugation.




6.  Collect the extract and then repeat the extraction two more




    times using fresh portions of solvent.




7.  Combine the three extracts and discard the now extracted




    waste.

-------
                                                                    8.84-3
 8.  Filter the extract and then dry it by passing it through a



     drying column containing 10 cm of anhydrous sodium sulfate.




 9.  Transfer the dried extract to the K-D apparatus.  Add 1-2




     clean boiling chips to the flask and attach a three-ball




     Snyder column.  Prewet the Snyder column by adding about 1




     ml extraction solvent to the top.  Place the K-D apparatus




     on a hot water bath (60-65° C) so that the concentrator tube




     is partially immersed in the hot water, and the entire lower




     rounded surface of the flask is bathed in vapor.  Adjust the




     vertical position of the apparatus and the water temperature




     as required to complete the concentration in 15-20 minutes.




     At the proper rate of distillation the balls of the column




     will actively chatter but the chambers will not flood.  When




     the apparent volume of liquid reaches 1 ml, remove the K-D




     apparatus and allow it to drain for at least 10 minutes




     while cooling.




10.  Transfer to 10 ml volumetric flask and dilute to volume.

-------
                           Table  8.84-1




                      EXTRACTION  CONDITIONS
                                                              8.84-4
Compound
Acetonitrile
Acrolein
Acrylamlde
Acrylonltrlle
Benzene
|B en zo( a) anthracene
Benzo(a) pyrene
Benzotrichloride
Benzyl chloride
Benzo(b)fluoranthene
Bis (2-chloroethoxy-
methane)
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl)
ether
Carbon disulfide
Carbon tetrachloride
Chlordane
Chlorinated dibenzo
dioxins
Chlorinated biphenyls
Chloroacetaldehyde
Chlorobenzene
Extraction pH
NA
NA
NA
NA
NA
5-9
> 11
5-9 or > 11
5-9 or > 11
5-9
NA
NA
NA
NA
NA
5-9 or >11
6-8
5-9 or >11
NA
NA
Extraction
Solvent
NA
NA
NA
NA
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
NA
NA
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
NA = Method not applicable to analysis for this compound.

-------
EXTRACTION CONDITIONS cont .  (2)
                                                       8.84-5
Compound
2-Chlorophenol
Chrysene
Creosote
Cresol(s)
Cresylic acid(s)
Dichlorobenzene(a)
Dichloroethane(s)
Dichloromethane
Dichlorophenoxy-
acetic acid
Dichloropropanol
2,4-Dimethylphenol
Dinltrobenzene
4,6-Dlnltro-O-cresol
2,4-Dinitro toluene
Endrln
Ethyl Ether
Formaldehyde
Formic Acid
Heptachlor
Hexachlorobenzene
Hexachloro butadiene
Hexachloroe thane
Extraction pH
12
5-9
5-9 or > 11
12
12
5-9 or > 11
NA
NA
> 7 or > 11
5-9 or > 11
12
5-9 or > 11
12
5-9 or > 11
5-9 or > 11
NA
NA
5-9 or > 11
5-9 or > 11

5-9 or > 11
5-9 or > 11
Extraction
Solvent
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
Ethyl Ether or
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
Methylene Chloride
Methylene Chloride

Methylene Chloride
Methylene Chloride

-------
EXTRACTION  CONDITIONS cont. (3)
                                                    8.84-6
Compound
Hexachlorocyclo-
pentadiene
Lindane
Maleic anhydride
Me t h a n o 1
Methomyl
Methyl ethyl ketone
Methyl isobutyl ketone
Naphthalene
Napthoquinone
Nit robenz ene
4-Nitrophenol
Paraldehyde (trimer of
acetaldehyde
Pentachlorophenol
Phenol
Phorate
Pho spho rodi thioic acid
esters
Phthalic anhydride
2-Picoline
Pyridine
Tetrachlorobenzene(s)
Tetrachloroethane(s)
Extraction pH
5-9 or > 11
5-9 or > 11
5-9 or > 11
NA
6.5 - 7.5
> 11
> 11
5-9 or > 11
5-9 or > 11
5-9
12
NA
12
12
6-8
5-9
5-9 or > 11
5-9 or > 11
5-9 or > 11
5-9 or > 11
'NA
Extrac tion
Solvent
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA

-------
EXTRACTION CONDITIONS  cont.  (4)
                                                   8.84-7
Compound
Tetrachloroethene
Tetrachlorophenol
Toluene
Toluenediamlne
Toluene diisocyanate( s)
Toxaphene
Trlchloroethane
Trichloroethene(s)
Trichlorof luorome thane
Trichlorophenol(s)
2,4,5-TP(Silvex)
Trichloropropane
Vinyl chloride
Vlnylldene chloride
Xylene
Extraction pH
NA
12
NA
> 11
59
5-9 or > 11
NA
NA
NA
12
<7 or > 11
.
NA
NA
NA
NA
Extraction
Solvent
NA
Methylene Chloride
NA
Methylene Chloride
Methylene Chloride
Methylene Chloride
NA
NA
NA
Methylene Chloride
Ethyl Ether or
Methylene Chloride
NA
NA
NA
NA

-------
                                                                  8.85-1
                           Method 8.85

                        SONICATION METHOD


Scope and Application

     This method covers a procedure for the extraction of non-

volatile and semi-volatile organic compounds from solids.  The

sonication produces solid disruption to ensure intimate contact

of the sample matrix with the extraction solvent.1

Summary of Method

     A weighed sample of the solid waste is ground, mixed with

the extraction medium, then dispersed into the solvent using

sonication.  The resulting solution may then be cleaned up further

or analyzed directly using the appropriate technique (Methods

8 .24 through 8 .25) .

Apparatus

1.  Apparatus for Grinding.*t

    The necessity for grinding and the choice of grinding

    apparatus will depend on the physical and chemical charac-

    teristics of the solid waste material in question.  Any of
1 The high energy vibrations produced by this method may produce
  artifacts and may drive off some semi-volatile compounds*

* Grinding is only necessary if the waste cannot either pass
  through a 1-mm standard seive or be extracted through a 1-mm
  diameter hole.

t Specific equipment listed in this method are for descriptive
  purposes only.  Equivalent equipment is available from other
  manufactures and laboratory supply companies.

-------
                                                                  8.85-2
    the following grinders, or their equivalent, would be




    suitable:




    a.  Fisher Mortar Model 155 Grinder or equivalent.




        Fisher Scientific Co., Catalogue Number 8-323.  This




        grinder handles all except gummy, fibrous or oily




        materials.




Sonication




     For purposes of solid waste dispersion, ultra-sonication




must be performed by use of a horn-type sonicator.  The




following equipment or its equivalent is suitable.




    a.  Sonifer/Cell disruptor, model W-350, Ultrasonics Inc.




    b.  Sonic Dismembrator model 300, Fisher Scientific Co.,




    Catalogue Number 15-338-40.




     With either apparatus a sonicator probe with a titanium




tip must be used.




Reagents




1.  Any solvent appropriate for GC or GC/MS analysis.  Choice of




    solvent will depend on the substances being analyzed for.




    The solvent of choice should be appropriate for the method




    of measurement to be used and which will give an analyte to




    solvent partition coefficient of at least 1 to 1000.




2.  Sodium sulfate, (ACS) Granular anhydrous (purified by heating




    at 400° C for 4 hours in a shallow tray).




Procedure




1.  Grind, or otherwise subdivide the waste, in a manner




    such that it either passes through a 1-mm seive or can be




    extruded through a 1-mm hole.  Introduce sufficient sample

-------
                                                                  8.85-3
    into the grinding apparatus to yield at least 10 gms after




    grinding.




2.  Weigh 10.0 gm of suitably dispersed material into a 75




    ml glass flask,  add 30 ml of an appropriate solvent.  Sonicate




    with agitation for approximately 15 minutes.  Filter the




    resulting  suspension.   Reextract the solid residue with an




    additional 30 ml portion of solvent.  Repeat the extraction




    a third time so  as to  sonicate for a total of 45 minutes*




    Solvent of choice should be one with properties which




    allow for  efficient GC,  LC, or GC/MS analysis, and which




    has an analyte to solvent partition coefficient on the




    order of 1 to 1000.




3.  After the  extraction is complete,  filter the extract and dry




    it by passing it through a 4-inch  column of sodium sulfate




    which has  been washed  with the extracting solvent.  Collect




    the dried  extract in a 500-ml Kuderna-Danish (K-D) flask



    fitted with a 10 ml graduated concentrator tube and a 3




    ball Snyder column.  Wash the extractor flask and sodium




    sulfate column with 100-125 ml of  the extracting solvent.




    If the extract is expected to contain no interfering organics




    (therefore requiring no clean-up step), it may be concentrated




    using the  K-D apparatus and analyzed by the appropriate gas




    or liquid  chromatographic technique.  If further clean-up is




    required proceed accordingly (see  Section 9 of this manual)




    after concentration of the extract.

-------
                                                                  8.85-4
4.  Heat the K-D apparatus on a steam bath until the liquid



    level in the collection tube is below 5 ml.  Turn off the



    heat and allow K-D to cool.  Transfer to 10 ml volumetric



    flask and adjust volume to 10 ml.

-------
                                                                  8.86-1
                           Method 8.86




                    SOXHLET EXTRACTION METHOD






Scope and Application




     This method provides a procedure for the extraction of




semi-volatile and nonvolatile organic compounds from waste materials




which are in a "solid" state, prior to analysis by the appropriate




gas chromatographic or liquid chromatographic technique.




Summary of Method




     The solid sample is mixed with anhydrous sodium sulfate,




placed in an extraction thimble or between two plugs of glass




wool and extracted using an appropriate solvent in a Soxhlet




extractor.  The extract is then concentrated, and may either be




cleaned up further, or analyzed directly by the appropriate




measurement technique (Methods 8.04 through 8.25).




Apparatus




1.  Soxhlet extractor - 40 mm ID, with 500-ml round bottom




    flask.




2.  Kuderna-Danish Apparatus [Kontes K-570000 or equivalent]



    with 3-ball Snyder column.




3.  Chromatographic column—Pyrex, 20 mm ID, approxi-




    mately 400 mm long, with coarse fritted plate on bottom



    and an appropriate packing medium.




Reagents




1.  An appropriate solvent or solvent mixture yielding no




    measurable residue on evaporation.

-------
                                                                  8.86-2
2.  Anhydrous granular sodium sulfate, ACS (purified




    by heating at 400° C for 4 hours in a shallow tray) .




Procedure




1.  Blend 10 grams of the solid sample with an equal weight of




    anhydrous sodium sulfate and place in either a glass  or




    paper extraction thimble.




2.  Place the sample in the extractor thimble.  (If any




    problems are encountered in using the thimble, e.g.,  if the




    sample clogs the thimble, an alternative to the thimble




    would be to place a plug of glass wool in the extraction




    chamber, transfer the sample into the chamber, then cover




    the sample with another plug of glass wool.)




3.  Place 300 ml of the solvent into a 500-ml roundbottom flask




    containing a boiling stone; attach the flask to the extractor,




    and extract the solids for 16' hours.




4.  After the extraction is complete, cool the extract; then




    filter the extract and dry it by passing it through a 4-inch




    column of sodium sulfate which has been washed with the




    extracting solvent.  Collect the dried extract in a 500-ml




    Kuderna-Danish (K-D) flask fitted with a 10ml graduated




    concentrator tube.  Wash the extractor flask and sodium




    sulfate column with 100-125 ml of the extracting solvent.




    If the extract is expected to contain no interfering  organics




    (therefore requiring no clean-up step), it may be concen-




    trated using the K-D apparatus and analyzed by the appropriate




    gas or liquid chromatographic technique.   If further  clean-up




    is required proceed accordingly (see  Section 9 of this




    manual) after concentration of the extract.

-------
                                                                 8.86-3
5.  Add 1-2 clean boiling chips to the flask and attach




    a three-ball Snyder column.  Prewet the Snyder column by




    adding about 1 ml solvent to the top.   Place the K-D apparatus




    on a steam or hot water bath so that the concentrator tube and




    the entire lower rounded surface of the flask is bathed in




    hot water or vapor.  Adjust the vertical position of the




    apparatus and the water temperature as required to complete




    the concentration in 15-20 minutes.  At the proper rate of




    distillation the balls of the column will actively chatter




    but the chambers will not flood.  When the apparent volume of




    liquid reaches 1 ml, remove the K-D apparatus and allow it to




    drain for at least 10 minutes while cooling.




6.  Transfer to 10 ml volumetric flask and adjust volume to 10 ml.

-------
                                                                   8.86-4


                            References


1.   "Interim Methods for the Sampling and Analysis of Priority
     Pollutants In Sediments and Fish Tissue", U.S. Environmental
     Protection Agency;  Environmental Monitoring and Support
     Laboratory;  Cincinnati, Ohio  45268.

2.   "Recovery of Organic Compounds from Environmentally Contami-
     nated Bottom Materials", T. Bellar, J. Lichtenberg, S. Lonneman;
     U.S. Environmental  Protection Agency; Environmental Monitoring
     and Support  Laboratory; Cincinnati, OH  45268.

-------
                                                                   9.01-1
                         Method 9.01




                  LIQUID - LIQUID EXTRACTION
Introduction
     The following procedure provides a method of sample




clean-up to be used when interferences prevent direct




chromatographic measurement of the compound being analyzed




for.  The method makes use of the differential solubility of




the compounds of interest and interfering species.




Summary of Method




     Removal of interferences is accomplished by a series of




liquid-liquid extractions conducted at different pHs and with




a variety of solvents.




Apparatus




1.  Separatory funnel with Teflon stopcock.




2.  Kuderna-Danish (K-D) Apparatus [Kontes-K-570000 or




    equivalent! equipped with a three ball Snyder column.




3.  Boiling chips - solvent extracted, approximately 10/40




    mesh.




4.  Drying column - 20 mm I.D. Pyrex chromatographic column




    with coarse frit.




5.  Water or steam bath.




Reagents




1.  Sodium hydroxide-(ACS) 10 N in distilled water.




2.  Sulfuric acid-(l + 1) Mix equal volumes of concentrated




          (ACS) with distilled water.

-------
                                                                   9.01-2
3.  Methylene chloride, acetone, 2-propanol, hexane, toluene-




    Pesticide quality or equivalent.




4.  Sodium sulfate-(ACS) Granular, anhydrous (purified by




    heating at 400°C for 4 hrs. in a shallow tray).




5.  Distilled Water




Procedure




1.  Place 10 gms of the extract or organic liquid waste to




    be cleaned up into the separatory funnel.




2.  Add 20 ml of the solvent indicated in Table 9.01-1.




3.  Add 20 ml of distilled water and adjust the pH to 12-13




    with sodium hydroxide.  Partition the sample into the solvent




    and aqueous phases by shaking the funnel for one minute with




    periodic venting to release vapor pressure.  Allow the organic




    layer to separate from the water phase for a minimum of ten




    minutes.  If the emulsion interface between layers is more




    than one-third the size of the solvent layer, the analyst




    must employ mechanical techniques to complete the phase




    separation.  The optimum technique depends upon the sample,




    but may include stirring, filtration of the emulsion through




    glass wool, or centrifugation layer.




4«  Separate the aqueous phase and transfer to a 125 ml




    Erlenmeyer flask.




5.  Reextract the solvent layer twice more with 20 ml portions




    of distilled water at pH 12-13.  Combine aqueous extract.




6.  At this point the species being analyzed for will be




    in either the organic or aqueous phase (See Table 9.01-1).  If




    in the aqueous phase discard the organic phase and proceed to

-------
                                                                    9.01-3
     step  7.   If  in  the  organic  phase  discard  the  aqueous  phase




     and proceed  to  step 12.




 7.   Transfer  the aqueous phase  to  a  clean separatory funnel.




 8.   Adjust  the  aqueous  layer  to a  pH  of  1-2 with  sulfuric




     acid.




 9.   Add  20  ml of solvent to  the funnel and shake  for two




     minutes.   Allow the solvent to separate  from  the aqueous




     phase and collect  the solvent  in  a 100 ml Erlenmeyer




     flask.




10.   Add  a second 20 ml  volume of solvent to  the separatory




     funnel  and reextract at  pH  1-2 a  second  time, combining




     the  extracts in the Erlenmeyer flask.




11.   Perform a third extraction  in  the same manner.




12.   Pour  the  combined  organic extracts through a  drying




     column  containing  10 cm  of  anhydrous sodium sulfate,  and




     collect it in a Kuderna-Danish (K-D) flask equipped with




     a 10  ml concentrator tube.   Rinse the Erlenmeyer flask




     and  column with 20  ml of  solvent  to complete  the quantitive




     transfer.




13.   Add  1-2 clean boiling chips to the flask  and  attach




     a three-ball Snyder column.  Prewet the  Snyder column by




     adding  about 1  ml  solvent to the top.  Place  the K-D apparatus




     on a  steam or hot  water  bath so that the  concentrator tube and




     the  entire lower rounded  surface of the flask is bathed in




     hot  water or vapor.  Adjust the vertical position of the




     apparatus and the  water  temperature as required to complete

-------
                                                                 9.0^-4
     the concentration in 15-20 minutes.  At the proper rate of




     distillation the balls of the column will actively chatter




     but the chambers will not flood.  When the apparent volume of




     liquid reaches 1 ml, remove the R-D apparatus and allow it to




     drain for at least 10 minutes while cooling.




14.  If the appropriate analytical solvent is the same as




     that used for the above extraction then transfer extract to




     10 ml volumetric flask and adjust volume to 10 ml.  If a




     different solvent is to be used for sample measurement proceed




     as in step 15 where 2 propanol is used for illustrative




     purposes.  Other solvents should be used as appropriate.




15.  Increase the temperature of the hot water bath to 95-100°C.




     Remove the Snyder column and rinse the flask and its lower




     joint into the concentrator tube with 1-2 ml of 2-propanol.




     Note:  A 5-ml syringe is recommended for this operation.




     Attach a micro-Snyder column to the concentrator tube




     and prewet the column by adding about 0.5 ml 2-propanol




     to the top.  Place the micro K-D apparatus on the water




     bath so that the concentrator tube is partially immersed




     in the hot water.  Adjust the vertical position of the




     apparatus and the water temperature as required to




     complete concentration in 5-10 minutes.  At the proper




     rate of distillation, the balls of the column will




     actively chatter but the chambers will not flood.  When




     the apparent volume of the liquid reaches 2.5 ml, remove




     the K-D apparatus and allow it to drain for at least 10

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                                                             9.01-5
minutes while cooling.  Add an additional 2 ml of 2-




propanol through the top of the mlcro-Snyder column and resume




concentrating as hefore.  When the apparent volume of liquid




reaches 0.5 ml, remove the K-D apparatus and allow it to




drain for at least 10 minutes while cooling.  Remove the




micro-Snyder column and rinse its lower joint into the




concentrator tube with a minimum amount of 2-propanol.




Transfer to a 10 ml volumetric flask and adjust the extract




volume to 10 ml.  Store in refrigerator, if further processing




will not be performed immediately.  If the sample extract




requires no further cleanup, proceed with gas chromatographic




analysis.  If the sample requires further cleanup, proceed




as appropriate.

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                                                                9.01-6
                              Table 9.01-1

             APPROPRIATE CLEAN-UP SOLVENT AND STEP 6 PHASE
Compound Being Analyzed For

 Benzo(a)anthracene

 Benzo(a)pyrene

 Benzotrichloride

 Benzyl chloride

 Benzo(b)fluoranthene
   Solvent

Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane
Step 6 Phase

   Solvent

   Solvent

   Solvent

   Solvent

   Solvent
 Chlordane

 Chlorinated dibenzodioxins

 2-Chlorophenol

 Chrysene
Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane
   Solvent

   Solvent

   Aqueous

   Solvent
 Creosote

 Cresol(s)

 Cresylic acid(s)

 Dichlorobenzene(s)

 Dichlorophenoxy-
   acetic acid
Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane

Ethyl ether
   Solvent

   Aqueous

   Aqueous

   Solvent

   Aqueous
 Dichloropropanol

 2,4-Dimethylphenol

 Dinitrobenzene

 4,6-Dinitro-o-cresol

 2,4-Dinitrotoluene
Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane
   Solvent

   Aqueous

   Solvent

   Aqueous

   Solvent

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                                                                   9.01-7
                        Table  9.01-1 (cont.)

        APPROPRIATE CLEAN-UP SOLVENT AND STEP 6 PHASE
Compound Being Analyzed For

 Endrin

 Heptachlor

 Hexachlorobenzene

 Hexachlorobutadiene

 Hexachloroethane

 Hexachlorocyclopentadiene

 Lindane

 Maleic anhydride

 Methomyl
   Solvent

Dichloromethane

Dlchloromethane

Dlchloromethane

Dlchloromethane

Dlchloromethane

Dlchloromethane

Dichloromethane

Dichloromethane

Dichloromethane
Step 6 Phase

   Solvent

   Solvent

   Solvent

   Solvent

   Solvent

   Solvent

   Solvent

   Solvent

   Solvent
 Napthalene

 Napthoquinone

 Nitrobenzene

 4-Nltrophenol

 Pentachlorophenol
Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane

Dichloromethane
   Solvent

   Solvent

   Solvent

   Aqueous

   Aqueous
 Phenol

 Phorate

 Phosphorodithlolc acid
    esters

 Phthallc anhydride

 2-Plcollne
Dichloromethane

Dichloromethane

Dichloromethane


Dichloromethane

Dichloromethane
   Aqueous

   Aqueous

   Solvent


   Solvent

   Solvent

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                                                                   9.01-8
                     Table 9.01-1 (cont.)




        APPROPRIATE CLEAN-UP SOLVENT AND STEP 6 PHASE
Compound Being Analyzed For




 Pyridine




 Tetrachlorobenzene(s)




 Tetrachlorophenol




 Toluenediamine




 Toxaphene




 Trlchlorophenol(s)




 2,4,5-TP (Silvex)
   Solvent




Dlchloromethane




Dichloromethane




Dlchloromethane




Dlchloromethane




Dichloromethane



Dlchloromethane




Ethyl ether
Step 6 Phase




   Solvent




   Solvent




   Aqueous




   Solvent




   Solvent



   Aqueous




   Aqueous

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                                                                    10.0-1




                          Section 10.0




              QUALITY CONTROL, QUALIFY ASSURANCE




                         INTRODUCTION






     The procedures and methods that make up  the  body  of  this




manual outline how to test  for hazardous characteristics  in




solid wastes.  If performed by qualified analysts  the  Agency




feels that the procedures and methods will  give a  true verdict




of the wastes being tested.




     Yet, the described techniques are only valuable  if they




are performed with proper care.  Unless the stated  criteria of




the quality controls and assurances called  for  in  every




technique are met the derived data will be  of little  value  to




either the Agency or the generator.




     Section 10 is meant to give guidance to  qualified analysts




who will be testing solid wastes for hazardous  characteristics.




Since it was developed for  use in the testing of  dilute




aqueous samples, it is not  to be followed exactly.  Rather  it




should be used as a guideline that outlines acceptable quality




control procedures.




     In the hands of a qualified analyst Section  10 can be  used




as a yardstick to compare the acceptability of  data derived




by generators of solid wastes.  In future editions  of  this




manual EPA will provide more specific quality assurance and




control criteria for use in solid waste testing programs.

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                                           EPA-600/4-79-019
    HANDBOOK FOR ANALYTICAL QUALITY CONTROL
      IN WATER AND WASTEWATER LABORATORIES
                    March 1979
ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
      U.S. ENVIRONMENTAL PROTECTION AGENCY
      OFFICE OF RESEARCH AND DEVELOPMENT
              CINCINNATI, OHIO 45268

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                                 DISCLAIMER

The mention of trade  names or commercial products in this handbook is for illustration
purposes and does not constitute endorsement or recommendation for use by the U.S.
Environmental Protection Agency.
                                       11

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                                    ABSTRACT

One of the  fundamental  responsibilities  of water and  wastewater management is  the
establishment  of continuing programs to  insure the reliability and validity of analytical
laboratory  and field  data  gathered in water treatment and wastewater pollution control
activities.

This handbook is addressed to laboratory directors, leaders of field investigations, and other
personnel  who bear responsibility for water and wastewater data. Subject matter of the
handbook is concerned primarily with quality control (QC) for chemical and biological tests
and measurements. Chapters are also included on QC aspects  of sampling, microbiology,
biology, radiochemistry, and safety  as  they  relate  to water and wastewater pollution
control. Sufficient  information is offered  to  allow the reader to  inaugurate or reinforce
programs of analytical QC  that emphasize early recognition, prevention, and correction of
factors leading to breakdowns in the validity of water and wastewater pollution control
data.
                                         in

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                               ACKNOWLEDGMENTS

This handbook was prepared by the Environmental Monitoring and Support Laboratory
(EMSL) of the United States Environmental Protection Agency. The contributions of the
following individuals in preparing the handbook are gratefully acknowledged:

       J. B. Anderson
       D. G. Ballinger
       E. L. Berg
       R. L. Booth
       R. H. Bordner
       P. W. Britton
       J. F. Kopp
       H. L. Krieger
       J. J. Lichtenberg
       L. B. Lobring
       J. E. Longbottom
       C. I. Weber
       J. A. Winter

Technical editing and preparation of the final manuscript were performed under contract to
John F. Holman & Co. Inc., 1346 Connecticut Avenue, N.W., Washington, D.C.  20036.

Inquiries  regarding material  contained in the handbook should be made to Environmental
Protection Agency, Environmental Research Center, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268.
                                        IV

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Chapter
                              TABLE OF CONTENTS
                                                                           Page

           PREFACE	    iii
           ACKNOWLEDGMENTS	    v
    1       IMPORTANCE OF QUALITY CONTROL   	   1-1
           1.1    General  	   1-1
           1.2    Quality Assurance Programs	   1-1
           1.3    Analytical Methods  	   1-2
           1.4    Reference	   1-4

    2       LABORATORY SERVICES	   2-1
           2.1    General  	   2-1
           2.2    Distilled Water	   2-1
           2.3    Compressed Air	   2-5
           2.4    Vacuum	   2-5
           2.5    Hood System  	   2-5
           2.6    Electrical Services	   2-6
           2.7    References	   2-6

    3       INSTRUMENT SELECTION   	   3-1
           3.1    Introduction	   3-1
           3.2    Analytical Balances  	   3-1
           3.3    pH/Selective-Ion Meters	   3-3
           3.4    Conductivity Meters	   3-6
           3.5    Turbidimeters (Nephelometers)	   3-7
           3.6    Spectrometers	   3-8
           3.7    Organic Carbon Analyzers	3-13
           3.8    Gas Chromatographs   	3-14
           3.9    References	3-14

    4       GLASSWARE  	  4-1
           4.1    General  	  4-1
           4.2    Types of Glassware  	  4-2
           4.3    Volumetric Analyses   	  4-3
           4.4    Federal Specifications for Volumetric Glassware  	  4-4
           4.5    Cleaning of Glass and Porcelain	  4-5
           4.6    Special Cleaning Requirements  	  4-6
           4.7    Disposable Glassware  	  4-7
           4.8    Specialized Glassware	  4-7
           4.9    Fritted Ware	  4-8
           4.10  References	  4-9

    5       REAGENTS, SOLVENTS, AND GASES   	   5-1
           5.1    Introduction	   5-1
           5.2    Reagent Quality	   5-1

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        5.3   Elimination of Determinate Errors  	   5-4
        5.4   References	   5-4

 6      QUALITY CONTROL FOR ANALYTICAL PERFORMANCE	   6-1
        6.1   Introduction	   6-1
        6.2   The Industrial Approach to QC	   6-1
        6.3   Applying Control Charts in Environmental Laboratories  	   6-2
        6.4   Recommended Laboratory Quality Assurance Program	   6-9
        6.5   Outline of a Comprehensive Quality Assurance Program  	6-10
        6,6   Related Topics   	6-13
        6.7   References	6-13

 7      DATA HANDLING AND REPORTING	   7-1
        7.1   Introduction	   7-1
        7.2   The Analytical Value  	•.	   7-1
        7.3   Glossary of Statistical Terms   	   7-3
        7.4   Report Forms	   7-5
        7.5   References	7-11

 8      SPECIAL REQUIREMENTS FOR TRACE ORGANIC ANALYSIS  ...   8-1
        8.1   Introduction	   8-1
        8.2   Sampling and Sample Handling	   8-1
        8.3   Extract Handling   	   8^
        8.4   Supplies and Reagents	   8-5
        8.5   Quality Assurance	   8-7
        8.6   References	8-10

 9      SKILLS AND TRAINING	   9-1
        9.1   General  	   9-1
        9.2   Skills   	   9-2
        9.3   Training	   9-4

10      WATER AND WASTEWATER SAMPLING	10-1
        10.1  Introduction	10-1
        10.2  Areas of Sampling	10-2
        10.3  References	10-6

11      RADIOCHEMISTRY	11-1
        11.1  Introduction	11-1
        11.2  Sample Collection	11-1
        11.3  Laboratory Practices  	11-2
        11.4  Quality Control  .	11-4
        11.5  References	11-5

12      MICROBIOLOGY	12-1
        12.1  Background	12-1
        12.2  Specific Needs in Microbiology  	12-1
        12.3  Intralaboratory Quality Control	12-2
        12.4  Intel-laboratory Quality Control	12-2
        12.5  Development of a Formal  Quality Assurance Program   	12-3
        12.6  Documentation of a Quality Assurance Program  	12-3
                                    VI

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           12.7  Chain-of-Custody Procedures for Microbiological Samples   ....   12-3
           12.8  References	12-10

  13       AQUATIC BIOLOGY   	   13-1
           13.1  Summary of General Guidelines	13-1
           13.2  Discussion	13-2
           13.3  Reference	13-4

  14       LABORATORY SAFETY	   14-1
           14.1  Law and Authority for Safety and Health	   14-1
           14.2  EPA Policy on Laboratory Safety	14-5
           14.3  Laboratory Safety Practices	14-7
           14.4  Report of Unsafe or Unhealthful Condition	14-15
           14.5  References	14-15

Appendix A-Suggested Checklist for the Safety Evaluation of EPA Laboratory Areas   A-l
                                        VII

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                                  LIST OF FIGURES


Figure No.                                                                     Page

    4-1     Example of Markings on Glassware   	   4-5

    6-1     Essentials of a Control Chart	   6-2
    6-2     Shewhart Control Chart for Percent Recovery Data	   6-5
    6-3     Procedure for Evaluating QC Data From a Monitoring Study   	6-12

    7-1     Example of Bench Sheet	   7-8
    7-2     Example of Summary Data Sheet  	   7-9
    7-3     Example of STORE! Report Form	7-10
    7-4     Flow Chart  of the Sequence of Events During a Controlled Series of
              Laboratory Measurements	7-12

   12-1     Example of Chain-of-Custody Sample Tag (a) Front, (b) Back	12-5
   12-2     Example of a Sample Log Sheet	12-6
   12-3     Example of a Chain-of-Custody Record  	12-7

   14-1     Health and Safety Inspection Checklist  	14-8
   14-2     Report of Unhealthful or Unsafe Condition	14-16
   14-3     Notice of Unhealthful or Unsafe Condition   	14-17


                                  LIST OF TABLES

Table No.                                                                     Page

    2-1     Water Purity	    2-1
    2-2     Requirements for Reagent Water	    2-2
    2-3     Comparison of Distillates From Glass and Metal Stills	    2-3

    3-1     Performance  Characteristics of Typical pH/Selective-Ion Meter	   3-5
    3-2     Electrical Conductivity of Potassium Chloride Reference Solutions  .  . .   3-7

    4-1     Tolerances for Volumetric Glassware   	   4-4
    4-2     Fritted Ware  Porosity  	  4-8

    6-1     Analyses  of  Total  Phosphate-Phosphorus  Standards, in Milligrams Per
              Liter of Total PO4-P	   64
    6-2     Estimates of  the Range (R = \A - B\) and the Industrial Statistic (I=\A-
              B\I(A + B) of Three Different Parameters for Various Concentration
              Ranges	   6-7
    6-3     Shewhart Upper Control  Limits UCL and Critical Range Rc  Values for
              the Differences  Between Duplicate Analyses Within Specific Con-
              centration Ranges for Three Parameters	   6-8
    6-4     Critical Range Values for Varying Concentration Levels	   6-9

    9-1     Skill-Time Rating of Standard Analytical Operations   	   9-3
                                        via

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10-1      Guidance for Water/Wastewater Sampling	10-2

11-1      Sample Handling, Preservation, Methodology, and Major Instrumentation
           Required	11-2
                                    IX

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                                        Chapter 1

                           IMPORTANCE OF QUALITY CONTROL
1.1  General

The analytical laboratory provides qualitative and quantitative  data  for use in decision-
making.  To be  valuable,  the data  must  accurately describe  the  characteristics  and
concentrations of constituents in  the samples  submitted to the laboratory. In many cases,
because they lead to faulty interpretations, approximate or incorrect results are worse than
no result at all.

Ambient water quality standards for pH, dissolved oxygen, heavy metals, and pesticides are
set  to  establish  satisfactory  conditions  for drinking water,  fishing,  irrigation, power
generation, or other water uses. The laboratory data define whether conditions are being
met and whether the water can be used for its intended purposes. In wastewater analyses,
the laboratory data identify the characteristics of the treatment plant influent and the final
load imposed upon receiving water resources, as well  as  the effectiveness of steps in  the
treatment  process. Decisions on process changes, plant modifications, or the construction of
new facilities may be  based upon the  results of water laboratory analyses. The financial
implications of such decisions suggest that extreme care  be  taken in analysis.

Effective  research in water pollution control also depends upon a valid laboratory data base,
which in turn may contribute to sound evaluations of both the progress  of the research itself
and the viability of available water pollution-control alternatives.

The analytical data from  water and wastewater laboratories may  also be used to determine
the extent of compliance of a polluting industry with discharge or surface water standards.
If the laboratory results indicate a violation of a standard, remedial action is required by  the
responsible parties. Both .legal and social  pressures can be brought to bear to protect  the
environment. The analyst should realize not only that he has considerable responsibility for
providing reliable laboratory descriptions  of the samples at issue, but  also that his profes-
sional competence, the validity of the procedures used, and the resulting values reported
may be challenged (perhaps in court). For the analyst to meet such challenges, he should
support the laboratory data with an adequate documentation program that provides valid
records of the control measures applied to all  factors bearing on  the final results of investi-
gations.

1.2  Quality Assurance Programs


Because of the importance of laboratory analyses in determining practical courses of action
that may be followed, quality  assurance programs  to insure the reliability of the water and
wastewater data are essential. Although  all  analysts practice quality control (QC) in amounts
depending upon  their training, professional pride, and the  importance of their particular
projects, under actual working conditions sufficiently detailed QC may be neglected.  An
established, routine, quality assurance  program applied to each  analytical test can relieve
analysts of the necessity of originating individual QC efforts.
                                          1-1

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Quality assurance programs have  two  primary functions in the laboratory.  First, the
programs should continually monitor the reliability (accuracy and precision) of the results
reported; i.e., they should continually provide answers to the question "How good (accurate
and precise) are the results obtained?" This function is the determination of quality. The
second function is the control of quality (to meet the program requirements for reliability).
As an example of the distinction between the two  functions,  the  processing of spiked
samples may be a determination of measurement quality, but the use of analytical grade
reagents is a control measure.

Each  analytical method has a rigid  protocol. Similarly,  QC associated with a test  must
include definite required steps  for  monitoring the test  and insuring that its results are
correct. The steps  in  QC vary  with the type  of  analysis.  For example, in a  titration,
standardization of the  titrant on  a frequent basis is an element of QC. In any instrumental
method, calibration and checking out of instrumental response are also QC functions. All of
the experimental variables that affect the final results should be considered, evaluated, and
controlled.

In summary, laboratory data, in quantitative terms,  e.g., in milligrams per liter, are reported
by  the analyst.  These  values   are  interpreted by industrial  plant engineers  to show
compliance or noncompliance with permits for discharge, by state pollution control agencies
to define the need for additional sampling and analysis to confirm violations, or by EPA to
demonstrate that prescribed waste treatment  was sufficient  to protect the surface waters
affected by the discharge.

This  handbook  discusses  the  basic  factors of water  and wastewater measurements that
determine the value of analytical results and provides recommendations for the control of
these  factors  to insure  that  analytical results are the best possible. Quality  assurance
programs  initiated from,  and   based   upon,  these  recommendations  should increase
confidence in the reliability of the reported analytical results.

Because ultimately a laboratory director must assume full responsibility for the reliability of
the analytical results submitted,  the laboratory director must also assume full responsibility
in both design and implementation for the corresponding quality assurance program.

1.3 Analytical Methods

Many analytical methods for common water pollutants have been in use for many years and
are used in  most environmental  laboratories.  Examples are tests for chloride, nitrate, pH,
specific conductance,  and dissolved  oxygen.  Widespread use of an analytical method in
water and wastewater  testing  usually indicates that the method is reliable, and therefore
tends  to support the validity of the reported test results. Conversely, the use of little-known
analytical  techniques forces the water and wastewater data user to rely on the judgment of
the laboratory analyst, who must then defend his choice of analytical  technique as well as
his conclusions. Present Federal regulations, notably section  304(h) of Public Law 92-500
(Federal Water Pollution Control Amendments  of  1977)  and the Interim Drinking Water
Regulations specifically require the use of EPA-approved methods of analysis.

Uniformity  of methodology  within  a single  laboratory  as well as among a group of
cooperating  laboratories is required  to  remove methodology as a variable when there are
many  data  users. Uniformity of  methodology is  particularly  important  when  several
                                         1-2

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laboratories provide data to a common data bank (such as STORET*) or cooperate in joint
field surveys. A lack of uniformity of methodology may  raise doubts as to the validity of
the reported  results.  If  the  same  constituents  are  measured by  different  analytical
procedures within a single laboratory, or by a different procedure in different laboratories,
it  may  be asked  which  procedure  is  superior, why the superior  method is not used
throughout, and what effects the various methods and procedures have on the data  values
and their interpretations.

Physical  and chemical  measurement  methods used  in water  or wastewater laboratories
should be selected by the following criteria:

   a.  The selected  methods should measure desired constituents of water samples  in the
       presence of normal interferences with sufficient precision and accuracy to meet the
       water data needs.

   b.  The selected procedures should use  equipment and skills ordinarily available  in the
       average water pollution control laboratory or water supply laboratory.

   c.  The selected methods should  be sufficiently tested to have established their validity.

   d.  The selected methods should  be sufficiently rapid  to permit repetitive routine use in
       the examination of large numbers of water samples.

The restriction  to the use of EPA methods in all laboratories providing data to EPA permits
the combination of data from different EPA programs and supports the validity of decisions
made by EPA.

Regardless  of which analytical methods are used in a laboratory, the methodology should be
carefully documented.  In some reports it is stated  that a standard method  from an
authoritative  reference (such as  ref.  1)  was used throughout an investigation, when close
examination has indicated, however,  that this was not strictly true. Standard methods may
be modified  or entirely replaced because  of recent advances in the  state of  the  art or
personal preferences of the laboratory  staff. Documentation of measurement procedures
used in  arriving at laboratory data should be clear, honest,  and adequately referenced; and
the procedures should be applied exactly as documented.

Reviewers  can apply the associated precision and accuracy of each specific method when
interpreting  the  laboratory  results.  If the accuracy  and  precision  of the  analytical
methodology are unknown or uncertain, the data user may have to establish the reliability
of the result he or she is interpreting before proceeding with the interpretation.

The  necessarily strict  adherence to  accepted  methods in  water and  wastewater  analyses
should not stifle investigations leading to improvements in analytical procedures. Even with
accepted  and  documented procedures, occasions  arise when  the  procedures  must be
modified; e.g., to eliminate unusual interferences, or to yield increased sensitivities. When a
*STORET is  the  acronym  used to identify the  computer-oriented  U.S.  Environmental
 Protection Agency water quality control information system; STORET stands for STOrage
 and RETrieval of data and information.
                                         1-3

-------
modification of a procedure is necessary, it should  be carefully  formulated. Data should
then  be assembled  using  both the original and  the modified procedures to show the
superiority of the latter. Such results can be brought to the attention of the organizations
responsible  for standardization of  procedures. To  increase the benefit,  the  modified
procedures should  be written in  a  standard  format for routine use as  applicable.  The
standard format usually  includes  scope and application, principle,  equipment, reagents,
procedure, calculation of results, and expected precision and accuracy.

Responsibility for the results obtained  from use of a nonstandard procedure (i.e., one that
has not become accepted through wide use) rests with the analyst and his supervisor.

In field operations, because it may be difficult to transport samples to the laboratory, or to
examine large numbers of samples (e.g., for gross characteristics), the use  of rapid field
methods yielding approximate answers is sometimes required.  Such methods should be used
only  with a clear  understanding  that the results obtained.are not  as reliable as those
obtained from standard laboratory procedures. The fact that  such methods have been used
should be documented, and the results .should not be reported in the same context with
more  reliable analytical information. When only approximate values are available, perhaps
obtained for screening purposes in the  field only, the data user would  then be so informed.

1.4 Reference

1.  Standard  Methods for  the Examination  of Water and Wastewater,  14th Edition,
    American Public Health Association, New York (1975).
                                        1-4

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                                       Chapter 2

                               LABORATORY SERVICES
2.1  General
Quality control of water and wastewater laboratory analyses involves consideration and
control of the many variables that affect the production of reliable data. The quality of the
laboratory services available to the analyst must be included among  these variables. An
abundant supply  of  distilled  water,  free  from  interferences  and  other  undesirable
contaminants, is an absolute necessity. An adequate source of clean, dry, compressed air is
needed.  Electrical power  for routine  laboratory use  and voltage-regulated  sources for
delicate  electronic instrumentation must be  provided. This chapter, therefore, will  be
devoted to describing methods of maintaining the quality of these services, as used in water
and wastewater laboratory operations.

2.2 Distilled Water

Distilled or demineralized water is used in the laboratory for dilution, preparation of reagent
solutions, and final rinsing of glassware. Ordinary distilled water is usually not pure. It may
be contaminated by dissolved gases and by materials leached from the container in which it
has been stored. Volatile organics  distilled over from the feed water may be present, and
nonvolatile impurities may occasionally be carried over by the steam, in the form of a spray.
The concentration of these contaminants is usually  quite small, and distilled water is used
for many analyses without further purification. However, it is highly important that the
still, storage tank, and any associated piping be carefully selected, installed, and maintained
in such a way as to insure minimum contamination.

Water purity has been defined in many different ways, but one generally accepted definition
states that high-purity water is water that  has been distilled or deionized, or both, so that it
will have a specific resistance of 500,000 n or greater (or a conductivity less than 2.0
//mho/cm).  This definition is satisfactory as a base to work from, but for more  critical
requirements, the breakdown shown in table 2-1 has been suggested to express degrees of
purity (1).
                                       Table 2-1
                                   WATER PURITY
Degree of Purity
Pure
Very Pure
Ultrapure
Theoretically Pure
Maximum
Conductivity
(/imho/cm)
10
1
0.1
0.055
Approximate
Concentration
of Electrolyte
(mg/1)
2-5
0.2-0.5
0.01-0.02
0.00
                                          2-1

-------
The  American Society for Testing and Materials (ASTM) specifies four different grades of
water  for  use  in methods of  chemical analysis  and  physical testing. The method of
preparation of the various grades of reagent water determines the limits of impurities. The
various types of reagent water and ASTM requirements are listed in table 2-2.

Type  I grade water is  prepared by the distillation  of feed water  having a maximum
conductivity  of  20  jumho/cm  at 25°C  followed by  polishing with a mixed bed of
ion-exchange materials and a 0.2-jum membrane filter.

Type II grade water  is prepared by using a still designed to produce a distillate having a
conductivity  of less  than  1.0  /zmno/cm at 25°C. This may be accomplished by double
distillation or the use  of a still incorporating special baffling and degassing features.

Type III grade water  is prepared by distillation, ion exchange, or reverse osmosis, followed
by polishing with the  0.45-jum membrane filter.

Type  IV  grade  water  is prepared  by distillation,  ion exchange,  reverse  osmosis, or
electrodialysis.

Properly designed metal stills from reputable manufacturers offer convenient and reliable
sources of distilled water. These stills are usually constructed of  copper, brass, and bronze.
All surfaces  that contact the  distillate  should be heavily coated with pure  tin to prevent
metallic contamination.  The metal storage tank should be of sturdy construction  with a
tight-fitting cover, and have a filter in the air vent to remove airborne dust, gases, and  fumes.

For  special purposes, an  all-glass distillation unit may be preferable to the metal still. These
stills are  usually smaller,  and of more limited capacity than the  metal stills.  An actual
comparison in which the distillates from an  all-glass still and a metal still  were analyzed
spectrographically for certain trace metal contaminants is given in table 2-3. It can be seen
that the all-glass still  produced a product that had  substantially lower contamination from
zinc, copper, and lead.

All stills require periodic cleaning to  remove solids that have been deposited from the feed
water.  Hard  water  and  high-dissolved-solids content  promote scale formation  in  the
                                      Table 2-2
                      REQUIREMENTS FOR REAGENT WATER
Grade
of Water
Type I
Type II
Type III
Type IV
Maximum
Total
Matter
(mg/1)
0.1
0.1
1.0
2.0
Maximum
Electrical
Conductivity
at 25°C
(jumho/cm)
0.06
1.0
1.0
5.0
Minimum
Electrical
Resistivity*
at 25°C
(Mn • cm)
16.67
1.0
1.0
0.2
pH at 25°C
6.2-7.5
5.0-8.0
Minimum Color
Retention Time
ofKMnO4
(min)
60
60
10
10
 "See reference 2.
                                         2-2

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                                       Table 2-3
                 COMPARISON OF DISTILLATES FROM GLASS AND
                                   METAL STILLS

                                    Element and Concentration Gug/1)
                  Source
                              Zn    B   Fe    Mn    Al   Cu   Ni    Pb
All-Glass Still
Metal Still
9
12
13
1 <
2 <
:i 
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A piping system for delivering distilled water to the area of use within the laboratory is a
convenient feature. In this case, special care should be taken that the quality of the water is
not degraded between the still and the point of use. Piping may be of tin, tin-lined brass,
stainless steel,  plastic, or chemically resistant glass, depending on the quality of the water
desired, its intended use, and on available funds. Tin is best, but is also very expensive. As a
compromise, plastic pipe  or glass pipe  with  Teflon* O-rings at all connecting joints is
satisfactory for most  purposes. The glass pipe has an obvious advantage when freedom from
trace amounts of organic materials is important.

When  there  is no  piped-in  supply,  distilled  water  will  probably  be transported  to  the
laboratory  and stored in polyethylene or glass  bottles of about 5-gal capacity. If stored in
glass containers, distilled water will gradually leach the more soluble materials from the glass
and cause an increase in dissolved solids. On the other hand, polyethylene bottles contain
organic plasticizers, and traces of these materials may be  leached from the container walls.
These  are of little  consequence, except in  some organic analyses.  Rubber stoppers often
used in storage containers contain leachable materials, including significant quantities of
zinc. This is usually no problem, because the water is not in direct contact with the stopper.
However, the analyst should be aware of the potential for contamination, especially when
the supply is not replenished by frequent use.

The delivery tube may consist of a piece of glass tubing that extends almost to the bottom
of the  bottle, and that is bent downward above the bottle neck, with a 3- to 4-ft piece of
flexible tubing attached for mobility. Vinyl tubing is preferable to latex rubber, because  it is
less leachable; however, a short piece of latex tubing may be required at the outlet for better
control of  the pinchcock.  The vent  tube in the stopper should  be protected against  the
entrance of dust.

Ordinary distilled water *is quite adequate for many analyses, including the determination of
major  cations  and  anions.   Certain  needs may  require  the  use of double- or even
triple-distilled water. Redistillation from an alkaline permanganate solution can be used to
obtain a water with low organic background.  When determining trace organics by solvent
extraction and gas chromatography, distilled water with sufficiently low background may be
extremely difficult  to obtain. In this case, preextraction of the water with the solvent used
in the respective analysis  may  be helpful  in  eliminating undesirable peaks in the blank.
Certain analyses require special treatment or conditioning of the distilled  water, and these
will now be discussed.

2.2.1 Ammonia-Free Water

Removal of ammonia can be accomplished by shaking ordinary distilled water with a strong
cation  exchanger, or by  passing distilled water through a column of such material.  For
limited volumes  of ammonia-free  water, use  of the Quikpure (Box 254, Chicago,  111.)
500-ml bottle is highly recommended. The ion-free water described in section 2.2.3 is  also
suitable for use in the determination of ammonia.

2.2.2 Carbon-Dioxide-Free Water

Carbon-dioxide-free water may be prepared by boiling distilled water for  15 min and cooling
to room temperature. As an  alternative, distilled water may be vigorously aerated with a
Trademark of E. I. duPont de Nemours & Co.
                                         2-4

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stream of inert gas for a period sufficient to achieve saturation and CO2 removal. Nitrogen is
most  frequently used. The final pH of the water should lie between 6.2 and 7.2. It is not
advisable to store CO2 -free water for extended periods.

2.2.3 Ion-Free Water

A multipurpose high  purity water, free from trace amounts  of the common ions, may be
conveniently  prepared by slowly passing  distilled water through an ion-exchange column
containing  one  part of a  strongly acidic cation-exchange resin in the hydroxyl form. Resins
of a quality  suitable  for analytical  work must  be used.  Ion-exchange cartridges of the
research  grade,  available  from scientific supply houses, have been found satisfactory. By
using a fresh column  and high-quality distilled water, a water corresponding to the ASTM
designation for type I  reagent water (2) (maximum 0.1 mg/1  of total matter and maximum
conductivity  of 0.06  mho/cm) can be  obtained.  This water  is suitable  for  use in the
determination  of ammonia,  trace metals, and  low concentrations  of most cations  and
anions. It  is  not suited  to some  organic analyses, however, because this  treatment  adds
organic contaminants to the water by contact with the ion-exchange materials.

2.3 Compressed Air

The quality of compressed air required in the laboratory is  usually  very high,  and special
attention should be given to producing and maintaining clean air until it reaches the outlet.
Oil, water,  and dirt are undesirable contaminants in compressed air,  and it  is important to
install equipment that generates  dry, oil-free air. When pressures of less than 50 psi are
required, a rotary-type compressor, using  a water seal and no  oil, eliminates any addition of
oil that  would subsequently have to  be removed from  the  system.  Large,  horizontal,
water-cooled  compressors will usually be used when higher pressures are required.

Compression  heats  air, thus increasing its tendency to retain moisture. An aftercooler is
therefore necessary  to remove water. Absorption filters should be used at the compressor to
prevent moisture from entering  the piping  system. Galvanized steel pipe  with threaded,
malleable-iron fittings, or solder-joint copper tubing should be used for piping the air to the
laboratory.

When the compressed air entering the laboratory is of low quality, an efficient filter should
be  installed between the outlet  and the point  of use to trap oil, moisture, and other
contaminants.  As  an  alternative,  high-quality  compressed  air  of  the  dry  grade is
commercially available in cylinders when no other source exists.

2.4 Vacuum

A source of vacuum in the chemical laboratory, while not an absolute necessity,  can be  a
most useful item. While used primarily as an aid in filtration, it is also sometimes used in
pipetting and in speeding up the drying of pipets.

2.5 Hood System

An efficient hood system is a requirement for all laboratories. In addition  to removing the
various toxic and hazardous fumes that may be  generated when using organic solvents, or
that may  be  formed  during an acid digestion step,  a hood system may  also be used to
remove  toxic  gases that may  be formed  during  atomic  absorption  analyses or  other
                                         2-5

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reactions. A regular fume hood should have a face velocity of 100 ft/min (linear) with the
sash fully open.

2.6  Electrical Services

An  adequate electrical  system is  indispensable to the modern laboratory.  This involves
having both 115- and 230-V sources in sufficient capacity for the type of work that must be
done. Requirements for satisfactory lighting, proper  functioning of sensitive instruments,
and operation of high-current devices must be considered. Any specialized equipment may
present unusual demands on the electrical supply.

Because of the special type of work, requirements for a laboratory lighting system are quite
different from  those in other areas. Accurate readings of glassware graduations, balance
verniers,  and other measuring lines must be made. Titration endpoints, sometimes involving
subtle  changes in color or shading,  must be observed.  Levels of illumination, brightness,
glare, and location  of light  sources should be controlled to facilitate ease in  making these
measurements and to'provide maximum comfort for the employees.

Such instruments as spectrophotometers, flame photometers, atomic absorption equipment,
emission spectrographs, and gas chromatographs  have complicated electronic circuits that
require relatively constant voltage  to maintain stable,  drift-free instrument operation. If the
voltage of these circuits varies, there is a resulting change in resistance, temperature, current,
efficiency, light output, and component life. These characteristics are interrelated, and one
cannot be changed  without affecting the others. Voltage regulation is therefore necessary to
eliminate these conditions.

Many instruments have  built-in voltage regulators that perform  this  function  satisfactorily.
In the  absence of these, a small, portable, constant-voltage transformer should be placed in
the circuit between the electrical outlet and  the instrument. Such units are available from
Sola Basic Industries, Elk Grove Village, 111., and are capable of supplying a constant output
of 118 V from an  input that varies between 95 and  130 V.  When  requirements are more
stringent, special transformer-regulated circuits can be used to supply constant  voltage. Only
the instrument receiving the regulated voltage should be operated from such a  circuit at any
given time. These lines are in addition to, and separate from, the ordinary circuits used for
operation of equipment  with less critical requirements.

Electrical heating  devices provide desirable  heat  sources, and should offer  continuously
variable  temperature control. Hot  plates and muffle furnaces wired for  230-V current will
probably give better service than those that operate on 115V, especially if the lower voltage
circuit is only marginally adequate. Water  baths  and laboratory  ovens with maximum
operating temperatures of about  200°C perform well  at 115 V. Care must be taken to
ground all equipment that could  constitute  a shock  hazard.  The three-pronged plugs that
incorporate grounds are best for this  purpose.

2.7  References

1.  Applebaum, S.  B., and  Crits,  G. J.,  "Producing High Purity  Water," Industrial Water
    Engineering (Sept./Oct. 1964).
2.  "Water," Part 31 of 1977  Book of ASTM  Standards,  p. 20,  American  Society for
    Testing and Materials, Philadelphia (1977).
                                         2-6

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                                      Chapter 3

                               INSTRUMENT SELECTION
3.1  Introduction
The  modern  analytical  laboratory  depends  very heavily upon  instrumentation.  This
statement may be completely obvious, but it should be remembered that the exceptional
emphasis on electronic equipment has really begun since the development of the transistor
and  the computer.  To  a certain  extent,  analytical  instrumentation  is  always in the
development   stage,  with  manufacturers  continually  redesigning and upgrading  their
products,  striving for  miniaturization,  better  durability  and  sensitivity,  and  improved
automation. For laboratory supervisors and staff members the net result is a bewildering
stream of advertising brochures, announcements, and catalogs of newly available equipment.
Consequently, the selection of analytical equipment is always difficult.

The instruments commonly used in water and wastewater analysis include the following:

       Analytical balance
       pH/selective-ion meter
       Conductivity meter
       Turbidimeter
       Spectrometers (visible, ultraviolet (UV), infrared (IR), and atomic absorption (AA))
       Total carbon analyzer
       Gas chromatograph (GC)
       Gas chromatograph/mass spectrometer (GC/MS)
       Temperature devices (such as ovens and water baths)
       Recorders

These devices represent basic equipment used in routine work and should be the subject of
careful consideration before purchase. Further, their operation and maintenance ought  to be
primary considerations in sustained production of satisfactory data. Obviously, fundamental
understanding of instrument  design will assist the analyst in the correct  use of instruments
and in some cases will aid in detecting instrumental failures. Calibration of all laboratory
instruments  with primary  standards is  encouraged  whenever practical.  This normally
involves a  National  Bureau  of Standards standard reference  material  or  calibration and
certification  procedures.  Calibration checks with  secondary standards,  made in  each
laboratory  or available from private  sources, are encouraged  on a frequent basis if not
required by the analytical method each time an analysis is made.

In the pages  that follow  an attempt is made to discuss basic instrument design and to offer
some remarks about desirable instrumental features.

3.2 Analytical  Balances

The  most  important piece of equipment in any analytical laboratory is the  analytical
balance. The degree of accuracy of the balance is reflected in the accuracy of all data related
to weight-prepared standards. Although the balance should therefore be the most protected
and  cared-for  instrument  in the laboratory,  proper  care of the balance is frequently
overlooked.
                                         3-1

-------
There are many fine balances on the market designed to meet a variety of needs. Types of
balances include top-loading, two-pan,  microanalytical,  electroanalytical, semianalytical,
analytical, and  other special-purpose instruments. Each type of balance has its own place in
the scheme  of laboratory operation, but analytical  single-pan balances are by far the most
important in the production of reliable data.

Single-pan analytical balances range in capacity from the 20-g to the popular 200-g models
with sensitivities from 0.01 to 1 mg. Features of single-pan balances may include mechanical
and  electronic  switching of weights, digital readout, automatic zeroing of the empty
balance, and automatic preweighing  and  taring capabilities. Even with  all the design
improvements,  however,  modern  analytical balances  are still fragile  instruments, the
operation of which is subject to shock, temperature, and humidity changes, to mishandling,
and to  various  other  insults. Some of the precautions  to be  observed in maintaining and
prolonging the dependable life of a balance are as follows:

   a.  Analytical balances should be mounted on a  heavy, shockproof table, preferably one
       with an adequately large working surface  and with a suitable drawer for storage of
       balance accessories.  The balance  level should be checked frequently and adjusted
       when necessary.

   b.  Balances should be located away from laboratory traffic and protected from sudden
       drafts and humidity changes.

   c.  Balance  temperatures  should  be  equilibrated  with  room temperature;  this  is
       especially important  if building heat is shut off or reduced during nonworking hours.

   d.  When the balance is  not  in use, the beam should be raised from the knife edges, the
       weights returned to the beam,  objects such  as the  weighing dish removed from the
       pan, and the weighing compartment closed.

   e.  Special  precautions should be taken to avoid spillage of corrosive chemicals on the
       pan  or inside  the balance case; the interior of the balance housing should be kept
       scrupulously clean.

   f.  Balances should be checked and adjusted  periodically by a company service man or
       balance consultant; if service is not available locally, the manufacturer's instructions
       should be followed as closely as possible.  Service contracts, including an automatic
       preventive maintenance schedule, are encouraged.

   g.  The  balance should be  operated  at  all times according  to the manufacturer's
       instructions.

Standardized weights  to be  used in checking balance accuracy,  traceable  to the National
Bureau  of Standards,  may be purchased from various  supply houses. A complete set of
directions for checking the performance of a balance  is  contained in part 41 of ASTM
Standards (1).

Because  all  analytical  balances  of the 200-g capacity suitable  for  water and wastewater
laboratories  have  about  the  same  design  specifications with  reference  to sensitivity,
precision, convenience, and  price, it is safe to assume that there  is no clear preference for a
certain model, and selection can be made on the basis of availability of service.
                                         3-2

-------
3.3 pH/Selective-lon Meters

The concept  of pH as a means of expressing the degree of effective acidity or alkalinity
instead of total acidity or alkalinity was developed in 1909 by Sorenson (2). It was not until
about 1940 that commercial instruments were developed for routine laboratory measure-
ment of pH.
 »
A basic meter consists of a voltage source, amplifier, and scale or digital readout device.
Certain additional refinements produce varying performance characteristics between models.
Some models incorporate expanded scales for increased readability, solid state circuitry for
operating stability  and extreme accuracy, and temperature and slope adjustment to correct
for asymmetric potential of glass electrodes. Other features are scales that facilitate use of
selective-ion  electrodes,  recorder output,  and interfacing  with complex  data-handling
systems.

In routine  pH measurements the glass electrode is used as the indicator and the calomel
electrode as the reference. Glass electrodes have a very fast response time in highly buffered
solutions. However, accurate readings are obtained slowly in  poorly buffered samples, and
particularly so when changing from buffered to unbuffered samples. Electrodes, both glass
and calomel, should be well rinsed  with distilled water after each reading, and should be
rinsed with, or dipped several  times into,  the next test sample before  the final reading is
taken. Weakly buffered samples should  be  stirred during measurement. When not in use,
glass electrodes  should not be  allowed  to become dry, but  should  be immersed in  an
appropriate solution  consistent with the manufacturer's instructions.  The  first  steps in
calibrating  an instrument  are to immerse the glass and calomel electrodes into a buffer of
known pH, set the  meter to the  pH of the buffer, and adjust the proper controls to bring the
circuit into balance. The temperature-compensating dial should be set at the temperature of
the buffer solution.  For best accuracy,  the instrument should be calibrated against two
buffers that bracket the expected pH of the samples.

The presence of a faulty  electrode is indicated by  failure to  obtain a reasonably correct
value  for the  pH  of the second reference  buffer solution  after the  meter has  been
standardized with  the first  reference buffer solution.  A cracked glass electrode will often
yield  pH readings that  are essentially  the  same  for  both standards.  The response of
electrodes  may also  be impaired  by failure to maintain the KC1 level in the  calomel
electrode,  by  improper  electrode  maintenance,  or  by certain materials  such  as oily
substances  and precipitates that may coat the electrode surface. Faulty electrodes can often
be restored to normal by an appropriate cleaning procedure. Complete and detailed cleaning
methods are given in  part 31 of ASTM Standards (3), and are  also usually supplied by the
electrode manufacturer.

Because  of the asymmetric potential of the glass electrode, most pH meters are built with a
slope  adjustment  that enables  the analyst  to correct for slight electrode errors observed
during calibration with two different pH buffers.  Exact details of slope adjustment and
slope  check may vary with different models of instruments. The slope adjustment must be
made whenever electrodes are changed, subjected to vigorous cleaning, or refilled with fresh
electrolyte. The slope adjustment feature  is  highly  desirable and recommended  for
consideration when purchasing a new meter.

Most  pH meters now available are built with transistorized circuits  rather than  vacuum
tubes,  which greatly  reduces the warmup time  and increases  the stability  of  the meters.
                                          3-3

-------
Also, many instruments are designed with a switching circuit so that the entire conventional
0 to 14 scale of pH may be used to read a single pH unit with a corresponding increase in
accuracy.

This expanded-scale feature  is of definite value when the meter is used for potentiometric
titrations  and selective-ion  work. It is of dubious value, however,  in  routine analyses,
because pH  readings more precise than ±0.1 are seldom required. Primary standard buffer
salts are available from the National Bureau of Standards* and should be used in situations
where extreme accuracy is necessary.  Preparation of reference solutions from these  salts
requires some special precautions and handling  (3,4) such as the  use of low-conductivity
dilution water, drying ovens, and carbon-dioxide-free purge gas. These solutions should  be
replaced at least once each month.

Secondary standard buffers may be prepared from NBS salts or purchased as solutions from
commercial vendors. Routine use of these commercially available solutions, which have been
validated by comparison to NBS standards, is recommended.

The electrometric measurement of pH varies with temperature because of two effects. The
first effect is the change in electrode output  with temperature. This interference  can  be
controlled by use  of instruments having temperature compensation or by calibrating the
instrument system including the  electrode at  the temperature of the samples. The second
effect is the change of pH of the sample with  temperature. This error is sample dependent
and cannot  be controlled; it  should therefore  be noted by reporting both the pH and
temperature at the time of analysis.

Typical characteristics of a conventional expanded-scale meter are shown in table 3-1.

3.3.1 pH Electrodes

A wide variety of special- and general-purpose pH electrodes  are now available to meet  all
applications  in the general analytical laboratory. A survey through any laboratory  supply
catalog may confuse more than clarify the selection process.  A rugged, full-range, glass-  or
plastic-bodied  combination  electrode  is  a  good choice   for routine use.  An  added
convenience is an  electrode that contains solid  geltype filling materials not requiring the
normal maintenance of an electrode containing liquid filling solutions.

3.3.2 Selective-Ion Electrodes

Electrodes have been developed  to measure almost every common inorganic ion normally
measured in the water and  wastewater laboratory. Application of these electrodes has
progressed at a much slower pace and currently only three are approved for EPA monitoring
applications.

Reference 5  includes  methods  for  use  of  fluoride,  ammonia,  and  dissolved  oxygen
electrodes. Various techniques  for use of these  and  other electrodes are reviewed  in
references 6 through 9. A major problem in measuring the total parameter with electrodes is
that of relating the ion activity to ion concentration. Because the electrodes  only measure
 *NBS, Office of Standard Reference Materials, Institute for Materials Research, Washington,
  D.C. 20234.
                                         3-4

-------












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activity, the challenge is to put all of the parameters of interest into the same measurable
ionic  form and then  to  modify the activity to be proportional to the concentration. The
technique of known addition (spiking of samples) is recommended when unproven electrode
methods are being used or when sample matrix problems are suspected or not controlled by
prior  distillation or separation techniques.

3.4  Conductivity Meters

Solutions  of electrolytes conduct  an electric current by the migration  of ions under the
influence  of an electric  field.  For  a constant applied EMF,  the current flowing between
opposing electrodes immersed in the electrolyte will vary inversely with the resistance of the
solution. The reciprocal of the resistance is called conductance and is expressed in reciprocal
ohms (mhos).  For natural water  samples where the resistance is high, the usual reporting
unit is micromhos.

Most  conductivity meters on the market today use a cathode-ray tube, commonly known as
the "magic eye," for  indicating  solution  conductivity.  A stepping switch for varying
resistances in  steps  of  10X facilitates reading conductivities from  about 0.1 to about
250,000 nmho. The sensing element for a  conductivity measurement is the  conductivity
cell, which normally consists of two thin plates of platinized metal, rigidly supported with a
very precise parallel spacing. For protection, the plates are mounted inside a glass tube with
openings in the  side  walls and  submersible  end for access of sample.  Variations in designs
have included  use of hard rubber  and plastics for protection of the cell plates. Glass may be
preferable, in that the plates may be visually observed for cleanliness and possible damage,
but the more durable encasements  have the advantage of greater protection and reduced cell
breakage.  Selection of various  cell designs is normally based  on personal preference with
consideration of sample type and durability requirements.

In routine use, cells should be frequently examined to insure that (a) the platinized coating
of plates is intact; (b) plates are not coated with suspended matter; (c) plates  are not bent,
distorted,  or misalined; and (d) lead wires are properly spaced.

Temperature  has a  pronounced  effect  on  the conductance of  solutions, and must  be
corrected  for when results  are reported. The specified temperature for reporting data used
by  most  analytical groups  (and  all EPA laboratories) is  25°C. Data correction  may  be
accomplished  by adjusting  sample temperatures to 25°C, or by  use of mathematical or
electronic adjustment.

Instrumental  troubles are  seldom  encountered  with conductivity meters because of the
design simplicity. When troubles occur, they are usually in the cell, and  for most accurate
work  the following procedures should be used:

    a.  Standardize  the cell and establish a cell  factor by measuring the conductivity of a
       standard  potassium chloride solution (standard conductivity tables may be found in
       various handbooks).

    b.  Rinse the cell by repeated immersion in distilled water.

    c.  Again,  immerse the cell in the sample several times before obtaining a reading.
                                         3-6

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   d.  If the meter is equipped with a magic eye, determine the maximum width of the
       shadow  at  least  twice,  once by approaching the endpoint  from a low  reading
       upward, and once from a high reading downward.

Because the cell constants  are subject  to  slow  change  even under ideal conditions, and
sometimes to more rapid change under adverse conditions, it is recommended that the cell
constant be periodically established. Table 3-2 can be used for this operation.

For instruments reading in mhos, the cell constant is calculated as follows:

                                      .I\ -i ' ./Y f\
                                   L =


where
                                        106 Kx
        L = cell constant

       ATj = conductivity,  in micromhos  per centimeter,  of  the  KC1  solution at the
            temperature of measurement

       K2 = conductivity, in micromhos per centimeter, of the KC1 solution at the  same
            temperature as the distilled water used to prepare the reference solution

       KX = measured conductance, in mhos

Many different manufacturers produce  conductivity meters that perform well on water and
wastewater samples.  Selection should be  made  consistent  with  sampling  requirements,
availability of service and sales, and individual personal preference.

3.5 Turbidimeters (Nephelometers)

Many different instrument designs have been used for the optical measurement of turbidity
by measurement of either  transmission  or reflection of light. An equal or even greater


                                     Table 3-2
ELECTRICAL CONDUCTIVITY OF POTASSIUM CHLORIDE REFERENCE SOLUTIONS
Solution
A


B


C
Normality
0.1


0.01


0.001
Method of Preparation
7.4365 g/1 KC1 at 20°C


0.7440 g/1 KC1 at 20°C


Dilute 1 00 ml of B to 1 .0 1 at 20°C
Temperature
(°C)
0
18
25
0
18
25
25
Conductivity
(jimho/cm)
7,138
11,167
12,856
773
1,220
1,408
147
                                        3-7

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number of materials have been used or proposed as calibration standards. As described in
reference  10, EPA has standardized on the instrument design and the standard turbidity
suspension of Formazin for instrument calibration.

Both  the  analyst and  the user  of turbidity data  should  keep in mind  that a turbidity
measurement  is  not a  substitute  for  particle weight  or residue  analysis. Turbidity
instruments  can be calibrated to give gravimetric  data on specific sample types, but  the
influence  of particle geometry, specific gravity, refractive index, and color make estimates
of total weight impractical on a variety of sample types.

For production of data with  maximum accuracy and precision, the following precautions
should be  observed:

   a.  Protect the sample cuvette from scratches and fingerprints.

   b.  Use a constant orientation of the sample cuvette while  calibrating the instrument
       and analyzing samples.

   c.  Use a well-mixed sample in the sample  cuvette; do not take readings until finely
       dispersed bubbles have disappeared.

   d.  Dilute samples  containing excess turbidity to some value below 40 nephelometric
       turbidity units (NTU); take reading; and multiply results by correct dilution factor.

3.6 Spectrometers

Because a large portion of routine  quantitative measurements are  performed colorimetri-
cally, the spectrometer or filter photometer is usually the workhorse of any analytical
laboratory. Indeed, the versatility of such instruments and the number of demands imposed
upon  them have resulted  in a variety of designs and price ranges. Systematic listing and
detailed discussion of all instrumental types are beyond the scope of this chapter; however,
ultraviolet, visible, infrared, and atomic absorption instruments will be discussed.

A spectrometer is an instrument  for measuring the amount of  light or radiant energy
transmitted through a solution or solid material as a function of wavelength. A spectrometer
differs from a  filter photometer in that it  uses continuously variable, and more nearly
monochromatic,  bands  of   light.  Because  filter  photometers lack  the  versatility of
spectrometers, they are used most profitably where standard methodologies are  used for
routine analysis.

The essential parts of a spectrometer include the following:

   a.  A source of radiant energy

   b.  Monochromator or other device for isolating narrow spectral bands of light

   c.  Cells (cuvettes) or sample holders for containing samples under investigation

   d.  A  photodetector (a device to detect and measure the radiant energy passing through
       the sample)
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Each  of the essential features listed, especially the monochromator and the photodetector
system,  varies in design  principles  from  one  instrument  to  another.  Some of  the
characteristics of  the  commonly used  Perkin-Elmer model  124 double-beam grating
spectrometer are the following:

Light source
     Visible region	  Tungsten
     Lamp UV region	  Deuterium lamp

Wavelength accuracy	  ±0.5 nm

Spectral bandwidth	  0.5,  1.0, and 2.0 nm

Photometric presentation
     Linear transmittance	  0 to 100 percent
     Linear absorbance	  0 to \A or 0 to 2A

Photodetector R-136	  190 to 800 nm

Sample cells	  1.0 to 10 cm


3.6.1 Visible Range

Desirable features on a visible-range spectrometer are determined by the anticipated use of
the instrument.  Simple,  limited  programs requiring use of  only a few parameters  can
probably be supported  by inexpensive but reliable filter photometers. On the other hand, if
the laboratory programs require a wide variety of measurements on diverse samples at low
concentrations, more versatile instruments may be needed. One of the prime considerations
is adaptability to various sample cell sizes from 1.0 to 10.0 cm.

3.6.2 Ultraviolet Range

A  UV spectrometer is similar in design to a visible-range instrument except for differences in
the light source and in the optics. The UV light source is a hydrogen- or deuterium-discharge
lamp, which emits radiation in the UV portion of the spectrum, generally from  about  200
nm to  the low-visible-wavelength  region. The optical  system and sample cells must be
constructed of UV-transparent material,  which is usually quartz. A grating used in a UV
system may be specially cut (blazed) in the UV region for greater sensitivity.

3.6.3 Infrared Range

A  number of instrumental modifications are required in the construction of spectrometers
for measurements  in the IR region because materials such as glass and quartz absorb IR
radiant energy, and ordinary photocells do  not respond  to it. Most IR spectrometers use
front-surfaced mirrors  to  eliminate the  necessity for the transmission of  radiant energy
through quartz,  glass, or other lens materials. These mirrors are usually parabolic to focus
the diffuse IR energy. Such instruments must be protected from high humidities and water
vapor  to avoid  deterioration  of the optical system and the  presence  of extraneous
absorption bands in the IR.
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The energy or light source for an IR instrument may be a Nernst glower or a Globar. Each
of these sources has certain characteristics that recommend it for use, but the more rugged
Globar is more commonly used because it also has a more stable emission. The receiving or
detection unit may be a thermocouple, bolometer, thermistor, or photoconductor cell. The
type of analysis being performed  dictates  the degree of sophistication required in the IR
instrumentation selected to acquire usable data.

3.6.4 Proper Use of Spectrometers

The spectrometer manufacturer's instructions for proper use should be followed in all cases.
Several safeguards against misuse of the instruments, however, are mandatory.

Instruments should be checked for wavelength alinement. If a particular colored solution is
to  be  used  at a  closely  specified  wavelength, considerable loss  of sensitivity can be
encountered  if the wavelength control is misalined. In visible-range instruments, an excellent
reference  point  is  the  maximum  absorption for  a  diluted  solution  of potassium
permanganate, which has dual peaks at 526 and 546 nm. On inexpensive instruments with
less resolution the permanganate peak appears at  525  to 550 nm  as a single, flat-topped
peak.

For both  UV and IR  instruments, standard absorption curves for many organic materials
have been published  so  that  reference material for  standard peaks  is easily available.
Standard films of styrene and other transparent plastics are available  for IR wavelength
checks.  A very  good discussion  of factors  that  affect  the  proper  performance of
spectrometers and standard reference materials available to calibrate them can be found in
publications of the National Bureau of Standards.*  Use of certified standards is encouraged
whenever practical.

Too much emphasis cannot be placed on care of absorption cells. All absorption cells should
be  kept scrupulously clean, free of scratches,  fingerprints, smudges, and evaporated film
residues. Matched  cells should be  checked  to see  that they are  equivalent,  and any
differences should be .accounted for during use or in the final data. Directions for cleaning
cells are given in chapter 4.

Generally speaking, trained  technicians may operate any of the spectrometers successfully;
however, because interpretation  of data from both the  UV and IR instruments is becoming
increasingly complex,  mere compliance with the operations manual may not be sufficient
for completely accomplishing the  special  techniques of sample preparation,  instrument
operation, and interpretation of absorption curves.

3.6.5 Atomic Absorption

There are a number of differences in the basic design and accessories for atomic absorption
(AA) equipment  that  require consideration before purchase and during subsequent use.
These choices concern the light sources, nebulizer burners, optical systems, readout devices,
and mode conversions. Because some of these choices  are not  readily obvious, the purchaser
or user  must be familiar  with the types and  numbers of samples to be analyzed and the
*NBS, Office of Standard Reference Materials, Institute for Materials Research, Washington,
 D.C. 20234.
                                         3-10

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specific elements to be measured before making the choice. For a program analyzing a wide
variety of samples for a number of elements at varying concentrations, an instrument of
maximum versatility would be best. Most of the discussion that follows applies to use of
instrumentation in absorption, emission, or fluorescence modes.

3.6.5.1  Lamps

Hollow-cathode (HC) lamps or electrodeless-discharge lamps (EDL) are available for over 70
elements with single-element or multielement capability. Multielement lamps are consid-
erably  cheaper per element than single-element lamps, but the savings may not be realized if
the lamps are not used strategically, because all the elements in the cathode deteriorate
when  the  lamp  is used,  regardless  of which element is measured.  The  deterioration
phenomena result from the different volatilities of metals used in the cathode. One metal
volatilizes (sputters) more  rapidly than the others and redeposits upon an area of the other
cathode metals. Thus,  with continual use, a drift in signal will be noted with at least  one
metal increasing and the  other  (or others)  decreasing. If one can ignore the dubious cost
savings of multielement lamps, use of single-element lamps could result in more precise and
accurate data.

The line intensities of one element in a multielement HC lamp will usually be less than those
of a lamp containing a pure cathode of the same element because this element must share
the discharge energy with the other elements present.  However, this reduction should not
affect  the output  by a  factor of more  than one-sixth to one-half, depending on  the
particular combination and  the  number of elements  combined. The output  can  be even
greater in some multielement lamps because alloying may permit a higher operating current
than for the case of the pure cathode. All HC lamps have life expectancies that are related to
the volatility of the cathode metal, and. for this reason the manufacturer's recommendations
for operating should be closely followed.

Recent improvements in  design  and manufacture of HC lamps and EDLs  have resulted in
lamps  with more  constant output and longer life. Under normal conditions an HC lamp may
be expected to operate satisfactorily for several years. HC lamps used to be  guaranteed for a
certain minimum ampere-hour period, but this has been changed to a 90-day warranty.  It is
good practice to date newly purchased lamps and to inspect them immediately upon receipt.
The operating current and voltage indicated on the lamp should not be exceeded during use.
An increase in background noise or a loss of sensitivity are signs of lamp deterioration.

A basic design feature of AA spectrometers is the  convenience of the HC lamp changeover
system. Some  instruments  provide for  as  many  as  six  lamps in  a rotating turret, all
electronically  stabilized and ready for use  by  simply rotating the lamp  turret.  Other
instruments provide for use of only one lamp at  a time in the lamp housing, and require
manual removal and replacement whenever more  than one element is to be  measured. A
quick-changeover system enables frequent lamp changes during the period of  operation. If
necessary lamp changes are infrequent, however, multilamp mounts do not  represent a great
convenience.

After the proper lamp has been selected, the HC current should be adjusted according to the
manufacturer's recommendations and allowed to electronically stabilize (warm up) before
use. During this  15-min period, the monochromator may be  positioned at the correct
wavelength, and the proper slit  width may be selected. For those instruments employing a
multilamp turret, a  warmup current  is  provided to  those  lamps not  in  use, thereby
                                        3-11

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minimizing the warmup period after the turret is rotated.  In a single-lamp instrument, the
instability exhibited during warmup is minimized by the use of a double-beam optical
system.

3.6.5.2 Burner Types

The most difficult  and inefficient step in  the AA process is converting the metal in the
sample from an ion or a molecule to the  neutral atomic state. It  is the function of the
atomizer/burner to produce the desired neutral atomic condition  of the elements. With
minor modifications burners are the same as those used for  flame photometry.

Basically there are two different types of burners. They are the total-consumption,  or
surface-mix burner, and the laminar-flow or premix burner. There  are many variations  of
these two basic types, such as the Doling, the high-solids,  the turbulent-flow, the triflame,
the  nitrous  oxide  burners,  and many others.   As one  might expect,  there are many
similarities among  the  various burners, the  different  names resulting from  the  different
manufacturers. The element being determined and the type of sample solution dictate the
type  of  burner to be  used. Generally, all types and makes of burner  can be adjusted
laterally, rotationally, and vertically for selection of the most sensitive area of the flame for
the specific element sought.

Nonflame techniques have gained wide acceptance in AA analysis because of the extreme
sensitivity  and the capability  to directly  introduce very diverse sample matrices. These
systems, which replace the conventional  flame burner, come  in various designs using
electrical resistance to produce temperatures as high as 3,500°C.

3.6.5.3 Single- and Double- (Split-) Beam Instruments

There is a great deal of existing uncertainty among instrument users about the relative
merits of single- and double-beam instruments. Neither system is appropriate for all cases.

With a single-beam instrument the  light beam from the source passes directly through the
flame to the detector.  In a double-beam system the light from the source is divided by a
beam  splitter into two  paths. One path, the reference beam, goes directly to the detector.
The second path,  the sample beam, goes through the  flame to the detector. The chopper
alternately reflects and passes each beam, creating two equal beams falling alternately upon
the  detector.  If the beams are equal, they cancel the  alternate  impulses  reaching the
detector,  and  no  signal is generated.  If the beams are different, the  resulting imbalance
causes the detector to generate a signal that is amplified and measured. The difference
between the  reference and sample beams is then determined as a direct function of absorbed
light. The advantages of the double-beam design are that any variations in the source are of
reduced  importance,  and smaller dependence is  placed  upon  the  stability of the power
supply. Conversely, stabilization of the power supply can eliminate the apparent need for
the split-beam  system. Furthermore, the beam splitter requires additional mirrors or optical
accessories that cause some loss of radiant energy.

A  single-beam system does not  monitor  source variations,  but offers certain other
advantages. It allows use of low-intensity lamps, smaller slit settings, and smaller gain. As a
consequence, the single-beam instrument,  properly designed, is capable of operating with
lower noise  and  better signal-to-noise ratio,  and  therefore with  better precision and
improved  sensitivity.  Because  the  simplified  optical system  conserves radiant  energy,
                                        3-12

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especially in the shorter wavelengths, it facilitates operation in the low-wavelength range.
With this advantage, it should be possible to obtain better sensitivity for those elements with
a strong  resonance line below 350 nm and particularly those below 300 nm. Background
correction techniques are also available in single-beam systems.

Double-beam instruments, however, offer the  opportunity  to perform more sophisticated
techniques like background correction, two-channel multielement analysis, use of internal
standards, and element rationing. If  one of these techniques is necessary, a double-beam
instrument must be considered.

3.6.5.4 Readout Devices

Readout  devices  in  even the lower  cost AA instruments include digital concentration
display. Using high-speed digital electronics, data-handling  techniques encompass multiple
calibration standards,  regression analysis to  characterize  the calibration curves,  mean
variance  and standard deviation statistical  programs for sample calculations, and various
forms of printout reports in  addition to recorder output.  Choice of a  readout system is
predicated largely upon laboratory needs and availability of budget.  In general, any step
toward automation is desirable, but the degree of automation should be compatible with the
laboratory program.

3.6.5.5 Miscellaneous Accessories

A number of instruments contain a mode selector, making  an instrument usable for either
absorption or emission. The conversion to emission may  be  a desirable  feature because
certain elements  are  more amenable to analysis by this method. Some models  offer an
option of atomic  fluorescence and can also be used as a UV/visible spectrometer.

Automatic sample changers are offered for almost all instruments on the  market, and as has
been previously stated, any automation feature is desirable. However, unless a laboratory
program  performs a large number of repetitious measurements daily, an automatic sample
changer  is not required.  As a practical measure, other commonly used sample-changing
devices,  although not expressly  designed for AA use, can be interfaced with most AA
instruments.

3.7 Organic Carbon Analyzers

A number of instruments designed to measure total  organic carbon (TOC) in waters and
wastes have  appeared on the market in  the past several  years. The first of these units
involved  pyrolysis followed by IR  measurement  of  the carbon dioxide formed. Sample
injection  of 20 to 200 n\ in a carrier gas of air or oxygen was performed with a syringe.
Combustion at 800°C to 900°C followed by IR analysis was performed automatically with
final output  on an analog recorder.  Systems using these principles are  still  produced and
represent a large part of the TOC market.

Other .techniques of TOC analysis that modify every phase  of the original TOC instruments
have been introduced. Sample presentation in small metallic boats and purging of CO2 from
solution  are two  new techniques. Wet chemical oxidation, either external to the instrument
or within the instrument, using various oxidants including  ultraviolet  irradiation is now in
wide use. Measurement of the CO2 by reduction to methane (CH4) and quantitation with a
flame ionization  detector are also available. Various methods of data handling are now used,
                                        3-13

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ranging from recorder output to direct readings and printouts of concentration. Techniques
are also  available  for measuring materials  like soil  and sludges,  and also  the  volatile
component  of the TOC. Sensitivity on some systems has been  extended down to the
microgram  per  liter  level. The major problems  associated with TOC  measurements are
interference from forms of inorganic carbon and the difficulty of obtaining a representative
sample in the presence of particulate matter. Each system has its own procedure for sample
pretreatment or for  accounting for these problems.  When  choosing  a TOC instrument,
consideration should  be given to  the  types  of samples to be analyzed, the expected
concentration range, and the  forms of carbon to be measured.


3.8 Gas Chromatographs

Because GC's are available from a large number of manufacturers, selection of a particular
manufacturer may be  based  on convenience. No single multipurpose GC instrument permits
analysis of  a wide range of compounds. In this case, a GC/MS could be considered (11). If,
however, relatively few types of environmentally significant compounds are being surveyed,
an inexpensive system equipped with a glass-lined injection port, electrolytic conductivity
detector, and analog recorder is a good choice. A review of the organic methods (12) to be
used  will  give   the analyst  all  the necessary information  on the specific  instrument,
apparatus,  and materials necessary for  each type  or class of  compounds. A discussion of
various quality control considerations in GC analysis is given in  chapter 8 of this manual.

Data handling requirements  vary  widely, and the need to automate GC data collection is
determined  by  the extent  of the sample load.  In a routine monitoring laboratory, GC
systems incorporating their own microprocessers and report generating capabilities would be
useful in solving this  problem. Because  such systems greatly increase the cost, the overall
economy of this  choice must be considered.

3.9  References

 1. "Single Arm Balances Testing," Part 41 of 1976 Book of ASTM Standards, American
    Society for Testing and Materials, Philadelphia (1976).
 2. Sorenson, S. P. L., Biochem. Z., 21, 201 (1909).
 3. "pH of Water and Wastewater," from Part 31  of 1976 Book of ASTM Standards,
    American Society for Testing and Materials, Philadelphia (1976).
 4. Catalog of NBS Standard  Reference Materials, NBS Special Publication 260, National
    Bureau of Standards (1975-76).
 5. Methods for Chemical Analysis of Water and Wastes, U.S.  EPA, Office of Research and
    Development, EMSL, Cincinnati (1978).
 6. Rechnitz, G. A.,  "Ion-Selective Electrodes," Chem. Eng. News (June 12, 1967), p. 146.
 7. Riseman, Jean M., "Measurement  of Inorganic  Water  Pollutants  by Specific Ion
    Electrode," American Laboratory (July 1969), p. 32.
 8. Koryta, Jiri, "Theory and  Application of Ion-Selective Electrodes," Anal.  Chim.  Acta,
    61, 329-411  (1972).
 9. Covington, A.  L, "Ion-Selective Electrodes," CRC Critical Review in Anal.  Chem. (Jan.
    1974),  pp. 355-406.
10. Black,  A.  P., and  Hannah, S. A., "Measurement of  Low Turbidities," J. Am. Water
    Works Assoc.,57,  901 (1965).
11. EPA GC/MS Procedural Manual, Budde, W.  L., and  Eichelberger, J. W.,  Editors, 1st
    Edition, Vol. 1, U.S. EPA, Office of Research and Development, EMSL, Cincinnati (in
    press).
                                       3-14

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12.  Methods for Organic Analysis of Water and Wastes, U.S. EPA, EMSL, Environmental
    Research Center, Cincinnati (in preparation).
                                       3-15

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                                       Chapter 4

                                     GLASSWARE
4.1  General
The measurement of trace constituents  in water  demands methods capable of maximum
sensitivity. This is especially true for metals and trace organics such as pesticides, as well as
for the  determination  of ammonia and phosphorus. In addition to sensitive  methods,
however, there are other areas that require special consideration. One such area is that of the
cleanliness of laboratory glassware. Obviously, the very sensitive analytical systems are more
sensitive to errors resulting from  the improper use or choice  of apparatus, as well  as to
contamination  effects due to an improper method of cleaning the apparatus. The purpose of
this chapter is to discuss the kinds of glassware available, the use of volumetric ware, and
various cleaning requirements.

4.2 Types of Glassware

Laboratory vessels serve three functions: storage of reagents, measurement  of solution
volumes, and  confinement of reactions.  For special purposes, vessels made from materials
such as porcelain, nickel,  iron, aluminum, platinum,  stainless steel, and plastic may be
employed to advantage. Glass, however, is the most widely used material of construction.
There are many grades and types of glassware from which to choose, ranging from student
grade to others possessing specific properties such as super strength, low boron content, and
resistance to thermal shock or alkali. Soft glass containers are not recommended for general
use, especially  for storage of reagents because of the possibility of dissolving of the glass (or
of some of the constituents of the glass). The mainstay of the modern analytical laboratory
is  a highly resistant borosilicate glass, such as that manufactured by Corning Glass Works
under the name "Pyrex" or by Kimble Glass Co. as "Kimax." This glassware is satisfactory
for all analyses included in reference  1.

Depending on the particular manufacturer, various trade names are used for specific brands
possessing  special properties such as resistance to  heat, shock, and alkalies. Examples of
some of these special brands follow:

    a.  Kimax- or Pyrex-brand glass is a relatively inert all-purpose borosilicate glass.

    b.  Vycor-brand glass is a  silica  glass (96 percent) made  to withstand  continuous
       temperatures up to 900° C and can be down-shocked  in ice water without breakage.

    c.  Coming-brand glass  is  claimed  to  be 50 times more resistant to alkalies  than
       conventional ware and practically boron-free (maximum 0.2 percent).

    d.  Ray-Sorb- or Low-Actinic-brand glass is used when the reagents or materials are light
       sensitive.

    e.  Corex-brand labware is harder than conventional borosilicates and therefore better
       able to resist clouding and scratching.

The use of plastic vessels, containers, and other apparatus made of Teflon, polyethylene,
polystyrene, and  polypropylene has increased markedly  over recent years. Some of  these


                                         4-1

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materials, such  as  Teflon,  are quite expensive; however,  Teflon stopcock  plugs  have
practically  replaced glass plugs in burets, separatory funnels, etc., because lubrication to
avoid sticking or "freezing"  is not required. Polypropylene, a methylpentene polymer, is
available as laboratory bottles, graduates, beakers, and even volumetric flasks.  It is crystal
clear, shatterproof, autoclavable, and chemically resistant.

The following are some points to consider in choosing glassware or plasticware:

   a.  The special types of glass listed above, other than Pyrex or Kimax, generally are not
       required to perform the analyses given in "Methods for Chemical Analysis of Water
       and Wastes" (1).

   b.  Unless instructed otherwise, borosilicate or polyethylene bottles may be used for the
       storage of reagents and standard solutions.

   c.  Dilute metal solutions are prone to plate out  on container walls over long periods of
       storage. Thus, dilute metal standard solutions must be prepared fresh at the time of
       analysis.

   d.  For some operations, disposable glassware is entirely satisfactory. One example is
       the use of disposable test tubes as  sample containers for use with the Technicon
       automatic sampler.

   e.  Plastic bottles  of polyethylene  and Teflon  have been found satisfactory for  the
       shipment of water samples. Strong mineral acids (such as sulfuric  acid) and organic
       solvents will readily attack polyethylene and are to be  avoided.

   f.  Borosilicate glassware is  not completely inert, particularly to alkalies; therefore,
       standard  solutions  of  silica, boron, and the alkali  metals are  usually  stored  in
       polyethylene bottles.

For  additional  information  the reader  is referred to the catalogs  of the various glass and
plastic manufacturers. These catalogs contain  a wealth  of information such as  specific
properties, uses, and sizes.

4.3 Volumetric Analyses

By common usage, accurately calibrated glassware for precise measurements of volume has
become  known as volumetric  glassware. This group includes volumetric flasks, volumetric
pipets,  and  accurately  calibrated  burets.  Less  accurate types  of glassware  including
graduated  cylinders and serological  and measuring pipets also  have specific uses in  the
analytical laboratory when exact volumes are unnecessary.

The  precision of volumetric work depends in part upon the accuracy with  which volumes of
solutions can  be measured.  There are certain sources  of  error  that must be  carefully
considered. The volumetric apparatus must be read correctly; that is, the bottom of the
meniscus should be tangent  to  the calibration mark. There  are other  sources  of  error,
however, such as changes in  temperature, which result in changes in the actual capacity of
glass apparatus and in the volume of the solutions. The capacity of an ordinary glass flask of
1000-ml volume increases 0.025  ml/deg with rise in  temperature, but if the flask is made of
borosilicate glass, the increase is much  less. One thousand milliliters of water or of most
O.IN solutions increases in volume by  approximately  0.20  ml/deg increase  at  room
                                         4-2

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temperature. Thus  solutions must be measured at the temperature at which the apparatus
was  calibrated. This temperature (usually 20°C) will  be indicated on all volumetric ware.
There may also be  errors of calibration of the apparatus; that is, the volume marked on the
apparatus may not  be  the true volume. Such  errors can  be eliminated only by recalibrating
the apparatus or by replacing it.

Volumetric apparatus is  calibrated to contain or to deliver a definite volume of liquid. This
will be indicated on the  apparatus with the letters "TC" (to contain) or "TD" (to deliver).
Volumetric flasks are calibrated to contain a given volume and are available in various shapes
and sizes.

Volumetric pipets  are calibrated  to deliver  a  fixed  volume.  The  usual capacities are  1
through  100 ml although micropipets are also available. Micropipets are  most useful in
furnace work and are available in sizes ranging from 1 to 100 n\.

In emptying volumetric  pipets, they should be  held in a vertical position and  the outflow
should be unrestricted. The tip of the pipet is kept in contact with the wall of the receiving
vessel for a second  or  two after the  free flow has stopped. The liquid remaining in the tip is
not removed; this is most important.

Measuring  and serological pipets should also  be held  in a vertical position for dispensing
liquids; however, the tip of the pipet is  only touched to the  wet surface of the receiving
vessel after the  outflow has  ceased. For those pipets where  the small amount of liquid
remaining in the tip is  to be blown out and added, indication  is  made by a frosted band near
the top.

Burets are  used to  deliver definite volumes. The more  common types  are usually of 25- or
50-ml capacity,  graduated to  tenths of a milliliter,  and  are provided with  stopcocks. For
precise  analytical  methods in microchemistry, microburets  are also  used.  Microburets
generally are of 5- or  10-ml capacity, graduated in  divisions of hundredths of a milliliter.
Automatic burets with reservoirs are also  available ranging in capacity from 10 to 100 ml.
Reservoir capacity ranges from 100 to 4,000 ml.

General rules in  regard to the manipulation of a buret are as follows: Do not attempt to dry
a buret that has been cleaned for use, but rinse it two or three times with a small volume of
the solution with which  it is to be filled.  Do not allow alkaline solutions to stand in a buret
because  the glass will  be attacked,  and the stopcock, unless made of Teflon,  will tend to
freeze. A 50-ml buret should not be emptied faster than 0.7 ml/s, otherwise too much liquid
will  adhere to the  walls and as the  solution drains down, the  meniscus  will gradually rise,
giving a high false reading. It should be emphasized that improper use or reading of burets
can result in serious calculation errors.

In the case of all apparatus for delivering liquids, the glass must be absolutely clean  so that
the film  of liquid never breaks at any point. Careful attention  must be paid to this  fact or
the required amount of solution will not be delivered.  The various cleaning agents and their
use are described later.

4.4 Federal Specifications for Volumetric Glassware

Reference 2 contains a description of Federal specifications for volumetric glassware. The
National Bureau of Standards  no  longer  accepts stock  quantities of volumetric apparatus
                                         4-3

-------
from manufacturers or dealers for certification and return for future sale to consumers. This
certification service is still available, but apparatus will be tested only when submitted by
the ultimate  user, and  then only  after an agreement has been reached with the Bureau
concerning the work to be done.

Consequently, the various glass manufacturers have discontinued the listing of NBS-certified
ware.  In its  place catalog  listings of volumetric glass apparatus that meet the Federal
specifications are  designated as class A and all such glassware is permanently marked with a
large "A." These NBS  specifications  are  listed in  table 4-1. The  glassware in question
includes the usual burets, volumetric flasks, and volumetric pipets.

In addition to the "A" marking found on calibrated glassware and the temperature at which
the calibration was made, other markings also appear. These include the type of glass, such


                                      Table 4-1
                           TOLERANCES FOR VOLUMETRIC
                                   GLASSWARE*
Type
of
Glassware
Graduated flask








Transfer pipet







Buret3




Capacity2
(ml)
25
50
100
200
250
300
500
1,000
2,000
2
5
10
25
30
50
100
200
5
10
30
50
100
Limit of Error
(ml)
0.03
0.05
0.08
0.10
0.11
0.12
0.15
0.30
0.50
0.006
0.01
0.02
0.025
0.03
0.05
0.08
0.10
0.01
0.02
0.03
0.05
0.10
                   1 Abridged from reference 3.
                   2 Less than and including.
                   3 Limits of error are  of total or partial  capacity.
                    Customary practice is to test the capacity at five
                    intervals.
                                        4-4

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as Pyrex, Corex, or Kimax; the stock number of the particular item; and the capacity of the
vessel.  If the vessel contains a  ground-glass connection, this will also be included along with
the TD or TC symbol.  An example of the  markings usually found on volumetric ware is
shown  in  figure  4-1. Class  A glassware need not be recalibrated before use. However,  if it
should become necessary to calibrate a particular piece of glassware, directions may be
found in texts (4) on quantitative analysis.

4.5 Cleaning of Glass and Porcelain

The method of cleaning should be adapted to both the substances that are to be removed,
and the determination to be performed. Water-soluble substances are simply  washed out
with hot or cold water,  and the  vessel is finally rinsed with successive small  amounts of
distilled water. Other substances more difficult  to remove may  require  the  use  of a
detergent, organic solvent, dichromate cleaning solution, nitric acid,  or aqua  regia  (25
percent by volume concentrated HNO3  in concentrated HC1). In all cases it is good practice
to rinse a vessel with tap water as soon as  possible after use. Material allowed to dry on
glassware is much more difficult to remove.

Volumetric glassware, especially burets, may  be thoroughly cleaned by a mixture containing
the following: 30 g of sodium hydroxide, 4  g of sodium hexametaphosphate (trade name,
Calgon), 8 g of  trisodium phosphate, and 1 1 of water. A gram or two of sodium lauryl
sulfate or other  surfactant will improve its  action in some cases. This solution should be
used with a buret brush.

Dichromate cleaning solution (chromic acid) is a powerful cleaning agent; however, because
of its destructive nature upon clothing and upon laboratory furniture, extreme care must be
taken when using this  mixture. If any of the solution is spilled, it must be cleaned up
immediately.  Chromic acid solution may be prepared in the laboratory by  adding 1  1 of
concentrated sulfuric acid slowly,  with stirring,  to a 35-ml  saturated sodium  dichromate
solution. This mixture must be allowed to stand for approximately 15 min in the vessel that
is being cleaned and  may then be  returned to a storage bottle. Following the chromic acid
wash, the  vessels are rinsed thoroughly with  tap water, then with small successive portions
of distilled water. The analyst should be cautioned that when chromium is included in the
PYREX fl
USA
y*-
J 1 0

-*•
500 ml ± 0.20 ml <*-
TP ?n°r ^

NO 5680 *
GLASS CO.
TYPE
STANDARD j
	 TAPER » 5 ^
SIZE 19

TO
CONTAIN
, ., STOCK
NO.
KIMAX
* USA
s
V


,. *. TP 9n°r

^ NO 28013
                     Figure 4-1. Example of markings on glassware.
                                        4-5

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scheme of analysis, it is imperative that the last traces of dichromate be removed from the
apparatus. To this end, a substitute for dichromate cleaning solution, called Nochromix,* is
available and may be  used  to  advantage. Fuming  nitric acid is another powerful cleaning
agent,  but is disagreeable to handle. As with dichromate, when the acid becomes dilute, the
cleaning mixture is no longer effective. A mixture of concentrated sulfuric and fuming nitric
acids is even more efficient but is also hazardous to  use. A persistent greasy layer or spot
may be removed by acetone or by allowing a warm  solution of sodium hydroxide, about  1 g
per 50 ml of water, to stand in the vessel for 10 to 15 min; after rinsing with water, dilute
hydrochloric  acid, and  water again, the  vessel  is usually  clean. Alcoholic potassium
hydroxide is also effective in removing grease. To dry glass apparatus, rinse with acetone and
blow or draw air through it.

4.6 Special Cleaning  Requirements

Absorption  cells, used in spectrophotometers, should be  kept scrupulously  clean,  free of
scratches, fingerprints, smudges, and evaporated film residues. The cells may be cleaned with
detergent solutions for removal of organic residues, but should not be soaked for prolonged
periods in caustic solutions because of the  possibility of etching. Organic solvents may be
used  to rinse  cells in which  organic materials  have  been  used. Nitric acid  rinses  are
permissible,  but  dichromate solutions are  not recommended because of the adsorptive
properties of dichromate on glass. Rinsing and drying  of cells with alcohol or acetone before
storage is  a preferred practice. Matched cells should be checked to see that  they  are
equivalent by placing portions  of the same solution in both cells and taking several readings
of the transmittance (T, percent) or optical density  (OD) values.

For certain  determinations-, especially trace metals, the glassware should also be rinsed with
a  1:1  nitric acid-water mixture. This operation is followed by thoroughly rinsing with tap
water and successive portions of distilled water. This may require as many as 12 to  15 rinses,
especially if chromium is being determined. The nitric acid rinse is also especially important
if lead is being determined.

Glassware to be used  for phosphate  determinations should not be washed with detergents
containing  phosphates.  This  glassware  must  be  thoroughly rinsed  with tap water and
distilled water.  For ammonia and  Kjeldahl nitrogen, the glassware must be rinsed with
ammonia-free water. (See ch. 2.)

Glassware to  be used  in the determination of trace  organic constituents in water, such as
chlorinated  pesticides, should be as free as possible  of organic contaminants. A chromic acid
wash of at least 15 min is necessary to destroy these organic residues. Rinse thoroughly with
tap water and, finally, with distilled water. Glassware may be dried for immediate use by
rinsing with redistilled acetone. Otherwise glassware may be oven dried or drip  dried.
Glassware should  be stored immediately after drying to prevent any accumulation of dust
and stored inverted or with mouth of glassware covered with foil.

Bottles to  be  used for  the collection of  samples for organic analyses should  be  rinsed
successively with  chromic  acid cleaning  solution,  tap water,  distilled water, and,  finally,
several times with a redistilled  solvent such as acetone,  hexane,  petroleum  ether, or
chloroform. Caps are washed  with detergent, rinsed with tap water,  distilled water, and
*Available from Godax Laboratories, 6 Varick Street, New York, N.Y.  10013.
                                         4-6

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solvent.  Liners are treated in the same way as  the bottles and are stored  in  a sealed
container.

4.7 Disposable Glassware

When the risk of washing a pipet for reuse becomes too great, as in  the case of  use with
toxic materials,  or when the cost of washing glassware becomes prohibitive, disposable
vessels may be the answer, provided they  meet the necessary specification. Various types are
available including bacteriological, serological, and microdilution  pipets.  Disposable glass-
ware generally is made of soft glass although plastic vessels and pipets are also available.

4.8 Specialized Glassware

The use of vessels and glassware fitted with standard-taper, ground-glass, and ball-and-socket
joints has increased because of certain advantages such as less leakage  and fewer freezeups.
Standard-taper, interchangeable ground joints save time and trouble in assembling apparatus.
They are precision-ground with tested abrasives to insure an accurate fit and freedom from
leakage. Ball and socket joints increase flexibility of operation and eliminate the  need for
exact alinements  of apparatus. Symbols and  their meaning as applied to standard joints,
stoppers, and stopcocks are shown below.

4.8.1 Standard Taper (1)

The symbol  J is used  to  designate  interchangeable joints, stoppers, and stopcocks that
comply with the  requirements of reference  5. All mating parts are finished to a 1:10 taper.

The size of a particular piece appears after the appropriate symbol. Primarily because of
greater  variety of apparatus  equipped with  5 fittings, a number of different types of
identifications are used:

    a.  For joints-a two-part number as  5 24/40, with 24 being the approximate diameter
       in millimeters  at the large end of the taper and 40  the axial length of taper, also in
       millimeters

    b.  For stopcocks-a single number, as J 2, with 2 mm being the approximate diameter
       of the hole or holes through the plug

    c.  For bottles-a single number, as J 19, with 19  mm being the appropriate diameter at
       top of neck. However, there are  differences in dimensions between the bottle and
       flask stoppers

    d.  For flasks and similar containers—a  single number,  as J 19, with 19 mm being the
       appropriate diameter of the opening at top of neck

4.8.2 Spherical Joints (?)

The designation f is for spherical (semiball) joints complying with reference 5. The complete
designation of a spherical joint also consists of a two-part number, as 12/2, with  12 being
the approximate  diameter  of the ball and  2  the bore of the ball and the socket, also in
millimeters.
                                         4-7

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4.8.3 Product Standard (§)

The symbol £  is used for stopcocks with Teflon plugs, the mating surfaces being finished to
a 1:5  taper. As with £ stopcocks, a single number is used. Thus,  |  2  means  a  Teflon
stopcock with a hole of approximately 2-mm diameter in the plug.

4.9  Fritted Ware

For certain laboratory  operations  the  use  of fritted  ware for filtration, gas dispersion,
absorption, or extractions may be advantageous.

There  are six  different  porosities of fritted ware available, depending on its intended use.
Porosity is controlled in manufacture, and disks are individually tested and graded into these
classifications. The  extra-coarse  and coarse  porosities are held toward the maximum pore
diameter as listed. The medium, fine, very fine, and ultrafme are held  toward the minimum
pore diameter as listed in table 4-2.

Pore sizes are determined by the method specified in reference 6.

4.9.1 Recommended Procedures for Maximum Filter Life

    a.  New Filters. Wash new filters by suction with hot hydrochloric acid, followed by a
       water rinse.

    b.  Pressure Limits. The maximum, safe, differential pressure on a disk is 15 lb/in2.

    c.  Thermal  Shock. Fritted  ware has less resistance to thermal shock than nonporous
       glassware. Hence,  excessive, rapid  temperature  changes and  direct exposure to a
       flame  should be avoided.  Heating  in a furnace  to  500° C  may  be  done  safely,
       provided the heating and cooling are gradual. Dry ware may be brought to constant
       weight by heating at 105°C to 110°C.

Never  subject a  damp filter of ultrafine porosity  to a sudden temperature change. Steam
produced in the interior may cause cracking.
                                      Table 4-2
                            FRITTED-WARE POROSITY
Porosity
Grade
Extra Coarse

Coarse

Medium
Fine
Very Fine
Ultrafine
Designation
EC

C

M
F
VF
UF
Pore Size
(Mm)
170-220

40-60

10-15
4-5.5
2-2.5
0.9-1.4
Principal Uses
Coarse filtration ; gas dispersion,
absorption
Coarse filtration; gas dispersion,
absorption
Filtration and extraction
Filtration and extraction
General bacterial filtration
General bacterial filtration

washing, and

washing, and





                                         4-8

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4.9.2 Cleaning of Used Filters

In many cases, precipitates can be removed by rinsing with water, passed through from the
underside,  with the pressure not exceeding 15 lb/in2.  The suggestions that follow will be
helpful in dealing with material that will not be removed by such a reverse water-wash:

              Material                                Removal Agent

Albumen	  Hot ammonia or hydrochloric acid

Aluminous and siliceous residues	  Hydrofluoric acid (2 percent) followed by concen-
                                        trated  sdlfuric  acid; rinse  immediately  with
                                        water  until no trace  of acid can be  detected.

Copper or iron oxides	  Hot hydrochloric acid plus potassium chlorate

Fatty materials	  Carbon tetrachloride

Mercuric sulfide	  Hot aqua regia

Organic matter	  Hot, concentrated cleaning solution, or  hot, con-
                                        centrated sulfuric acid with a few drops of sodi-
                                        ium nitrite

Silver chloride	  Ammonium or sodium hyposulfite

4.10 References

1. Methods for Chemical Analysis of Water and  Wastes, U.S.  EPA, Office of Research and
   Development, EMSL (1978).
2. Hughes,  J.  C., Testing of Glass Volumetric Apparatus,  NBS Circular 602, National
   Bureau of Standards (1959).
3. Peffer, E. L., and Mulligan, G. C., Testing of  Glass Volumetric Apparatus, NBS Circular
   434, National Bureau of Standards (1941).
4. Willard,  H. H.,  and  Furman,  N. H.,  Elementary Quantitative  Analysis—Theory and
   Practice, D. Van Nostrand Co., Inc., New York (1947).
5. Interchangeable Ground  Glass Joints, Commercial Standard  CS-21-30, National Bureau
   of Standards (Aug. 25, 1930).
6. Maximum  Pore Diameter and Permeability of Rigid Porous Filters for Laboratory Use,
   E-128, American Society for Testing and Materials, Philadelphia (1968).
                                        4-9

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                                       Chapter 5

                           REAGENTS, SOLVENTS, AND GASES
5.1  Introduction
The  objective of this chapter is to provide general information and suggestions  that will
serve to  keep the analyst conscious of his responsibilities in analytical quality control, as
they relate to reagents, solvents, and gases. While the material presented here will assist the
analyst in producing high-quality data, it is by no means complete. It is incumbent on the
analyst  to  obtain details  of special  precautions  required to insure proper selection,
preparation, and storage of reagents, solvents, and gases from the descriptions of individual
methods.

5.2  Reagent Quality

Chemical  reagents, solvents, and gases are available in a  wide variety of grades of purity,
ranging  from  technical grade to various ultrapure grades.  The purity of these materials
required  in analytical chemistry varies with  the type of  analysis.  The  parameter being
measured and the sensitivity and specificity of the detection system are important factors in
determining  the  purity of the  reagents  required. For  many  analyses,  including most
inorganic  analyses, analytical reagent  grade  is satisfactory. Other analyses, such as trace
organic and radiological, frequently require special ultrapure reagents,  solvents, and gases. In
methods where the purity of reagents is not specified  it is intended that analytical reagent
grade be used. Reagents of lesser purity than that specified by the method  should not be
used. The  labels  on the container should be checked and the contents examined to verify
that the purity of the reagents meets  the needs  of the  particular method  involved. The
quality of reagents, solvents, and gases required for the various classes of analyses—inorganic,
metals, radiological, and organic—are discussed in this section.

Reagents must always be prepared and standardized with the utmost  of care and technique
against reliable primary standards. They must be restandardized or prepared fresh as often as
required  by their stability.  Stock and working standard solutions must be checked regularly
for signs  of deterioration;  e.g.,  discoloration, formation  of precipitates, and change of
concentration.  Standard solutions should be properly labeled as to compound, concentra-
tion, solvent, date, and preparer.

Primary standards must be  obtained from a reliable source, pretreated (e.g., dried, under
specified conditions), accurately prepared in calibrated volumetric glassware, and stored in
containers that will not alter the reagent. A large number of primary standards are available
from the  National Bureau of Standards (NBS). A complete listing of available standards is
given in  reference  1. Primary standards may also be obtained from many chemical supply
companies.  Suppliers for special quality reagents,  solvents, and gases are noted in  later
discussions of the various classes of analyses. Reagents and solvents of  all grades are available
from many chemical supply houses.

There is some confusion among  chemists as  to  the  definition of the terms "Analytical
Reagent Grade,"  "Reagent Grade," and "ACS Analytical  Reagent Grade." A review of the
literature  and chemical supply catalogs indicates  that the three terms are synonymous.
Hereafter,  in this document, the term "Analytical Reagent  Grade" (AR) will be used. It is
                                         5-1

-------
intended that AR-grade chemicals and solvents shall conform to the current specifications of
the Committee on Analytical Reagents of the American Chemical Society (2).

References  3   through 5  devote several  chapters to problems related  to preparation,
standardization, and storage of reagents. The information provided therein is particularly
appropriate to inorganic determinations. The type of volumetric glassware to be used, the
effect  of  certain  reagents on glassware,  the  effect  of  temperature  on  volumetric
measurements, purity of  reagents,  absorption of gases and water vapor  from the air,
standardization of solutions, instability, and the need for frequent standardization of certain
reagents  are among  the  topics discussed. It  is  recommended  that the analyst become
thoroughly familiar with these publications.

5.2.1 General Inorganic Analyses

In general, AR-grade reagents and solvents are satisfactory for inorganic analyses. Primary
standard reagents must,  of course, be used  for standardizing all volumetric solutions.
Commercially  prepared reagents and standard solutions are very convenient and may  be
used when it  is demonstrated that they meet the method  requirements. All prepared
reagents must be checked for accuracy.

The individual methods specify  the reagents  that require frequent standardization, or other
special treatment, and the  analyst must follow through with these essential operations. To
avoid waste, the analyst should prepare a limited volume of such reagents, depending on the
quantity required over a given period of time. Examples and brief discussions of the kind of
problems that  occur are given in section 5.3.

As  far  as possible, distilled water used for  preparation of reagent solutions must be free of
measurable amounts of the constituent to  be determined. Special requirements for distilled
water are given in chapter 3 of this manual and in individual method descriptions.

Compressed gases, such as oxygen and nitrogen, used for total organic carbon determination
may be of commercial grade.

5.2.2 Metals Analyses

All standards  used  for  atomic  absorption and emission  spectroscopy  should  be  of
spectroquality. It is recommended that other reagents and solvents also be of spectroquality,
although AR grade  is sometimes satisfactory. Standards may be prepared by the analyst in
the laboratory, or  spectrographically standardized materials may be purchased commer-
cially.  Standards  required  for determination of metals  in water are not  generally available
from the National Bureau of Standards.

Analytical-reagent-grade  nitric  and   hydrochloric  acids  must  be specially prepared by
distillation in borosilicate glass and diluted with deionized distilled water. All other reagents
and standards are also prepared in deionized water.

In general, fuel and oxidant gases used for atomic absorption can be of commercial grade.
Air supplied by an ordinary laboratory compressor is quite satisfactory, if adequate pressure
is maintained  and necessary precautions are taken to filter oil, water,  and possible trace
metals  from the line. For certain determinations such as aluminum, AR-grade nitrous oxide
is required.
                                          5-2

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5.2.3 Radiological Analyses

The great  sensitivity of radioactive counting instruments requires that scintillation-grade
reagents and solvents, or equivalent, be used for all radioactivity determinations. Some of
the reagents,  for example, strontium carbonate and yttrium oxide  carriers used for the
determination of strontium-90 and yttrium-90, must be stable, that is, free of radioactivity.
Barium sulfate, used for coprecipitation of radium, must be free from all traces of radium.
These reagents and solvents are commercially available from chemical supply houses.

Calibrated  standard sources of specific radioactive materials with known count and date of
counting are available from various suppliers. No single company supplies all standards.

Gases used for radioactive counting must be of high purity and  extra dry. Gases such as
helium  and air are aged for about 30 days to allow radioactive background to decay. All
gases are checked for background before use. Some cylinders contain  inherent radioactivity
that is  imparted  to the gas. When this background is above normal, the gas should not be
used for radioactivity determinations.

5.2.4 Organic Chemical Analyses

The minimum purity  of reagents that  can be used  for organic analyses  is AR  grade.
Reference-grade standards should be used whenever available. Special note should be taken
of  the assay  of standard  materials.  Owing  to  the great sensitivity  (nanogram  and
subnanogram  quantities)  of gas chromatography (GC), which is often used to quantitate
organic results, much greater purity is frequently required (6). The specificity of some GC
detectors requires that reagents and solvents be free of certain  classes of compounds. For
example,  analyses  by  electron  capture  require  that  reagents and  solvents  be free of
electronegative materials that would interfere with the determination of specific compounds
in the sample. Similarly, use of the flame photometric  detector requires that reagents and
solvents be free  from sulfur  and  phosphorus  interference.  Pesticide-quality solvents,
available from several sources, are required when doing low-level  work. AR-grade solvents
are permissible when analyzing industrial waste samples.

However, the  contents  of each container must be checked to assure  its suitability for the
analyses. Similarly,  all analytical reagents and  other  chemicals  must  also be checked
routinely.

The quality of gases required for GC determinations  varies somewhat with the type of
detector. In general, the compressed gases are a prepurified dry grade.  Grade A helium from
the U.S. Bureau of Mines has always been satisfactory. The Dohrmann nitrogen detection
system requires the use of ultrapure hydrogen for satisfactory results. Argon-methane used
for electron-capture work should  be  oxygen free and should have an  oxygen trap  in the
supply line. The  use  of molecular-sieve, carrier-gas filters  and drying tubes is required on
combustion gases and is recommended for use on all other gases. It is recommended that the
analyst familiarize himself with an article by Burke (7) on practical aspects of GC.

All reagents, solvents, and adsorbents used for thin-layer chromatography must be checked
to be certain that  there are no  impurities present  that will react with the chromogenic
reagent  or  otherwise  interfere with subsequent qualitative or quantitative determinations.
Glass-backed  layers  prepared in  the laboratory  or  precoated  layers  supplied  by  a
manufacturer  may  be used; however,  precoated  layers  are more  difficult to scrape. It is
                                         5-3

-------
recommended, therefore, that layers prepared in the laboratory be used when zones are to
be scraped to recover isolated compounds. Plastic-backed layers are generally unsatisfactory
for this type of analysis.

Adsorbents most commonly used for column chromatographic cleanup of sample extracts
are Florisil,* silica gel, and alumina. These must be preactivated according to the method
specifications and checked for interfering constituents.

5.3 Elimination of Determinate Errors

To produce high-quality analytical  data, determinate errors must be eliminated or at least
minimized. For purposes of this discussion, we assume that a competent analyst and reliable
equipment in  optimum  operating condition are available. Thus,  determinate errors that
might result from an inexperienced  or careless analyst and poor equipment are eliminated.
The remaining sources of error are the reagents, solvents, and gases that are used throughout
the analyses. The quality of these materials, even though they are AR grade or better, may
vary from one source to another, from one lot  to another, and even within the same lot.
Therefore,  the analyst must predetermine that all of these materials are free of interfering
substances  under the conditions of the analyses. To do this he must have a regular check
program. Materials that do not meet requirements are replaced or purified so that they can
be used.

5.3.1 Reagent Blank

The first step the analyst must take is to determine the background or blank of each of the
reagents and solvents used in a given method of analysis. The conditions for determining the
blank must be identical to those  used throughout the analysis,  including the detection
system. If the  reagents  and  solvents contain substances that interfere with a  particular
analysis,  they should be treated so  that they  can be used, or satisfactory reagents and
solvents must be found.

5.3.2 Method Blank

After determining the individual reagent or solvent blanks, the analyst  must determine the
method blank to see if the cumulative blank interferes with the analyses. The method blank
is  determined by following the procedure step  by  step, including all  of the reagents and
solvents,  in the quantity required by the method. If the cumulative blank interferes with the
determination, steps must be taken to eliminate or reduce the interference to a level that
will permit this  combination of solvents and reagents to be used. If the blank cannot be
eliminated, the  magnitude of the  interference  must  be considered when calculating the
concentration of specific  constituents in  the samples  being analyzed.

A method blank should be determined whenever an analysis is made. The number of blanks
to be  run  is determined by the method of analysis  and the  number of samples being
analyzed at a given time. In some methods, such as the AutoAnalyzer procedures, the
method blank is automatically and continuously compensated  for because a continuous
flow of  the reagents passes  through the detector. In other  procedures, such as the  gas
chromatographic determination  of  pesticides, a method blank is  run  with each series of
samples analyzed. Usually this is one blank for every  nine samples.
"Trademark of Floridin Co.
                                         5-4

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5.3.3 Elimination of Interferences and Other Sources of Error

Procedures  for  eliminating  or  at least  minimizing  impurities  that  produce  specific
interferences or high general background vary with the reagent and method involved. These
procedures may include the following: recrystallization, precipitation, distillation, washing
with an appropriate solvent, or a combination of these. Examples of procedures used for
various types of analyses are given below. For complete information, the analyst should
consult the individual methods.

5.3.3.1 General Inorganic Analyses

Analytical-reagent-grade chemicals and solvents usually present no interference problems in
inorganic analyses. However, some reagents do not always meet  methods requirements. An
example  is  potassium  persulfate used in phosphorus and  nitrogen  determinations. This
reagent  is frequently contaminated with ammonia.  Therefore, it is routinely purified by
passing air through a heated water solution of the reagent. The purified potassium persulfate
is recovered by recrystallization.

A problem more commonly encountered in inorganic analyses is the rapid deterioration of
the standard reagents and other ingredients.  To minimize or eliminate this problem, some
reagents, for example, ferrous ammonium sulfate, must be standardized daily. Others, such
as  sodium thiosulfate used for dissolved oxygen determination, may require a substitute
reagent  such as phenylarsine oxide.  Solid phenol, which readily oxidizes and acquires a
reddish color, can be purified by distillation. Starch  indicator used for idiometric titrations
may be prepared for each use or preserved by refrigeration or by addition of zinc chloride or
other suitable compounds.

5.3.3.2 Metals Analyses

In general, spectrograde chemicals, solvents, and gases present no interference problems in
atomic absorption or emission  spectrographic determinations. However,  standards that do
not meet the requirements of the  method are sometimes obtained.  Ordinarily, no effort  is
made to purify them. They are simply replaced by new reagents of sufficient purity. Some
reagents  may form  precipitates on  standing. Such  reagents will reduce the accuracy of
quantitative analyses and should not be used.

5.3.3.3  Radiological Analyses

In general, reagents that do not meet the purity requirements  for radiological determina-
tions  are  replaced  with  reagents  that are satisfactory.  However,  in some instances (for
example, barium sulfate used for coprecipitation of radium) it may be necessary to perform
repeated recrystallization to remove all forms of radium, and reduce the background count
to a usable level. In some instances, solvents that do not meet requirements may be distilled
to produce adequate purity. In some  cases, gases having background counts may be usable
after  aging  as  described earlier.  If  not,  they should  be  replaced with gases  that are
satisfactory.

5.3.3.4 Organic Analyses

Many AR-grade chemicals and solvents, and at times pesticide-quality solvents, do not meet
the specifications required for the determination of specific organic compounds. Impurities
                                         5-5

-------
that are considered trace, or insignificant, for many analytical uses are often present  in
greater  quantities  than the  organic  constituents being  measured.  Coupled with the
several-hundred-fold concentration of  the  sample extract  that is  usually required, such
impurities can  cause very significant interferences in trace organic analyses.  Reagents and
solvents found  to be unsatisfactory, under the conditions of the analyses, must be replaced
or cleaned up so that they are usable.  Some useful cleanup procedures are—

    a.  Washing the inorganic reagents with each solvent that the reagent contacts during
       the analysis

    b.  Washing the adsorbents, such as silica gel G and Florisil, with the solvents that are
       used for a specified column or thin-layer chromatographic procedure, or reactivating
       the Florisil by firing to 630°C

    c.  Preextracting distilled water with solvents used for the particular analysis involved

    d.  Preextracting aqueous reagent solutions with the solvents involved

    e.  Redistilling solvents in all-glass systems using an efficient fractionating column

    f.  Recrystallizing reagents  and dyes used in colorimetric or thin-layer determinations

If the reagents and solvents  thus produced  are not  of sufficient  purity, they should  be
replaced.

Dirty gases (quality less than specified) are particularly troublesome in  gas chromatographic
analyses. They  may reduce the sensitivity of the detector, and produce a  high or  noisy
baseline. If this occurs, the cylinder should be replaced immediately. Similarly, if cylinders
of compressed  gases are completely emptied in use, the end volumes of  the gas may produce
a similar and often more severe effect. Oils and  water may get into the system and foul the
detector. When this occurs the system must be dismantled and cleaned.  Overhaul of the
detector may  be required. To  reduce chances of this, it is  recommended that all gas
cylinders be replaced when the pressure falls to 100 to 200 psi. Filter driers are of little help
in coping with this type of contamination.

5.3.4 Storing and Maintaining Quality of Reagents and Solvents

Having performed the tasks of selecting, preparing, and verifying the suitability of reagents,
solvents, and gases, the analyst  must properly store  them to  prevent contamination and
deterioration prior to  their use. Borosilicate glass bottles with ground-glass stoppers are
recommended  for  most  standard  solutions and solvents.  Plastic  containers  such  as
polyethylene are recommended  for alkaline solutions. Plastic containers must not be used
for reagents  or solvents intended for organic analyses. However, plastic containers may  be
used for reagents not involved with organic analyses if they maintain a constant volume, and
if it is demonstrated that they do not produce interferences and do not absorb constituents
of interest. It is important that all containers be properly cleaned and stored prior to use.
(Refer to ch. 4 for details.)

Standard reagents  and solvents must  always be stored according  to the manufacturer's
directions. Reagents  or solvents that  are sensitive to the light should be stored in dark
bottles and in  a cool,  dark place. It is particularly important to store materials used for
                                          5-6

-------
radiological determinations in dark bottles, because photoluminescence will produce high
background  if light-sensitive  detectors  are  used for counting. Some  reagents require
refrigeration.

Adsorbents for thin-layer and column chromatography are stored in the containers that they
are supplied in,  or according to the requirements of individual methods. When new stock
solutions are necessary, dilutions  of the old and new standard should be compared to
determine their accuracy.

The analyst  should  pay  particular  attention to the stability of the standard reagents.
Standards should not be  kept longer than recommended by the manufacturer  or in the
method.  Some standards are susceptible to changes in normality because of absorption of
gases  or water  vapor  from  the air. Provisions for minimizing this effect are given in
reference 4.

The concentration of the standards will change as a result of evaporation of solvent. This is
especially true of standards prepared in volatile organic solvents. Therefore,  the reagent
bottles should be kept stoppered, except when actually in use. The chemical composition of
certain standards may  change on standing. Certain pesticides,  for instance, will degrade if
prepared in acetone that contains small quantities of water. Thus, it is essential that working
standards be frequently checked to determine changes in concentration or composition.
Stock solutions should be checked before preparing new working standards from them.

5.4 References

1.  Catalog of Standard Reference  Materials, NBS Special Publication 260, National Bureau
    of Standards  (June 1975).
2.  "Reagent  Chemicals," American Chemical Society Specifications, 5th Edition, American
    Chemical Society, Washington, D.C. (1974).
3.  Manual on Industrial  Water  and Industrial Waste Water, 2nd  Edition, ASTM  Special
    Publication 148-H, American  Society for Testing and Materials (1965), p.  869.
4.  "Standard Methods for Preparation, Standardization, and Storage of Standard Solutions
    for Chemical Analysis," from  Part 31 of 1976 Book of ASTM Standards, American
    Society for Testing and Materials, Philadelphia (1977).
5.  Standard  Methods  for  the  Examination of  Water  and  Wastewater,  13th Edition,
    American Public Health Association, New York (1971).
6.  Methods for Organic Pesticides in Water and Wastewater, U.S. EPA,  Environmental
    Research Center,  Cincinnati (1971).
7.  Burke,  J.,  "Gas Chromatography  for  Pesticide  Residue Analysis;  Some Practical
    Aspects," J. Assoc. Off. Anal. Chem., 48, 1037 (1965).
                                         5-7

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                                      Chapter 6

                  QUALITY CONTROL FOR ANALYTICAL PERFORMANCE
6.1  Introduction
Previous chapters discussed basic elements of quality control (QC) pertaining to laboratory
services, instrumentation, glassware, reagents, solvents, and gases; the reader should refer to
the appropriate sections to determine necessary specifications and requirements for QC.
Assuming that  these basic  variables are under QC, that approved methods are being used,
and that the complete system is initially under QC, valid precision and accuracy data must
initially be developed for each method and analyst. Then, to insure that valid data continue
to be produced, systematic daily checks must show that the test results remain reproducible,
and that the methodology is actually measuring the quantity in each sample. In addition,
QC must begin with sample collection and must  not end until the resulting data have been
reported. QC of analytical performance within the laboratory is thus but one vital link in
the dissemination of valid  data to the public. Understanding and conscientious use  of QC
among  all  field sampling personnel, analytical  personnel,  and management personnel is
imperative. Technical approaches are discussed in  the following sections.

6.2 The  Industrial Approach to QC

In the 1920's,  Dr. Walter A. Shewhart of Bell Telephone Laboratories, Inc.  developed the
theory  of  control charts as a basic method  for evaluating the quality of products from
manufacturing  processes. His book (1) on statistical QC grew out of this original work.
Later, acceptance of his concepts  and related statistical techniques within industry led to
refined, quantitative evaluations of product quality in manufacturing. Dr. Shewhart's work
on production  processes assumed  a uniform  product manufactured  in large numbers and
inspected on a continuous basis through the periodic analysis of samples of « production
units. The  resulting data, Xj, x2, . . .xn,  were  then used to  estimate _precision,  as the
standard deviation S or range .R, and accuracy,  as the arithmetic mean X. These statistics
were calculated as follows:
                    S =
                                    n- 1

                   R = the largest of the Xi - the smallest of the X.
                    _
                    V —
These statistics were evaluated by plotting them on control charts developed from similar
statistics taken while  the  process was under properly  controlled operation. The elements
common to such control  charts are represented in figure 6-1.  They include an expected
value (the central line) and an acceptable range of occurrence (the region between upper and
lower control limits).
                                         6-1

-------
                  CO

                  <
                  u.
                  O
                  UJ
                                     UPPER CONTROL LIMIT
                                       CENTRAL LINE
                                   LOWER CONTROL LIMIT
                                                    I
                                         10          15

                                      SAMPLE NUMBER
20
                         Figure 6-1. Essentials of a control chart.

 There are many reference sources available that discuss in great detail the classic Shewhart
 control charts and related statistics that have since been developed for specific industrial
 applications (2-4). In addition, many authors have discussed applications of a related type of
 control chart called  a cumulative-summation (cusum) chart (2,4). Rather than evaluating
 each sample independently, the cusum chart evaluates the cumulative trend of the statistics
 from a series of samples. Because each successive point is based upon  a cumulative data
 trend, cusum  charts are  often considered more effective than control charts in recognizing
 process changes and, therefore, may minimize losses from production of unacceptable units;
 however, cusum  charts  require the more difficult  calculations,  and  optimally designed
 Shewhart techniques have been found to be almost as effective (2,4), so there is no universal
 agreement on  the choice between them.

 6.3 Applying Control Charts in Environmental Laboratories

 In industrial applications, separate control charts  are recommended for each product, each
 machine, and  each operator. Analogous system variables in an environmental laboratory are
 the  parameter, the  instrument,  and  the  analyst.  However, environmental  laboratories
 routinely have to contend with  a variable that has no industrial  counterpart—the true
 concentration  level  of the  investigated parameter,  which may vary considerably among
 samples.  Unfortunately,  the  statistics that work well for industry are sensitive to the
 variability in true concentration that is common in environmental analysis; e.g.,  the classic X
 and  R statistic values increase substantially as  concentration increases.  This variability in
 true concentration means there are no expected values for randomly selected samples, so
 that the accuracy of testing methodology must be evaluated indirectly through  the recovery
 of standards and spikes. As a result, it  has been difficult for environmental laboratories to
 satisfactorily apply industrial QC techniques.

 There are two possible approaches to the solution of the problem of variation in the true
 concentration  level;  either use  of a  statistic  that is not sensitive to this  variation or
 application of the industrial techniques within restricted concentration ranges. Obviously,
 the former should be preferred because it actually solves the problem and does not require
 the development and maintenance of a series of charts for each parameter.

 6.3.1  Quality Control Charts for Accuracy

 Two replacements for the Shewhart X  control chart have been suggested for evaluating the
recovery of a series of different standards or spikes. One  of these, a cusum chart using the
                                         6-2

-------
square of the difference  between the  observed  and true values, is described in an EPA
Region  VI QC manual (5). The other alternative uses the classic Shewhart technique to
evaluate the percent recovery instead of X. It is recommended that the percent recovery be
calculated as

                                          observed
                                  P= 100	
                                           known


for standards, or

                                    observed - background
                                            spike

for recovery of spikes into natural water backgrounds. An example of the linear relationship
between percent recovery  and the known concentration of standards and spikes is demon-
strated in  the accuracy plots of a recent EPA method study  report on  analysis of mercury
(6). Both  approaches are being used on  a daily basis  by various environmental laboratories.

The  data in table  6-1 were used in the EPA  Region VI  manual (5) to illustrate the
development of a  cusum  chart.  The actual data have been reordered here to  appear in
ascending order of the known values. Note that the  mean and the range of the df2 values
increase with increasing concentration level, and this violates a basic premise for acceptable
control chart statistics. Because the percent recovery data do not show any such trend, it is
the recommended control chart statistic  for controlling accuracy.

From the data in table 6-1, a Shewhart  control chart for percent recovery can be calculated
in the following way:

Average percent recovery
The standard deviation for percent recovery
                                             22
                                        6-3

-------
                             '234,074- (2,310)2/23
                                      22
                         = 9.70

Therefore, the upper control limit becomes the following:

                           UCL = P + 3Sp

                               = 100.4 + 3(9.70)

                               = 129.5

                                Table 6-1
    ANALYSIS1 OF TOTAL PHOSPHATE-PHOSPHORUS STANDARDS, IN mg/1
                              TOTAL PO4-P
Point
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Known
0.34
0.34
0.40
0.49
0.49
0.49
0.50
0.50
0.50
0.52
0.66
0.66
0.67
0.68
0.83
0.98
1.3
1.3
1.6
2.3
2.3
3.3
4.9
Obtained
0.33
0.34
0.40
0.49
0.49
0.63
0.47
0.53
0.56
0.59
0.70
0.60
0.65
0.65
0.80
0.75
1.2
1.3
1.7
2.3
2.4
3.3
4.6
Difference
0.01
0.00
0.00
0.00
0.00
-0.14
0.03
-0.03
-0.06
-0.07
-0.04
0.06
0.02
0.03
0.03
0.23
0.10
0.00
-0.10
0.00
-0.10
0.00
0.30
«>
0.0001
0.0000
0.0000
0.0000
0.0000
0.0196
0.0009
0.0009
0.0036
0.0049
0.0016
0.0036
0.0004
0.0009
0.0009
0.0529
0.0100
0.0000
0.0100
0.0000
0.0100
0.0000
0.0900
Percent
Recovery
Pi
97
100
100
100
100
129
94
106
112
113
106
91
97
96
96
77
92
100
106
100
104
100
94
Pi2
9,409
10,000
10,000
10,000
10,000
16,641
8,836
11,236
12,544
12,769
11,236
8,281
9,409
9,216
9,216
5,929
8,464
10,000
11,236
10,000
10,816
10,000
8,836
      Totals
2,310
234,074
  1 Using a colorimetric method with persulfate digestion.
                                    6-4

-------
and the lower control limit becomes

                                  LCL= 100.4- 29.1

                                       = 71.3


The completed control chart is shown in figure 6-2.

Following normal procedures, the control chart must indicate the conditions under which it
was developed; i.e., laboratory name, parameter, method of analysis, date of preparation,
and any  other information  unique to the initializing data,  such as range of concentration
and identification  of  analyst(s). A control chart is not generally applicable under other
conditions.
To verify the control chart, the initializing data should be checked to be sure that none of
the values exceeds these new control limits. In addition, if its distribution is proper, about
68  percent  of the  initializing  data  should  fall within the interval P ± SP. It has been
suggested that the control chart is not valid if less than 50 percent of the initializing data
falls within this interval.
In applying the control chart, either of the  following two conditions  would indicate an
out-of-control situation:

   a.  Any point beyond the control limits

   b.  Seven successive points on the same side of the value P of the central line

When an out-of-control situation occurs, analyses must be stopped until the problem has
been identified and resolved, after which the frequency should be increased for the next few
percent-recovery QC checks. The problem and its solution  must be documented, and all
analyses since the last in-control point must be repeated or discarded.
               140r-
£ 120

O
O
!r 100
H-

ULl
£  80
LU
Q.
                60
                                                                    UCL
                                                                  .-  P
                                                                    LCL
                                     10        15
                                    SAMPLE NUMBER
                                            20
                                                                  25
              Figure 6-2.  Shewhart control chart for percent recovery data.
                                         6-5

-------
A final note of caution regarding use of a single percent-recovery P control chart over a
broad concentration range is necessary.  As noted earlier for the analysis of mercury, a good
linear relationship of the form

                           X = P (known concentration) + K

where K is a constant, seems appropriate for many parameters. However, to justify  use of a
single  percent-recovery control  chart, K must  be small enough relative to the /"(known
concentration) term that it has little or no practical effect upon the value of X. This will
usually be true for  moderate or high concentration levels, but may not be true at very low
concentration levels.  As a  result,  for some parameters it may be necessary to develop a
separate percent-recovery or Shewhart X chart for each standardized low concentration level
sample.

6.3.2 Quality Control  Charts for Precision

Because the characteristics of the range  statistic change as concentration changes, two
alternatives  to Shewhart's R  chart have been used in environmental laboratories to evaluate
the precision of routine sample analyses.

One alternative is a cusum chart using the sum of the squared difference between duplicate
determinations on randomly selected routine samples (5). Because the range R for duplicate
analyses is equal to the difference between them, the cusum statistic equals  the  sum of
squared ranees^""!/?2. However, if R  changes significantly as concentration level changes,
then R2 is affected even more  and, therefore, is not as good a criterion  for judging  whether
precision of the system is within acceptable limits.

The other alternative uses a chart  similar tq_the R chart, but the chart statistic is either the
percent relative standard deviation (lOOS/AT), the coefficient of variation (CV or S/X), or
the industrial statistic /. For the  duplicate determinations A and B, I equals the absolute
value of their difference divided by their sum, or \A - B\/(A  +B), and can be shown to be
equivalent to the other two statistics:

                                  lOO(CV)=100-=
                                          = ,oo
                                          = 100
                                            200 [A - B\
                                                A+B
(A+B)/2

 1    R
    A+B
                                            2007
 For the sake of computational ease, / seems to be a logical alternative to R.
                                         6-6

-------
The next concern is whether / is independent of changes in concentration level. Based upon
experience with duplicates on routine samples taken during the last 2 years by EPA Region
VII, / appears to decrease substantially as concentration increases. In recognition of this
possible dependency, control charts for / should only be developed  from and applied to
results within a limited concentration range. Note that control charts for R could be applied
under similar limitations.

As an illustration of the  concentration dependency of these precision statistics,  table 6-2
provides estimates of R and / for different concentration ranges of three parameters. These
parameters  were selected because approximately  100 sets of duplicates were available that
were well distributed over a reasonably broad concentration range. The ranges for the sum
of duplicates  A + B used  in table 6-2 were selected because they were convenient and the
data tended to be well distributed among them.  Data judged  to be out of control were
discarded before any calculations were made.

Table  6-2 indicates the concentration dependence of  both the range R and the industrial
statistic / for  these three parameters. Because / is  not independent of  concentration and is

                                     Table 6-2
ESTIMATES  OF THE RANGE (R = \A-B\)  AND THE  INDUSTRIAL STATISTIC
[/= \A-B\I(A+B)]  OF  THREE  DIFFERENT  PARAMETERS FOR VARIOUS CON-
CENTRATION RANGES1
Parameter
BOD, 5-day (mg/1)






Chromium 0/g/l)





Copper (ptg/1)





Range of
A+B
2 to <20
20 to <50
50 to <1 00
100to<300
300 to <600
600 to <2,000
2,000 up
10 to <20
20 to <50
50 to <1 00
100 to <300
300 to <1, 000
1 ,000 up
10to<30
30 to <50
50 to <100
100to<200
200 to <400
400 up
No. of
Sets of
Duplicates
21
30
27
29
17
12
3
32
15
16
15
8
5
16
23
21
26
10
3
*A+B
11.7
35.2
72.2
204.1
394.4
1,041
6,683
12.3
33.4
72.4
170.3
480.3
6,340
22.2
38.2
70.8
131.9
268.0
702.0
2fl
1.04
1.94
3.33
6.52
11.1
12.1
177
0.32
0.57
1.12
3.80
5.25
76.0
0.93
1.35
1.14
2.33
2.81
4.56
27
0.0888
0.0552
0.0462
0.0319
0.0282
0.0116
0.0264
0.0306
0.0170
0.0155
0.0223
0.0109
0.0120
0.0617
0.0368
0.0169
0.0177
0.0105
0.0065
1 From EPA Surveillance and Analysis Laboratory, Region VII.
2 Average values.
                                       6-7

-------
                                  Table 6-3
            SHEWHART UPPER CONTROL LIMITS (UCL) AND CRIT-
            ICAL RANGE Rc VALUES FOR THE DIFFERENCES BE-
            TWEEN DUPLICATE ANALYSES WITHIN SPECIFIC CON-
            CENTRATION RANGES FOR THREE PARAMETERS1
Parameter
BOD, 5-day (mg/1)






Chromium (Mg/1)





Copper (jug/1)





Concentration
Range2
1 to<10
10to<25
25 to <50
50 to <1 50
I50to<300
300 to <1, 000
1,000 up
5to<10
10to<25
25 to <50
50to<150
1 50 to <500
500 up
5 to <1 5
1 5 to <25
25 to <50
50 to <1 00
100to<200
200 up
UCL
3.40
6.34
10.9
21.3
36.3
39.6
579
1.05
1.86
3.66
12.4
17.2
249
3.04
4.41
3.73
7.62
9.19
14.9
Rc
3.5
6
11
21
36
3 40
3579
1
2
4
12
317
3249
3
4
5
8
39
315
             1 From EPA Surveillance and Analysis Laboratory, Region VII.
             2 Equal to half of the range of A + B given in table 6-2.
             3 Based on fewer than 1 5 sets of duplicate analyses.

more difficult to calculate and  develop control charts for, the use of R charts for a series of
sequential concentration ranges for each parameter seems practical. However, because the
primary concern when using any range chart is whether the upper control limit has been
exceeded, an even more practical approach would be to develop a table of these limits for all
concentration levels of each parameter. As an example, table  6-3 contains the calculated
Shewhart upper control limits  for the range R from duplicate  analyses within the various
concentration levels for the three parameters in table 6-2. These limits were calculated, as
usual, from  the Shewhart factor  D4  for ranges based upon  duplicate analyses and the
appropriate average value of the range R given in table 6-2. For example, the UCL for 25 to
50 mg/1 of BOD was calculated as follows:
                               UCL =
                                    = 3.27(3.33)

                                    = 10.9
                                      6-8

-------
Table 6-3 also contains a critical range Rc column. Because the data from EPA Region VII
were almost always whole units with only a very occasional half unit reported, the Rc value
is the UCL value rounded to the nearest whole unit at higher concentration levels and to the
nearest half unit for the lowest concentration level. However, there is an exception to this
rule  among the low-concentration Rc values for copper that demonstrates an advantage
beyond  the simplicity of using such tables. The UCL value for copper at 25 to 50 Mg/1 is
inconsistent with the UCL values  for  adjacent  concentration levels, and the Rc value has
been adjusted to resolve this inconsistency.  Without  the table, such inconsistencies could
very easily go unnoticed.

The examples in table 6-4 illustrate how  to use the Rc values in table 6-3. This technique,
consisting of the development and use of a  table of critical-range Rc values  at  different
concentration levels, is recommended to control precision. Normal control chart procedures
should be followed as in section 6.3.1  regarding identification and verification of the table.
The  table should  be updated periodically as additional, or more current, data become
available,  or  whenever  the basic   analytical system  undergoes  a major change. If  any
difference between duplicate analyses  exceeds  the critical-range value for the appropriate
concentration  level, then  analyses  must be  stopped  until the problem is identified  and
resolved, and the frequency should be increased for the next few precision checks. After
resolution, the problem and its solution must be documented, and all analyses since the last
in-control check must be repeated or discarded.

6.4  Recommended Laboratory Quality Assurance Program

A minimum laboratory  quality assurance program should include control procedures for
each parameter as described in the following sections.

6.4.1 Standard Curves

A new standard curve should be established with each new batch of reagents, using at  least
seven concentration levels.

6.4.2 Quality Control Checks for Each Analytical Run

With each batch of analyses, the following tests should be run:

    a.  One blank on water and reagents

                                       Table 6-4
         CRITICAL  RANGE  VALUES FOR VARYING  CONCENTRATION
                                       LEVELS
Parameter
BOD (mg/1)
Chromium (Mg/1)
Copper (Mg/1)
Duplicates
20 and 24
60 and 75
46 and 51
R
4
15
5
RC
6
12
15
R
-------
   b.  One midpoint standard

   c.  One spike to determine recovery

   d.  One set of duplicate analysis

The results from b through d should be compared with previous in-control data by using the
appropriate technique recommended in section 6.3.

6.4.3 Intel-laboratory QC

An interlaboratory QC program would require each laboratory to do the following:

   a.  Analyze  reference-type samples  to provide independent checks on the analytical
       system. These may  be available from EPA as QC samples, from the National Bureau
       of Standards  as  standard reference  materials, or from commercial  sources.  If
       performance limits are not provided, the results should fall within the routine limits
       of each laboratory for a standard  at a level comparable to the specified true value.

   b.  Participate  in  performance evaluation and  method  studies as available from  EPA,
       from the American Society for Testing and Materials, and from other agencies.

6.5 Outline of a Comprehensive Quality Assurance Program

In the following discussion the symbols used represent the results of analysis according to
the scheme:

        A j = first replicate of sample A

        AI = second replicate of sample A

          B = sample taken simultaneously with sample A

       B$ F = field spike  into sample B

       BSL - laboratory spike into sample B

        DF = field spike into distilled water

        DL = laboratory spike into distilled water
          T = true value for all spikes

The  laboratory spikes BSL and DL  are the only analyses  that may not be necessary. All
other analyses must be done simultaneously.

6.5.1 Steps for the Field Personnel

A comprehensive  quality assurance program would include  the following steps  for  each
parameter in the monitoring study:

   a.  Take  independent  simultaneous  samples  A  and B at  the same sampling point.
       Depending  on the parameter,  this might involve side-by-side  grab  samples  or
       composite samplers  mounted in parallel.
                                        6-10

-------
    b.   Split sample A into the equal-volume samples A t and A 2.

    c.   Split sample B into equal volumes and add a spike T to one  of them; the latter
        sample becomes  sample  5SF.  As  with all  spikes,  the addition of  T  should
        approximately double the anticipated concentration level.

    d.   Add the same spike T to a distilled water sample furnished by the laboratory and
        designate this sample as DF.

These QC samples must be treated in the same way as routine samples; i.e., the volume, type
of container, preservation, labeling, and transportation must be the same for all.


6.5.2 Steps for the Laboratory

The laboratory personnel should perform the following steps for quality  assurance:

    a.   Analyze the blank and midpoint standard recommended in section 6.4. If results are
        unsatisfactory, resolve  problems before continuing.

    b.   Analyze sample DF. If the percent  recovery of T is unsatisfactory (see section
        6.3.1), create a similarly spiked, distilled-water sample DL and analyze to test for a
        systematic error in the laboratory or fundamental problems with the spike.  If the
        percent recovery of T from DL is satisfactory, any systematic error occurred before
        the samples reached the laboratory.

    c.   Analyze samples B and Bs F. If B is below the detection limit, or if B is greater than
        1071 or less than 0.1 T, disregard the remainder of this step and proceed to step d. If
        the percent recovery of T from 5SF  is unsatisfactory (see section 6.3.1), spike an
        aliquot of  sample B the same way in the laboratory so that a similar recovery can be
        anticipated. Analyze this sample 5SL to test for immediate sample interferences or a
        bad  background result B. If the percent recovery from Bs L is satisfactory, then the
        interference must require a longer delay before analysis, or other special conditions
        not present in the laboratory, in order to have a noticeable effect upon recovery of
        the spike.

    d.   Analyze A^  and A2.  If the absolute (unsigned)  difference between these  results
        exceeds the critical value (see section 6.3.2), then precision is out of control.

    e.   Calculate the absolute difference between A^  and  B. If it is  unsatisfactory (see
        section 6.3.2), the field sampling procedure did not provide representative samples.

If initial results at each of the laboratory steps were satisfactory, then the validity of the
related  data has been indisputably established. If results at any step are unsatisfactory,
resolution depends upon the problem identified. Laboratory problems may just require that
the analyses be repeated, but field problems will usually require new samples. Figure 6-3 is
intended to clarify the interdependence of the  preceding laboratory steps b through e.

In figure 6-3 it must be noted that there is no  way to identify additive sample interferences;
i.e., those that have an equal effect upon the background-plus-spike results (5SF or 5SL)
and the background result B. Recovery  of a spike will not show such interferences.
                                         6-11

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Problems causing systematic errors that may occur in the field include the following:

    a.  Contaminated preservative, distilled water, or containers

    b.  Contamination by sampling personnel

    c.  Deterioration through excessive holding  time or use of an ineffectual preservation
       technique

    d.  Use of a bad field-spiking procedure

6.6  Related Topics

6.6.1 Advanced Laboratory Automation and Its Effect on QC

Advanced laboratory automation systems under development analyze samples automatically
and use a control computer to interpret the resulting data and produce an analytical report.
The primary  benefits of such a  system are not only that the data-recording and calculation
errors common to manual analyses have been inherently eliminated, but also that extensive
QC can be  accomplished quite easily and cheaply. The  computer can  be programed  to
automatically recognize different kinds of QC samples and to establish or  recall appropriate
control limits. Thus the QC overhead is reduced considerably and QC procedures previously
too costly or complex become practical.

As an example of a QC procedure  that is considered impractical for manual use, regression
could be used to determine the relationship between concentration change and the accuracy
and precision statistics discussed earlier. Using these relationships, very  responsive, single
accuracy and precision charts could be developed for each parameter. As  computer-assisted
analysis becomes  common, automated  laboratories will  very  likely replace  the  manual
procedures  recommended  earlier  in  this  chapter  with  evaluation criteria based  upon
regressions.

6.6.2 Method Comparability (Equivalency)

Requirements for method comparability are under development for proposed alternatives to
the methodology specified in Public  Law 92-500, section 304(g).  A final version of these
requirements should be available from  EPA at a later date.

6.7  References

1. Shewhart, W. A.,  Economic  Control of Quality of Manufactured Product, Van Nostrand
   Reinhold Co., Princeton, N.J. (1931).
2. Duncan, A. J., Quality Control  and Industrial Statistics, 3d Edition, Ch.  18, R. D. Irwin,
   Inc., Homewood, 111. (1965).
3. Grant, E. L.,  and  Leavenworth,  R. S., Statistical  Quality  Control, 4th  Edition,
   McGraw-Hill Book Co., Inc.,  New York (1972).
4. Davies, O. L.,  and Goldsmith, P. L., Statistical Methods in Research and  Production, 4th
   Edition, Hafner Publishing Co., New York (1972).
5. Laboratory Quality Control  Manual, 2d Edition, U.S. EPA, Region VI, Surveillance and
   Analysis Division, Ada, Okla. (1972).
                                        6-13

-------
6.  Winter, J., Britton, P., Clements,  H., and Kroner, R., "Total Mercury in Water," EPA
   Method Study 8, pp. 35-36, U.S. EPA, Office of Research and Development, EMSL, Cin-
   cinnati (Feb. 1977).
                                      6-14

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                                       Chapter 7

                           DATA HANDLING AND REPORTING
7.1  Introduction
To  obtain  meaningful  data  on  water  quality,  the  sample  collector  must  obtain a
representative sample and then deliver it unchanged for analysis. The analyst must perform
the proper analysis in the prescribed fashion, complete calculations, and convert results to
final form for permanent recording of the analytical data in meaningfu.1, exact terms. These
results are transferred to a storage facility for future interpretation and use.

The following sections discuss processing of actual values, recording and reporting of data in
the proper way, some means of quality control of data, and the storage and retrieval of data.

7.2  The Analytical Value

7.2.1 Significant Figures

The term "significant figure"  is used, sometimes rather loosely, to describe a judgment of
the reportable digits in a result.  When the judgment is not soundly based, meaningful digits
are lost or meaningless digits  are  reported. On the other hand, proper use of significant
figures gives an indication of the  reliability of the analytical method used.

The following discussion describes the process of retention of significant figures.

A number is an expression of quantity. A figure or digit is any of the characters 0, 1,2, 3, 4,
5, 6, 7, 8, 9, which, alone or in combination, serve to express a number. A significant figure
is a digit that denotes the amount of the quantity in the particular decimal place in which it
stands. Reported analytical values should contain only significant figures. A value is made
up  of  significant figures  when it contains all digits known to be true and one last digit in
doubt. For example, if a value is reported as 18.8 mg/1, the 18 must be firm while the 0.8 is
somewhat uncertain, but  presumably better than one of the values 0.7 or 0.9 would be.

The number zero may or may not be a significant figure depending  on the situation.

Final  zeros after a decimal point are always meant to be significant figures. For example, to
the nearest milligram, 9.8 g is reported as 9.800 g.

Zeros before a decimal point with nonzero digits preceding them are significant. With no
preceding nonzero digit, a zero before the decimal point is not significant.

If there are no nonzero digits  preceding a decimal point, the zeros after the  decimal point
but preceding other nonzero digits are not significant. These zeros only indicate the position
of the decimal point.

Final   zeros  in  a  whole  number may  or may not  be significant.  In a  conductivity
measurement of 1,000 /zmho/cm, there is no implication by convention that the conductiv-
ity is 1,000 ± 1 jumho. Rather, the zeros only indicate the magnitude of the number.
                                       7-1

-------
A good measure of the significance of one or more zeros interspersed in a number is to
determine whether the zeros can be dropped by expressing the number in exponential form.
If they can, the zeros may not be significant. For example, no zeros can be dropped when
expressing a weight of 100.08  g in exponential form; therefore the  zeros are significant.
However, a weight of 0.0008 g can be expressed in exponential form as 8  X 10~4 g, so the
zeros are not significant. Significant figures reflect the limits in accuracy of the  particular
method of analysis. It must be decided whether the number of significant digits obtained for
resulting values is sufficient for interpretation  purposes. If not, there is little that  can be
done within the limits of the given laboratory operations to improve these values. If more
significant  figures are needed, a further improvement  in method  or selection of another
method will be required.

Once the number of significant figures obtainable from a type of analysis is  established, data
resulting from such analyses are reduced according to set rules for rounding  off.

7.2.2  Rounding Off Numbers

Rounding off of numbers is a necessary operation in all analytical areas. It is automatically
applied by  the limits of measurement of every instrument and all glassware. However, when
it is  applied in chemical calculations incorrectly or prematurely, it can adversely affect the
final results. Rounding off should be applied only as described in the following sections.

7.2.2.1 Rounding-Off Rules

If the figure following those to be retained is less than 5, the figure is dropped, and the
retained figures are .kept unchanged. As an example,  11.443 is rounded off to 11.44.

If the figure following those  to be retained is greater than  5, the figure is dropped, and the
last retained figure is raised by 1. As an example, 11.446 is rounded off to 11.45.

If the figure following those  to be retained is 5, and if there are no figures other  than zeros
beyond the five,  the figure 5 is dropped, and the last-place figure retained is increased by
one  if it is an odd number or it is kept unchanged if an even number. As an  example,  11.435
is rounded off to 11.44, while 11.425 is rounded off to  11.42.

7.2.2.2 Rounding Off Arithmetic Operations

When a series of numbers is added, the sum should be rounded off to the same number of
decimal places as  the addend with the smallest number of places. However, the operation is
completed  with all  decimal places intact,  and rounding off is  done afterward.  As  an
example,
The sum must be rounded off to 33.4.
                                         7-2

-------
When one number is subtracted from another, rounding off should be completed after the
subtraction operation, to avoid possible invalidation of the operation.

When two numbers  are to be multiplied, all digits are carried through the operation, then
the product is rounded off to the number of significant digits of the multiplier with the
fewer significant digits.

When two numbers are to be divided, the division is carried out on the two numbers using
all digits.  Then the quotient is  rounded off to the number of significant digits of the divisor
or dividend, whichever has the fewer.

When a number contains n significant digits, its root can be relied on for n digits, but its
power can rarely be relied on for n digits.

7.2.2.3 Rounding Off the  Results of a Series of Arithmetic Operations

The preceding rules  for rounding off are reasonable for  most calculations; however, when
dealing  with two nearly equal  numbers, there is a danger of loss of all  significance when
applied  to a series of computations that rely on a  relatively small  difference in two values.
Examples are calculation of variance and standard deviation. The recommended procedure is
to carry several extra figures through the calculations and then to round off the final answer
to the proper number of significant figures.

7.3 Glossary of Statistical  Terms

To clarify the meanings of statistical reports  and evaluations of water quality data, the
following statistical terms are introduced. They are derived in part from  usage (1,2) of the
American Society for Quality Control.

Accuracy— The difference between an average  value and the true value  when the latter is
known or assumed.

Arithmetic mean— The arithmetic mean  (or average) of a set of n  values is the sum of the
values divided by n :
                                     y — _,_-- ___________
                                            n

Bias— A systematic error due to the experimental method that causes the measured values to
deviate from the true value.


Confidence limit, 95 percent— The limits of the range of analytical values within which a
single analysis will be included 95 percent of the time,


                              95 percent CL = X ± 1 .965

where CL is the confidence level and S is the estimate of the standard deviation.
                                         7-3

-------
Constant—A nonvarying qualitative or quantitative characteristic of the population.

Geometric mean—A  measure of  central tendency  for data  from a  positively  skewed
distribution (log normal),
                              _           -
                              Xa = antilog	
                               g             n
Interference-A biological or chemical attribute of a test sample that positively or negatively
offsets the measured  result  from the true value. If interference that is not segregated and
identified is present, it enlarges or reduces the method bias.

Median—Middle value of all data ranked in ascending order.  If there are two middle values,
the median is the mean of these values.

n—The number of values Xt reported for a sample.

N—The total number of values X{ of the entire population or universal set of data.

Population—The total set of units, items, or measurements under consideration.

Precision-Relative to the data from a single test procedure, the degree of mutual agreement
among individual measurements made under prescribed conditions.

Precision  data—Factors that relate to the variations among the test results themselves; i.e.,
the  scatter or dispersion  of a series  of  test  results, without  assumption  of any prior
information.

Range—The difference between the highest and lowest values  reported for a sample.

Relative deviation (coefficient of variation)—The ratio of the standard deviation S of a set of
numbers to their mean X expressed as percent. It relates standard deviation (or precision) of
a set of data to the size of the numbers:
                                                     £
                             CV = RD (percent) =100—
                                                     X

Relative error—The mean error of a series of measured data values as a percentage of the
true value Xt,

                                                \X- X\
                             RE (percent) = 100	
                                                 %t

Sample-Groups of units  or portions of material, taken from a larger collection of units or
quantity of material, that provide information to be used for judging the quality of the total
collection or entire material as a basis for action on them or on their production processes.
                                        7-4

-------
Series—A number of test results with common properties that identify them uniquely.

Skewness—A measure of the asymmetry of a frequency distribution,

                                        (Xt ~ X)3
                                    K =
                                           no*
This measure is a pure signed number. If the data are perfectly symmetrical, the skewness is
zero.  If K is negative, the long tail of the distribution is to the left. If K is positive, the long
tail extends to the right.


Standard deviation—The square root of the variance of the universe,
                            a =
                                                    \ 2
                                                  •(,  /N
Standard deviation estimate-The most widely used measure to describe the dispersion of a
set of data.  Normally X ± S will include 68 percent, and X ± 2S will  include about 95
percent of the data from a study:
                            S =
                                            n- 1
Standard deviation, single analyst—A measure  of dispersion for data from a single analyst
that is calculated here using an equation developed by Youden for his nonreplicate study
design (3),
where D = the difference in paired values obtained from a single analyst.

Universe—The total set of items or measurements.

Variable—An experimentally determined estimate denoted X for a particular quality or trait
of the population.

7.4 Report Forms

The analytical information reported should include the  measured parameters; the details of
the analysis  such as burette readings, absorbance, wavelength, normalities  of reagents,
correction factors, blanks;  and the reported data values.
                                         7-5

-------
To  reduce errors in manipulation of numbers a  general rule is to reduce handling and
transposition of data to an absolute minimum. Ideally, a report form includes preliminary
information about  the  sample and its analysis,  and the same form is used  for the final
entering of data into a computer; however, such report forms are not yet common. Rather,
a variety of methods is used to record data.

7.4.1 Loose Sheets

Reporting of data onto  loose or ring-binder forms is a means of recording data that allows
easy addition of new sheets, removal of older data, or collection of specific data segments.
However,  the easy  facility for addition or removal also permits loss  or  misplacement of
sheets, mixups in date sequence, and ultimately questionable status of the data for formal
display or presentation as courtroom evidence.

7.4.2 Bound Books

The use  of bound  books is an improvement  in data recording that  tends to result  in a
chronological sequence of data insertion. Modification beyond a simple lined book improves
its effectiveness  with little additional effort. Numbering of pages encourages use of data in
sequence and also aids in referencing data through  a table of contents ordered according to
time, type of analysis, kind of sample, and identity of analyst.

Validation can be easily  accomplished by requiring the analyst to date and sign  each analysis
on  the day  completed.  This validation can be  strengthened further by providing space for
the laboratory supervisor to witness the date and the completion of the analyses.

A  further development of the bound  notebook  is the commercially  available  version
designed   for research-type work.  These notebooks  are preprinted with  book and page
numbers,  and  spaces  for title of project, project number,  analyst signature,  witness
signature,  and  dates. Each report sheet has a  detachable duplicate sheet that  allows
up-to-date review by management without disruption of the notebook in the laboratory.
The cost  of research-type bound  notebooks  is  about  four times that of ordinary note-
books.*

Use of bound  notebooks has been limited to research and development work where an
analysis is part of a relatively long-term project, and where the  recording in the notebook is
the prime  disposition of the data until an intermediate or final report is written.

However,  bound notebooks can and should be used  in routine analytical laboratories such as
those concerned with water quality. The need for repeated information on sampling and
analyses can be answered by use of preprinted pages in the bound notebooks.

7.4.3 Preprinted Report Forms

Most field laboratories and installations repetitively  analyzing fixed parameters  develop their
own system of compiling laboratory  data that  may include bound  notebooks, but a means
of forwarding data  is also required. Usually, laboratories design forms to fit a  related group
*Scientific Notebook Co., 719 Wisconsin Ave., Oak Park, 111. 60304.
                                        7-6

-------
of analyses or to  report  a single  type of analysis  for  a series of samples. As  much
information as possible  is  preprinted  to simplify  use of  the  form. With  loose-sheet,
multicopy forms (using carbon  or NCR paper) information can be forwarded on the desired
schedule while also allowing retention of data in the  laboratory. Still, the most common
means for  recording data in rough form are internal  bench sheets or bound books. The
bench sheet or book never leaves the laboratory but serves as the  source of information for
transfer of data to appropriate report forms. (See fig. 7-1.)

In most instances the supervisor and analyst wish to look at the data from a sampling point
or station in relation to other sampling points or stations on a particular river or lake. This
review of data by the supervisor prior to release is a very important part of the QC program
of the laboratory; however, such reviews are not easily accomplished with bench sheets. For
review purposes, a summary sheet can be prepared that displays a related group of analyses
from  a number of stations such as shown in figure 7-2. Because the form contains space for
all of the information necessary for reporting data, the completed form can also be, used to
complete the data forms forwarded to the computer storage and retrieval system.

The forms  used to report data to storage systems provide spaces for identification of the
sampling point, the  parameter  code,   the  type  of  analysis  used,  and  the reporting
terminology. Failure to provide the correct information can result in rejection of the data,
or insertion of the data into incorrect parameter fields. As  sample analyses are  completed,
the data values are usually reported in floating decimal form along with the code numbers
for identifying the parameter  data  fields and the sampling point data  fields.  Figure 7-3
shows an example of a preprinted report form used for forwarding data to  keypunch.

7.4.4  Plastic-Coated Labels and Forms

A recent addition to  good sample  handling  and data management is the availability of
plastic-coated  (blank or preprinted)  labels, report forms,  and bound report books.  These
materials are waterproof, do not disintegrate when wet or handled, can be written on while
wet, and retain pencil or waterproof ink markings though handled when wet.

7.4.5  Digital Readout

Instrumental analyses, including automated, wet-chemistry  instruments such as the Tech-
nicon AutoAnalyzer, the atomic absorption spectrophotometer, the  pH meter, and the
selective electrode meter, provide digital readout of concentrations, which can be recorded
directly onto report sheets without further calculation. Programmed calculators can be used
to construct  best-fit curves,  to perform regression  analyses, and  to perform  series of
calculations leading to final reported values.

7.4.6  Keypunch Cards and Paper Tape

Because  much of the analytical data generated  in laboratories is first recorded on  bench
sheets,  then  transferred to  data report  forms,  keypunched,  and manipulated  on small
terminal computers (or manipulated and stored  in a larger data storage system), there is a
danger of transfer error that increases with each data copy. The analyst can reduce this error
by recording  data directly from bench sheets onto punch cards that can be retained or
forwarded immediately to the data storage system. Small hand-operated keypunch machines
are available.
                                         7-7

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LABORATORY BENCH DATA
*— y. rr
DATE OP COMPOSITE SAMPLE

LL

M 1 1 1 1 1 1 II


1 1


i i
Fecal Cohform llkll^

MF/100
1 1 1 1 1 M 1 1 1 1 1 1 1


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1 II II 1 1 1 II

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mg/1
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1 1 M 1 1 1 1 1 1 MM


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1 I 1 1 1 0 0 0 0 0
1 II 1 II 1 1 II
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ITEM _
I I
P, Total
I 1 1 I 1 0 0 0 0 0
mg/1

M II 1 1 II 1 	


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1 1
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P, Soluble
1 1 1 1 1 0 0 0 0 0
II 1 1 1 1 1 1 II

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II 1 II 1 1 1 II
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1 M 1 II 1 1 II
6S43210133
Cyanide
till 100000
II 1 1 1 II 1 II
6543210123
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COMPUTER CODED DATA
II 1 1 1 M M M 1
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13-18
N'N'M 1 1 1 1 1 IIJI 1
19-23 24-27 28 29 30

MM M- 1 1 1 1 Ml II 1
31-35 36-39 40 41 42

l°|0|6|3|5 Ml 	 ||
43-47 48-51 52 53 54

|0|0|6|1|0| | (I 1 Mi II 1
55-59 60-63 64 65 66
COLUMN 80 (BLANK)
CHG
|0|0|6|3|0 | || 1 1 II II II 1
67-71 72-75 76 77 78 79
NEXT CARD. REPEAT COLUMNS 1 80 ABOVE
|0|0|6J6|5| | || | Ml || |
19-23 24-27 28 29 30

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31-35 36-39 40 41 42

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43-47 48-51 52 53 54

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55-59 60-63 64 65 66
COLUMN 80 (BLANK)
CMS.
|OJO|7|2|0|| I I I I 1 II II II 1
67-71 72-75 76 77 78 79
                     Figure 7-3. Example of STORET report form.
7.4.7 STORET-Computerized Storage and Retrieval of Water Quality Data

Because of their ability to record, store, retrieve, and manipulate huge amounts of data, the
use of computers is a natural outgrowth of demands for meaningful interpretation of the
great masses of data generated in almost all technical activities.

In August  1961, numerous ideas were brought together concerning the basic design of a
system  called STORET  for  storage  and retrieval of  water pollution  control' data. A
                                        7-10

-------
refinement of this system is now operated by the Technical Data and Information Branch,
Division of Applied Technology, Office of Water Programs, EPA.

This is a  State/Federal cooperative activity that  provides State  water pollution control
agencies with direct, rapid access into a central computer system for the storage, retrieval,
and analysis of water quality-control information.

If properly stored, the data can be retrieved according to such descriptors as the point of
sampling, the date, and the specific parameters stored, or all data at a sample point or series
of points can be extracted as a unit.

Full details on use  of the  STORET system are  given  in the  recently revised  STORET
handbook (4).

7.4.8 Automated Laboratory Systems

The use of digital  readout, keypunch cards,  and paper tape have  been overshadowed by the
development of customized, fully automated online computer systems that make measure-
ments, calculate results, perform quality control, and report analytical data simultaneously
from a full range  of laboratory instruments.  (See fig. 7-4.) Such  systems can contain the
following functions:

    a.  Manual or automatic  sampling and  testing  of  a  series  of  samples,  standards,
       replicates, and check samples

    b.  Detection of the measurement signals from the series of samples

    c.  Conversion of signals  to concentrations, generation of  a standard curve, and
       calculation of sample values in final units

    d.  Calculation of the deviation and recovery  values  of the results and indication  of
       acceptance or nonacceptance based on limits established by the analyst

    e.  Provision of  the output in a form designated by the analyst: dial, paper recording
       chart, digital readout, cathode ray tube, or printed report form

The degree of hands-on operation required in the system is specified by the analyst.

If an automated system is properly  designed and operated, most calculation and transposi-
tion errors are avoided and the proper level  of quality control is automatically exerted.
Laboratory automation systems for water analyses are being developed and coordinated by
EMSL-Cincinnati for use in a number of EPA laboratories (5).

7.5 References

1. "Guide for Measure of Precision and Accuracy," Anal. Chem. 33, 480 (1961).
2. "Glossary of General Terms Used in Quality Control," Quality Progress, Standard Group
   of the Standards Committee, American Society for Quality Control, 11(1), 21-2 (1969).
3. Youden, W. J., Statistical Techniques for Collaborative Tests, Association of Official
   Analytical Chemists, Washington, D.C. (1967).
                                        7-11

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           MEASURE TIMING,
           BASELINE, AND
           CALIBRATION STANDARDS
              MEASURE SAMPLES,
              CHECK STANDARDS,
              REPLICATES, SPIKES,
              AND BLANKS
            COMPUTE AND DISPLAY
            INTERIM RESULTS AND
            STATISTICS
                                     ALERT
                                     OPERATOR
                                     TO
                                     ACTION
Figure 7-4.  Flow chart of the sequence of events
            during a controlled series of laboratory
            measurements.
                     7-12

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4.  "STORET, EPA's Computerized Water Quality Data Base, the Right Answer," U.S. EPA,
   Office of Water and Hazardous Materials, Washington, D.C. (1977).
5.  Budde, W. L., Almich, B. P., and Teuschler, J. M., The Status of the EPA Laboratory
   Automation Project, EPA-600/4-77-025, U.S. EPA,  Office of Research and Develop-
   ment, EMSL, Cincinnati (1977).
                                      7-13

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                                       Chapter 8

                SPECIAL REQUIREMENTS FOR TRACE ORGANIC ANALYSIS
8.1  Introduction
The high sensitivity of the instrumentation used in trace organic chemical analysis and the
low concentration of organic compounds being investigated dictate that special attention
must be given to this analytical field. Contamination of the sample from any possible source
must  be  diligently guarded  against,  and interferences in the sample must  be carefully
controlled. Strict attention to method and highly refined technique are required to produce
valid quantitative and qualitative results.

Two manuals have been developed by the Environmental Monitoring and Support Labora-
tory (EMSL) in Cincinnati covering the two broad areas of quantitative and qualitative trace
organic analysis. Reference 1 contains both general and specific quality assurance programs
designed to insure  the production of acceptable  measurements when using the methods
contained in that manual.  Reference 2 contains specific, detailed quality assurance programs
covering both the performance of the instrument  and  the  interpretation of  the resulting
spectra.

This chapter is organized with three sections devoted to general material applicable to all
organic analysis,  and one section abstracting highly specialized materials from each of the
two manuals cited.

8.2 Sampling and Sample Handling

Regardless of the intent, all numbers generated by a water quality laboratory are ultimately
represented as the concentration levels in the sample  matrix at the time of collection. Such
numbers tend, automatically, to endorse the  sample collection, preservation, and shipment
procedures. Thus, quality assurance programs limited to the care of the sample beginning
with its receipt by the laboratory are inadequate. The laboratory must share responsibility
for the preservation and shipment  of all samples that  it will accredit with concentration
values.  Two approaches  are  available that   will  generally  protect  the laboratory from
generating numbers that may not reflect actual conditions of the sample at the time of
collection. The best, but usually least practical solution, is for the laboratory  personnel to
collect all samples. The alternative is for the laboratory to adopt a policy of sample rejection
based on minimum standards of sample identification and age.  Guidelines for establishing
these standards are discussed in this  section.  It is recommended that copies of this material
be supplied to all sample collectors along with an understanding of the specific  policy of the
laboratory toward rejecting samples that do not meet these criteria.

In all  of the cases to be discussed, it is the responsibility of the project director  to (a)
coordinate his sampling, preservation, and shipment  with the laboratory, (b) obtain clean
sample  containers from the laboratory, (c)  provide adequate  sample identification  and
compositing instructions,  and  (d)  provide  duplicates  and blanks  as required by  the
laboratory. Additional prearrangements should be made with the  laboratory  if sample
splitting is desired,  to create  separate supernatant and settleable  matter  samples, or if
calculations on a wet-weight basis in addition to the standard dry-weight calculations are
desired.
                                         8-1

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Bottles and caps are to be supplied by the laboratory because rigorous cleaning is required
even for new bottles.  New and recycled bottles should be washed as described in reference
1. Samples received in bottles of unknown origin or questionable cleanliness should be
rejected by the laboratory.  For water samples that are to be analyzed by solvent extraction
methods, narrow-mouthed, screw-cap bottles such as  Boston  rounds are preferred because
they have less tendency to  leak and are easy to handle in the laboratory. One-liter bottles
are generally  more expensive than quart bottles, thus  most laboratories use the clear 32-oz
containers. The bottle should be sealed with Teflon (du Pont) lined caps. For water samples
of intermediate pH, aluminum-foil-lined caps may be used when  Teflon (du Pont) is not
available. Oil  and grease samples can be collected with Polyseal caps-the conical liner pro-
vides  an excellent seal against pressure during shipment and sample extraction. Screw-cap,
widemouthed glass bottles  are  preferred for sediment samples because they are easier to
handle in tlie field and in the laboratory. Precleaned,  16- or 32-oz bottles with Teflon (du
Pont) or foil-lined screw-cap closures should be provided by the laboratory. Masking tape or
other suitable labels should be applied to the dry bottles.

Sampling  for purgeable organics requires special consideration and equipment. The sample
container  should  consist of a 45-ml, screw-cap vial fitted with a Teflon (du Pont) faced, sili-
cone  septum.* The vials, septa, and caps should be washed in hot detergent water and thor-
oughly rinsed with tapwater and  organic-free water, then dried at  105°C for 1 h. The vials
should then be cooled to room temperature in a contaminant-free area. When cool, the vials
should be sealed  with the septa, Teflon (du  Pont) side down, and screw cap and maintained
in this sealed  condition until filled with sample.

The bottles used  for collecting water samples for solvent extraction should not be overfilled
or  prerinsed  with  sample  before  filling  because oil and other material  that can cause
erroneously high  results  may remain in the sample bottle after rinsing. Bottles should be
filled with sample  to about 90  percent of capacity, and the level should be marked to
determine if  leakage occurs.  Because full sample bottles are difficult to pour from  during
extractions,  complete  filling should  be avoided. In  the  collection of sediment samples,
nonrepresentative debris such as large stones  or wood should be discarded.

Multiple samples  are usually required for purgeable organics analysis because of leakage and
because the measurement process is destructive to the sample. All vials should be identified
with waterproof labels. The water sample vials are filled to overflowing from a bubble-free
source so  that a convex meniscus is formed  at the top. They are sealed by carefully placing
the septum,  Teflon (du Pont)  side down on the opening of the vial and screwing the cap
firmly in place.

Shipment  and receipt of samples must be coordinated with the laboratory to minimize time
in transit  because it is the prerogative of the laboratory to reject samples where delays in
shipment have caused them to age beyond acceptable holding times. To avoid the need to
resample, the sampler should determine in advance the most efficient and reliable form of
transportation for  the  samples.  All samples for organic analysis should arrive  at the
laboratory on the same day collected, or should be shipped and maintained at less than 4°C
for arrival by the next day. The samples are usually shipped  in insulated ice chests. Water
samples should be prechilled before packing to reduce the ice requirements during shipment.
*Vial and  septum  are available from Pierce Chemical Co., P.O. Box  117, Rockford, 111.
 61105. Vial: No. 13074; septum: No. 12722.
                                         8-2

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The bottles should be stabilized in the container with styrofoam and covered with ice. The
information needed to identify the samples should be attached to the outside of the ice
chest.

A part of the quality assurance  program for a laboratory must be the development of a clear
policy for accepting or rejecting samples. Because organic analyses are expensive in terms of
manpower and supplies, it is poor management to commit such resources just to obtain data
of questionable validity. Water samples that clearly have not met  the preservation criteria
during shipment  (e.g., in the  case of a  spill) should  be  accepted only if resampling is
impossible. Results from such samples must be qualified in the laboratory report.

Upon receipt, the samples should be checked for adequate identification, sample tempera-
ture  or presence  of ice in  the  chest, and leakage. Samples for volatile organics should be
checked for air bubbles, although it is extremely difficult to avoid  the development of very
small bubbles  regardless of the  type of sample bottle employed. The samples are logged in
with the receipt time noted. Unless the condition of the samples fails to meet the criteria for
acceptance by the laboratory, required preservatives are added immediately and the samples
are all refrigerated.

The  laboratory staff should be alerted  to the arrival of the samples, so that the required
analysis can begin as  soon as  possible. When sediment samples are to  be reported on a
wet-weight basis, or when a water sample is to be filtered or divided into supernatant  and
settleable subsamples for separate analysis, the sample processing should begin promptly.

When  analysis of water samples is to be restricted to  the  water  phase  only, filtration is
required. This may be accomplished with 4.7-cm, glass-fiber filter disks that  have been
preextracted with acetone  and allowed to dry.  The filter  disks must not contain organic
binder. The disks are placed on a membrane filter holder and up to a liter of water is
filtered. The filtrate is transferred without rinsing to a clean sample container and treated as
a normal, whole-water sample.

When separate reporting is required for the settleable and supernatant  phases, the water
sample (or a large portion of it) is allowed to  settle overnight in a closed glass container at
4°C. If phase separation occurs, the supernatant phase is carefully decanted or siphoned into
a graduated cylinder without disturbing the surface of the settled material. After the volume
of supernatant is noted, the supernatant is filtered  as just  described into a clean glass
container and  stored at 4°C. The volume of settled material  is determined  either by marking
the slurry level on the side of the sample  container for later calibration,  or by transferring
the slurry  without  washing  into  a  calibrated vessel.  A portion  of well-mixed slurry is
removed for a determination of percent solids. The remaining slurry is  stored in a  sealed
glass container at  4°C.

When  both dry-weight an'd wet-weight results are required for sediments and sludges, a
percent-solids  determination should  be  performed soon  after receipt  of the sample. A
representative  portion  (ideally  10 to 25 g) of well-mixed  sample is weighed into a tared
Erlenmeyer flask and dried at  105°C  to a  constant  weight.  Then percent  solids are
calculated for  the sample.

Routine laboratory management involves  detailed recordkeeping beginning with the initial
contact with the  sample collector. A master flowsheet should be prepared for each sample,
listing parameters to be determined and  pretreatment operations to be performed. The
                                         8-3

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master  flowsheet  is kept  at a fixed location and is designed to handle dated entries
indicating when operations are completed. Methods  requiring  extraction permit double
entry on the master flowsheet so laboratory throughput times can be calculated in terms of
receipt-to-extraction and receipt-to-completion times.  A separate set of forms  follows the
sample  through the laboratory. Each sample  form  records information for a class of
parameters and details  cleanup operations and other method options. Calculations and cross
references to chromatograph files are entered on the sample form  also.

A chain-of-custody program lends  significant  legal support to the results generated. The
program begins when the laboratory dispatches the sample collectors. Each time a sample is
collected, a form is initiated stating where and when the sample was collected, with cross
reference to a  number on  the sample container.  The sample collectors return to  the
laboratory with the samples in their guarded possession and deliver them  personally to the
responsible person in the laboratory. The person (custodian) receiving  the samples in turn
signs each ledger to acknowledge receipt and locks the sample in a refrigerator. The analyst
then comes to the custodian and signs for the sample that he is  taking for analysis. In this
way full  documentation  of the sample handling is maintained  from sample collection
through completion of  the analysis.

8.3 Extract Handling

Each  method in reference 1 is prepared  in  sections identified  by titles. This style of
presentation is  aimed at presenting the analyst  logical places to interrupt his analysis. Often,
because of the length of the method, the analyst is unable to complete an analysis in a single
day. When planning a partial  analysis,  certain factors  must be considered. Because the
organics are generally more stable in solvent than in water, it is always preferable to extract
a sample and hold the  extract rather than to hold the sample. Extracts to be held overnight
or longer should first be dried by treatment with sodium sulfate.

The methods include several transfers of the solvent  extract from one piece of glassware to
another. These quantitative transfers are made using several small portions of solvent to
wash the walls  of the previous container. A 5-ml, luer-lock glass syringe with a 2-in., 20-gage
needle is convenient for this purpose. Solvents  tend  to creep  up  the outside of a container,
such as an ampoule, while  pouring. To minimize contamination during  transfer, solvent ex-
tracts are poured as rapidly as possible. Extracts can become contaminated not only from
oils from the skin of  the handler but also from other extracts handled at the same  time
where deposits on the outside of the container are unintentionally transferred from one con-
tainer to another. Instead  of using labels, contamination  problems from this source canjbe
reduced by etching permanent numbers on ampoules. Sample log sheets should be used1 to
index the extract with a numbered ampoule, eliminating the need for tape or wax pencils.

Of the  several  ways to dry a  solvent extract with sodium sulfate, passing it through a
chromatographic column  packed  with  2  to  3  in. of  anhydrous crystals  is the  most
convenient and  quantitative. When  a wet  extract is being transferred from a separatory
funnel  to a Kuderna-Danish (K-D) concentrator, it should be drained directly through the
column to eliminate the  need  for  an intermediate piece of glassware and the  resulting
transfer  step. Prewashing  the sodium sulfate  column with  extracting solvent is recom-
mended, although interferences can be controlled by preheating the salt in a shallow tray at
400°C  for 30 min.  After  the  extract has passed through the column,  20 to 30 ml of
extracting solvent are used to wash the residual  extract from the column.
                                         8-4

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The standard K-D concentration apparatus consists of a three-ball Snyder column, a 500-ml
flask, and a calibrated ampoule. It is designed to concentrate 100- to 300-ml volumes of
extract to a final volume of 5 to 10 ml. To use the apparatus, one 10/20 mesh boiling chip
(previously rinsed with solvent and heated for 1/2 h) is added, and the assembly is supported
above a concentric-ring water bath with the  tip of the ampoule below the surface of the
water.  The lower ground-glass joint must be kept above the  water. The water temperature
should be adjusted for mild distillation, with no chamber flooding or splashing (about 10°C
to 20° C above the boiling point of the solvent). When the volume of liquid reaches 1 to 2 ml
(checked frequently), the assembly should be removed  and allowed to cool. The chambers
and flask will drain to a final volume near 10  ml. The flask and the lower ground-glass joint
are rinsed  with a  minimum of solvent. The evaporation can  be continued  with the
microscale K-D concentrator if further concentration is required.

The microscale K-D concentrator is designed to concentrate extracts from 5 to 10 ml to 1.0
ml. A fresh boiling chip must be added, and a two-ball  micro-Snyder column is attached to
the  ampoule. The  ampoule is  supported above the water bath,  and the  extract  is
concentrated to about 0.7 ml. The column and ground-glass joint are rinsed with a minimum
of solvent, and the volume is adjusted to  1.0 ml.

The K-D concentrator can be used to exchange solvents. When the sample is dissolved in a
solvent  unsuitable  for a cleanup operation or for gas chromatography (GC), it can be
displaced by a suitable  higher boiling solvent. The actual volumes that should be used to
effect the exchange  vary with the solvent pairs depending upon the difference in boiling
points and  azeotrope formations, but a general procedure is to concentrate the extract to 10
ml, add 20  ml of the higher  boiling solvent, and reconcentrate to 10 ml.

After extractions and subsequent K-D concentrations, solubilities of some materials may be
exceeded. High sulfur levels are  a particular problem encountered in sediment extractions.
Extracts should be decanted from ampoules where sulfur has crystallized. In some samples
the extractable  organic levels  are so high  the  extract  tends  to solidify  and  will  not
concentrate further.  When  this  occurs, a small aliquot  of the extract should be taken and
diluted as appropriate for final analysis.

A significant source of the  variation in GC analysis can be attributed to the injection of a
portion of  the extract into  the analytical system. Manual injections of 2 to 3 n\ with the use
of a  10-/il syringe will introduce variance even when the injection volumes are determined to
the nearest 0.05  pi. Of a variety of injection techniques in use, the solvent flush technique
h^s been found to  be acceptable for quantitative work.  This technique is described in detail
in reference 1.

8.4 Supplies and Reagents

Reference  compounds of materials should be assayed and of 98 percent purity or higher. If
the purity  is less than 98 percent, the appropriate correction factor must be included in all
calculations of standard concentration. The reference materials should  be cataloged, dated,
and stored  in a refrigerator.

Stock solutions  of these reference materials  should be prepared in  a high-boiling,  inert
solvent, if  possible, to minimize errors  due to evaporation or  solvent-induced decomposi-
                                         8-5

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 tion. The laboratory should have an accurate six-place balance for preparing small quantities
 of reference standards. The following method of preparing stock solutions is recommended:
 Weigh  10 mg (to the nearest 0.01  mg) of reference standard into a small aluminum weighing
 pan.* Drop the entire pan  into a  10-ml volumetric flask. Dissolve the reference material in
 about  5  ml of solvent, then dilute to volume. Label the solution  with compound name,
 concentration, solvent used, date prepared, and initials of preparer. Store the volumetric in a
 refrigerator, except when preparing dilutions. When the standard is a replacement for an
 existing stock solution,  the two solutions should be compared, and the results as well as the
 suspected reason for any variation should be  permanently recorded in the laboratory files.

 Working standards are prepared from one or more stock solutions after they have warmed to
 room temperature. As  these  working standards  usually  represent three to six orders of
 magnitude of dilution of the stock standards, it is obviously necessary to take great care in
 preparing them. Serial dilutions are recommended with a maximum of 1:100  dilution for
 each step.  Although 10-jul  volumes can be read within 1 percent with a 10-jul  syringe, the
 inherent problems with the dead volume in the syringe make the use of such equipment less
 desirable for preparing  working standards than volumetric pipets. New working standards
 should be  prepared frequently unless long-term stability has been demonstrated. When
 several compounds are combined  into a single standard for simultaneous GC, they must be
 closely monitored  for chemical interactions.

 Pesticide-quality solvents are  usually required, and each new lot should be checked for
 interferences prior to use. The solvent check, representing approximately 10 percent more
 solvent than  required for any  method,  should  be concentrated and analyzed  for method
 interferences under all GC conditions applicable  to that  solvent. If interfering peaks or a
 broad solvent  front are  observed, the solvent should be redistilled in an all-glass distillation
 system, with  a distillation column.**  If interferences persist, the  solvent lot should be
 discarded. This preliminary lot check does not eliminate the need for routine solvent blanks
 to monitor for purity changes over a period of time.

 Diethyl ether must be shown to be free of peroxides before use. Peroxide test stripst can be
 used for a quick,  convenient test. The alumina column procedure for removing peroxides,
 described in literature supplied with the test strips, has been  used successfully to remove all
 peroxides from the solvent.  The  solvent should  always be  stabilized  with 2 percent
 volume/volume  ethyl  alcohol. Chromatographic  elution patterns are based on  ether
 containing this alcohol.

 Granular sodium sulfate should be purchased in  glass  containers.  If purchased in a large
 container (5-lb bottles or larger),  it should be transferred to smaller bottles for daily use.
 Before sodium sulfate is used for chromatographic work, it should be heated to 400°C for
 30 min and shown not to be contaminated. When the sodium sulfate is used to dry extracts
 before concentration, the heating is usually unnecessary because impurities will be removed
 by preelution of the drying column with solvent.
 *Available from The Perkin-Elmer Corp., Norwalk, Conn.; No. 219-0041.
**Available  from  Lab Glass,  Inc., North West Blvd., Vineland, N.J. 08360; Widner No.
  LG-5930.
 tAvailable  from Scientific  Products, 1430 Waukegan Rd., McGaw Park, 111. 60085; Quant
  peroxide test strip, No. PI 126-8.
                                          8-6

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Florisil (Floridin Co.) is purchased from the manufacturer preactivated at 630°C and trans-
ferred to glass  containers with Teflon (du Pont) or foil-lined lids. Prior to use the Florisil
(Floridin Co.) is heated in a shallow open dish for 5 h in a 130°C oven. The Florisil (Floridin
Co.) can then be transferred into a sealed,  glass bottle and stored indefinitely at 130°C until
needed. Cleanup methods using Florisil (Floridin  Co.)  require that a  lauric acid value be
determined for each lot before use. In addition, the determination  of a pesticide elution pat-
tern is recommended. These procedures are described in detail in reference 1.

Carrier gases  are a very important part of the chromatographic system; therefore, special
care should be  taken in their selection and handling. Only high-purity or equivalent carrier
gases should  be purchased, and they should be filtered, online,  through a 5-A molecular
sieve. Porous polymer and other column  packings degrade at elevated  temperatures  in the
presence of trace quantities of oxygen. Oxygen in  the carrier gas  also adversely affects the
performance  of electron-capture detectors. Therefore, some type  of online oxygen-removal
system is recommended  for these  applications.  The chemical traps should  be changed or
regenerated with each new  cylinder of carrier gas. One purifier* has been  found to  last
through  many cylinders  without replacement. A better  grade of gas is required  for
temperature programing than for isothermal operation. Combustion gases  may be of lower
quality but should be at least  equivalent to dry air or purified hydrogen. Regulators should
have stainless steel internal parts and be of two-stage design. External tubing should be of
good quality, such as  refrigeration tubing. Such tubing should be rinsed  with solvent  and
heated at 200°C under gas flow before use  in the  analytical system.

The purchase  of  precoated  GC  column packings is strongly  recommended  over  the
preparation of  coated materials in  the laboratory.  The  commercial products are, generally,
of higher quality and  consistency than those prepared by  the average analyst. All tubing
should be cleaned before packing by passing a series of solvents (e.g., hexane, chloroform,
and acetone) through it. Glass columns should also be silylated. (Instructions are included
with the purchase of silylating  agents.) Dry the tubing thoroughly before packing it.

A vibrator should never be used to settle the packing material in the column. Such vibration
may fracture  the solid support material, expose  uncoated active sites, and produce inferior
chromatographic  separations.  When  vacuum alone is inadequate  and further settling  is
required, the column may be tapped with a pencil or similar object while the vacuum is
being applied. Unless  otherwise stated, stainless-steel tubing should be packed before coiling
it to fit the GC apparatus.

 8.5 Quality Assurance

 8.5.1  Measurements

 Most of the  quality assurance programs suggested in chapter 6 of this manual cannot easily
 be adapted to  the methods for organic compounds. The reasons  for this, and the suggested
 approach for a suitable program for the organic analytical laboratory are discussed in detail
 in  reference  1 and only summarized here.

 Reference 1  suggests  that quality  assurance  for organic  analysis be divided into three
 separate categories.  The first category  represents the determination of purgeable com-
*Available from  Matheson  Gas Products, P.O. Box E, Lyndhurst,  N.J. 07071; Hydrox
 Purifier model No. 8301.
                                         8-7

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pounds. This determination is performed in a closed analytical system; the complete analysis
can be performed in 1 h; and the number of theoretically possible interferences is somewhat
limited. The second category represents liquid/liquid partition methods in  a  regulatory
situation.  Here a very  limited number of compounds are being measured; there is a high
occurrence of positive results; and it is important  to  establish that  the  method works
satisfactorily on the particular sample matrix. The third category represents  liquid/liquid
partition methods in a monitoring situation. Here a large number of compounds are often
being measured  simultaneously; there is a  low occurrence of positive results; and  each
sample  matrix may be different.  Quality  assurance is aimed at  establishing that the
laboratory is using the method correctly.

The purgeable methods are unique among organic methods because the standards are treated
in exactly the same way as the samples, and there is no inherent method bias. The methods
are amenable to  a variety of quality assurance programs. The approach that has been found
applicable to all  types of samples and provides the maximum data for the expended effort
consists of the addition of one or more internal standards to the matrix before purging.  Data
generated  in this program provide a continuous monitoring of the equipment and establishes
matrix applicability  for the test.

For liquid/liquid extraction methods  in a regulatory  situation, the emphasis  is placed on
duplicates and dosed samples. Both field duplicates and laboratory duplicates are used in the
program to establish sampling and subsampling validity.  Trie dosing  of samples to establish
method accuracy for the matrix is an integral  part of this program. Where the analytical
program will  extend  over  a long period  of time the  construction of control charts is
recommended.

When the  liquid/liquid  extraction methods are used for monitoring,  the emphasis is placed
on an external control  series. A standard laboratory matrix is developed. With each series of
samples the  matrix is dosed and  analyzed with the samples. Data generated over a period of
time can  be used to monitor the  performance of the equipment  and the analyst,  with
relatively  tight specifications to  define problems  that  arise.  Control charts  can be  con-
structed to alert the analyst to problems, but there is no provision for rejection of results for
samples of this type.

8.5.2 Identifications

The  combined gas chromatography/mass spectrometer (GC/MS) has emerged as the most
important single instrument at the disposal of the environmental analytical chemist. It alone
can  provide  both  the sensitivity  and the high  degree  of certainty  necessary for an
identification culled from  a complex environmental matrix. The instrument has generated
an aura of well-deserved respect, and its results are seldom questioned. For these reasons it is
mandatory that strict quality assurance programs be followed in both the generation and the
interpretation  of mass spectra. The EMSL, with the cooperation of many other EPA GC/MS
users, has  produced a procedural manual (2) generally for use with a Finnigan quadrupole
instrument. A detailed  quality assurance program constitutes an integral part of the manual.
The actual detailed  program is beyond the scope of this manual but has been summarized in
the following paragraphs.

To insure that a quadrupole  mass spectrometer generates  quality  spectra, the program
provides for  at  least  daily  performance  evaluation with  a reference  compound,  and

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readjustment of the instrument as necessary. The operator prepares a solution of decafluoro-
triphenylphosphine (DFTPP).* When this compound is injected into the GC/MS using any
of several compatible GC columns, the resulting elaborate spectrum can be evaluated using
criteria developed at EMSL-Cincinnati (3).

Decafluorotriphenylphosphine  key ions  and the  ion-abundance  criteria that are used for
determining whether the mass spectrometer is generating high-quality spectra are as follows:

                                 Abundance Criteria

               Mass (amu)             Ion Abundance Criteria

                   51         30 to 60 percent of mass 198

                   68         Less than 2 percent of mass 69

                   70         Less than 2 percent of mass 69

                  127         40 to 60 percent of mass ! 98

                  197         Less than 1 percent of mass 198

                  198       .  Base peak, ] 00 percent relative abundance

                  199         5 to 9 percent of mass 198

                  275         10 to 30 percent of mass 198

                  365         1 percent (or greater) of mass 198

                  441         Less than mass 443

                  442         Greater than 40 percent of mass ] 98

                  443         17 to 23 percent of mass 442

If these specifications are not met, the guidelines provided for adjusting the instrument (2,3)
must be considered.

Having produced quality spectra, the analyst must always ascertain, by analyzing a method
blank under exactly the same  analytical and instrumental conditions, that the spectra are
relevant. Most commercial systems have  a software program, extracted  ion current  profile
(EICP), that permits the sample and the blank to be overlayed on a graphic display device
when each is scanned for a particular mass. When large numbers of spectra result ffrom a
sample and the blank must be checked for a match for each one, this technique simplifies
the screening process.

If the  spectra are  found  to be  unique to the sample, it is  normally processed through a
mass-spectral search-and-match system. The computerized version of such a system consists
*Available from PCR Research Chemicals, Inc., P.O. Box 1778, Gainsville, Fla. 32602; No.
 11898-4.
                                        8-9

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of an organized collection of many thousands of compound spectra stored in a large central
computer accessed by the analyst through telephone linkups. On the basis of 8 or 10 major
masses the computer can rapidly  search the  complete system for similar spectra. These
spectra are ranked for similarity  to the unknown  using a mathematical algorithm. The
resulting  similarity index (SI), which can be  further refined to a quality index (2), is a
measure of the degree of confidence the analyst may place in the identification. If a match
is not found, the analyst must revert to manual interpretation of the spectra and deduce the
structure of the compound by its fragmentation patterns.

After a tentative  identification is  made, several other types  of supporting  experiments
become possible.  Retention-time GC/MS data of a pure compound (standard) may be
compared with analogous data from the sample component. Similarly,  the mass spectrum of
the standard, obtained under the same conditions that were used for the sample, may be
compared with the sample component spectrum. The standard may be dissolved in water at
an appropriate concentration, isolated, and measured. The recovery of  this spike in the same
fraction in which the  suspected component appeared and the observation of equivalent mass
spectra for  the spike and the sample component constitute strong evidence for confirmation
of the identification.

8.6 References

1.  Methods for Organic Analysis of Water and pastes, U.S. EPA, EMSL, Environmental
   Research Center, Cincinnati (in preparation).
2.  EPA GC/MS Procedural Manual,  Budde, W.  L., and Eichelberger, J. W., editors, 1st
   Edition, Vol.  1, U.S. EPA, Office of  Research and Development,  EMSL, Cincinnati (in
   press).
3.  Eichelberger, J. W., Harris, L. E., and Budde, W. L, Anal. Chem., 47, 995 (1975).
                                        8-10

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                                      Chapter 9

                                SKILLS AND TRAINING
9.1  General
Analytical  operations  in the  laboratory  can  be  graded  according  to  the degree  of
complexity. Some analyses require  no sample  treatment, and the measurement can  be
performed  in minutes  on a simple instrument. Other  determinations require extensive
sample  preparation  prior  to  complex  instrumental  examination. Consequently,  work
assignments in the laboratory should be clearly defined. Each analyst should be completely
trained  and should fully understand all the assignments of his job before being given new
responsibilities.  In  this  regard, all  analysts,  subprofessional or professional, should  be
thoroughly instructed in basic laboratory operations, according to the degree of professional
maturity. Some  of the basic operations that should be reviewed periodically with laboratory
personnel follow.

9.1.1 Sample Logging

Routine procedure  for recording of samples entering the laboratory and assigning primary
responsibility should be emphasized. The information that is required and the routing of the
sample to the analyst is then established. The stability, preservation, and storage of samples
prior to analyses are then discussed.

9.1.2 Sample Handling

The analyst should understand thoroughly at which points in his procedures the sample is to
be settled, agitated, pipetted, etc., before he removes it from the original container.

9.1.3 Measuring

The analysts, especially new employees and subprofessionals, should  be instructed in the use
of volumetric glassware. The correct use of pipettes and graduates should be emphasized as
discussed in chapter 4 of this manual.

9.1.4 Weighing

Because almost every measuring operation in the analytical laboratory is ultimately related
to  a weighing  operation,  the proper use of  the  analytical balance should be strongly
emphasized.  Maintenance of the balance, including periodic standardization, should  be
repeatedly  emphasized  to  all  personnel. The correct use and maintenance of balances is
discussed in chapter 3 of this manual.

9.1.5 Glassware

All glassware should be washed and rinsed  according to the requirements of the analysis to
be performed. Not only must the personnel assigned to these tasks be instructed, but also all
lab personnel should know the routine for washing and special requirements for particular
uses of glassware. In addition, the precision tools of the laboratory such as pipets, burets,
                                         9-1

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graduates, and Nessler tubes should be inspected before use for cleanliness, broken delivery
tips, and clarity of marking. Defective glassware should be discarded or segregated.

9.1.6 Instrumentation

Operation and maintenance of analytical instrumentation is of primary consideration in the
production  of valid  data. All instruments  must be properly calibrated,  quality-control
checks documented, and standard curves verified on a routine basis. Details on instrumental
quality control are presented in chapter 3 of this manual.

9.1.7 Data Handling and Reporting

As with sample logging, the routine procedure for recording results of analyses and pertinent
observations, including quality control checks, should  be  emphasized.  Analytical  data
should be permanently recorded in meaningful, exact  terms and reported in a form that
permits future interpretation  and unlimited  use. Details are discussed in chapter 7 of this
manual.

9.1.8 Quality Control

The need to continuously assess precision and  recovery values of methodology is a prime
responsibility of the analyst.  Self-evaluation through the analyses of replicates and recovery
of  spikes from  samples  representative  of the  daily workload provides  confidence and
documentation of the quality of the reported  data.

9.1.9 Safety

Laboratory  safety should be discussed  on a continuing basis with all  employees, but it
should be emphasized when an employee is assigned to perform new duties.

9.1.10 Improvement

In summary, quality  control begins with basic laboratory techniques. Individual operator
error and  laboratory  error  can be  minimized if approved techniques are  consistently
practiced. To insure the continued use of good technique,  laboratory supervisors should
periodically review the basic techniques and point out  areas of needed improvement  with
each analyst.

Continuing improvement of technical competence by all laboratory personnel is, of course,
the final responsibility of the laboratory supervisor. In a  well-organized laboratory, however,
a big-brother attitude of higher ranking to lower grade personnel should be encouraged; each
person should be eager to share experience, tricks of  the trade, special skills, and special
knowledge with subordinates. Obviously, efficiency and results will improve.

9.2  Skills

The cost of data production in the analytical laboratory is based largely upon two factors:
the pay  scale of the  analyst, and the  number of data units produced per unit of time.
However, because of  the  large variety of factors involved,  estimates of the number of
measurements that can be made per unit of time are difficult. If the analyst is pushed to
                                         9-2

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                              Table 9-1
    SKILL-TIME RATING OF STANDARD ANALYTICAL OPERATIONS
Measurement
Simple Instrumental:
pH
Conductivity
Turbidity
Color
Dissolved Oxygen (Probe)
Fluoride (Probe)
Simple Volumetric:
Alkalinity (Potentiometric)
Acidity (Potentiometric)
Chloride
Hardness
Dissolved Oxygen (Winkler)
Simple Gravimetric:
Solids, Suspended
Solids, Dissolved
Solids, Total
Solids, Volatile
Simple Colorimetric:
Nitrite N (Manual)
Nitrate N (Manual)
Sulfate (Turbidimetric)
Silica
Arsenic
Complex, Volumetric, or Colorimetric:
BOD
COD
TKN
Ammonia
Phosphorus, Total
Phenol (Distillation Included)
Oil and Grease
Fluoride (Distillation Included)
Cyanide
Special Instrumental:
TOC
Metals (by AA), No Preliminary Treatment
Metals (by AA), With Preliminary Treatment
Organics (by GC), Pesticides, Without Cleanup
Organics (by GC), Pesticides, With Cleanup
Skill Required
(Rating No.)1

1
1
1
1
1,2
1,2

1
1
1
1
1,2

1,2
1,2
1,2
1,2

2
2
2
2
2,3

2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3

2,3
2,3
2,3
3,4
3,4
Number
Per Day

100-125
100-125
75-100
60-75
100-125
100-125

50-75
50-75
100-125
100-125
75-100

20-25
20-25
25-30
25-30

75-100
40-50
70-80
70-80
20-30

2 15-20
25-30
25-30
25-30
50-60
20-30
15-20
25-30
8-10

75-100
150
60-80
3-5
2-4
1 Skill-required rating numbers are defined as follows:
    1 -aide who is a semiskilled subprofessional with minimum background or
      training, comparable to GS-3 through GS-5.  (Continued)
                                9-3

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produce data at a rate beyond his capabilities, unreliable results may be produced. On the
other hand, the analyst should be under some compulsion to produce a minimum number of
measurements per unit of time, lest the cost of data production become prohibitive. In table
9-1,  estimates are given for  the  number of determinations that an analyst should be
expected to perform on a routine basis. The degree of skill required for reliable performance
is also indicated.

The  time limits presented in the table are  based on use of approved methodology. A tacit
assumption has been made that multiple analytical units are available for measurements re-
quiring special equipment, as for cyanides, phenols, ammonia, nitrogen, and COD. For some
of the simple instrumental or simple volumetric measurements,  it is assumed that other
operations such as filtration, dilution, or duplicate readings are required; in such cases the
number of measurements performed per day may appear to be fewer than one would nor-
mally anticipate.

9.3 Training

For  more experienced, higher grade personnel, formal training in special fields, possibly
leading  to  specialization, should  be  almost mandatory. Such training can  be fostered
through local institutions and through the  training courses provided by the EPA.  Regional
policies on after-hours, Government-supported training should be properly publicized.

Formalized training for lower grade personnel, comparable to GS-3 to GS-5, is relatively
scarce. However, skills can  be most efficiently improved at the bench level on a personal,
informal basis by more  experienced analysts  working in  the  same area.  Exposure of
personnel to pertinent literature should also be a definite program policy.
(Continued)
         2—aide  with special training or professional with minimum training with
            background  in general laboratory techniques  and  some knowledge of
            chemistry, comparable to GS-5 through GS-7.
         3-experienced  analyst capable of following complex procedures with good
            background in analytical techniques, professional,  comparable to GS-9
            through GS-12.
         4-experienced  analyst specialized in  highly complex procedures, profes-
            sional, comparable to GS-11 through GS-13.
     2 Rate depends on type of samples.
                                        9-4

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                                      Chapter 10

                         WATER AND WASTEWATER SAMPLING
10.1  Introduction

The  quality of data resulting from  water and wastewater sampling surveys is dependent
upon the following six major activities: (a) formulating the particular objectives of the water
sampling program, (b) collecting representative water samples, (c) maintaining the integrity
of the water samples through proper  handling and preservation, (d) adhering to adequate
chain-of-custody and sample identification procedures, (e) practicing quality assurance in
the field,  and (f) properly analyzing the pollutants in the water samples. These areas are
equally important for insuring  that  environmental data are of the highest validity and
quality.

The  present section addresses aspects of quality control (QC) concerned with the collection
of environmental samples and data in the  field. It includes a capsule summary of the specific
areas mentioned previously  and  a  list  of references  (table 10-1) that provide  specific
guidance in these areas, rather than a collection of guidelines on sampling procedures.

10.2  Areas of Sampling

The specific areas that comprise an overall water sampling program are as follows.

10.2.1 Objectives of the Particular Sampling Program

The  objectives of the sampling program affect all the other aspects of the sampling program.

Sampling  program  objectives are determined by  the following activities:  (a)  planning
(areawide  or basin), (b) permitting, (c) compliance, (d) enforcement, (e) design, (f) process
control, and (g) research and development. The types of water sampling programs to  be
employed, depending on suitability to program objectives, include reconnaissance surveys;
point-source characterization; intensive surveys; fixed-station-network monitoring; ground-
water monitoring; and special surveys involving chemical, biological, microbiological, and
radiological monitoring.

Factors that must be considered in meeting the objectives of the sampling program are the
extent of the  manpower  resources, the complexity  of the parameters of  interest,  the
duration of the survey, the number  of  samples, the frequency of sampling, the  type  of
samples (grab or composite), and the method of sample  collection (manual or automatic).

10.2.2 Collection of Representative Samples

The  objective of all water and wastewater sampling is to obtain a representative portion of
the total environment under investigation. The techniques for obtaining representative water
samples may vary with the length, width, and depth of a body of water, its physical and
chemical parameters, and its type to be sampled (such as municipal or industrial effluents,
surface  waters  and  bottom  sediments,   agricultural  runoff,  and sludges).  In  collecting
representative samples, the following factors should be considered.
                                        10-1

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10.2.2.1 Site Selection

The  location of the sampling site is critical in obtaining representative data. Preferably,
water sampling sites for point sources of pollution from municipal and industrial effluents
are located at points of highly turbulent flow to insure good mixing; however, inaccessi-
bility, lack of site security, or power unavailability may preclude use of the best sites, but
these impediments should not be used as reasons for collecting samples at unacceptable
locations.  Locations  of sampling sites  for  streams, lakes, impoundments, estuaries, and
coastal areas vary, but in general occur in  the following bodies: (a) in water bodies for
sensitive  uses (swimming and  drinking water supply), (b) in major  impoundments or
reservoirs  near the mouths of major tributaries and in the rivers entering and leaving the
impoundments, (c) in water bodies polluted by man's activities,  (d) in rivers upstream and
downstream from tributaries, and (e) where hydrological conditions change significantly.

10.2.2.2 Types

The basic  types of water and wastewater sampling methods are grab sampling and composite
sampling.  Composite sampling may be conducted manually  or  automatically.  The six
methods for  forming composite samples, all of which depend  on  either a continuous or
periodic sampling mode,  are the following:  (a) constant sample pumping rates,  (b) sample
pumping rates proportional to stream flow rates,  (c) constant sample volumes and constant
time intervals between  samples,  (d) constant sample volumes and time intervals between
samples proportional to stream flow rates, (e) constant time intervals between samples and
sample volumes  proportional  to total  stream  flow volumes since last sample, and (f)
constant time intervals  between samples, and sample volumes proportional to total stream
flow rates at  time of sampling. The choice of using the grab sampling method or one of the
six compositing sampling methods is determined by program objectives and the parameters
to be sampled.

10.2.2.3 Automatic Samplers

The  use of automatic samplers eliminates errors caused by the  human element in manual
sampling,  reduces personnel cost, provides more frequent sampling than practical for manual
sampling,  and eliminates the performance of routine tasks by personnel. Criteria for brand
selection of automatic  samplers include evaluations of the intake device, intake pumping
rates, sample transport  lines, sample gathering systems (including pumps and scoops), power
supplies and power controls, sample storage systems, and additional desirable features to fit
particular sampling conditions. There are many commercially available automatic samplers;
however,  because no single automatic sampler is ideally suited for all situations, the user
carefully selects the automatic sampler most suited for the particular water or wastewater to
be characterized. Precautions must be taken in regard to using  certain types of samples in
potentially explosive atmospheres.

10.2.2.4 Flow Measurement

An  essential part of  any  water or wastewater sampling survey as well  as  a necessary
requirement  of  the National  Pollution  Discharge  Elimination System (NPDES)  permit
program is accurate flow measurement, which can be divided into four categories:

    a.  Flow measurement in  completely  filled pipes  under  pressure—common devices
       employed  are  orifices, Venturi tubes, flow nozzles, Pitot tubes, magnetic  flow
       meters, ultrasonic flow meters, and elbow  meters.
                                        10-3

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    b.  Trajectory methods,  either  full or partially full, measured at the  end of  the
       pipe--common flow  measurement  methods are the California and Purdue pipe
       methods.  These methods are normally considered as estimates rather than accurate
       measurements.

    c.  Flow measurement in open channels and sewers—common methods are the velocity-
       area measurement, time-of-passage  measurement, and level  measurement methods
       using weirs and flumes.

    d.  Miscellaneous flow measurement methods-common methods include  use of Man-
       ning formula, tracer  and salt dilution-techniques,  water meters, pump rates, and
       measurements of level changes in tanks and calibrated vessels.

Flow measurement  data  may be instantaneous or continuous. For continuous measure-
ments, a typical system consists  of primary devices such as weirs and flumes and secondary
devices  such  as  flow sensors,  transmitting equipment,  recorders,  and  totalizers.  The
improper  installation or  design  of a primary device  or  malfunction  of any  part of a
secondary device  results in erroneous flow data.  The accuracy of flow  measurement data
also varies  widely, depending principally on the accuracy  of the primary  device and the
particular flow measurement  method used.  In any case,  an  experienced investigator should
be able to measure flow rates within  ±10 percent of the true values.

10.2.2.5 Statistical Approach to Sampling

Four factors  must be established for every sampling program: (a) number of samples, (b)
frequency of sampling, (c) parameters to be measured, and (d) sampling locations.  These
factors are usually  determined in varying  degrees  by details of the pertinent  discharge
permits  or  are  more arbitrarily set  by the  program resource limitations. Nevertheless, ,the
nature of the statistical methods selected and scientific judgment should be used to establish
the best procedures.

10.2.2.6 Special Sampling Procedures

Special sampling procedures should  be employed for municipal, industrial, and agricultural
waters,  surface waters  as well as  bottom sediments  and  sludges, and  for biological,
microbiological, and  radiological studies.

10.2.3 Sample Preservation and Handling

During and after collection,  if  immediate analysis  is not possible, the sample must be
preserved to  maintain its  integrity. The only legally binding reference EPA has for sample
preservation methods is the  NPDES permit program specified  in reference 13.  However,
these sample preservation procedures serve as a guide for other program objectives.

Proper handling of the samples helps insure valid data; consideration must also be given to
care of the field container material and cap material, cleaning, structure of containers,
container preparation for determination of specific parameters, container identification, and
volumes of samples.
                                        10-4

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10.2.4 Chain-of-Custody Procedures

All programs involved in water and wastewater surveys should document and implement a
chain of possession and custody  of any sample collected, whether or not the resulting data
are to be used in enforcement cases.  Such procedures insure that the samples are collected,
transferred, stored, analyzed, and destroyed only by authorized personnel. See section 12.7
for detailed procedures that can be used on all sample types.

10.2.5 Quality Assurance in the Field

Quality assurance programs for sampling equipment and for field measurement  procedures
(of such parameters as temperature, dissolved oxygen, pH, and conductance) are necessary
to insure data of the highest quality. A field quality assurance program administered by a
quality assurance coordinator should contain the following documented elements:

   a.  The analytical methodology; the special sample handling procedures; and the preci-
       sion, accuracy, and detection limits of all analytical methods used.

   b.  The  basis for selection of analytical and sampling  methodology. For example, all
       analytical methodology for NPDES permits shall be that specified in reference 13, or
       shall  consist of approved alternative test procedures. Where methodology does not
       exist,  the quality  assurance plan  should  state how  the new method  will be
       documented, justified, and approved for use.

   c.  The  amount of analyses for quality  control (QC), expressed as a percentage of
       overall analyses,  to  assess the  validity of data.  Generally,  the  complete quality
       assurance program should approximate 15 percent of the overall program with 10
       and 5 percent assigned to laboratory QC and field QC, respectively. The plan should
       include a shifting of these allocations or a decrease in the  allocations depending
       upon the degree of confidence established for collected data.

   d.  Procedures for the recording, processing, and reporting  of data;  procedures  for
       review of data and invalidation of data based upon QC results.

   e.  Procedures for calibration and  maintenance  of  field instruments and automatic
       samplers.

   f.  A performance evaluation  system, administered through  the quality assurance
       coordinator, allowing field sampling personnel to cover the following areas:

       (1) Qualifications of field personnel for a particular sampling situation.

       (2) Determination of the best representative sampling site.

       (3) Sampling technique including location of the points of sampling within the body
          of water,  the choice of grab  or composite  sampling,  the type of automatic
          sampler, special handling procedures, sample preservation, and sample identifi-
          cation.

       (4) Flow measurement, where applicable.
                                        10-5

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       (5) Completeness of data, data recording, processing, and reporting.

       (6) Calibration and maintenance of field instruments and equipment.

       (7) The use of QC samples such as duplicate, split, or spiked samples to assess the
           validity of data.

   g.  Training of all personnel involved in any function affecting the data quality.

Quality assurance in sample collection should be implemented to minimize such common
errors as improper sampling methodology, poor sample preservation, and lack of adequate
mixing during compositing  and testing. The checks listed in the following sections will help
the quality assurance coordinator to determine when the sample collection system is out of
control.

10.2.5.1  Duplicate Samples

At selected stations on a random  time frame duplicate samples are collected from two sets
of field equipment installed at the site, or duplicate grab samples are collected.  This provides
a check of sampling equipment and technique for precision.

10.2.5.2 Split Samples

A representative subsample from the collected sample is removed and both are analyzed for
the pollutants  of interest.  The samples may  be reanalyzed by the same  laboratory or
analyzed by two different laboratories for a check of the analytical procedures.

10.2.5.3 Spiked Samples

Known amounts  of a particular constituent are added to an actual sample or to blanks of
deionized water at concentrations at which the accuracy of the test method is satisfactory.
The  amount added  should be coordinated with the laboratory. This method provides a
proficiency check for accuracy of the analytical procedures.

10.2.5.4 Sample Preservative Blanks

Acids and chemical preservatives can become contaminated after a period of use in the field.
The  sampler should  add the same quantity of preservative to some distilled water as
normally  would be added  to  a wastewater sample. This preservative blank is  sent to the
laboratory for analysis of the same parameters that  are measured in the sample and values
for the blank are then  subtracted from the  sample values. Liquid chemical preservatives
should be changed every 2 weeks—or sooner, if contamination increases above predeter-
mined levels.

10.2.5.5 Precision, Accuracy, and Control Charts

A minimum of seven sets each of comparative data for duplicates, spikes, split samples, and
blanks should be  collected  to define acceptable estimates of precision and accuracy criteria
for data validation.
                                         10-6

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10.2.5.6 Calibration of Field Equipment

Plans should be developed and implemented for calibrating all field analysis test equipment
and calibration standards to include the following: (a) calibration and maintenance intervals,
(b) listing of required calibration standards, (c) environmental conditions requiring calibra-
tion, and (d) a documented record  system.  Written calibration  procedures should  be
documented and should include mention of the following:

   a.  To what tests the procedure is applicable.

   b.  A brief description of the calibration  procedure. (A copy of the manufacturer's
       instructions is usually adequate.)

   c.  A listing of the calibration  standard, the reagents, and  any accessory equipment
       required.

   d.  Provisions for indicating  that the  field equipment  is  labeled and contains the
       calibration expiration date.

10.3  References

 1. Huibregtse, K.  R., and Moser, J. H., Handbook for Sampling and Sample Preservation of
    Water and Waste water, EPA-600/4-76-049 (Sept. 1976).
 2. Olson, D. M., Berg, E. L., Christensen, R.,  Otto, H., Ciancia J., Bryant, G., Lair, M. D.,
    Birch,  M.,  Keffer,  W.,   Dahl, T.,  and  Wehner,  T., Compliance Sampling  Manual,
    Enforcement Division, Office  of Water Enforcement, Compliance Branch (June 1977).
 3. Weber, C. I., Biological  Field and Laboratory Methods for  Measuring the Quality of
    Surface Waters and Effluents, EPA-670/4-73-001, U.S. EPA (July 1973).
 4. Lauch, R. P., A Survey  of Commercially Available  Automatic Wastewater Samplers,
    EPA-600/4-76-051, U.S.  EPA (Sept. 1976).
 5. Shelly, P.  E., and  Kirkpatrick, G.  A., An  Assessment of Automatic Sewer Flow
    Samplers, EPA-600/2-75-065, U.S. EPA (Dec. 1975).
 6. Handbook for Monitoring Industrial Wastewater, U.S. EPA, Technology Transfer (Aug.
    1973).
 7. Areawide Assessment Procedures  Manual,  Vol.  II, App. D, EPA-600/9-76-014, U.S.
    EPA (July 1976).
 8. Winter, J. A.,  Bordner,  R., and Scarpino, P.,  Microbiological Methods for Monitoring
    the Environment, Part I-"Water and Wastes" U.S. EPA, EMSL, Cincinnati (1977).
 9. Water Measurement Manual, 2d Edition (Revised), U.S. Department of the  Interior,
    Bureau of Reclamation (1974).
10. Kulin, G., and Compton, P.,  A Guide to Methods and Standards for Measurement of
    Water Flow, Special Publication 421, National Bureau of Standards (May 1975).
11. Methods  for  Chemical  Analysis of Water and  Wastewater, U.S. EPA Technology
    Transfer (1974).
12. Harris, D.  J.,  and  Keffer, W. J.,  Wastewater  Sampling  Methodologies and Flow
    Measurement Techniques, EPA-907/9-74-005 (Sept. 1974).
13. Guidelines Establishing Test Procedures for the Analysis of Pollutants, Federal Register,
    41, No. 232 (Dec. 1976).
                                        10-7

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                                      Chapter 11

                                   RADIOCHEMISTRY
11.1  Introduction
The objective of this chapter is to provide general information and suggestions that enable
the analyst to execute his responsibilities in analytical quality control (QC) as they relate to
radiochemical analyses.  Because chemical and  radiochemical  responsibilities  should be
considered together, the  following requirements could be included with the items specified
in the preceding chapters as tasks for the radiochemist: verifying the validity of laboratory
data,  recommending methodology,  interpreting  the results, and examining the need for
standard procedures.

Environmental radiation  measurements are made  daily by Federal, State,  local, and private
agencies. The data obtained from these measurements are used by the U.S. EPA and other
agencies  for such  purposes  as  estimating doses,  describing health effects, establishing
standards and guides,  and conducting regulatory activities. It  is  imperative to  insure the
precision  and accuracy  of the data, so  that policy decisions  concerning environmental
quality are based on valid and comparable data.

A radiation  QC program  should be designed to encourage the development and implementa-
tion  of QC procedures  at all levels of sample  collection, analysis, data processing, and
reporting. It should enable the analyst to verify his  analyses and document the  validity of
the data. In addition, such a program allows the determination of the  precision and accuracy
of environmental radiochemical analyses.

11.2 Sample Collection

Analytical results can  be no more  meaningful than the integrity of the samples that are
analyzed. Representative samples  must be collected so  the data for any aliquot can be
related to a well-defined  pollution source. For most analyses (table 11-1) the sample should
be preserved at  the sampling site  to maintain its integrity  and to minimize activity losses
from absorption on container walls.  If at all possible, analyses should be performed soon
after receipt of the samples at the laboratory.

Sample  container types and descriptions have already been discussed. Both plastic and  glass
containers have  been  recommended, and each has its particular merit.  Cost most likely
determines which of the many types of  plastic  containers will be  used; in general, those
more expensive should be more resistant to adsorption losses. Because sample analyses are
recommended soon after collection,  less  expensive  plastic  ware can be tolerated. In any
event, containers should be discarded  after use  to  prevent contamination of subsequent
samples.

Glass  bottles are popular items, readily available in all sizes. Although the possibility of
breakage either in handling or shipping is obviously great, the very small sizes for radioactive
tracer standards and calibration  sources  can withstand  breakage.  Use of the  larger size
bottles  for  these  purposes should  therefore be avoided.  It is poor  economics to  ship
radioactive samples in fragile  glass containers when unbreakable types serve the purpose
much better.
                                         11-1

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11.3  Laboratory Practices

11.3.1 Laboratory Safety

The  general principles of laboratory  safety are covered in chapter 14. The hazards to be
avoided are listed, and the  importance of good housekeeping practices is  stressed. These
practices reduce the potential hazard  of the many chemical operations being performed. In
the  radiochemical laboratory  they  eliminate the  probability  of  radiological  cross-
contamination from sample  to sample and from sample to glassware. Many of the materials
used in the laboratory are potentially  hazardous because of their chemical properties or
their radioactivity and therefore should be handled with the utmost care and  respect.

In the radiochemical  laboratory, the  prevention of contamination by radioactive materials
requires attention  to  radiation-protection practices, an ongoing personnel-monitoring pro-
gram, and the designation of a segregated storage area for radioactive sources following use
in radiochemical analyses. Adequate labeling  of work  areas, of samples for analysis, of
aliquots, and of separated  fractions helps  to  control  radiation hazards  and  to  insure
personnel safety.

The handling of radioactive materials involves safety hazards of a type not usually associated
with a chemical laboratory.  Special precautions and instruments should be used to insure
the greatest  personal  safety.  It  is imperative  to wear monitoring devices (personal film
badges) at all times.

A number of health and contamination hazards are to  be considered. Many radioactive
materials are dangerous even in extremely  minute  quantities if inhaled or ingested. All
radioactive materials  are capable of contaminating laboratories, instruments, and clothing.
All radioactive materials in large  concentrations are dangerous because of the effects of their
radiation external to their containers. To control these hazards, the following rules should
be in effect at all times.
             *
   a.  For the case of radioactive materials that are capable of being volatilized or airborne,
       perform all work in a closed area or  hood.  Perform distillations, evaporations, and
       other such processes  in a  well-ventilated hood.

   b.  Do not bring  food or liquid  refreshments into a laboratory engaged in work  with
       radioactive materials. The same applies to the counting rooms.

   c.  Do not smoke when handling radioactive materials.

   d.  After working with  radioactive materials, wash hands thoroughly before eating or
       handling uncontaminated materials.

11.3.2 Laboratory Analyses

Standard radiochemical procedures or their equivalent are needed to comply with sensitivity
detection limits  for  each nuclide as  designated by the quality  assurance  program (2).
Radiochemical procedures have  been  compiled for a multitude of nuclides in a multitude of
media (3-9) and  descriptions of  specific separations are to be  found in the scientific
literature.  As laboratory techniques  become  more sophisticated and as  more sensitive
instrumentation is developed, these procedures Will be improved.
                                         11-3

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Depending on the media, the radioactivity levels, and the nuclide composition, there are
several approaches that can be made when a sample is received for QC determination. The
requirements for an acceptable QC program are described in section 11.4.

Before starting such a program, the laboratory should be already set up for radiochemical
analyses and the analysts should have the prescribed education and experience.

11.3.3 Laboratory Radiation Instruments

The  types  of radiation counting systems  (described in ref. 2) needed to comply with the
requirements are set forth in the following paragraphs. Only those instruments needed for
analyzing specific radionuclides  are required.  Such instruments should  meet the specifica-
tions discussed in the next sections.

11.3.3.1  Liquid Scintillation System

A liquid scintillation system  must measure  tritium  with the  sensitivity required  by the
National Interim Primary Drinking Water Regulations. Efficiency  of the system should be
greater than  57 percent for tritium. The tritium figure of merit (ET)i/B should be  greater
than 100.

11.3.3.2  Gas-Flow Proportional Counting System or Alternative

A gas-flow  proportional counter, or  the alternative  described later, is required for
measurement of gross alpha- and gross beta-particle  activities, «radium-228, strontium-89,
cesium-134, and iodine-131. The detector may be either windowless (internal proportional
counter) or of the thin-window  type. A minimum shielding equivalent of 5 cm of lead must
surround the detector. A cosmic (guard) detector should be operated  in anticoincidence
with the main detector. The main detector should have an efficiency greater than 20 percent
for polonium-210 and carbon-14 and greater than 40 percent for strontium-90. The detector
background should be less than 1.3 counts per minute.

The detector plateau should be less than 1.5 percent per 100 V and should be at least 100 V
wide for carbon-14 and less than 2 percent per 100 V for strontium-90.

A scintillation system designed for alpha- and beta-particle counting may be substituted for
the  gas-flow proportional counter described.  In such a system a Mylar disk coated with a
phosphor (silver-activated zinc sulfide) is either placed  directly on the sample (for alpha
measurements)  or on the face of a photomultiplier tube,  enclosed  within a  light-tight
container along with the appropriate electronics  (high-voltage supply,  amplifier(s), timer,
and  sealer). Radiation shielding, although desirable, is not required for this system.

11.3.3.3 Gamma Spectrometer System

A sodium  iodide (Nal) detector connected  to a multichannel  analyzer is required  for
determination of manmade photon emitters.  A  7.5- by 7.5-cm Nal crystal is satisfactory;
however, a 10-  by 10-cm crystal is recommended. The crystal detector must be shielded
with a minimum of 10 cm of iron or equivalent.

It is recommended but not required that the distance from the center of  the crystal detector
to any  part  on the shield should not be less  than 30  cm. The multichannel  analyzer, in
                                         11-4

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addition to  the appropriate  electronics  (high-voltage  supply,  preamplifier,  and linear
amplifier),  must contain a memory of not less than 200 channels and at least one readout
device.

11.3.3.4 Scintillation Cell System

A scintillation system  must be designed to accept scintillation flasks (Lucas cells)  for
measurement  of radium-226 by  the radon-emanation method. The system consists of a
light-tight enclosure for the  scintillation flasks, a detector (phototube), and the appropriate
electronics  (high-voltage supply,  amplifier, timers, and sealers).  The scintillation flasks
required for this measurement may either be purchased  from  commercial suppliers  or
constructed according to published specifications.

11.4 Quality Control

The following requirements are  recommended for all laboratories:

    a.  All  QC data should  be  available for inspection to determine validity of laboratory
       results.

    b.  Each  laboratory should participate at  least twice each  year in  EPA  laboratory
       intercomparison studies  (10).

    c.  Each   laboratory  should  participate once each year in  an appropriate EPA-
       administered  parformance study on unknowns. Results must be within the control
       limits established by  EPA for each analysis.

    d.  Counting-instrument operating manuals and calibration protocols should be available
       to analysts and technicians.

    e.  Calibration data and maintenance records on all radiation instruments and analytical
       balances must be maintained in a permanent record.

    f.  Minimum daily QC

       (1) To verify precision of methods, a minimum of 10 percent of the samples shall be
           duplicates. Checks must be within ±2 standard deviations of the  mean range.

       (2) If less than 20  samples per day are analyzed, a performance standard and a
           background  sample  must be measured. If 20 or more samples are analyzed  per
           day, a performance standard and a background sample imast be measured with
           each 20 samples. Checks must  be within ±2 standard deviations of the mean
           range.

       (3) Quality control performance charts or performance records must be maintained.

11.5 References

 1.  Federal Register^, No.  133 (July 9, 1976).
 2.  Jarvis,  A. N., et  al.,  The  Status and  Quality of Radiation Measurements of Water,
    EPA-600/4-76-017(Apr. 1976).
                                        11-5

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 3.  Krieger, H. L., Interim Radiochemical Methodology for Drinking Water, EPA-600/4-
    75-008 (Revised), U.S. EPA, Office of Research and Development, Cincinnati (Mar.
    1976).
 4.  Doublas, G.  S., Editor, Radioassay  Procedures for Environmental Samples, Environ-
    mental Health Series,  Publication 999-RH-27,  U.S. DHEW,  Public Health Service,
    National Center for Radiological Health (Jan. 1967).
 5.  Harley, J. H., HASL Procedures Manual, HASL-300, U.S. ERDA, Health and Safety
    Laboratory, New York (1972).
 6.  Kleinberg,  J., Editor, Collected  Radiochemical  Procedures, LA-1721  (Revised), Los
    Alamos Scientific Laboratory, Los Alamos (Nov. 1955).
 7.  Krieger,  H. L., et al., Radionuclide Analysis of  Environmental  Samples, Technical
    Report R59-6 (Revised), U.S. DHEW, Public Health Service (Feb. 1966).
 8.  Nuclear Science Series, Reports NAS-NS-3001  to NAS-NS-3115, National Academy of
    Sciences, National Research Council  Technical Information 'Center, Office of Informa-
    tion Services (1960).
 9.  "Water," Part  31  of 1977 Annual Bo'ok of ASTM Standards, American Society for
    Testing and Materials, Philadelphia (1977).
10.  Jarvis, A. N.,  et al., Environmental Radioactivity Laboratory Intercomparison Studies
    Program 1975, EPA-680/4-75-002b, U.S. EPA, Office of Research and Development,
    Las Vegas (1975).
11.  Ziegler, L. H., and Hunt, H. M., Quality Control for Environmental Measurements Using
    Gamma-Ray Spectrometry, U.S. EPA, EPA-600/7-77-144 (Dec.  1977).
12.  Kanipe, L. G., Handbook for Analytical Quality Control in Radioanalytical Labora-
    tories, U.S. EPA, EPA-600/7-77-088 (Aug. 1977).
                                       11-6

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                                      Chapter 12

                                    MICROBIOLOGY
12.1  Background

The  quality assurance program described in this chapter is a synopsis of a detailed program
prescribed  in  parts IV and  V of the EPA microbiological methods manual (1).  Quality
assurance is a  program  of integration of all intralaboratory and interlaboratory quality
control (QC),  methods  standardization,  and  QC management practices  into  a  formal,
coordinated, continuing effort.

12.2  Specific Needs in Microbiology

A quality assurance program  for microbiological analyses must emphasize the  control of
laboratory  operations and analytical procedures because the tests measure living organisms
that  continually  change in response to their  environment. Further, because true values
cannot be  provided for the  microbial parameters, microbiologists do not yet have the
advantages of  analytical standards,  QC  charts, and spiked samples  available to other
disciplines  for measurement of accuracy. Because known values  cannot be applied, it is im-
portant that careful and  continuous control be exerted over sampling, personnel, analytical
methodology, materials, supplies, and equipment.

12.3  Intralaboratory Quality Control

Intralaboratory QC is the  orderly  application within a single laboratory  of  laboratory
practices necessary  to  eliminate or reduce systematic error and to control random error.
This  within-laboratory program must be practical, integrated, and time-efficient or it will be
bypassed. When properly administered, such a  program helps to  insure high-quality data
without interfering with the primary analytical functions of the  laboratory. This within-
laboratory  program should  be supplemented  by  participation of the laboratory in an
interlaboratory quality assurance program such as that conducted by EPA.

Intralaboratory QC  for microbiology should cover the  following areas:

   a.  Laboratory operations

       (1) Sample collection and handling
       (2) Laboratory facilities
       (3) Laboratory personnel
       (4) Laboratory equipment and instrumentation
       (5) Laboratory supplies
       (6) Culture media
       (7) Analytical methodology

   b.  Analytical QC

       (1) Sterility checks
       (2) Positive  and negative controls
                                         12-1

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       (3) Duplicate analyses
       (4) Single-analyst precision
       (5) Comparison of results between analysts
       (6) Verification of membrane filter analyses
       (7) Completion of most probable number analyses,
       (8) Data handling

12.4 Interlaboratory Quality Control

An interlaboratory  quality -assurance  program  is  an agreed-upon  system  of minimal
requirements necessary to maintain a quality standard among a group of laboratories. Such a
program  may be voluntary or compulsory for participants. It may include the following
activities:

   a.  Selection and approval of uniform sampling methodology and  analytical methodol-
       ogy

   b.  Collaborative studies to establish the precision and  accuracy of selected methodol-
       ogy

   c.  Preparation of guidelines to set minimal group standards  for personnel, equipment,
       instrumentation, facilities, and intralaboratory QC programs

   d.  Onsite inspection of laboratory capabilities

   e.  Periodic evaluation of laboratory performance on unknown samples

   f.  Followup on problems identified in onsite inspections and performance evaluations

As a part of its interlaboratory quality assurance program, EPA has selected microbiological
methodology and  standards for laboratory operations (1). EMSL-Cincinnati is currently
conducting research  on the development of QC samples for use in performance testing and
method-validation studies.

12.5  Development of a  Formal Quality Assurance Program

Unless records  are  kept of the QC  checks and procedures, there is no proof of performance,
no value in  future reference, and  for practical purposes, no quality assurance program in
operation. To insure a viable quality assurance program, management must first recognize
the need and require the development of a formal program, and then commit  15 percent of
the laboratory  man-years to QC  activities. The laboratory manager  holds meetings  with
supervisors  and staff workers  to  establish  levels  of responsibility  and  functions  of
management, supervisor, and analyst in  the quality assurance program. Laboratory person-
nel participate in planning and structuring the program.

Once the quality assurance program is functioning, supervisors review laboratory operations
and QC with analysts on a frequent (weekly) basis. Supervisors use the results  of the regular
meetings with laboratory personnel to inform management of the status of the program on a
regular (monthly) basis. These meetings identify problems through participation of labora-
tory personnel and  provide the backing of management  for actions required to correct
problems.
                                        12-2

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12.6 Documentation of a Quality Assurance Program

A laboratory operating manual should be prepared that describes operation, maintenance,
and QC of laboratory operations and analyses as practiced. The review mechanisms and the
frequency of review in the quality-assurance program are included.

12.6.1 Sampling

A sample log is used  to record information on samples received in the laboratory including
details of sample identification  and origin, the  necessary  chain-of-custody information,
analyses performed, and final results.

12.6.2 Laboratory Operations

A QC record is maintained  on media preparation,  instrument calibration,  purchase of
supplies, QC  checks on  materials,  supplies, equipment, instrumentation, facilities,  and
analyses.

12.6.3 Analytical Quality Control

A record of analytical QC checks is maintained on positive  and negative controls, sterility
checks,  single-analyst precision,  precision between  analysts,  and  use-test results from
comparison  of lots of media, membrane filters, and other supplies.

12.7 CKain-of-Custody Procedures for Microbiological Samples

12.7.1 General

A regulatory agency must demonstrate the reliability of its evidence by proving the chain of
possession and custody of any samples that are offered for evidence or that form the basis
of  analytical  test  results  introduced into  evidence  in any  water  pollution case.  It  is
imperative that the office and  the laboratory prepare  procedures to be followed whenever
evidence samples  are collected,  transferred, stored, analyzed, or destroyed.

The primary objective of these  procedures is to create an accurate written record that can be
used to trace the possession of the sample from the  moment of its collection through its
introduction into evidence. A sample is in custody if it is in any one of the following states:

    a.  In actual physical possession

    b.  In view, after being in physical possession

    c.  In physical possession and locked up so that no one can tamper with it

    d.  In a secured area, restricted to authorized personnel

Personnel should receive copies of study plans prior to the study of a water pollution case.
Prestudy briefings  should  then be held  to  apprise participants of the objectives, sample
locations, and chain-of-custody procedures  to be followed.  After  the  chain-of-custody
samples are collected, a debriefing is held in the field  to verify the adherence to the
chain-of-custody  procedures and to determine whether additional samples are required.
                                         12-3

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12.7.2 Rules for Sample Collection

An agency or laboratory engaged in sample study activities should follow these rules:

   a.  Involve a minimum number of trained persons in sample collection and handling.

   b.  Establish guidelines for particular  procedures to be used for each type of sample
       collection, preservation, and handling.

   c.  Handle samples as little as possible.

   d.  Obtain stream and effluent samples using the appropriate sampling techniques.

   e.  Attach sample  tag or label securely (see fig. 12-1) to the sample container at the
       time the  sample is  collected.  The tag should contain the following items as a
       minimum: the  serial number of the tag, the station number and location, the date
       and time taken, the type of sample, the sequence number (e.g., first sample of the
       day—sequence No. 1), the preservative used, the analyses required, and the name of
       the sample collector.  Tags should be completed legibly in waterproof ink.

   f.  Use  bound  field notebooks to record  field measurements and  other pertinent
       information  necessary to reconstruct the sample collection processes in the event of
       a later enforcement proceeding. Maintain a separate set of field notebooks for each
       study and store them in a safe place where they can be protected and accounted for
       at all times.  Establish a sample log sheet with a standard format to minimize field
       entries and include the serial number of the sheet, the date, time, survey, type of
       samples taken,  volume of each sample, type of analyses, (unique) sample numbers,
       sampling location, field measurements (such as temperature, conductivity, dissolved
       oxygen (DO), and pH), and any other pertinent information or observation. (See fig.
       12-2.)  The entries should be signed by the sample collector. The responsibility for
       preparing and retaining field notebooks during and after a study should be assigned
       to a study coordinator or his designated representative.

   g.  The sample collector is responsible for the care and custody of the samples until the
       samples are properly dispatched to the receiving laboratory or  given to an assigned
       custodian. The sample collector must insure that each container is in his physical
       possession or in his view at all times, or stored in a locked  place where no one can
       tamper with it.

   h.  Take  color slides or photographs of the sample locations and any visible water
       pollution. Sign  and indicate time, date, and site location on the back of the photo.
       To prevent  alteration, handle  such  photographs according  to  the established
       chain-of-custody procedures.

12.7.3 Transfer of Custody and Shipment

In transfer-of-custody procedures, each custodian or sampler must sign, record, and date the
transfer.  Most environmental  regulatory agencies develop  chain-of-custody  procedures
tailored to their needs. These procedures may vary in format  and language but contain the
same essential elements. Historically, sample transfer under chain of custody has been on a
                                        12-4

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UVS. ENVIRONMENTAL PROTECTION AGENCY
Station No. Date Time Sequence No.
Station Location
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 (a)
                  ENVIRONMENTAL PROTECTION AGENCY
                               (Local Address)
 (b)
        Figure 12-1. Example of chain-of-custody sample tag. (a) Front, (b) Back.
sample-by-sample basis, which is awkward and time consuming. However, the EPA National
Enforcement Investigation Center (NEIC) at Denver has set precedent with its bulk transfer
of samples. Bulk transfer is  speedier and reduces paperwork and the number of sample
custodians. The following description of bulk transfer of custody is essentially that of the
Office of Enforcement (2).
                                     12-5

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a.  Samples must be accompanied by a chain-of-custody record that includes the name
   of the study, collectors' signatures, station number, station location, date, time, type
   of sample, sequence number, number of containers, and analyses required. (See fig.
   12-3.) When turning over possession of samples, the transferor and transferee sign,
   date, and time the record sheet. This record sheet allows transfer of custody of a

                       CHAIN OF CUSTODY RECORD

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Relinquished by:^™^™/
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              Figure 12-3.  Example of chain-of-custody record.
                                    12-7

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      group of samples in the field to the mobile laboratory or to the central laboratory.
      When a custodian transfers a portion of the samples identified  on the sheet to the
      mobile laboratory, the individual samples must be noted in the  column with the
      signature  of the person relinquishing the samples. The laboratory person receiving
      the samples acknowledges receipt by signing in the appropriate column.

   b.  If the custodian has not been assigned, the field custodian or field sampler has the
      responsibility  of packaging and dispatching samples to the laboratory for analysis.
      The dispatch portion  of the chain-of-custody record must be filled out,  dated, and
      signed.

   c.  To avoid  breakage, samples must be carefully packed in shipment containers such as
      ice chests.  The shipping  containers are padlocked  for shipment to the receiving
      laboratory.

   d.  Packages  must be accompanied by the  chain-of-custody record showing identifica-
      tion of the  contents.  The original must accompany the shipment. A copy is retained
      by the survey  coordinator.

   e.  If sent by  mail, register the package  with return  receipt requested.  If sent by
      common  carrier, a Government bill of lading should be obtained. Receipts from post
      offices and  bills of lading will be retained as part of the permanent chain-of-custody
      documentation.

   f.  If delivered to the laboratory when appropriate personnel are  not there to receive
      them, the samples must be locked in a designated area within the laboratory, so that
      no one can tamper with them or must be placed in a secure area. The recipient must
      return to the  laboratory, unlock the samples, and deliver custody to the appropriate
      custodian.

12.7.4  Laboratory Custody Procedures

Suitable laboratory procedures during custody of samples include the following:

   a.  The laboratory shall designate a sample custodian and an alternate custodian to act
      in his absence. In addition, the laboratory shall set aside a sample storage security
      area. This should be  a clean, dry, isolated room with sufficient  refrigerator space
      that can be securely  locked  from the outside.

   b.  Samples should be handled by the minimum possible number of  persons.

   c.  Incoming samples shall be received only by the custodian who  will  indicate receipt
      by  signing  the  chain-of-custody record  sheet  accompanying  the  samples and
      retaining  the sheet as a permanent record. Couriers picking up samples at the airport
      or post office  shall sign jointly with the laboratory custodian.

   d.  Immediately upon receipt, the  custodian places the samples in the sample room,
      which will be locked at all times except when samples are removed or replaced by
      the  custodian. To the maximum  extent possible, only  the  custodian shall be
      permitted in the sample room.
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    e.  The custodian shall insure that microbiological samples are properly stored and
       maintained at 4°C.

    f.  Only the custodian will distribute samples to personnel who are to perform tests.

    g.  The analyst records in his laboratory notebook or analytical worksheet, identifying
       information describing the sample, the procedures performed, and the results of the
       testing. The notes shall be dated, shall indicate who performed the tests, and should
       include any  abnormalities that occurred during the testing procedure.  The notes
       shall be retained as a permanent record in the laboratory. In  the event that the
       person who performed the tests is not available as a witness at the time of a trial, the
       Government  may  be able to  introduce the  notes in evidence under the Federal
       Business Records Act.

    h.  Approved methods of laboratory analyses shall be used as required by Public Laws
       92-500, 93-523, 92-532, and amendments.

    i.  Laboratory personnel are responsible for the care and custody of a sample once it is
       handed to them and  should  be prepared  to  testify that the sample  was in their
       possession and view or secured in the laboratory at all times from the moment it was
       received from the custodian until the tests were run.

    j.  The laboratory area shall be maintained as a secured area and shall be restricted to
       authorized personnel.

    k.  Once the sample analyses are completed, the unused portion of the sample, together
       with identifying labels and other documentation, must be returned to the custodian.
       The  returned,  tagged  sample  should  be  retained  in the custody room  until
       permission to destroy the sample is received by the custodian.

    1.  Samples should be destroyed  only upon the order of the  laboratory director, in
       consultation with previously designated enforcement officials, or when it is certain
       that the information is no longer required, or that  the samples have deteriorated.
       The same destruction procedure is true for tags and laboratory records.


12.7.5 Evidentiary Considerations

Reducing chain-of-custody procedures and promulgated analytical procedures to writing will
facilitate the admission of evidence under Rule 803  (6) of the Federal Rules of Evidence
(Public Law 93-575). Under this statute, written records of regularly conducted business
activities may be introduced into evidence as an exception to the hearsay rule without the
testimony of the person(s) who  made the record. Although it would be  preferable, it is not
always possible for the  individuals who collected, kept, and analyzed samples to testify in
court. In addition, if the  opposing party does not intend to contest  the integrity of the
sample or testing evidence, admission  under Rule 803(6) can save a great deal of trial time.
For these reasons, it is important that the procedures followed in the collection and analyses
of evidentiary samples be standardized and described in an instruction manual, which, if
need be,  can be offered as evidence of the regularly conducted business activity followed by
the laboratory or office in generating any given record.
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In criminal cases, however, records and reports of matter observed by police officers and
other law enforcement personnel are not included under the business record exceptions to
the hearsay rule previously cited. (See Rule 803(8), Public Law 93-595.) It is arguable that
those portions of the compliance inspection report dealing with matters other than sampling
and analysis results come within this exception. For this reason,  in criminal actions, records
and  reports of matter  observed by field investigators may not be admissible,  and the
evidence may still have to be presented in the form of oral testimony by the person(s) who
made the record or report, even though the materials come within the definition of business
records.  In a criminal proceeding,  the  opposing  counsel  may be  able to obtain copies of
reports  prepared by witnesses  (even if the witness does not  refer to  the records while
testifying), which may be used for cross-examination purposes.

Admission of records is not automatic under either  of these  sections. The business records
section  authorizes  admission  "unless the source  of information or the method  or circum-
stances  of preparation indicate lack of trustworthiness," and the caveat under the public
records  exception reads "unless the sources of information or other circumstances indicate
lack of trustworthiness."

Thus, whether or not the inspector anticipates that  a report will be introduced as evidence,
the inspector should make certain that the report is as accurate and objective as possible.

12.8 References

1.  Winter, J. A., Bordner, R., and Scarpino, P., Microbiological Methods for Monitoring the
    Environment, Part I-"Water and Wastes," U.S. EPA, EMSL, Cincinnati (1978).
2.  NPDES Compliance Sampling Manual, U.S. EPA, Office of Water Enforcement (June
    1977).
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                                      Chapter 13

                                  AQUATIC BIOLOGY
Quality assurance  guidelines for aquatic biology programs (fully described in ref. 1) are
summarized in the following section.

13.1 Summary of General Guidelines

Successful quality assurance programs in aquatic biology are based on the following essential
elements:

   a.  An  understanding and acceptance of the importance of quality control (QC) and a
       commitment  on the part of the biology staff to fully integrate QC practices into
       field and laboratory operations

   b.  A staff with  adequate formal  training and experience  and proper specialization to
       meet program needs

   c.  Adequate field  equipment, storage and laboratory  space,  instrumentation, and
       taxonomic references

   d.  Careful advance preparation and design of field and laboratory studies

   e.  Strict adherence to approved methodology, where  available, and careful consider-
       ation of the technical defensibility of the methods and their application

   f.   Use of replication in sample collection and analysis where feasible,  and determina-
       tion of the accuracy and precision of the data

   g.  Frequent calibration of field and laboratory instruments

   h.  Proper sample identification  and handling to prevent misidentification or inter-
       mixing of samples

   i.   Use of blind, split, or other control samples to evaluate performance

   j.   Development and regular use of in-house reference specimen collections, and use of
       outside  taxonomic experts to  confirm or  provide  identifications for  problem
       specimens

   k.  Meticulous, dual-level review of the results of manual arithmetical  data manipula-
       tions  and transcriptions before the data are used in reports or placed in BIO-
       STORET (2)

   1.   Participation  in  EPA formal interlaboratory aquatic biology methods  studies, and
       use  of EPA biological reference materials

   m. Documentation of methodology and QC practices employed in the program
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 13.2 Discussion

 A brief  description of each of the areas mentioned in section  13.1  is provided here to
 indicate the scope of the quality assurance program.

 13.2.1 Staff Commitment

 To establish and maintain an effective quality assurance  program in aquatic biology, the
 supervisor  must  actively  support  and frequently monitor the use of QC practices in all
 aquatic biology activities. This will require the commitment of 10 to 15 percent of the total
 manpower resources. The supervisor  must review field and laboratory operations with his
 staff  frequently  (weekly) to insure that QC practices are  followed  and properly docu-
 mented.

 13.2.2 Staff

The quality and reliability of the data rest heavily on the competence of the staff. The range
of aquatic  organisms studied by biological programs is very broad,  and each community
requires unique skills in sample collection and analysis, and in data interpretation. Several
disciplines,  therefore, must  be represented on the staff  to  deal  effectively  with  the
taxonomy  and ecology of the major groups  of aquatic organisms, which include  the
phytoplankton, zooplankton, periphyton, macrophyton, macroinvertebrates, and fish.

 13.2.3 Facilities

The quality of the data also depends upon the availability and performance  of laboratory
equipment.  Such items as sampling gear,  current  meters, spectrophotometers, and micro-
scopes must be available  and must meet  performance standards related to the biological
parameters measured. Laboratory instrumentation must provide the sensitivity and accuracy
required  by the state of the art in sample analysis. Adequate laboratory and  storage space
must also be provided.

 13.2.4 Advance Planning

Thorough advance  planning of field and  laboratory projects is  necessary to  maintain the
required  control  over the technical aspects of the project and to insure the  collection of
meaningful  data.  Factors  taken into consideration include the objectives of the study, the
parameters  to  be  measured,  station selection, the sampling frequency  and replication,
seasonal cycles in the properties of communities of aquatic organisms, and QC measures to
be incorporated into the various phases of the project.

 13.2.5 Use of Approved Methodology

Methods in the EPA manual "Biological Field and Laboratory Methods for Measuring the
Quality of Surface Waters and Effluents" (1) should be  employed where applicable.  The
manual contains  concensus  methods selected by a committee  of senior Agency aquatic
biologists as the  preferred  methods  for  use within  EPA.  If program activities require
methods for parameters not covered by reference 1, methods may be selected from other
sources if their application is technically defensible.
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13.2.6 Replication

Comparisons of biological  parameters measured in control and affected regions of water
bodies, and  in laboratory experiments, may be meaningless if the precision of the results is
not known.  Preliminary measurements must be made in each study to determine the scatter
in the data and to establish the number of replicate samples required to achieve the level of
precision required to detect differences in the responses measured.

13.2.7 Instrument Calibration and Maintenance

Sampling equipment and laboratory instrumentation with mechanical metering devices and
electronic components are calibrated on a regularly scheduled basis to insure the accuracy of
the data. Standards are obtained, such as  NBS-certified  thermometers for temperature-
measuring devices, class-S weights for balances, and absorption filters for spectrophotom-
eters. Records  of calibrations, regular performance checks, and service for each device  are
maintained  in bound log books in such a manner that the history of performance  of  the
instruments may be easily  reviewed.  Analytical  reagents are  labeled  and dated when
received, and are  protected from deterioration if labile. The expected shelf life of each
reagent is recorded on the label, and the material is not used after the expiration date.

13.2.8 Sample Labeling

Samples  are securely labeled in the field and recorded in a bound log. Information on  the
label should include the station, date, time of day, depth, and other relevant information. A
unique lot number is assigned to  the sample and  recorded on the label. Waterproof paper
and ink must be used for the labels, and are recommended for the field logs.  Depending on
requirements, labels are placed inside samples such as macroinvertebrates.

13.2.9 Quality Control Samples

The  accuracy  of  the  data from  routine  analyses such  as counts and identification of
organisms and  chlorophyll and biomass  measurments  is determined by introducing blind,
split,  or reference  samples  in  the sample  processing stream. These  samples are  either
prepared  by  the  supervisory aquatic biologist,  laboratory quality control  officer,  or
analytical QC coordinator, or are obtained from EMSL-Cincinnati. The results are discussed
at regularly scheduled staff meetings and  any  problems identified  are  discussed  and
corrected.

13.2.10 Organism Identification and Reference Specimens

Accurate  identification  of aquatic  organisms to the species level is essential to   the
interpretation of biological  data. A set of reference specimens is established within each
laboratory, to be used  as taxonomic (identification) standards in processing samples  and in
training new personnel. The set is  representative of the aquatic organisms collected by  the
program, and each specimen embodies the  morphological characteristics essential to  the
identification  of that taxon. The  identity  of these  specimens is verified  by outside
taxonomic experts, who also examine organisms that pose unusually difficult identification
problems in  routine sample analysis.
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13.2.11 Data Records, Editing (Proofing), Review

Data collected manually are entered in a bound log or on specialized bench sheets that fully
describe the origin  and nature of the sample and that are maintained in a binder or file.
Source data  such as organism abundance, metabolic rates, and  chlorophyll, which  are
manually or  electronically manipulated  or transcribed from one record to another,  are
doublechecked by a second person. All manual calculations and all electronic calculations,
where data are manually keyboarded, are performed twice, except where the source (input)
data are included in the output and can be proofed. Keyboarded data are carefully proofed
before they are submitted for computer manipulation.

13.2.12 Interlaboratory Methods Studies

The aquatic  biology programs participate  in  formal  interlaboratory  biological  methods
studies performed  by EMSL-Cincinnati. Studies  on  chlorophyll and macroinvertebrate
identification methods have been completed, and additional studies on phytoplankton and
periphyton identification methods are planned in the future.

13.2.13 Documentation for the Quality Assurance Program

A laboratory operations manual is available (1) that describes the scope of the  program,
organizational  structure,  qualifications  of  the staff, available  space and equipment,
methodology employed for sample collection and analysis, and QC procedures.

13.3 References

1. Weber, C. I., Editor, Biological Field and Laboratory Methods for Measuring the Quality
   of Surface Waters and Effluents, 2d Edition, EPA-670/4-73-001, U.S. EPA (July 1973).
2. Nacht, L., and Weber, C. I., BIO-STORET Final Design Specification, U.S. EPA (1976).
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                                      Chapter 14

                                LABORATORY SAFETY
14.1  Law and Authority for Safety and Health

Public Law 91-596 is the Occupational Safety and Health Act of 1970 (1). The purpose of
this act is the following:

   To assure safe and healthful working conditions for  working men  and women; by
   authorizing enforcement of the standards developed under the act; by assisting and
   encouraging the States  in  their  efforts to assure  safe and  healthful working
   conditions; by providing  for research, information, education, and training in the
   field of occupational safety and health; and for other purposes.

The intent  of the act (1) is "to assure so far as possible every working man and woman in
the Nation safe and healthful working conditions and to preserve our human resources."

The responsibility for promulgating and enforcing occupational safety and health standards
rests with the Department of Labor. The Department of  Health, Education, and Welfare is
responsible  for conducting  research  on  which  new standards can  be  based,  and  for
implementing  education and training programs for producing an adequate  supply of
manpower to implement the purposes of the act. These responsibilities are performed by the
National Institute for Occupational Safety and Health (NIOSH).

Section 19(a) of Public Law 91-596 states the following (1):

   It shall be  the responsibility of the head of each Federal agency to  establish and
   maintain an effective and comprehensive occupational safety and  health program
   that is consistent with the standards promulgated under section 6. The head of each
   agency shall (after consultation with representatives of the employees thereof)-

       (1)  provide safe and healthful places and conditions of employment, consistent
           with the standards set under section 6;

       (2)  acquire,  maintain, and  require  the  use of  safety equipment,  personal
           protective equipment, and devices reasonably  necessary to protect employ-
           ees;

       (3)  keep adequate records of all occupational accidents and illnesses for proper
           evaluation and necessary corrective action;

       (4)  consult with the  Secretary with regard  to the adequacy  as  to  form and
           content of records kept pursuant to subsection (a)(3) of this section; and

       (5)  make an annual report to  the Secretary  of Labor with  respect to occupa-
           tional  accidents and injuries and  the agency's program under this section.
           Such report shall include any report submitted under section 7902(e)(2) of
           title 5, United States Code.
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Executive Order 11807 was issued in the fall of 1974 to provide general direction to the
heads of Federal agencies and to the Secretary of Labor in establishing occupational safety
and health programs in the Federal Government. The executive order  details the following
duties:

    a.  Appointment of a Safety and Health Official.

    b.  Establishment of a management information system.

    c.  Establishment of an occupational safety and health program.

       (1) Adoption  of safety and health standards as effective as the Secretary of Labor's
           standards.

       (2) Institution of procedures  for. processing reports from employees on hazardous
           conditions.

       (3) Institution of periodic inspection of facilities.

       (4) Provision for abatement of hazards in facilities.

    d.  Provision for training of agency personnel.

       (1) Training of supervisors  at all levels.

       (2) Training of those responsible for conducting inspections of facilities.

       (3) Training of other  employees. Attention is called  to the list of OSHA training
           requirements.

    e.  Assistance of the  Secretary of Labor.

       (1) Compliance with the recordkeeping and reporting requirements.

       (2) Observation of the guidelines issued in 28 CFR 1960.

       (3) Cooperation with  the  Secretary of Labor in the  performance of his responsi-
           bilities.

    f.  Issuance of guidelines for a safety and health program.

    g.  Prescription of recordkeeping and reporting requirements.

    h.  Provision of consulting services to Federal agencies in adoption  of standards, training
       agency personnel, and  in other matters.

    i.  Upon  request and  subject  to reimbursement,  performance  of such  services as
       evaluation of safety and health conditions in the agency, recommendation on the
       adoption  of standards,  inspection of facilities  for safety and health hazards, and
       training of agency personnel in safety and health matters.
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    j.   Evaluation of agency programs and report of the condition to the President. This
        item in the executive order gives to the Secretary of Labor a degree of enforcement
        of safety and health rules and regulations within Federal agencies.

    k.   Section 4 continues the Federal Advisory  Council  on Occupational  Safety  and
        Health. Note that at least one-third of the members are to be labor representatives.

 14.1.1 Occupational Safety and Health Administration Regulations


 The Occupational Safety and Health Act of 1970 covers laboratory workplaces as well as
 industrial and  manufacturing workplaces (1). Many large  laboratories  have already come
 under the scrutiny of the Occupational Safety  and Health Administration (OSHA); small
 and medium-sized laboratories can expect direct involvement in the future.

 The 1970 act set up NIOSH within the U.S. Department of Health, Education, and Welfare.
 NIOSH provides  OSHA  with the scientific information it  needs to effectively  perform its
 regulatory function.

 The initial OSHA regulations were, and in some measure still are, a collection of many
 well-established standards taken  from industry and from standards-making groups. The
 American National Standards Institute, the  National Safety Council, the National Fire
 Protection  Association, and the American  Society for Testing and Materials were  some of
 the prime  sources for these OSHA  standards.  Certain  existing State health  and safety
 regulations that predated OSHA were used to develop the Federal OSHA regulations.

 Efforts  are continually underway to refine  and quantify current OHSA regulations  through
 court decisions resulting from appeals of compliance citations, through continuing reviews
 of standards by OSHA safety compliance officers, through the work of NIOSH, and  through
 internal reviews.

 Because of the continual publication of revisions of the regulations consisting of refinements
 and clarifications, as well as dissemination of newly issued regulations, laboratory operators
 must expend great efforts to keep  strictly  up to date. What was permitted yesterday may
 not be permitted today.

 The first place  to start in keeping up to date on OSHA regulations is to obtain a copy of the
 Federal  or State regulations  that apply. In  States not operating their own OSHA function,
 copies of applicable regulations are  usually  available without charge from the local office of
 the U.S. Department of Labor. In other States, copies of their regulations are available from
similar State offices and boards either free or at a nominal charge. In either case, appropriate
 steps must be taken to keep up to date on  revisions and reissues. Usually this means getting
on a mailing list  for automatic receipt of  this  material as it is published. Because entire
sections of the regulations may be reissued to incorporate only a  few changes, it is usually
necessary to completely study these reissues to determine the actual change that has been
made.

As OSHA moves  more into the complicated areas of chemical and biological  laboratory
workplaces,   the  level  of  the   compliance  inspector's  knowledge must  be increased
accordingly.
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14.1.2 Federal and State OSHA

There is no completely identical OSHA standard in force throughout the United States.

A provision of the act of 1970 permits Federal OSHA  to certify individual State OSHA
operations  when  they  are  satisfied  that  applicable State  regulations and compliance
enforcement methods fulfill the provisions of the Federal act (1).

While many State OSHA applications are in process, the following States and territories are
certified or at least provisionally certified to permit their own OSHA operation:

       Alaska
       Arizona
       California
       Colorado
       Connecticut
       Hawaii
       Indiana
       Iowa
       Kentucky
       Maryland
       Michigan
       Minnesota
       Nevada
       North Carolina
       Oregon
       South Carolina
       Tennessee
       Utah
       Vermont
       Washington
       Wyoming
       Virgin Islands

All other states and territories are under Federal OSHA jurisdiction.

Even though  the Federal Government supports 50 percent  of the cost of State OSHA
programs, these States apparently would prefer that the Federal Government take on the
entire cost burden for them.,

An  important difference between  Federal  and  State  OSHA operations  lies in  their
jurisdictions.  While  State  OSHAs are responsible for State-operated workplaces, Federal
OSHA  can only  inspect  Federal  workplaces.  It  cannot enforce compliance. There is,
however, a current effort by the General Accounting Office to urge Congress to remove this
restriction on Federal OSHA's effectiveness in dealing with Federal workplaces.

While Federal OSHA is not permitted to offer a consulting service,  most State OSHAs can
and  do. Some who were unaware of this difference have called local Federal OSHA offices
for advice. All they  succeeded in doing was  to invite an inspection. Normally, however,
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inspections  of facilities, be  they  manufacturing  or laboratories, are triggered  by  an
employee's complaint  or an accident report, either as required by law or  through police,
fire, or hospital channels.

Reactions to OSHA operations vary widely. Many laboratories have been cited for violations
and have been heavily  fined. Yet Dr. David Pettit, Technical Director of Kelco's operations
in San Diego, says, "We feel that OSHA standards are not unrealistic, just good laboratory
practice."

14.2 EPA Policy on Laboratory Safety

EPA has issued an Occupational Safety and Health Manual (3) in  which policy, responsi-
bilities, accident  reporting,  inspections, standards, and training are  described. The Agency
has also issued  a Safety Management Manual (4) that contains  information  on safety
protection plans at EPA facilities and air, water, and road safety.

The EPA Occupational Safety and Health Manual (3) establishes policy, responsibilities, and
procedures for the conduct of the EPA safety and health program.

The policy  of EPA is  to  administer its  programs  in  a  manner that assures  adequate
protection  of its own  employees and property, and that for which it has a responsibility.
Every manager, supervisor,  and employee is responsible for identifying risks, hazards, and
unsafe situations  or practices and for taking steps to insure adequate safety in the activities
under his supervison.

A facility safety officer designated for each unit  must be responsible for assisting the
officer-in-charge in developing,  organizing,  directing, and evaluating the safety and health
program and coordinating  illness and  inquiry reporting  and recordkeeping requirements;
analyzing accidents and injuries for  prevention and control; and providing technical advice
in the implementation of program standards and policy.

Safety in any laboratory requires continuing attention. Use of new or different techniques,
chemicals, and equipment requires  careful  reading, instruction, and supervision, and may
require consultation with other people with special knowledge or experience.

Prevention of laboratory accidents  requires  positive attitudes toward safety and training,
and suitable information for understanding laboratory  and  chemical hazards  and  their
consequences.

Responsibility for safety  within the laboratories for an organization may be considered to
exist at three different levels—individual, supervisory (or instructional), and organizational
(or institutional).

The division of responsibility needs to be clearly assigned  and accepted, steps need to be
taken to see that  the responsibilities  are exercised, and the assignments need  to be reassessed
if unexpected problems develop.

Each individual who works  in a laboratory is responsible  for learning the health and safety
hazards of the chemicals he will be using or producing,  and the hazards that may occur from
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the equipment  and techniques he  will  employ, so  that  he  can design  his setup  and
procedures to limit the effects of  any accident. The individual  should investigate  any
accident that occurs, and record and report the apparent causes and the preventive measures
that may be needed to prevent similar accidents.

The supervisor has the  responsibility for  giving all the necessary directions, including the
safety measures  to be used, and the responsibility of seeing that employees  carry out their
individual  responsibilities.  Whoever  directs the  activities  of  others has  a  concurrent
responsibility to  prevent accidental injuries from occurring as a result of the activities.

The organization  of which the laboratories are  part has a fundamental responsibility to
provide the facilities, equipment, and maintenance for a safe working environment and to
provide an organized program to make  the improvements necessary for a safe working
environment.  Unless the  organization fulfills  its responsibilities, it  cannot expect its
supervisors, employees, or students to fulfill their responsibilities for laboratory safety.

The Environmental Protection Agency  has  a" designated safety  and health  official who is
responsible for assuring  that formal safety and health inspections are conducted at all EPA
workplaces. He  will  notify  the  Administrator regarding  uncorrected safety  and health
deficiencies.

14.2.1 Formal Safety Inspections

Formal safety and health  inspections  at workplaces where there  is an increased risk of
accident, injury, or illness because of the nature of the work performed, as in the case of
chemical operations and material-handling or material-loading operations, must be made by
a safety  and health specialist. A "Safety  and  Health Specialist" is defined  in  29 CFR
1960.2(h)  as a  person  who  meets the  Civil Service standards for  the position of Safety
Manager/Specialist  GS-018,  Safety  Engineer GS-803,  Fire  Protection Engineer  GS-804,
Industrial Hygienist GS-690,  Fire Protection Specialist/Marshall GS-081, or Health Physicist
GS-1306,  or who is an employee  of an  equally qualified military agency or nongovernment
organization.

Formal safety and health inspections need not be made by a safety and health specialist at
workplaces where  there is little risk involved, but should be conducted by a person having
sufficient  training  and experience in the safety and health needs  of the workplaces involved
to adequately perform  the duties of an inspector as set forth in Executive Order 11807.
Inspectors  should  be accompanied on formal safety and health inspections by representa-
tives of the officer in charge of the reporting unit being inspected and representatives of the
employees of such establishments. Management and employee representatives should be
familiar with and maintain OSHA standards.

To insure  safe  and healthful working  conditions for EPA  employees, safety and health
inspectors  are authorized to  enter without delay and  at  reasonable times, any building,
installation, facility, construction site, or other area, workplace, or environment where work
is performed by employees of the Agency, to inspect and investigate during regular working
hours  and at other reasonable times,  and within reasonable  limits and in a reasonable
manner, any such place of employment and all pertinent conditions, structures, machines,
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apparatus, devices,  equipment, and materials  therein;  and to  question privately  any
employee, or any supervisory employee, or any officer in charge of a reporting unit.

14.2.2  Informal Safety Inspections

An informal safety and health inspection is performed on either a scheduled or unscheduled
basis by  the  facility safety officer, regional  safety  officer, supervisory management, or
members  of  a safety and health  committee.  EPA Form 1440-2,  Health and Safety
Inspection Checklist (fig.  14-1), shall be used by the inspector or spokesman of a safety and
health committee conducting the inspection to note safety and health deficiencies identified
during the inspection process.

A more detailed checklist for safety evaluation of the laboratory is given in appendix A.
This inspection list contains many specific recommendations and guidelines for laboratory
safety.

14.3 Laboratory Safety Practices*

14.3.1  Introduction

14.3.1.1 Safe Use, Handling, and Storage of Chemicals

Chemicals in any form can be safely stored, handled, and used if their hazardous  physical
and  chemical  properties are fully understood and the necessary  precautions,  including the
use of proper safeguards and personal protective equipment are observed.

The  management of every unit within a manufacturing establishment  must give whole-
hearted support to a well-integrated safety policy.

14.3.1.2 General Rules for Laboratory Safety

Supervisory personnel should think "safety." Their attitude toward fire and safety standard
practices is reflected in the behavior of their entire staff.

A safety program is only  as strong as the worker's will to do the correct  things at the right
time.

The fundamental weakness of most  safety programs lies in too  much lip service to safety
rules and not enough action in putting them into practice.

Safety practices should be practical and enforceable.

Accident  prevention is based on certain common standards of  education and training of
personnel, and provision of safeguards against accidents.
This description was  prepared by Paul  F.  Hallbach,  Chemist, National Training and
 Operational Technology Center, U.S. EPA, Cincinnati, Ohio 45268.
                                         14-7

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HEALTH AND SAFETY INSPECTION CHECKLIST


1 TITLE
NAME 'NUMBER OF BUILDING INSPECTED (Use separate form for each huiltiingl [ REPORTING UNIT
DATE

PART 1 PHYSICAL CONDITIONS (Check each applicable Item)
ITEM

8 EGRESS
9 LIGHTING
10 VENTILATION
7 1 FLAMMABLE OR NOXIOUS OUST OR VAPORS


IS FIRE SUPRESSiON (Including extinguishers)


SAT








UNSAT








ITEM
19 WATER (anri-svphi>ne and cross connections)
20 ELECTRICAL (fuses, grounding, etc ;
23 PARKING AREA
27 HAZARDOUS WARNING SIGNS
28 EMISSION OF POLLUTANTS lair fluid, solids)
29 OCCUPATIONAL NOISE EXPOSURE
31 PROVISIONS FOR HANDICAPPED


32 OTHER


SAT








UNSAT








PART ll PROCEDURES AND INSTRUCTIONS {Check each applicable item}
33 MATERIALS HANDLING

35 BUILDING MAINTENANCE

EQUIPMENT
38 HA2ABO MONITORING EQUIPMENT
/carton monoxide radiation, etc /


41 BOATING OPERATIONS


































AND HEALTH




53 OTHER
























REMARKS fConrinueon back, if necessary) (NOTE Use EPA Form )44Cf> '
9
EPA Form 1440-2 (Rev 5-771
                            PREVIOUS EDITION MAV BE USED UNTIL SUPPLY IS EXHAUSTED
                    Figure 14-1.  Health and safety inspection checklist.

14.3.2 Laboratory Design and Equipment
14.3.2.1 Type of Construction
The construction of the laboratory should generally be fire resistant or noncombustible.
                                             14-8

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 Multiple story buildings should have adequate means of exit.

 Stairways should be enclosed with brick or concrete walls.

 Laboratories should have adequate exit doors to permit quick, safe escape in an emergency
 and to protect the occupants from fires or accidents in adjoining rooms. Each room should
 be  checked to make sure there is.no chance of a person being trapped by fire, explosions, or
 release of dangerous gases.

 Laboratory rooms in which most of the work is performed with flammable liquids or gases
 should be provided with explosion-venting windows.

 14.3.2.2 Arrangement of Furniture and Equipment

 Furniture should be  arranged  for maximum use of available space and  should provide
 working conditions that are efficient and safe.

 Aisles between benches should be at least 4 ft wide to provide adequate room for passage of
 personnel and equipment.

 Desks should be isolated from benches or adequately protected.

 Every laboratory should have an eyewash station and a safety shower.

 14.3.2.3 Hoods and Ventilation

 Adequate hood facilities should be installed where highly  toxic  or highly  flammable
 materials are used.

 Hoods should be ventilated separately and  the  exhaust  should  be terminated at a  safe
 distance from the building.

 Makeup air should be supplied to rooms or to hoods to replace the quantity of air exhausted
 through the hoods.

 Hood ventilation systems are best designed to have an airflow of not  less  than 60 ft/min
 (linear) across the  face of the hood with all doors open, and 150 ft/min (linear) if toxic
 materials are involved.

 Exhaust  fans should be sparkproof if exhausting flammable vapors and corrosive resistant if
handling corrosive fumes.

Controls for all services should be located at the front of the hood and should be operable
when the hood door is closed.

All  laboratory rooms should have the air changed continuously at a rate depending on the
materials being handled.

 Recent California OSHA regulations require the presence of a means  of visual indication of
 the existence of the airflow in the hood and specify the height and type of hood exhaust
 permitted.
                                         14-9

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14.3.2.4  Electrical Services

Electrical outlets should be placed outside of hoods to afford easy access and thus protect
them from spills and corrosion by gases.

Noninterchangeable plugs should be provided for multiple electrical services.
                                                     *

Adequate outlets should be provided  and should be of the three-pole-type to provide for
adequate grounding.

Rubber  or  nonconductive  composition shoe  soles  should be  required  (except when
flammable vapors are present). Shoe soles should not be of a type that readily absorbs water
or other liquids.

14.3.2.5  Storage

Laboratories should provide  for adequate  storage space for mechanical equipment  and
glassware that will be used regularly.

Flammable solvents should not be stored in glass bottles over 1 1 in size. Large quantities
should  be stored in metal safety  cans. Quantities requiring containers larger than  1 gal
should be stored outside the laboratory.

Explosionproof refrigerators should be used for the storage of highly volatile and flammable
solvents.

Cylinders of compressed or liquefied gases should not be stored in the laboratory.

Alphabetized storage of chemicals should be avoided to prevent the unintentional mixing of
two incompatible chemicals in an accident situation.

An appropriate antidote must be readily available for every stored chemical compound for
which an antidote is specified.

U.3.2.6  Housekeeping

Housekeeping plays an important role in reducing the frequency of laboratory accidents.
Rooms  should be kept in a neat and orderly condition. Floors, shelves, and tables should be
kept free from dirt and from all apparatus and chemicals not in use.

A cluttered  laboratory is a dangerous place to work. Maintenance of a clean and orderly
work space is indicative of interest, personal pride, and safetymindedness.

Passageways should be  kept clear to all building exits and stairways.

Metal containers should be provided for the disposal of broken  glassware and should be
properly labeled.

Separate approved waste  disposal cans should be  provided  for  the  disposal  of waste
chemicals.
                                        14-10

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Flammable liquids  not miscible with water and corrosive materials or compounds that are
likely to give off toxic vapors should never be poured into the sink.

Laboratory operators  must be sure that unguarded rotating equipment such as belt-driven
vacuum pumps is provided with guards all the way around and that the guards are always in
place.

Whenever heavy laboratory  equipment must be moved  frequently,  rollers should be
provided. In other cases, proper lifting equipment should be available.

14.3.2.7 Fire Protection

Laboratory  personnel should be  adequately  trained  regarding  pertinent  fire hazards
associated with their work.

Personnel should know rules of fire  prevention and methods of combating fires.

Fire extinguishers (CO2  type) should be provided at convenient locations and personnel
should be instructed in their use.

Automatic sprinkler systems are effective for the control of fires in chemical laboratories.

14.3.2.8 Alarms

An approved fire-alarm system should be provided.

Wherever a hazard  of accidental release of toxic gases exists, a gas alarm system to warn
occupants to evacuate the building should be provided.

Gas  masks of oxygen or compressed-air-type should be located near exits  and selected
personnel trained to use them.

14.3.3 Handling Glassware

14.3.3.1  Receiving, Inspection, and Storage

Packages containing glassware should be opened and inspected for cracked or nicked pieces,
pieces with flaws that may become cracked in use, and badly shaped pieces.

Glassware should be stored on well-lighted stockroom shelves designed and having a coping
of sufficient height  around the edges to prevent the pieces from falling off.

14.3.3.2 Laboratory Practice

Select glassware that is designed for  the type of work planned.

To cut glass  tubing or a rod, make a straight, clean  cut with a  cutter or file at the point
where  the piece is  to  be  severed. Place a towel over the piece  to protect the hands and
fingers, then break away from the body.
                                        14-11

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Large size tubing is cut by means of a heated nichrome wire looped around the piece at the
point of severance.

When it is necessary to insert a piece of glass tubing or a rod through a perforated rubber or
cork stopper, select the correct bore so that the insertion can be made without excessive
strain.

Use electric mantels for heating distillation apparatus, etc.

To remove glass splinters, use a whisk broom and a dustpan. Very small pieces can be picked
up with a large piece of wet cotton.

14.3.4 Gases and Flammable Solvents

14.3.4.1  Gas Cylinders

Large cylinders must be securely fastened so that they cannot be dislodged or tipped in any
direction.

Connections, gages, regulators, or fittings  used with other  cylinders must not be  inter-
changed with oxygen cylinder fittings because of the possibility of fire or explosion from a
reaction between oxygen and residual oil in the fitting.

Return  empty cylinders promptly with protective caps replaced.

 14.3.4.2 Flammable Solvents

Store in well-ventilated designated areas.

Flash point: the temperature at which a liquid gives off vapor sufficient to form an ignitible
mixture with the air near the surface of the liquid or within the vessel used.

Ignition temperature:  the minimum temperature required to initiate or cause self-sustained
combustion independently of the heating or heated element.

Explosive or flammable  limits:  for  most flammable liquids, gases, and solids there is a
minimum concentration of vapor in air or oxygen below which propagation of flame does
not  occur on contact  with a source of ignition. There  is also  a maximum proportion  of
vapor or gas in air above which propagation of flame does not occur. These limit mixtures of
vapor or gas with air, which if ignited will just propagate flame, are known as the "lower and
higher explosive or  flammable limits."

Explosive range: the difference between the lower and higher explosive or flammable limits,
expressed in terms of percentage of vapor or gas in air by volume.

 Vapor density: the  relative density of the vapor as compared with air.
                                         14-12

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Underwriter's Laboratories classification: a standard classification for grading the relative
hazard of the various flammable liquids. This classification is based on the following scale:

       Ether class                   100
       Gasoline class              90 to 100
       Alcohol (ethyl) class        60 to 70
       Kerosene class              30 to 40
       Paraffin oil class            10 to 20

Extinguishing agents that are appropriate for each of the four classes of fires are required.

14.3.5 Chemical Hazards

14.3.5.1  Acids and Alkalies

Some of the most hazardous chemicals are the strong or mineral acids such as hydrochloric,
hydrofluoric, sulfuric, and nitric.

Organic acids are less hazardous because of their comparatively low ionization potentials;
however,  such  acids as phenol (carbolic acid),  hydrocyanic, and oxalic  are extremely
hazardous because of their toxic properties.

Classification of acids is according to mineral or  organic composition.  Acids should be
stored together, except that perchloric acid should not be placed next to glacial acetic acid.
Picric acid should be stored separately.

14.3.5.2  Oxidizing Materials

Oxidizing agents, in contact with  organic matter, can cause  explosions and fire.  They are
exothermic  and decompose  rapidly,  liberating oxygen,  which reacts with organic  com-
pounds.

Typical hazardous oxidizing agents are-

       Chlorine dioxide
       Sodium chlorate; chlorates
       Potassium chromate
       Chromium trioxide
       Perchloric acid; perchlorates

 14.3.5.3 Explosive Power

 Many chemicals are explosive or form compounds that are explosive and  should be treated
 accordingly.

 A few of the more common examples  of this class  of hazardous materials are-

        Acetylides
        Silver fulminate
                                         14-13

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       Peroxides
       Peracetic acid
       Nitroglycerine
       Picric acid
       Chlorine and ethylene
       Sodium metal
       Calcium carbide

14.3.5.4 Toxicity

Laboratory chemicals improperly stored or handled can cause injury to personnel by virtue
of their toxicity.

There are four types of exposure to chemicals:

    a.  Contact with the skin and eyes

    b.  Inhalation

    c.  Swallowing

    d.  Injection

Special classes of toxic agents:

    a.  Carcinogens-laboratory operators  should  recheck the  OSHA  1974 regulations  on
       carcinogens.

    b.  Mercury—complete cleaning of spills is essential for compliance with OSHA limits.

14.3.6 Precautionary Measures

14.3.6.1  Clothing and Personal Protective Equipment

Chemical  laboratories  should have  special  protective  clothing and equipment readily
available for emergency  use  and  for secondary  protection  of personnel  working  with
hazardous materials.

Equipment should be provided for adequate—

    a.  Eye protection

    b.  Body protection

    c.  Respiratory protection

    d.  Foot protection

    e.  Hand protection
                                         14-14

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14.3.6.2 Bodily Injury

Burns, eye injuries, and poisoning are the injuries with which laboratory people must be
most concerned.

First emphasis in the laboratory should be on preventing accidents. This means observing all
recognized safe practices using  necessary personal protective equipment and exercising
proper control over poisonous substances at the source of exposure.

So that a physician can be summoned promptly, every laboratory should post the names,
telephone numbers, and addresses of doctors to be called in an emergency requiring medical
care.

A consulting physician should specify the type and extent of first aid materials required for
the laboratory.

14.4  Report of Unsafe or Unhealthful Condition

In EPA a procedure has been established for reporting an unsafe or unhealthful condition by
the employee  or supervisor. The procedure  also provides for communication between the
employees; supervisors; safety official; head of the unit;  and, in  the case of an unresolved
report, the Department of Labor.

A sample of an unsafe or unhealthful condition reporting form is shown in figure 14-2, and
a sample notice of an unhealthful or unsafe condition is shown in figure 14-3.

14.5  References

1. Public Law 91-596, Occupational Safety and Health Act of 1970 (Dec. 29, 1970).
2. Occupational Safety and Health Manual, U.S. EPA (Jan. 8, 1976).
3. Safety Management Manual, U.S. EPA, TN 1440.1 (Dec. 4,  1972).
                                        14-15

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                                                                                         RNN1440.011
                            REPORT OF UNHEALTHFUL OR UNSAFE CONDITION
 BRIEF DESCRIPTION OF UNHEALTHFUL OR UNSAFE CONDITION
 OCCUPATIONAL SAFETY AND HEALTH STANDARD VIOLATEO (If  LOCATION (Include organization. Facility and Building/
 ACYlON TAKEN BY SUPERVISOR
 •IONATURI
                                        EMPLOYING ORGANIZATION
                                                                              DATE
EPA Perm 14404 
-------
NOTICE OF UNHEALTHFUL OR
TO (Name of Offtcer-tn-Chargt of Reporting Unit)
REPORTING UNIT
An inipection conducted by me or
following violationd) of EPA Occ
with the Occupational Safety and t
ITEM
MO.

STANDARD, REGULATION
OR SECTION VIOLATED


UNSAFE WORKING CONDITION
FROM (Name of Inspector)
Occupational Health and Safety Office
Washington. IXC 20460

upational Health and Safety Standards. These Standards have been adopted in compliance
he Health Act of 1970, PL 91-956, Section 19.
DESCRIPTION OF
VIOLATION

LOCATION OF
VIOLATION

NO. OF WORKING DAVS
BY WHICH VIOLATION
MUST BE CORRECTED
AND DATE

Subpart 0 of 29CFR 1960.33, Safety and Health Provisions for Federal Employees, requires that a copy of this Notice shall
be posted immediately in a prominent ptace at or near each place that the violation(s) referred to in the Notice occurred. The
Notice must remained posted until all violations cited therein are corrected, or for three (3) working* days, whichever period is
longer. A copy of this Notice shall be sent to the Health and Safety Committee of the establishment or Reporting Unit and to
any person(s) who made a report of the unhealthful or unsafe condition which precipitated this inspection pursuant to the
provisions of 29CFR 1960.31.
Subpart D of 29CFR 1960.34 requires the Officer-m-Charge of the Reporting Unit to immediately submit an abatement plan
to the Designated Agency Safety and Health Official, if, in his judgment, the correction of the violation will not be possible
within thirty (30) working days*. Such plan shall contain an explanation of the circumstances of the delay in abatement; a
proposed timetable for the abatement, and a summary of steps being taken in the interim to protect employees. A copy of
the plan shall be sent to the Health and Safety Committee of the establishment or Reporting Unit and to any person(s) who
made a report of the unhealthful or unsafe condition which precipitated this inspection pursuant to the provisions of 29CFR
1960.31.
"Under the Occupational Safety and Health Act, the term "Working Day" means Monday through Friday but does not
inc ude Saturday, Sunday, or Federal Holidays.
SIGNATURE OF HEALTH AND SAFETY OFFICER
DATE
EPA Hq Form 14408 (8 771
            Figure 14-3. Notice of unhealthful or unsafe condition.
                                    14-17

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                           APPENDIX A
SUGGESTED CHECKLIST FOR THE SAFETY EVALUATION OF EPA LABORATORY AREAS
                              A-1

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 Organization:

 Location:  	
 Room(s):  	
      Date:
Building:

By: 	
Item Inspected
Yes
No
N.A.
Comments
                                            Fire Prevention

   I.  Is fire alarm facility available? [.36(b)(7)]

   2.  Are all exits maintained to provide free and unob-
      structed egress from all parts of building? [.36(b)(4)]

   3.  Are all exits free of locks or fastening devices that
      could prevent free escape? l.36(b)(4)]
   4.  a. Is the fire detection system in working order?
      b. Is the sprinkler system in working order?
      c. Are fire doors in working order? [.36(d)(2>]
   5.  Are corridors and hallways at least 44 in wide?
   6.  Do all exits discharge directly to a street, yard,
      court, or other open space? [.37(h)(l)]

   7.  Are all exits marked by proper sign and illuminated?
      Are letters in sign not less than 6 in high, 3/4 in
      wide? [.37(q)(8)]

   8.  Is access to exits marked in all cases where the exit or
      the way to reach it is not immediately visible?
      [.37(q)(5)]

   9.  Is care taken to insure that no exit signs are obscured
      by decorations, furniture, or equipment? [.37(q)(3)J

  1 0.  Is exit access arranged so that it is not necessary to
      travel toward any high hazard area to escape?
      t.37(f)(5)J
Note:  Adapted  from a safety inspection work sheet developed by the Center for Disease Control (CDC).
The pertinent section'of the Code of Federal Regulations, title 29, part 1910 is given within brackets at the
end of each item.
                                                A-2

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Listed  below are explanations given by OSHA to questions that are not immediately clear on the safety
checklist for laboratory areas. Each explanation is numbered according to the corresponding question on
the facing page.
   1.   Self-explanatory.

   2.   Self-explanatory.


   3.   At no  time  should  an exit door be locked or fastened in a manner that  prevents it from being
       immediately opened from the inside of the building in the event of emergency. Safety inspectors
       should check all doors marked "EXIT" to insure that they can be readily opened.

4a,b.   The  building manager should conduct periodic  tests (as recommended by  the manufacturer or as
       required by local code) to insure  proper working order of the fire detection system  and the
       automatic sprinkler system.

  4c.   Fire  doors are designed to be closed in  the event  of  fire. Automatic fire  doors normally remain
       open; however, the heat produced by a fire will cause them to close. Regular fire doors are designed
       to stay closed at all times, except for the passage of personnel. No fire door should ever be blocked
       open as this will interfere with its function. Fire doors are typically used to enclose stairways and to
       separate buildings and corridors.

   5.   Self-explanatory.


   6.   An exit should never discharge into a location that  could  potentially trap personnel. For example,
       an exit should not discharge into a closed  courtyard.

   7.   Self-explanatory.
   8.   A sign reading "EXIT" or similar designation, with an arrow indicating the direction, shall be placed
       in every location where the direction of travel to reach the nearest exit is not immediately apparent.
   9.   Self-explanatory.
  10.  In designing and maintaining  exit routes from a building, care should be taken to avoid routing
       people through or near a high hazard area. An example of a high hazard area is a corridor or room
       where flammable liquids are stored.
                                                A-3

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Item Inspected
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
Are aisles maintained clear and unobstructed for
movement of personnel and fire-fighting equipment?
[.22(b)(l)l
Is all fire protection equipment and apparatus identi-
fied with the color red? [.144(a)(l)l
Are portable fire extinguishers maintained fully
charged and operable and kept in designated places at
all times? [.157(a)(l)J
Are fire extinguishers conspicuously located, readily
accessible, and available along normal paths of travel?
[.157(a)(2)]
Are extinguishers and locations conspicuously
marked to indicate intended usage? [.157(a)(4)J
Are extinguishers mounted so that the top is not
more than 5 ft above floor; not more than 3Vi ft if
weight equals more than 40 Ib? [.157(a)(6)l
Are all extinguishers mounted in cabinets placed so
that the instructions face outward? [.157(a)(7)l
Are extinguishers available suited to the class of fire
anticipated in each area? [.157(b)(l)l
Are extinguishers placed according to distances for
proper coverage?
Within 75 ft-class A.
Within 50 in-class B. [.157(c)J
Are extinguishers inspected, maintained, and re-
placed by spares when they are discharged or miss-
ing? [.157(d)]
Are laboratory rooms with potential fire hazards
equipped with proper extinguishers for emergency
situations? [.157(b)l
If flammable liquids are used in a laboratory, is the
mechanical ventilation sufficient to remove vapors
before they reach a hazardous concentration?
[.106(e)(2)(iii)]
Yes












No












N.A.












Comments












A-4

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11.   Self-explanatory.
12.  Self-explanatory.


13.  Self-explanatory. During a safety  inspection all fire extinguishers should be  checked aginst the
     requirements of this question.


14.  Fire extinguishers should never be located in places where they are concealed from general view.
15.   Fire extinguishers must be clearly labeled to indicate the type of fire they are capable of fighting.
     The following code is used to classify types of fires:

         Class A -fires in ordinary combustible materials such as wood, cloth, paper, and rubber
         Class fi-fires in  flammable liquids, gases, and greases
         Class C-fires that involve energized electrical equipment where the electrical nonconductivity
            of the extinguishing medium  is of importance; when electrical equipment is deenergized,
            extinguishers for class A or B fires may be safely used
         Class D~fires in combustible metals such  as magnesium, titanium, zirconium,  sodium, and
            potassium

16.   Inspector should make certain that no fire extinguishers (other than wheeled-type extinguishers) are
     placed on the floor.
17.  Self-explanatory.


18.  See explanation to question No.  15 for classification of fire hazards. Fire extinguishers (of more
     than one type, if necessary) should be selected and located according to anticipated fire hazards.

19.  Self-explanatory.
20.   Self-explanatory.
21.   In certain instances, laboratories can be fire traps. When this is the case, fire extinguishers should be
      provided  inside the laboratory so that occupants can fight their way out of a fire emergency. Safety
      inspectors should check for escape routes to the nearest corridor when considering this question.

22.   Self-explanatory.
                                                A-5

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Item Inspected
23. Are hose outlets within easy reach of persons stand-
ing on floor and not over 6 ft from floor?
24. Do all connections on dry standpipes have a sign
reading "DRY STANDPIPE-FOR FIRE DEPART-
MENT USE ONLY"? [.158(b)(7)]
25. Are automatic sprinkler systems provided with at
least one fire department connection with at least
4-in pipe size? (.159(b)(l)]
26. Are fire department connections designated "AUTO
SPKR" or "OPEN SPKR"? [.159(b)(4)(v)J
27. Is there a water flow detection device on the sprin-
kler system that will activate the fire alarm?
28. Are fire alarm boxes readily accessible and within
normal path distance of 200 ft? [.163(b)(3)]
29. Are all fire alarm systems inspected and tested at
weekly intervals? [.163(c>]
30. Are "NO SMOKING" signs posted in prohibited
areas? [.106(d)(7)(iii)]
Yes








No








N.A.








Comments








                                   Flammable Liquid Storage
3 1 .  Are drums which contain flammable liquids con-
     structed of noncombustible materials?
32.  Are storage drums vented? [.106(b)(2)(iv)l

33.  Are flammable liquids stored in proper containers?
34.  Are safety cans and portable containers of flammable
     liquids painted red with yellow band or name of con-
     tents? [.144(a)(l)(ii)J

35.  Are storage cabinets being used for storing flammable
     liquids? [.106(d)(3)l

36.  Are storage cabinets labeled "FLAMMABLE-KEEP
     FIRE AWAY"? (.106(d,)(3)(ii)]
                                              A-6

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23.  This question applies to buildings equipped with water and hose standpipe systems. Hose outlets are
     normally located in stairways or in the corridor immediately outside the stairway.
24.  Self-explanatory. The building manager should be able to answer this question.
25.  Fire department connections to automatic sprinkler systems are normally located on the outside of
     the building being protected. The size of the connection is usually embossed on a metal plate or on
     the connection itself.

26.  The designations "AUTO-SPKR"  or  "OPEN-SPKR" are  found embossed on a plate at the fire
     department connection. Failure to display one of the designations is a violation of OSHA.

27.  This question is self-explanatory. The building manager should know if the facility is equipped with
     a sprinkler waterflow detection device.
28.   Self-explanatory.


29.   This procedure should be part of a regular maintenance program.
 30.   The laboratory supervisor shall designate areas where smoking is prohibited and "NO SMOKING"
      signs shall be placed in these areas.
31.   Flammable  liquid storage  drums should  be  constructed of steel or some other noncombustible
      material.
32.   Self-explanatory.

33.   Flammable liquids may be safely stored in glass containers if the total capacity of the container is 1
      gal or less.  Larger quantities of flammable liquids should  be stored in safety cans approved by a
      recognized testing laboratory.

34.   Self-explanatory.
 35.   Self-explanatory.


 36.   Self-explanatory.
                                               A-7

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Item Inspected
37. Is the storage area provided with either a gravity or
mechanical exhaust ventilation system?
M06(d)(4)(iv)]
38. Are extinguishers available where flammable or com-
bustible liquids are stored? [.106(d)(7>]
39. Is at least one portable fire extinguisher of rating not
less than 12-B units located outside of, but not more
than 10 ft from, door opening into room used for
storage? [.106(d)(7)(i)(a)]
40. Is at least one portable fire extinguisher with rating
not less than 12-B units located not less than 10 ft
nor more than 25 ft from flammable liquid storage
located outside of a storage room but inside of a
building? [.106(d)(7)(i)(b)]
41. Are "NO SMOKING" signs posted in the flammable
or combustible liquid storage areas? [.106(d)(7)(iii)]
Yes
*




No





N.A.





Comments





                                       Electrical Hazards
42.  Are all new electrical installations and all replace-
     ments, modifications, or repairs made and being
     maintained in accordance with the National Electri-
     cal Code? [.309]

43.  Does the interior wiring system have a grounded con-
     ductor? i.e., three-wire system? [.309-NEC(200-2)J

44.  Do all electrical appliances have Underwriter's Labo-
     ratories Inc. approval, or that of some other na-
     tionally recognized testing laboratory?
     [.309-NEC(90-8>]

45.  Are the cords of all electrical equipment in good
     condition, not frayed or spliced, etc.?
     [.309-NEC(400-5)J

46.  Are cords used properly (not run under rugs)?
     [.309-NEC(400-4)J

47.  Is there only one plug-in per socket outlet; i.e., no
     multiple plug-ins to one socket? f.309-NEC(240-2)]

48.  Are the lighting levels such that good illumination is
     provided in all walking, working, and service areas to
     insure safety? [.309-NEC(110-16(e))]
                                              A-8

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37.  The building manager or engineering department should know the answer to this question.
38.  Self-explanatory. Fire  extinguishers approved  for fighting  class B fires  should be available in
     flammable liquids storage areas.

39.  This question is  self-explanatory but should be reread several times for full comprehension. Fire
     extinguisher ratings are often stamped on the title plate along with other specifications. Note: This
     question is to be used only when inspecting flammable-liquid storage rooms.
40.  This question is self-explanatory, but should be reread several times for full comprehension. Note:
     This question is to be used only when inspecting flammable liquid storage outside of a special desig-
     nated room, but inside of a building.
41.  Self-explanatory.
42.  Prior to adding any new electrical facilities to a laboratory, it is the responsibility of the laboratory
     supervisor or building manager to check with the electrical contractor to insure that the National
     Electrical Code is observed. This rule is retroactive to Mar. 15, 1972.
43.  All convenience outlets shall be of the three-pronged type. These outlets should be checked with a
     grounding tester to insure proper wiring.

44.  Approved appliances will bear the label of a recognized testing laboratory.
45.   Self-explanatory.
46.   Self-explanatory.
47.  Multiple outlet (cube) adaptors or extension cords with multiple outlet ends should not be used to
     plug more than one appliance into a single socket.

48.  Self-explanatory.
                                                A-9

-------
Item Inspected
49. Are circuit breaker panels and cutoff switches
located so as to be readily accessible?
[.309-NEC(240-25(b)) and (1926.400(e))]
50. Are all circuit breaker switches marked or labeled?
[.309-NEC(240-25(e)>]
Yes

No

N.A.

Comments

                                A isles, Exits, Floors, and Stairways

51.  Are all floors kept clean and dry? [.22(a)(2)J

52.  Are all floors, areas, and passageways free from pro-
     truding nails, splinters, holes, and loose boards?
     [.22(a)(3)J

53.  Are aisles and passageways clear of all obstructions
     and in good repair? [.22(b)(l)]

54.  Are aisles and passageways wide enough to operate
     equipment safely? [.22(b)(l)]

55.  Is floor loading within posted maximum limits?
     l.22(d)]

56.  Does every floor opening having standard guarded
     railings? [.23(a)(l)]
57.  Do fixed stairs make an angle to the horizontal be-
     tween 30° to 50°? [.24(e)J
58.  Are all opensided floors, platforms, ramps, 4 ft above
     adjacent floor or ground, guarded with railing?
     t.23(c)(l)]
                                               A-10

-------
49.  Circuit breaker cabinets should never be locked.



50.  Each circuit breaker switch shall be labeled as to the lights, outlets, or appliances it controls.




51.  Self-explanatory.

52.  Self-explanatory.



53.  Self-explanatory.


54.  Self-explanatory.


55.  Safe floor loadings must be posted and observed in all buildings and on all floors.
56.  Specifications for standard railing:  A standard railing shall consist of a top rail, intermediate rail,
     and posts. It  shall have a vertical height of 42 in nominal from upper surface top rail to floor,
     platform, runway, or ramp level. The top rail shall be smooth surfaced throughout its length. The
     intermediate rail shall be approximately  halfway between the top rail and the floor, platform,
     runway, or ramp.

     Specifications for standard railing to be used on stairways: A stair railing shall be of construction
     similar to a  standard railing (for a floor opening), but the vertical height shall not be more than 34
     in nor less than 30 in from upper surface of top rail  to surface of tread in line with face of visor at
     forward edge of tread.

57.  All fixed stairways must rise at an angle within the limits shown:
                                                 ACCEPTABLE SAFE ZONE
                                                 _L
                                       50°
                                   30°        HORIZONTAL

 58.   Self-explanatory.
                                               A-ll

-------
Item Inspected
59. Are flights of stairs having four or more risers
equipped with railings or handrails? [.23(d)(l )]
60. Are stair treads reasonably uniform and slip resist-
ant? f.24(f)]
61. Are all places kept clean and orderly and in a sanitary
condition? [.141(a)(lXi)]
62. Are trash receptacles of approved use? [.141(a)(3)]
63. Is every enclosed work place so constructed and
maintained to prevent entrance and harborage of
rodents, insects, and vermin? [.141(a)(4)J
64. Is drinking water potable and available within 200 ft
of location at which employees work?
65. Are toilet facilities adequate for both sexes and in
accordance with regulations listed? [.141(c)(l)]
66. Are toilet rooms constructed so that each water
closet occupies a separate compartment equipped
with door, latch, and clothes hanger? {.141(c)(2)(i)]
67. Does door to toilet room have a self-closing device,
and is entrance screened so interior is not visible
from outside? [.141(e)(2)(iii)]
68. Does every water closet have a hinged open-front seat
made of nonabsorbent material? [.141(c)(3)(ii))
69. Are suitable washing facilities available and main-
tained in a sanitary condition? [.141(d)(l)]
70. If employees are allowed to lunch on the premises, is
an adequate space provided for that purpose?
7 1 . Are adequate waste disposal containers provided?
72. Are change rooms provided for each sex where it is
necessary to change clothes? [.141(e)(l)]
73. Are change rooms provided with separate storage
facilities for street clothes and protective clothing?
74. Are noise levels acceptable? [.95]
Yes
















No
















N.A.
















Comments
















A-12

-------
59.   Self-explanatory.


60.   Stair treads should be free of cracks and other uneven areas.


61.   Self-explanatory.


62.   Trash receptacles used for garbage disposal should be equipped with tight-fitting lids.

63.   Self-explanatory.



64.   Self-explanatory.



65.   Self-explanatory.


66.   Self-explanatory.



67.   Self-explanatory.



68.   Self-explanatory.


69.   Suitable washing facilities consist of a lavatory with hot and cold water, a suitable cleansing agent,
      and individual hand towels.

70.   Self-explanatory. Employees are  not permitted to eat in any laboratory that uses agents that are
      dangerous to health if ingested. It is the responsibility of the laboratory supervisor to enforce this
      rule.

71.   Self-explanatory.


72.   Self-explanatory.


73.   Self-explanatory.
74.  If any employees are exposed to noise levels greater than 90 dB at any time during the day, a safety
     expert should be consulted to determine if corrective measures need to be taken.
                                                A-13

-------
Item Inspected
75. Is necessary protective equipment provided, used, and
maintained in a sanitary, safe, and reliable condition?
[.132(a)J
76. Are eye protectors provided where machines or
operations present the hazard of flying objects, glare,
liquids, radiation? [.133(a)J
77. Are sufficient washing facilities (including eye washes
and deluge showers) available for all persons required
to handle liquids that may burn, irritate, etc.?
I.lSl(c)]
78. Are employees in the area exposed to air contami-
nants only in accordance with proper limits?
79. Is a respiratory protection program used where
needed? [.134(a)(2)l
80. Are written standard operating procedures governing
the selection and use of respirators established?
8 1 . Has the user of the respirator been instructed and
trained in the proper use and limitations of the respi-
rator? [.134(b)(3)l
82. Are respirators regularly cleaned, disinfected, in-
spected, and stored in a convenient, clean, and sani-
tary location? [.134(b)(5)l
83. Has the person assigned the task requiring a respira-
tor been determined physically able to perform the
work and use the equipment by the local physician?
[.134(b)(10)]
84. Are breathing gas containers marked in accordance
with the American National Standards identifying
contents? [.134(d)(4)]
85. Can gas mask canisters be identified by properly
worded labels and color code or atmospheric con-
taminant? [.134(g)(l)]
86. Is the compressor for supplying air to respirators
equipped with necessary safety and standby equip-
ment? [.134(d)(2)(ii)l
Yes












No












N.A.












Comments












A-14

-------
75.  Protective  equipment, including personal protective  equipment,  shall be  provided,  used,  and
     maintained in a sanitary and reliable condition wherever work-associated hazards may cause injury
     or impairment in function of any part of the  body through absorption, inhalation,  or physical
     contact.  Laboratory supervisors should recognize such hazards  and take the action necessary to
     insure that employees use adequate personal protection to avoid injury.

76.  Safety glasses or goggles may be obtained through the CDC Safety Office.
77.  All laboratories using liquids that may burn  or irritate must be equipped with some type of
     emergency eye wash equipment.
78.  If laboratory supervisors have any questions concerning safety concentrations of air contaminants,
     they should contact the CDC Office of Biosafety.
79.  Respirators  that are applicable and suitable for the purpose intended shall be provided when such
     equipment is  necessary  to  protect the  health of  employees. The CDC  Office of Biosafety will
     provide the proper respirators for a given hazard.

80.  Self-explanatory.
81.  Self-explanatory.
82.  Self-explanatory. Respirators should be cleaned and disinfected after each use.
83.  Self-explanatory.
84.   Self-explanatory.
85.  Self-explanatory.
86.  Compressors for breathing air should be equipped with receivers of sufficient capacity to enable the
     respirator wearer to escape from a  contaminated atmosphere in  the event of compressor failure;
     alarms to indicate compressor failure and overheating shall be installed in the system.
                                               A-15

-------
Item Inspected
87. Is each employee who works in an area where radio-
active material is used furnished and wearing film
badge? [.96(d)(2)l
88. Is radiation exposure of individuals to the body
limited to 1% rems per calendar quarter? [.96(o)j
89. Is each radiation area posted with the proper radia-
tion caution sign? [.96(e)(2)]
90. Are all radiation area employees instructed in the
safety problems, precautions, and devices to mini-
mize exposure? [.96(i)l
91. Are records maintained of the radiation exposure of
all employees who are monitored? [.96(n)]
92. Are radioactive materials stored and disposed prop-
erly? Are storage containers labeled? [.96(j,k)]
Yes














No














N.A.














Comments














98.  Is each mobile hydrogen supply unit secured to pre-
     vent movement? [.103(b)(l)(iv)(e)]

99.  Is the hydrogen storage area permanently marked
     "HYDROGEN-FLAMMABLE GAS-NO SMOKING
     OR OPEN FLAMES"? [.103(b)(l)(v)J
                                       Compressed Gases

93.  Is each portable gas container for gases such as hy-
     drogen legibly marked with the name of contents?
     [.252(aX2)(i)(a)l

94.  Are compressed gas cylinders determined in safe con-
     dition by visual and other inspection required in
     regulations? [.101(a)l

95.  Does the compressed gas cylinder or tank have an
     installed pressure relief device? [.101(c)]

96.  Are all compressed gas cylinders stored and secured
     so they cannot fall? [.252(a)(2)(ii)(b)]
97.  Are protection caps in place on compressed gas cylin-
     ders except when in use? [.2S2(a)(2)(ii)(d)l
                                              A-16

-------
87.  Self-explanatory.



88.  Self-explanatory.


89.  Self-explanatory.


90.  Self-explanatory.



91.  Self-explanatory.


92.  Self-explanatory.




93.  Self-explanatory.



94.  Deep dents or heavy corrosion of a gas cylinder might indicate a dangerous situation.



95.  Self-explanatory.


96.  When either storing or moving a compressed gas cylinder, care must be taken to prevent the cylinder
     from  falling.  OSHA requires that compressed gas  cylinders either be chained or strapped in an
     upright position at all times.

97.  Self-explanatory.

                                 Preface to Questions 98 through 107

A gaseous hydrogen system is one in which the hydrogen is delivered, stored, and discharged in the gaseous
form to the consumer's piping. The system includes stationary or movable containers, pressure regulators,
safety  relief devices, manifolds, interconnecting piping, and controls. The system terminates at the point
where  hydrogen at service pressure first enters the consumer's distribution piping. Systems having a total
hydrogen content of less than 400 ft^ are not covered by the following questions.

98.  Mobile supply units should be strapped or chained to prohibit movement.


99.  Self-explanatory.
                                               A-17

-------
Item Inspected
100. Is the hydrogen system in an adequately ventilated
area? [.103(b)(2)(ii)(d)(l)]
101. Is the hydrogen system 20 ft from stored flammable
materials or oxidizing gases? [ . 1 03(b)(2Xii)(d)(2)]
102. Is it 25 ft from open flames, electrical equipment, or
other sources of ignition? [.103(b)(2)(iiXd)(3)]
103. Is it 25 ft from concentrations of people?
104. Is it 50 ft from intakes of ventilation or air-
conditioning equipment and air compressors?
[ . 1 03(b)(2Xii)(d)(5)l
105. Is it 50 ft from other flammable gas storage?
106. Is it protected from damage due to falling objects or
working activity in the area? [.103(b)(2Xii)(d)(7)]
107. Are safety relief devices arranged to discharge up-
ward and unobstructed to the open air and prevent
impingement of gas upon container, adjacent struc-
ture, or personnel? [.109(b)(0(u)(b)I
Yes








No








N.A.








Comments








                                              Storage

108.  Is storage of material stable and secure against slid-
      ing, collapse, falls, or spills? [.176(b)]

109.  Are storage areas kept free from accumulation of
      materials that constitute hazards from tripping, fire,
      explosion, or pest harborage? (.176(e)J

110.  Are dangerous parts of machines or energized equip-
      ment, which may injure, colored orange where ex-
      posed? [.144(a)(2)J

111.  Is yellow the color  used for designating physical
      hazards and  caution in the particular environment?
      [.144(a)(3)J

112.  Is the color green used to designate "SAFETY" and
      location of first aid equipment? t-144(a)(4)]

113.  Is purple the color used to designate radiation
      hazards? [.144(a)(6)l

114.  Are the colors black and white used for traffic and
      housekeeping markings? [.144(a)(7)l
                                               A-18

-------
100.  Self-explanatory.






101.  Self-explanatory.






102.  Self-explanatory.






103.  Self-explanatory.






104.  Self-explanatory.









105.  Self-explanatory.






106.  Self-explanatory.






107.  Self-explanatory.
108.   Self-explanatory but very important.






109.   Self-explanatory.








110.   Self-explanatory.








111.   Self-explanatory.








 112.   Self-explanatory.






 113.   Self-explanatory.






 114.   Self-explanatory.
                                                 A-19

-------
Item Inspected
115.
116.
117.
118.
Are all accident prevention signs used to minimize
workplace hazards? [.145(e)(e)j
Are all exposed steam and hot water pipes within 7 ft
of floor or working platform covered with an insulat-
ing material or guarded? [.264(e)(4)(iii)]
At all loading docks employing powered industrial
trucks, are wheel chocks used to prevent trailers or
railroad cars from rolling? [.178(k)(l)]
Is medical help readily available through personnel
and first aid supplies approved by consulting physi-
cian? [.151(b)]
Yes
*



No




N.A.




Comments




A-20

-------
115.   Self-explanatory.


116.   Self-explanatory.



117.   Self-explanatory.
118.   In the absence of an infirmary, clinic, or hospital in near proximity to the workplace that is used for
       treating all injured  employees, a person or persons shall be adequately trained to render first aid.
       First aid supplies approved by the consulting physician shall be readily available.
                                                A-21

-------
1 REPORT NO.                   2.
   EPA-600A-79-OJ9	
 . TITLE AND SUBTITLE

   Handbook' for Analytical Quality Control in Water
   and Wastewater Laboratories

7. AUTHOR(S)
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
                                                           3. RECIPIENT'S ACCESSION«NO.
                            5. REPORT DATE
                             March 1979 issuing date
                            6. PERFORMING ORGANIZATION CODE
                           8. PERFORMING ORGANIZATION REPORT NO.
   Editor:   Robert L. Booth,  EMSL-Cincinnati
9. PERFORMING ORGANIZATION NAME AND ADDRESS

   SAME AS  BELOW
12. SPONSORING AGENCY NAME AND ADDRESS
   Environmental Monitoring and  Support Lab. - Cinn, OH
   Office of  Research and Development
   U.S.  Environmental Protection Agency
   Cincinnati, Ohio  45268
15. SUPPLEMENTARY NOTES
                            10. PROGRAM ELEMENT NO.

                              1BD801
                            11. CONTRACT/GRANT NO.

                               In house

                            13. TYPE OF REPORT AND PERIOD COVERED
                              Final
                            14. SPONSORING AGENCY CODE
                              EPA/600/06
   Project Officer:  Robert L.  Booth, EMSL-Cincinnati
16. ABSTRACT

   This  handbook is addressed  to  laboratory directors,  leaders of field investigations,
   and other personnel who bear responsibility for water  and wastewater data.   Subject
   matter of the handbook is concerned primarily with quality control (QC)  for  chemical
   and biological tests and measurements.   Chapters are also included on QC aspects of
   sampling, microbiology, biology,  radiochemistry, and safety as they relate to  water
   and wastewater pollution control.   Sufficient information is offered to  allow  the
   reader to inaugurate or reinforce  programs of analytical  QC that emphasize early
   recognition, prevention, and correction of factors leading to breakdowns in  the
   validity of water and wastewater  pollution control data.
17.

a.
                  DESCRIPTORS
   Quality Assurance
   Quality Control
   Water Analysis
   Laboratory Performance
   Valid Data
   Analytical Quality Control
KEY WORDS AND DOCUMENT ANALYSIS
              b.IDENTIFIERS/OPEN ENDED TERMS  C.  COS AT I Field/Group

              Quality Assurance Techniq  es
              Analytical  Measurements
              Laboratory Services
              Instrument Selection             07/B
              Data  Handling
              Skills and Training
18. DISTRIBUTION STATEMENT



  Release  to  Public
EPA Form 2220-1 (9-73)
              19. SECURITY CLASS (This Report)
              Unclassified
              20. SECURITY CLASS (Thispage)
              Unclassified
21. NO. OF PAGES
   164
22. PRICE

-------
                                                                  11.0-1
                          Section 1LO




                          SUPPLIERS






Ace Glass Co.




Vineland, NJ  08360






Acurex Corporation




485 Clyde Avenue




Mountain View, CA 94042






Aldrich Chemical Co.




940 W. St. Paul Avenue




Milwaukee, WI  53233






Associated Design and Manufacturing Co




814 North Henry St.




Alexandria, VA  22314






Bethlehem Apparatus Co .




Front and Depot Streets




Hellertown, PA  18055






Calgon Corporation




Pittsburg, PA  15230






Calspan Corporation




Buffalo, NY 14225






Davison Chemical Co.




Div. W.R. Grace




Charles & Baltimore Sts.




Baltimore, MD 21202
(609) 692-3333
(415) 964-3200
(414) 273-3850
(703) 549-5999
(215) 838-7034
(412) 923-2345
(716) 632-7500
(301) 727-3900

-------
                                                                   ii. o-:
EM Laboratories




Elmsford, NY






Fisher Scientific Co.




711 Forbes Avenue




Pittsburg, PA  15219






Gelman Instrument Co .




600 S. Wagner Road




Ann Arbor, MI  48106






Goldsmith Division




National Lead Co.




Ill Broadway




New York, NY  10006






J.T. Baker Chemical Co.




222 Red School Lane




Phillipsburg, NJ  08865






John Manville Co.




P.O. Box 5108




Denver, CO  80217






Kontes Glass Co.




Spruce Street




Vineland, NJ  08360






Micro Filtration Systems




8 Stransbury Court




Fredericksburg, VA  22401
(914) 592-4660
(412) 562-8300
(800) 521-5120
(212) 732-9400
(201) 859-2151
(303) 979-1000
(609) 692-8500
(703) 786-7315

-------
                                                                   11.0-3
Mlllipore Corporation




Bedford, MA  01730






Nalge Co.




75 Panorama Creek Dr.




Rochester, NY  14602






Nuclepore Corporation




7035 Commerce Circle




Pleasanton, CA  94566






Pall Trincor Corporation




2395 Springfield Avenue




Vauxhall, NJ  07088






Quicksilver Products, Inc.




350 Brannan




San Francisco, CA  94107






Scientific Glass & Instruments, Inc.




Houston, TX  77001






Selas Corporation of America




1957 Pioneer Road




Huntington Valley, PA  19006






Supelco, Inc .




Supelco Park




Bellefonte, PA  16823
(800) 225-1380
(716) 586-8800
(415) 462-2230
(201) 245-8400
(415) 781-1988
(713) 868-1481
(215) 672-0400
(814) 359-2784

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                                                                   11.0-
Ultrasonics Instruments International Ltd.      (516)  333-0213




200 T Shames Drive




Westburg, NY  11580

-------
                         APPENDIX 1

SAMPLERS AND SAMPLING PROCEDURES FOR HAZARDOUS WASTE STREAMS
                             by

             Emil R. deVera,  Bart P.  Simmons,
          Robert D. Stephens  and David L.  Storm
       California Department  of Health Services
               Berkeley,  California  94704

-------
                                               EPA-600/2-80-018
                                               January 1980
SAMPLERS AND SAMPLING PROCEDURES FOR HAZARDOUS WASTE STREAMS
                             by

              Emil R.  deVera, Bart P.  Simmons,
            Robert D.  Stephens and David L.  Storm
          California Department of Health Services
                 Berkeley,  California   94704
                    Grant No.  R804692010
                       Project Officer

                      Richard A.  Carnes
         Solid and Hazardous Waste Research Division
         Municipal Environmental  Research Laboratory
                   Cincinnati, Ohio  45268
         MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
             OFFICE OF RESEARCH AND DEVELOPMENT
            U.S.  ENVIRONMENTAL PROTECTION AGENCY
                   CINCINNATI, OHIO  45268

-------
                               DISCLAIMER
     This report has been reviewed by the Municipal Environmental
Research Laboratory, U.S. Environmental Protection Agency, and approved
for publication.  Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
                                    ii

-------
                               FOREWORD
The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the
health and welfare of the American people.  Noxious air, foul water,
and spoiled land are tragic testimony to the deterioration of our
natural environment.  The complexity of that environment and the inter-
play between its components require a concentrated and integrated
attack on the problem.

Research and development is that necessary first step in problem solu-
tion and it involves defining the problem, measuring its impact, and
searching for solutions.  The Municipal Environmental Research Laboratory
develops new and improved technology and systems for the prevention,
treatment, and management of wastewater and solid and hazardous waste
pollutant discharges from municipal and community sources, for the
preservation and treatment of public drinking water supplies, and to
minimize the adverse economic, social, health, and aesthetic effects of
pollution.  This publication is one of the products of that research;
a most vital communications link between the researcher and the user
community.

This study involved the development of simple but effective sampling
equipment and procedures for collecting, handling, storing, and record-
ing of hazardous wastes.  A variety of sampling devices were developed
and/or selected to meet the needs of those who regulate and manage
hazardous wastes.  Of particular importance is the development of the
composite liquid waste sampler, the Coliwasa.  The sampling procedures
developed were designed to provide maximum protection for the sample
collector, collection of representative samples of the bulk of wastes,
and proper containment, identification, preservation, and handling of
the samples.

                                     Francis T. Mayo, Director
                                     Municipal Environmental Research
                                     Laboratory
                                 iii

-------
                                ABSTRACT
     The goal of this project was to develop simple but effective sampl-
ing equipment and procedures for collecting, handling, storing, and
recording samples of hazardous wastes.   The report describes a variety
of sampling devices designed to meet the needs of those who regulate
and manage hazardous wastes.  Particular emphasis is given to the
development of a composite liquid waste sampler, the Coliwasa.  This
simple device is designed for use on liquid and semi-liquid wastes in
a variety of containers, tanks, and ponds.  Devices for sampling solids
and soils are also described.

     In addition to the sampling devices, the report describes pro-
cedures for development of a sampling plan, sample handling, safety
precautions, proper recordkeeping and chain of custody, and sample
containment, preservation, and transport.  Also discussed are certain
limitations and potential sources of error that exist in the sampling
equipment and the procedures.  The statistics of sampling are covered
briefly, and additional references in this area are given.

     This report was submitted in partial fulfillment of Research Grant
No. R804692010 by the California Department of Health Services under
sponsorship of the U.S. Environmental Protection Agency.
                                   iv

-------
                               CONTENTS
Foreword	    ill
Abstract	     iv
Figures   	     vi
Tables    	    vit

  1.  Introduction  	      1
  2.  Conclusions   	 ........      3
  3.  Recommendations   	      4
  4.  Samplers          	      5
        Composite liquid waste sampler  	      5
        Solid waste samplers  	      9
        Soil samplers	     13
        Procedure for use     	     14
        Pond sampler          	     20
  5.  Preparation for Sampling	     24
  6.  Sampling Procedures       	     26
        General considerations		     26
        Sample handling         	     39
        Field log book          	     41
        Chain of custody record   ..... 	     42
        Sample analysis request sheet   	     42
        Sample delivery to the laboratory 	     42
        Shipping of sample                	     45
  7.  Receipt and Logging of Sample       	     45
  8.  Preservation and Storage of Samples 	     4g

References                      	     50
Appendices                      	     52
  A.  Development of the composite liquid	     52
        waste sampler (Coliwasa)    . 	
  B.  Parts for constructing the coliwasa	     62
  C.  Checklist of items required in the field	     63
        sampling of hazardous wastes  	 •
  D.  Random sampling	•     67
  E.  Systematic errors in using the coliwasa 	     68

-------
                               FIGURES
Number
 1           Composite liquid waste sampler (Coliwasa) ...     6
 2           Grain sampler   	    10
 3           Sampling trier  	    11
 k           Trowel or scoop with calibrations   	    13
 5           Soil auger      	    15
 6           Veihmeyer sampler   	    16
 7           Waste pile sampler  	 .....    20
 8           Pond sampler        	    21
 9           Weighted bottle sampler   	    23
10           Example of waste manifest   	    28
11           Official sample label       	    40
12           Example of official sample seal   	    40
13           Example of chain of custody record  	    43
14           Example of hazardous waste sample
               analysis request sheet    	    44
A-l          Coliwasa, Model 1           	    53
A-2          Coliwasa, Model 2           	    55
A-3          Coliwasa, Model 3           	    56
A-4          Coliwasa, Model 4           	    58
A-5          Coliwasa, Model 5           	    58
                                vi

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                               TABLES
Number                                                            Pagj

  1       Basic Parts and Costs of a Veihmeyer Soil Sampler ...  17
  2       Basic Parts and Approximate Costs of a
            Pond Sampler      	21
  3       Samplers Recommended for Various Types of Waste ....  29
  4       Sample Containers and Closures Recommended
            for Various Types of Waste	31
  5       Sampling Points Recommended for Most Waste
            Containers                  	32
  6       Number of Samples to be Collected	34
  7       Respiratory Protective Devices Recommended
            for Various Hazards	35
  8       Methods of Preservation for Hazardous Wastes  	  49
 A-l      Relative Volumes of Liquids in the
            Two-Phase Mixture   	  60
 A-2      Relative Volumes of Liquids in the
            Three-Phase Mixture 	  60

APPENDIX B. Parts for Constructing the Coliwasa 	  62
APPENDIX C. Checklist of Items Required in the
              Field Sampling of Hazardous Wastes.  .  .   63, 64, 65, 66
APPENDIX D. Random Sampling     	 .....  67
APPENDIX E-l Sample Volume      	  69
                                  vii

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                               SECTION 1

                              INTRODUCTION
     The growth in the size and complexity of industry and the imple-
mentation of air and waste pollution abatement technology has confronted
the nation with the immensely difficult problem of managing large volumes
of waste products that are often toxic, flammable, corrosive, and explo-
sive.  The problem is further exacerbated by the complexity of the waste.
This difficult situation is now being addressed at many levels of govern-
ment through a variety of regulatory agencies.  Solution is being sought
through a "cradle-to-grave" regulation of waste generation, transport,
reprocessing, and disposal.  Significant progress toward a solution is
also being made by the private waste management industry with improved
techniques in handling, resource recovery, and disposal.

     The management of hazardous wastes may be addressed primarily as a
chemical problem.  With this approach, management decisions must be
founded on proper knowledge of waste chemical compositions.  Defining
the information needed on waste composition to support management
decisions presents an additional complication, for such information
varies with waste type and with handling or disposal objectives.  Re-
gardless of the details, the required information results from chemical
and physical testing of the waste.

     Industrial waste predominantly occurs in volumes that are large
enough to preclude testing or analysis of the entire body of the waste.
Obtaining samples adequate in size for the required testing and repre-
sentative of the bulk volumes of the wastes is therefore necessary.
The obtainment of such representative samples presents special problem,
for many wastes are complex, multiphase mixtures that vary greatly in
viscosity, corrosivity, volatility, flammability, or capability to
generate toxic gases.

     This study was conducted to deve?.op specialized equipment and pro-
cedures designed to handle the widest possible variety of waste sampling
situations.

     The equipment and procedures that have been developed and described
in this report had their origins in the hazardous waste regulatory pro-
gram of the California Department of Health Services.  Early in this
program, the necessity of reliable analytical data on waste composition
became apprent.  As a result, the problem of proper sampling of hazardous

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wastes was  addressed.  Review  of  the wide variety of  industrial wastes
produced  in California revealed that liquids or  liquid-sludge mixtures
accounted for  the  greatest volume of wastes.  Most of  these materials
at  some point  are  contained  and/or  transported in tank (vacuum) trucks
or  barrels.  A primary concern, therefore, was to develop  the capa-
bility for  sampling  these wastes.

     The  first prototype of  a  liquid waste sampler was the tube sampler,
which was designated the composite  liquid waste  sampler or Coliwasa.1
This sampling  device, fabricated  from readily available materials, was
taken to  the field and tested  for its usability  and reliability.

     The  first large-scale sampling of hazardous wastes was conducted
jointly by  the California Department of Health Services and the Univer-
sity of Southern California  under the sponsorship of  the U.S. Environ-
mental Protection  Agency (EPA)2   in this sampling program, approxi-
mately 400  waste samples were  collected.  These  samples varied greatly
in  composition and in physical characteristics.

     Approximately 90% of all  wastes sampled were liquids  or sludges and
could be  sampled with the Coliwasa.  The sampling program  established the
utility of  this sampler.  In addition, however,  several deficiencies and
needed improvments were demonstrated.  Along with the  need for liquid
sampling  equipment,  a need was also demonstrated for  simple but effective
equipment for  sampling solids, soils, and liquids in  large tanks or  ponds.
This early  study also clearly  indicated the need for  development of  good
safety procedures  and sample handling, preservation,  and custody procedures.

     In November 1976, under a grant from the EPA, the  California Depart-
ment of Health Services embarked on a development program  to establish
recommended procedures and equipment for the sampling of hazardous wastes.
Commercially available liquid samplers were investigated, but none was
found to be adaptable to sampling hazardous wastes.   Equipment development
centered on the Coliwasa,  which had been conceived and  initially designed
by waste management personnel of the Department.   Solid, soil, and pond
sampling equipment was obtained after an extensive review of the litera-
ture and testing of available equipment for efficiency.  Criteria used in
choosing candidate procedures were ready availability,  reasonable cost,
simplicity of design and operation,  and chemical inertness.  Candidate
methods and samplers were subjected to laboratory and field tests.   Lab-
oratory tests for the liquid samplers consisted of sampling water as well
as multiphase waste mixtures.  The samplers were examined for leakage,
ease of use and transfer,  and cross contamination.   In  field tests, the
samplers for liquids and solids were used on actual wastes existing in a
variety of containers,  ponds, or soils.

     The body of the report gives detailed discussions of recommended
samplers,  preparation for sampling,  sampling procedures, sample handling,
and recordkeeping.   The appendices present a variety of practical support
data for the body of the report.

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                               SECTION  2

                              CONCLUSIONS
     The present study was designed to develop simple but effective
sampling equipment for collecting represenative samples of hazardous
wastes.  In addition, recommended procedures for sample collection,
handling, storage, and recording were to be developed.  These primary
objectives have been met, and the resulting sampling equipment and
procedures are presented here.

     The sampling equipment and procedures were designed to insure the
widest possible applicability in the sampling of various types of
hazardous wastes.  The methods, however, are not intended to cover
all possible sampling situations.  Professional judgment on applica-
bility must be exercised.

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                               SECTION  3

                            RECOMMENDATIONS
     The next step in the development of standardized sampling methods
should be user verfication.  Additional data on applicability, reli-
ability, and other performance characteristics need to be developed
before these recommended methods can become standard methods.  This
next phase will require considerable effort by a large number of
collaborators, for the methodology described in this report is
intended to be satisfactory for essentially the entire waste-producing
industry.  Significant benefit is to be gained by both industry and
environmental regulatory agencies if efficient, reliable hazardous
waste sampling methods can be established.  We therefore strongly recommend
that work on this validation begin immediately.

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                               SECTION  4

                                SAMPLERS
     Sampling of hazardous wastes requires different types of samplers.
Some of these samplers are commercially available,  but the others have
to be fabricated.  This section lists and describes suitable samplers.
Their uses and commercial availability as well as directions for their
use are reported.  Directions for fabricating the commercially unavail-
able samplers are also outlined.

COMPOSITE LIQUID WASTE SAMPLER (COLIWASA)

     The Coliwasa is the single most important hazardous waste sampler
discussed in this report.  It was chosen from a number of other liquid
samplers, based on laboratory and field tests, as the most practical.
It permits the representative sampling of multiphase wastes of a wide
range of viscosity, corrosivity,  volatility, and solids content.  Its
simple design makes it easy to use and allow the rapid collection of
samples, thus minimizing the exposure of the sample collector to po-
tential hazards from the wastes.   The sampler is not commercially
available, but it is relatively easy and inexpensive to fabricate.  The
cost of fabrication is low enough that the contaminated parts may be
discarded after a single use when they cannot be easily cleaned.

     The recommended model of the Coliwasa is shown in Figure 1.  The
history and development of this sampler is discussed in detail in Appendix
A.  The main parts of the Coliwasa consist of the sampling tube, the
closure-locking mechanism, and the closure system.

     The sampling tube consists of a 1.52-m(5-ft.)  by 4.13-cm(l 5/8-in.)
I.D. translucent plastic pipe, usually polyvinyl chloride (PVC) or boro-
silicate glass plumbing tube.  The closure-locking mechanism consists of
a short-length, channeled aluminum bar attached to the sampler's stopper
rod by an adjustable swivel.  The aluminum bar serves both as a T-handle
and lock for the sampler's closure system.  When the sampler is in
the open position, the handle is place in the T-position and pushed
down against the locking block.  This manipulation pushes out the
neoprene stopper and opens the sampling tube.  In the close position,
the handle is rotated until one leg of the T is squarely perpendicular
against the locking block.  This tightly seats the neoprene stopper
against the bottom opening of the sampling tube and positively locks
the sampler in the close position.  The closure tension can be adjusted
by shortening or lengthening the stopper rod by screwing it in or out

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of the T-handle swivel.  The closure system of the sampler consists of
a sharply taped neoprene stopper attached to a 0.95-cm (3/8-in.) O.D.
rod, usually PVC.  The upper end of the stopper rod is connected to
the swivel of the aluminum T-handle.  The sharply tapered neoprene
stopper can be fabricated according to specifications by plastic products
manufacturers at an extremely high price, or it can be made in-house by
grinding down the inexpensive stopper with a shop grinder as described in
Note 1 of Appendix B.

     Two types of Coliwasa samplers are made, namely plastic or glass.
The plastic type consists of translucent plastic (usually PVC) sampling
tube.  The glass Coliwasa uses borosilicate glass plumbing pipe as the
sampling tube and Teflon plastic stopper rod.

     The complete list of parts for constructing the two types of Coliwasa
samplers is given in Appendix B.  The suppliers and approximate costs of
the parts as well as the directions for fabricating the commercially
unavailable parts are also given.

     The sampler is assembled as shown in Figure 1 and as follows:

  1.  Attach the swivel to the T-handle with the 3.18 cm(l% in.) long
      bolt and secure with the 0.48 cm(3/16 in.) National Coarse(NC)
      washer and lock nut.

  2.  Attach the neoprene stopper to one end of the stopper rod and
      secure with the 0.95 cm(3/8 in.) washer and lock nut.

  3.  Install the stopper and stopper rod assembly in the sampling tube.

  4.  Secure the locking block sleeve on the block with glue or screws.
      This block can also be fashioned by shaping a solid plastic rod
      on a lathe to the required dimensions.

  5.  Position the locking block on top of the sampling tube such that
      the sleeveless portion of the block fits inside the tube, the
      sleeve sits against the top end of the tube, and the upper end of
      the stopper rod slips through the center hole of the block.

  6.  Attach the upper end of the stopper rod to the swivel of the
      T-handle.

  7.  Place the sampler in the close position and adjust the tension on
      the stopper by screwing the T-handle in or out.

Uses

     The plastic Coliwasa is used to sample most containerized liquid
wastes except wastes that contain ketones, nitrobenzene, dimethylforamide,
mesityl oxide, and tetrahydrofuran. '

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     The glass Coliwasa is used to sample all other containerized liquid
wastes that cannot be sampled with the plastic Coliwasa except strong
alkali and hydrofluoric acid solutions.

Procedure for Use

  1.  Choose the plastic or glass Coliwasa for the liquid waste to be
      sampled and assemble the sampler as shown in Figure 1.

  2.  Make sure that the sampler is clean (see Section 5).

  3.  Check to make sure the sampler is functioning properly.  Adjust
      the locking mechanism* if necessary to make sure the neoprene
      rubber stopper provides a tight closure.

  4.  Wear necessary protective clothing and gear and observe required
      sampling precautions (see Section 6).

  5.  Put the sampler in the open position by placing the stopper rod
      handle in the T-position and pushing the rod down until the handle
      sits against the sampler's locking block.

  6.  Slowly lower the sampler into the liquid waste.  (Lower the sampler
      at a rate that permits the levels of the liquid inside and outside
      the sampler tube to be about the same.  If the level of the liquid
      in the sampler tube is lower than that outside the sampler, the
      sampling rate is too fast and will result in a nonrepresentative
      sample).

  7.  When the sampler stopper hits the bottom of the waste container,
      push the sampler tube downward against the stopper to close the
      sampler.  Lock the sampler in the close position by turning the T
      handle until it is upright and one end rests tightly on the locking
      block.

  8.  Slowly withdraw the sampler from the waste container with one hand
      while wiping the sampler tube with a disposable cloth or rag with
      the other hand.

  9.  Carefully discharge the sample into a suitable sample container
      (see Section 6) by slowly opening the sampler.   This is done by
      slowly pulling the lower end of the T handle away from the locking
      block while the lower end of the sampler is positioned in a sample
      container.

 10.  Cap the sample container; attach label and seal; record in field
      log book; and complete sample analysis request sheet and chain of
      custody record.

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 11.  Unscrew the T handle of the sampler and disengage the locking
      block.  Clean sampler on site (see Section 5) or store the con-
      taminated parts of the sampler in a plastic storage tube for
      subsequent cleaning.  Store used rags in plastic bags for
      subsequent disposal.

 12.  Deliver the sample to the laboratory for analysis (see Section 6).

SOLID WASTE SAMPLERS

     A number of tools are available for sampling solid substances.  The
most suitable of these for sampling hazardous solid wastes are the grain
sampler, sampling trier, and the trowel or scoop. •

Grain Sampler

     The grain sampler (Figure 2) consists of two slotted telescoping
tubes, usually made of brass or stainless steel.  The outer tube has a
conical, pointed tip on one end that permits the sampler to penetrate the
material being sampled.  The sampler is opened and closed by rotating the
inner tube.  Grain samplers are generally 61 to 100 cm (24 to 40 in.)
long by 1.27 to 2.54 cm (% to 1 in.) in diameter, and they are commercially
available at laboratory supply houses.

Uses—

     The grain sampler is used for sampling powdered or granular wastes
or materials in bags, fiberdrums, sacks or similar containers.  This
sampler is most useful when the solids are no greater than 0.6 cm  Os in.)
in diameter.

Procedure for Use—

  1.  While the sampler is in the close position, insert it into the
      granular or powdered material or waste being sampled from a point
      near a top edge or corner, through the center, and to a point
      diagonally opposite the point of entry.5

  2.  Rotate the inner tube of the sampler into the open position.

  3.  Wiggle the sampler a few times to allow materials to enter the
      open slots.

  4.  Place the sampler in the close position and withdraw from the
      material being sampled.

  5.  Place the sampler in a horizontal position with the slots facing
      upward.

  6.  Rotate and slide out the outer tube from the inner tube.

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 7.  Transfer the collected sample in the inner tube into a suitable
     sample container (see Section 6).

 8.  Collect two or more core samples at different points (see Section
     6), and combine the samples in the same container.

 9.  Cap the sample container; attach label and seal; record in field
     log book; and complete sample analysis request sheet and chain
     of custody record.

10.  Clean (see Section  5) or store the sampler in plastic bag for    ^
     subsequent cleaning.

11.  Deliver the sample  to the laboratory for analysis (see Section 6).
                     61-100 cm,
                      (24-40")
                          1.27-2.54 cm (%-!")
                      Figure 2•   Grain  sampler.
                                  10

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                             \
                      61-100 cm,
                       (24-40")
                             N
                               \
                                      h
                           1.27-2.54 cm (%-!")
                       Figure 3.  Sampling trier.
Sampling trier
     A typical sampling trier (Figure 3) is a long tube with a slot that
extends almost its entire length.  The tip and edges of the tube slot are
sharpened to allow the trier to cut a core of the material to be sampled
when rotated after insertion into the material.  Sampling triers are
usually made of stainless steel with wooden handles.  They are about 61
to 100 cm (24 to 40 in.) long and 1.27 to 2.54 cm (% to 1 in.) in diameter.
They can be purchased readily from laboratory supply houses.

Uses—

     The use of the trier is similar to that of the grain sampler dis-
cussed above.  It is preferred over the grain sampler when the powdered or
                                   11

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granular material to be sampled is moist or sticky.

     In addition, the sampling trier can be used to obtain soft or loosened
soil samples up to a depth of 61 cm(24 in.) as outlined below.

Procedure for Use—

  1.  Insert the trier into the waste material at a 0 to 45° angle from
      horizontal.  This orientation minimizes the spillage of sample
      from the sampler.  Extraction of samples might require tilting of
      the containers.

  2.  Rotate the trier once or twice to cut a core of material.

  3.  Slowly withdraw the trier, making sure that the slot is facing
      upward.

  4.  Transfer the sample into a suitable container (see Section 6) with
      the aid of a spatula and/or brush.

  5.  Repeat the sampling at different points (see Section 6).  Two or
      more times and combine the samples in the same sample container.

  6.  Cap the sample container; attach the label and seal; record in
      field log book; and complete sample analysis request sheet and
      chain of custody record.

  7.  Wipe the sampler clean, or store it in a plastic bag for subsequent
      cleaning.

  8.  Deliver the sample to the laboratory for analysis (see Section 6).

Trowel or Scoop

     A garden-variety trowel looks like a small shovel  (Figure 4).  The
blade is usually about 7 by 13 cm(3 by 5 in.) with a sharp tip.  A labor-
atory scoop is similar to the trowel, but the blade is usually more curved
and has a closed upper end to permit the containment of material.  Scoops
come in different sizes and makes.  Stainless steel or polypropylene scoops
with 7 by 15-cm(2 3/4 by 6-in.) blades are preferred.   A trowel can be
bought from hardware stores; the scoop can be bought from laboratory supply
houses.

Uses—

     An ordinary zinc-plated garden trowel can be used in some cases for
sampling dry granular or powdered materials in bins or other shallow con-
tainers.  The laboratory scoop, however, is a superior choice.  It is
usually made of materials less subject to corrosion or chemical reactions,
thus lessening the probability of sample contamination.
                                    12

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      The trowel or scoop can also be used in collecting top surface soil
 samples.

 Procedure for Use—

   1.   At regular intervals (see Section 6),  take small, equal portions of
       sample from the surface or near the surface of the material to be
       sampled.

   2.  ,Combine the samples in a suitable container (see Section 6).

   3.   Cap the container; attach the label and seal;  record in field log
       book; and complete sample analysis request sheet and chain of
       custody record.
i
   4.   Deliver the sample to the laboratory for analysis (see Section 6).

 SOIL SAMPLERS

      There is a variety of soil samplers used.   For  taking soil core
 samples, the scoop, sample trier, soil auger, and Veihmeyer sampler can be
 used.  These samplers are commercially available and relatively inexpensive.

 Scoop or Trowel

      See the preceding section on solid waste samplers for the description
 of a  scoop or trowel (Figure 4).
                                                       \
               Figure  4.   Trowel  or scoop with calibrations.
                                     13

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Uses—

     The scoop is used to collect soil samples up to 8 cm(3 in.) deep.
It is simple to use, but identical mass sample units for a composite sample
are difficult to collect with this sampler.  The procedure for use of the
scoop is outlined in the preceding section on solid waste samplers.

Sampling Trier

     See the preceding section on solid waste samplers for the description
of a sampling trier (Figure 3).

Uses—

     This sampler can be used to collect soil samples at a depth greater
than 8 cm(3 in.)-  The sampling depth is determined by the hardness and
types of soil being sampled.  This sampler can be difficult to use in
stony, dry, very heavy, or sandy soil.  The collected sample tends to be
slightly compacted, but this method permits observation of the core sample
before removal.

Procedure for Use—

     Procedure for use of the sampling trier can be found in the section
on solid waste samplers.

Soil Auger

     This tool consists of a hard metal central shaft and sharpened spiral
blades  (Figure 5).  When the tool is rotated clockwise by its wooden
T handle, it cuts the soil as it moves forward and discharges most of the
loose soil upward.  The cutting diameter is about 5 cm(2 in.).  The length
is about 1 m(40 in.), with graduations every 15.2 cm(6 in.).  The length
can be increased up to 2 m(80 in.).  This tool can be bought from stores
and, in some cases, from laboratory supply houses.

Uses—

     The auger is particularly useful in collecting soil samples at depths
greater than 8 cm(3 in.).  This sampler destroys the structure of cohesive
soil and does not distinguish between samples collected near the surface
or toward the bottom.  It is not recommended, therefore, when an undis-
turbed soil sample is desired.

Procedure for Use—

  1.  Select the sampling point  (see Section 6) and remove unnecessary
      rocks, twigs, and other non-soil materials.
                                    14

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 2.   Install the sampler's wooden T handle in its socket.

 3.   Bore a hole through the middle of an aluminum pie pan large enough to
     allow the blades of the auger to pass through.  The pan will be used
     to catch the sample brought to the surface by the auger.

 4.   Spot the pan against the selected sampling point.

 5.   Start augering through the hole in the pan until the  desired sampling
     depth is reached.

 6.   Back off the auger and transfer the sample collected  in the catch pan
     and the sample adhering to the auger to a suitable container (see
     Section 6).  Spoon out the rest of the loosened sample with a sampling
     trier.

 7.   Repeat the sampling at different sampling points (see Section 6), and
     combine the samples in the same container as in step  6.

 8.   Cap the sample container; attach label and seal; record in field log
     book; and complete sample analysis request sheet and chain of cus-
     tody record.

 9.   Brush off and wipe the sampler clean, or store it in a plastic bag
     for subsequent cleaning.

10.   Deliver the sample to the laboratory for analysis (see Section 6).
                                 •—tt—
                    101.6 cm (40")
                               5.08 cm (2")
                        Figure 5.  Soil auger.
                                   15

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        A.   Drive hammer
n
        B.   Head
        C.   Tube
         D.   Point
                                                Standard point
                                                Constricted point
             Bulge point
                                                Special  point
                                     Point  types
Puller jack and grip
            Figure 6.  Veihmeyer sampler
                             16

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Veihmeyer Soil Sampler

     This sampler was developed by Professor F.J.  Veihmeyer of the Univer-
sity of California in Davis.'   The parts of a basic sampler and the corres-
ponding costs are given in Table 1, and the basic  sampler is shown in
Figure 6.

      TABLE 1.  BASIC PARTS AND COSTS OF A VEIHMEYER SOIL SAMPLER

    Part3                                              Costb

   Tube, 1.5 m (5 ft.)                                $   50.40

   Tube, 3 m (10 ft.)                                     84.75

   Tip, type A, general use                               25.80

   Drive head                                             29.05

   Drop hammer, 6.8 kg (15 Ib.)                           71.85

   Puller jack and gripc                                 161.90

       Total                                         $   433.75
  a Only one of each part is needed.   They are manufactured by
    Hansen Machine Works, 334 N. 12th Street, Sacramento, CA
    95815.

  k Based on August 1, 1977, price list.

  c Recommended for deep soil sampling.

     The tube is chromium-molybdenum steel and comes in various standard
lengths from 0.91 to 4.9 m(3 to 16 ft.) and calibrated every 30.48 cm(12
in.).  Longer tubes can be obtained on special order.  Different points
(Figure 6) are also available for different types of soil and sampling.
Each point is shaped to penetrate specific types of soil without pushing
the soil ahead of it, thus preventing the core from compacting in the tube.
The standard point is adequate for most general sampling purposes.  The
inside taper of each point is designed to keep the sample from being
sucked out of the tube as it is pulled frcm the ground.  The drive head
protects the top of the tube from deforming when the tube is driven into
the ground with the drive hammer.   The hammer doubles as a drive weight
and handle when pulling the sampler from the ground.  When the sampler tube
cannot be pulled easily from the ground, a special puller jack and grip
                                    17

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are also available.  Specifications for the various parts of the Veihmeyer
sampler are given as follows:

     Points 	 Chrome-molly steel, heat-treated.  Includes a
                      standard point for general use, a constricted
                      point for deep sampling in heavy clay (keeps
                      core from being sucked out of the tube), a
                      bulge point for shallow sampling in heavy clay,
                      and a special point for dry sand.  (See Figure
                      6D).

     Drive hammer . . Standard weight is 6.8 kg (15 lb.).  (See Figure 6A)
     Tubes        . , Chrome-molly steel.  Maximum length is 4.9 m
                      (16 ft.).  (See Figure 6C).
     Head         . . Chrome-molly steel, heat-treated.  (See Figure 6B).
     Puller jack  . . Cast aluminum frame with steel roller assembly
                      and handle.'
     Grip         . . Chrome-molly steel, heat-treated.

Uses—

     The Veihmeyer sampler is recommended for core sampling of most types
of soil.  It may not be applicable to sampling stony, rocky, or very wet
soil.

Procedure for Use—

  1.  Assemble the sampler by screwing in the tip  and the drive head on
      the sampling tube.

  2.  Insert the tapered handle (drive guide) of the drive hammer through
      the drive head.

  3.  Place the sampler in a perpendicular position on the soil to be
      sampled.

  4.  With the left hand holding the tube, drive the sampler into the
      ground to the desired sampling depth by pounding the drive head
      with the drive hammer.  Do not drive the tube further than the
      tip of the hammer's drive guide.

  5.  Record the length of the tube that penetrated the ground.

  6.  Remove the drive hammer and fit the keyhole-like opening on the flat
      side of the hammer onto the drive head.  In  this position, the ham-
      mer serves as a handle for the sampler.
                                   18

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   7.  Rotate the sampler at least two revolutions to shear off the sample
      at the bottom.

   8.  Lower the sampler handle  (hammer) until it just clears the two ear-
      like protrusions on the drive head and rotate about 90°.

   9.  Withdraw the sampler from the ground by pulling the handle (hammer)
      upwards.  When the sampler cannot be withdrawn by hand, as in deep
      soil sampling, use the puller jack and grip.

 10.  Dislodge the hammer from the sampler; turn the sampler tube upside
      down; tap the head gently against the hammer; and carefully recover
      the sample from the tube.  The sample should slip out easily.

 11.  Store the core sample, preferably, in a rigid, transparent, or trans-
      lucent plastic tube when observation of soil layers is to be made.
      The use of the tube will keep the sample relatively undisturbed.  In
      other cases, use a 1000-or 2000-ml (l«-qt. or %-gal) sample container
      (see Section 6) to store the sample.

 12.  Collect additional core samples at different points (see Section 6).

 13.  Label the samples; affix the seals; record in the field log book;
      complete analysis request sheet and chain of custody record; and
      deliver the samples to the laboratory for analysis (see Section 6).

Waste Pile Sampler

     A waste pile sampler (Figure 7) is essentially a large sampling trier.
It is commercially available, but it can be easily fabricated from sheet
metal plastic pipe.  A polyvinyl chloride plumbing pipe 1.52 m(5 ft ) long
by 3.2 cm(l% in.) I.D. by 0.32 cm(1/8 in.) wall thickness is adequate.  The
pipe is sawed lengthwise  (about 60/40 split)  until the last 10 cm(4 in.)
The narrower piece is sawn off and hence forms a slot in the pipe.  The
edges of the slot and the tip of the pipe are sharpened to permit the
sampler to cut into the waste material being sampled.  The unsplit length
of the pipe serves as the handle.  The plastic pipe can be purchased from
hardware stores.

Uses—

     The waste pile sampler is used for sampling wastes in large heaps with
cross-sectional diameters greater than 1 m(39. 4 in.).  It can also be used
for sampling granular or powdered wastes or materials in large bins, barges,
or silos where the grain sampler or sampling trier is not long enough.
This sampler does not collect representative samples when the diameters of
the solid particles are greater than half the diameter of the tube.

Procedure for Use—
                                    19

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  1.   Insert  the  sampler  into  the waste material being  sampled  at  0  to  45°
      from horizontal.

  2.   Rotate  the  sampler  two or  three  times  in order  to cut  a core of the
      material.

  3.   Slowly  withdraw the sampler,  making sure that the slot is facing
      upward.

  4.   Transfer the  sample into a suitable container  (see Section 6)  with
      the  aid of  a  spatula and/or brush.

  5.   Repeat  the  sampling at different sampling points  (see  Section  6)  two
      or more times and combine  the samples  in the same sample  container in
      step 4.

  6.   Cap  the container;  attach  label  and seal; record  in field log  book;
      and  complete  sample analysis  request sheet  and  chain of custody
      record.

  7.   Wipe the sampler clean or  store  it  in a plastic bag for subsequent
      cleaning.

  8.   Deliver the sample  to the  laboratory for analysis (see Section 6).
                                                        i
                        122-183 cm
                         (48-72")
                                                            5.08-7.62 cm
                                                            (2-3") I.D.
                    Figure 7.  Waste pile sampler.

Pond Sampler

     The pond sampler (Figure 8) consists of an adjustable clamp attached
to the end of a two or three piece telescoping aluminum tube that serves
as the handle.  The clamp is used to secure a sampling beaker.  The sampler
is not commercially available, but it is easily and inexpensively fabri-
                                    20

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cated.  The tubes can be readily purchased from most hardware or swimming
pool supply stores.   The adjustable clamp and sampling beaker can be
obtained from most laboratory supply houses.   The materials required to
fabricate the sampler are given in Table 2.
                                                         Bolt hole
                                                         Beaker, polyprop-
                                                          ylene, 250 ml
                                                          (1 qt)
                                    Pole, telescoping, aluminum, heavy
                                     duty, 250-450 cm (96-180")
                        Figure 8.  Pond sampler.
       TABLE 2.  BASIC PARTS AND APPROXIMATE COSTS OF A POND SAMPLER
 Quantity
Item
Supplier
Approximate
   Cost	
          Clamp, adjustable, 6.4 to
          8.9 cm(2%  to 3% in.) for
          250-to 600-ml(% to 1%-pt.)
          beakers
          Tube, aluminum, heavy duty,
          telescoping extends  2.5 to
          4.5 m(8  to 15  ft.) with
          joint cam  locking mechanism.
          Pole diameters 2.54  cm(l in.)
          I.D. and 3.18  011(1%  in.) I.D.
                      Laboratory supply      $ 7.00
                      houses
                      Olympic Swimming        16.24
                      Pool Co. 807 Buena
                      Vista Street, Alameda,
                      Calif. 94501 or other
                      general swimming pool
                      supply houses.
1
4
4

Beaker, polypropylene,
Bolts, 6.35 by 0.64 cm(2k, by
k in.) NC
Nuts, 0.64 cmft in.) NC
Total
Laboratory supply
houses .
Hardware stores
Hardware stores

1.00
.20
.20
$24.64
                                    21

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Uses—

     The pond  sampler  is used  to  collect  liquid waste  samples  from disposal
ponds, pits, lagoons,  and  similar reservoirs.  Grab  samples  can be obtained
at  distances as  far  as 3.5 m(ll%  ft  ) from  the edge  of the ponds.   The
tubular aluminum handle may bow when sampling very viscous liquids if
sampling is not  done slowly.

Procedure for  Use—

  1.  Assemble the pond sampler.   Make sure that the sampling  beaker and
      the bolts  and  nuts that  secure the  clamp to the  pole are tightened
      properly.

  2.  With proper protective garment and  gear (see Section 6), take grab
      samples  from the pond at different  distances and depths  (see Section
      6).

  3.  Combine  the samples in one  suitable container  (see Section 6).

  4.  Cap the  container; label and affix  the seal; record in field log
      book; and  complete sample analysis  request sheet and chain of
      custody  record.

  5.  Dismantle  the  sampler; wipe  the parts with terry towels  or rags and
      store them in  plastic bags  for subsequent cleaning.  Store used
      towels or  rags in garbage bags for  subsequent disposal.

  6.  Deliver  the sample to the laboratory for analysis (see Section 6).

Weighted Bottle  Sampler

     This sampler (Figure 9) consists of a bottle, usually glass,  a weight
sinker, a bottle stopper, and a line that is used to open the  bottle and to
lower and raise  the  sampler during sampling.  There are a few  variations
of this sampler, as  illustrated in the ASTM Methods D  2708 and E 3009.
The ASTM sampler, which uses a metallic bottle basket  that also serves as
weight sinker,  is preferred.  The weighted bottle sampler can  either be
fabricated or purchased.

Uses—

     The weighted bottle sampler can be used to sample  liquids in  storage
tanks, wells, sumps, or other containers that cannot be adequately  sampled
with a Coliwasa.   The sampler cannot be used to collect liquids that are
incompatible or  that react chemically with the weight  sinker and line.

Procedure for use—

  1.  Assemble  the weighted bottle sampler as shown in Figure  9.
                                    22

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Using protective sampling equipment, in turn, lower the sampler to
proper depths to collect the following samples:
a) upper sample - middle of upper third of tank contents.
b) middle sample - middle of tank contents.
c) lower sample - near bottom of tank contents.
Pull out the bottle stopper with a sharp jerk of the sampler line.

Allow the bottle to fill completely, as evidence by the cessation of
air bubbles.
Raise the sampler and retrieve and cap the bottle.  Wipe off the out-
side of the bottle with a terry towel or rag.  The bottle can serve
as the sample container.
Label each of the three samples collected; affix seal^ fill out sample
analysis request sheet and chain of custody record; record in the
field log book.
Clean onsite or store contaminated sampler in a plastic bag for sub-
sequent cleaning.
Deliver the sample to the laboratory for analysis (see Section 6).
Instruct the laboratory to perform analysis on each sample or a
composite of the samples.
                                        Washer
                                       Pin
Eyelet
                                          Nut
         1000-ml (1-quart) weighted
               bottle catcher
            Figure 9.  Weighted bottle sampler.
                                23

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                               SECTION  5

                       PREPARATION FOR SAMPLING
GENERAL CONSIDERATIONS

     Adequate preparation for sampling is necessary to perform proper sam-
pling of any hazardous waste.  A checklist of items required for field
sampling helps to ensure proper preparation.  Such a checklist is given in
Appendix C.  The appendix lists the minimal equipment, accessories, and
supplies necessary to sample any type of solid or liquid waste.  When the
type of waste to be sampled is known beforehand, the list can be narrowed
down to the actual pieces of equipment to be used.

     When sample analyses are to be performed in the field, such as for pH,
flammability, or explosivity, then the necessary apparatus for such tests
should also be included in the preparation for sampling.

CLEANING AND STORAGE OF SAMPLER

     All samplers must be clean before use.  Used samplers must be washed
with warm detergent solution (i.e., Liquinox or Alconox), rinsed several
times with tap water, rinsed with distilled water, drained of excess water,
and air dried or dried with a stream of warm, dry air or wiped dry.  For
samplers that have been used to sample petroleum products and oil residues,
it may be necessary first to wipe the samplers with absorbent cloth to
eliminate the residues.  The equipment is then rinsed with an organic sol-
vent such as petroleum naphtha or trichloroethane, followed by washing with
the detergent solution and rinsing with water.  A necessary piece of equip-
ment for cleaning the tube of a Coliwasa is a bottle brush that fits tight-
ly the inside diameter of the tube.  The brush is connected to a rod of
sufficient length to allow for reaching the entire length of the sampler
tube.  Using this ramrod and fiber-reinforced paper towels, the Coliwasa
tube may be quickly cleaned.

     Improper cleaning of sampling equipment will cause cross contamination
of samples.  Such contamination is of particular importance in samples
taken for legal or regulatory purposes.  Also, contamination becomes im-
portant when sampling wastes from different production sources within the
same time frame.   A detailed study of cross contamination as a function of
cleaning procedures has not been carried out.  A recommended policy is that
if samples are to be taken for legal or regulatory purposes, or if analysis
is to be performed on samples expected to contain low-level (low ppm range)
                                    24

-------
concentrations of hazardous components, that a fresh, unused sampler be
used.  The Coliwasa in particular was designed to be semidisposable.  Parts
of the device that become contaminated during sampling (i.e., the tube, the
stopper rod, and the stopper mechanism) may be discarded at little expense.
In addition, or these parts may later be disassembled, secured, and returned
to the laboratory for thorough decontamination and reused.

     If the cleaning process has the potential for producing toxic fumes,
ensure adequate ventilation.  If the washings are hazardous, store them
in closed waste containers and dispose of them properly in approved dis-
posal sites.  Locations of these sites close to one's area may be obtained
by calling the agency in the State responsible for the regulation of hazard-
ous wastes.  Store the clean samplers in a clean and protected area.  Poly-
ethylene plastic tubes or bags are usually adequate for storing the samplers.
                                     25

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                                SECTION 6

                           SAMPLING PROCEDURES
 PURPOSES AND GENERAL CONSIDERATIONS

      Sampling of hazardous wastes is conducted for different purposes.  In
 most instances, it is performed to determine compliance with existing regu-
 lations promulgated by the different regulatory agencies.  In some cases,
 it is conducted to obtain data for purposes of classifying, treating, reco-
 vering, recycling, or determining compatibility characteristics of the
 wastes.  Sampling is also conducted as an important part of research activ-
 ities.

      In general, sampling of hazardous wastes requires the collection of
 adequate sized, representative samples of the body of wastes.  Sampling
 situations vary widely and therefore no universal sampling procedure can be
 recommended.  Rather, several procedures are outlined for sampling different
 types of wastes in various states and containers.

      These procedures require a plan of action to maximize safety of sam-
 pling personnel, minimize sampling time and cost, reduce errors in sampling,
 and protect the integrity of the samples after sampling.  The following
 steps are essential in this plan of action:

 1.  Research background information about the waste.
 2.  Determine what should be sampled.
 3.  Select the proper sampler.
 4.  Select the proper sample container and closure.
 5.  Design an adequate sampling plan that includes the following:
     a) Choice of the proper sampling point.
     b) Determination of the number of samples to be taken.
     c) Determination of the volumes of samples to be taken.

 6.  Observe proper sampling precautions.
 7.  Handle samples properly.
 8.  Identify samples and protect them from tampering.
 9.  Record all sample information in a field notebook.
10.  Fill out chain of custody record.
11.  Fill out the sample analysis request sheet.
12.  Deliver or ship the samples to the laboratory for analysis.
                                     26

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BACKGROUND INFORMATION ABOUT THE WASTE

     Accurate background information about the waste to be sampled is very
important in planning any sampling activity.   The information is used to
determine the types of protective sampling equipment to be used, sampling
precautions to be observed, as well as the types of samplers, sample con-
tainers, container closures, and preservatives (when needed) required.
Generally, the information about the waste determines the kind of sampling
scheme to be used.

     Most often, the information about the waste is incomplete.  In these
instances, as much information as possible must be obtained by examining
any documentation pertaining to the wastes, such as the hauler's manifest
(Figure 10).  When documentation is not available, information may be
obtained from the generator, hauler, disposer, or processor.  The informa-
tion obtained is checked for hazardous properties against references such
as the Dangerous Properties of Industrial Materials,10 the Merck Index,3
the Condensed Chemical Dictionary,H Toxic and Hazardous Industrial Chemi-
cals Safety Manual for Handling and Disposal with Toxicity and Hazardous
Data,l^ or other chemical references.

SELECTION OF SAMPLER

     Hazardous wastes are usually complex, multiphase mixtures of liquids,
semisolids, sludges, or solids.1  The liquid and semisolid mixtures vary
greatly in viscosity, corrosivity, volatility, explosivity, and flamma-
bility.  The solid wastes can range from powders to granules to big lumps.
The wastes are contained' in drums, barrels, sacks, bins, vacuum trucks,
ponds, and other containers.,  No single type of sampler can therefore be
used to collect representative samples of all types of wastes.  Table 3
lists most waste types and the corresponding recommended samplers to be
used.

SELECTION OF SAMPLE CONTAINER, CONTAINER CLOSURE, AND CLOSURE LINING

Containers

     The most important factors to consider when choosing containers for
hazardous waste samples are compatibility, resistance to breakage, and
volume.  Containers must not melt, rupture, or leak as a result of chemical
reactions with constituents of waste samples.  Thus, it is important to
have some idea of the components of the waste.  The containers must have
adequate wall thickness to withstand handling during sample collection and
transport to the laboratory.  Containers with wide mouths are desirable to
facilitate transfer of samples from samplers to containers.  Also, the
containers must be large enough to contain the required volume  of samplers
or the entire volume of a sample contained in samplers.

     Plastic and glass containers are generally used for collection and
storage of hazardous waste samples.  Commonly available plastic containers
                                    27

-------
are made of high-density or linear polyethylene (LPE), conventional poly-
ethylene, polypropylene, polycarbonate, teflon FEP (fluorinated ethylene
propylene), polyvinyl chloride (PVC), or polymethylpentene.  Teflon FEP is
the most inert plastic, but LPE offers the best combination of chemical
resistance and low cost.

     Glass containers are relatively inert to most chemicals and can be
used to collect and store almost all hazardous waste  samples except those
that contain strong alkali and hydrofluoric acid.  Soda glass bottles are
the cheapest and most readily available.  Borosilicate such as Pyrex and
Corex glass containers are also commercially available, but they are ex-
pensive and not always readily obtainable.  Glass containers are breakable
and much heavier than plastic containers.
                    CALIFORNIA LIQUID WASTE HAULER RECORD
                           STATE WATCH RESOURCES CONTROL BOARD
                             STATS DEPARTMENT OF HEALTH
009-Q00928
mODUCCfl Of WAffTf (MM M fHM br pradwv> ]
Name 1
(**•••* •* TTM) COM N«.
Fkk us Addreac
(MUH«««| (•T»B«T} (CITY)
TatapMone Numfaw. i . _! 	 mll , f> 0 or Canute! No
Or« H*.
wefteiMater treatment, pkkling bath, petroleum refining)
DMcaifTJOW OF WASTE MM* b* fitted by pradWMrlJ
Cheek type of «W«MM:
1 Q Acid solution 6. G Tetreothyl lead (Judge t D Contaminated Mil and atnd
J Q Alkaline tolution 7 D Chemical toilet wwn* 2 Q Cannery warn
3 O Penkldea B. D Tank bottom Mdlfn«ni 3 Q L»t«n wMf«
4 Q P»tot •ludot 9 D Oil 4 Q Mud and wM*r
« DSolvwtt 10 D Drilling «nud B Q Brlr*
G Oth« (SP«ifV) 1 |] 1
ComporMnn. ***" ™"
(ExamplM Hvdroctiforic »CK|, tHrt*. eaufffe tod*, Cone«ntr«tfon.
pn«nolic«. *ol«*mt (list). m«t»lf (Mn), Upow Lowor % ppm
orffjntea Ul«), cv*nld«)
1
a
4.
B
0.
M*ivdou« PropwtiM ol W«t«
DM O non« O to^te D fl«mnMbt« O corrocfev D mMo^w
Bulk Volume Q t*i O ton* C «2 »•* J O otftw ,_
rAn*.iMr.- n ^«.«« 1 1 »»AM n H,^ n -.K—
•hyiieiri Sun G ioi(d G liquid D tfud** G otft*r_Ts.__p_T.
^B«eW Huu4l.ftf In^ni^l^M )!# any^-


Th« w#t« i» d«crlbod to th« b«M of mv •bMltv «nd n w*> dMivorM to • iteonwtf liquid WWM hwl«r (If
•ppliertMl
I eonrfv (or doctwo) und«r ptnotty of portury
ihM tM IwvfOtn* to tru« and comet.
•MMATVN* •» «W«HOllW«0 *•••« AN* TCTVM
HAULER OF WASTE (MM be (Htod by hniM |
LLU
coe> na.
own
Plrb 1.1 p Ttm* Dom
*' a
•*«• Liquid W«t. M*ulM'i RtfiMmten No (tf »pplicM>l«) . , ._ 	 9.. .. .

VatileM: D vacuum truck _ b*rf *lt. D flMlMri, Doth*/....
(«*«ei^»)
facility nomod baloov «od «*M •ccoptod
1 conifv (or d*cl*r«) undor p*n«lty of porfury
that MM forMDlrw ta tru« and eorract.
«MM«rwN« «* *VT*t0Kt>«» Jt«VMT 4MB TITtB
DISPOSER OF WASTE (Mutt b» HM«1 by dnpOO»r> 1

COOK N*.
Th« haular abova daUvarad tha daacribod watta to thfe dlapOMl facility and it vwa» an •ccaptaWa
matarUI undar tha ttrmt of RWOCS raquirarnann, Stm O#P*rtmant of Haaltfi rwgultttom. and
local raatrtetlona.
Qiuntitv m*Murad at ilta (If aoalicablat: _ 	 Statafaa (if anwl: , . ,
Handing Matt>od(«):
Dracovory r~r~I
n *rMtrMr» iMMelfwI. 1 1 1
Q dtapoort (apOBffy): Q pond O aprMdin* G landftH G Infactfon «rotl , — . — .
coaa t*a.
n*^»*f-' °«»-- 	 .
1 corttfy (or daclara) undar ponarty of partury
that tna foregoing <• true and eorract.
Tha turn 9««nrror tfwll *wbm>t • iaoibia copy of aach completed Record to tha State Department of
FOR INFORMATION RELATED TO SIM L US Oft OTHER EMERGENCIES INVOLVING
HAZARDOUS WA»T» Oft OTHKH MATERIALS CAUL «QOl 434-9300.
Q a.T. *TBBM BMppInf MMM
                  Figure 10.  Example of waste manifest
                                    28

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       TABLE 3.  SAMPLERS RECOMMENDED FOR VARIOUS TYPES OF WASTE
   Waste type
Recommended
  sampler
        Limitations
Liquids, sludges,  Coliwasa
and slurries in
drums, vacuum       a) Plastic
trucks, barrels,
and similar
containers          , N „,
                    b) Glass
Liquids and
sludges in ponds,
pits, or lagoons
Powdered or gran-
ular solids in
bags,  drums,
barrels,  and
similar con-
tainers
Dry wastes in
shallow contain-
ers and surface
soil

Waste piles
Soil deeper
than 8 cm(3 in.)
Pond
Wastes in
storage tanks
 a) Grain
    sampler
 b) Sampling
    trier
Trowel or
scoop
Waste pile
sampler
 a) Soil auger
 b) Veihmeyer
    sampler

Weighted
bottle sampler
Not for containers 1.5 m(5 ft ) deep.

Not for wastes containing ketones,
nitrobenzene, dimethylformamide,
mesityl oxide, or tetrahydrofuran^'^.

Not for wastes containing hydro-
fluoric acid and concentrated alkali
solutions.

Cannot be used to collect samples
beyond 3.5 m(11.5 ft ).  Dip and
retrieve sampler slowly to avoid
bending the tubular aluminum handle.

Limited application for sampling moist
and sticky solids with a diameter
0.6 cmOs in.).

May incur difficulty in retaining core
sample of very dry granular materials
during sampling.

Not applicable to sampling deeper than
8 cm(3 in.).  Difficult to obtain
reproducible mass of samples.
Not applicable to sampling solid
wastes with dimensions greater than
half the diameter of the sampling tube.

Does not collect undisturbed core
sample.

Difficult to use on stony, rocky, or
very wet soil.

May be difficult to use on very
viscous liquids.
                                   29

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     Wide-mouth 1000-and 2000-ml(l qt-and ^-gal.) glass bottles are recom-
mended for waste samples containing petroleum distillates, chlorinated
hydrocarbons, pesticides, and petroleum residues that are mostly incom-
patible with plastic containers.  For all other types of samples, 1000-and
2000-ml(l-qt and %-gal.) wide-mouth LPE bottles are recommended.

Container Closures and Closure Linings

     The containers must have tight, screw-type lids.  Plastic bottles are
usually provided with screw caps made of the same material as the bottles.
No cap liners are usually required.  Glass containers usually come with
glass or rigid plastic screw caps such as Bakelite.  The plastic caps are
popularly provided with waxed paper liners.  Other liner materials are
polyethylene, polypropylene, neoprene, and Teflon FEP plastics.  For con-
taining hazardous waste samples requiring petroleum distillates, chlori-
nated hydrocarbons, pesticides, and petroleum residue analyses.  Bakelite
caps with Teflon liners are recommended to be used with glass bottles.
Teflon liners may be purchased from plastic specialty supply houses (e.g.,
Scientific Specialties Service, Inc., P.O. Box 352, Randallstown, Md.
21133).

     Table 4 shows most types of wastes and the corresponding sampling
containers and closures recommended.

SAMPLING PLAN

     The sampling plan should be well formulated before any actual sampling
is attempted.  The plan must be consistent with the objectives of the
sampling.  It must include the selected point(s) of sampling and the in-
tended number, volumes, and types (i.e., composite, grab, etc.) of samples
to be taken.  These requirements are discussed below.

POINT OF SAMPLING

     A representative sample is crucial to the sampling plan.  This sample
depends on proper selection of sampling points in the bulk of the waste.
Hazardous wastes are usually multiphase mixtures and are contained and
stored in containers of different sizes and shapes.  No single sampling
point can be specified for all types of containers.  Table 5 lists most
types of containers used for hazardous wastes and the corresponding
recommended sampling pqints.

NUMBER OF SAMPLES

     The number of samples to be taken primarily depends on the information
desired.  Table 6 lists the recommended number of samples to be collected
consistent with the information sought and the types of wastes to be
sampled.  In hazardous waste management, the properties and the average
concentrations of the hazardous components are usually desired.  In this
                                    30

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      TABLE 4.  SAMPLE CONTAINERS AND CLOSURES RECOMMENDED FOR

                             VARIOUS TYPES OF WASTE
Waste type
item
Recommended
container
Recommended
closure
Oil wastes except
pesticides, HC,
chlorinated HC, and
photosensitive
wastes


Pesticides, HC,
and chlorinated
HC
Linear polyethylene (LPE)
bottles,3 1000-and 2000-
ml (1-qt. and ^-gal.),
wide mouth
Glass bottles,b wide-
mouth, 1000-and 2000-ml
(1-qt. and ^-
 LPE caps
Bakelite caps
with Teflon
liner0
Photosensitive
wastes
Amber LPE or brown
glass** bottles, wide-
mouth, 1000-and 200-ml
(1-qt. and %-gal.)
LPE caps for
the LPE bottles;
Bakelite caps
with Teflon
liner for the
glass bottles
aNalgene, Cat. Nos. 2104-0032 and 2120-0005, or equivalent.

Scientific Products, Cat. Nos. 87519-32 and B7519-64, or equivalent.

Available from Scientific Specialities, P.O. Box 352, Randallstown,
 Md.

Scientific Products, Cat. Nos. B7528-050 and 7528-2L, or equivalent.
                                  31

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   TABLE 5.  SAMPLING POINTS RECOMMENDED FOR MOST .WASTE CONTAINERS
   Container type
                 Sampling point
Drum, bung on one end

Drum, bung on side
Barrel, fiberdrum,
buckets, sacks, bags
Vacuum truck and
similar containers

Pond, pit, lagoons
Waste pile
Storage tank


Soil
Withdraw sample through the bung opening.

Lay drum on side with bung up.  Withdraw
sample through the bung opening.

Withdraw samples through the top of barrels,
fiberdrums, buckets, and similar containers.
Withdraw samples through fill openings of
bags and sacks.  Withdraw samples through
the center of the containers and to different
points diagonally opposite the point of entry.

Withdraw sample through open hatch.  Sample
all other hatches.

Divide surface area into an imaginary grid.3
Take three samples, if possible:  one sample
near the surface, one sample at mid-depth or
at center, and one sample at the bottom.
Repeat the sampling at each grid over the
entire pond or site.

Withdraw samples through at least three
different points near the top of pile to
points diagonally opposite the point of
entry.

Sample from the top through the sampling hole.


Divide the surface area into an imaginary
grid.3   Sample each grid.
3The number of grid is determined by the desired number of samples
 to be collected, which when combined should give a representative
 sample of the wastes.
                                  32

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respect, collecting one representative sample of a given waste is usually
adequate.  This sample can either be collected from a single sampling point
with a composite sampler, or several samples can be collected from various
sampling points and combine into one composite sample.

     When gathering evidence for possible legal actions, multiple samples
of a waste are usually collected.  Three identical samples are desirable:
one sample is given to the company or organization responsible for the
waste, the second sample is submitted to the laboratory for analysis, and
the third sample is kept in storage for possible use as a referee sample.
Subdividing a waste sample is not recommended unless it is homogeneous.

VOLUME OF SAMPLES

     Sufficient volume of a sample, representative of the main body of the
waste, must be collected.  This sample must be adequate in size for all
needs, including laboratory analysis, splitting with other organizations
involved, etc.  In collecting liquid waste samples in drums, vacuum trucks,
or similar containers, the volume collected in the Coliwasa usually deter-
mines the volume of the sample.  This volume can range from 200 to 1800
(% pt. to 1.9 qt.).  In most cases, 1000 ml(l qt.) of a sample is usually
sufficient.  Hazardous wastes usually contain high concentrations of the
hazardous components, and only a small aliquot of the sample is used for
analysis.

SAMPLING PRECAUTIONS AND PROTECTIVE GEAR

     Proper safety precautions must always be observed when sampling ha-
zardous wastes.  In all cases, a person collecting a sample must be aware
that the waste can be a strong sensitizer and can be corrosive, flammable,
explosive, toxic, and capable of releasing extremely poisonous gases.^
The background information obtained about the waste should be helpful in
deciding the extent of sampling safety precautions to be observed and in
choosing protective equipment to be used..

     For full protection, the person collecting the sample must use a self-
contained breathing apparatus, protective clothing, hard hat, neoprene
rubber gloves, goggles, and rubber boots.

     A self-contained breathing apparatus consists of an air-tight face
mask and a supply of air in a pressure tank equipped with a pressure
regulator.  Protective clothing consists of long-sleeved neoprene rubber
coat and pants, or long-sleeved coverall and oil-and-acid proof apron.  In
hot weather, the coverall-apron combination might be preferred.  Table 7
lists the uses and commercial availability of respiratory protective equip-
ment.  All equipment except the respirator must be properly washed and
cleaned between uses (see Section 5).
                                    33

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          TABLE 6.   NUMBER OF SAMPLES TO BE COLLECTED
Case   Information
 No.     desired
Waste
  type
                                Container type
                         Number of samples
                          to be collected
  1  Average
     concentration


  2  Average
     concentration
  3  Average
     concentration
  4  Average
     concentration
  5  Average
     concentration
  6  Concentration
     range
  7   Concentration
     range
  8   Concentration
     range
  9   Concentration
     range

 10   Concentration
     range
 11  Average
    concentration
    for  legal
    evidence
 12  Average
    concentration

 13  Average
    concentration
Liquid   Drum, vacuum  truck,
         and similar
         containers

Liquid   Pond, pit, lagoon
Bag, drum, bin
Solid
(powder
or gran
ular)

Waste
pile
Soil
Liquid   Drum, vacuum truck,
         storage tank
Liquid   Ponds,  pit, lagoon
Solid    Bag, drum, bin
(powder
or gran-
ular)
Waste         —
 pile
Soil
All      All containers
types
Liquid   Storage tank
Liquid   Storage tank
                      1 Collected with
                        Coliwasa
1 Composite sample of
  several samples
  collected at differ-
  ent, sampling points
  or levels

  Same as Case #2
                        Same as Case #2

                      1 Composite sample of
                        several samples
                        collected at differ-
                        ent sampling areas

                      3 to 10 separate sam-
                        ples, each from a
                        different depth of
                        the liquid
                      3 to 20 separate sam-
                        ples from different
                        sampling points and
                        depths

                      3 to 5 samples from
                        different sampling
                        points

                        Same as Case #8

                      3 to 20 separate sam-
                        ples from different
                        sampling areas

                      3 Identical samples or
                        1 composite sample
                        divided into 3
                        identical samples if
                        homogeneous

                        Same as Case #2
                        Same as  Case #6
                                   34

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       TABLE 7.   RESPIRATORY PROTECTIVE DEVICES RECOMMENDED

                            FOR VARIOUS HAZARDS
 Type of hazard
Recommended respiratory device
Oxygen deficiency
Gaseous contaminant
immediately dangerous
to life

Gaseous contaminant
not immediately
dangerous to life

Particulate contaminant
Combination of gaseous and
particulate contaminants
immediately dangerous to
life

Combination of gaseous
and particulate contaminants
not immediately
dangerous to life
Self-contained breathing apparatus,
hose mask with blower

Self-contained breathing apparatus,
hose mask with blower,
gas mask

Air-line respirator,
hose mask without blower,
chemical-cartridge respirator

Dust, mist, or fume respirator,
air-line respirator,
abrasive-blasting respirator

Self-contained breathing apparatus,
hose mask with blower,
gas mask with special filter
Air-line respirator,
hose mask without blower,
chemical-cartridge respirator
  with special filter
Source:  Reference 14.
                                 35

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     The self-contained breathing apparatus may not be required in all
sampling situations.  In some cases, gas masks or chemical cartridge-type
respirators with filters will suffice.  Table 7 may be used to select the
proper protective respiratory device.

    » For added protection in sampling, a second person with a radio-
telephone and first-aid kit must be present to render any necessary
help or call for assistance.

SAMPLING PROCEDURES

     The following procedures are recommended for sampling different types
of hazardous wastes in various containers.

Sampling a Drum

     Drums containing liquid wastes can be under pressure or vacuum.  A
bulging drum usually indicates that it is under high pressure and should
not be sampled until the pressure can be safely relieved.  A heavily
corroded or rusted drum can readily rupture and spill its contents when
disturbed; it should only be sampled with extreme caution.  Opening the
bung of a drum can produce a spark that might detonate an explosive gas
mixture in the drum.  This situation is difficult to predict and must be
taken into consideration every time a drum is opened.  The need for full
protective sampling equipment cannot be overemphasized when sampling a
drum.

1.  Position the drum so that the bung is up (drums with the bung on the
    end should be positioned upright; drums with bungs on the side should
    be laid on its side, with the bungs up).

2.  Allow the contents of the drum to settle.

3.  Slowly loosen the bung with a bung wrench, allowing any gas pressure
    to release.

4.  Remove the bung and collect a sample through the bung hole with a
    Coliwasa, as directed in Section 4.

5.  When there is more than one drum of waste at a site, segregate and
    sample the drums according to waste types, using a table of random
    numbers as outlined in Appendix D.

Sampling a Vacuum Truck

     Sampling a vacuum truck requires the person collecting the sample to
climb onto the truck and walk along a narrow catwalk.  In some trucks, it
requires climbing access rungs to the tank hatch.  These situations pre-
sent accessability problems to the sample collector, who most usually
                                   36

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wear full protective sampling gear.  Preferably, two persons should
perform the sampling:  One person should do the actual sampling and the
other should hand the sampling device, stand ready with the sample con-
tainer, arid help deal with any problems.  The sample collector should
position himself to collect samples only after the truck driver has
opened the tank hatch.  The tank is usually under pressure or vacuum.
The driver should open the hatch slowly to release pressure or to break
the vacuum.

1.  Let the truck driver open the tank hatch.

2.  Using protective sampling gear, assume a stable stance on the tank
    catwalk or access rung to the hatch.

3.  Collect a sample through the hatch opening with a Coliwasa, as
    directed in Section 4.

4.  If the tank truck is not horizontal, take one additional sample each
    from the rear and front clean out hatches and combine all three
    samples in one sample container.

5.  When necessary, carefully take sediment sample from the tank through
    the drain spigot.

Sampling a Barrel, Fiberdrum, Can, Bags, or Sacks Containing Powder
or Granular Waste

     The proper protective respirator  (see Table 7), in addition to the
other protective gear, must be worn when sampling dry powdered or granu-
lar wastes in these containers.  These wastes tend to generate airborne
particles when the containers are disturbed.  The containers must be
opened slowly.  The barrels, fiberdrums, and cans must be positioned
upright.  If possible,, sample sacks or bags in  the position you find
them, since standing them upright might rupture the bags or sacks.

1.  Collect a composite sample from the container with a grain sampler
    or sampler trier, as directed  in Section 4.

2.  When there is more than one container of waste at a site, segregate
    and sample the containers according to a table of random numbers, as
    outlined in Appendix D.

Sampling a Pond

     Storage or evaporation ponds  for hazardous wastes vary greatly in
size from a few to a hundred meters.   It is difficult to collect repre-
sentative samples from the large ponds without  incurring huge expense
and assuming excessive risks.  Any samples desired beyond S.SmCll^ ft)
from the bank may require the use  of a boat, which is very risky, or
the use of a crane or a helicopter, which is very expensive.  The
                                   37

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 information sought must be weighed against the risk and expense of col-
 lecting the samples.  The pond sampler described in Section 4 can be used
 to collect samples as far as 3.5 m(ll% ft ) from the bank.

 1.  Collect a composite sample with pond sampler, as directed in Section
     4.

 Sampling Soil

      The techniques of soil sampling are numerous.  The procedures out-
 lined below are adopted from ASTM methods.15  The procedures are consist-
 ent with the hazardous waste management objective of collecting soil
 samples which is usually to determine the amount of hazardous material
 deposited on a particular area of land or to determine the leaching rate
 of the material and/or determine the residue level on the soil.  Elaborate
 statistically designed patterns have been designed for sampling soils.  If
 one of these patterns is to be used, a good statistics book may have to be
consulted.  In the following procedures, soil samples are  taken in a grid
pattern over the entire site to ensure a uniform coverage.

1.  Divide the area into an imaginary grid (see Table 5).

2.  Sample each grid and combine the samples into one.

3.  To sample up to 8 cm(3 in.) deep, collect samples with a scoop, as
    directed in Section 4.

4.  To sample beyond 8 cm(3 in.) deep, collect samples with a soil auger
    or Veihmeyer soil sampler, as directed in Section 4.

Sampling a Waste Pile

     Waste piles can range from small heaps to a large aggregates of
wastes.  The wastes are predominantly solid and can be a mixture of powders,
granules, and chunks as large as or greater than 2.54 cm(l in.) average
diameter.  A number of core samples have to be taken at different angles
and composited to obtain a sample that, on analysis, will give average
values for the hazardous components in the waste pile.

1.   Determine the sampling points (see Table 5).

2.   Collect a composite sample with a waste pile sampler according to the
    directions in Section 4.

Sampling a Storage Tank

     The collection of liquid samples in storage tanks is extremely dis-
cussed in the ASTM methods.   The procedure used here is adopted from one
of those methods.16
                                    38

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      Sampling a storage tank requires a great deal of manual dexterity.
Usually it requires climbing to the top of the tank through a narrow
vertical or spiral stairway while wearing protective sampling equipment
and  carry sampling paraphernalia.  At least two persons must always per-
form the sampling:  One should collect the actual samples and the other
should stand back, usually at the head of the stairway, and observe, ready
to assist or call for help.  The sample collectors must be accompanied by
a representative of the company, who must open the sampling hole, usually
on the tank roof.

1.   Collect one sample each from the upper, middle, and lower sections of
     the tank contents with a weighted bottle sampler, as outlined in
     Section 4.

2.   Combine the samples one container and submit it as a composite sample.

SAMPLE HANDLING

      After a sample is transferred into the proper sample container, the
container must be tightly capped as quickly as possible to prevent the
loss  of volatile components and to exclude possible oxidation from the air.

     The use of a preservative or additive is  not recommended.   However,
if only one or two components of a waste are of interest,  and if these
components are known to rapidly degrade or deteriorate chemically or bio-
chemically,  the sample may be refrigerated at  4 to 6°C.(39.2 to 42.8°F.)
or treated with preservatives according to Section 8.

     To split or withdraw an aliquot of a sample, considerable mixing,
homogenization, or quartering is required to ensure that representative
or identical portions are obtained.  When transferring a sample aliquot,
open the container as briefly as possible.

IDENTIFICATION OF SAMPLE

     Each sample must be labeled and sealed properly immediately after
collection.

Sample Labels

     Sample labels (Figure 11)  are necessary to prevent misidentification
of samples.   Gummed paper labels or tags are adequate.   The label must
include at least the following information:

     Name of collector.

     Date and time of collection.

     Place of collection.
     Collector's sample number, which uniquely identifies the sample.
                                    39

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                       OFFICIAL SAMPLE LABEL

Collector	  Collector's Sample No.

Place of Collection            	   .
Date Sampled	  Time Sampled_

Field Information	
             Figure 11.  Example of official sample  label.
                       OFFICIAL SAMPLE   SEAL
     State of California                       Public  Health Division
Department of Health Services               Hazardous  Materials Laboratory

Collected by	Collector's  Sample No.	
                   (signature)
Date Collected                         Time Collected  	
Place Collected
             Figure 12.  Example of official sample seal
                                  40

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Sample Seals
     Sample seals are used to preserve the integrity of the sample from the
time it is collected until it is opened in the laboratory.  Gummed paper
seals can be used as official sample seals.  The paper seal must carry
information such as:
     Collector's name
     Date and time of sampling
     Collector's sample number.   (This number must be identical with the
     number on the sample label).
     The seal must be attached in such a way that it is necessary to break
it in order to open the sample container.  An example of a sample seal is
shown in Figure 12.
FIELD LOG BOOK
     All information pertinent to a field survey and/or sampling must be
recorded in a log book.  This must be a bound book, preferabley with con-
secutively numbered pages that are 21.6 by 27.9 cm(8% by 11 in.).  Entries
in the log book must include at least the following:
     Purpose of sampling (e.g.,  surveillance, etc.)
     Location of sampling (e.g., hauler, disposal site, etc.) and address
     Name and address of field contact
     Producer of waste and address
     Type of process (if known)  producing waste
     Type of waste (e.g., sludge,  wastewater, etc.)
     Declared waste components and concentrations
     Number and volume of sample taken
     Description of sampling point
     Date and time of collection
     Collector's sample identification number(s)
     Sample distribution (e.g.,  laboratory, hauler, etc.)
     References such as maps or photographs of the sampling site
     Field observations
     Any field measurements made such as pH, flammability, explositivity,
     etc.
     Sampling situations vary widely.  No general rule can be given as to
the extent of information that must be entered in the log book.  A good
                                   41

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 rule, however, is to record  sufficient information so that someone  can
 reconstruct  the sampling situation without reliance on the collector's
 memory.

     The log book must be protected and kept in a safe place.

 CHAIN OF CUSTODY RECORD

     To establish the documentation necessary to trace sample possession
 from the time of collection, a chain of custody record must be filled out
 and accompany every sample.  This record becomes especially important when
 the sample is to be introduced as evidence in a court litigation.   An
 example of a chain of custody record is illustrated in Figure 13.

     The record must contain the following minimum information:

     Collector's sample number

     Signature of collector

     Date and time of collection

     Place and address of collection

     Waste type

     Signatures of persons involved in the chain of possession

     Inclusive dates of possession

 SAMPLE ANALYSIS REQUEST SHEET

     The sample analysis request sheet (Figure 14) is intended to accom-
 pany the sample on delivery to the laboratory.   The field portion of this
 form must be completed by the person collecting the sample and should
 include most of the pertinent information noted in the log book.  The
 laboratory portion of this form is intended to be completed by laboratory
 personnel and to include:

     Name of person receiving the sample
     Laboratory sample number
     Date of sample receipt

     Sample allocation
     Analyses to be performed

 SAMPLE DELIVERY TO THE LABORATORY

     Preferably,  the sample must be delivered in person to the laboratory
 for analysis as soon as practicable—usually the same day as the sampling.
Consult Section 8 when.sample preservation is required.   The sample must
                                    42

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California Department of Health
  Hazardous Materials Laboratory
                Collector's  Sample No,
                       CHAIN OF CUSTODY  RECORD
                            Hazardous  Materials


Location of Sampling:  	 Producer     	 Hauler

                       	 Other:	

Company's Name	

Address
                             Disposal Site
                        Telephone  (	)_
         number  street

Co11ector's Name	

Date Sampled	
        city
 state        zip

Telephone (	)	
signature
          Time Sampled_
Type of Process Producing Waste_

Waste Type Code	 Other_
Field Information
          hours
Sample Allocation:

1.

2.

3.
1.

2.

3.
name of organization
name of organization
n of Possession
signature
signature
signature
name of organization
title
title
title

inclusive dates
inclusive dates
inclusive dates
                Figure 13.   Example of chain  of  custody record

                                     43

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PRIORITY	                          California Department of Health Services
(explain)	             Hazardous Materials Laboratory
            HAZARDOUS MATERIALS SAMPLE ANALYSIS REQUEST

PART I;  FIELD SECTION	

Collector	 Date Sampled	 Time	hours

Location of Sampling	
                            name of company, disposal site, etc.
Addres s   	
          number      street        city            state          zip
Telephone (	)	  Company Contact	
  HML NO.   COLLECTOR'S   TYPE  OF                        »
(Lab only)  SAMPLE NO.    SAMPLE*                 FIELD INFORMATION**
Analysis Requested_
Special Handling and/or Storage_
PART II:  LABORATORY SECTION
Received by	 Title	 Date_
Sample Allocation:   	HML    	LBL     	LABL     	SRL       Date_
Analysis Required	
    *Indicate whether sample  is  sludge, soil, etc.;**Use back of page for
additional information.
 Figure 14.  Example of hazardous waste sample analysis request sheet

                                     44

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be accompanied by the chain of custody record and by a sample analysis
request sheet (Figure 14).   The sample must be delivered to the person
in the laboratory authorized to receive samples (often referred to as
the sample custodian).

SHIPPING OF SAMPLES

     When a sample is shipped to the laboratory, it must be packaged in a
proper shipping container to avoid leakage and/or breakage.  A cardboard
box that will provide at least 10 cm(4 in.) of tight packing around the
sample container must be used.  Acceptable packing materials include saw-
dust, crumpled newspapers,  vermiculite, polyurethane chips, etc.  Other
samples that require refrigeration must be packed with reusable plastic
packs or cans of frozen freezing gels in molded polyurethane boxes with
sturdy fiberboard protective case.  The boxes must be taped closed with
masking tape or fiber plastic tape.

     All packages must be accompanied by a sample analysis sheet and chain
of custody record.  Complete address of the sender and the receiving lab-
oratory must legibly appear on each package.  When sent by mail, register
the package with return receipt requested.  When sent by common carrier,
obtain a copy of the bill of lading.  Post office receipts and bill of
lading copies may be used as part of the chain of custody documentation.^
                                    45

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                              SECTION  7

                    RECEIPT AND LOGGING OF SAMPLE
     Field samples are delivered to the laboratory either personally or
through a public carrier.  In the laboratory, a sample custodian should
be assigned to receive the samples.  Upon receipt of a sample, the custo-
dian should inspect the condition of the sample and the sample sea],
reconcile the information on the sample label and seal against that on the
chain of custody record, assign a laboratory number, leg in the sample in
the laboratory log book, and store the sample in a secured sample storage
room or cabinet until assigned to an analyst for analysis.

SAMPLE INSPECTION

     The sample custodian should inspect the sample for any leakage from
the container.  A leaky container containing multiphase sample should
not be accepted for analysis.  This sample will no longer be a represen-
tative sample.  If the sample is contained in a plastic bottle and the
walls show any bulging or collapsing, the custodian should note that the
sample is under pressure or releasing gases, respectively.  A sample
under pressure should be treated with caution.  It can be explosive or
release extremely poisonous gases.   The custodian should examine whether
the sample seal is intact or broken,  since broken seal may mean sample
tampering and would make analysis results inadmissible in court as evi-
dence.  Discrepancies between the information on the sample label and seal
and that on the chain of custody record and the sample analysis request
sheet should be resolved before the sample is assigned for analysis.   This
effort might require communication with the sample collector.   Results of
the inspection should be noted on the sample analysis request  sheet and
on the laboratory sample log book.

ASSIGNMENT OF LABORATORY NUMBER

     Incoming samples usually carry the inspector's or collector's identi-
fication numbers.   To further identify these samples, the laboratory
should assign its own identification numbers, which normally are given
consecutively.  Each sample should be marked with the assigned laboratory
number.   This number is correspondingly recorded on a laboratory sample
log book along with the information describing the sample.  The sample
information is copied from the sample analysis request sheet and cross-
checked against that on the sample label.
                                    46

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 ASSIGNMENT OF SAMPLE FOR ANALYSIS

     In most cases, the laboratory supervisor assigns the sample for ana-
lysis.  The supervisor should review the information on the sample analysis
request sheet, which now includes inspection notes recorded by the labora-
tory sample custodian.  The supervisor should then decide what analyses
are to be performed.  The sample may have to be split with other labora-
tories to obtain tne necessary information about the sample.  The super-
visor should decide on the sample allocation and delineate the types of
analyses to be performed on each allocation.  In his own laboratory, the
supervisor should assign the sample analysis to at least one chemist, who
is to be responsible for the care and custody of the sample once it is
handed to him.  He should be prepared to testify that the sample was in
his possession or secured in the laboratory at all times from the moment
it was received from the custodian until the analyses were performed.

    • The receiving chemist should record in his laboratory notebook the
identifying information about the sample, the date of receipt, and other
pertinent information.  This record should also include the subsequent
analytical data and calculations.
                                    47

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                              SECTION  8

                   PRESERVATION AND STORAGE OF SAMPLES
     Ideally, hazardous waste samples should be analyzed immediately after
collection for maximum reliability of the analytical results.  Hazardous
wastes are such complex mixtures that it is difficult to exactly predict
the physical, biological, and chemical changes that occur in the samples
with time.  After collection of samples, pH may change significantly in a
matter of minutes; sulfides and cyanides may be oxidized or evolve as
gases; and hexavalent chromium may slowly be reduced to the trivalent
state.  Certain cations may be partly lost as a result of adsorption to
the walls of the sample containers.  Growth of microorganisms may also
cause changes to certain constituents of the sample.  Volatile compounds
may be rapidly lost.

     In a number of cases, the above changes may be slowed down or pre-
vented by refrigeration at 4 to 6°C, or by the addition of preservatives.
However, these treatments mostly apply to one or two components or pro-
perties.  Refrigeration may deter the evolution of volatile components and
acid gases such as hydrogen sulfides and hydrogen cyanides, but it also
introduces the uncertainty that some salts may precipitate at lower temper-
ature.  On warming to room temperature for analysis, the precipitates may
not redissolve, thus incurring error in determining the actual concentra-
tions of dissolved sample constituents.  Addition or preservatives may
retard biochemical changes, whereas other additives may convert some
constituents to stable hydroxides, salts, or compounds.  Unknown in these
treatments, however, is the possible conversion of other compounds to other
forms (such as the products of nitration, sulfonation, oxidation, etc., of
organic components).  In subsequent analyses, the results may not reflect
the original identity of the components.

     Thus, both advantages and disadvantages are associated with the refri-
geration and/or addition of preservatives or additives to waste samples.
These methods of preservation or stabilization are not recommended for
hazardous waste samples unless only one or two components or properties
are to be analyzed.

     Standard methods books 1"»19 have compilations of useful preservatives
for various constitutents.  Table 8 is excerpted from these lists and shows
only the preservation methods that may be used for hazardous wastes.
                                     48

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        TABLE 8.   METHODS OF PRESERVATION FOR HAZARDOUS WASTES
Waste constituent
to be preserved
Acidity
Alkalinity
Ammonia
Arsenic
Chlorine
Chromium (VI)
Cyanides
Fluoride
Metals:
1) dissolved
2) suspended
3) Total
Mercury
1) dissolved
2) Total
PH
Phenolics
Residue, volatile
Selenium
Specific
conductance
Sulfide
Sulfide
Zinc
Preservation method Storage time
Cool to 4° C
Cool to 4° C
Add 1 ml cone. H2S04/&
Add 6 ml cone. HN03/ &
Cool to 4° C
Add 6 ml cone. H2S04/£
Add 2.5 ml of 50% NaOH/& ;
cool to 4° C
Cool to 4° C

Filter on site; add 5 ml
cone. HN03/&
Filter on site
Add 5 ml cone. HN03/£
Filter; add 5 ml cone. HN03/&
Add 5 ml cone. HN03/£
Determine on site; cool to 4° C
Add H3P04 to pH 4 and 1 g.
CuS04/& ; refrigerate at 4° C
Cool to 4° C
Add 5 ml cone. HN03/£
Cool to 4° C
Add 2 ml of 2N 7
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                                REFERENCES


 1.  Stephens, R. D. 1976. Hazardous Sampling; Residual Management by Land
     Disposal.  Proceedings of the Hazardous Waste Research Symposium,
     University of Arizona, Tucson, Ariz.

 2.  Eichenberger, B.,  J.  R. Edwards, K.  Y.  Chen,  and R. D. Stephens.  1977.
     A Case Study of Hazardous Wastes Input  Into Class I Landfills.  U.S.
     Environmental Protection Agency, Cincinnati,  Ohio.

 3.  Merck Index, An Encyclopedia of Chemicals and Drugs.  1968.   9th Ed.
     Merck & Co., Rahway.

 4.  Chemical Resistance of Excelon R-4000.   1977.  Thermoplastic Process,
     Inc., Stirling, N.J.

 5.  Sampling Procedure for Animal Feed.   Official Methods-of Analysis of
     the Association of Official Analytical  Chemists.  1975.   12th Ed.
     Washington,  D.C.,  p.  129.

 6.  Guidelines on Sampling and Statistical  Methodologies for Ambient Pesti-
     cide Monitoring.   1974.  Federal Working Group on Pest Management, U.S.
     Environmental Protection Agency, Washington,  D.C., p. III-5.

 7.  Veihmeyer, F. J.  1929.  An Improved  Soil-Sampling Tube.   Soil Science
     27/2): 147-152.

 8.  American Society for Testing and  Materials.   1975.  ASTM D270.   ASTM
     Standards.  The Society, Philadelphia,  Pa.

 9.  American Society for Testing and Materials.  1973.  ASTM E 300.   ASTM
     Standards.  The Society, Philadelphia,  Pa.

10.  Sax,  I. N. 1968.   Dangerous Properties  of Industrial Materials.   3rd
     Ed. Van Nostrand Reinhold Co. New York, N.Y.

11.  Condensed Chemical Dictionary.  1977.  8th Ed. Van Nostrand  Reinhold
     Co.,  New York, N.Y.

12.  Toxic and Hazardous Industrial Chemicals Safety Manual for Handling
     and Disposal With Toxicity and Hazardous Data.  1976.  International
     Technical Information Institute, Tokyo, Japan.

13.  Dunlap, J.  1972.   Industrial Waste  Law (AB 596), State of California.
                                    50

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14.  Bureau of Labor Standards.   Respiratory Protective Equipment.
     Bulletin 226.   Safety in Industry;  Environmental and Chemical
     Hazards, No.  3.  U.S. Department of Labor,  Washington,  D.C.

15.  American Society for Testing and Materials.  ASTM D1452,  D1586 and
     D3550.  ASTM Standards.   The Society,  Philadelphia, Pa.

16.  American Society for Testing and Materials.  ASTM D270  and E 300
     ASTM Standards.  The Society, Philadelphia, Pa.

17.  Compliance Monitoring Procedures.  1974.  EPA 330/1-74-/002.  U.S.
     Environmental Protection Agency, Denver, Colo.

18.  Manual of Methods for Chemical Analysis of Water and Wastewater.
     1974.  EPA-625/6-74-003.  U.S. Environmental Protection Agency,
     Washington, D.C.

19.  Standard Methods for Examination of Water and Wastewater.  1975.  14th
     Ed. American Public Health Association, New York, N.Y.

20.  Collection, Storage, Transportation, and Pretreatment of Water and
     Wastewater Samples.  1971.   California Department of Health Services,
     Berkeley, Ca.
                                     51

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                               APPENDICES
  APPENDIX A.  DEVELOPMENT OF THE COMPOSITE LIQUID WASTE SAMPLER (COLIWASA)

     Early in the development of the California waste management program,
the needs were recognized for accurate information about waste composition
and adequate equipment and procedures for sampling and analysis.

     In 1975, the California Department of Health Services engaged in a
cooperative study with the University of Southern California (Environmental
Engineering Department) under U.S. Environmental Protection Agency's spon-
sorship to collect and analyze a large number of hazardous waste samples
at a number of Class I disposal sites in Los Angeles County.  In the prep-
aration ' of this study, the Department of Health Services personnel designed
and constructed a simple tube sampler suitable for use in liquid and sludge
wastes.  The objective of the sampler design was to obtain samples represent-
ative of complex, heterogeneous wastes contained in vacuum trucks and drums.
In preliminary testing, the prototype design shown in Figure A-l appeared to
give good representative samples.  At this time, the sampling device was
named the composite liquid waste sampler, or Coliwasa for short.

Requirements for Hazardous Waste Sampling Procedures and Equipment

     Approximately 24 of these devices were constructed for use in the Los
Angeles County sampling program.  During a 2-week period in 1975, 400 samples
of hazardous wastes were taken from vacuum trucks and drums.  The wastes
represented an extremely wide variety of chemical compositions and physical
characteristics.  The experience given by this sampling program emphasized
the following important requirements of hazardous waste sampling procedures
and equipment:

1)  Sampling equipment must be of simple design to facilitate easy cleaning
    or to allow discard if necessary to prevent sample cross contamination.
    Many wastes, because of their chemical composition and/or physical nature,
    so fouled sampling equipment that it required discarding or extensive
    cleaning.  Extensive cleaning produces a significant volume of cleaning
    waste that must be properly disposed.  Equipment that has complicated
    valves, levers, and other fittings would never survive many hazardous
    wastes.

2)  Equipment must be light weight and leak proof.  Sampling personnel are
    required to climb and move about on tank trucks and other dangerous areas
    while holding sampling equipment.  Once the sampler is filled with its
                                     52

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    charge of hazardous  waste,  it  must  not  discharge  until property
    a sample receptacle.  Thus, a  positive  locking mechanism is needed.

3)  Several types of sampling equipment must be available, for no one de-
    sign or material meets all hazardous waste sampling requirements.

4)  Sampling requires a  minimum of two  persons equipped with the proper
    and complete complement of safety equipment.   Even at a well-run waste
    disposal site using  an approved manifest system,  surprises occur. A
    waste sample collector never knows  for  sure what  he will find when a
    vacuum truck or barrel is opened.
                  183 cm (72")
           152 cm (60")
                                        Rod, PVC, 0.95 cm (3/8") O.D.
                                        Pipe, WC, 4.13 cm (1 5/8") I.D.,
                                         A.78 cm (1 7/8") O.D.
                                        Stopper, neoprene, #9
                                        Nut and washer, stainless steel,
                                         0.95 cm (3/8")
                     Figure 1.  Coliwasa, Model 1.
Sampler Selection
     A review of the literature was conducted to investigate the availabil-
ity of commercial equipment: that would better suit the sampling require-
ments than the Coliwasa.  The guidelines used in the selections were
commercial availability, cost, simplicity in design, chemical inertness,
and adaptability for use in composite sampling of liquid hazardous wastes.

     Preliminary tests were performed on a number of candidate liquid
samplers.  The tests included physical inspections of the sampling mechan-
isms for ease of operation and applicability.  Water was the initial test
liquid.  The test water was placed in a fabricated tank made out of a
                                    53

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122-cm(4-ft) tall by 15.2-cm(6-in.) I.D. glass cylinder.  Each sampler
under test was lowered slowly into the tank to determine whether the check
valve or closing device or sampling orifice would allow the sample to flow
in the sampler.  The sampler was then withdrawn and tested for leakage and
ease of transfer of the collected sample.

     None of the commercially available samplers was found to be satis-
factory.  The Coliwasa designed by the Department of Health Services
appeared to be the most promising.

First Coliwasa Model

     The early design of the Coliwasa (Model 1; Figure A-l) consisted of
1.52-m(5-ft.) by 4.13-cm(l ,5/8-in.) I.D., opaque PVC pipe as the sampling
tube and a neoprene stopper attached to one end of a 0.95-cm(3/8-in.) O.D.
PVC rod as the closing mechanism.  To collect a sample with this sampler,
the stopper is pushed out about 5 cm(2 in.) from the bottom end of the
sampling tube.  Then the sampler is lowered straight down through the body
of liquid waste to be sampled to the bottom of the waste container.  The
liquid in the tube is trapped by plugging the bottom of the tube with the
stopper by pulling up the stopper rod with one hand and holding the tube
with the other hand.

     This early design of the Coliwasa, albeit functional, was deficient in
a number of aspects.  First, it was difficult to put the sampler in the
close position.  The stopper did not easily line up with the bottom opening
of the sampling tube.  Several manipulations of the stopper rod were usually
required to effect closure.  This difficulty tended to disturb the bottom
layer of the waste being sampled and undoubtedly contributed to the col-
lection of nonrepresentative samples.

     Second, the sampler was not equipped with a mechanism that positively
and independently locked it closed.  Closure was maintained by using one
hand to hold the sampling tube and the other hand to maintain a constant
upward pressure on the upper end of the stopper rod to keep the stopper
tightly seated against the bottom opening of the sampler.  In some samp-
ling instances, this method of closure was not always practical.  When
sampling waste containers as deep as the length of the sampler, the opera-
tor could not withdraw the sampler without freeing the hand that maintains
the closing pressure on the stopper rod.  Thus, the snug contact between
the  neoprene stopper and the inner opening of the sampling tube was the
only force that locked the sampler closed.  The weight of the sample con-
tained in the sampling tube has in some cases pushed out the stopper,
resulting in lost samples and exposure of the sample collector to unneces-
sary hazards.

     Third, samples contained in the sampler were difficult to transfer
into sample containers at regulated rates, and caused some samples to be
lost from splashings.

-------
    Attempts were made to improve the first model of the Coliwasa.  These
efforts led to fabrication of the other models shown in Figures A-2 through
A-5, and finally to the recommended version as shown in Figure 1 of the text.

Models 2 and 3

     The improvement in the second model of the Coliwasa (Figure A-2) con-
sisted of making diametrical slits, 5 cm(2 in.) deep by 2 cm(0.79 in.) wide,
and indentations 90° from the slits at the top of the sampler tube.  The
slits accommodate the T-handle of the stopper rod in the open position, which
allows the stopper to extend down about 5 cm(2 in.)  below the bottom of the
sampler.  The indentations serve as support for the T-handle when the sam-
pler is placed in the close position.  When this improved Coliwasa was tested
the neoprene stopper still did not readily line up with the bottom opening
of the sampling tube.  Several twisting manipulations of the stopper rod
were required to bring the sampler into the close position.  This problem
was remedied by installing three stainless steel guide wires (18 gauge) on
the stopper, with the upper wire ends secured to the stopper rod, as shown
in Figure A-3.  This version (Model 3) of the sampler was again tested.  The
sampler was found functional and relatively easy to operate.  It can be dis-
assembled and reassembled for cleaning in about 2 minutes.   It can be built
for less than $10.00.  The closing tension on the stopper of this sampler,
however, is not easily adjusted while sampling.  This drawback might incur
some sample loss.
                                 1.91 cm (3/4")
                                    O.D. rod
                                   V
      152 cm (60")
          155 cm (61")
                           T~r
t
                    EXPANDED VIEW OF
                     TOP OF SAMPLER
0.95 cm (3/8") O.D.
  rod, PVC


4.13 cm (1 5/8")
  I.D. pipe, PVC
OPEN
                                                  CLOSE
                        S topper, neoprene,
                         #9, with PVC nut
                         and washer
                       Figure A-2.  Coliwasa, Model 2.
                                     55

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p
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                                                                                                 to
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                                                                                                 0)
                                                                                                 I
                                        56

-------
Model 4

     Further investigation into improving the design of the Coliwasa re-
sulted in Model 4(Figure A-4).   In this version, the locking mechanism of
the sampler consisted of a threaded PVC plug that rides on a short threaded
0.95-cm(3/8-in.) O.D. metal rod.  The metal rod is coupled with the PVC
stopper rod.  To sample, the plug is screwed out about 5 cm and then the
stopper rod is pushed downward to open the sampler.   The sampler is lowered
slowly into the liquid.  Upon reaching the bottom of the container, the
stopper rod is pulled up to close the sampler.  The PVC plug is screwed in
until tight to secure the stopper in the close position.  This design of
the Coliwasa is simple, functional, and provides the person collecting the
sample with control over the tightness of the stopper against the bottom
of the sampler.  It is, likewise, easily disassembled and reassembled for
cleaning.  This sampler, however, is slow to operate, the PVC plug does not
screw in and out fast enough.  This drawback tends to expose the sample col-
lector to the liquid waste during sampling longer than is perhaps necessary.

Model 5

     Another model of the Coliwasa was fabricated using a closing principle
similar to a float valve (Figure A-5).  This sampler was fabricated from a
1.52-m(5-ft) by 5.1-cm(2-in.) I.D. plastic, pipe.  At the bottom end is a
plastic reducer fitting (5.1-cm(2-in.) to 3.18-cm(1.5-in.) I.D.).  A manu-
ally operated neoprene rubber plug attached to a rod is used as the closing
device.  When sampling, the rubber plug is raised about 5 cm(2-in.) above
its seat, and the sampler is slowly lowered into the liquid.  On reaching
the bottom of the container, the sampler is closed by slowly lowering the
plug back to its seat.  The sampler is withdrawn and the sample is dischar-
ged into a sample container.  Tests performed on this sampler showed no
leakage of collected samples.  This sampler was also found to be the easiest
to disassemble and reassemble for cleaning.  However, the annular clearance
between the outside diameter of the stopper and the inside diameter of,, the
sampling tube was too narrow.  The sampler tended to stir the liquid mixture
on filling, which could incur the collection of nonrepresentative sample.
In addition, the sampler tended to exclude large particles in the wastes.
Increasing the tube/stopper annular clearance did not seem practical because
it conversely reduced the opening of the reducer fitting of the sampling
tube.

Final Design

     A much improved and recommended model of the Coliwasa is shown in Fig-
ure 1 of the text.  This model  features three main improvements over the
previous models.  The first improvement consists of the use of a positive,
quick engaging closing and locking mechanism.  This mechanism consists of a
short-length, channeled aluminum bar that is attached to the sampler's
stopper rod by an adjustable swivel.  The aluminum bar serves both as a
T-handle and lock for the sampler's closure system.  When the sampler is in
the open position, the handle is placed in the T-position and pushed
down agains the locking block.  This manipulation pushes out the
                                    57

-------
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58

-------
neoprene stopper and opens the sampling tube.  In the cl ose position, the
handle is rotated until one leg of the T is squarely perpendicular against
the locking block.  This tightly seats the neoprene stopper against the
bottom opening of the sampling tube and positively locks the sampler in the
close position.  The closure tension can be adjusted by shortening or length-
ening   the stopper rod by slightly screwing it in or out of the T handle
swivel.  In discharging a collected sample, the T handle is slowly brought
into the T-position.  This facilitates the opening of the sampler at a con-
trollable rate and permits the transfer of the sample into a sample container
at a regulated rate, thus minimizing splashing or loss of sample.

    The second improvement made is the use of a sharply tapered neoprene
stopper.  The sharp taper of the stopper eliminates the use of guide wires
and facilitates the proper seating of the stopper against the opening of the
sampling tube on closure.  This stopper can be fabricated to specfications by
plastic products manufacturers at an extremely high price, or it can be made
by simply grinding down the inexpensive and commercially available neoprene
stopper to the desired taper with a shop grinder (Note 1 in Appendix B).

     The third improvement is the use of translucent PVC and glass pipes
as the sampling tubes.  These tubes permit the observation of the phases of
the liquid waste sample collected in the sampler.  The glass sampling tube
is usually used with a Teflon stopper rod.  Each tube is used for different
purposes, as described in Section 4 of the text.

     The improved model of the Coliwasa was tested in the field and in the
laboratory and found to be the most practical and capable of collecting
representative samples of multiphase liquid wastes samples.

Laboratory Tests

     In the laboratory, the testing was conducted using test liquid mixtures
in a 122-cm (4-ft) tall by 15.2-cm(6-in.) I.D. glass cylindrical tank.  The
glass tank was ideal for the tests because it permitted observation and
measurement of the relative heights of the liquid phases.

     A two-phase liquid mixture consisting of about 13.9 liters of water
and 3.29 liters of waste oil was sampled with the Coliwasa.  The sample
was  emptied into a 1000-ml (1.056 qt) graduated cylinder.  The relative
volumes of the liquids were determined and  given in Table A-l.

     The results indicate that the Coliwasa is capable of obtaining a repre-
sentative sample of a two-phase liquid mixture.
                                     59

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                                TABLE A-l.

           Relative Volumes of Liquids in the Two-Phase Mixture


    Item                             Oil              Water

 % by height of
 phases in tank                       19               81


 % by volume collected                22               78


      A three-phase mixture was sampled next.  The mixture was prepared by
 combining waste oil, water, and trichloroethylene (TCE) in the test tank.
 The TCE extracted some of the waste oil and foamy emulsions formed at the
 oil/water and the water/TCE interfaces.  However, three distinct phases
 were still obtained.  Just like the previous experiment, the starting
 heights of the liquid phases for each trial were measured.  The mixture
 was sampled with the ColiVasa.  The samples were each discharged into
 1000-ml (1.056 qt) graduated cylinders and the relative volumes of the
 liquid phases were determined (Table A-2).

                               TABLE A-2.

          Relative Volumes of Liquids in the Three-Phase Mixture
    Item                        Oil          Aqueous          TCE

Trial I:
 % by height of
 phases in tank                 7.9           77.4           14.7

 % by volume collected          9.7           79.6           10.8

Trial II:
 % by height of
 phases in tank                 9.3           75.0           15.0

 % by volume collected         10.2           79.0           10.7

Average:
 % by height of
 phases in tank                 8.8           76.0           15.0

 % by volume collected          9.8           79.0           11.0
                                   60

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     The results indicate that the Coliwasa is capable of collecting a
representative sample of a three-phase mixture  within 5%  accuracy.  The
greatest nonrepresentative error, as anticipated, occured at the bottom
phase because the samplers   rubber stopper prevents sampling of the last
2.54 cm(l in.) to the bottom of the container.  This  error decreases as
the bottom phase increases in volume as compared to the upper phases.
With less viscous and completely immiscible test liquids, the representa-
tiveness of the sample collected approaches unity.

Field Tests

     The field tests consisted of sampling liquid wastes in drums and in
vacuum trucks.  Drums of unknown liquid wastes are sampled at a hazardous
waste (Class I) disposal site in California.  The sampler, which has a
4.8-cm (1 7/8-in.) O.D., easily cleared through the drum's bung holes.

     Sampling was relatively fast.  From the time a drum was opened, a
sample was collected and transferred into a container in less than 5
minutes.  While a sample was in the sampler, no leakage was detected,
indicating a positive seal by the sampler's closing mechanism.  On the
transfer of sample to a container, no splashings were observed, showing
that the sampler's content can be discharged at a regulated rate.

     A drum containing a two-phase liquid waste mixture was also sampled.
Replicate samples were obtained, and each was placed in separate contain-
ers.  The ratios of the liquid phases in each of the samples were deter-
mined and found to be approximately the same, indicating that reproducible
samples can be collected with the sampler.
            i
     Incoming vacuum trucks carrying liquid wastes to the disposal site
were sampled next with the Coliwasa.  Again, the sampler was found to be
functional and very easy to use.  Collection of samples was very fast,
minimizing the exposure of the sample collector to hazardous fumes and
other emissions from the wastes.  Only one vacuum truck with a narrow hatch
opening and a total depth of  about  163  cm(5.3  ft)  was not  successfully
sampled.  The  sampling  tube  of  the  Coliwasa is  only 152  cm(5  ft) long.
A longer  sampling  tube  (i.e.,183  cm(6  ft)  long)  could have  remedied
the problem.
                                     61

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            APPENDIX B.  PARTS FOR CONSTRUCTING THE COLIWASA
   Item
Supplier
Approximate
    Cost3
Sample tube, PVC plastic, trans-
lucent, 4.13 cm(l 5/8 in.) I.D. X
1.52 m(5 ft) long X 0.4 cm(5/32 in.)

Sample tube, glass borosilicate,
4.13 cm(l 5/8 in.) I.D. X 1.52 m
(5 ft) long, Code 72-1602.
Stopper, rubber, neoprene, #9,
modified as described in footnote.*3

Stopper rod, PVC, 0.95 cm(3/8 in.)
O.D. X 1.67 m(5h ft) long.

Stopper rod, Teflon, 0.95 cm(3/8 in.)
O.D. X 1.67 m(5% ft) long.

Locking block without sleeve, PVC,
3.8 ccadh in.)  O.D.  X 10.2 cm(4 in.)
long with l.ll-cm(7/16 in.)  hole
drilled through center.

Sleeve, PVC, 4.13 cm(l 5/8 in.) I.D.
X 6.35 (2% in.) long.
T-handle, aluminum, 18 cm(7 in.)long
X 2.86 cm(l 1/8 in.) wide with 1.27
cm(% in.) wide channel.

Swivel, aluminum bar, 1.27 cm(^ in.)
square X 3.8 cm(l% in.)long with
3/8 National Coarse (NC) inside
thread to attach stopper rod.

Nut, PVC, 3/8 in. NC thread

Washer, PVC, 3/8 in.

Nut, SS, 3/8 in., NC

Washer, SS, 3/8 in.

Bolt, 3.12 cm(l k in.)long X 3/16 in.

Nut, 3/16 in., NC

Washer, lock 3/16 in.
Plastic supply houses  $ 4.00 each
Corning Glass Works,
Corning, N.Y.
  $18.00 each
Laboratory supply      $ 6.00/0.45
                         kg(lb)

Plastic supply houses  $ 5.00/6.1 m
                         (20 ft)

Plastic supply houses  $30.00/3.05 m
                         (10 ft)

Fabricate. Rods avail-
able at plastic supply
houses. Can be bought
in 30.48 cm(l ft)length

Fabricate from stock of $ .80/30.48
4.13 cm(l 5/8 in.) I.D.   cm(ft)
PVC pipe. Available at
plastic supply houses
Fabricate. Aluminum bar $3.00/1.83
stock available at hard-  m(6 ft)
ware stores.

Fabricate. Aluminum bar $ 3.00/1.83
stock available at hard-  m(6
ware stores.
Plastic supply houses
Plastic supply houses
Hardware stores

Hardware stores

Hardware stores

Hardware stores

Hardware stores
   $ .03 each
   $ .03 each
   $ .10 each

   $ .10 each

   $ .10 each

   $ .03 each

   $ .03 each
  1977 prices
                                    62

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  'Shape the stopper into a cone as follows:  Bore a 0.95-cm(3/8-in.)
   diameter center hole through the stopper.  Insert a short piece of
   0.95-cm(3/S in.) O.D. handle through the hole until the end of the
   handle is flush against the bottom (smaller diameter) surface of
   the stopper.  Carefully and uniformly turn the stopper into a cone
   against a grinding wheel.  This is done by turning the stopper with
   the handle and grinding it down conically from about 0.5 cm(3/16 in.)
   of the top (larger diameter) surface to the edge of the 0.95-cm(3/8-in.)
   hole on the bottom surface.
APPENDIX C.  CHECKLIST OF ITEMS REQUIRED IN THE FIELD SAMPLING OF HAZARDOUS

                                  WASTES.
Quantity
             Item
    Use
  Supplier
Approximate
    Cost
          Coliwasa,
          plastic
          type
          (Section 4)
          Coliwasa,
          glass type
          (Section 4)
          Soil samp-
          ler > auger
          (Section 4)
          Grain
          sampler
          (Section 4)
          Scoop,
          stainless
          steel blade
          (Section 4)
To sample liquid
wastes, except
ketones, nitro-
benzene, dimethyl-
foraraide, tetra-
hydrofuran and
pesticides
Fabricate; Parts
can be purchased
from hardware
stores (see
Section 4)
 $ 16.00
To sample liquid       Fabricate; Glass   $ 25.00
waste with pesticides, tube available from
and other wastes that  Corning Glass Co.
cannot be sampled with Corning, N.Y. 14830
plastic Coliwasa ex-   (see Section 4)
cept strong alkali and
hydrofluoric acid
solution

To sample contaminated  Weyco Distributor $ 70.00
soil, dried ponds, etc. 1417 Heskett Way
                        Sacramento,Calif.
                             95825
To sample powdered
or granular wastes
 Laboratory supply $ 50.00
 houses
To sample top soil or   Cole-Parmer
shallow layers of solid Instruments
wastes                  Chicago, 111.
                   $ 25.00
                                    63

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                        APPENDIX C (continued).
Quantity    Item
                  Use
 Supplier
Apprgxima
te
1 Veihmeyer
soil samp-
ler
(Section 4)
1 Pond samp-
ler
(Section 4)





To collect soil core Hansen Machine, $
samples 334 N. 125h St.,
Sacramento , Calif .
95815
To sample ponds, pits, Fabricate (see $
etc. Section 4). Clamps
available at
Cole-Parmer
Instrument
3060 Gibraltar Ave.
Costa Mesa, Calif .
92626
200.00



9.00







    1
  pair
          Trier,
          single  slot
          (Section 4)
          Waste pile
          sampler
          (Section 4)
             To sample granular
             and powdered material
             in piles, sacks,
             fiberdrums, etc.
             To sample waste piles
          1000-,2000-   To contain solid and
          ml(l-qt,2-qt) liquid samples except
          linear       pesticides and ch]or-
          polyethylene  inated hydrocarbons
          Coverall,     Protective garment
          long-
          sleeved,
          cotton
          Suit,
          neoprene
          rubber,  long-
          sleeved
             Protective garment
Gloves, neo- Protective garment
prene rubber
Telescoping handle $  16.24
available at
swimming pool
supply houses

Curtin-Matheson    $  25.00
Scientific
470 Valley Drive
P.O.Box 386
Brisbane,Calif.
94005

Fabricate. PVC     $   3.00
pipe available at
hardware stores
(see Section 4)

Laboratory supply  $  11.OO/
houses                pkg.6
                                    Clothing stores    $  14.00
MSA,Catalog #33496 $ 210.00
Laboratory supply  $   4.20
houses
                                   64

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                         APPENDIX C (continued).
Quantity
    Item
    Use
  Supplier
Approximate
    Cost
    1
  pair
    1
    1

    1
   12
  each
         Self-contained For use in atmospheres MSA,Catalog
         breathing      deficient in oxygen    #461704,
         apparatus      or otherwise immedi-   Model 401 or
                        ately dangerous to     equivalent
                        life.
         Respirator,    For use in atmospheres Comfo 11 Respir-
         chemical       not immediately        ator, MSA,Catalog
         cartridge      dangerous to life      #460968
         type                                  or equivalent

         Cartridges for For use in atmospheres CMC Cartridge,MSA
         respirator     not immediately        Cat.#459317 & GMD
                        dangerous to life      Cartridge, MSA
                                               Cat.#459318 or
                                               equivalent
Goggles

Portable
eyewash
Fire extin-
quisher

Hard hat

Gas mask
         18.9-liter
         (5-gal) water
         in cubitainer
         or equivalent
         with spigot

         Teflon liners
         for Bakelite
         caps
Eye protection

For emergency
eyewash
Fire suppression
Head protection


For use in contami-
nated atmospheres
immediately dangerous
to life

For miscellaneous
washing purposes
               To provide inert cap
               liners
Sample labels, To document sample
seals, sample
analysis re-
quest sheets,
chain of
custody
records
                           65
MSA,Cat.#79179 or
equivalent

Laboratory supply
houses

Scientific Products
S1365-1 or equiva-
lent

MSA, Cat.#454740 or
equivalent

MSA, Cat.#448983 or
equivalent
                                      Laboratory supply
                                      houses
                       Scientific Special-
                       ties, P.O.Box 352
                       Randallstown, Md.
                       21133 or other
                       suppliers
                       Design using infor-
                       mation from Section
                       6
                                                           $580.00
                                                           $  9.00
                                                           $  5.00
   $  5.00

   $  4.00

   $ 60.00


   $  5.00

   $ 70.00



   $  5.50
                     $  9.00

-------
APPENDIX C (continued).
Quantity Item
1

1


1



6

12

4

1



1


1




1


Field log book
(Section 6)
Weighted bottom
sampler
(Section 4)
Disposable
towels or
rags

Large poly-
ethylene bags
Polyethylene
bags
Waterproof
pens
Technical
grade
trichloro-
ethylene
Apron, oil
and acid
proof
Face mask




18.9 liter
(5-gal)
can
Use
To keep sample records

To sample storage
tanks or similar
containers
To clean sampling
equipment


To store waste papers,
rags, etc.
To store sample
containers
To complete records
and labels
To clean samplers



Protective garment


Protective garment




To store used
cleaning solvent

Supplier Approximate
Cost
Office supply
stores
Fabricate (see
Section 4 and
Figure 9)
Terry towels or
$ 2.00

$ 25.00


$ 4.00/
equivalent. Avail- pkg.
able at chemical
supply houses
Plastic supply
houses
Plastic supply
houses
Stationery stores

Chemical supply
stores


McMaster-Carr Co.
P.O.Box 4355
Chicago, 111.
MSA
400 Penn Center
Blvd.
Pittsburg, Pa.
15235
Hardware stores




$ 11. OO/
pkg/100
$ 4.00/
pkg/100
$ 3.00

$ 22. 00 /
gal.


$ 9.00


$ 4.00




$ 5.00


           66

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                     APPENDIX D.   RANDOM SAMPLING

                            Random Numbers

03
97
16
12
55
16
84
63
33
57
18
26
23
52
37
70
56
99
16
31

47
74
76
56
59
22
42
01
21
60
18
62
42
36
85
29
62
49
08
16

43
24
62
85
56
77
17
63
12
86
07
38
40
28
94
17
18
57
15
93

73
67
27
99
35
94
53
78
34
32
92
97
64
19
35
12
37
22
04
32

86
62
66
26
64
39
31
59
29
44
46
75
74
95
12
13
35
77
72
43

36
42
56
96
38
49
57
16
78
09
44
84
82
50
83
40
96
88
33
50

96
81
50
96
54
54
24
95
64
47
17
16
97
92
39
33
83
42
27
27

47
14
26
68
82
43
55
55
56
27
16
07
77
26
50
20
50
95
14
89

36
57
71
27
46
54
06
67
07
96
58
44
77
11
08
38
87
45
34
87

61
20
07
31
22
82
88
19
82
54
09
99
81
97
30
26
75
72
09
19

46
42
32
05
31
17
77
98
52
49
79
83
07
00
42
13
97
16
45
20

98
53
90
03
62
37
04
10
42
17
83
11
45
56
34
89
12
64
59
15

63
32
79
72
43
93
74
50
07
46
86
46
32
76
07
51
25
36
34
37

71
37
78
93
09
23
47
71
44
09
19
32
14
31
96
03
93
16
68
00
i
62
32
53
15
90
78
67
75
38
62
62
24
08
38
88
74
47
00
49
49
HOW TO USE THE TABLE OF RANDOM NUMBERS:

1.  Based on available information, segregate the containers (i.e., drums,
    sacks, etc.) according to waste types.
2.  Number the containers containing the same waste types consecutively,
    starting from 01.
3.  Decide on how many samples you wish to take.  This number is usually
    determined by the objective of the sampling.  For regular surveil-
    lance sampling, the collection of one or two samples is usually
    adequate.  In this case, random sampling is not necessary.  But for
    regulatory or research purposes, more samples (such as one sample for
    every group of five containers) taken at random will generate more
    statistically valid data.  Hence if there were 20 drums containing
    the same type of waste, 5 drums have to be sampled.
4.  Using the set of random numbers above, choose any number as a starting
    point.
5.  From this number, go down the column, then to the next column to the
    right, or go in any predetermined direction until you have selected
    five numbers between 01 and 20, with no repetitions. Larger numbers
    are ineligible.
    Example:  If you were to choose 19 as the starting point on column
              four, the next eligible numbers as you go down this
              oolumn are 12 and 04.  So far you have chosen only three
                                   67

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               eligible numbers.  Proceed to the next column to the right.
               Going down and starting from the top of this column, the
               next eligible numbers are 12 and 13.  But 12 is already
               chosen.  Proceeding to the sixth column, the next eligible
               number is 16.  Your five random numbers, therefore, are
               19, 12, 04, 13 and 16.  Thus the drums with corresponding
               numbers have to be sampled.


          APPENDIX E.  SYSTEMATIC ERRORS USING THE COLIWASA
     Certain systematic errors may occur in the determination of relative
phase composition of waste when using the Coliwasa.  This error, in which
certain phases are disproportionately represented, results from the use
of a straight-sided sample tube to sample a container (tank truck) with
a circular cross section.  On the basis of a two-phase system, error is
at a minimum when the phase interface is at the tank center and at a
maximum when the interface is near the bottom or top of the tank.  These
errors do not occur when sampling a drum or other container when sampling
is done down the axis of the container (cylinder).

     Errors in relative phase composition encountered in sampling the
typical cylindrical vacuum truck may be estimated using Table E-l.  Num-
bers given in the table are representative values calculated from the
equations given below, which relate the geometry of the sample tube to
the geometry of the tank truck.
% A(tank) =


% A(sample) = 1-Cos % 9
                                   (9-Sin 9)
                                      2TT
                                                         Vacuum truck
                                                     Sample tube
                                    68

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           TABLE E-l.  SAMPLE VOLUME CORRECTION FACTORS WHEN
             SAMPLING CYLINDRICAL TANKS WITH COLIWASA

% A in sample               % A in tank               Correction  (%)
10
20
30
40
50
60
70
80
90
100
5.20
14.2
25.2
37.4
50
62.6
74.8
85.8
94.8
100
+ 4.80
+ 5.8
+ 4.8
+ 2.6
0
- 2.6
- 4.8
- 5.8
- 4.8
0
                                  69

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/2-80-018
4. TITLE ANDSUBTITLE
Samplers and Sampling Procedures for Hazardous
Waste Streams
7' AUTHORifmil R. deVera, Bart P. Simmons, Robert D.
Stephens and David L. Storm,
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Hazardous Materials Laboratory
California Department of Health Services
2151 Berkeley Way
Berkeley, CA 94704
12. SPONSORING AGENCY NAME AND ADDRESS Cln . , UH
Municipal Environmental Research Laboratory —
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
3. RECIPIENT'S ACCESSIOWNO.
5. REPORT DATE
January 1980 (Issuing Date
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT
10. PROGRAM ELEMENT NO.
C73D1C, SOS #1, Task 32
11. CONTRACT/GRANT NO.
R 804692010
13. TYPE OF REPORT AND PERIOD COVEI
Final
14. SPONSORING AGENCY CODE
EPA/ 600/14
15. SUPPLEMENTARY NOTES
Richard A. Games, Project Officer (513/684-7871)
 16. ABSTRACT
     The  goal  of  this  project was to develop simple but effective sampling equipment
 and procedures for  collecting, handling, storing, and recording samples of hazardous
 wastes.   The report describes a variety of sampling devices designed to meet the nee
 of those  who regulate  and manage hazardous wastes.  Particular emphasis is given to
 the development of  a composite liquid waste sampler, the Coliwasa.  This simple devi
 is designed for use on liquid and semi-liquid wastes in a variety of containers, tan
 and ponds.  Devices for sampling solids and soils are also described.

     In addition  to the sampling devices, the report describes procedures for develc
 ment of a sampling  plan,  sample handling, safety precautions, proper recordkeeping
 and chain of custody,  and sample containment, preservation, and transport.  Also
 discussed are  certain  limitations and potential sources of error that exist in the
 sampling  equipment  and the procedures.  The statistics of sampling are covered
 briefly,  and additional references in this area are given.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
Samplers
Lagoons (ponds) — waste disposal
Hazardous materials
13. DISTRIBUTION STATEMENT
Release unlimited
b. IDENTIFIERS/OPEN ENDED TERMS
Representative sampling
Composite sampling
Sampling plans
Sampling procedures
Hazardous waste
Composite liquid waste
sampler
19. SECURITY CLASS (This Report)
unclassified
20. SECURITY CLASS (This page)
unclassified
c. COSATI Field/Grou
68C
21. NO. OF PAGES
78
22. PRICE
EPA Form 2220-1 (9-73)
70
                                                                   - U S €0VCffl¥M£iV7 WW7WG OfFICf 1960-6 57-1

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    APPENDIX II






   FOR CHEMICAL ANALYSIS




OF WATER AND WASTES

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                                          EI'A-600 4-79-020
    METHODS FOR CHEMICAL ANALYSIS
          OF WATER AND WASTES
                 March 1979
ENVIRONMENTAL MONITORING AND SUPPORT
              LABORATORY
  OFFICE OF RESEARCH AND DEVELOPMENT
 U.S. ENVIRONMENTAL PROTECTION AGENCY
            CINCINNATI, OHIO 45268

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                                 DISCLAIMER
The mention of trade names or commercial products in this manual is for illustration purposes, and
does not constitute endorsement or recommendation for use by the U.S. Environmental Protection
Agency.

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                                    FOREWORD
The accomplishment of our objective in protecting the environment requires a reliable assessment of
the present condition and a determination of the effectiveness of corrective measures. Decisions
which must be made on the need for pollution abatement and the most efficient means of achieving
environmental quality depend upon the availability of sound data. Test procedures for measurement
of the presence and concentration of substances hazardous to human health as well as an evaluation
of the quality of the environment are essential to satisfactory decision-making.

This manual of chemical methods was prepared by the staff of the Environmental Monitoring and
Support Laboratory of the Environmental Research Laboratory, Cincinnati to provide procedures
for monitoring water supplies, waste discharges,  and the quality of ambient waters.  These, test
methods have been carefully selected to meet the needs of Federal Legislation and to provide
guidance to laboratories engaged in protecting human health and the  aquatic environment. The
contributions and counsel of scientists in other EPA laboratories are gratefully acknowledged.

Test  procedures contained herein, that are approved for water and waste monitoring under the Safe
Drinking Water Act (SOWA) and the National Pollutant Discharge Elimination System (NPDES),
of PL 92-500 are  so indicated at the bottom of each title page. These approved methods are also
recommended for ambient monitoring needs of Section 106 and 208 of PL 92-500. Methods without
this stated approval are presented for information only. Correspondence on these methods is invited.
Dwight G. Ballinger
Director,  Environmental Monitoring and
Support Laboratory, Cincinnati,  Ohio  45268
                                            111

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                                   ABSTRACT
This manual provides test procedures approved for the monitoring of water supplies, waste
discharges, and ambient waters, under the Safe Drinking Water Act, the National Pollutant
Discharge Elimination System, and Ambient Monitoring Requirements of Section 106 and 208
of Public Law 92-500. The test methods have been selected to meet the needs of federal legislation
and to provide guidance to  laboratories engaged in the protection of human health and the
aquatic environment.
                                        IV

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                                 CONTENTS


Foreword	iii
Abstract	iv
Introduction 	xiii
Sample Preservation 	xv
EPA Quality Assurance Coordinators	xx

                             100  Physical Properties

     Color
          Colorimetric, ADMI	 Method  110.1
          Colorimetric, Platinum-Cobalt	 Method  110,2
          Spectrophotometric	 Method.  110.3

     Conductance
          Specific Conductance	 Method  120.1

     Hardness, Total (mg/1 as CaCO3)
          Colorimetric, Automated EDTA	 Method  130.1
          Titrimetric, EDTA	 Method  130.2

     Odor
          Threshold Odor (Consistent Series)	 Method  140,1

     PH
          Electrometric	 Method  150.1

     Residue
          Filterable
               Gravimetric, Dried at 180°C	 Method  160.1
          Non-Filterable
               Gravimetric, Dried at 103-105°C	 Method  160.2
          Total
               Gravimetric, Dried at 103-105°C	 Method  160.3
          Volatile
               Gravimetric, Ignition at 550°C	 Method  160.4
          Settleable   Matter
               Volumetric, Imhoff Cone	 Method  160.5

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Temperature
     Thermometric	 Method 170.1

Turbidity
     Nephelometric	 Method 180.1

                             200  Metals

Atomic Absorption Methods	  Section 200.0

Aluminum
     AA, Direct Aspiration	 Method 202.1
     AA, Furnace	 Method 202.2

Antimony
     AA, Direct Aspiration	 Method 204.1
     AA, Furnace	 Method 204.2

Arsenic
     AA, Furnace	 Method 206.2
     AA, Hydride	  Method 206.3
     Spectrophotometric,  SDDC	 Method 206.4
     Digestion  Method for Hydride  and SDDC	 Method 206.5

Barium
     AA, Direct  Aspiration	 Method 208.1
     AA, Furnace	  Method 208.2

Beryllium
     AA, Direct  Aspiration	  Method 210.1
     AA, Furnace	  Method 210.2

Boron
     Colorimetric, Curcumin	  Method 212.3

Cadmium
     AA, Direct  Aspiration	  Method 213.1
     AA, Furnace	  Method 213.2

Calcium
     AA, Direct  Aspiration	  Method 215.1
     Titrimetric,  EDTA	  Method 215.2
                                  VI

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Chromium
     AA, Direct Aspiration	  Method  218.1
     AA, Furnace	  Method  218.2
     Chelation-Extraction	  Method  218.3
     Hexavalent, Chelation-Extraction	  Method  218.4

Cobalt
     AA, Direct Aspiration	  Method  219.1
     AA, Furnace	  Method  219.2

Copper
     AA, Direct Aspiration	  Method  220.1
     AA, Furnace	  Method  220.2

Gold
     AA, Direct Aspiration	  Method  231.1
     AA, Furnace	  Method  231.2

Iridium
     AA, Direct Aspiration	  Method  235.1
     AA, Furnace	  Method  235.2

Iron
     AA, Direct Aspiration	  Method  236.1
     AA, Furnace	  Method  236.2
Lead
     AA, Direct Aspiration	  Method  239.1
     AA, Furnace	  Method  239.2

Magnesium
     AA, Direct Aspiration	  Method  242.1

Manganese
     AA, Direct Aspiration	  Method  243.1
     AA, Furnace	  Method  243.2

Mercury
     Cold Vapor, Manual	  Method  245.1
     Cold Vapor, Automated	  Method  245.2
     Cold Vapor, Sediments	  Method  245.5
                                   vn

-------
Molybdenum
     AA, Direct  Aspiration	 Method 246.1
     AA, Furnace	 Method 246.2

Nickel
     AA, Direct  Aspiration	 Method 249.1
     AA, Furnace	 Method 249.2

Osmium
     AA, Direct  Aspiration	 Method 252.1
     AA, Furnace	 Method 252.2

Palladium
     AA, Direct  Aspiration	 Method 253.1
     AA, Furnace	 Method 253.2

Platinum
     AA, Direct  Aspiration	 Method 255.1
     AA, Furnace	 Method 255.2

Potassium
     AA, Direct  Aspiration	 Method 258.1

Rhenium
     AA, Direct  Aspiration	 Method 264.1
     AA, Furnace	 Method 264.2

Rhodium
     AA, Direct  Aspiration	 Method 265.1
     AA, Furnace	 Method 265.2

Ruthenium
     AA, Direct  Aspiration	 Method 267.1
     AA, Furnace	 Method 267.2

Selenium
     AA, Furnace	 Method 270.2
     AA, Hydride	 Method 270.3

Silver
     AA, Direct  Aspiration	 Method 272.1
     AA, Furnace	 Method 272.2
                                   VIM

-------
Sodium
     AA, Direct Aspiration	 Method 273.1

Thallium
     AA, Direct Aspiration	 Method 279.1
     AA, Furnace	 Method 279.2

Tin
     AA, Direct Aspiration	 Method 282.1
     AA, Furnace	 Method 282.2

Titanium
     AA, Direct Aspiration	 Method 283.1
     AA, Furnace	 Method 283.2

Vanadium
     AA, Direct Aspiration	 Method 286.1
     AA, Furnace	 Method 286.2

Zinc
     AA, Direct Aspiration	 Method 289.1
     AA, Furnace	 Method 289.2

                      300  Inorganic, Non-metallics

Acidity
     Titrimetric	 Method 305.1

Alkalinity
     Titrimetric (pH 4.5)	 Method 310.1
     Colorimetric, Automated Methyl Orange	 Method 310.2

Bromide
     Titrimetric	 Method 320.1

Chloride
     Colorimetric, Automated Ferricyanide, AA  I	 Method 325.1
     Colorimetric, Automated Ferricyanide, AA  II	 Method 325.2
     Titrimetric, Mercuric Nitrate	 Method 325.3

Chlorine, Total Residual
     Titrimetric, Amperometric	 Method 330.1
     Titrimetric, Back-Iodometric	 Method 330.2
                                   IX

-------
     Titrimetric, lodometric	 Method 330.3
     Titrimetric, DPD-FAS	 Method 330.4
     Spectrophotometric, DPD	 Method 330.5

Cyanide
     Amenable to Chlorination
          Titrimetric, Spectrophotometric	 Method 335.1
     Total
          Titrimetric, Spectrophotometric	 Method 335.2
          Colorimetric, Automated UV	 Method 335.3

Fluoride
     Colorimetric, SPADNS  with Bellack
       Distillation	 Method 340.1
     Potentiometric,  Ion Selective Electrode	 Method 340.2
     Colorimetric, Automated Complexone	 Method 340.3

Iodide
     Titrimetric	 Method 345.1

Nitrogen
     Ammonia
          Colorimetric,  Automated Phenate	 Method 350.1
          Colorimetric;  Titrimetric;  Potentiometric -
            Distillation Procedure	 Method 350.2
          Potentiometric,  Ion Selective Electrode	 Method 350.3

     Kjeldahl,  Total
          Colorimetric,  Automated Phenate	 Method 351.1
          Colorimetric,  Semi-Automated
            Block Digester  AAII	 Method 351.2
          Colorimetric;  Titrimetric;  Potentiometric	 Method 351.3
          Potentiometric,  Ion Selective Electrode	 Method 351.4

     Nitrate
          Colorimetric,  Brucine	 Method 352.1

     Nitrate-Nitrite
          Colorimetric,  Automated  Hydrazine
            Reduction	 Method 353.1
          Colorimetric,  Automated  Cadmium Reduction	 Method 353.2
          Colorimetric,  Manual Cadmium Reduction	 Method 353.3

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   Nitrite
          Spectrophotometric	 Method  354.1/

Oxygen, Dissolved
     Membrane Electrode	 Method 360.1
     Modified Winkler (Full Bottle Technique)	 Method 360.2

Phosphorus
     All Forms
          Colorimetric, Automated, Ascorbic Acid	 Method 365.1
          Colorimetric, Ascorbic Acid,
            Single Reagent	 Method 365.2
          Colorimetric, Ascorbic Acid,
            Two Reagent	 Method 365.3
     Total
          Colorimetric, Automated, Block Digestor, AA II	 Method 365.4

Silica, Dissolved
     Colorimetric	 Method 370.1

Sulfate
     Colorimetric, Automated Chloranilate	 Method 375.1
     Colorimetric, Automated Methyl  Thymol Blue, AA II	 Method 375.2
     Gravimetric	 Method 375.3
     Turbidimetric	 Method 375.4

Sulfide
     Titrimetric, Iodine	 Method 376.1
     Colorimetric, Metnylene Blue	 Method 376.2

Sulfite
     Titrimetric	 Method 377.1

                             400   Organics

Biochemical  Oxygen Demand
     BOD (5 day, 20°C)	 Method 405.1

Chemical Oxygen  Demand
     Titrimetric, Mid-Level	 Method 410.1
     Titrimetric, Low Level	 Method 410.2
     Titrimetric, High  Level for Saline Waters	 Method 410.3
     Colorimetric, Automated; Manual	 Method 410.4
                                  XI

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Oil and Grease, Total  Recoverable
     Gravimetric, Separatory  Funnel Extraction	.-.	 Method 413.1
     Spectrophotometric, Infrared	 Method 413.2

Organic Carbon, Total
     Combustion  or Oxidation	 Method 415.1

Petroleum Hydrocarbons, Total, Recoverable
     Spectrophotometric, Infrared	 Method 418.1

Phenolics, Total Recoverable
     Spectrophotometric, Manual 4-AAP with Distillation	 Method 420.1
     Colorimetric, Automated 4-AAP with Distillation	 Method 420.2
     Spectrophotometric, MBTH with Distillation	 Method 420.3

Methylene Blue Active Substances (MbAS)
     Colorimetric	 Method 425.1

NTA
     Colorimetric, Manual, Zinc-Zincon	 Method 430.1
     Colorimetric, Automated, Zinc-Zincon,	 Method 430.2
                                   xn

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                                  INTRODUCTION

This third edition of "Methods for Chemical Analysis of Water and Wastes" contains the chemical
analytical procedures used in U.S. Environmental Protection Agency (EPA) laboratories for the
examination of ground and surface waters, domestic and industrial waste effluents, and treatment
process samples. Except where noted under "Scope and Application", the methods are applicable to
both water and wastewaters, and both fresh and saline water samples. The manual provides test
procedures for the measurement of physical,  inorganic, and selected  organic constituents  and
parameters. Methods for pesticides, industrial organic waste materials, and sludges are given in other
publications of the Agency. The methods were chosen through the combined efforts of the EPA
Regional Quality Assurance Coordinators, the staff of the Physical and Chemical Methods Branch,
Environmental Monitoring and Support Laboratory, and other senior chemists in both federal and
state laboratories.  Method selection was based on the following criteria:

     (1)  The method should measure  the  desired  property  or  constituent  with  precision,
          accuracy, and specificity sufficient to meet the data needs of EPA, in the presence of the
          interfering materials encountered in water and waste samples.
     (2)  The procedure should utilize  the  equipment and skills  available in modern water
          pollution control laboratories.
     (3)  The selected method is in use in many  laboratories or has been sufficiently tested to
          establish its validity.
     (4)  The method should be rapid enough to permit routine use for the examination of a large
          number of samples.
                                                                 •
Instrumental methods  have  been selected in  preference to manual  procedures because  of the
improved speed, accuracy, and precision. In keeping with this policy, procedures for the Technicon
AutoAnalyzer have  been included  for  laboratories  having this equipment available.  Other
continuous flow automated systems using these identical procedures are acceptable.

Intralaboratory and interlaboratory precision and accuracy statements are provided where such data
are available. These interlaboratory statements are derived from interlaboratory studies conducted
by the  Quality Assurance Branch,  Environmental Monitoring and Support  Laboratory;  the
American Society for Testing Materials; or the Analytical Reference Service of the US Public Health
Service, DHEW. These methods may be used for measuring both total and dissolved constituents of
the sample. When the dissolved concentration is to be determined, the sample is filtered through a
0.45-micron membrane filter and the filtrate analyzed by the procedure specified. The sample should
be filtered as soon as possible after it is collected, preferably in the field. Where field filtration is not
practical, the sample should be filtered as soon as it is received in the laboratory.

Many water  and  waste samples are unstable.  In situations where the interval between sample
collection and analysis is long enough to produce changes in either the concentration or the physical
state of the constituent to be measured, the preservation practices in Table I are recommended.

                                          xiii

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This manual is  a basic  reference for  monitoring water and wastes in compliance with the
requirements of the Federal Water Pollution Control Act Amendments of 1972. Although other test
procedures may be used, as provided in the Federal Register issue of October 16,1973 (38FR 28758)
and  in subsequent amendments,  the methods described in this manual will  be used by the
Environmental Protection Agency in determining compliance with applicable water and effluent
standards established by the Agency.

Although a sincere effort has been made to select methods that are applicable to the widest range of
sample types, significant  interferences may be encountered in certain isolated samples. In these
situations, the analyst will be providing a valuable service to EPA by defining the nature of the
interference with the  method and bringing  this information  to the  attention  of  the Director,
Environmental Monitoring and Support Laboratory, through the appropriate Quality Assurance
Coordinator.
                                            xiv

-------
                            SAMPLE  PRESERVATION
Complete and unequivocal preservation of samples, either domestic sewage, industrial wastes, or
natural waters, is a practical impossibility. Regardless of the nature of the sample, complete stability
for every constituent can never be achieved. At best, preservation techniques can only retard the
chemical and biological changes that inevitably continue after the sample is removed from the parent
source. The changes that take place in a sample are either chemical or biological. In the former case,
certain changes occur in the chemical structure of the constituents that are a function of physical
conditions. Metal cations may precipitate as hydroxides or form complexes with other constituents;
cations or anions may change valence states under certain reducing or oxidizing conditions; other
constituents may dissolve or volatilize with the passage of time. Metal cations may also adsorb onto
surfaces (glass, plastic, quartz, etc.), such as, iron and lead. Biological  changes taking place in a
sample may change the valence of an element or a radical to a different valence. Soluble constituents
may be converted to organically bound materials in cell structures, or cell lysis may result in release
of cellular material into solution. The well known nitrogen and phosphorus cycles are examples of
biological influence  on sample composition. Therefore, as a general rule, it is best to analyze the
samples as soon as possible after collection. This is especially true when the analyte concentration is
expected to be in the low ug/1 range.

Methods of preservation are relatively limited and are intended generally to (1) retard biological
action, (2) retard hydrolysis  of chemical  compounds and  complexes, (3)  reduce volatility of
constituents, and (4) reduce absorption effects. Preservation methods are generally limited to pH
control, chemical addition, refrigeration, and freezing.

The recommended preservative for various constituents is given in Table 1. These choices are based
on the  accompanying references and on  information supplied by various Quality Assurance
Coordinators. As more data become available, these recommended holding times will be adjusted to
reflect new information.  Other information  provided in the table is an estimation of the volume of
sample required for  the analysis, the suggested type of container, and the maximum recommended
holding times for samples properly preserved.
                                           xv

-------
                        TABLE 1
RECOMMENDATION FOR SAMPLING AND PRESERVATION
     OF SAMPLES ACCORDING TO MEASUREMENT'15

Measurement
100 Physical Properties
Color
Conductance
Hardness
Odor
pH
Residue
Filterable
Non-
Filterable
Total
Volatile
Settleable Matter
Temperature
Turbidity
200 Metals
Dissolved
Suspended
Total
Vol.
Req.
(ml)
50
100
100
200
25

100
100
100
100
1000
1000
100
200
200
100

Container(2)

P,G
P,G
P,G
G only
P,G

P,G
P,G
P,G
P,G
P,G
P,G
P,G
P,G

P,G

Preservative

Cool, 4°C
Cool, 48C
Cool, 4'C
HNO3 to pH<2
Cool, 4°C
Det. on site

Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
None Req.
Det. on site
Cool, 4°C
Filter on site
HNO3 to pH<2
Filter on site
HNO3 to pH<2
                                                      Holding
                                                      Time(3)
                                                        24 Hrs.

                                                        24 Hrs.(4)

                                                        6 Mos.<5)


                                                        24 Hrs.

                                                         6 Hrs.



                                                         7 Days


                                                         7 Days

                                                         7 Days

                                                         7 Days

                                                        24 Hrs.

                                                      No Holding

                                                        7 Days



                                                        6 Mos.(!)


                                                         6 Mos.

                                                        6 Mos.("
                            XVI

-------
TABLE 1 (CONT)
Vol.
Req.
Measurement (ml)
Mercury
Dissolved
Total
300 Inorganics, Non-Metallics
Acidity
Alkalinity
Bromide
Chloride
Chlorine
Cyanides
Fluoride
Iodide
Nitrogen
Ammonia
Kjeldahl, Total
Nitrate plus Nitrite
Nitrate
Nitrite
100
100
100
100
100
50
200
500
300
100

400
500
100
100
50
Container"' Preservative
P,G
P,G
P,G
P,G
P,G
P,G
P,G
P,G
P,G
P,G

P,G
P,G
P,G
P,G
P,G
Filter on site
HNO3 to pH<2
HNO3 to pH<2
None Req
Cool, 4°C
Cool, 48C
None Req.
Det. on site
Cool, 4°C
NaOH to pH 12
None Req.
Cool, 4°C

Cool,4°C
H2SO4 to pH<2
Cool, 4°C
H2SO4 to pH<2
Cool, 4°C
H2SO4 to pH<2
Cool, 4°C
Cool, 4°C
Holding
Time(3)
38 Days
(Glass)
13 Days
(Hard
Plastic)
38 Days
(Glass)
13 Days
(Hard
Plastic)
24 Hrs.
24 Hrs.
24 Hrs.
7 Days
No Holding
24 Hrs.
7 Days
24 Hrs.

24 Hrs.
24 Hrs.(6)
24 Hrs.(6)
24 Hrs.
48 Hrs.
      XVII

-------
                         TABLE 1 (CONT)

Measurement
Dissolved Oxygen
Probe
Winkler
Phosphorus
Ortho-
phosphate,
Dissolved
Hydrolyzable
Total
Total,
Dissolved
Silica
Sulfate
Sulfide

Sulfite
400 Organics
BOD
COD
Oil & Grease
Organic carbon
Phenolics
Vol.
Req.
(ml)
300
300

50
50
50
50
50
50
500

50

1000
50
1000
25
500

Container"'
G only
G only

P,G
P,G
P,G
P,G
P only
P,G
P,G

P,G

P,G
P,G
G only
P,G
G only

Preservative
Det. on site
Fix on site

Filter on site
Cool, 4°C
Cool, 4'C
H2SO4 to pH<2
Cool, 4'C
H2S04 to pH<2
Filter on site
Cool, 4'C
H2SO4 to pH<2
Cool, 4°C
Cool, 4°C
2 ml zinc
acetate
Det. on site

Cool, 4°C
H2SO4 to pH<2
Cool, 4"C
H2SO4 or HC1 to pH<2
Cool, 4°C
H2SO4 or HC1 to pH<2
Cool, 4°C

Holding
Time(3)
No Holding
4-8 Hours

24 Hrs.
24 Hrs.(<)
24 Hrs.("
24 Hrs.'"
7 Days
7 Days
24 Hrs.

No Holding

24 Hrs.
7 Days'"
24 Hrs.
24 Hrs.
24 Hrs.
MBAS
250
P,G
H3PO4 to pH<4
1.0 g CuSO4/l

Cool, 4°C
24 Hrs.
                                 XVlll

-------
                                 TABLE 1 (CONT)


                          Vol.
                          Req.                                               Holding

   Measurement         (ml)    Container*2*    Preservative               Time(3)


   NTA                     50     P,G              Cool, 4°C                     24 Hrs.


1.    More specific instructions for preservation and sampling are found with each procedure as
     detailed in this manual. A general discussion on sampling water and industrial wastewater may
     be found in ASTM, Part 31, p. 72-82 (1976) Method D-3370.

2.    Plastic (P) or Glass (G). For metals, polyethylene with a polypropylene  cap (no liner) is
     preferred.

3.    It should be pointed out that  holding  times listed above are recommended for properly
     preserved samples based on currently available data. It is recognized that  for some sample
     types, extension of these times may be possible while for other types, these times may be too
     long. Where shipping regulations prevent the use of the proper preservation technique or the
     holding time is exceeded, such as the case of a 24-hour composite, the final reported data for
     these samples should indicate the specific variance.


4.    If the sample is stabilized by cooling, it should be warmed to 25°C for reading, or temperature
     correction made and results reported at 25°C.

5.    Where HNO3 cannot be used because of shipping restrictions,  the sample may be initially
     preserved by icing and immediately shipped to the laboratory. Upon receipt in the laboratory,
     the  sample must be acidified to a pH <2 with  HNO3 (normally 3 ml 1:1  HNO3/liter is
     sufficient). At the time of analysis, the sample container should be thoroughly rinsed with 1:1
     HNO3 and the washings added to the sample (volume correction may be required).


6.    Data obtained from National Enforcement Investigations Center-Denver, Colorado, support a
     four-week holding time for this parameter in Sewerage Systems. (SIC 4952).
                                          xix

-------
                ENVIRONMENTAL PROTECTION  AGENCY
          REGIONAL  QUALITY ASSURANCE COORDINATORS
REGION I

Warren H. Oldaker
New England Region Laboratory
60 Westview Street
Lexington, MA 02173
(617-861-6700)
FTS  861-6700

REGION II

Gerard  F. McKenna
Edison Environmental Lab.
Edison, NJ 08817
(201-321-6645)
FTS  340-6645
REGION V

David Payne
Central Regional Lab.
536 South Clark Street
Chicago, IL 60605
(312-353-9351)
FTS  353-9351

REGION VI

Myron Knudson
1201  Elm St., First Int'l Bldg.
Dallas, TX 75270   •
(214-767-2697)
FTS  729-2697
REGION IX

Dr. Ho Young
215 Fremont Street
San Francisco, CA 94102
(415-556-2270)
FTS 555-2270
REGION X

Arnold R. Gahler
1555 Alaskan Way, South
Bldg 3
Seattle, WA 98134
(206-442-5840)
FTS 399-5840
REGION III

Charles Jones, Jr.
(3SA60)
6th & Walnut Streets
Philadelphia, PA 19106
(215-597-9162)
FTS 597-9162

REGION IV

Bobby J. Carroll
Southeast Envr.  Res. Lab.
College Station Road
Athens, GA 30601
(404-546-3111)
FTS 250-3111
REGION VII

Dr. Harold G. Brown
25 Funston Road
Kansas City,  KS 66115
(816-374-4285)
FTS 758-4285
REGION VIII

Douglas  M. Skie
1860 Lincoln St.
Denver,  CO 80295
(303-837-4935)
FTS 327-4935
                                         xx

-------
                                          pH

                            Method 150.1 (Electrometric)

                                                                      STORET NO.
                                                          Determined on site  00400
                                                                   Laboratory  00403

1.    Scope and Application
     1.1  This method is applicable to drinking, surface, and saline waters, domestic and industrial
          wastes.
2.    Summary of Method
     2.1  The pH of a sample is determined electrometrically using either a glass electrode in
          combination with a reference potential or a combination electrode.
3.    Sample Handling and Preservation
     3.1  Samples should be analyzed as soon as possible preferably in the field at the time of
          sampling.
     3.2  High-purity waters and waters not at equilibrium with the atmosphere are subject to
          changes when exposed to the atmosphere, therefore the sample containers should be
          filled completely and kept sealed prior to analysis.
4.    Interferences
     4.1  The glass electrode,  in  general, is not subject to solution interferences from  color,
          turbidity, colloidal matter, oxidants, reductants or high salinity.
     4.2  Sodium error at pH levels greater than 10 can be reduced or eliminated by using a "low
          sodium error" electrode.
     4.3  Coatings of oily material or paniculate matter can impair electrode response.  These
          coatings can usually  be removed by gentle wiping or detergent washing, followed by
          distilled water rinsing. An additional treatment with hydrochloric acid (1+9) may be
          necessary to remove any remaining film.
     4.4  Temperature effects on the electrometric measurement of pH arise from  two sources.
          The first is caused by the change in electrode output at various temperatures. This
          interference can be controlled with instruments having temperature compensation or by
          calibrating the electrode-instrument system at  the temperature of the samples. The
          second source is the change of pH inherent in the sample at various temperatures. This
          error is sample dependent and cannot be controlled, it  should therefore be noted by
          reporting both the pH and temperature at the time of analysis.
5.    Apparatus
     5.1  pH Meter-laboratory or field model. A wide variety of instruments are commercially
          available with various specifications and optional equipment.


Approved for  NPDES
Issued  1971
Editorial revision 1978

                                        150.1-1

-------
     5.2  Glass electrode.
     5.3  Reference electrode-a calomel, silver-silver chloride or other reference electrode of
          constant potential may be used.
          NOTE 1:  Combination electrodes  incorporating  both  measuring  and reference
          functions are convenient to use and are available with solid, gel type filling materials that
          require minimal maintenance.
     5.4  Magnetic stirrer and Teflon-coated stirring bar.
     5.5  Thermometer or temperature sensor for automatic compensation.
6.    Reagents
     6.1  Primary standard buffer salts are available from the National Bureau of Standards and
          should be used in situations where extreme accuracy is necessary.
          6.1.1 Preparation of reference solutions from these salts require some special precautions
                and handling'" such as low conductivity dilution water, drying ovens, and carbon
                dioxide free purge gas. These solutions should be replaced at least  once each
                month.
     6.2  Secondary standard buffers may be prepared from NBS salts or purchased as a solution
          from commercial vendors. Use of these commercially available solutions, that have been
          validated by comparison to NBS standards, are recommended for routine use.
7.    Calibration
     7.1  Because of the wide variety of pH meters and accessories, detailed operating procedures
          cannot be incorporated into this method. Each analyst must be  acquainted with the
          operation of each system and familiar with all instrument functions. Special attention to
          care of the electrodes is recommended.
     7.2  Each instrument/electrode system must be calibrated at a minimum of two points that
          bracket the expected pH of the samples and are approximately three pH units or more
          apart.
          7.2.1 Various instrument designs  may involve use of a "balance" or "standardize" dial
                and/or a slope adjustment as outlined in the  manufacturer's instructions. Repeat
                adjustments on successive  portions of the two buffer solutions as outlined in
                procedure 8.2 until readings are within 0.05 pH units of the buffer solution value.
8.    Procedure
     8.1  Standardize the meter and electrode system as outlined in Section 7.
     8.2  Place the sample or buffer solution in a clean glass beaker using a sufficient volume to
          cover the sensing elements of  the electrodes and  to give adequate clearance for the
          magnetic stirring bar.
          8.2.1 If field measurements are being made the electrodes may be immersed directly in
                the sample stream to an adequate depth and moved in a manner to insure sufficient
                sample movement across the electrode sensing element as indicated by drift free
                ( < 0.1 pH) readings.
     8.3  If the sample temperature differs by more than 2°C from the buffer solution the measured
          pH values must be corrected. Instruments are equipped with automatic  or manual
                  "'National Bureau of Standards  Special Publication  260.

                                          150.1-2

-------
           compensators  that  electronically  adjust  for temperature differences.  Refer  to
           manufacturer's instructions.
     8.4   After rinsing and gently wiping the electrodes, if necessary, immerse them into the
           sample beaker or sample stream and stir at a constant rate to provide homogeneity and
           suspension of solids. Rate of stirring should minimize the air transfer rate at the air water
           interface  of the sample.  Note  and  record  sample  pH and  temperature.  Repeat
           measurement on successive volumes of sample until values differ by less than 0.1 pH
           units. Two or three volume changes are usually sufficient.
9.    Calculation
     9.1   pH meters read directly in pH units. Report pH to the nearest 0.1 unit and temperature
           to the nearest °C.
10.  Precision and Accuracy
     10.1  Forty-four  analysts in  twenty laboratories  analyzed six  synthetic  water samples
           containing exact increments of hydrogen-hydroxyl ions, with the following results:
        pH Units
           3.5
           3.5
           7.1
           7.2
           8.0
           8.0
Standard  Deviation
    pH Units

       0.10
       0.11
       0.20
       0.18
       0.13
       0.12
 Bias,
  %
                                                                   Accuracy as
 -0.29
 -0.00
+ 1.01
 -0.03
 -0.12
+0.16
  Bias,
pH Units

   -0.01

  +0.07
   -0.002
   -0.01
  +0.01
(FWPCA Method  Study  1, Mineral and Physical Analyses)
      10.2  In a single laboratory (EMSL), using surface water samples at an average pH of 7.7, the
           standard deviation was  ±0.1.

                                       Bibliography

1.    Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 460, (1975).
2.    Annual Book of ASTM Standards, Part 31, "Water", Standard D1293-65, p 178 (1976).
                                          150.1-3

-------
                                       METALS

                            (Atomic  Absorption Methods)

1.    Scope and Application
     1.1  Metals in solution may be readily determined by atomic absorption spectroscopy. The
          method is simple, rapid, and applicable to a large number of metals in drinking, surface,
          and saline waters, and domestic and industrial wastes. While drinking waters free of
          particulate matter may be analyzed directly, domestic and industrial wastes require
          processing to solubilize suspended material. Sludges,  sediments and other solid type
          samples may also be analyzed after proper pretreatment.
     1.2  Detection limits, sensitivity and optimum ranges of the metals will vary with the various
          makes and  models of satisfactory  atomic absorption spectrophotometers.  The data
          shown in Table 1, however, provide some indication of the actual concentration ranges
          measurable  by direct aspiration  and using furnace techniques. In the  majority of
          instances the  concentration range  shown in the table by direct aspiration may be
          extended much lower with scale expansion  and conversely extended upwards by using a
          less sensitive wavelength or by rotating the burner head. Detection  limits by direct
          aspiration may also be extended through concentration of the sample and/or through
          solvent extraction techniques. Lower concentrations may also be determined using the
          furnace techniques. The concentration ranges given in Table 1 are somewhat dependent
          on equipment such as the type of spectrophotometer and furnace accessory, the energy
          source and the degree of electrical expansion of the output signal. When using furnace
          techniques, however, the analyst should be cautioned as to possible chemical'reactions
          occurring at  elevated temperatures which  may  result  in  either  suppression or
          enhancement of the analysis element. To insure valid data with  furnace techniques, the
          analyst must examine each matrix for interference effects (see 5.2.1) and if detected, treat
          accordingly  using either successive dilution, matrix modification or method of standard
          additions (see 8.5).
     1.3  Where  direct  aspiration  atomic  absorption techniques  do  not  provide adequate
          sensitivity, in  addition to the furnace procedure,  reference  is made  to specialized
          procedures such as the gaseous hydride method for arsenic and selenium, the cold  vapor
          technique for  mercury, and  the  chelation-extraction  procedure for  selected metals.
          Reference to approved colorimetric methods is also made.
     1.4  Atomic absorption procedures are provided as the  methods of choice; however,  other
          instrumental methods have also been shown to  be capable of producing precise and
          accurate analytical data. These instrumental techniques include emission spectroscopy,
          X-ray fluorescence, spark source mass spectroscopy, and anodic stripping to name but a
          few.  The analyst should  be  cautioned that these methods  are  highly specialized
          techniques requiring a high degree of skill to interpret results and obtain valid data.

Approved for NPDES and  SDWA
Issued  1969
Editorial revision 1974 and 1978

                                        METALS-1

-------
          These above mentioned techniques are presently considered as alternate test procedures
          and approval must be obtained prior to their use.
2.    Summary of Method
     2.1  In direct aspiration atomic absorption spectroscopy a sample is aspirated and atomized
          in a flame. A light beam  from a hollow cathode lamp whose cathode is made of the
          element to be determined is directed through the flame into a monochromator, and onto
          a detector that measures the amount of light absorbed. Absorption depends upon the
          presence of free unexcited ground state atoms in the flame. Since the wavelength of the
          light beam is characteristic of only the metal being determined, the light energy absorbed
          by the flame is a measure of the concentration of that metal in the sample. This principle
          is the basis of atomic absorption spectroscopy.
     2.2  Although methods  have been reported for the analysis of solids by atomic absorption
          spectroscopy (Spectrochim Acta, 24B 53, 1969) the technique generally is limited to
          metals in solution or solubilized through some form of sample processing.
          2.2.1  Preliminary treatment of  wastewater  and/or  industrial effluents  is  usually
                necessary because of the  complexity  and variability of the sample  matrix.
                Suspended material  must be subjected to a solubilization process before analysis.
                This process may vary because of the metals to be determined and the nature of the
                sample being  analyzed. When the breakdown of organic material is necessitated,
                the process should include a wet digestion with nitric acid.
          2.2.2 In those  instances where complete characterization of a sample is desired,  the
                suspended material  must be analyzed separately. This may be accomplished by
                filtration and acid digestion of the suspended material. Metallic constituents in this
                acid digest are subsequently  determined and the sum of the dissolved plus
                suspended concentrations will then provide the total concentrations present. The
                sample should be filtered as soon  as  possible after collection and the filtrate
                acidified immediately.
          2.2.3 The total sample may also be treated with acid without prior filtration to measure
                what may be termed "total recoverable" concentrations.
     2.3  When using  the  furnace  technique  in conjunction with an  atomic  absorption
          spectrophotometer, a representative aliquot of a sample is placed in the graphite tube in
          the furnace, evaporated to dryness, charred,  and atomized. As a greater percentage of
          available analyte atoms are vaporized and dissociated for absorption in the tube than the
          flame, the use of small sample volumes or detection of low concentrations of elements is
          possible. The principle is essentially the. same as with direct aspiration atomic absorption
          except a furnace,  rather than a flame, is used to atomize the sample. Radiation from a
          given excited element is passed through the vapor containing ground state atoms of that
          element. The intensity of the transmitted radiation decreases in proportion to the amount
          of the ground state element in the vapor.
                                        METALS-2

-------
                                                 TABLE 1

                              Atomic Absorption  Concentration Ranges'"

                              Direct Aspiration                        Furnace  Procedure'415)


Metal
Aluminum
Antimony
Arsenic'21
Barium(p)
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Gold
Iridium(p)
Iron
Lead
Magnesium
Manganese
Mercury"1
Molybdenum(p)
Nickel(p)
Osmium
Palladium(p)
Platinum(p)
Potassium
Rhenium(p)
Rhodium(p)
Ruthenium
Selenium"1
Silver
Sodium
Thallium
Tin
Titanium (p)
Vanadium (p)
Zinc
Detection
Limit
mg/1
0.1
0.2
0.002
0.1
0.005
0.005
0.01
0.05
0.05
0.02
0.1
3
0.03
0.1
0.001
0.01
0.0002
0.1
0.04
0.3
0.1
0.2
0.01
5
0.05
0.2
0.002
0.01
0.002
0.1
0.8
0.4
0.2
0.005
Optimum
Concentration
Sensitivity
mg/1
1
0.5
_
0.4
0.025
0.025
0.08
0.25
0.2
0.1
0.25
8
0.12
0.5
0.007
0.05
-
0.4
0.15
1
0.25
2
0.04
15
0.3
0.5
_
0.06
0.015
0.5
4
2
0.8
0.02


5
1
0.002
1
0.05
0.05
0.2
0.5
0.5
0.2
0.5
20
0.3
1
0.02
0.1
0.0002
1
0.3
2
0.5
5
0.1
50
1
1
0.002
0.1
0.03
1
10
5
2
0.05
Range
mg/1
50
40
0.02
20
2
2
7
10
5
5
20
- 500
_ 5
20
0.5
3
0.01
40
5
- 100
15
75
^
- 1000
30
50
0.02
4
1
20
- 300
- 100
- 100
1
Detection
Limit
ug/1
3
3
1
2
0.2
0.1
-
1
1
1
1
30
1
1
-
0.2
-
1
1
20
5
20
-
200
5
20
2
0.2
-
1
5
10
4
0.05
Optimum
Concentration
Range
ug/1
20
20
5
10
1 —
0.5 -
-
5
5
5
5
100
5
5
-
1
-
3
'5
50
20
100
-
500
20
100
5
1
-
5
20
50
10
0.2 -


200
300
too
200
30
10
-
100
100
100
100
1500
100
too
-
30
-
60
100
500
400
2000

5000
400
2000
100
25
-
100
300
500
200
4
(1)     The concentrations shown  are not contrived values and  should be obtainable with any satisfactory  atomic absorption
       spectrophotometer.
(2)     Gaseous hydride method.
(3)     Cold vapor technique.
(4)     For furnace sensitivity values consult instrument operating manual.
(5)     The listed furnace values are those expected when using a 20 ul injection and normal gas flow except in the case of arsenic and
       selenium where gas interrupt is used. The symbol (p) indicates the use of pyrolytic graphite with the furnace procedure.
                                                 METALS-3

-------
The metal atoms to be measured are placed in the beam of radiation by increasing the temperature of
the furnace thereby causing the injected specimen to be volatilized. A monochromator isolates the
characteristic radiation from the hollow cathode lamp and a photosensitive device measures the
attenuated transmitted radiation.
3.    Definition of Terms
     3.1   Optimum Concentration Range: A range, defined by limits expressed in concentration,
           below which scale expansion must be  used and above which curve correction should be
           considered. This range will vary with the sensitivity of the instrument and the operating
           condition employed.
     3.2   Sensitivity:  The concentration  in  milligrams  of metal per liter  that produces an
           absorption of 1%.
     3.3   Detection Limit: Detection limits can be expressed as either an instrumental or method
           parameter. The limiting factor of the former using acid water standards would be the
           signal to noise ratio and degree of scale expansion used; while the latter would be more
           affected by the sample matrix and preparation procedure used. The Scientific Apparatus
           Makers  Association (SAMA) has approved the following definition for detection limit:
           that concentration  of an element which would yield an absorbance  equal to twice the
           standard deviation of a series of measurements of a solution, the concentraton of which is
           distinctly detectable above, but close to  blank absorbance measurement. The detection
           limit values listed in Table I and on the individual analysis sheets are to be  considered
           minimum working  limits  achievable with the procedures given in this manual. These
           values may differ from the optimum detection limit reported by the various instrument
           manufacturers.
     3.4   Dissolved  Metals:  Those  constituents  (metals)  which will pass through a 0.45 u
           membrane filter.
     3.5   Suspended Metals: Those constituents (metals) which are retained by a 0.45 u membrane
           filter.
     3.6   Total Metals: The concentration  of metals determined on an unfiltered sample following
           vigorous digestion (Section 4.1.3), or the sum of the concentrations of metals in both the
           dissolved and suspended fractions.
     3.7   Total Recoverable Metals: The concentration of metals in an unfiltered sample following
           treatment with hot dilute mineral acid (Section 4.1.4).
4.    Sample Handling and Preservation
     4.1   For the determination of trace metals, contamination and loss are of prime concern. Dust
           in the laboratory environment,  impurities in  reagents and impurities on  laboratory
           apparatus which the sample contacts are all sources of potential contamination.  For
           liquid samples,  containers  can  introduce either positive or negative errors in the
           measurement of trace metals  by (a)  contributing contaminants through leaching or
           surface desorption  and (b) by depleting concentrations through adsorption. Thus the
           collection and treatment of the sample prior to analysis requires particular attention. The
           sample bottle whether borosilicate glass, linear polyethylene, polyproplyene or Teflon
           should be thoroughly washed with detergent and tap water; rinsed with 1:1 nitric acid,
                                        METALS-4

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tap water, 1:1 hydrochloric acid, tap water and finally deionized distilled water in that
order.
NOTE 1:  Chromic acid  may be useful to remove organic deposits from glassware;
however, the analyst should be cautioned that the glassware must be thoroughly rinsed
with water to remove the last  traces of chromium. This is especially important  if
chromium  is to be included in  the analytical scheme.  A  commercial  product—
NOCHROMIX—available from Godax Laboratories,  6 Varick  St. New York, N.Y.
10013, may be used in place of chromic acid.  [Chromic acid should not be used with
plastic bottles.]
NOTE 2: If it can be documented through an active analytical quality control program
using spiked samples, reagent and sample blanks,  that certain steps in the cleaning
procedure are not required for routine samples, those steps may be eliminated from the
procedure.
Before collection of the sample a decision must be made as to the type of data desired, i.e.,
dissolved, suspended, total or total  recoverable.  For container preference, maximum
holding time and sample preservation at time of collection see Table 1 in the front part of
this manual. Drinking water samples containing suspended and setteable material should
be prepared using the total recoverable metal procedure (section 4.1.4).
4.1.1 For the  determination of dissolved constituents the sample must be  filtered
     through a 0.45 u membrane filter as soon as practical after collection. (Glass or
     plastic filtering apparatus using plain, non-grid marked, membrane filters are
     recommended to avoid possible contamination.) Use the first 50-100 ml to rinse
     the filter flask. Discard this portion and collect the required  volume of filtrate.
     Acidify the filtrate with 1:1 redistilled HNO3  to a pH of <2.  Normally,  3 ml of
     (1:1) acid per liter should be sufficient to preserve the sample (See Note 3).  If
     hexavalent chromium is to be included in the  analytical scheme, a portion of the
     filtrate should be transferred  before acidification  to a separate container and
     analyzed as soon as possible using Method 218.3. Analyses performed on a sample
     so treated shall be reported as "dissolved" concentrations.
NOTE 3:  If a precipitate is formed upon acidification, the filtrate  should be digested
using 4.1.3. Also, it has been suggested (International Biological Program, Symposium
on Analytical Methods, Amsterdam, Oct. 1966) that  additional acid, as much as 25 ml of
cone. HCl/liter, may be required to stabilize certain types of highly buffered samples if
they are  to be stored for any length of time. Therefore, special precautions should be
observed for preservation and storage of unusual samples intended for metal analysis.
4.1.2 For the determination of suspended metals a representative volume of unpreserved
     sample must be filtered through a 0.45  u  membrane filter.  When considerable
     suspended material is present, as little as  100 ml of a well mixed sample is filtered.
     Record the  volume filtered and transfer  the membrane filter  containing the
     insoluble material to a 250 ml Griffin beaker and add 3 ml cone, redistilled HNO3.
     Cover the beaker with a watch glass and heat gently. The warm acid will soon
     dissolve the membrane. Increase the temperature of the hot plate and digest the
     material. When the acid has nearly evaporated, cool the beaker and watch glass
     and add another 3 ml of cone, redistilled HNO3. Cover and continue heating until


                             METALS-5

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     the  digestion is  complete, generally  indicated by a light colored digestate.
     Evaporate to near dryness (DO NOT BAKE), add 5 ml distilled HC1 (1:1) and
     warm the beaker gently to dissolve any soluble material. (If the sample is to be
     analyzed by the furnace procedure, 1 ml of 1:1 distilled HNO3 per 100 ml dilution
     should be substituted for the distilled 1:1 HC1.) Wash down the watch glass and
     beaker walls with deionized distilled water and filter the sample to remove silicates
     and  other insoluble material that could clog the atomizer. Adjust the volume to
     some predetermined value based on the expected concentrations of metals present.
     This volume will vary depending on the metal to be determined. The sample is now
     ready for analysis. Concentrations so determined shall be reported as "suspended"
     (See Note 4.)
     NOTE  4: Certain  metals such as antimony arsenic, gold, iridium, mercury,
     osmium, palladium, platinium, rhenium, rhodium,  ruthenium, selenium, silver,
     thallium, tin and titanium require modification of the digestion procedure and the
     individual sheets for these metals should be consulted.
4.1.3 For  the determination  of total metals the sample is acidified with 1:1 redistilled
     HNO3 to a pH of less than 2 at the time of collection. The sample is not filtered
     before processing. Choose a volume of sample appropriate for the expected level of
     metals. If much suspended material is present, as little as 50-100 ml of well mixed
     sample will most probably be sufficient. (The  sample volume required may also
     vary proportionally with the number of metals to be determined.)
     Transfer a representative aliquot of the well mixed sample to a Griffin beaker and
     add  3 ml of cone, redistilled HNO3. Place the beaker on a hot plate and evaporate
     to near dryness cautiously, making certain that the sample does not boil. (DO NOT
     BAKE.) Cool the beaker and add another 3 ml portion of cone, redistilled HNO3.
     Cover  the beaker with a  watch glass and return to the hot plate. Increase  the
     temperature of the hot plate so that a gentle reflux action occurs. Continue heating,
     adding additional acid as necessary, until the digestion is  complete (generally
     indicated when the digestate is light in color or does not change in appearance with
     continued refluxing). Again, evaporate to near dryness and cool the beaker. Add a
     small quantity of redistilled 1:1  HC1 (5 ml/100 ml of final solution) and warm the
     beaker to dissolve any precipitate or residue resulting from evaporation. (If the
     sample is to be analyzed by the furnace procedure, substitute distilled HNO3 for 1:1
     HC1 so that the final dilution contains 0.5% (v/v) HNO3.) Wash down the beaker
     walls and watch glass with distilled water and filter the sample to remove silicates
     and other insoluble material that could clog the atomizer. Adjust the volume to
     some predetermined value based on the expected metal concentrations. The sample
     is now ready for analysis.  Concentrations  so determined shall  be  reported as
     "total" (see Note 4).
4.1.4 To determine total recoverable metals, acidify the  entire  sample at  the time of
     collection with cone, redistilled HNO3, 5 ml/1. At the time of analysis a 100 ml
     aliquot of well mixed sample is transferred to a beaker or flask. Five ml of distilled
     HC1 (1:1) is added  and the sample heated on a steam bath or hot plate until the
                             METALS-6

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                volume has been reduced to 15-20 ml making certain the samples do not boil. (If
                the sample is being prepared for furnace analysis,  the  same process should be
                followed except HC1 should be omitted.) After this treatment the sample is filtered
                to remove silicates and other insoluble material that could clog the atomizer and
                the  volume  adjusted to  100 ml.  The  sample is  then ready  for  analysis.
                Concentrations so determined shall be reported as "total". (See Notes 4, 5, and 6.)
                NOTE 5: The analyst should be cautioned that this digestion procedure may not be
                sufficiently vigorous to destroy certain metal complexes if a colorimetric procedure
                is to be employed  for the final determination. When this is suspect, the more
                vigorous digestion given in 4.1.3 should be followed.
                NOTE 6: For drinking water analyses by direct aspiration, the final volume may be
                reduced to effect up to a  10X concentration of the sample, provided  the total
                dissolved solids in the original sample do not exceed  500  mg/1, the determination
                is corrected for any non-specific absorbance and there is no loss by precipitation.
5.    Interferences
     5.1  Direct Aspiration
          5.1.1 The   most   troublesome   type   of   interference   in   atomic  absorption
                spectrophotometry   is usually  termed "chemical"  and is  caused by  lack  of
                absorption of atoms bound in  molecular combination in the  flame. This
                phenomenon can occur when the flame  is not sufficiently hot to  dissociate the
                molecule, as in the case of phosphate interference with magnesium, or because the
                dissociated atom is immediately oxidized to a compound that will  not dissociate
                further at the temperature of the flame. The addition of lanthanum will overcome
                the phosphate interference in the magnesium, calcium and barium determinations.
                Similarly, silica interference in the determination of  manganese can be eliminated
                by the addition of calcium.
          5.1.2 Chemical interferences may also be eliminated  by separating the metal from the
                interfering material. While complexing agents are primarily employed to increase
                the  sensitivity of the analysis,  they may also be  used to eliminate or reduce
                interferences.
          5.1.3 The presence of high dissolved solids in the sample  may result in an interference
                from non-atomic absorbance such as light scattering. If background correction is
                not  available,  a non-absorbing wavelength should be checked. Preferably, high
                solids type samples  should be extracted (see 5.1.1 and 9.2).
          5.1.4 lonization interferences occur where the flame temperature is sufficiently high to
                generate  the removal of an electron from a neutral atom, giving a positive charged
                ion. This type  of interference can generally be controlled by the addition, to both
                standard and sample solutions, of a large excess of an  easily ionized element.
          5.1.5 Although quite rare,  spectral  interference  can  occur when   an  absorbing
                wavelength of an element present in the sample but not  being determined falls
                within the width of the absorption line of the element of interest. The results of the
                determination  will  then be erroneously  high,  due to  the contribution of the
                interfering element to the atomic absorption signal. Also, interference can occur
                                        METALS-7

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          when resonant energy from another element in a multi-element lamp or a metal
          impurity in the lamp cathode falls within the bandpass of the slit setting and that
          metal is present in the sample. This type of interference may sometimes be reduced
          by narrowing the slit width.
5.2   Flameless Atomization
     5.2.1 Although the problem of oxide formation  is greatly  reduced with furnace
          procedures because atomization occurs in an inert atmosphere, the technique is
          still subject to chemical and matrix interferences. The composition of the sample
          matrix can have a major effect on the analysis. It is those effects which must be
          determined and taken into consideration in the analysis of each different matrix
          encountered. To help verify the absence of matrix or chemical interference use the
          following procedure. Withdraw from the sample two equal aliquots. To one of the
          aliquots add a known  amount of analyte and dilute both aliquots to the  same
          predetermined volume. [The dilution volume should be based on the analysis of the
          undiluted sample. Preferably, the dilution should be 1:4 while keeping in mind the
          optimum concentration range of the analysis. Under no circumstances should the
          dilution be less than  1:1]. The  diluted aliquots should then be analyzed and the
          unspiked results multiplied by the  dilution factor  should be compared to the
          original determination. Agreement of the results (within ±10%) indicates the
          absence of interference. Comparison of the actual signal from the spike to the
          expected response from the analyte in an aqueous standard should help confirm the
          finding from the dilution analysis. Those samples which indicate the presence of
          interference, should be treated in one or more of the following ways.
                a.    The  samples  should  be  successively diluted and reanalyzed to
                     determine if the interference can be eliminated.
                b.    The matrix of the sample should be modified in the furnace. Examples
                     are the addition of ammonium nitrate to  remove alkali chlorides,
                     ammonium phosphate  to retain  cadmium, and  nickel  nitrate for
                     arsenic   and   selenium  analyses  [ATOMIC   ABSORPTION
                     NEWSLETTER Vol. 14, No. 5, p 127, Sept-Oct 1975]. The mixing of
                     hydrogen with the inert  purge gas has also been used  to  suppress
                     chemical interference. The hydrogen acts as a reducing agent and aids
                     in molecular dissociation.
                c.    Analyze the sample by method of standard additions while noting the
                     precautions and limitations of its use (See 8.5).
     5.2.2 Gases generated in the furnace during atomization may have molecular absorption
          bands encompassing the analytical wavelength. When this occurs, either the use of
          background correction or choosing an alternate wavelength outside the absorption
          band should eliminate this interference. Non-specific broad band  absorption
          interference can also be compensated for with background correction.
     5.2.3 Interference from a smoke-producing sample matrix can sometimes be reduced by
          extending the charring time at a higher temperature or utilizing an ashing cycle in
                                  METALS-8

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          the presence of air. Care must be taken, however, to prevent loss of the analysis
          element.
     5.2.4 Samples containing large amounts of organic materials  should be oxidized by
          conventional acid digestion prior to being placed in the furnace. In this way broad
          band absorption will be minimized.
     5.2.5 From anion interference studies in the graphite furnace it is generally accepted that
          nitrate is the preferred anion. Therefore nitric acid is preferable for any digestion or
          solubilization step. If another acid in addition to HN03 is required a minimum
          amount should be used. This applies particularly to hydrochloric and to a lesser
          extent to sulfuric and phosphoric acids.
     5.2.6 Carbide formation resulting from the chemical environment of the furnace has
          been observed with  certain elements that form carbides at high temperatures.
          Molybdenum may be cited as an example. When this takes place, the metal will be
          released very slowly from the carbide as atomization continues. For molybdenum,
          one may be required to atomize for 30 seconds or more before the signal returns to
          baseline levels. This problem is greatly reduced and the sensitivity increased with
          the use of pyrolytically-coated graphite.
     5.2.7 lonization interferences have to date not been reported with furnace techniques.
     5.2.8 For comments on spectral interference see section 5.1.5.
     5.2.9 Contamination of the sample can be a major source of error because of the extreme
          sensitivities achieved with the furnace. The sample preparation work area should
          be kept scrupulously clean. All glassware should be cleaned as directed in part 6.9
          of the Atomic Absorption Methods section  of this manual. Pipet tips have been
          known to be a source of contamination. If suspected, they should be acid soaked
          with 1:5 HNO3 and rinsed thoroughly with tap and deionized water. The use of a
          better grade pipet tip can greatly reduce this problem. It is very important that
          special attention be given to reagent blanks in both analysis and the correction of
          analytical results. Lastly, pyrolytic graphite because of the production process and
          handling can become  contaminated. As many as  five to possibly  ten  high
          temperature burns may be required to clean the tube before use.
Apparatus
6.1   Atomic absorption spectrophotometer: Single or dual channel, single-or double-beam
     instrument having a grating monochromator, photomultiplier detector, adjustable slits, a
     wavelength range of 190 to 800 nm, and provisions for interfacing with a strip chart
     recorder.
6.2   Burner: The burner recommended by the particular instrument manufacturer  should be
     used. For certain elements the nitrous oxide burner is required.
6.3   Hollow cathode lamps: Single element lamps are to be preferred but multi-element lamps
     may be used. Electrodeless discharge lamps may also be used when available.
6.4   Graphite furnace: Any furnace device capable of reaching the specified temperatures is
     satisfactory.
                                   METALS-9

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     6.5   Strip chart recorder: A recorder is strongly recommended for furnace work so that there
           will be a permanent record and any problems with the analysis such as drift, incomplete
           atomization, losses during charring, changes in sensitivity, etc., can be easily recognized.
     6.6   Pipets: Microliter  with  disposable tips. Sizes  can  range from 5  to  100 microliters as
           required. NOTE 7: Pipet tips  which are white in color, do not contain CdS, and have
           been found suitable for research work are available from Ulster Scientific, Inc. 53 Main
           St. Highland, NY 12528 (914) 691-7500.
     6.7   Pressure-reducing  valves: The supplies of fuel and oxidant shall  be maintained at
           pressures somewhat higher than the controlled operating pressure of the instrument by
           suitable valves.
     6.8   Separatory flasks: 250 ml, or larger, for extraction with organic solvents.
     6.9   Glassware: All glassware, linear polyethylene, polyproplyene  or Teflon containers,
           including  sample bottles, should be washed with detergent, rinsed with tap water, 1:1
           nitric acid, tap water, 1:1  hydrochloric acid, tap water and deionized distilled water in
           that order. [See Notes 1 and 2 under (4.1)  concerning the use of chromic acid and the
           cleaning procedure.]
     6.10  Borosilicate glass distillation apparatus.
7.    Reagents
     7.1   Deionized distilled water:  Prepare by passing distilled water through a mixed bed of
           cation and anion exchange resins. Use deionized distilled water for the preparation of all
           reagents, calibration standards, and as dilution water.
     7.2   Nitric acid (cone.):  If metal impurities are found to be present, distill reagent grade
           nitric acid in a borosilicate glass distillation apparatus or use a spectrograde acid.
           Caution:   Distillation should be performed in hood with protective sash in place.
                 7.2.1 Nitric Acid  (1:1):  Prepare a 1:1 dilution with deionized, distilled water by
                      adding the cone, acid to an equal volume of water.
     7.3   Hydrochloric acid  (1:1):   Prepare a 1:1 solution of reagent grade hydrochloric acid and
           deionized  distilled  water. If metal impurities are found to be present,  distill this mixture
           from a borosilicate glass distillation apparatus or use a spectrograde acid.
     7.4   Stock standard metal solutions:   Prepare as directed in (8.1) and under the individual
           metal procedures. Commercially available stock standard solutions may also be used.
     7.5   Calibration standards:  Prepare a series of standards of the metal  by dilution of the
           appropriate stock metal solution to cover the concentration range desired.
     7.6   Fuel and  oxidant:   Commercial  grade acetylene is generally acceptable. Air may be
           supplied from a compressed  air line, a laboratory compressor, or from a cylinder of
           compressed air. Reagent grade nitrous oxide is also required for certain determinations.
           Standard,  commercially available argon and nitrogen are required for furnace work.
     7.7   Special reagents for the extraction procedure.
           7.7.1  Pyrrolidine dithiocarbamic acid (PDCA) "see footnote":   Prepare by adding 18
                 ml of analytical reagent grade pyrrolidine to 500 ml of chloroform in a liter flask.
The name pyrrolidine dithiocarbamic acid (PDCA), although  commonly  referenced in the scientific
literature is ambiguous.   From  the chemical reaction of pyrrolidine and carbon disulfide a more
proper name would be  1-pyrrolidine carbodithioic acid,  PCD A (CAS Registry No. 25769-03-3).

                                        METALS-10

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                (See Note 8) Cool and add 15 ml of carbon disulfide in small portions and with
                swirling.  Dilute to 1 liter with chloroform. The solution can be used for several
                months if stored in a brown bottle in a refrigerator.

           NOTE 8:  An  acceptable grade of pyrrolidine may be  obtained  from the Aldrich
           Chemical Co., 940 West St. Paul Ave., Milwaukee, WI. 53233 (414,273-3850).

           7.7.2 Ammonium hydroxide, 2N:  Dilute 3 ml cone. NH4OH to 100 ml with deionized
                distilled water.
           7.7.3 Bromph'enol blue indicator (Ig/liter):  Dissolve O.lg bromphenol blue in 100 ml
                of 50 percent ethanol or isopropanol.
           7.7.4 HC1, 2.5% v/v: Dilute 2 ml redistilled HC1 to 40 ml with deionized distilled water.
8.    Preparation of Standards and Calibration
     8.1   Stock standard solutions are prepared from high purity metals, oxides or nonhygroscopic
           reagent grade salts using deionized distilled water and redistilled nitric or hydrochloric
           acids. (See individual  analysis sheets for specific instruction.) Sulfuric or  phosphoric
           acids should be avoided as they produce an adverse effect on many elements. The stock
           solutions are prepared at concentrations of 1000 mg of the metal per liter. Commercially
           available standard solutions may also be used.
     8.2   Calibration standards  are prepared by diluting the stock metal solutions at the time of
           analysis. For best results, calibration standards should be prepared fresh each time an
           analysis is to  be made and discarded after use.  Prepare a blank, and  at least four
           calibration standards in graduated amounts in the appropriate range. The calibration
           standards should be prepared using the same type of acid or combination of acids and at
           the same concentration as will result in the samples following processing. As filtered
           water samples are preserved with 1:1  redistilled  HNO3  (3 ml per liter), calibration
           standards for these analyses should be similarly prepared with HNO3. Beginning with
           the blank and working toward the highest standard, aspirate the solutions and record the
           readings.  Repeat the operation with both the calibration standards and the samples a
           sufficient number  of  times to  secure  a reliable  average  reading  for each solution.
           Calibration standards for furnace procedures should be prepared  as  described  on the
           individual sheets for that metal.
     8.3   Where the sample matrix is so complex that viscosity, surface tension and components
           cannot be accurately matched with standards,  the method of standard addition must be
           used.  This technique relies on the addition of small, known amounts of the analysis
           element to portions of the sample—the absorbance  difference between those and the
           original solution giving the slope of the calibration curve. The method of standard
           addition is described in greater detail in (8.5).
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8.4  For those instruments which do not read out directly in concentration, a calibration
     curve is prepared to cover the appropriate concentration range. Usually, this means the
     preparation of standards which produce an absorption of 0 to 80 percent. The correct
     method is to convert the percent absorption readings to absorbance and plot that value
     against concentration. The following relationship is used to convert absorption values to
     absorbance:

           absorbance = log (100/%T) = 2-log % T
           where % T = 100-% absorption

     As the curves are frequently nonlinear, especially at high absorption values, the number
     of standards should be increased in that portion of the curve.
8.5  Method of Standard Additions:   In this method, equal volumes of sample are added to a
     deionized distilled water blank and to  three standards  containing different  known
     amounts of the test element. The volume of the blank and the standards must be the
     same. The absorbance of each solution is determined and then plotted on the vertical axis
     of a graph, with the concentrations of the known standards plotted on the horizontal
     axis. When the resulting line is extrapolated  back to zero absorbance, the point of
     interception of the abscissa is the concentration of the unknown. The abscissa on the left
     of the ordinate is scaled the same as on the right side, but in the opposite direction from
     the ordinate. An example of a plot so obtained is shown in Fig. 1.
                                                                       Concentration
     I Cone, of
      Sample
Addn 0
No Addn
Addn I
Addn of 50%
of Expected
Amount
Addn 2
Addn of 100%
of Expected
Amount
Addn 3
Addn of 150%
of Expected
Amount
                     FIGURE 1.  STANDARD  ADDITION PLOT
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           The method of standard additions can be very useful, however, for the results to be valid
           the following limitations must be taken into consideration:
                a)    the absorbance plot of sample  and standards must  be linear  over  the
                     concentration range of concern. For best results the slope of the plot should
                     be nearly the same as the slope of the aqueous standard curve. If the slope is
                     significantly different (more than 20%) caution should be exercised.
                b)    the effect of the interference should  not vary as the  ratio of analyte
                     concentration to sample matrix changes and the standard addition should
                     respond in a similar manner as the analyte.
                c)    the determination must be free of spectral interference and corrected for non-
                     specific background interference.
9.    General Procedure for Analysis by Atomic Absorption
     9.1   Direct Aspiration: Differences  between  the various makes and  models of satisfactory
           atomic absorption spectrophotometers prevent the formulation of detailed instructions
           applicable to every instrument. The analyst should follow the manufacturer's  operating
           instructions for his particular instrument.  In general, after choosing the proper hollow
           cathode lamp for the analysis, the lamp should be allowed to warm up for a minimum of
           15  minutes unless operated  in a double  beam  mode. During  this period,  align the
           instrument, position the monochromator at the  correct wavelength,  select the proper
           monochromator slit width, and adjust  the hollow  cathode current  according to the
           manufactuerer's recommendation. Subsequently, light the flame and regulate the flow of
           fuel and  oxidant, adjust the burner and nebulizer flow rate for  maximum percent
           absorption and stability, and balance the photometer.  Run a series  of standards of the
           element under analysis and construct a calibration curve by plotting the concentrations
           of the standards against the absorbance. For those instruments  which read directly in
           concentration set the curve corrector to read out the proper concentration. Aspirate the
           samples and determine the concentrations either  directly or from the calibration curve.
           Standards must be run each time a sample or series of samples are run.
           9.1.1 Calculation - Direct determination of liquid  samples: Read  the  metal value in
                mg/1 from the calibration curve or directly from the readout system of the
                instrument.
                9.1.1.1     If dilution of sample was required:


                mg/1 metal in sample = A

                where:

                A = mg/1 of metal indiluted aliquot from calibration curve
                B = ml of deionized distilled water used for dilution
                C = ml of sample aliquot
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          9.1.2  For samples containing particulates:

                mg/1 metal in sample = A I -X-


                where:

                A =  mg/1 of metal in processed sample from calibration curve
                V =  final volume of the processed sample in ml
                C=  ml of sample aliquot processed
          9.1.3  For solid samples: report all concentrations as mg/kg dry weight
                9.1.3.1     Dry sample:
                mg metal/kg sample = — —
                where:

                A —  mg/1 of metal in processed sample from calibration curve
                V =  final volume of the processed sample in ml
                D =  weight of dry sample in grams
                9.1.3.2     Wet sample:

                                    A  x  V
                mg metal/kg sample = ^    -


                where:

                A =  mg/1 of metal in processed sample from calibration curve
                V =  final volume of the processed sample in ml
                W = weight of wet sample in grams
                P =  % solids
     9.2  Special Extraction Procedure:  When the concentration of the metal is not sufficiently
          high to determine directly, or when considerable dissolved solids are present in the
          sample, certain metals may be chelated and extracted with organic solvents. Ammonium
          pyrrolidine dithiocarbamate (APDC) (see footnote) in methyl isobutyl ketone (MIBK) is
          widely used  for  this  purpose and  is  particularly useful  for  zinc, cadmium, iron,
          manganese, copper, silver, lead and chromium+6. Tri-valent chromium does not react
          with APDC unless it has first been converted to the hexavalent form [Atomic Absorption
          Newsletter 6, p  128  (1967)]. This procedure  is described under method  218.3.
The name ammonium pyrrolidine dithiocarbamate (APDC) is somewhat ambiguous and should more
properly be  called ammonium,  1-pyrollidine carbodithioate (APCD), CAS Registry No. 5108-96-3.

                                       METALS-14

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Aluminum, beryllium, barium and strontium also do not react with APDC. While the
APDC-MIBK chelating-solvent system can be used satisfactorily, it  is  possible to
experience difficulties. (See Note 9.)
NOTE 9:  Certain metal chelates,  manganese-APDC in particular, are not  stable in
MIBK and will redissolve into the aqueous phase on standing. The extraction of other
metals is sensitive to both shaking rate and time. As with cadmium, prolonged extraction
beyond  1 minute, will reduce  the extraction efficiency, whereas  3 minutes  of vigorous
shaking is required for chromium.
Also, when multiple metals are to be determined either larger sample volumes must be
extracted or individual extractions made for each metal being determined. The acid form
of APDC-pyrrolidine dithiocarbamic acid prepared directly in chloroform as described
by Lakanen, [Atomic Absorption Newsletter 5, p 17 (1966)], (see 7.7.1) has been found
to be most advantageous. In this procedure the more dense chloroform layer allows for
easy combination of multiple extractions which are carried out over a broader pH range
favorable to multielement extractions. Pyrrolidine dithiocarbamic acid in chloroform is
very stable and may be stored  in a brown bottle in the refrigerator for months. Because
chloroform is used as the solvent, it may not be aspirated into the flame. The following
procedure is suggested.
9.2.1 Extraction  procedure  with  pyrrolidine  dithiocarbamic  acid  (PDCA)  in
      chloroform.
      9.2.1.1     Transfer 200 ml of sample into a 250 ml separatory funnel,  add 2 drops
                bromphenol blue indicator solution (7.7.3) and mix.
      9.2.1.2     Prepare a blank and sufficient standards in the same manner and adjust
                the volume of each to approximately 200  ml with deionized distilled
                water. All of the metals to be determined may be combined into single
                solutions at the appropriate concentration levels.
      9.2.1.3     Adjust the pH by addition of 2N NH4OH solution (7:7.2) until a blue
                color persists. Add HC1  (7.7.4) dropwise until the blue color just
                disappears; then add 2.0 ml HC1 (7.7.4) in excess. The pH at this point
                should be  2.3. (The pH  adjustment may  be made with a pH meter
                instead of using indicator.)
      9.2.1.4     Add 5  ml of PDCA-chloroform reagent (7.7.1) and shake vigorously
                for 2 minutes. Allow the phases to separate and drain the chloroform
                layer into a 100 ml beaker. (See NOTE 10.)
                NOTE 10: If hexavalent chromium is to be extracted, the aqueous
                phase must be readjusted back to a pH of 2.3 after the addition of
                PDCA-chloroform  and  maintained at  that  pH  throughout  the
                extraction. For multielement extraction, the pH may adjusted upward
                after the chromium has been extracted.
                             METALS-15

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           9.2.1.5     Add a second portion of 5 ml PDCA-chloroform reagent (7.7.1) and
                     shake vigorously for  2 minutes. Allow the phases to separate and
                     combine the chloroform phase with that obtained in step (9.2.1.4).
           9.2.1.6     Determine the pH of the aqueous phase and adjust to 4.5.
           9.2.1.7     Repeat step (9.2.1.4) again combining the solvent extracts.
           9.2.1.8     Readjust the pH to 5.5, and extract a fourth time. Combine all extracts
                     and evaporate to dryness on a steam bath.
           9.2.1.9     Hold the beaker at a  45  degree angle,  and slowly add 2 ml  of cone.
                     distilled nitric acid, rotating the beaker to effect thorough contact of
                     the acid with the residue.
           9.2.1.10   Place the beaker on a low temperature hotplate or steam bath and
                     evaporate just to dryness.
           9.2.1.11    Add 2 ml of nitric acid (1:1) to the beaker and heat for 1 minute. Cool,
                     quantitatively transfer the solution to  a 10 ml  volumetric flask and
                     bring to volume with  distilled  water.  The sample is  now ready for
                     analysis.
     9.2.2 Prepare a calibration curve by plotting absorbance versus the concentration of the
           metal standard 0/g/l) in the 200 ml extracted standard solution. To calculate
           sample concentration read  the metal value in ug/1 from the calibration curve or
           directly from the readout system of the instrument. If dilution of the sample was
           required use the following equation:
           mg/1 metal in sample =
                where:

                     Z = ug/1 of metal in diluted aliquot from calibration curve
                     B = ml of deionized distilled water used for dilution
                     C= ml of sample aliquot
9.3  Furnace Procedure: Furnace devices (flameless atomization) are a most useful means of
     extending detection limits. Because of differences between various makes and models of
     satisfactory instruments, no  detailed operating instuctions can be  given  for  each
     instrument. Instead,  the analyst  should follow the  instructions  provided by the
     manufacturer of his particular instrument and use as a guide the temperature settings
     and  other instrument conditions listed  on the individual  analysis  sheets which are
     recommended for the Perkin-Elmer HGA-2100. In addition, the following points may be
     helpful.
     9.3.1  With flameless atomization, background correction becomes of high importance
           especially below 350 nm.  This is because  certain samples, when atomized, may
           absorb or scatter light from  the hollow cathode  lamp. It can be caused by the
           presence of gaseous molecular species,  salt particules,  or smoke in the sample
                                   METALS-16

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     beam. If no correction is made, sample absorbance will be greater than it should be,
     and the analytical result will be erroneously high.
9.3.2 If during atomization  all the analyte is not volatilized and removed from the
     furnace, memory effects will occur. This condition is dependent on several factors
     such as the volatility of  the  element and its chemical form, whether pyrolytic
     graphite is used, the rate of atomization and furnace design. If this situation is
     detected through blank burns, the tube should be cleaned by operating the furnace
     at full power for the required time period as needed at regular intervals in the
     analytical scheme.
9.3.3 Some of the smaller size furnace devices, or newer furnaces equipped with feedback
     temperature control (Instrumentation Laboratories MODEL 555, Perkin-Elmer
     MODELS HGA 2200 and HGA 76B, and Varian MODEL CRA-90) employing
     faster rates of atomization, can be operated using  lower atomization temperatures
     for shorter time periods than those listed in this manual.
9.3.4 Although prior digestion  of the sample  in many cases is not required providing a
     representative aliquot of sample can be pipeted into the furnace, it will provide for a
     more uniform matrix and  possibly lessen matrix effects.
9.3.5 Inject a measured microliter aliquot of sample into the furnace and atomize. If the
     concentration found is greater than the highest standard, the sample  should be
     diluted in the same acid matrix and reanalyzed. The use of multiple injections can
     improve accuracy and help detect furnace pipetting errors.
9.3.6 To verify the absence of interference, follow the procedure as given in part 5.2.1.
9.3.7 A check standard  should be run approximately after every  10 sample injections.
     Standards are run in part  to monitor the life and performance of the graphite tube.
     Lack of reproducibility  or significant change in  the signal for the standard
     indicates  that the tube should be replaced. Even  though  tube life depends on
     sample matrix and atomization temperature, a conservative estimate would be that
     a tube will last at least 50 firings. A pyrolytic-coating would extend that estimate
     by a factor of 3.
9.3.8 Calculation-For determination of metal concentration by the furnace: Read the
     metal value in ug/1 from  the calibration curve or directly from the readout system
     of the instrument.
     9.3.8.1     If different size furnace injection volumes are used for samples than for
                standards:
     ug/1 of metal in sample = Z  I -TT- j

     where:

     Z =  ug/1 of metal read from calibration curve or readout system
     S =  ul volume standard injected into furnace for calibration curve
     U = ul volume of sample injected for analysis



                             METALS-17

-------
     9.3.8.2    If dilution of sample was required but sample injection volume same as
               for standard:

                               / C^ 4- R
     ug/1 of metal in sample = Z
     where:

     Z = ug/1 metal in diluted aliquot from calibration curve
     B = ml of deionized distilled water used for dilution
     C= ml of sample aliquot
9.3.9 For sample containing particulates:
     ug/1 of metal in sample = Z
     where:
(*)
     Z = ug/1 of metal in processed sample from calibration curve (See 9.3.8.1)
     V = final volume of processed sample in ml
     C = ml of sample aliquot processed
9.3.10     For solid samples: Report all concentrations as mg Ag dry weight
          9.3.10.1    Dry sample:

                          V 1,000 )V
     mg metal/kg sample =  -
                                D
     where:

     Z = ug/1 of metal in processed sample from calibration curve (See 9.3.8.1)
     V = final volume of processed sample in ml
     D = weight of dry sample in grams
          9.3.10.2    Wet sample:
     mg metal/ kg sample =
                             W x  P
     where:

     Z = ug/1 of metal in processed sample from calibration curve (See 9.3.8. 1)
     V = final volume of processed sample in ml
     W = weight of wet sample in grams
     P= % solids
                            METALS-18

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10   Quality Control For Drinking Water Analysis
     10.1  Minimum requirements
          10.1.1      All  quality control  data should be  maintained  and available  for easy
                     reference or inspection.
          10.1.2      An unknown performance sample (when available) must be analyzed once
                     per year for the metals measured. Results must be within the control limit
                     established by  EPA.  If problems arise, they should be corrected, and a
                     follow-up performance sample should be analyzed.
     10.2  Minimum Daily control
          10.2.1      After a calibration curve composed of a minimum of a reagent blank and
                     three standards has been prepared,  subsequent calibration  curves must be
                     verified by use of at  least a reagent  blank and one standard at or near the
                     MCL. Daily checks must be within ± 10 percent of original curve.
          10.2.2      If 20 or more samples per day are analyzed, the working standard curve must
                     be verified by running an additional standard at or near the MCL every 20
                     samples. Checks must be within ± 10 percent of original curve.
     10.3  Optional Requirements
          10.3.1      A current service  contract should be in effect on balances  and the atomic
                     absorption spectrophotometer.
          10.3.2      Class S weights should be available to make periodic checks on balances.
          10.3.3      Chemicals should be dated upon receipt of shipment and replaced as needed
                     or before shelf life has been exceeded.
          10.3.4      A known reference sample (when available) should be analyzed once per
                     quarter for the metals measured. The measured value should be within the
                     control limits established by EPA.
          10.3.5      At least  one duplicate sample should be run every 10 samples, or with each
                     set of samples to verify precision of the method. Checks should be within the
                     control limit established by EPA.
          10.3.6      Standard  deviation  should   be   obtained  and   documented  for  all
                     measurements being conducted.
          10.3.7      Quality  Control charts or a tabulation of mean and standard deviation
                     should be used to document validity of data on a daily basis.
                                       METALS-19

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                                     ANTIMONY

               Method  204.1  (Atomic absorption, direct aspiration)

                                                         STORET  NO. Total 01097
                                                                      Dissolved 01095
                                                                     Suspended 01096

Optimum Concentration Range:    1-40 mg/1 using a wavelength of 217.6 nm
Sensitivity:      0.5 mg/1
Detection Limit:      0.2 mg/1

Preparation of Standard Solution
      1.    Stock Solution: Carefully weigh 2.7426 g of antimony potassium tartrate (analytical
           reagent grade) and dissolve in deionized distilled water. Dilute to 1 liter with deionized
           distilled water. 1 ml = 1 mgSb( 1000 mg/1).
      2.    Prepare dilutions of the stock solution to be used as calibration standards at the time of
           analysis. The calibration standards should be prepared using the same type of acid and at
           the same concentration as will result in the sample to be analyzed either directly or after
           processing.

Sample Preservation
      1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.    The procedures for preparation of the sample as given in parts 4.1.1 through 4.1.4 of the
           Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
      1.    Antimony hollow cathode lamp
      2.    Wavelength: 217.6 nm
      3.    Fuel: Acetylene
      4.    Oxidant: Air
      5.    Type of flame: Fuel lean

Analysis Procedure
      1.    For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
           Absorption Methods section of this manual.


Approved for NPDES
Issued 1974
Editorial revision 1978

                                        204.1-1

-------
Interferences
     1.    In the presence of lead (1000 mg/1), a spectral interference may occur at the 217.6 nm
           resonance line. In this case the 231.1 nm antimony line should be used.
     2.    Increasing acid concentrations decrease antimony absorption.  To avoid this effect, the
           acid concentration in the samples and in the standards should be matched.

Notes
     1.    Data to be entered into STORET must be reported as ug/1.
     2.    For concentrations of antimony below 0.35 mg/1, the furnace procedure (Method 204.2)
           is recommended.

Precision and Accuracy
     1.    In  a single  laboratory (EMSL), using a  mixed industrial-domestic waste effluent at
           concentrations of 5.0 and 15 mg Sb/1, the standard deviations were ±0.08 and  ±0.1,
           respectively. Recoveries at these levels were 96% and 97%, respectively.
                                          204.1-2

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                                    ANTIMONY

              Method 204.2 (Atomic  Absorption, furnace technique)

                                                        STORET  NO. Total 01097
                                                                     Dissolved 01095
                                                                    Suspended 01096
Optimum Concentration Range:   20-300 ug/1
Detection Limit:      3 ug/1

Preparation of Standard Solution
     1.    Stock solution: Prepare as described under "direct aspiration method".
     2.    Prepare dilutions of the stock solution to be used as calibration standards at the time of
          analysis. These solutions are also to be used for "standard additions".
     3.    The calibration standard should be diluted to contain 0.2% (v/v) HNO3.

Sample Preservation
     1.    For sample handling and preservation, see part 4.1  of the Atomic Absorption Methods
          section of this manual.

Sample Preparation
     1.    The procedures for preparation of the sample  as given in parts 4.1.1 thru 4.1.3 of the
          Atomic Absorption Methods section of this manual should be followed including the
          addition of sufficient  1:1 HC1 to  dissolve the digested residue for the  analysis of
          suspended or total antimony. The sample solutions used for analysis should contain 2%
          (v/v) HNO3.

Instrument Parameters (General)
     1.    Drying Time and Temp:  30sec-125°C.
     2.    Ashing Time and Temp:  30 sec-800°C.
     3.    Atomizing Time and Temp:   10 sec-2700°C.
     4.    Purge Gas Atmosphere:  Argon
     5.    Wavelength:  217.6nm
     6.    Other operating parameters should be set as specified  by the  particular instrument
          manufacturer.

Analysis Procedure
     1.    For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
          Atomic Absorption Methods section of this manual.
Approved for NPDES
Issued  1978

                                        204.2-1

-------
Notes
     1.     l he above concentration values and instrument conditions are for a Perkin-Elmer HGA-
           2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
           graphite. Smaller size furnace devices or those employing faster rates of atomization can
           be operated using lower atomization temperatures for shorter time periods than the
           above recommended settings.
     2.     The use of background correction is recommended.
     3.     Nitrogen may also be used as the purge gas.
     4.     If chloride concentration presents a matrix problem or causes a loss  previous  to
           atomization, add an excess of 5 mg of ammonium nitrate to the furnace and ash using a
           ramp accessory or with incremental steps until the recommended ashing temperature is
           reached.
     5.     For every sample matrix analyzed, verification is necessary to determine that method of
           standard addition is not required (see part 5.2.1 of the Atomic Absorption Methods
           section of this manual).
     6.     If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods section of this manual.
     7.     Data to be entered in to STORET must be reported as ug/1.

Precision and Accuracy
     1.     Precision and accuracy data are not available at this time.
                                         204.2-2

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                                      ARSENIC

              Method 206.2 (Atomic Absorption,  furnace  technique)

                                                          STORE! NO. Total  01002
                                                                      Dissolved  01000
                                                                     Suspended  01001
Optimum Concentration Range: 5-100 ug/1
Detection Limit: 1 ug/1

Preparation of Standard Solution
     1.    Stock solution: Dissolve 1.320 g of arsenic trioxide, As203 (analytical reagent grade) in
           100 ml of deionized distilled water containing 4 g NaOH. Acidify the solution with 20 ml
           cone. HNO3 and dilute to 1 liter. 1 ml = 1 mg As (1000 mg/1).

     2.    Nickel Nitrate Solution, 5 %: Dissolve 24.780 g of ACS reagent grade Ni(NO3)2»6H2O in
           deionized distilled water and make up to 100ml.

     3.    Nickel Nitrate Solution, 1%: Dilute 20 ml of the 5% nickel nitrate to  100 ml with
           deionized distilled water.

     4.    Working Arsenic Solution:  Prepare dilutions  of the  stock solution  to  be used as
           calibration standards at the time of analysis. Withdraw appropriate aliquots of the stock
           solution, add 1 ml of cone. HNO3, 2ml of 30% H2O2 and  2ml of the 5% nickel nitrate
           solution. Dilute to 100 ml with deionized distilled water.

Sample Preservation
     1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
     1.    Transfer 100 ml of well-mixed sample to a 250 ml Griffin beaker, add 2 ml of 30% H2O2
           and sufficient cone. HNO3 to result in an acid concentration of 1 %(v/v). Heat for 1 hour
           at 95°C or until the volume is slightly less than 50 ml.

     2.    Cool and bring back to 50 ml with deionized distilled water.

     3.    Pipet 5  ml of this digested solution into a 10-ml volumetric flask, add 1 ml of the 1%
           nickel nitrate solution and dilute to 10 ml with deionized distilled water. The sample is
           now ready for injection into the furnace.
Approved for  NPDES and SDWA
Issued  1978

                                         206.2-1

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          NOTE: If solubilization or digestion is not required, adjust the HNO3 concentration of
          the sample to 1% (v/v) and add 2 ml of 30%H2O2 and 2 ml of 5% nickel nitrate to each
          100 ml of sample. The volume of the calibration standard should be adjusted with
          deionized distilled water to match the volume change of the sample.

Instrument Parameters (General)
     1.    Drying Time and Temp: 30 sec-125°C.
     2.    Ashing Time and Temp: 30 sec-1100°C.
     3.    Atomizing Time and Temp: 10 sec-2700°C.
     4.    Purge Gas Atmosphere: Argon
     5.    Wavelength: 193.7 nm
     6.    Other operating parameters should be set as specified by the particular instrument
          manufacturer.

Analysis Procedure
     1.    For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
          Atomic Absorption Methods section of this manual.

Notes
     1.    The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
          2100, based  on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
          graphite. Smaller size furnace devices or those employing faster rates of atomization can
          be operated using lower  atomization temperatures for shorter time periods than the
          above recommended settings.
     2.    The use of background correction is recommended.
     3.    For every sample matrix analyzed, verification is necessary to determine that method of
          standard addition  is not  required (see part 5.2.1  of the Atomic Absorption Methods
          section of this manual).
     4.    If method of standard addition is required, follow the procedure given earlier in part 8.5
          of the Atomic Absorption Methods section of this manual.
     5.    For quality control requirements and optional recommendations for  use in drinking
          water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     6.    Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.    In a single laboratory (EMSL), using  a mixed  industrial-domestic  waste effluent
          containing 15 ug/1 and spiked with concentrations of 2, 10 and 25 ug/1, recoveries of
          85%, 90% and 88% were obtained respectively. The relative standard deviation at these
          concentrations levels were ±8.8%,  ±8.2%,  ±5.4% and ±8.7%, respectively.
     2.    In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
          of 20,  50 and 100 ug  As/1,  the standard deviations  were ±0.7,  ±1.1  and ±1.6
          respectively. Recoveries at these levels were 105%, 106% and 101%, respectively.
                                         206.2-2

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                                      ARSENIC

              Method 206.3  (Atomic Absorption—gaseous  hydride)
                                                         STORET NO.  Total  01002
                                                                     Dissolved  01000
                                                                    Suspended  01001
1.    Scope and Application
     1.1  The  gaseous  hydride  method  determines  inorganic  arsenic when  present  in
          concentrations at or above 2 ug/1. The method is applicable to drinking water and most
          fresh  and saline waters  in the absence of high concentrations of chromium, cobalt,
          copper, mercury, molybdenum, nickel and silver.
2.    Summary of Method
     2.1  Arsenic in the sample is first reduced to the trivalent form using SnCl2 and converted to
          arsine, AsH3, using zinc metal. The gaseous hydride is swept into an argon-hydrogen
          flame of an atomic absorption spectrophotometer. The working range of the mehtod is
          2-20 ug/1. The 193.7 nm wavelength line is used.
3.    Comments
     3.1  In analyzing drinking water and most surface and ground waters, interferences are rarely
          encountered. Industrial waste samples should be spiked with a known amount of arsenic
          to establish adequate recovery.
     3.2  Organic forms of arsenic must be converted to inorganic compounds and organic matter
          must  be oxidized before beginning the analysis.  The oxidation procedure given in
          Method 206.5  (Standard Methods, 14th Edition, Method 404B, p. 285, Procedure 4.a)
          has been found suitable.
     3.3  For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
          section of this manual.
     3.4  For quality  control requirements and optional recommendations for use in drinking
          water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     3.5  Data to be entered into STORET must be reported as ug/1.
4.    Precision and Accuracy
     4.1  Ten replicate solutions of o-arsenilic acid at the 5,10 and 20 ug/1 level were analyzed by
          a single laboratory. Standard deviations were ±0.3,  ±0.9 and  ±1.1 with recoveries of 94,
          93  and 85%,  respectively.  (Caldwell, J.  S.,  Lishka,  R. J., and McFarren, E. F.,
          "Evaluation of a Low Cost Arsenic and Selenium Determination at Microgram per Liter
          Levels", JAWWA., vol 65, p 731, Nov., 1973.)
Approved for NPDES and SDWA
Issued  1974
                                        206.3-1

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5.    References
     5.1,   Except for the perchloric acid step, the procedure to be used for this determination is
           found in: Standard Methods for the Examination of Water and Wastewater,  14th
           Edition, p!59, Method 301A(VII),(1975)
                                         206.3-2

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                                      BARIUM

               Method 208.1  (Atomic Absorption,  direct aspiration)

                                                        STORET NO.  Total 01007
                                                                     Dissolved 01005
                                                                    Suspended 01006

Optimum Concentration Range;   1-20 mg/1 using a wavelength of 553.6 nm
Sensitivity:      0.4 mg/1
Detection Limit:     0.1 mg/1

Preparation of Standard Solution
      1.    Stock Solution: Dissolve  1.7787 g barium chloride (BaQ2»2H2O, analytical reagent
           grade) in deionized distilled water and dilute to 1 liter. 1 ml =  1 mg Ba (1000 mg/1).
      2.    Potassium chloride solution: Dissolve 95 g potassium chloride,  KC1, in deionized
           distilled water and make up to 1 liter.
      3.    Prepare dilutions of the stock barium solution to be used as calibration standards at the
           time of analysis. To each  100 ml of standard and sample alike add 2.0 ml potassium
           chloride solution. The calibration standards should be prepared using the same type of
           acid and the same concentration as will result in the sample to be analyzed either directly
           or after processing.
                                                                                      i
Sample Preservation
      1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.    The procedures for preparation of the sample as given in parts 4.1.1 through 4.1.4 of the
           Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
      1.    Barium hollow cathode lamp
      2.    Wavelength: 553.6 nm
      3.    Fuel: Acetylene
      4.    Oxidant: Nitrous oxide
      5.    Type of flame: Fuel rich
Approved  for NPDES and  SDWA
Issued  1974
                                        208.1-1

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Analysis Procedure
     1.    For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
           Absorption Methods section of this manual.

Interferences
     1.    The use of a nitrous oxide-acetylene flame virtually eliminates chemical interference;
           however, barium is easily ionized in this flame and potassium must be added (1000 mg/1)
           to standards and samples alike to control this effect.
     2.    If the nitrous oxide flame is not available and acetylene-air is used, phosphate, silicon and
           aluminum will severely depress the barium absorbance. This may be overcome by  the
           addition of 2000 mg/1 lanthanum.

Notes
     1.    Data to be entered into STORET must be reported as ug/1.
     2.    For concentrations of barium below 0.2 mg/1, the furnace procedure (Method 208.2) is
           recommended.
     3.    For quality control requirements and optional recommendations for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.

Precision and Accuracy
     1.    In  a single laboratory (EMSL), using a mixed industrial-domestic waste effluent at
           concentrations of 0.40 and 2.0 mg  Ba/1,  the  standard  deviations were ±0.043
           and ±0.13, respectively. Recovereis at these levels were 94% and 113%, respectively.
     2.    In  a round-robin study reported by  Standard Methods (13th Edition, p215, method
           129A,  1971),  three  synthetic  samples  containing  barium  were analyzed  by  13
           laboratories. At concentrations of 500, 1000 and 5000 ug Ba/1, the reported standard
           deviations were ±50, ±89 and ±185 ug,  respectively. The  relative error at these
           concentrations was 8.6%, 2.7% and 1.4%, respectively.
                                         208.1-2

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                                      BARIUM

              Method 208.2 (Atomic  Absorption, furnace technique)

                                                                STORE! NO.  01007
                                                                     Dissolved  01005
                                                                    Suspended  01006
Optimum Concentration Range:   10-200 ug/1
Detection Limit:      2 ug/1

Preparation of Standard Solution
      1.     Stock solution: Prepare as described under "direct aspiration method".
      2.     Prepare dilutions, of the stock solution to be used as calibration standards at the time of
           analysis. These solutions are also to used for "standard additions".
      3.     The calibration standard should be diluted to contain 0.5% (v/v) HNO3.

Sample Preservation
      1.     For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.     Prepare as described under "direct aspiration method". Sample solutions for analysis
           should contain 0.5% (v/v) HNO3.

Instrument Parameters (General)
      1.     Drying Time and Temp:   30 sec-125°C.
      2.     Ashing Time and Temp:   30sec-1200°C.
      3.     Atomizing Time and Temp:   10 sec-2800°C.
      4.     Purge Gas Atmosphere:  Argon
      5.     Wavelength:  553.6 nm
      6.     Other operating  parameters should be set as specified by the  particular instrument
           manufacturer.

Analysis Procedure
      1.     For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
           Atomic Absorption Methods section of this manual.

Notes
      1.     The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
           2100, based on the use of a 20 ul injection, continuous flow purge gas and pyrolytic
           graphite.

Approved  for NPDES and  SDWA
Issued 1978

                                        208.2-1

-------
     2.    The use of halide acid should be avoided.
     3.    Because of possible chemical interaction, nitrogen should not be used as a purge gas.
     4.    For every sample matrix analyzed, verification is necessary to determine that method of
           standard addition is not required (see part 5.2.1  of the Atomic Absorption Methods
           section of this manual).
     5.    If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods section of this manual.
     6.    For quality control  requirements and optional recommendations for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     7.    Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.    In a single laborator y (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
           of 500 and 1000 ug Ba/1, the standard deviations were  +2.5 and  ±2.2 ug, respectively.
           Recoveries at these  levels were 96% and 102%, respectively A dilution of 1:10 was
           required to bring the spikes within the analytical range of the method.
                                          208.2-2

-------
                                    BERYLLIUM

              Methods  210.1 (Atomic Absorption, direct aspiration)

                                                         STORET NO. Total  01012
                                                                     Dissolved  01010
                                                                    Suspended  01011

Optimum Concentration Range:   0.05-2 mg/1 using a wavelength of 234.9 nm
Sensitivity:     0.025 mg/1
Detection Limit:       0.005 mg/1

Preparation of Standard Solution
     1.    Stock solution: Dissolve 11.6586 g beryllium sulfate, BeSO4, in deionized distilled water
           containing 2 ml cone, nitric acid and dilute to 1 liter. 1 ml  =  1 mg Be (1000 mg/1).
     2.    Prepare dilutions of the stock solution to be used as calibration standards at the time of
           analysis. The calibration standards should be prepared using the same type of acid and at
           the same concentration as will result in the sample to be analyzed either directly or after
           processing.

Sample Preservation
     1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
     1.    The procedures for preparation of the sample as given in parts 4.1.1 through 4.1.4 of the
           Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
     1.    Beryllium hollow cathode lamp
     2.    Wavelength: 234.9 nm
     3.    Fuel: Acetylene
     4.    Oxidant: Nitrous oxide
     5.    Type of flame: Fuel rich

Analysis Procedure
     1.    For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
           Absorption Methods section of this manual.
Approved for NPDES
Issued  1974
                                        210.1-1

-------
Interferences
     1.    Sodium and silicon at concentrations in excess of 1000 mg/1 have been found to severely
           depress the beryllium absorbance.
     2.    Bicarbonate ion is reported to interfere; however, its effect is eliminated when samples
           are acidified to a pH of 1.5.
     3.    Aluminum  at concentrations of  500 ug/1 is reported  to depress the sensitivity of
           beryllium [Spectrochim Acta 22,1325 (1966)].

Notes
     1.    Data to be entered into STORET must be reported as ug/1.
     2,    The "aluminon color imetric method" may also be used  (Standard  Methods, 14th
           Edition, p 177). The minimum detectable concentration by this method is 5 ug/1.
     3.    For concentrations of beryllium below 0.02 mg/1, the furnace procedure (Method 210.2)
           is recommended.

Precision and Accuracy
     1.    In a single laboratory (EMSL), using a mixed industrial-domestic waste effluent at
           concentrations of 0.01, 0.05 and 0.25 mg Be/1,  the standard deviations were  ±0.001,
           ±0.001 and ±0.002, respectively. Recoveries at these levels were 100%, 98% and 97%,
           respectively.
                                          210.1-2

-------
                                   BERYLLIUM

              Method 210.2  (Atomic Absorption,  furnace  technique)

                                                               STORET NO. 01012
                                                                     Dissolved 01010
                                                                    Suspended 01011
Optimum Concentration Range:   1-30 ug/1
Detection Limit:      0.2 ug/1

Preparation of Standard Solution
     1.    Stock solution: Prepare as described under "direct aspiration method".
     2.    Prepare dilutions of the stock solution to be used as calibration standards at the time of
          analysis. These solutions are also to be used for "standard additions".
     3.    The calibration standard should be diluted to contain 0.5% (v/v) HNO3.

Sample Preservation
     1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
          section of this manual.

Sample Preparation
     1.    Prepare as described under "direct aspiration method". Sample solutions for analysis
          should contain 0.5% (v/v) HNO3.

Instrument Parameters (General)
     1.    Drying Time and Temp:  30 sec-125°C.
     2.    Ashing Time and Temp:  30 sec-1000°C.
     3.    Atomizing Time and Temp:  10 sec-2800°C.
     4.    Purge Gas Atmosphere:  Argon
     5.    Wavelength:  234.9 nm
     6.    The operating parameters should be set  as specified by the particular  instrument
          manufacturer.

Analysis Procedure
     1.    For the analysis procedure and the calculation see "Furnace Procedure" part 9.3 of the-
          Atomic Absorption methods section of this manual.

Notes
     1.    The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
          2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
          graphite. Smaller size furnace devices or those employing faster rates of atomization can

Approved for  NPDES
Issued  1978

                                        210.2-1

-------
           be operated using lower atomization temperatures for shorter time periods than the
           above recommended settings.
     2.    The use of background correction is recommended.
     3.    Because of possible chemical interaction and reported lower sensitivity, nitrogen should
           not be used as the purge gas.
     4.    For every sample matrix analyzed, verification is necessary to determine that method of
           standard addition  is not required (see part 5.2.1 of the Atomic  Absorption Methods
           section of this manual).
     5.    If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods section of this manual.
     6.    Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.    Precision and Accuracy data are not available at this time.
                                          210.2-2

-------
                                     CADMIUM

               Method 213.1  (Atomic Absorption,  direct aspiration)

                                                         STORE! NO.  Total  01027
                                                                      Dissolved  01025
                                                                    Suspended  01026

Optimum Concentration Range:   0.05-2 mg/1 using a wavelength of 228.8 nm
Sensitivity:     0.025 mg/1
Detection Limit:      0.005 mg/1

Preparation of Standard Solution
     1.   Stock Solution: Carefully weigh 2.282 g of cadmium sulfate (3CdSO4»8H2O, analytical
          reagent grade) and dissolve in deionized distilled water. 1 ml = 1 mg Cd (1000 mg/1).
     2.   Prepare dilutions of the stock solution to be used as calibration standards at the time of
          analysis. The calibration standards should be prepared using the same type of acid and at
          the same concentration as will result in the sample to be analyzed either directly or after
          processing.

Sample Preservation
     1.   For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
          section of this manual.

Sample Preparation
     1.   The procedures for preparation of the sample as given in parts 4.1.1 through 4.1.4 of the
          Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
     1.   Cadmium hollow cathode lamp
     2.   Wavelength: 228.8 nm
     3.   Fuel: Acetylene
     4.   Oxidant: Air
     5.   Type of flame: Oxidizing

Analysis Procedure
     1.   For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
          Absorption Methods section of this manual.
Approved for NPDES  and SDWA
Issued 1971
Editorial revision 1974

                                        213.1-1

-------
Notes
     1.    For levels of cadmium below 20 og/1, either the Special Extraction Procedure given in
           Part 9.2 of the Atomic Absorption methods section as the furnace technique, Method
           213.2 is recommended.
     2.    Data to be entered into STORET must be reported as(ug/l.
     3.    For quality control requirements and optional  recommendations for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.

Precision and Accuracy
     1.    An interlaboratory study on trace metal analyses by atomic absorption was conducted by
           the Quality Assurance and Laboratory Evaluation Branch of EMSL. Six synthetic
           concentrates containing varying levels of aluminum, cadmium, chromium, copper, iron,
           manganese, lead and zinc were added to natural water samples. The statistical results for
           cadmium were as follows:
Number
of Labs

  74
  73
  63
  68
  55
  51
True Values
  «g/liter

   71
   78
   14
   18
    1.4
    2.8
Mean Value
  ug/liter

   70
   74
   16.8
   18.3
    3.3
    2.9
Standard
Deviation
 ug/liter

  21
  18
  11.0
  10.3
   5.0
   2.8
Accuracy as
  % Bias

   -2.2
   -5.7
   19.8
    1.9
  135
    4.7
                                         213.1-2

-------
                                     CADMIUM

              Method 213.2 (Atomic  Absorption,  furnace  technique)

                                                               STORE!  NO. 01027
                                                                     Dissolved 01025
                                                                    Suspended 01026
Optimum Concentration Range:   0.5-10 og/1
Detection Limit:       0.1 ug/\

Preparation of Standard Solution
     1.     Stock solution: Prepare as described under "direct aspiration method".
     2.     Ammonium Phosphate solution  (40%); Dissolve 40 grams of ammonium phosphate,
           (NH4)2HPO4 (analytical reagent grade) in deionized distilled water and dilute to 100 ml.
     3.     Prepare dilutions of the stock cadmium solution to be used as calibration standards at the
           time of analysis. To each  100 ml of standard and sample alike add  2.0 ml of the
           ammonium phosphate solution. The calibration standards should be prepared to contain
           0.5% (v/v) HNO3.

Sample Preservation
     1.     For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
     1.     Prepare as described under "direct aspiration method". Sample solutions for analysis
           should contain 0.5% (v/v) HNO3.

Instrument Parameters (General)
     1.     Drying Time and Temp:  30sec-125°C.
     2.     Ashing Time and Temp:  30 sec-500°C.
     3.     Atomizing Time and Temp:  10sec-1900°C.
     4.     Purge Gas Atmosphere:  Argon
     5.     Wavelength:  228.8 nm
     6.     Other operating parameters should  be set as specified by the particular instrument
           manufacturer.

Analysis Procedure
     1.     For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
           Atomic Absorption Methods section of this manual.
Approved  for NPDES and SDWA
Issued  1978

                                        213.2-1

-------
Notes
     1.    The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
          2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
          graphite. Smaller size furnace devices or those employing faster rates of atomization can
          be operated using lower atomization temperatures for shorter time periods than the
          above recommended settings.
     2.    The use of background correction is recommended.
     3.    Contamination from the work area is critical in cadmium analysis.  Use of pi pet tips
          which are free of cadmium is of particular importance. (See part 5.5.7 of the Atomic
          Absorption Methods section of this manual.)
     4.    For every sample matrix analyzed, verification is necessary to determine that method of
          standard addition  is not required (see part 5.2.1 of the Atomic Absorption Methods
          section of this manual).
     5.    If method of standard addition is required, follow the procedure given earlier in part 8.5
          of the Atomic Absorption Methods section of this manual.
     6.    For quality control requirements and optional  recommendations for use in drinking
          water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     7.    Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.    In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
          of 2.5, 5.0  and 10.0 ug Cd/1, the standard deviations were ±0.10,  ±0.16 and ±0.33,
          respectively. Recoveries at these levels were 96%,  99% and 98%, respectively.
                                         213.2-2

-------
                                    CHROMIUM

               Method 218.1 (Atomic  Absorption, direct aspiration)

                                                         STORET NO.  Total 01034
                                                                      Dissolved 01030
                                                                     Suspended 01031

Optimum Concentration Range:   0.5-10 mg/1 using a wavelength of 357.9 nm
Sensitivity:     0.25 mg/1
Detection Limit:      0.05 mg/1

Preparation of Standard Solution
     1.    Stock Solution: Dissolve 1.923 g of chromium trioxide (CrO3, reagent grade) in deionized
          distilled water. When solution is complete, acidify with redistilled HNO3 and dilute to 1
          liter with deionized distilled water. 1 ml  = 1 mg Cr (1000 mg/1).
     2.    Prepare dilutions of the stock solution to be  used as calibration standards at the time of
          analysis. The calibration standards should be prepared using the same type of acid and at
          the same concentration as will result in the sample to be analyzed either directly or after
          processing.

Sample Preservation
     1.    For sample handling  and preservation, see part 4.1 of the Atomic Absorption Methods
          section of this manual.

Sample Preparation
     1.    The procedures for preparation of the sample as given in parts 4.1.1 thru 4.1.4 of the
          Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
     1.    Chromium hollow cathode lamp
     2.    Wavelength: 357.9 nm
     3.    Fuel: Acetylene
     4.    Oxidant: Nitrous oxide
     5.    Type of flame: Fuel rich

Analysis Procedure
     1.    For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
          Absorption Methods section of this manual.


Approved for  NPDES and SDWA
Issued  1971
Editorial  revision  1974 and  1978

                                      218.1-1

-------
Notes
     1.    The following wavelengths may also be used:
           359.3 nm Relative Sensitivity 1.4
           425.4 nm Relative Sensitivity 2
           427.5 nm Relative Sensitivity 3
           428.9 nm Relative Sensitivity 4

     2.    The fuel rich air-acetylene flame provides greater sensitivity but is subject to chemical
           and matrix interference from iron, nickel, and other metals. If the analysis is performed
           in a lean flame the interference can be lessened but the sensitivity will also be reduced.
     3.    The suppression of both Cr (III) and Cr (VI) absorption by most interfering ions in fuel
           rich air-acetylene flames is reportedly controlled  by the addition of 1% ammonium
           bifluoride in 0.2% sodium sulfate [Talanta 20, 631  (1973)]. A 1% oxine solution is also
           reported to be useful.
     4.    For levels of chromium between 50 and 200 ug/1 where the air-acetylene flame can not
           be used or for levels below 50 ug/1,  either the furnace procedure  or the extraction
           procedure is recommended. See Method 218.2 for the furnace procedure and Method
           218.3 for the chelation-extraction procedure.
     5.    For quality control requirements and optional recommendations  for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     6.    Data to be entered into STORE! must be reported as ug/1.
Precision and Accuracy
      1.    An interlaboratory study on trace metal analyses by atomic absorption was conducted by
           the Quality Assurance and Laboratory Evaluation Branch of EMSL.  Six synthetic
           concentrates containing varying levels of aluminum, cadmium, chromium, copper, iron,
           manganese, lead and zinc were added to natural water samples. The statistical results for
           chromium were as follows:
                                                          Standard
 Number        True Values          Mean Value           Deviation            Accuracy as
 of Labs          tig/liter              ug/liter              ug/liter               % Bias

   74              370                 353                  105                  -4.5
   76              407                 380                  128                  -6.5
   72               74                  72                   29                  -3.1
   70               93                  84                   35                 -10.2
   47                7.4                 10.2                  7.8                 37.7
   47               15.0                 16.0                  9.0                   6.8
                                          218.1-2

-------
                                    CHROMIUM

              Method 218.2 (Atomic  Absorption, furnace technique)

                                                                STORET NO.  01034
                                                                     Dissolved  01030
                                                                    Suspended  01031

Optimum Concentration Range:   5-100ug/l
Detection Limit:       1 ug/1

Preparation of Standard Solution
      1.     Stock solution: Prepare as described under "direct aspiration method".
      2.     Calcium Nitrate Solution: Dissolve 11.8 grams of calcium nitrate,  Ca(NO3)2 • 4H2O
           (analytical reagent grade) in deionized distilled water and dilute to 100 ml. 1 ml = 20 mg
           Ca.
      3.     Prepare dilutions of the stock chromium solution to be used as calibration standards at
           the time of analysis. The calibration standards should be prepared to contain 0.5% (v/v)
           HNO3. To each 100 ml of standard and sample alike, add 1 ml of 30% H2O2 and 1 ml of
           the calcium nitrate solution.

Sample Preservation
      1.     For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           secton of this manual.

Sample Preparation
      1.     Prepare as described under "direct aspiration method". Sample solutions for analysis
           should contain 0.5% v/v HNO3.

Instrument Parameters (General)
      1.     Drying Time and Temp: 30 sec-125°C.
      2.     Ashing Time and Temp: 30 sec-1000°C.
      3.     Atomizing Time and Temp: 10 sec-2700°C.
      4.     Purge Gas Atmosphere: Argon
      5.     Wavelength: 357.9 nm
      6.     Other operating parameters should be set as specified by the particular instrument
           manufacturer.

Analysis Procedure
      1.     For the  analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
           Atomic  Absorption Methods section of this manual.

Approved  for NPDES and SDWA
Issued 1978

                                        218.2-1

-------
Notes
     1.     The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
           2100, based on the use of a 20 ul injecton, continuous flow purge gas and non-pyrolytic
           graphite.
     2.     Hydrogen peroxide is added to the acidified solution to convert all chromium to the
           trivalent state. Calcium  is added to a level above 200 mg/1 where its suppressive effect
           becomes constant up to 1000 mg/1.
     3.     Background correction may be required if the sample contains high dissolved solids.
     4.     Nitrogen should not be used as a purge gas because of possible CN band interference.
     5.     Pipet tips have been reported to be a possible source of contamination. (See part 5.5.7 of
           the Atomic Absorption Methods section of this manual.)
     6.     For every sample matrix analyzed, verification is necessary to determine that method of
           standard addition is not required (see part 5.2.1 of the Atomic Absorption  Methods
           section of this manual).
     7.     If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods section of this manua-1.
     8.     For quality control requirements and optional recommendations for use in  drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     9.     Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.     In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
           of 19, 48, and  77 ug  Cr/1,  the  standard deviations were   ±0.1, ±0.2, and  ±0.8,
           respectively. Recoveries at these levels were 97%, 101%, and 102%, respectively.
                                          218.2-2

-------
                                        LEAD
               Method 239.1 (Atomic Absorption, direct  aspiration)

                                                         STORET  NO.  Total  01051
                                                                      Dissolved  01049
                                                                     Suspended  01050

Optimum Concentration Range:   1-20 mg/1 using a wavelength of 283.3 nm
Sensitivity:      0.5 mg/1
Detection Limit:      0.1 mg/1

Preparation of Standard Solution
      1.    Stock Solution: Carefully weigh 1.599 g of lead nitrate,  Pb(NO3)2 (analytical reagent
           grade), and dissolve in deionized distilled water. When solution is complete acidify with
           10 ml redistilled HNO3 and dilute to 1 liter with deionized distilled water. 1 ml =  1 mg
           Pb (1000 mg/1).
     2.    Prepare dilutions of the stock solution to be used as calibration standards at the  time of
           analysis. The calibration standards should be prepared using the same type of acid and at
           the same concentration as will result in the sample to be analyzed either directly or after
           processing.

Sample Preservation
      1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.    The procedures for preparation of the sample as given in parts 4.1.1 thru 4.1.4 of the
           Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
      1.    Lead hollow cathode lamp
     2.    Wavelength: 283.3 nm
     3.    Fuel: Acetylene
     4.    Oxidant: Air
     5.    Type of flame: Oxidizing

Analysis Procedure
      1.    For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
           Absorption Methods section of this manual.
Approved for NPDES  and SDWA
Issued 1971
Editorial revision 1974 and  1978

                                         239.1-1

-------
Notes
     1.    The analysis of this metal is exceptionally sensitive to turbulence and absorption bands in
           the flame. Therefore, some care should be taken to position the light beam in the most
           stable, center portion of the flame. To do this, first adjust the burner to maximize the
           absorbance reading with a lead standard. Then, aspirate a water blank and make minute
           adjustments in the burner alignment to minimize the signal.
     2.    For levels of lead below 200 ug/1, either the Special Extraction Procedure given in part
           9.2 of the Atomic Absorption Methods section or the furnace technique, Method 239.2,
           is recommended.
     3.    The following lines may also be used:
           217.0 nm Relative Sensitivity 0.4
           261.4 nm Relative Sensitivity 10
     4.    For quality control  requirements and optional recommendations for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     5.    Data to be entered into STORET must be reported as ug/1.
Precision and Accuracy
      1.    An interlaboratory study on trace metal analyses by atomic absorption was conducted by
           the Quality Assurance and Laboratory Evaluation  Branch of EMSL. Six synthetic
           concentrates containing varying levels of aluminum, cadmium, chromium, copper, iron,
           manganese, lead and zinc were added to natural water samples. The statistical results for
           lead were as follows:
                                                          Standard
 Number        True Values          Mean Value            Deviation            Accuracy as
 of Labs           ug/liter              ug/liter              ug/liter              % Bias

   74              367                  377                  128                   2.9
   74              334                  340                  111                   1.8
   64              101                  101                   46                  -0.2
   64               84                  85                   40                   1.1
   61               37                  41                   25                   9.6
   60               25                  31                   22                  25.7
                                         239.1-2

-------
                                       LEAD
              Method 239.2  (Atomic Absorption,  furnace  technique)

                                                        STORE! NO. Total  01051
                                                                     Dissolved  01049
                                                                   Suspended  01050

Optimum Concentration Range:    5-100 ug/1
Detection Limit:       1 ug/1

Preparation of Standard Solution
     1.    Stock solution: Prepare as described under "direct aspiration method".
     2.    Lanthanum Nitrate Solution: Dissolve 58.64 g of ACS reagent grade La2O3 in 100 ml
          cone. HNO3 and dilute to 1000 ml with deionized distilled water. 1 ml = 50 mg La.
     3.    Working Lead Solution: Prepare  dilutions of the  stock lead solution  to be used as
          calibration standards at the time of analysis. Each calibration standard should contain
          0.5% (v/v) HNO3. To each 100 ml of diluted standard add 10 ml of the  lanthanum
          nitrate solution.

Sample Preservation
     1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
          section of this manual.

Sample Preparation
     1.    Prepare as described under "direct aspiration method". Sample solutions for analysis
          should contain 0.5% (v/v) HNO3.
     2.    To each 100 ml of prepared sample solution add 10 ml of the lanthanum nitrate solution.

Instrument Parameters (General)
     1.    Drying Time and Temp: 30 sec-125°C.
     2.    Ashing Time and Temp: 30 sec-500°C.
     3.    Atomizing Time and Temp: 10 sec-2700°C.
     4.    Purge Gas Atmosphere: Argon
     5.    Wavelength: 283.3 nm
     6.    Other operating parameters should  be set as specified by the particular  instrument
          manufacturer.

Analysis Procedure
     1.    For the analysis procedure in the calculation see "Furnace Procedure", part 9.3 of the
          Atomic Absorption Methods section of this manual.
Approved for NPDES and  SDWA
Issued  1978

                                        239.2-1

-------
Notes
     1.    The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
          2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
          graphite. Smaller size furnace devices or those employing faster rates of atomization can
          be operated using lower atomization temperatures for shorter time periods than the
          above recommended settings.
     2.    The use of background correction is recommended.
     3.    Greater  sensitivity can be achieved using the  217.0  nm  line, but  the  optimum
          concentration range is reduced. The use of a lead electrodeless discharge lamp at this
          lower wavelength has been  found to be advantageous. Also  a lower atomization
          temperature (2400°C) may be preferred.
     4.    To suppress sulfate interference (up to 1500 ppm) lanthanum is added as the nitrate to
          both samples and calibration standards. (Atomic Absorption Newsletter Vol.  15, No. 3,
          p 71, May-June 1976.)
     5.    Since glassware contamination is a severe problem in lead analysis, all glassware should
          be  cleaned immediately prior to use, and once cleaned, should not be open to the
          atmosphere except when necessary.
     6.    For every sample matrix analyzed, verification is necessary to determine that method of
          standard addition is not required (see part 5.2.1 of the Atomic Absorption Methods
          section of this manual).
     7.    For quality control requirements and optional recommendations  for use in drinking
          water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     8.    If method of standard addition is required, follow the procedure given earlier in  part 8.5
          of the Atomic Absorption Methods section of this manual.
     9.    Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.    In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
          of  25,  50, and 100 ug Pb/1, the standard  deviations  were  ±1.3, ±1.6, and  ±3.7,
          respectively. Recoveries at these levels were 88%, 92%, and 95% respectively.
                                         239.2-2

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                                      MERCURY
                  Method  245.1  (Manual  Cold Vapor  Technique)

                                                         STORE! NO.  Total  7190r
                                                                      Dissolved  71890
                                                                     Suspended  71895

 1.     Scope and Application
      1.1   This method is applicable to drinking, surface, and saline waters, domestic and industrial
           wastes.
      1.2   In addition to inorganic forms of mercury, organic mercurials may also be present. These
           organo-mercury compounds  will not respond to  the  cold vapor atomic  absorption
           technique unless they are first broken down and converted to mercuric ions. Potassium
           permanganate oxidizes many of these compounds, but recent studies have shown that a
           number of organic mercurials, including phenyl mercuric acetate and methyl mercuric
           chloride, are only partially oxidized by this reagent. Potasssium persulfate has been
           found to  give approximately 100% recovery when  used as  the oxidant  with these
           compounds. Therefore, a persulfate oxidation step following the addition  of the
           permanganate has been included to insure that organo-mercury compounds, if present,
           will be oxidized to the mercuric  ion before measurement. A heat step is required for
           methyl mercuric chloride when present in or spiked to  a natural system. For distilled
           water the heat step is not necessary.
      1.3   The range of the method may be varied through instrument and/or recorder expansion.
           Using a 100 ml sample, a detection limit of 0.2 ug Hg/1 can be achieved; concentrations
           below this level should be reported as <  0.2 (see Appendix 11.2).
2.     Summary of Method
      2.1   The flameless A A procedure is a physical method based on the absorption of radiation at
           253.7 nm by mercury vapor. The  mercury is reduced to the elemental state and aerated
           from solution in a closed system. The mercury vapor passes through a cell positioned in
           the light path of an atomic absorption spectrophotometer. Absorbance (peak height) is
           measured as a function of mercury concentration and recorded in the usual manner.
3.     Sample Handling and Preservation
      3.1   Until more conclusive data are obtained, samples should be preserved by acidification
           with nitric acid to a pH of 2 or  lower  immediately at  the time of collection. If only
           dissolved mercury is to be determined, the sample should be filtered through an all glass
           apparatus before the acid is added. For total mercury the filtration is omitted.
4.     Interference
      4.1   Possible  interference from  sulfide  is eliminated  by the  addition of  potassium
           permanganate. Concentrations as high as 20 mg/1  of sulfide as sodium sulfide do not
           interfere with the recovery of added inorganic mercury from distilled water.
Approved for NPDES  and SDWA
Issued  1974

                                         245.1-1

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     4.2  Copper has also been reported to interfere; however, copper concentrations as high as 10
          mg/1 had no effect on recovery of mercury from spiked samples.
     4.3  Sea  waters,  brines  and  industrial  effluents  high in  chlorides require additional
          permanganate (as much as 25 ml). During the oxidation step, chlorides are converted to
          free chlorine which will also absorb radiation of 253 nm. Care must be taken to assure
          that free chlorine is absent before  the mercury is reduced and swept into the cell. This
          may be accomplished by using an excess of hydroxylamine sulfate reagent (25 ml). In
          addition, the dead air space in the BOD bottle must be purged before the addition of
          stannous sulfate. Both  inorganic and organic mercury spikes have been quantitatively
          recovered from sea water using this technique.
     4.4  Interference from certain volatile organic materials which will absorb at this wavelength
          is also possible. A preliminary  run without  reagents should determine if this type of
          interference is present (see Appendix 11.1).
5.    Apparatus
     5.1  Atomic Absorption Spectrophotometer: (See Note 1) Any atomic absorption unit having
          an open  sample presentation area in which to mount the absorption cell is suitable.
          Instrument settings recommended by the particular manufacturer should be followed.
          Note 1: Instruments designed specifically for the measurement of mercury using the cold
          vapor technique  are commercially available and may be substituted for the atomic
          absorption spectfophotometer.
     5.2  Mercury Hollow  Cathode Lamp:  Westinghouse WL-22847, argon filled, or equivalent.
     5.3  Recorder: Any multi-range variable speed recorder that is  compatible with the UV
          detection system is suitable.
     5.4  Absorption  Cell: Standard  spectrophotometer cells  10 cm  long, having quartz end
          windows may be used.  Suitable cells may be constructed from plexiglass tubing, 1" O.D.
          X 4-1/2".  The ends  are ground perpendicular to the longitudinal axis and  quartz
          windows (1" diameter X 1/16" thickness), are cemented in place. The cell is strapped to a
          burner for support and aligned in the light beam by use of two 2" by 2" cards. One inch
          diameter holes are cut in the middle of each card; the cards are then placed over each end
          of the cell. The cell is then positioned  and adjusted vertically and horizontally to give the
          maximum transmittance.
     5.5  Air Pump: Any peristaltic pump capable of delivering 1 liter of air per minute may be
          used. A Masterflex pump with electronic speed control has been found to be satisfactory.
     5.6  Flowmeter: Capable of measuring an air flow of 1 liter per minute.
     5.7  Aeration Tubing: A straight glass frit having a coarse porosity. Tygon tubing is used for
          passage of the mercury vapor from the sample bottle to the absorption cell and return.
     5.8  Drying Tube: 6"  X 3/4" diameter tube  containing 20 g of magnesium perchlorate (see
          Note 2). The apparatus is assembled as shown in Figure 1.
          NOTE 2: In place of the magnesium perchlorate drying tube, a small reading lamp with
          60W bulb may be used to prevent condensation of moisture inside the cell. The lamp is
          positioned to shine on the absorption cell maintaining the air temperature in the cell
          about 10°C above ambient.
                                          245.1-2

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6.    Reagents
     6.1  Sulfuric Acid, Cone.: Reagent grade.
         6.1.1  Sulfuric acid, 0.5 N: Dilute 14.0 ml of cone, sulfuric acid to 1.0 liter.
     6.2  Nitric Acid, Cone: Reagent grade of low mercury content (See Note 3).
         NOTE 3: If a high reagent blank is obtained, it may be necessary to distill the nitric acid.
     6.3  Stannous Sulfate: Add 25 g stannous sulfate to 250 ml of 0.5 N sulfuric acid. This
         mixture is a suspension and should be stirred continuously during use. (Stannous
         chloride may be used in place of stannous sulfate.)
     6.4  Sodium Chloride-Hydroxylamine Sulfate Solution: Dissolve 12 g of sodium chloride and
         12 g of hydroxylamine sulfate in distilled water and dilute to 100 ml. (Hydroxylamine
         hydrochloride may be used in place of hydroxylamine sulfate.)
     6.5  Potassium Permanganate: 5% solution, w/v. Dissolve 5 g of potassium permanganate in
         100 ml of distilled water.
     6.6  Potassium Persulfate: 5% solution, w/v. Dissolve 5 g of potassium persulfate in 100 ml
         of distilled water.
     6.7  Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 ml of distilled
         water. Add 10 ml of cone, nitric acid and adjust the volume to 100.0 ml. 1 ml  = 1 mg
         Hg-
             O * BUBBLER
                ABSORPTION
                     CELL
     SAMPLE
     IN BOO
SOLUTION
BOTTLE
SCRUBBER
CONTAINING
A MERCURY
ABSORBING
MEDIA
          FIGURE  1.  APPARATUS  FOR  FLAMELESS
                         MERCURY  DETERMINATION
                                    245.1-3

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     6.8  Working Mercury Solution: Make successive dilutions of the stock mercury solution to
          obtain a working standard containing 0.1 ug per ml. This working standard and the
          dilutions of the stock mercury solution should be prepared fresh daily. Acidity of the
          working standard should be maintained at 0.15% nitric acid. This acid should be added
          to the flask as needed before the addition of the aliquot.
7.    Calibration
     7.1  Transfer 0, 0.5, 1.0, 2.0,  5.0 and  10.0 ml aliquots  of the working mercury solution
          containing 0 to 1.0 ug of mercury to a series of 300 ml BOD bottles. Add enough distilled
          water to each bottle to make a total volume of 100 ml. Mix thoroughly and add 5 ml of
          cone, sulfuric acid (6.1) and 2.5 ml of cone, nitric acid (6.2) to each bottle. Add 15 ml of
          KMnO4 (6.5) solution to each bottle and allow to stand at least 15 minutes. Add 8 ml of
          potassium persulfate (6.6) to each bottle and heat for 2 hours in a water bath mainlined at
          95°C. Cool and add 6 ml of sodium chloride-hydroxylamine  sulfate solution (6.4) to
          reduce  the excess permanganate.  When the solution has been decolorized wait 30
          seconds, add 5 ml of the stannous sulfate solution (6.3) and immediately attach the bottle
          to the aeration apparatus forming a closed system. At this point the sample is allowed to
          stand quietly without manual agitation. The circulating pump, which has previously
          been adjusted to a rate of 1 liter per minute, is allowed to run continuously (See Note 4).
          The absorbance will increase and reach maximum within 30 seconds. As soon as the
          recorder pen levels off, approximately 1 minute, open the bypass valve and continue the
          aeration until the absorbance returns to its minimum value (see Note 5). Close the bypass
          valve, remove the stopper and frit from the BOD bottle and continue the aeration.
          Proceed with  the standards and construct a standard curve by plotting peak  height
          versus micrograms of mercury.
          NOTE 4: An open system where the mercury vapor is passed through the absorption cell
          only once may be used instead of the closed system.
          NOTE 5: Because of the toxic nature of mercury vapor precaution must be taken to avoid
          its inhalation. Therefore, a bypass has been included in the system to either vent the
          mercury vapor into an exhaust hood or pass the vapor through some absorbing media,
          such as:
                a)    equal volumes of 0.1 M KMnO4 and 10% H2SO4
                b)   0.25 % iodine in a 3 % KI solution
          A specially treated  charcoal that  will adsorb mercury vapor is also available from
          Barnebey and Cheney, E. 8th Ave. and N. Cassidy St., Columbus, Ohio 43219,
          Cat. #580-13 or #580-22.
8.    Procedure
     8.1  Transfer 100 ml,  or an aliquot diluted to 100 ml, containing not more than 1.0 ug of
          mercury, to a  300 ml BOD bottle. Add 5 ml of sulfuric acid (6.1) and 2.5 ml of cone.
          nitric acid (6.2) mixing after each addition. Add 15 ml of potassium permanganate
          solution (6.5) to each sample bottle. For sewage samples additional permanganate may
          be required. Shake and add additional portions of potassium permanganate solution, if
          necessary, until the purple color persists for at least 15 minutes. Add 8 ml of potassium
          persulfate (6.6) to each bottle and heat for 2 hours in a water bath at 95°C. Cool and add 6
                                         245.1-4

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                                     MERCURY

                Method  245.2  (Automated Cold Vapor Technique)

                                                         STORET NO.  Total  71900
                                                                      Dissolved  71890
                                                                     Suspended  71895

1.    Scope and Application
     1.1  This method is applicable to surface waters. It may be applicable to saline  waters,
          wastewaters, effluents, and domestic sewages providing potential interferences  are not
          present (See Interference 4).
     1.2  The working range is 0.2 to 20.0 ug Hg/1.
2.    Summary of Method
     2.1  The flameless AA procedure is a physical method based on the absorption of radiation at
          253.7 nm by mercury vapor. The mercury is reduced to the elemental state and  aerated
          from solution. The mercury vapor passes through a cell positioned in the light path of an
          atomic absorption spectrophotometer. Absorbance (peak height)  is measured as a
          function of mercury concentration and recorded in the usual manner.
     2.2  In addition to inorganic forms of mercury, organic mercurials may also be present. These
          organo-mercury  compounds will not respond  to the  flameless atomic absorption
          technique unless they are first broken down and converted to mercuric ions. Potassium
          permanganate oxidizes many of these compounds but recent studies have shown that a
          number of organic mercurials, including phenyl mercuric acetate and methyl mercuric
          chloride, are only partially oxidized by this reagent. Potassium persulfate has been found
          to give approximately 100% recovery when used as the oxidant with these compounds.
          Therefore, an automated persulfate oxidation step following the automated addition of
          the  permanganate has  been  included to insure that organo-mercury  compounds, if
          present, will be oxidized to the mercuric ion before measurement.
3.    Sample Handling and Preservation
     3.1  Until more conclusive data are obtained, samples should be preserved by acidification
          with nitric  acid to a pH of 2 or lower immediately at the time of collection."'  If only
          dissolved mercury is to be determined, the sample should be filtered before the acid is
          added. For total mercury the filtration is omitted.
4.    Interference (See NOTE 1)
     4.1  Some sea waters and waste-waters high in chlorides have shown a positive interference,
          probably due to the formation of free chlorine.
     4.2  Interference from certain volatile organic materials which will absorb at this wavelength
          is also possible. A preliminary run under oxidizing conditions, without stannous  sulfate,
          would determine if this type of interference is present.


Approved for NPDES and SDWA
Issued  1974

                                         245.2-1

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     4.3  Formation of a heavy precipitate, in some wastewaters and effluents, has been reported
          upon addition of concentrated sulfuric acid. If this is encountered, the problem sample
          cannot be analyzed by this method.
     4.4  Samples containing solids must be blended and then mixed while being sampled if total
          mercury vlaues are to be reported.
          NOTE  1: All the above interferences can be overcome by use of the Manual Mercury
          method in this manual.
5.    Apparatus
     5.1  Technicon Auto Analyzer consisting of:
          5.1.1 Sampler II with provision for sample mixing.
          5.1.2 Manifold.
          5.1.3 Proportioning Pump II or III.
          5.1.4 High  temperature heating  bath with  two distillation coils  (Technicon Part
                #116-0163) in series.
     5.2  Vapor-liquid separator (Figure 1).
     5.3  Absorption cell, 100 mm long, 10 mm diameter with quartz windows.
     5.4  Atomic Absorption Spectrophotometer (See Note 2): Any atomic absorption unit having
          an open sample presentation area in which to  mount the absorption cell is suitable.
          Instrument settings recommended by the particular manufacturer should be followed.
          NOTE  2: Instruments designed specifically for the measurement of mercury using the
          cold vapor technique are commercially available and may be substituted  for the atomic
          absorption Spectrophotometer.
     5.5  Mercury Hollow Cathode Lamp: Westinghouse  WL-22847, argon filled, or equivalent.
     5.6  Recorder: Any multi-range variable  speed recorder that is compatible with the UV
          detection system is suitable.
     5.7  Source of cooling water for jacketed mixing coil and connector A-7.
     5.8  Heat lamp: A small reading lamp with 60W bulb  may be used to prevent condensation of
          moisture  inside the cell: The  lamp  is positioned  to  shine  on the absorption cell
          maintaining the air temperature in the cell about 10°C above ambient.
6.    Reagents
     6.1  Sulfuric Acid, Cone:  Reagent grade
          6.1.1 Sulfuric acid, 2 N: Dilute 56 ml of cone, sulfuric acid to 1  liter with distilled water.
          6.1.2 Sulfuric acid, 10%: Dilute 100 ml cone, sulfuric acid to 1  liter with distilled water.
     6.2  Nitric acid, Cone: Reagent grade of low mercury content.
          6.2.1 Nitric Acid, 0.5% Wash Solution: Dilute 5 ml of cone, nitric acid to 1 liter with
                distilled water.
     6.3  Stannous Sulfate: Add 50 g stannous sulfate to 500 ml of 2 N sulfuric acid (6.1.1). This
          mixture is a suspension and should be stirred continuously during use.

          NOTE 3: Stannous chloride may be used in place of stannous sulfate.

     6.4  Sodium Chloride-Hydroxylamine  Sulfate  Solution:  Dissolve  30 g of sodium chloride
          and 30 g of hydroxylamine sulfate in distilled water to 1 liter.
                                         245.2-2

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           ml of sodium chloride-hydroxylamine sulfate (6.4) to reduce the excess permanganate.
           After a delay of at least 30 seconds add 5 ml of stannous sulfate (6.3) and immediately
           attach the bottle to the aeration apparatus. Continue as described under Calibration.
9.   Calculation
     9.1   Determine the peak height of the unknown from the chart and read the mercury value
           from the standard curve.
     9.2   Calculate the mercury concentration in the sample by the formula:
           ugHg/l =
            66
                      V aliquot  I  \ volume of aliquot in ml
)
     9.3   Report mercury concentrations as follows: Below 0.2 ug/1, <0.2; between  1 and 10
           ug/1, one decimal; above 10 ug/1, whole numbers.
10.  Precision and Accuracy
     10.1  In a single laboratory (EMSL),  using an Ohio River  composite  sample with  a
           background mercury concentration of 0.35 ug/1, spiked with concentrations of 1.0, 3.0
           and 4.0 ug/1,  the  standard deviations were  ±0.14,  ±0.10 and  ±0.08, respectively.
           Standard deviation at the 0.35 level was ±0.16. Percent recoveries at the three levels
           were 89, 87, and 87%, respectively.
     10.2  In a joint EPA/ASTM interlaboratory study of the  cold vapor technique  for total
           mercury in water, increments of organic and inorganic mercury were added to natural
           waters. Recoveries were determined by difference. A statistical summary of this study
           follows:
                                                          Standard
Number        True Values          Mean Value            Deviation           Accuracy as
of Labs           ug/liter              ug/liter               ug/liter               % Bias

  76               0.21                 0.349                0.276               66
  80               0.27                 0.414                0.279               53
  82               0.51                 0.674                0.541               32
  77               0.60                 0.709                0.390               18
  82               3.4                  3.41                 1.49                 0.34
  79               4.1                  3.81                 1.12                -7.1
  79               8.8                  8.77                 3.69                -0.4
  78               9.6                  9.10                 3.57                -5.2
11.   Appendix
     11.1 While the possibility of absorption from certain organic substances actually being present
          in the sample does exist, EMSL has not encountered such samples. This is mentioned
          only to caution the analyst of the possibility. A simple correction that may be used is as
          follows: If an interference has been found to be present (4.4), the sample should  be
          analyzed both by using the regular procedure and again under oxidizing conditions only,
                                         245.1-5

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          that is without the reducing reagents. The true mercury value can then be obtained by
          subtracting the two values.
     11.2 If additional sensitivity is required, a 200 ml sample with recorder expansion may be used
          provided the instrument does not produce undue noise. Using a Coleman MAS-50 with a
          drying tube of magnesium perchlorate and a variable recorder, 2 mv was set to read full
          scale. With these  conditions,  and distilled water solutions  of mercuric  chloride at
          concentrations of  0.15,  0.10,  0.05  and  0.025  ug/1  the  standard   deviations
          were +0.027,  ±0.006, ±0.01 and ±0.004. Percent recoveries at these levels were 107,
          83, 84 and 96%, respectively.
     11.3 Directions for the disposal of mercury-containing wastes are given in ASTM Standards,
          Part 31, "Water", p 349, Method D3223 (1976).

                                       Bibliography

1.    Kopp,  J. F., Longbottom, M. C. and Lobring, L.  B., "Cold Vapor Method for Determining
     Mercury", AWWA, vol 64, p. 20, Jan., 1972.
2.    Annual Book of ASTM Standards, Part 31, "Water", Standard D3223-73, p 343 (1976).
3.    Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 156 (1975).
                                         245.1-6

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           NOTE 4: Hydroxylamine hydrochloride may be used in place of hydroxylamine sulfate.

     6.5   Potassium Permanganate: 0.5% solution, w/v. Dissolve 5 g of potassium permanganate
           in 1 liter of distilled water.
     6.6   Potassium Permanganate, 0.1 N: Dissolve 3.16 g of potassium permanganate in distilled
           water and dilute to 1 liter.
     6.7   Potassium Persulfate: 0.5% solution, w/v. Dissolve 5 g potassium persulfate in 1 liter of
           distilled water.
     6.8   Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 ml of distilled
           water. Add  10 ml of cone, nitric acid and adjust the volume to 100.0 ml. 1.0 ml =  1.0
           mgHg.
     6.9   Working  Mercury Solution: Make successive dilutions of the stock mercury solution
           (6.8) to obtain a working standard containing 0.1 ug per ml. This working standard and
           the dilutions of the stock mercury solution should be prepared fresh daily. Acidity of the
           working standard should be maintained at 0.15% nitric acid. This acid should be added
           to  the flask as needed before the addition of the  aliquot.  From this solution prepare
           standards containing 0.2,0.5, 1.0,2.0, 5.0, 10.0,15.0 and 20.0 ug Hg/1.
     6.10  Air Scrubber Solution: Mix equal volumes of 0.1 N potassium permanganate (6.6) and
           10% sulfuric acid (6.1.2).
7,    Procedure
     7.1   Set up manifold as shown in Figure 2.
     7.2   Feeding all the reagents through the system with acid wash solution (6.2.1) through the
           sample line,  adjust heating bath to 105°C.
     7.3   Turn  on  atomic  absorption  spectrophotometer,  adjust  instrument  settings   as
           recommended by the manufacturer, align absorption cell  in light path for maximum
           transmittance and place heat lamp directly over absorption cell.
     7.4   Arrange working mercury standards from 0.2 to  20.0 ug Hg/1 in sampler and start
           sampling. Complete loading of sample tray with unknown samples.
     7.5   Prepare  standard curve by plotting  peak height of  processed standards  against
           concentration  values.  Determine concentration of samples by comparing sample peak
           height with standard curve.
           NOTE 5: Because of the toxic nature of mercury  vapor, precaution must be taken to
           avoid its inhalation. Venting the mercury vapor into an exhaust hood or passing the
           vapor through some absorbing media such as:
           a)    equal volumes of 0.1 N KMnO4 (6.6) and 10% H2SO4 (6.1.2).
           b)    0.25% iodine in a 3% KI solution, is recommended.
           A  specially  treated charcoal that will adsorb mercury vapor is  also available from
           Barnebey and Cheney, E. 8th Ave. and North Cassidy St., Columbus, Ohio 43219,
           Cat. #580-13 or #580-22.
     7.6   After the analysis is complete put all lines except the H2SO4 line in distilled water to wash
           out system.  After flushing, wash out the H2SO4 line. Also flush the coils in the high
           temperature heating bath by pumping stannous sulfate (6.3) through the sample lines
           followed by distilled water. This will prevent build-up of oxides of manganese.
                                         245.2-3

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8.    Precision and Accuracy
     8.1  In a single laboratory (SEWL), using distilled water standards at concentrations of 0.5,
          1.0,   2.0,   5.0,   10.0   and   20.0   ug   Hg/1,   the   standard   deviations
          were  ±0.04, ±0.07,  ±0.09, ±0.20, ±0.40 and ±0.84 ug/1, respectively.
     8.2  In a single laboratory (SEWL), using surface water samples spiked with ten organic
          mercurials at the 10 ug/1 level, recoveries ranged from 87 to 117%. Recoveries of the
          same ten organic mercurials in distilled water at the 10 ug/1 level, ranged from 92% to
          125%.

                                      Bibliography

1.    Wallace, R. A., Fulkerson, W., Shults, W. D., and Lyon, W. S., "Mercury in the Environment-
     The Human Element", Oak Ridge National Laboratory, ORNL-NSF-EP-1, p 31, (January,
     1971).
2.    Hatch, W. R. and Ott, W. L., "Determination of Sub-Microgram Quantities of Mercury by
     Atomic Absorption Spectrophotometry", Anal. Chem. 40, 2085 (1968).
3.    Brandenberger, H. and Bader, H., "The Determination  of Nanogram Levels of Mercury in
     Solution  by  a Flameless Atomic Absorption Technique", Atomic Absorption Newsletter 6^
     101 (1967).
4.    Brandenberger,  H. and Bader, H., "The Determination of Mercury by Flameless Atomic
     Absorption II, A Static Vapor Method", Atomic Absorption Newsletter 7^53 (1968).
5.    Goulden, P. D. and Afghan, B. K., "An Automated Method for Determining Mercury in
     Water", Technicon, Adv. in Auto. Anal. 2, p 317 (1970).
                                         245.2-4

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                            MERCURY IN  SEDIMENT

                  Method  245.5 (Manual  Cold Vapor  Technique)

1.   Scope and Application
     1.1   This  procedure'0 measures total mercury (organic  f inorganic) in soils, sediments,
           bottom deposits and sludge type materials.
     1.2   The range of the method is 0.2 to 5 ug/g. The range may be extended above or below the
           normal range by  increasing or decreasing sample  size or  through instrument and
           recorder control.
2.   Summary of Method
     2.1   A weighed portion of the sample is digested in aqua regia for 2 minutes at 95°C, followed
           by oxidation with potassium permanganate. Mercury in the digested sample is then
           measured by the conventional cold vapor technique.
     2.2   An alternate digestion'2' involving the use of an autoclave is described in (8.2).
3.   Sample Handling and Preservation
     3.1   Because of the extreme sensitivity of the analytical procedure and the omnipresence of
           mercury, care must be taken to avoid  extraneous contamination. Sampling devices and
           sample containers should be ascertained to be free of mercury; the sample should not be
           exposed to any condition in the laboratory that may result in contact or air-borne
           mercury contamination.
     3.2   While the sample may  be  analyzed  without drying, it has been found to be more
           convenient to analyze a dry sample. Moisture may be driven off in a drying oven at a
           temperature of 60°C. No mercury losses have been observed by using this drying step.
           The dry sample should be pulverized and thoroughly mixed  before the aliquot is
           weighed.
4.    Interferences
     4.1   The same types of interferences that may occur in water samples are also possible with
           sediments, i.e., sulfides, high copper, high chlorides, etc.
     4.2   Volatile materials which absorb at 253.7 nm will cause a positive interference. In order to
           remove any interfering volatile materials, the dead air space in the BOD bottle should be
           purged before the addition of stannous  sulfate.
5.    Apparatus
     5.1   Atomic Absorption Spectrophotometer (See Note  1):   Any atomic absorption  unit
           having an open sample presentation  area in which to irfount the absorption cell is
           suitable. Instrument settings recommended by the particular manufacturer should be
           followed.
           NOTE 1: Instruments designed specifically for the measurement of mercury using the
           cold vapor technique are commercially available and may be substituted for the atomic
           absorption Spectrophotometer.
Issued 1974

                                         245.5-1

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     5.2  Mercury Hollow Cathode Lamp: Westinghouse WL-22847, argon filled, or equivalent.
     5.3  Recorder: Any multi-range variable speed recorder that is compatible  with the UV
          detection system is suitable.
     5.4  Absorption  Cell:  Standard spectrophotometer cells 10 cm long, having  quartz end
          windows may be used. Suitable cells may be constructed from plexiglass tubing, 1" O.D.
          X 4-1/2". The ends are ground perpendicular to the longitudinal axis  and quartz
          windows (1" diameter X 1/16" thickness) are cemented in place. Gas inlet and outlet
          ports (also of plexiglass but 1/4" O.D.) are attached approximately 1/2" from each end.
          The cell is strapped to a burner for support and aligned in the light beam to give the
          maximum transmittance.
          NOTE 2: Two 2" X 2" cards with one inch diameter holes may be placed over each end
          of the cell to assist in positioning the cell for maximum transmittance.
     5.5  Air Pump: Any peristaltic pump capable of delivering 1 liter of air per minute may be
          used. A Masterflex pump with electronic speed control has been found to be satisfactory.
          (Regulated compressed air can be used in an open one-pass system.)
     5.6  Flowmeter: Capable of measuring an air flow of 1 liter per minute.
     5.7  Aeration Tubing: Tygon tubing is used for passage of the mercury vapor from the sample
          bottle to the absorption cell and return. Straight glass tubing terminating in  a coarse
          porous frit is used for sparging air into the sample.
     5.8  Drying Tube: 6" X 3/4" diameter tube containing 20 g of magnesium  perchlorate (See
          Note 3). The apparatus is assembled as shown in the accompanying diagram.
          NOTE 3: In place of the magnesium perchlorate drying tube, a small reading lamp with
          60W bulb may be used to prevent condensation of moisture inside the cell. The lamp is
          positioned to shine on the absorption  cell maintaining the air temperature in the cell
          about 10°C above ambient.
6.    Reagents
     6.1  Aqua Regia: Prepare immediately before use by carefully adding three volumes of cone.
          HC1 to one volume of cone. HNO3.
     6.2  Sulfuric Acid, 0.5 N: Dilute 14.0 ml of cone, sulfuric acid to 1 liter.
     6.3  Stannous Sulfate: Add 25 g stannous sulfate to 250 ml of 0.5 N sulfuric acid (6.2). This
          mixture is a suspension and should be stirred continuously during use.
     6.4  Sodium Chloride-Hydroxylamine Sulfate  Solution:   Dissolve 12 g of  sodium chloride
          and 12 g of hydroxylamine sulfate in distilled water and dilute to 100 ml.
          NOTE  4: A 10%  solution of stannous chloride  may be substituted  for (6.3) and
          hydroxylamine hydrochloride may be used in place of hydroxylamine sulfate in (6.4).
     6.5  Potassium Permanganate: 5% solution, w/v. Dissolve 5 g of potassium permanganate in
          100 ml of distilled water.
     6.6  Stock Mercury Solution: Dissolve 0.1354 g of mercuric chloride in 75 ml of distilled
          water. Add  10 ml of cone, nitric acid and  adjust the volume to 100.0 ml. 1.0 ml =  1.0
          mgHg.
     6.7  Working  Mercury Solution: Make successive dilutions of the stock mercury solution
          (6.6) to obtain a working standard containing 0.1 ug/ml. This working standard and the
          dilution of the  stock mercury solutions should be prepared fresh daily. Acidity of the
                                         245.5-2

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                                     AIR
                                     OUT
AIR AND
SOLUTION
IN
W 7/25 T




J   0.7 cm ID
             0.4cm ID
l4cm
                                        SOLUTION
                                         OUT
     FIGURE 1. VAPOR LIQUID SEPARATOR
                       245.2-5

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245.2-6

-------
           working standard should be maintained at 0.15% nitric acid. This acid should be added
           to the flask as needed before the addition of the aliquot.
7.    Calibration
     7.1   Transfer 0, 0.5,  1.0, 2.0, 5.0 and 10 ml aliquots of the working mercury solution (6.7)
           containing 0 to 1.0 ug of mercury to a series of 300 ml BOD bottles. Add enough distilled
           water to each bottle to make a total volume of 10 ml.  Add 5 ml of aqua regia (6.1) and
           heat 2 minutes in a water bath at 95°C. Allow the sample to cool and add 50 ml distilled
           water and 15 ml of KMnO4 solution (6.5) to each bottle and return to the water bath for
           30 minutes. Cool and add 6 ml of sodium chloride-hydroxylamine sulfate solution (6.4)
           to reduce the excess permanganate. Add 50 ml  of distilled water. Treating each bottle
           individually, add 5 ml of stannous sulfate solution (6.3) and immediately attach  the
           bottle to the aeration apparatus. At this point,  the sample is allowed to stand  quietly
           without manual agitation. The circulating pump, which has previously been adjusted to
           rate of 1 liter per minute, is allowed to run continuously. The absorbance,  as exhibited
           either on the  spectrophotometer or the  recorder, will increase and reach maximum
           within 30 seconds. As soon as the recorder pen levels off, approximately 1 minute, open
           the bypass value and continue the aeration until  the absorbance returns to its minimum
           value (See Note 5). Close the bypass value, remove the fritted tubing from the BOD
           bottle and continue the aeration. Proceed with the standards and construct a standard
           curve by plotting peak height versus micrograms of mercury.
           NOTE 5: Because of the toxic nature of mercury vapor  precaution must be taken to avoid
           its inhalation.  Therefore, a bypass has been included in the  system to either vent  the
           mercury vapor into an exhaust hood or pass the vapor through some absorbing  media,
           such as:
           a)    equal volumes of 0.1 N KMnO4 and 10% H2SO4
           b)    0.25% iodine in a 3% KI solution.
           A specially treated charcoal that  will absorb mercury vapor is also available from
           Barnebey and Cheney, E. 8th Ave., and North Cassidy  St., Columbus, Ohio 43219,
           Cat. #580-13 or #580-22.
8.    Procedure
     8.1   Weigh triplicate 0.2 g portions of dry sample and place  in bottom of a BOD bottle. Add 5
           ml of distilled water and 5 ml of aqua regia (6.1).  Heat  2 minutes in a water bath at 95°C.
           Cool, add 50 ml distilled water and 15 ml potassium permanganate solution (6.5) to each
           sample bottle.  Mix thoroughly and place in the water bath for 30 minutes at 95°C. Cool
           and add 6 ml of sodium chloride-hydroxylamine sulfate (6.4) to reduce the  excess
           permanganate. Add 55 ml of distilled water. Treating each bottle individually, add 5 ml
           of stannous sulfate (6.3) and immediately attach the  bottle to the aeration apparatus.
           Continue as described under (7.1).
     8.2   An alternate digestion procedure employing an autoclave may also be used. In this
           method 5 ml of cone. H2SO4 and 2 ml of cone. HNO3 are added to  the 0.2 g  of sample. 5
           ml of saturated KMnO4 solution is added and the bottle  covered  with a piece  of
           aluminum foil. The samples are autoclaved at 121°C and 15 Ibs. for 15 minutes. Cool,
           make up to a volume of 100 ml with distilled water and add 6 ml of sodium chloride-
                                         245.5-3

-------
          hydroxylamine sulfate solution (6.4) to reduce the excess permanganate. Purge the dead
          air space and continue as described under (7.1).

9.    Calculation
     9.1  Measure the peak height of the unknown from the chart and read the mercury value from
          the standard curve.
     9.2  Calculate the mercury concentration in the sample by the formula:

                .  _  ug Hg in the aliquot
          tfgHg/g - wt Qf t^e ajjquot [n gms


     9.3  Report mercury concentrations as follows: Below 0.1 ug/gm, <0.1; between 0.1 and 1
          ug/gm,  to the nearest 0.01 ug; between 1  and 10 ug/gm, to nearest 0.1 ug; above 10
          ug/gm, to nearest ug.
10.   Precision and Accuracy
     10.1 The following standard deviations on replicate sediment samples were recorded at the
          indicated levels; 0.29 ug/g ±0.02 and 0.82 ug/g  ±0.03. Recovery  of mercury at these
          levels, added as methyl mercuric chloride, was 97% and 94%, respectively.

                                      Bibliography

1.    Bishop, J. N., "Mercury in Sediments", Ontario Water Resources Comm., Toronto, Ontario,
     Canada, 1971.
2.    Salma, M., private communication, EPA Cal/Nev Basin Office, Almeda, California.
                                        245.5-4

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                                       NICKEL
               Method 249.1 (Atomic Absorption, direct  aspiration)

                                                         STORET  NO. Total 01067
                                                                      Dissolved 01065
                                                                     Suspended 01066

Optimum Concentration Range:   0.3-5 mg/1 using a wavelength of 232.0 nm
Sensitivity:      0.15 mg/1
Detection Limit:      0.04 mg/1

Preparation of Standard Solution
      1.    Stock Solution: Dissolve 4.953 g of nickel nitrate, Ni(NO3)2»6H2O (analytical reagent
           grade) in deionized distilled water. Add 10 ml of cone, nitric acid and dilute to 1 liter
           with deionized distilled water. 1 ml = 1 mg Ni (1000 mg/1).
      2.    Prepare dilutions of the stock nickel solution to be used as calibration standards at the
           time of analysis. The calibration standards should be prepared using the same type of
           acid and at the same concentration as will result in the sample to be analyzed either
           directly or after processing.

Sample Preservation
      1.    For  sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.    The procedures for preparation of the sample as given in parts 4.1.1 thru 4.1.4 of the
           Atomic Absorption Methods section of this manual have been found to be satisfactory.

Instrumental Parameters (General)
      1.    Nickel hollow cathode lamp
      2.    Wavelength: 232.0 nm
      3,    Fuel: Acetylene
      4.    Oxidant: Air
      5.   Type of Flame: Oxidizing

Analysis Procedure
      1.    For analysis procedure and calculation, see "Direct Aspiration", part 9.1 of the Atomic
           Absorption Methods section of this manual.
Approved for  NPDES
Issued  1974
Editorial revision 1978

                                        249.1-1

-------
Interferences
      1.    The 352.4 nm wavelength is less susceptible to spectral interference and may be used.
           The calibration curve is more linear at this wavelength; however, there is some loss of
           sensitivity.

Notes
      1.    For levels of nickel below 100 ug/1, either the Special Extraction Procedure, given in
           part 9.2 of the Atomic Absorption Methods section or the furnace technique, Method
           249.2, is recommended.
      2.    Data to be entered into STORET must be reported as ug/1.
      3.    The heptoxime method may also be used (Standard Methods, 14th Edition, p 232).

Precision and Accuracy
      1.    In a single laboratory (EMSL), using a mixed  industrial-domestic waste effluent at
           concentrations of 0.20,1.0and5.0mgNi/l, the standard deviations were ±0.011, ±0.02
           and ±0.04,  respectively. Recoveries  at these levels were 100%, 97%  and 93%,
           respectively.
                                          249.1-2

-------
                                      NICKEL
              Method 249.2 (Atomic  Absorption,  furnace technique)

                                                        STORET  NO. Total 01067
                                                                     Dissolved 01065
                                                                    Suspended 01066

Optimum Concentration Range:   5-100 ug/1
Detection Limit:       1 ug/1

Preparation of Standard Solution
      1.     Stock solution: Prepare as described under "direct aspiration method".
      2.     Prepare dilutions of the stock solution to be used as calibration standards at the time of
           analysis. These solutions are also to used for "standard additions".
      3.     The calibration standard should be diluted to contain 0.5% (v/v) HNO3.

Sample Preservation
      1.     For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.     Prepare as described under "direct aspiration method".  Sample solutions for analysis
           should contain 0.5% (v/v) HNO3.

Instrument Parameters (General)
      1.     Drying Time and Temp: 30 sec-125°C.
      2.     Ashing Time and Temp: 30 sec-900°C.
      3.     Atomizing Time and Temp: 10 sec-2700°C.
      4.     Purge Gas Atmosphere: Argon
      5.     Wavelength: 232.0 nm
      6.     Other operating parameters should be set as specified  by the particular instrument
           manufacturer.

Analysis Procedure
      1.     For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
           Atomic Absorption Methods section of this manual.

Notes
      1.     The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
           2100,  based on the use of a 20 ul injection, continuous flow purge gas and pyrolytic
Approved for NPDES
Issued  1978

                                        249.2-1

-------
           graphite. Smaller size furnace devices or those employing faster rates of atomization can
           be operated using lower atomization temperatures for shorter time periods than the
           above recommended settings.
     2.    The use of background correction is recommended.
     3.    Nitrogen may also be used as the purge gas.
     4.    For every sample matrix analyzed, verification is necessary to determine that method of
           standard addition is not required (see part 5.2.1 of the Atomic Absorption Methods
           section of this manual).
     5.    If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods section of this manual.
     6.    Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy
     1.    Precision and accuracy data are not available at this time.
                                         249.2-2

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                                     SELENIUM

              Method 270.2 (Atomic Absorption,  furnace  technique)

                                                         STORET  NO.  Total 01147
                                                                      Dissolved 01145
                                                                     Suspended 01146

Optimum Concentration Range:   5-100 ug/1
Detection Limit:      2 ug/1

Preparation of Standard Solution
      1.    Stock Selenium Solution: Dissolve 0.3453 g of selenous acid (actual assay 94.6% H2SeO3)
           in deionized distilled water and make up to 200 ml. 1 ml  =  1 mg Se (1000 mg/1).
      2.    Nickel Nitrate Solution, 5%: Dissolve 24.780 g of ACS reagent grade Ni(NO3)2»6H2O in
           deionized distilled water and make up to 100 ml.
      3.    Nickel Nitrate Solution, 1%: Dilute 20  ml  of the 5% nickel nitrate to  100 ml with
           deionized distilled water.
      4.    Working Selenium Solution: Prepare dilutions of the stock solution to be used as
           calibration standards at the time of analysis. Withdraw appropriate aliquots of the stock
           solution, add 1 ml of cone. HNO3, 2 ml of 30% H2O2 and 2 ml of the 5% nickel nitrate
           solution. Dilute to 100 ml with deionized distilled water.

Sample Preservation
      1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.    Transfer 100 ml of well-mixed sample to a 250 ml Griffin beaker, add 2 ml of 30% H2O2
           and sufficient cone. HNO3 to result in an acid concentration of l%(v/v). Heat for 1 hour
           at 95°C or until the volume is slightly less than 50 ml.
      2.    Cool and bring back to 50 ml with deionized distilled water.
      3.    Pipet 5 ml of this digested solution into a 10-ml volumetric flask, add 1 ml of the 1%
           nickel nitrate solution and dilute to 10 ml with deionized distilled water. The sample is
           now ready for injection into the furnace. NOTE: If solubilization or digestion  is not
           required adjust the HNO3 concentration of the sample to 1 % (v/v) and add 2 ml of 30%
           H2O2 and 2 ml of 5% nickel nitrate to  each  100 ml of sample. The volume of the
           calibration standard should be adjusted  with deionized distilled water to match the
           volume change of the sample.
Approved for NPDES  and SDWA
Issued  1978

                                         270.2-1

-------
Instrument Parameters
      1.    Drying time and temperature: 30 sec @ 125°C
      2.    Charring time and temperature: 30 sec © 1200°C
      3.    Atomizing time and temperature: 10 sec @ 2700°C
      4.    Purge Gas Atmosphere: Argon
      5.    Wavelength: 196.0 nm.
      6.    Other operating parameters should be set as  specified by  the particular instrument
           manufacturer.

Analysis Procedure
      1.    For the analysis procedure and the calculation see "Furnace  Procedure" part 9.3 of the
           Atomic Absorption Methods section of this manual.

Notes
      1.    The above concentration values and instrument conditions are for a Perkin-Elmer HG A-
           2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
           graphite. Smaller size furnace devices or those employing faster rates of atomization can
           be operated using lower atomization temperatures for shorter time periods than the
           above recommended settings.
      2.    The use of background correction is recommended.
      3.    Selenium analysis suffers interference from chlorides (> 800 mg/1) and sulfate (> 200
           mg/1). For the analysis of industrial effluents and samples with concentrations of sulfate
           from 200 to 2000 mg/1, both samples and standards should be prepared to contain 1%
           nickel.
     4.    For every sample matrix analyzed, verification is necessary to determine that method of
           standard addition is not required (see part 5.2.1 of the Atomic Absorption Methods
           section of this manual).
      5.    For quality control requirements and optional recommendations  for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
      6.    If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods section of this manual.
     7.    Data to entered into STORET must be reported as ug/1.

Precision and Accuracy
      1.    Using a sewage treatment  plant  effluent  containing <2  ug/1   and spiked  with  a
           concentration of 20 ug/1, a recovery of 99% was obtained.
     2.     Using a series of industrial waste effluents spiked at a 50 ug/1 level, recoveries ranged
           from 94 to 112%.
      3.    Using a 0.1% nickel nitrate solution as a synthetic matrix with selenium concentrations
           of 5, 10, 20, 40, 50, and 100 ug/1, relative standard deviations of 14.2, 11.6, 9.3, 7.2, 6.4
           and 4.1 %, respectively, were obtained at the 95% confidence level.
                                         270.2-2

-------
     4.   In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
          of  5,  10,  and 20  ug Se/1,  the  standard  deviations were ±0.6, ±0.4,  and ±0.5,
          respectively. Recoveries at these levels were 92%, 98%, and 100%, respectively.

Reference:
     "Determining Selenium in Water, Wastewater, Sediment and Sludge By Flameless Atomic
     Absorption Spectroscopy", Martin, T. D., Kopp, J.  F. and Ediger, R. D. Atomic Absorption
     Newsletter 14,109 (1975).
                                         270.2-3

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                                    SELENIUM

              Method  270.3 (Atomic Absorption, gaseous hydride)

                                                        STORE! NO.  Total  01147
                                                                    Dissolved  01145
                                                                   Suspended  01146

1.    Scope and Application
     1.1   The gaseous hydride method  determines  inorganic  selenium  when present in
          concentrations at or above 2 ug/1. The method is applicable to drinking water and most
          fresh and saline waters, in the  absence of high concentrations of chromium, cobalt,
          copper, mercury, molybdenum, nickel and silver.
2.    Summary of Method
     2.1   Selenium in the sample is reduced from the + 6 oxidation state to the + 4 oxidation state
          by the addition of SnCl2. Zinc is  added to the acidified sample, producing hydrogen and
          converting the selenium to the hydride, SeH2. The gaseous selenium hydride is swept into
          an  argon-hydrogen flame of an atomic absorption spectrophotometer.  The working
          range of the method is 2-20 ug/1 using the 196.0 nm wavelength.
3.    Comments
     3.1   In analyzing drinking water and most surface and ground waters, interferences are rarely
          encountered. Industrial waste samples should be spiked with a  known  amount of
          selenium to establish adequate recovery.
     3.2   Organic forms of selenium must be converted to an inorganic form and organic matter
          must be oxidized before beginning the analysis. The oxidation procedure given in method
          206.5 (Standard Methods, Uth Ed. 404B, p 285, Procedure 4.1) should be used.
     3.3   For sample handling and preservation,  see part 4.1 of the Atomic Absorption Methods
          section of this manual.
     3.4   For quality control requirements and  optional recommendations for  use in drinking
          water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     3.5   Data to be entered into STORET must be reported as ug/1.
4.    Precision and Accuracy
     4.1   Ten replicate solutions of selenium oxide at the 5, 10 and 15 ug/1 level were analyzed by
          a single laboratory. Standard deviations at these levels were  ±0.6, ±1.1 and ±2.9 with
          recoveries of 100, 100 and 101%. (Caldwell, J. S., Lishka, R.  J., and McFarren, E. F.,
          "Evaluation of a Low-Cost Arsenic and Selenium Determination at Microgram per Liter
          Levels", JAWWA, vol 65, p. 731, Nov. 1973.)
Approved for NPDES and SDWA
Issued 1974
                                        270.3-1

-------
5.    References
     5.1  Except for the perchloric acid step, the procedure to be used for this determination is
          found in:
          Standard Methods for the Examination of Water and Wastewater, 14th Edition, p 159,
          Method 301A(VII), (1975)
                                         270.3-2

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                                      SILVER

              Method 272.2  (Atomic Absorption, furnace  technique)

                                                        STORET NO. Total 01077
                                                                     Dissolved 01075
                                                                    Suspended 01076

Optimum Concentration Range:    1-25 ug/1
Detection Limit:      0.2 ug/1

Preparation of Standard Solution
     1.    Stock Solution: Prepare as described under "direct aspiration method".
     2.    Prepare dilutions of the stock solution to be used as calibration standards at the time of
          analysis. These solutions are also to be used for "standard additions".
     3.    The calibration standard should be diluted to contain 0.5% (v/v) HNO3.

Sample Preservation
     1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
          section of this manual.

Sample Preparation
     1.    Prepare as described under "direct aspiration method". Sample solutions for analysis
          should contain 0.5% (v/v) HNO3.

Instrument Parameters (General)
     1.    Drying Time and Temp: 30 sec-125°C.
     2.    Ashing Time and Tem p: 30 sec-400°C.
     3.    Atomizing Time and Temp: 10 sec-2700°C.
     4.    Purge Gas Atmosphere: Argon
     5.    Wavelength: 328.1 nm
     6.    Other  operating  parameters should be set as specified by the particular instrument
          manufacturer.

Analysis Procedure
     1.    For the analysis procedure and the calculation, see "Furnace Procedure" part 9.3 of the
          Atomic Absorption Methods section of this manual.
Approved for NPDES and SDWA
Issued 1978
                                        272.2-1

-------
Notes
     1.     The above concentration values and instrument conditions are for a Perkin-Elmer HGA-
           2100, based on the use of a 20 ul injection, continuous flow purge gas and non-pyrolytic
           graphite. Smaller size furnace devices or those employing faster rates of atomization can
           be operated using lower atomization temperatures for shorter  time periods than the
           above recommended settings.
     2.     Background correction may be required if the sample contains high dissolved solids.
     3.     The use of halide acids should be avoided.
     4.     If adsorption to container walls or formation of AgCl is suspected, see NOTE 3 under the
           Direct Aspiration Method 272.1.
     5.     For every sample matrix analyzed,  verification is necessary to determine that method of
           standard addition is not required  (see part  5.2.1 of the Atomic Absorption Methods
           section of this manual).
     6.     For quality control  requirements and optional  recommendations for use in drinking
           water analyses, see part 10 of the Atomic Absorption Methods section of this manual.
     7.     If method of standard addition is required, follow the procedure given earlier in part 8.5
           of the Atomic Absorption Methods  section of this manual.
     8.     Data to be entered into STORET must be reported as ug/1.

Precision and Accuracy:
     1.     In a single laboratory (EMSL), using Cincinnati, Ohio tap water spiked at concentrations
           of  25,  50, and  75  ug  Ag/1, the standard deviations were  tO.4,  iO.7,  and  +0.9,
           respectively. Recoveries at these levels were 94%, 100% and 104%, respectively.
                                         272.2-2

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                                       SILVER

               Method 272.1 (Atomic  Absorption,  direct aspiration)

                                                         STORET NO.  Total  01077
                                                                      Dissolved  01075
                                                                     Suspended  01076

Optimum Concentration Range:   0.1-4 mg/1 using a wavelength of 328.1 nm
Sensitivity:      0.06 mg/1
Detection Limit:      0.01 nig/1

Preparation of Standard Solution
      1.    Stock Solution: Dissolve 1.575 g of AgNO3 (analytical  reagent grade) in  deionized
           distilled water, add 10 ml cone. HNO3 and make up to 1 liter. 1 ml  =  1 mg Ag (1000
           mg/1).
      2.    Prepare dilutions of the stock solution to be used as calibration standards at the time of
           analysis. The calibration standards should be prepared using nitric acid and at the same
           concentration  as  will result in the  sample to  be analyzed  either directly or after
           processing.
      3.    Iodine Solution, 1 N: Dissolve 20 grams of potassium iodide, KI (analytical  reagent
           grade) in  50 ml of deionized distilled water, add 12.7 grams of iodine, I2 (analytical
           reagent grade) and dilute to 100 ml. Store in a brown bottle.
      4.    Cyanogen Iodide (CNI) Solution: To 50 ml of deionized distilled water add 4.0 ml cone.
           NH4OH, 6.5 grams KCN, and 5.0 ml of 1.0 NI2 solution. Mix and dilute to 100 ml with
           deionized distilled water. Fresh solution should be prepared every two weeks.'0

Sample Preservation
      1.    For sample handling and preservation, see part 4.1 of the Atomic Absorption Methods
           section of this manual.

Sample Preparation
      1.    The procedures for preparation of the sample as given in parts 4.1.1 thru 4.1.3 of the
           Atomic Absorption Methods section of this manual have been found to be satisfactory;
           however, the residue must be taken up in dilute nitric acid rather than hydrochloric to
           prevent precipitation of AgCl.
Approved for  NPDES and SDWA
Issued 1971
Editorial revision 1974
Technical revision 1978
                                         272.1-1

-------
Instrumental Parameters (General)
     1.   Silver hollow cathode lamp
     2.   Wavelength: 328.1 nm
     3.   Fuel: Acetylene
     4.   Oxidant: Air
     5.   Type of flame: Oxidizing

Analysis Procedure
     1.   For the analysis-procedure and the calculation, see "Direct Aspiration", part 9.1 of the
          Atomic Absorption Methods section of this manual.

Notes
     1.   For levels of silver below 30 ug/1, either the Special Extraction Procedure, given in part
          9.2 of the Atomic Absorption Methods section or the furnace procedure, Method 272.2,
          is recommended.
     2.   Silver nitrate standards are light sensitive. Dilutions of the stock should be discarded
          after use as concentrations below 10 mg/1 are not stable over long periods of time.
     3.   If absorption to container walls or the formation of AgCl is suspected, make the sample
          basic using cone. NH4OH and add  1 ml of (CNI) solution per 100 ml of sample. Mix the
          sample and allow to stand for 1 hour before proceeding with the analysis.'"
     4.   The 338.2 nm wavelength may also be used. This has a relative sensitivity of 2.
     5.   Data to be entered into STORET must be reported as ug/1.
Precision and Accuracy
     1.   In a round-robin study reported by Standard Methods, a synthetic sample containing 50
          ug Ag/1 was analyzed by 50 laboratories with a reported standard deviation of ±8.8 and
          a relative error 10.6%.

References                                                                       *
     1.   "The Use of Cyanogen Iodide (CNI) as a Stabilizing Agent for Silver in Photographic
          Processing Effluent Sample", Owerbach,  Daniel, Photographic Technology Division,
          Eastman Kodak Company, Rochester, N.Y. 14650.
     2.   Standard Methods for Examination of Water and Wastewater, 14th Edition, p. 148,
          Method 301A.
                                         272.1-2

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                     APPENDIX III






METHODS FOR BENZIDINE,  CHLORINATED  ORGANIC  COMPOUNDS,




           PENTACHLOROPHENOL AND PESTICIDES




               IN WATER AND WASTEWATER

-------
METHODS FOR BENZIDINE, CHLORINATED ORGANIC COMPOUNDS,
           PENTACHLOROPHENOL AND PESTICIDES
               IN WATER AND WASTEWATER
                       INTERIM
                 Pending Issuance of
             Methods for Organic Analysis
                 of  Water and Wastes
         U.S. ENVIRONMENTAL PROTECTION AGENCY
   ENVIRONMENTAL MONITORING AND SUPPORT LABORATORY
               CINCINNATI, OHIO  42568
                    September 1978

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                                 FOREWORD
       This collection of methods for the determination of benzidine,
chlorinated organic compounds, pentachlorophenol and pesticides has been
assembled by the staff of the Environmental Monitoring and Support
Laboratory - Cincinnati (EMSL-Cinti.) for use by the NPDES Permits
Program.

       These methods are as referenced in the Federal Register of
December 1, 1976 and are being provided only for the interim period until
the manual "Methods for Organic Analysis of Water and Wastes" becomes
available.
                      Dwight G. Ballinger, Director
       Environmental Monitoring and Support Laboratory - Cincinnati

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                                  DISCLAIMER

    The mention of trade names or commercial products in this manual  is for
illustration purposes, and does not constitute endorsement or recommendatior
by the U. S. Environmental Protection Agency.
                                      111

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                               TABLE OF CONTENTS
                                                                 Page
Method for Benzidine and Its Salts in Water and Wastewater          1
Method for Chlorinated Hydrocarbons in Water and Wastewater         7
Method for Organophosphorus Pesticides in Water and Waste-
     water                                                        25
Method for Polychlorinated Biphenyls (PCBs) in Water and Waste-
     water                                                        43
Method for Triazine Pesticides in Water and Wastewater            83
Method for 0-aryl Carbamate Pesticides in Water and Wastewater    94
Method for N-aryl Carbamate and Urea Pesticides in Water and
     Wastewater                                                   104
Method for Chlorophenoxy Acid Pesticides in Water and Wastewater  115
Method for Volatile Chlorinated Organic Compounds in Water  and
     Wastewater                                                   130
Method for Pentachlorphenol in Water and Wastewater               140
Appendix  I                                                        141
Appendix  II                                                       146
Appendix  III                                                      149
Appendix  IV                                                       151
Bibliography                                                      154
                                      IV

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                                PAGE REFERENCES
F.R.#   Parameter
14
94

95
      Benzidine
                           EPA
                      This Manual

                            1
           14th ed.
         Std.  Methods
ASTM
(1975)
USGS*
Chlorinated organic
    compounds:
Benzylchloride            130
Carbon tetrachloride      130
Chlorobenzene             130
Chloroform                130
Epichlorohydrin           130
Heptachloro epoxide
Methylene chloride        130
PCB-1016                   43
PCB-1221                   43
PCB-1232                   43
PCB-1242                   43
PCB-1248                   43
PCB-1254                   43
PCB-1260                   43
1,1,2,2-Tetrachloroethane 130
Tetrachloroethylene       130
1,2,4-Trichlorobenzene    130
1,1,2-Trichloroethane     130
Pentachlorophenol

Pesticides
Aldrin
Ametryn
Aminocarb
Atraton
Atrazine
Azinphos methyl
Bar ban
BHC
Captan
Carbaryl
Carbophenothion
Chlordane
Chlorpropham
2,4-D
140
                                 7
                                83
                                94
                                83
                                83
                                25
                               104
                                 7
                                 7
                                94

                                 7
                               104
                               115
                                           555
                       529
         30
            555
529 •    30
            555
            555
            555
529
529
                               30
                               35
STORE!
NUMBER

39120
         32102
         34301
         32160

         39420
         34423
         34671
         39488
         39492
         39496
         39500
         39504
         39508

         34475
         39032


         39330



         39033
         39640
         39750

         39350

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F.R.#   Parameter
     EPA
This Manual
  14th ed.
Std. Methods
ASTM
(1975)
USGS*
STORET
NUMBER
     ODD
     DDE
     DDT
     Demeton-0
     Diazinon
     Dicamba
     Dichlorofenthion
     Dichloran
     Dicofol
     Dieldrin
     Dioxathion
     Disulfoton
     Diuron
     Endosulfan
     Edrin
     Ethion
     Fenuron
     Fenuron - TCA
     Heptachlor
     Isodrin
     Lindane
     Linuron
     Malath ion
     Methiocarb
     Methoxychlor
     Mexacarbate
     Mi rex
     Monuron
     Monuron-TCA
     Neburon
     Parathion methyl
     Parathion ethyl
     PCNB
     Perthane
     Prometon
     Prometryn
     Propazine
     Propham
     Proporur
     Secbumeton
     Siduron
     Si 1 vex
     Simazine
     Strobane
     Swep
     2,4,5-T
     Terbuthylazine
      7
      7
      7
     25
     25
    115
   555
   555
   555
529
529
529
     25
    104
      7
      7

    104
    104
      7

      7
    104
     25
     94
      7
     94
      7
    104
    104
    104
     25
     25
      7

     83
     83
     83
    104
     94
     83
    104
    115
     83
      7
    104
    115
     83
                555
   555
   555
   555

   555

   555

   555

   555
   555
   555
   555
   555
                           529
529
529
529

529



529
              529
529
30
30
30

30"

30
                                   30
                                   30
30
30
30
30
30

30

30
        30
                      35
                      35
39360
39365
39370
39560
39570
                               39780
39010
39650
39388
39390
39398
39410
39430
39782

39530

39489

39755
         39600
         39540
         39029
         39034
         39056
         39057
         39024
         39052
                 39760
                 39055
                                     vi

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F.R.I   Parameter               EPA       14th ed.    ASTM    USGS*     STORET
                           This Manual  Std. Methods  (1975)            NUMBER


     Toxaphene                   7         555        529     30        39400
     Trifluraline                7          —         —       —       39030

*Goerlitz, D. & Brown, E. "Methods for Analysis of Organic Substances  In
Water," U.S. Geological Survey Techniques of Water-Resources  Inv. Book  5,  Ch.
A3 (1972).
                                    vii

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            METHOD FOR BENZIDINE AND ITS SALTS IN WASTEWATERS

1.   Scope and App1i cat i on
    1.1  This method covers the determination for benzidine and  its salts
         in water and wastewaters.  The method can be modified to  apply
         also to the determination of closely related materials  as des-
         cribed under Interferences (4.2).
    1.2  The salts of benzidine, such as benzidine sulfate, are  measured
         and reported as benzidine, STORET NO. 39120.
    1.3  The method detection limit is 0.2 ;jg/l when analyzing 1  liter of
         sample.
2.   Summary
    2.1  The water sample is made basic and the benzidine  is extracted
         with ethyl acetate.  Cleanup is accomplished by extracting the
         benzidine from the ethyl acetate with hydrochloric acid.
         Chloramine-T is added to the acid solution to oxidize the benzi-
         dine.  The yellow oxidation product  is extracted  with ethyl
         acetate and measured with a scanning spectrophotometer.   The
         spectrum from 510 nm to 370 nm is used for qualitative  identi-
         fication.
3.   Hazards
    3.1  Benzidine is a known carcinogen.  All manipulations of  this
         method should be carried out in a hood with protection

                                      1

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         provided for the hands and arms of the analyst.  Consult OSHA
         regulations (1) before working with benzidine.
4.  Interferences
    4.1  The multiple extractions effectively limit the interferences to
         organic bases.  The oxidation with Chloramine-T to form a yellow
         product is very selective and has been described in detail
         (2,3).  The use of the absorption spectrum for the identi-
         fication of benzidine results in a highly specific procedure.
    4.2  Some compounds having a structure very similar to benzidine will
         interfere with the quantification, if present.  Examples of
         these interfering compounds are dichlorobenzidine, o-tolidine,
         and dianisidine.
    4.3  A general yellow background color in the extract will limit the
         cell pathlength that can be employed and thus limit the sensi-
         tivity of the method.
5.  Apparatus and Materials
    5.1  Spectrophotometer-visible, scanning (510-370 nm).
    5.2  Separatory Funnels - 125 ml, 250 ml, 2000 ml.
    5.3  Cells - 1 to 5 cm pathlength, 20 ml volume maximum.
6.  Reagents, Solvents and Standards
    6.1  Ethyl acetate
    6.2  Hydrochloric acid (IN)- Add 83 ml cone, hydrochloric acid to
         water and dilute to one liter.
    6.3  Chloramine-T - 10% solution.  Prepare fresh daily by dissolving
         l.Og Chloramine-T in 10 ml distilled water.

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    6.4  Stock standard (0.2 jjg/jjl) - Dissolve  100.0 mg  purified  benzi-
         dine in about 30 ml 1 N HC1.  Dilute to 500 ml  with water.
7.  Preparation of Calibration Curve
    7.1  To a series of 125-ml separatory funnels,  add 45 ml of hydro-
         chloric acid and 10 ml of ethyl acetate.   Shake for one  minute
         to saturate the acid layers.  Discard  the  solvent  layers.   Dose
         the series with volumes from 1.0 to 20.0 /jl of  stock  standard,
         using syringes.
    7.2  Treat standards according to the Procedure beginning  with  8.5.
8.  Quality Control
    8.1  Duplicate and spiked sample analyses are recommended  as  quality
         control checks.  Quality control charts  should be developed
         and used as a check on the analytical  system.   Quality control
         check samples and performance evaluation samples should  be
         analyzed on a regular basis.
    8.2  Each time a set of samples is extracted, a method  blank  is
         determined on a volume of distilled water  equivalent  to  that
         used to dilute the sample.
9.  Procedure
    9.1  Adjust the sample pH to 8.5 to 9.0 with dilute  NaOH or HC1.
    9.2  Transfer 1 liter of sample to a 2000-ml separatory funnel.   Add
         150 ml ethyl acetate and shake for two minutes.  Allow the
         layers to separate, then drain the water layer  into a

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         second 2-liter separatory funnel.  Drain the solvent  layer  into
         a 250-ml separatory funnel.
    9.3  Repeat the extraction of the water layer twice more with
         50-ml portions of ethyl acetate.  Combine all solvent layers,
         then discard the water layer.
    9.4  Extract the solvent layer three times with 15-ml portions of
         hydrochloric acid by shaking 2 minutes and allowing the phases
         to separate.  Combine the acid layers in a glass stoppered
         container for cold storage until time is available for analysis,
         or transfer the layers directly into a 125-ml separatory funnel.
    9.5  Prepare the spectrophotometer so it is warmed and ready to  use.
         The remaining steps of the procedure must be performed rapidly
         on one sample at a time.
    9.6  To the hydrochloric acid solution in a 125 ml separatory funnel,
         add 1.0 ml chloramine-T solution and mix.  Add
         25.0-ml ethyl acetate with a pipet and shake for two minutes.
         Allow the layers to separate, then discard the aqueous phase.
    9.7  Filter the solvent layer through coarse filter paper and fill a
         5-cm cell with the filtrate.
    9.8  Scan the solvent from 510 nm to 370 nm.  Ethyl acetate is used
         for a blank with double beam instruments.  Shorter pathlength
         cells should be used in cases where absorbance exceeds 0.8.
10.  Calculation of Results
    10.1 Benzidine is identified by its absorbance maximum at
         436 nm. Dichlorobenzidine gives similar response but has its
         absorbance maximum at 445 nm.

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    10.2  Construct a baseline from the absorbance minimum at about 470 nm
         to  the  minimum at 390 nm (or 420 nm minimum for samples with a
         high  background).  Record the absorbance ofthe peak maximum and
         the absorbance of the constructed baseline at the 436 nm.  Treat
         samples and standards in the same fashion.
    10.3  Using the net absorbance values, prepare a calibration plot from
         the standards.  Determine the total micrograms in each sample
         from this plot.
    10.4  Divide the total micrograms by the sample volume, in liters, to
         determine /jg/1.  Correct results for cell pathlength if
         necessary.
11.  Reporting Results
    11.1  Report results in micrograms per liter as benzidine without
         correction for recovery data.  When duplicate and spike samples
         are analyzed all data obtained should be reported.
12.  Accuracy and Precision
    12.1  When 1 liter samples of river water were dosed with 1.80 pg of
         benzidine, an average of 1.24;jg was recovered.  The standard
         deviation was 0.092 ^g/1 (n«8).

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REFERENCES:
1.  Federal Register. Volume 39, Page 3779,  Paragraph 1910.93;  (January 29,
    T974Y:

2.  Glassman, J.  M., and Meigs, 0.  W., "Benzidine (4,4'-Diaminobiphenyl) and
    Substituted Benzidines", Arch.  Industr.  Hyg.. i,  519,  (1951).

3.  Butt, L. T. and Strafford, N.,  "Papilloma of the  Bladder in the Chemical
    Industry.  Anlaytical Methods for the Determination of Benzidine and
    B-Naphtylamine, Recommended by  A.B.C.M.  Sub-Committee", J.  Appl.  Chem.,
    6, 525 (1956).

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       METHOD FOR CHLORINATED HYDROCARBONS IN WATER AND WASTEWATER



1.   Scope and Application

    1.1   This method covers the determination of various organo-

          chlorine pesticides and heptachlor epoxide in water and

          wastewater.

    1.2   The following pesticides may be determined individually by this

          method:

                 Parameter                 Storet No.

                 Aldrin                      39330
                 BHC                         	
                 Captan                      39640
                 Chlordane                   39350
                 ODD                         39360
                 DDE                         39365
                 DDT                         39370
                 Dichloran                   	
                 Dieldrin                    39380
                 Endosulfan                  39388
                 Endrin                      39390
                 Heptachlor                  39410
                 Lindane                     39782
                 Methoxychlor                39480
                 Mi rex                       39755
                 PCNB                        39029
                 Strobane                    	
                 Toxaphene                   39400
                 Trifluralin                 39030

    1.3   The following chlorinated organic compound may be determined

          individually by this method:

                 Compound                 Storet No.

                 Heptachlor epoxide          	

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2.  Summary
    2.1   The method offers several analytical alternatives, dependent on
          the analyst's assessment of the nature and extent of interfer-
          ences and/or the complexity of the pesticide mixtures found.
          Specifically, the procedure describes the use of an effective
          co-solvent for efficient sample extraction; provides, through
          use of column chromatography and liquid-liquid partition,
          methods for elimination of non-pesticide interferences and the
          pre-separation of pesticide mixtures.  Identification is made
          by selective gas chromatographic separations and may be corro-
          borated through the use of two or more unlike columns.
          Detection and measurement is accomplished by electron capture,
          microcoulometric or electrolytic conductivity gas chromato-
          graphy.  Results are reported in micrograms per liter.
    2.2   Confirmation of the identity of the compounds should be made by
          6C-MS when a new or undefined sample type is being analyzed and
          the concentration is adequate for such determination.
    2.3   This method is recommended for use only by experienced pesti-
          cide analysts or under the close supervision of such qualified
          persons.
3.  Interferences
    3.1   Solvents, reagents, glassware, and other sample processing
          hardware may yield discrete artifacts and/or elevated
          baselines, causing misinterpretation of gas chromatograms.

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      All  of these materials must be demonstrated to be free from
      interferences under the conditions of the analysis.  Specific
      selection of reagents and purification of solvents by distill-
      ation in all-glass systems may be required.  Refer to Appendix
      I.
3.2   The interferences in industrial effluents are high and varied
      and often pose great difficulty in obtaining accurate and
      precise measurement of organochlorine pesticides.  Sample
      clean-up procedures are generally required and may result in
      the loss of certain organochlorine pesticides.  Therefore,
      great care should be exercised in the selection and use of
      methods for eliminating or minimizing interferences.  It  is not
      possible to describe procedures for overcoming all of the
      interferences that; may be encountered in industrial effluents.
3.3   Polychlorinated Biphenyls (PCBs) - Special attention is called
      to industrial plasticizers and hydraulic fluids such as the
      PCBs, which are a potential source of interference in pesticide
      analysis.  The presence of PCBs is indicated by a  large number
      of partially resolved or unresolved peaks which may occur
      throughout the entire chromatogram.  Particularly  severe  PCB
      interference will require special separation procedures (1, 2).
3.4   Phthalate Esters - These compounds, widely used as
      plasticizers, respond to the electron capture detector and are
      a source of interference in the determination of organochlorine
      pesticides using this detector.  Water leaches these materials
      from plastics, such as polyethylene bottles and tygon tubing.

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          The presence of phthalate esters is implicated in samples that
          respond to electron capture but not to the microcoulometric or
          electrolytic conductivity halogen detectors or to the flame
          photometric detector.
    3.5   Organophosphorus Pesticides - A number of organophosphorus
          pesticides, such as those containing a nitro group, e.g., para-
          thion, also respond to the electron capture detector and may
          interfere with the determination of the organochlorine pesti-
          cides.  Such compounds can be identified by their response to
          the flame photometric detector (3).
4.  Apparatus and Materials
    4.1   Gas Chromatograph - Equipped with glass lined injection port.
    4.2   Detector Options:
          4.2.1  Electron Capture - Radioactive (tritium or nickel-63)
          4.2.2  Microcoulometric Titration
          4.2.3  Electrolytic Conductivity
    4.3   Recorder - Potentiometric strip chart (10 in.) compatible with
          the detector.
    4.4   Gas Chromatographic Column Materials:
          4.4.1  Tubing - Pyrex (180 cm long X 4 mm ID)
          4.4.2  Glass Wool - Silanized
          4.4.3  Solid Support - Gas-Chrom-Q (100-120 mesh)
          4.4.4  Liquid Phases - Expressed as weight percent coated on
                    solid support.
                 4.4.4.1  OV-1, 3%
                 4.4.4.2  OV-210,  5%
                                      10

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                 4.4.4.3  OV-17,  1.5* plus QF-1 or OV-210, 1.95%
                 4.4.4.4  QF-1,  6% plus SE-30,  4%
    4.5    Kuderna-Danish (K-D)  Glassware
          4.5.1   Snyder Column  - three-ball (macro) and two-ball
                    (micro)
          4.5.2   Evaporative Flasks - 500 ml
          4.5.3   Receiver Ampuls - 10 ml, graduated
          4.5.4   Ampul Stoppers
    4.6    Chromatographic Column - Chromaflex (400 mm long x 19 mm ID)
          with coarse fritted plate on bottom and Teflon stopcock; 250-ml
          reservoir bulb at top of column with flared out funnel shape at
          top of bulb - a special order (Kontes K-420540- 9011).
    4.7    Chromatographic Column - pyrex (approximately 400 mm  long x 20
          mm ID) with coarse fritted plate on bottom.
    4.8    Micro  Syringes - 10,  25, 50 and 100 ;jl.
    4.9    Separatory funnels -  125 ml, 1000 ml  and 2000 ml with Teflon
          stopcock.
    4.10  Blender - High speed, glass or stainless steel cup.
    4.11  Graduated cylinders - 100 and 250 ml.
    4.12  Florisil - PR Grade (60-100 mesh); purchase activated at
          1250°F and store in the dark in glass containers with glass
          stoppers or foil-lined screw caps.  Before use, activate each
          batch  overnight at 130°C in foil-covered glass container.
          Determine lauric-acid value (See Appendix  II).
5.  Reagents, Solvents, and Standards
    5.1    Sodium Chloride - (ACS) Saturated solution in distilled water

                                      11

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          (pre-rinse NaCl with hexane).
    5.2   Sodium Hydroxide - (ACS) 10 N in distilled water.
    5.3   Sodium Sulfate - (ACS) Granular, anhydrous (conditioned at 400
          C for 4 hrs.).
    5.4   Sulfuric Acid - (ACS) Mix equal volumes of cone. f^SO^ with
          distilled water.
    5.5   Diethyl Ether - Nanograde, redistilled in glass, if necessary.
          5.5.1 Must be free of peroxides as indicated by EM Quant test
                strips.  (Test strips are available from EM Laboratories,
                Inc., 500 Executive Blvd., Elmsford, N.Y. 10523.)
          5.5.2 Procedures recommended for removal of peroxides are
                provided with the test strips.
    5.6   Acetonitrile, Hexane, Methanol, Methylene Chloride, Petroleum
          Ether (boiling range 30-60aC) - nanograde, redistill in glass
          if necessary.
    5.7   Pesticide Standards - Reference grade.
6.  Calibration
    6.1   Gas chromatographic operating conditions are considered accept-
          able if the response to dicapthon is at least 50% of full scale
          when < 0.06 ng is injected for electron capture detection and
          ^100 ng is injected for microcoulometric or electrolytic
          conductivity detection.  For all quantitative measurements, the
          detector must be operated within its linear response range and
          the detector noise level should be less than 2% of full scaJe.
    6.2   Standards are injected frequently as a check on the stability
          of operating conditions.  Gas chromatograms of several standard

                                      12

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          pesticides are shown in Figures 1, 2, 3 and 4 and provide
          reference operating conditions for the four recommended columns.
    6.3   The elution order and retention ratios of various organo-
          chlorine pesticides are provided in Table 1, as a guide.
7.  Quality Control
    7.1   Duplicate and spiked sample analyses are recommended as quality
          control checks.  Quality control charts (4) should be developed
          and used as a check on the analytical system.  Quality control
          check samples and performance evaluation samples should be
          analyzed on a regular basis.
    7.2   Each time a set of samples is extracted, a method blank is
          determined on a volume of distilled water equivalent to that
          used to dilute the sample.
8.  Sample Preparation
    8.1   The sample size taken for analysis  is dependent on the  type of
          sample and the sensitivity required for the purpose at  hand.
          Background information on the pesticide levels previously
          detected at a given sampling  site will assist  in determining
          the sample size required, as  well as  the final volume  to  which
          the extract needs to be concentrated.  A 1-liter sample  is
          usually  taken for drinking water  and  ambient water  analysis to
          provide  a detection  limit of  O.OBOto  0.100/jg/l.  One-hundred
          milliliters  is usually adequate  to  provide  a detection  limit of
          1 ;jg/l for industrial effluents.
                                       13

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1N3A10S
  wiviimiiu
    3H8* —

8N3d

NIH01V


]QIXOd3  id3H
   NIH013IO
                                         M01H3AXON13N
                         14

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        IS                10                 5                 0
                      RETENTION TIME IN MINUTES
Figure  2. Column Packing:  5%  OV-210,  Carrier Gas: Argon/Methane
          at 70  ml/ffiin, Column Temperature: 180 C, Detector:
          Electron Capture.
                            15

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     1N3A10S
   3H9»

   9N3d
NIHQ1V
 Niivanuiai

NVbOlHOIQ
NIUQ13IQ
                       I NVJinSOQN]
                                            1QQ .(I'd,
                                         H01H3AXOHJL3W
                                   X]8IW
                                                                      CO

                                                                      a>
                                                                      as  ..
                                                                      a> •»—
                                                                      "r-  o
                                                                      v_  a»
                                                                 ae   co
                                                                      oo cs
                                                                         CM
                                                              ra

                                                              a>
                                                                      a>

                                                                      3
                                                                      CxO
                          16

-------
 1N3A10S
   Nnvinuiu
            jHa>»
NVH01H3IO + 8N3d
   NIHQ13IO
                                                                   «  „;
                                                                   a>  co
                                 NNQH1
                                                                o   - CJ
                                         X3HIN
                          17

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                                    Table 1
    RETENTION RATIOS OF VARIOUS ORGANOCHLORINE PESTICIDES RELATIVE TO ALDRIN
Liquid
Phase1 1
Column Temp.
Argon/Methane
Carrier Flow
Pesticide
Trifluralin
«-BHC
PCNB
Lindane
Dichloran
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan I
p,p'-DDE
Dieldrin
Captan
Endrin
o,p'-DDT
p,p'-DDD
Endosulfan II
p,p'-DDT
Mi rex
Methoxychlor
Aldrin
(Win. absolute)
1.5% OV-17
+
.95% QF-12
200 C
60 ml/min
RR
0.39
0.54
0.68
0.69
0.77
0.82
1.00
1.54
1.95
2.23
2.40
2.59
2.93
3.16
3.48
3.59
4.18
6.1
7.6
3.5
5%
OV-210
180 C
70 ml/min
RR
1.11
0.64
0.85
0.81
1.29
0.87
1.00
1.93
2.48
2.10
3.00
4.09
3.56
2.70
3.75
4.59
4.07
3.78
6.5
2.6
3%
OV-1
180 C
70 ml/min
RR
0.33
0.35
0.49
0.44
0.49
0.78
1.00
1.28
1.62
2.00
1.93
1.22
2.18
2.69
2.61
2.25
3.50
6.6
5.7
4.0
6% QF-1
+
4% SE-30
200 C
60 ml/min
RR
0.57
0.49
0.63
0.60
0.70
0.83
1.00
1.43
1.79
1.82
2.12
1.94
2.42
2.39
2.55
2.72
3.12
4.79
4.60
5.6
     columns glass,  180 cm x 4 mm ID,  solid support Gas-Chrom Q (100/120
 mesh)
ZOV-210 also may be used

                                      18

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    8.2   Quantitatively transfer the proper aliquot of sample from the
          sample container into a two-liter separatory funnel.  If less
          than 800 ml is analyzed, dilute to one liter with interference
          free distilled water.
9.  Extraction
    9.1   Add 60 ml of 15% methylene chloride in hexane (v:v) to the
          sample in the separatory funnel and shake vigorously for two
          minutes.
    9.2   Allow the mixed solvent to separate from the sample, then draw
          the water into a one-liter Erlenmeyer flask.  Pour the organic
          layer into a 100 ml beaker and then pass it through a column
          containing 3-4 inches of anhydrous sodium sulfate, and collect
          it in a 500 ml K-D flask equipped with a 10 ml ampul.  Return
          the water phase to the separatory funnel.  Rinse the Erlenmeyer
          flask with a second 60-ml volume of solvent; add the solvent to
          the separatory funnel and complete the extraction procedure a
          second time.  Perform a third extraction in the same manner.
    9.3   Concentrate the extract in the K-D evaporator on a hot water
          bath.
    9.4   Analyze by gas chromatography unless a need for cleanup  is
          indicated (See Section  10).
10. Clean-up and Separation Procedures
    10.1  Interferences in the form of distinct peaks and/or high  back-
          ground  in the initial gas chromatographic analysis, as well as
          the physical characteristics of the extract (color, cloudiness,
          viscosity) and background knowledge of the sample will indicate
                                     19

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      whether clean-up is required.  When these interfere with
      measurement of the pesticides, or affect column life or
      detector sensitivity, proceed as directed below.
10.2  Acetonitrile Partition - This procedure is used to isolate fats
      and oils from the sample extracts.   It should be noted that not
      all pesticides are quantitatively recovered by this procedure.
      The analyst must be aware of this and demonstrate the effi-
      ciency of the partitioning for specific pesticides.  All of the
      pesticides listed in Scope (1.2) with the exception of mirex
      ,are efficiently recovered.
      10.2.1  Quantitatively transfer the previously concentrated
              extract to a 125-ml separatory funnel with enough
              hexane to bring the final volume to 15 ml.  Extract the
              sample four times by shaking vigorously for one minute
              with 30-ml portions of hexane-saturated acetonitrile.
      10.2.2  Combine and transfer the acetonitrile phases to a
              one-liter separatory funnel and add 650 ml of distilled
              water and 40 ml of saturated sodium chloride solution.
              Mix thoroughly for 30-45 seconds.   Extract with two
              100-ml portions of hexane by vigorously shaking about
              15 seconds.
      10.2.3  Combine the hexane extracts in a one-liter separatory
              funnel and wash with two 100-ml portions of distilled
              water.  Discard the water layer and pour the hexane
              layer through a 3-4 inch anhydrous sodium sulfate
              column into a 500-ml K-D flask equipped with a 10-ml
                                  20

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              ampul.   Rinse the separatory funnel and column with
              three 10-ml  portions of hexane.
      10.2.4  Concentrate  the extracts to 6-10 ml in the K-D evapor-
              ator in a hot water bath.
      10.2.5  Analyze by gas chromatography unless a need for further
              cleanup is indicated.
10.3  Florisil Column Adsorption Chromatography
      10.3.1  Adjust the sample extract volume to 10 ml.
      10.3.2  Place a charge of activated Florisil (weight determined
              by lauric-acid value, see Appendix II) in a  Chromaflex
              column.  After settling the Florisil by tapping the
              column, add about one-half inch layer of anhydrous
              granular sodium sulfate to the top.
      10.3.3  Pre-elute the column, after cooling, with 50-60 ml of
              petroleum ether.  Discard the eluate and just prior to
              exposure of the sulfate layer to air, quantitatively
              transfer the sample extract into the column by
              decantation and subsequent petroleum ether wash- ings.
              Adjust the elution rate to about 5 ml per minute and,
              separately,  collect up to three eluates in 500-ml K-D
              flasks equipped with 10-ml ampuls (see Eluate
              Composition 10.4.).  Perform the first elution with
              200 ml of 6% ethyl ether in petroleum ether, and the
              second elution with 200 ml of 15% ethyl ether in
                                  21

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                  petroleum ether.   Perform the third elution with 200 ml
                  of 50% ethyl ether - petroleum ether and the fourth
                  elution with 200  ml of 100* ethyl ether.
          10.3.4  Concentrate the eluates to 6-10 ml in the K-D eva-
                  porator in a hot  water bath.
          10.3.5  Analyze by gas chromatography.
    10.4  Eluate Composition  - By using an equivalent quantity of any
          batch of Florisil, as determined by its lauric acid value, the
          pesticides will be separated into the eluates indicated below:
                              6% Eluate
             Aldrin           DDT                 Mi rex
             BHC              Heptachlor          PCNB
             Chlordane        Heptachlor Epoxide  Strobane
             ODD              Lindane             Toxaphene
             DDE              Methoxychlor        Trifluralin
            15% Eluate                     50% Eluate
             Endosulfan I                   Endosulfan II
             Endrin                         Captan
             Dieldrin
             Dichloran
          Certain thiophosphate pesticides will occur in each of the
          above fractions as well as the 100% fraction.  For additional
          information regarding eluate composition, refer to the FDA
          Pesticide Analytical Manual (5).
11.  Calculation of Results
    11.1  Determine the pesticide concentration by using the absolute
          calibration procedure described below or the relative cali-
          bration procedure described in Appendix III.
                                     22

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             (1)    Micrograms/liter = (Aj  (Bj  (vt)
                                        (V-i) (Vs)
                   A - ng standard
                       Standard area

                   B = Sample aliquot area
                   V-j = Volume of extract injected (pi)
                   Vt= Volume of total extract (jul)
                   Vs= Volume of water extracted (ml)

12.   Reporting Results

     12.1  Report results in micrograms per liter without correction for

           recovery data.  When duplicate and spiked samples are  ana-

           lyzed., all data obtained should be reported.
                                     23

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REFERENCES:


1.  Monsanto Methodology for Aroclors - Analysis of Environmental  Materials
    for Biphenyls, Analytical Chemistry Method 71-35, Monsanto Company,
    St.  Louis, Missouri, 63166, 1970.

2.  "Method for Polychlorinated Biphenyls in Water and Wastewater", this
    manual,  p. 43.

3.  "Method for Organophosphorus Pesticides in Water and Wastewater", this
    manual,  p. 25.

4.  "Handbook for Analytical Quality Control in Water and Wastewater
    Laboratories", Chapter 6, Section 6.4, U.  S. Environmental Protection
    Agency,  National  Environmental  Research Center, Analytical Quality Con*
    trol Laboratory,  Cincinnati, Ohio, 45268,  1973.

5.  "Pesticide Analytical  Manual",  U. S.  Dept. of Health, Education and
    Welfare, Food and Drug Administration, Washington, D. C.
                                     24

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    METHOD  FOR  ORGANOPHOSPHORUS  PESTICIDES IN WATER AND WASTEWATER
 Scope  and  Application
 1.1  This  method  covers  the  determination of various organophosphorus
     pesticides  in  water and wastewater.
J.2  The following  pesticides may be determined individually by this
     method:
                  Parameter                    Storet No.
                  Azinphos methyl                   —
                  Demeton-0                       39560
                  Demeton-S                        —
                  Diazinon                        39570
                  Disulfoton                       39010
                  Malath ion                       39530
                  Parathion methyl                39600
                  Parathion ethyl                  39540
 Summary
 2.1  The method  offers several  analytical alternatives, dependent on
     the  analyst's  assessment of  the nature and extent of interferences
     and  the  complexity of the  pesticide mixtures found.   Specifically,
     the procedure  describes the  use of an effective co-solvent for
     efficient sample extraction; provides, through use of the column
     chromatography and liquid-liquid partition, methods for the
     elimination of non-pesticide interferences and the preseparation
     of pesticide mixtures.   Identification is made by selective gas
     chromatographic separation and may be corroborated through the use
     of two or more unlike columns.  Detection and measurement are best
      accomplished by flame photometric gas chromatography using a
                                   25

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         phosphorus specific filter.  The electron capture detector, though
         non-specific, may also be used for those compounds to which it
         responds.  Results are reported in micrograms per liter.
    2.2  Confirmation of the identity of the compounds should be made by
         GC-MS when a new or undefined sample type is being analyzed and
         the concentration is adequate for such determination.
    2.3  This method is recommended for use only by experienced pesticide
         analysts or under the close supervision of such qualified persons.
3.  Interferences
    3.1  Solvents, reagents, glassware, and other sample processing hard-
         ware may yield discrete artifacts and/or elevated baselines, caus-
         ing misinterpretation of gas chromatograms.   All of these
         materials must be demonstrated to be free from interferences under
         the conditions of the analysis.   Specific selection of reagents
         and purification of solvents by distillation in all-glass systems
         may be required.  Refer to Appendix I.
    3.2  The interferences in industrial  effluents are high and varied and
         often pose great difficulty in obtaining accurate and precise
         measurement of organophosphorus pesticides.   Sample clean-up
         procedures are generally required and may result in the loss of
         certain organophosphorus pesticides.  Therefore, great care should
         be exercised in the selection and use of methods for eliminating
         or minimizing interferences.  It is not possible to describe
         procedures for overcoming all of the interferences that may be
         encountered in industrial effluents.
                                      26

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    3.3  Compounds such as organochlorine pesticides, polychlorinated
         biphenyls and phthalate esters interfere with the analysis of
         organophosphorus pesticides by electron capture gas chro-
         matography.  When encountered, these interferences are overcome by
         the use of the phosphorus specific flame photometric detector.  If
         such a detector is not available, these interferences may be
         removed from the sample by using the clean-up procedures described
         in the EPA methods for those compounds (1, 2).
    3.4  Elemental sulfur will interfere with the determination of organo-
         phosphorus pesticides by flame photometric and electron capture
         gas chromatography.  The elimination of elemental sulfur as an
         interference is described in Section 10.5, Clean-up and Separation
         Procedures.
4.  Apparatus and Materials
    4.1  Gas Crhomatograph - Equipped with glass lined injection port.
    4.2  Detector options:
         4.2.1     Flame Photometric - 526 mu phosphorus filter.
         4.2.2     Electron Capture - Radioactive (tritium or nickel-63).
    4.3  Recorder - Potentiometric strip chart (10 in.) compatible with the
         detector.
    4.4  Gas Chromatographic Column Materials:
         4.4.1     Tubing - Pyrex (180 cm long x 4 mm ID)
         4.4.2     Glass Wool - Silanized
         4.4.3     Solid Support - Gas Chrom Q (100-120 mesh)
         4.4.4     Liquid Phases - Expressed as weight percent coated on
                   solid support.

                                      27

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          4.4.4.1   OV-1, 3%
          4.4.4.2   OV-210, 5%
          4.4.4.3   OV-17, 1.5% plus QF-1 or OV-210,  1.95%
          4.4.4.4   QF-1 or OV-210, 6% plus SE-30, 4%
4.5  Kuderna-Dam'sh (K-D) Glassware
     4.5.1     Snyder Column - three ball (macro) and two ball  (micro)
     4.5.2     Evaporative Flasks - 500 ml
     4.5.3     Receiver Ampuls - 10 ml, graduated
     4.5.4     Ampul Stoppers
4.6  Chromatographic Column - Chromaflex  (400 mm x 19 mm ID) with
     coarse fritted plate and Teflon stopcock on bottom; 250 ml
     reservoir bulb at top of column with flared out funnel shape  at
     top of bulb - a special order (Kontes K-420540-9011).
4.7  Chromatographic Column - pyrex (approximately 400 mm long  x 20 mm
     ID) with coarse fritted plate on bottom.
4.8  Micro Syringes - 10, 25, 50 and 100 >jl.
4.9  Separatory funnels - 125 ml, 1000 ml and 2000 ml with Teflon
     stopcock.
4.10 Micro-pipets - disposable (140 mm long x 5 mm ID).
4.11 Blender - High speed, glass or stainless steel cup.
4.12 Graduated cylinders - 100 and 250 ml.
4.13 Florisil - PR Grade (50-100 mesh); purchase activated at 1250°F
     and store in the dark in glass containers with glass stoppers, or
     foil-lined screw caps.  Before use,  activate each batch overnight
     at 130°C in foil-covered glass container.  Determine lauric-acid
     value (See Appendix II).
                                  28

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    4.14 Alumina - Woelm, neutral; deactivate by pipeting 1 ml of distilled
         water into 125 ml ground glass-stoppered Erlenmeyer flask.  Rotate
         flask to distribute water over surface of glass.  Immediately add
         19.0 g fresh alumina through small powder funnel.  Shake flask
         containing mixture for two hours on a mechanical shaker (3).
5.  Reagents, Solvents, and Standards
    5.1  Sodium Chloride - (ACS) Saturated solution in distilled water
         (pre-rinse NaC'l with hexane).
    5.2  Sodium Hydroxide - (ACS) 10 N in distilled water.
    5.3  Sodium Sulfate - (ACS) Granular, anhydrous (conditioned at 400°C
         for 4 hrs.).
    5.4  Sulfuric Acid - (ACS) Mix equal volumes of cone. H2S04 with
         distilled water.
    5.5  Diethyl Ether - Nanograde, redistilled  in glass, if  necessary.
         5.5.1     Must be free of peroxides as  indicated by  EM Quant test
                   strips.  (Test strips are available from EM
     *
                   Laboratories,  Inc., 500 Executive Blvd., Emslford, N.Y.
                   10523.)
         5.5.2     Procedures recommended for removal of  peroxides  are
                   provided with  the test strips.
    5.6  Acetonitrile, Hexane, Methanol, Methylene Chloride,  Petroleum
         Ether (boiling  range 30-60°C) - nanograde, redistill  in glass  if
         necessary.
    5.7  Pesticide Standards  - Reference grade.
                                        29

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6.  Calibration
    6.1  Gas chromatographic operating conditions are considered acceptable
         if the response to dicapthon is at least 50% of full scale when  <1.5
         ng is injected for flame photometric detection and  < 0.06 ng  is
         injected for electron capture detection.  For all quantitative
         measurements, the detector must be operated within  its linear
         response range and the detector noise level should  be less than  2%
         of full scale.
    6.2  Standards are injected frequently as a check on the stability of
         operating conditions.  Gas chromatograms of several standard
         pesticides are shown in Figures 1, 2, 3 and 4 and provide reference
         operating conditions for the four recommended columns.
    6.3  The elution order and retention ratios of various organophosphorus
         pesticides are provided in Table 1, as a guide.
7.  Quality Control
    7.1  Duplicate and spiked sample analyses are recommended as quality
         control checks.  Quality control charts (4) should  be developed  and
         used as a check on the analytical system.  Quality  control check
         samples and performance evaluation samples should be analyzed on a
         regular basis.
    7.2  Each time a set of samples is extracted, a method blank is
         determined on a volume of distilled water equivalent to that used
         to dilute the sample.
8.  Sample Preparation
    8.1  The sample size taken for analysis is dependent on  the type of
         sample and the sensitivity required for the purpose at hand.
                                      30

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                   10
12
          2        4         &         8
                RETENTION TIME IN MINUTES
Figure 1. Column Packing: 1.5%  OY-17  + 1.95 %  QF-1,
Carrier Gas: Nitrogen at  70 ml/min,  Column Temperature: 215 C,
Detector: Flame Photometric (Phosphorus).
31

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       rxi
0
10
           2468
             RETENTION TIME IN MINUTES
Figure 2. Column Packing: 5% OY-210, Carrier Gas: Nitrogen
at 60 ml/min, Column Temperature: 200 C, Detector:
Flame Photometric (Phosphorus).
                          32

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0
2
10
12
                     4         6        8
                 RETENTION TIME IN MINUTES
Figure 3. Column Packing: 6% QF-1 +4% SE-30, Carrier Gas: Nitrogen
at 70 ml/min, Column Temperature: 215 C,  Detector: Flame
Photometric (Phosphorus).
                            33

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I     I     I    I     I     I    I
2
10
                     4        6         8
               RETENTION TIME IN MINUTES
Figure 4. Column Packing: 3% OV-1, Carrier Gas: Nitrogen at
60 ml/min, Column Temperature: 200 C, Detector: Flame
Photometric (Phosphorus).
               34

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                                    TABLE 1

              RETENTION TIMES OF SOME ORGANOPHOSPHOROUS PESTICIDES
                             RELATIVE TO PARATHION
Liquid Phase1
Column Temp.
Nitrogen
Carrier Flow
Pesticide
Demeton3
Diazinon
Disulfoton
Ma lath ion
Parathion methyl
Parathion ethyl
Azinphos methyl
1.5% OV-17
+
1.95% QF-12
215 C
70 ml/min
RR
0.46
0.40
0.46
0.86
0.82
1.00
6.65
6% QF-1*
+
4% SE-30
215 C
70 ml/min
RR
0.26
0.43
0.38
0.45
0.78
0.80
1.00
4.15
5%
OV-210
200 C
60 ml/min
RR
0.20
0.38
0.25
0.31
0.73
0.81
1.00
4.44
7%
OV-1
200 C
60 ml/min
RR
0.74
0.59
0.62
0.92
0.79
1.00
4.68
Parathion
(min absolute)
I AT 1 rnlnmnc n
                          4,. 5
6.6
5.7
3.1
'All columns glass, 180 xm x 4 mm ID, solid support Gas-Chrom Q,  100/120
   mesh.
*May substitute OV-210 for QF-1.
^Anomalous, multipeak response often encountered.
                                      35

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         Background information on the pesticide  levels  previously  detected
         at a given sampling site will assist  in  determining  the  sample
         size required, as well as the final volume to which  the  extract
         needs to be concen- trated.  A 1-liter sample is usually taken for
         drinking water and ambient water analysis to provide a detection
         limit of 0.050 to 0.100^g/l.  One-hundred milliliters is  usually
         adequate to provide a detection limit of 1 ^ig/1 for  industrial
         effluents.
    8.2  Quantitatively transfer the proper aliquot of sample from  the
         sample container into a two-liter separatory funnel.  If less than
         a 800 ml is analyzed, dilute to one liter with  interference  free
         distilled water.
9.  Extraction
    9.1  Add 60 ml of 15% methylene chloride in hexane (v:v)  to the sample
         in the separatory funnel and shake vigorously for two minutes.
    9.2  Allow the mixed solvent to separate from the sample,  then  draw the
         water into a one-liter Erlenmeyer flask.  Pour  the organic layer
         into a 100 ml beaker and then pass it through a column containing
         3-4 inches of anhydrous sodium sulfate,  and collect  it in  a  500 ml
         K-D flask equipped with a 10 ml ampul.  Return  the water phase to
         the separatory funnel.  Rinse the Erlenmeyer flask with  a  second
         60 ml volume of solvent; add the solvent to the separatory funnel
         and complete the extraction procedure a second  time.  Perform a
         third extraction in the same manner.
    9.3  Concentrate the extract in the K-D evaporator on a hot water bath.
                                      36

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    9.4  Analyze by gas chromatography unless a need for cleanup is indi-
         cated.   (See Section 10).
10.  Clean-up and Separation Procedures
    10.1 Interferences in the form of distinct peaks and/or high background
         in the  initial gas chromatographic analysis, as well as the
         physical characteristics of the extract (color, cloudiness,
         viscosity) and background knowledge of the sample source will
         indicate whether clean-up is required.  When these interfere with
         measurement of the pesticides, or affect column life or detector
         sensitivity, proceed as directed below.  The use of these
         procedures is not required for samples free of interferences.
         They are provided as options to the analyst to be used when needed.
    10.2 Acetonitrile Partition - This procedure is used to separate fats
         and oils from the sample extracts.  It should be noted that not
         all pesticides are quantitatively recovered by this procedure.
         The analyst must be aware of this and demonstrate the efficiency
         of the partitioning for specific pesticides.
         10.2.1     Quantitatively transfer the previously concentrated
                   extract to a 125-ml separatory funnel with enough hexane
                   to bring the final volume to 15 ml.  Extract the sample
                   four times by shaking vigorously for one minute with 30
                   ml portions of hexane-saturated acetonitrile.
         10.2.2    Combine and transfer the  acetonitrile phases to a
                   one-liter separatory funnel and add 650 ml of distilled
                   water and 40 ml of saturated sodium chloride solution.
                   Mix thoroughly for 30-45  seconds.  Extract with two
                                      37

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               TOO  ml  portions of hexane by vigorously shaking about 15
               seconds.
     10.2.3     Combine the hexane extracts in a one-liter separatory
               funnel  and wash with two 100 ml portions of distilled
               water.   Discard the water layer and pour the hexane
               layer through a 3-4 inch anhydrous sodium sulfate column
               into a 500-ml K-D flask equipped with a 10-ml ampul.
               Rinse the separatory funnel and column with three 10 ml
               portions of hexane.
     10.2.4     Concentrate the extracts to 6-10 ml in the K-D
               evaporator in a hot water bath.
     10.2.5     Analyze by gas chromatography unless a need for further
               clean-up is indicated.
10.3  Florisil  Column Adsorption Chromatography
     10.3.1     Adjust the sample extract volume to 10 ml.
     10.3.2     Place a charge of activated Florisil (weight determined
               by lauric-acid value, see Appendix II) in a Chromaflex
               column.  After settling the Florisil by tapping the
               column, add about one-half inch layer of anhydrous
               granular sodium sulfate to the top.
     10.3.3     Pre-elute the column, after cooling, with 50-60 ml of
               petroleum  ether.   Discard  the  eluate  and  just  prior to
               exposure of the sulfate layer to air, quantitatively
               transfer the sample extract into the column by
               decantation and subsequent petro- leum ether washings.
               Adjust the elution rate to about 5 ml per minute and,
                                  38

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               separately,  collect up to four eluates in 500-ml K-D
               flasks  equipped with l(Hnl ampuls.   (See Eluate Compos-
               ition,  10.4.)   Perform the first elution with 200 ml of
               6% ethyl  ether in petroleum ether,  and the second
               elution with 200 ml of 15% ethyl ether in petroleum
               ether.   Perform the third elution with 200 ml of 50%
               ethyl  ether  - petroleum ether and the fourth elution
               with 200 ml  of 100% ethyl ether.
     10.3.4    Concentrate  the eluates to 6-10 ml  in the K-D evaporator
               in a hot water bath.
     10.3.5    Analyze by gas chromatography.
10.4 Eluate Composition - By using an equivalent quantity of any batch
     of Florisil as determined by its 1auric-acid value, the pesticides
     will be separated into the eluates indicated below:
             6% Eluate                  15% Eluate
             Demeton                    Diazinon
             Disulfoton                 Malathion (trace)
                                        Parathion Methyl
             50% Eluate                 100% Eluate
             Malathion                  Azinphos methyl (80%)
             Azinphos methyl (20%)
     For additional information regarding eluate composition, refer
     to the FDA Pesticide Analytical Manual (5).
10.5 Removal of Sulfur - If elemental sulfur interferes with the gas
     chromatographic analysis, it can be removed by the use of an
     alumina microcolumn.
     10.5.1 Adjust the sample extract volume to 0.5 ml  in a K-D
                                  39

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                apparatus,  using a two-ball Snyder mlcrocolumn.
         10.5.2 Plug a disposable pipet with a small quantity of glass
                wool.   Add  enough alumina to produce a 3-cm column after
                settling.   Top the alumina with a 0.5-cm layer of
                anhydrous  sodium sulfate.
         10.5.3 Quantitatively transfer the concentrated extract to the
                alumina microcolumn using a 100 yl syringe.  Rinse the
                ampul  with  200 ^1 of hexane and add to the microcolumn.
         10.5.4 Elute  the microcolumn with 3 ml of hexane and discard the
                first  eluate which contains the elemental sulfur.
         10.5.5 Next elute  the column with 5 ml of 10% hexane in
                methylene  chloride.  Collect the eluate in a 10 ml
                graduated  ampul.
         10.5.6 Analyze by  gas chromatography.
         NOTE:   If the electron capture detector is to be used methylene
                chloride must be removed.  To do this, attach the ampul
                to a K-D apparatus (500-ml flask and 3-ball Snyder
                column) and concentrate to about 0.5 ml.   Adjust volume
                as required prior to analysis.
11.  Calculation of Results
    11.1  Determine the pesticide concentration by using the absolute
         calibration procedure described below or the relative cali-
         bration procedure  described in Appendix III.
                                     40

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         (1)   Micrograms/liter = (A)   (B)   (Vt)
                                     W  (VS)
         A - ng standard
             Standard area
         B * Sample aliquot area
         V^ » Volume of extract injected (nl)
         Vt = Volume of total extract (jjl)
         Vs = Volume of water extracted (ml)
12.  Reporting Results
    12.1 Report results in micrograms per liter without correction for
         recovery data.  When duplicate and spiked samples are analyzed
         all data obtained should be reported.
                                      41

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REFERENCES:
1.  "Method for Chlorinated Hydrocarbons in Water and Wastewater", this
    manual, p.  7.

2.  "Method for Polychlorinated Biphenyls (PCBs) in Water and Wastewater",
    this manual, p. 43.

3.  Law, L. M.  and Georlitz, D. F., "Microcolumn Chromatographic Clean-up
    for the Analysis of Pesticides in Water", Journal of the Association
    for Analytical Chemists. 53_, 1276 (1970).

4.  "Handbook for Analytical Quality Control in Water and Wastewater
    Laboratories", Chapter 6, Section 6.4, U. S. Environmental Protection
    Agency, National Environmental Research Center, Analytical Quality Con-
    trol Laboratory, Cincinnati, Ohio, 45268, 1973.

5.  "Pesticide Analytical Manual", U. S. Dept. of Health, Education and
    Welfare, Food and Drug Administration, Washington, D. C.
                                     42

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     METHOD FOR POLYCHLORINATED BIPHENYLS (PCBs) IN WATER AND WASTEWATER

1.  Scope and Application
    1.1  This method covers the determination of various polychlorinated
         bipheny! (PCB) mixtures in water and wastewater.
    1.2  The following mixtures of chlorinated biphenyls (Aroclors) may be
         determined by this method:
                       Parameter                 Storet No.
                       PCB-1016                    34671
                       PCB-1221                    39488
                       PCB-1232                    39492
                       PCB-1242                    39496
                       PCB-1248                    39500
                       PCB-1254                    39504
                       PCB-1260                    39508
    1.3   The method is an extension of the Method for Chlorinated
          Hydrocarbons in Water and Wastewater (1).  It is designed so
          that determination of both the PCBs and the organochlorine
          pesticides may be made on the same sample.
2.  Summary
    2.1   The PCBs and the organochlorine pesticides are co-extracted by
          liquid-liquid extraction and, insofar as possible, the two
          classes of compounds separated from one another prior to gas
          chromatographic determination.  A combination of the standard
          Florisil column cleanup procedure and a silica gel microcolumn
          separation procedure (2)(3) are employed.  Identification is
                                      43

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          made from gas chromatographic patterns obtained through the use
          of two or more unlike columns.  Detection and measurement is
          accomplished using an electron capture, microcoulometric, or
          electrolytic conductivity detector.  Techniques for confirming
          qualitative identification are suggested.
3.  Interferences
    3.1   Solvents, reagents, glassware, and other sample processing
          hardware may yield discrete artifacts and/or elevated baselines
          causing misinterpretation of gas chromatograms.  All of these
          materials must be demonstrated to be free from interferences
          under the conditions of the analysis.  Specific selection of
          reagents and the purification of solvents by distillation in
          all-glass systems may be required.  Refer to Appendix I.
    3.2   The interferences in industrial effluents are high and varied
          and pose great difficulty in obtaining accurate and precise
          measurement of PCBs and organochlorine pesticides.  Separation
          and clean-up procedures are generally required and may result
          in the loss of certain organochlorine compounds.  Therefore,
          great care should be exercised in the selection and use of
          methods for eliminating or minimizing interferences.  It is not
          possible to describe procedures for overcoming all of the
          interferences that may be encountered in industrial effluents.
    3.3   Phthalate esters, certain organophosphorus pesticides, and
          elemental sulfur will interfere when using electron capture for
          detection.  These materials do not interfere when the
                                      44

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          microcoulometric or electrolytic conductivity detectors are
          used in the halogen mode.
    3.4   Organochlorine pesticides  and other halogenated compounds
          constitute interferences in the determination of PCBs.  Most of
          these are separated by the method described below.  However,
          certain compounds, if present in the sample, will occur with
          the PCBs.  Included are:  Sulfur, Heptachlor, aldrin, DDE,
          technical chlordane, mirex, and to some extent, o,p'-DDT and
          p,p'-DDT.
4.  Apparatus and Materials
    4.1   Gas Chromatograph - Equipped with glass lined injection port.
    4.2   Detector Options:
          4.2.1  Electron Capture - Radioactive (tritium or nickel-63)
          4.2.2  Microcoulometric Titration
          4.2.3  Electrolytic Conductivity
    4.3   Recorder - Potentiometric strip chart (10  in.) compatible with
          the detector.
    4.4   Gas Chromatographic Column Materials:
          4.4.1  Tubing - Pyrex (180 cm  long X 4 mm  ID)
          4.4.2  Glass Wool  - Silanized
          4.4.3  Solid Support -  Gas-Chrom Q (100-120 mesh)
          4.4.4  Liquid Phases -  Expressed as weight percent  coated  on
                 solid support.
                 4.4.4.1      SE-30 or OV-1, 3%
                 4.4.4.2      OV-17, 1.5* + QF-1 or  OV-210,  1.95%

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4.5   Kuderna-Danish (K-D) Glassware
      4.5.1  Snyder Column - three-ball (macro) and two-ball  (micro)
      4.5.2  Evaporative Flasks - 500 ml
      4.5.3  Receiver Ampuls - 10 ml, graduated
      4.5.4  Ampul Stoppers
4.6   Chromatographic Column - Chromaflex (400 mm  long x  19 mm  ID)
      with coarse fritted plate on bottom and Teflon stopcock;  250-ml
      reservoir bulb at top of column with flared  out funnel  shape  at
      top of bulb - a special order (Kontes K-420540-9011).
4.7   Chromatographic Column - pyrex (approximately 400 mm  long x 20
      mm ID) with coarse fritted plate on bottom.
4.8   Micro Column Pyrex - constructed according to Figure  1.
4.9   Capillary pipets disposable (5-3/4 in.) with rubber bulb
      (Scientific Products P5205-1).
4.10  Low pressure regulator - 0 to 5 PSIG - with  low-flow  needle
      valve (see Figure 1, Matheson Model 70).
4.H  Beaker - 100 ml
4.12  Micro Syringes - 10, 25, 50 and 100 ul.
4.13  Separatory funnels - 125 ml, 1000 ml and 2000 ml with Teflon
      stopcock.
4.14  Blender - High speed, glass or stainless steel cup.
4.15  Graduated cylinders - 100 and 250 ml.
4.16  Florisil - PR Grade (60-100 mesh); purchase  activated at
      1250°F and store in the dark in glass containers with glass
      stoppers or foil-lined screw caps.  Before use, activate  each
                                  46

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COMPRESSED
AIR	
SUPPLY
                         . ^PRESSURE
                         L^GAUGE
3X1
              SHUT-OFF
                VALVE
0-5
PSIG
             REGULATOR
                                           NEEDLE
                                            VALVE
                              I cm
                      FLEXIBLE
                       TUBING
              SILICA  GEL
                  5 cm
                    I cm
                                  §  10/30
                               _  15ml
                                RESERVOIR
                                  §  10/30
                                                 r
                                  23cm  x 4.2 mm I.D.
                                  2 cm  x 2 mm I.D.
          FIGURE  I.   MICROCOLUMN SYSTEM

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          batch overnight at 130°C in foil-covered glass container.
          Determine 1 auric-acid value (See Appendix II).
    4.17  Silica gel - Davison code 950-08008-226 (60/200 mesh).
    4.18  Glass Wool - Hexane extracted.
    4.19  Centrifuge Tubes - Pvrex calibrated (15 ml).
5.  Reagents, Solvents, and Standards
    5.1   Sodium Chloride - (ACS) Saturated solution  in distilled water
          (pre-rinse NaCl with hexane).
    5.2   Sodium Hydroxide - (ACS) 10 N in distilled  water.
    5.3   Sodium Sulfate - (ACS) Granular, anhydrous  (conditioned at 400
          C for 4 hrs.).
    5.4   SuIfuric Acid - (ACS) Mix equal volumes of  cone. H^SO^ with
          distilled water.
    5.5   Diethyl Ether - Nanograde, redistilled in glass, if necessary.
          5.5.1  Must be free of peroxides as indicated by EM Quant test
                 strips.  (Test strips are available  from EM Labora-
                 tories, Inc., 500 Executive Blvd.,   Elmsford, N.Y.
                 10523).
          5.5.2  Procedures recommended for removal of peroxides are
                 provided with the test strips.
    5,6   n-Hexane - Pesticide quality (NOT MIXED HEXANES).
    5.7   Acetonitrile, Hexane, Methanol, Methylene Chloride, Petroleum
          Ether (boiling range 30-60°C) - pesticide quality, redistill in
          glass if necessary.
    5.8   Standards - Aroclors 1221, 1232, 1242, 1248, 1254, 1260, and
          1016.

                                      48

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    5.9   Anti-static Solution - STATNUL, Daystrom, Inc., Weston  Instru-
          ment Division, Newark, N.J., 95212.
6.  Calibration
    6.1   Gas chromatographic operating conditions are considered accept-
          able if the response to dicapthon is at least 50% of full scale
          when < 0.06 ng is injected for electron capture detection and <
          100 ng is injected for microcoulometric or electrolytic con-
          ductivity detection.  For all quantitative measurements, the
          detector must be operated within its linear response range  and
          the detector noise  level should be  less than 2% of full scale.
    6.2   Standards are injected frequently as a check on the stability
          of operating conditions, detector and column.  Example  chro-
          matograms are shown in Figures 3 through 8 and provide
          reference operating conditions.
7.  Quality Control
    7.1   Duplicate and spiked sample analyses are recommended as quality
          control checks.  Quality control charts (4) should be developed
          and used as a check on the  analytical system.  Quality  control
          check samples and performance evaluation samples  should be
          analyzed on a regular basis.
    7.2   Each time a set of  samples  is extracted, a method blank is
          determined on a volume of distilled water equivalent to that
          used to dilute the  sample.
8.  Samp 1e Preparat i on
    8.1   Blend the sample  if suspended matter is present and adjust  pH
                                      49

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          to near neutral (pH 6.5-7.5) with 50# sulfuric acid or  10  N
          sodium hydroxide.
    8.2   For sensitivity requirement of  1 ug/1, when using micro-
          coulometric or electrolytic conductivity methods for detection
          take 1000 ml of sample for analysis.  If interferences  pose  no
          problem, the sensitivity of the electron capture detector
          should permit as little as 100 ml of sample to be used.  Back-
          ground information on the extent and nature of interferences
          will assist the analyst in choosing the required sample size
          and preferred detector.
    8.3   Quantitatively transfer the proper aliquot into a two-liter
          separatory funnel and dilute to one liter.
9.  Extraction
    9.1   Add 60 ml of 15% methylene chloride in hexane (v:v) to  the
          sample in the separatory funnel and shake vigorously for two
          minutes.
    9.2   Allow the mixed solvent to separate from the sample, then  draw
          the water into a one-liter Erlenmeyer flask.  Pour the  organic
          layer into a 100-ml beaker and then pass it through a column
          containing 3-4 inches of anhydrous sodium sulfate, and collect
          it in a 500-ml K-D flask equipped with a 10 mi-ampul.  Return
          the water phase to the separatory funnel.  Rinse the Erlenmeyer
          flask with a second 60-ml volume of solvent; add the solvent to
          the separatory funnel and complete the extraction procedure a
          second time.  Perform a third extraction in the same manner.
                                      50

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9.3   Concentrate the extract in the K-D evaporator on  a  hot  water
      bath.
9.4   Qualitatively analyze the sample by gas chromatography  with an
      electron capture detector.  From the response obtained  decide:
      a.  If there are any organochlorine pesticides present.
      b.  If there are any PCBs present.
      c.  If there is a combination of a and b.
      d.  If elemental sulfur is present.
      e.  If the response is too complex to determine a,  b  or c.
      f.  If no response, concentrate to 1.0 ml or less,  as required,
          and repeat the analysis looking for a, b, c,  d, and e.
          Samples containing Aroclors with a low percentage of
          chlorine, e.g., 1221 and  1232, may require this concentra-
          tion in order to achieve  the detection limit  of 1 yg/1.
          Trace quantities of PCBs  are often masked by  background
          which usually occur in samples.
9.5   If condition 
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    9.8   If condition d^ exists,  separate the sulfur from the sample
          using the method outlined in 10.3 followed by the method in
          10.5.
    9.9   If condition e exists,  the following macro cleanup and separa-
          tion procedures (10.2 and 10.3) should be employed and, if
          necessary, followed by  the micro separation procedures (10.4
          and 10.5).
10.  Cleanup and Separation Procedures
    10.1   Interferences in the form of distinct peaks and/or high back-
          ground in the initial gas chromatographic analysis, as well as
          the physical characteristics of the extract (color, cloudiness,
          viscosity) and background knowledge of the sample will indicate
          whether clean-up is required.   When these interfere with
          measurement of the PCBs,  or affect column life or detector
          sensitivity, proceed as directed below.
    10.2   Acetonitrile Partition  - This procedure is used to remove fats
          and oils from the sample extracts.  It should be noted that not
          all pesticides are quantitatively recovered by this procedure.
          The analyst must be aware of this and demonstrate the effi-
          ciency of the partitioning for the compounds of interest.
          10.2.1 Quantitatively transfer the previously concentrated
                 extract to a 125-ml separatory funnel with enough hexane
                 to bring the final volume to 15 ml.  Extract the sample
                 four times by shaking vigorously for one minute with
                 30-ml portions of hexane-saturated acetonitrile.
                                      52

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      10.2.2  Combine  and  transfer  the  acetonitrile phases to a
             one-liter  separatory  funnel  and add 650 ml  of distilled
             water  and  40 ml  of saturated sodium chloride solution.
             Mix  thoroughly for 30-45  seconds.   Extract  with two
             100-ml portions  of hexane by vigorously shaking about 15
             seconds.
      10.2.3  Combine  the  hexane extracts  in a one-liter  separatory
             funnel  and wash  with  two  100-ml portions of distilled
             water.   Discard  the water layer and pour the hexane
             layer  through a  3-4 inch  anhydrous sodium sulfate column
             into a 500-ml K-D flask equipped with a 10-ml ampul.
             Rinse  the  separatory  funnel  and column with three 10-ml
             portions of  hexane.
      10.2.4  Concentrate  the  extracts  to  6-10 ml in the K-D eva-
             porator  in a hot water bath.
      10.2.5  Analyze  by gas chromatography unless a need for further
             cleanup  is indicated.
10.3  Florisil Column Adsorption Chromatography
      10.3.1  Adjust the sample extract volume to 10 ml.
      10.3.2  Place  a  charge of activated  Florisil (weight determined
             by lauric-acid value, see Appendix II) in a Chromaflex
             column.   After settling the  Florisil by tapping the
             column,  add  about one-half  inch layer of anhydrous
             granular sodium sulfate to the top.
                                  53

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10.3.3 Pre-elute the column, after cooling, with 50-60 ml of
       petroleum ether.   Discard the eluate and just prior to
       exposure of the sulfate layer to air, quantitatively
       transfer the sample extract into the column by
       decantation and subsequent petroleum ether washings.
       Adjust the elution rate to about 5 ml per minute and,
       separately, collect up to three eluates in 500-ml K-D
       flasks equipped with 10-ml ampuls (see Eluate Composi-
       tion 10.4.).  Perform the first elution with 200 ml of
       6% ethyl ether in petroleum ether, and the second
       elution with 200 ml of 15% ethyl ether in petroleum
       ether.  Perform the third elution with 200 ml of 50%
       ethyl ether - petroleum ether and the fourth elution
       with 200 ml of 100% ethyl ether.
       10.3.3.1     Eluate Composition - By using an equivalent
                    quantity of any batch of Florisil as deter-
                    mined by its lauric acid value, the pesti-
                    cides will be separated into the eluates
                    indicated as follows.
                                 6% Eluate
                Aldrin      DDT                 Pentachloro-
                BHC         Heptachlor           nitrobenzene
                Chlordane   Heptachlor Epoxide  Strobane
                ODD         Lindane             Toxaphene
                DDE         Methoxychlor        Trifluralin
                            Mirex               PCBs
                   15% Eluate             50% Eluate
                   Endosulfan I           Endosulfan II.
                   Endrin                 Captan
                   Dieldrin
                   Dichloran
                   Phthalate esters
                            54

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                      Certain thiophosphate pesticides will occur in
                      each of the above fractions as well  as the 100%
                      fraction.   For additional information regarding
                      eluate composition,  refer to the FDA Pesticide
                      Analytical  Manual (5).
      10.3.4 Concentrate the eluates to 6-10 ml in the K-D evaporator
             in a hot water bath.
      10.3.5 Analyze by gas chromatography.
10.4  Silica Gel Micro-Column Separation Procedure (6)
      10.4.1 Activation for Silica Gel
             10.4.1.1 Place about 20 gm of silica gel in a 100-ml
                      beaker.  Activate at  180°C for approximately
                      16 hours.   Transfer the silica gel to a 100-ml
                      glass-stoppered bottle.  When cool,  cover with
                      about 35 ml of 0.50% diethyl ether in benzene
                      (volume:volume).  Keep bottle well sealed.  If
                      silica gel  collects on the ground glass
                      surfaces,  wash off with the above solvent
                      before resealing.  Always maintain an excess of
                      the mixed solvent in bottle (aproximately  1/2
                      in. above silica gel).  Silica gel can be
                      effectively stored in this manner for several
                      days.
      10.4.2 Preparation of the Chromatographic Column
             10.4.2.1 Pack the lower 2 mm  ID section of the micro-
                      column with glass wool.  Permanently mark
                                  55

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         the column 120 mm above the glass wool.  Using
         a clean rubber bulb from a disposable pipet
         seal the lower end of the microcolumn.  Fill
         the microcolumn with 0.50% ether in benzene
         (v:v) to the bottom of the 10/30 joint (Figure
         1).  Using a disposable capillary pipet,
         transfer several aliquots of the silica gel
         slurry into the microcolumn.   After approxi-
         mately 1 cm of silica gel collects in the
         bottom of the microcolumn, remove the rubber
         bulb seal,  tap the column to insure that the
         silica gel  reaches the 120 + 2 mm mark.  Be
         sure that there are no air bubbles in the
         column.  Add about 10 mm of sodium sulfate to
         the top of the silica gel.  Under low humidity
         conditions, the silica gel may coat the sides
         of the column and not settle properly.  This
         can be minimized by wiping the outside of the
         column with an anti-static solution.
10.4.2.2 Deactivation of the Silica Gel
         a.   Fill the microcolumn to the base of the
             10/30 joint with the 0.50% ether-benzene
             mixture,  assemble reservoir (using spring
             clamps) and fill with approximately 15 ml
             of the  0.50% ether-benzene mixture.  Attach
             the air pressure device (using spring
                     56

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    clamps) and adjust the elation rate to
    approximately 1 ml/min. with the air
    pressure control.  Release the air pressure
    and detach reservoir just as the last of
    the solvent enters the sodium sulfate.
    Fill the column with n-hexane (not mixed
    hexanes) to the base of the 10/30 fitting.
    Evaporate all residual benzene from the
    reservoir,, assemble the reservoir section
    and fill with 5 ml of n-hexane.  Apply air
    pressure and remove the reservoir just as
    the n-hexane enters the sodium sulfate.
    The column is now ready for use.
b.  Pipet a 1.0 ml aliquot of the concentrated
    sample extract (previously reduced to a
    total volume of 2.0 ml) on to the column.
    As the last of the sample passes into the
    sodium sulfate layer, rinse down the
    internal wall of the column twice with 0.25
    ml of n-hexane.  Then assemble the upper
    section of the column.  As the  last of the
    n-hexane rinse reaches the surface of the
    sodium sulfate, add enough n-hexane (volume
    predetermined, see 10.4.3) to just elute
    all of the PCBs present in the  sample.
    Apply air pressure and adjust until the
             57

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                    flow is 1 ml/min.   Collect the desired
                    volume of eluate (predetermined,  see
                    10.4.3) in an accurately calibrated ampul.
                    As the last of the n-hexane reaches the
                    surface of the sodium sulfate, release the
                    air pressure and change the collection
                    ampul.
                c.   Fill the column with 0.50% diethyl ether in
                    benzene, again apply air pressure and
                    adjust flow to 1 ml/min.  Collect the
                    eluate until all of the organochlorine
                    pesticides of interest have been  eluted
                    (volume predetermined, see 10.4.3).
                d.   Analyze the eluates by gas chromatography.
10.4.3 Determination of Elution Volumes
       10.4.3.1  The elution volumes for the PCBs and  the
                pesticides depend upon a number of factors
                which are difficult to control.  These include
                variation in:
                a.   Mesh size of the silica gel
                b.   Adsorption properties of the silica gel
                c.   Polar contaminants present in the eluting
                    solvent
                d.   Polar materials present in the sample and
                    sample solvent
                            58

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         e.   The  dimensions  of the  microcolumns
             Therefore,  the  optimum elution  volume must
             be experimentally determined  each time a
             factor  is  changed.   To determine the
             elution  volumes,  add standard mixtures of
             Aroclors and  pesticides to the  column and
             serially collect  1-ml  elution volumes.
             Analyze  the individual eluates  by gas
             chromatography  and determine  the cut-off
             volume  for n-hexane and for ether-benzene.
             Figure  2 shows  the retention  order of the
             various  PCB components and of the pesti-
             cides.   Using this information, prepare the
             mixtures required for  calibraton of the
             microcolumn.
10.4.3.2 In determining the  volume  of hexane required to
         elute the PCBs the  sample  volume  (1 ml) and the
         volume of n-hexane  used to rinse  the column
         wall must be considered.  Thus, if  it is
         determined  that a 10.0-ml  elution volume  is
         required to elute the PCBs, the volume of
         hexane to be added  in addition to the sample
         volume but  including  the rinse volume should be
         9.5 ml.
                    59

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                                60

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            10.4.3.3 Figure 2 shows that as the  average  chlorine
                     content of a PCB mixture decreases  the  solvent
                     volume for complete elution  increases.   Quali-
                     tative determination  (9.4)  indicates which
                     Aroclors are present  and provides the basis  for
                     selection of the ideal elution  volume.   This
                     helps to minimize  the quantity  of organo-
                     chlorine pesticides which will  elute along with
                     the  low percent chlorine PCBs and  insures the
                     most efficient separations  possible for
                     accurate analysis.
            10.4.3.4 For  critical  analysis where the PCBs and pesti-
                     cides are not  separated completely, the column
                     should be accurately  calibrated according to
                     (10.4.3.1)  to  determine the percent of  material
                     of  interest  that elutes  in  each fraction.  Then
                     flush the column with an  additional 15  ml of
                     0.50% ether  in benzene  followed by 5 ml of
                     n-hexane and use this reconditioned column for
                     the  sample  separation.   Using this technique
                     one  can  accurately predict  the  amount  (%) of
                     materials  in each  micro column  fraction.
10.5  Micro Column Separation  of  Sulfur, PCBs,  and Pesticides
      10.5.1 See procedure for preparation  and  packing micro column
             in PCB analysis  section (10.4.1  and 10,4.2).
                                  61

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10.5.2 Microcolumn Calibration
       10.5.2.1 Calibrate the microcolumn for sulfur and PCB
                separation by collecting 1.0-ml fractions and
                analyzing them by gas chromatography to
                determine the following:
                1)  The fraction with the first eluting PCBs
                    (those present in 1260),
                2)  The fraction with the last eluting PCBs
                    (those present in 1221),
                3)  The elution volume for sulfur,
                4)  The elution volume for the pesticides of
                    interest in the 0.50% ether-benzene
                    fraction.
                From these data determine the following:
                1)  The eluting volume containing only sulfur
                    (Fraction I),
                2)  The eluting volume containing the last of
                    the sulfur and the early eluting PCBs
                    (Fraction II),
                3)  The eluting volume containing the remaining
                    PCBs (Fraction III),
                4)  The ether-benzene eluting volume containing
                    the pesticides of interest (Fraction IV).
10.5.3  Separation Procedure
       10.5.3.1 Carefully concentrate the 6% eluate from the
                            62

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         florisil  column to 2.0 ml in the graduated
         ampul  on  a warm water bath.
10.5.3.2 Place  1.0 ml  (50%) of the concentrate into the
         microcolumn with a 1-ml pipet.  Be careful not
         to get any sulfur crystals into the pipet.
10.5.3.3 Collect Fractions I and II in calibrated
         centrifuge tubes.  Collect Fractions III and IV
         in calibrated ground glass stoppered ampuls.
10.5.3.4 Sulfur Removal (7) - Add 1 to 2 drops of
         mercury to Fraction II stopper and place on a
         wrist-action shaker.  A black precipitate
         indicates the presence of sulfur.  After
         approximately 20 minutes the mercury may become
         entirely reacted or deactivated by the
         precipitate.   The sample should be quanti-
         tatively transferred to a clean centrifuge tube
         and additional mercury added.  When crystals
         are present in the sample, three treatments may
         be necessary to remove all the sulfur.  After
         all the sulfur has been removedfrom Fraction II
         (check using gas chromatography) combine
         Fractions II and III.  Adjust the volume to 10
         ml and analyze by gas chromatography.  Be sure
         no mercury is transferred to the combined
         Fractions II and III, since  it can react with
         certain pesticides.
                    63

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                          By combining Fractions II and III, if PCBs are
                          present,  it is possible to identify the
                          Aroclor(s)  present and a quantitative analysis
                          can be performed accordingly.  Fraction I can
                          be discarded since it only contains the bulk of
                          the sulfur.  Analyze Fractions III and IV for
                          the PCBs  and pesticides.  If DDT and its
                          homologs,  aldrin,  heptachlor, or technical
                          chlordane  are present along with the PCBs, an
                          additional  microcolumn separation can be
                          performed  which may help to further separate
                          the PCBs  from the pesticides (See 10.4).
11.  Quantitative Determination
    11.1   Measure the volume of n-hexane eluate containing the PCBs and
          inject 1 to 5/
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                Microgram/liter  =   K| \P|/{v)W	x [N ]
                A _ ng  of Standard Injected    _ ng2
                                                 mm
                                                2
                B =  of Sample Peak  Areas - (mm )
                V^  = Volume of sample injected (yl)
                V.  = Volume of Extract (vl)  from which sample
                       is injected into gas  chromatograph
                V  = Volume of water sample  extracted (ml)
                N = 2 when micro column used
                    1 when micro column not  used
                Peak Area = Peak height (mm  x Peak Width at 1/2
                   height
11.2.2 For complex  situatons,  use the calibration method
       described below (8).  Small variations in components
       between different Aroclor batches make it necessary to
       obtain samples of several specific Aroclors.   These
       reference Aroclors can  be obtained from the Southeast
       Environmental Research  Laboratory, EPA, Athens, Georgia,
       30601.  The  procedure is as follows:
       11.2.2.1 Using the OV-1 column, chromatograph a known
                quantity of each Aroclor reference standard.
                Also chromatograph a sample  of p,p'-DDE.
                Suggested concentration of each standard is 0.1
                ng/yl for the  Aroclors and 0.02 ng/ul for the
                p,p'-DDE.
                            65

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11.2.2.2 Determine the relative retention time (RRT) of
         each PCB peak in the resulting chromatograms
         using p,p'-DDE as 100.
               RT x 100
         RRT =
               RTDDE
         RRT = Relative Retention Time
         RT  = Retention time of peak of interest
         RTDDE = Retention tinie °f P»P'-DDE
         Retention time is measured as that distance in
         mm between the first appearance of the solvent
         peak and the maximum for the compound.
11.2.2.3 To calibrate the instrument for each PCB
         measure the area of each peak.
         Area = Peak height (mm) x Peak width at 1/2
         height.  Using Tables 1 through 6 obtain the
         proper mean weight factor, then determine the
                              2
         response factor ng/mm .
         ng/mm  =
(ng.)     (mean weight percent)
   1               100
             (Area)
         rig,- = ng of Aroclor Standard Injected
         Mean weight percent - obtained from Tables 1
         through 6.
11.2.2.4 Calculate the RRT value and the area for each
         PCB peak in the sample chromatogram.  Compare
         the sample chromatogram to those obtained for
         each reference Aroclor standard.  If it is
                     66

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                                 Table 1

                     Composition of Aroclor 1221 (8)
RRTa
11
14
16
19
21
28

32

37
40
Mean
Weight
Percent
31.8
19.3
10.1
2.8
20.8
5.4

1.4

1.7

Relative
Std. Dev.b
15.8
9.1
9.7
9.7
9.3
13.9

30.1

48.8

Number of
Chlorines0
1
1
2
2
2
2 85%
3 15%
2 10%
3 90%
3

Detention time relative to p,p'-DDE=100.  Measured from first appearance
 of solvent.   Overlapping peaks that are quantitated as one peak are
 bracketed.

''Standard deviation of seventeen results as a percentage of the mean of
 the results.

cFrom GC-MS data.  Peaks containing mixtures of isomers of different
 chlorine numbers are bracketed.
                                      67

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                                 Table 2

                     Composition of Aroclor 1232 (8)
RRTa
11
14
16
20
21
28

32
37
40
47
54

58
70

78
Mean
Weight
Percent
16.2
9.9
7.1
17.8

9.6

3.9
6.8
6.4
4.2
3.4

2.6
4.6

1.7
Relative .
Std. Dev.
3.4
2.5
6.8
2.4

3.4

4.7
2.5
2.7
4.1
3.4

3.7
3.1

7.5
Number of
Chlorines
1
1
2
2

2
3
3
3
3
4
3
4
4
4
5
4





40%
60*




33%
67%

90%
10%

Total                94.2
Detention time relative to p.p'-DDE^lOO.  Measured from first appearance
 of solvent.  Overlapping peaks that are quantitated as one peak are
 bracketed.

^Standard deviation of four results as a mean of the results.

cFrom GC-MS data.  Peaks containing mixtures of isomers of different
 chlorine numbers are bracketed.
                                      68

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                                 Table 3

                     Composition of Aroclor 1242 (8)
RRTa
11
16
21
28

32
37
40
47
54*
.
58
70

78
84
98
104
125

146

Mean
Weight
Percent
1.1
2.9
11.3
11.0

6.1
11.5
11.1
8.8
6.8

5.6
10.3

3.6
2.7
1.5
2.3
1,6

1.0

Relative .
Std. Dev.
35.7
4.2
3.0
5.0

4.7
5.7
6.2
4.3
2.9

3.3
2.8

4.2
9.7
9.4
16.4
20.4

19.9

Number of
Chlorines
1
2
2
2
3
3
3
3
4
3
4
4
4
5
4
5
5
5
5
6
5
6



25%
75%




33%
67%

90%
10%




85%
15%
75%
25%
Detention time relative to p,p'-DDE=100.  Measured from first appearance
 of solvent.

^Standard deviation of six results as a percentage of the mean of the
 results.


cFrom GC-MS data.  Peaks containing mixtures of isomers of different
 chlorine numbers are bracketed.
                                     69

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                                 Table 4

                     Composition of Aroclor 1248 (8)
RRTa
21
28
32
47
40

47
54

58
70

78
84
98
104

112
125

146

Mean
Weight
Percent
1.2
5.2
3.2
8.3
8.3

15.6
9.7

9.3
19.0

6.6
4.9
3.2
3.3

1.2
2.6

1.5

Relative .
Std. Dev.
23.9
3.3
3.8
3.6
3.9

1.1
6.0

5.8
1.4

2.7
2.6
3.2
3.6

6.6
5.9

10.0

Number of
Chlorines0
2
3
3
3
3
4
4
3
4
4
4
5
4
5
5
4
5
5
5
6
5
6




85*
15%

10%
90%

80tf
20%



10%
90%

90%
10%
85%
15%
 Total             103.1
Detention time relative to p,p'-DDE=100.  Measured from first appearance
 of solvent.

''Standard deviation of six results as a percentage of the mean of the.
 results.

cFrom GC-MS data.  Peaks containing mixtures of isomers of different
 chlorine numbers are bracketed.
                                      70

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                                 Table 5

                     Composition of Aroclor 1254 (8)
RRTa
47
54
58
70

84
98
104
125
(
146

160
174
203
232
Mean
Weight
Percent
6.2
2.9
1.4
13.2

17.3
7.5
13.6
15.0

10.4

1.3
8.4
1.8
1.0
Relative .
Std. Dev.
3.7
2.6
2.8
2.7

1.9
5.3
3.8
2.4

2.7

8.4
5.5
18.6
26.1
Number of
Chlorines
4
4
4
4 25%
5 75*
5
5
5
5 70%
6 80*
5 30%
6 70515
6
6
6
7
 Total              100.0
Detention time relative to p,p'-DDE=100.  Measured from first appearance
 of solvent.

bStandard deviation of six results as a percentage of the mean of the
 results.

cFrom 6C-MS data.  Peaks containing mixtures of isomers are bracketed.
                                      71

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                                 Table 6

                     Composition of Aroclor 1260 (8)
RRTa
70
84
98
104

117
125

146
160

174
203

232
244

280
332
372
448
528
Mean
Weight
Percent
2.7
4.7
3.8


3.3
12.3

14.1
4.9

12.4
9.3


9.8

11.0
4.2
4.0
.6
1.5
Relative ,
Std. Dev.
6.3
1.6
3.5


6.7
3.3

3.6
2.2

2.7
4.0


3.4

2.4
5.0
8.6
25.3
10.2
Number of
Chlorines
5
5
d
5
6
6
5
6
6
6
7
6
6
7
e
6
7
7
7
8
8
8



60%
40%

15%
85%

50%
50%
i
10%
90%

10%
90%





 Total              98.6
Detention time relative to p,p'-DDE=100.  Measured from first appearance
 of solvent.   Overlapping peaks that are quantitated as one peak are
 bracketed.
^Standard deviation of six results as a mean of the results.
cFrom SC-MS data.  Peaks containing mixtures of isomers of different
 chlorine numbers are bracketed.
Composition  determined at the center of peak 104.
Composition  determined at the center of peak 232.
                                      72

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apparent that the PCB peaks present are due to
only one Aroclor, then calculate the concen-
tration of each PCB using the following formula:
              2
ng PCB = ng/mm  x Area
                     2
Where Area = Area (mm ) of sample peak
     2
ng/mm  = Response factor for that peak
     measured.
Then add the nanograms of PCBs present in the
injection to get the total number of nanograms
of PCBs present.  Use the following formula to
calculate the concentration of PCBs in the
sample:
Micrograms/Liter =
V  = volume of water extracted (ml)
V. = volume of extract (pi)
V.. = volume of sample  injected (pi)
ng = sum of all the PCBs in nanograms for that
     Aroclor  identified
N = 2 when microcolumn used
N = 1 when microcolumn not used
The value can then be  reported as micro-
grams/liter PCBs or as the Aroclor.  For
samples containing more than one Aroclor, use
Figure 9 chromatogram  divisional flow chart to
assign a proper response factor to each peak
and also identify the  "most  likely" Aroclors
            73

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                          present.  Calculate the ng of each PCB isomer
                          present and sum them according to the
                          divisional flow chart.  Using the formula
                          above, calculate the concentration of the
                          various Aroclors present in the sample.
12.  Reporting Results
    12.1   Report results in micrograms per liter without correction for
          recovery data.  When duplicate and spiked samples are analyzed,
          all data obtained should be reported.
                                     74

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               37
                   AROCLOR 1242
                                            146
Figure  3.  Column: 3% OV-1, Carrier Gas: Nitrogen  at 60 ml/min,
          Column  Temperature: 170  C, Detector:  Electron Capture
                              75

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                 70
                              AROCLOR 1254
                        104
                             125
                                                       232
Figure 4. Column: 3% OV-1, Carrier Gas: Nitrogen  at  60  ml/min,
         Column Temperature: 170 C, Detector:  Electron  Capture.
                             76

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•\J
                                AROCLOR  1260
                               280
Figure  5. Column: 3% OV-1, Carrier Gas: Nitrogen at 60 ml/min,
         Column  Temperature:  170  C,  Detector: Electron Capture,
                               77

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                       AROCLOR 1242
I
I
I
                              1
j
3
                                    21
                                    24
               6      9      12      15      18
                      RETENTION TIME  IN MINUTES
Figure  6. Column: 1.5% OV-17  +  1.95% QF-1, Carrier Gas: Nitrogen
at 60 ml/min,  Column Temperature: 200 C, Detector: Electron  Capture.
                        78

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                                                                             AROCLOR 1254
(0
                    Figure 7.  Column:  1.5% OV-17 + 1.95%
                              Detector: Electron Capture.
 RETENTION  TIME  IN MINUTES
QF-1, Carrier Gas: Nitrogen at 60 ml/min, Column Temperature:  200 C,

-------
CO
                                              AROCLOR 1260
                                                                                                                              _L
J
54
              3
12    15
18
36
39
42
45
48
51
                                                21      24     27     30     33

                                                 RETENTION TIME IN MINUTES

Figure ft. Column: 1.5% OV-17 + 1.95% QF-1, Carrier Gas: Nitrogen at 60 ml/min,  Column Temperature: 200C, Detector:  Electron Capture

-------
                RRT of first  peak < 47?  |


              YES/             \HO
     Is  there a distinct
     peak with RRT  78?
                       RRT
      YES
/      V
YES\
     47-58?  [
NO
   Use 1242 for
 peaks! RRT 84
          Use  1242 for
         peaks-  RRT  70
    Use  1254
    for peaks
   1  RRT 104
|RRT-i70?j
           Is there  a distinct
           peak with RRT 117?
                               Use 1260  for
                                 all peaks
         YES
              NO
                    Use 1254 for  all
                    peaks! RRT 174
     Use 1260 for
     all other peaks
Figure 9. Chromatogram Division Flowchart (8).
                          81

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REFERENCES:
1.  "Method for Chlorinated Hydrocarbons in Water and Wastewater", this
    manual, p. 7.

2.  Leoni, V., "The Separation of Fifty Pesticides and Related Compounds and
    Polychlorinated Biphenyls into Four Groups by Silica Gel  Microcolumn
    Chromatography", Journal of Chromatography, 62, 63 (1971).

3.  McClure, V. E., "Precisely Deactivated Adsorbents Applied to the Separa-
    tion of Chlorinated Hydrocarbons", Journal of Chromatography. 70, 168
    (1972).

4.  "Handbook for Analytical Quality Control in Water and Wastewater
    Laboratories",  Chapter 6, Section 6.4, U.  S. Environmental Protection
    Agency, National Environmental Research Center, Analytical Quality
    Control Laboratory, Cincinnati, Ohio, 45268, 1972.

5.  "Pesticide Analytical Manual", U. S. Dept. of Health, Education and
    Welfare, Food and Drug Administration, Washington, D. C.

6.  Bellar, T. A.  and Lichtenberg, J. J., "Method for the Determination of
    Polychlorinated Biphenyls in Water and Sediment", U. S.  Environmental
    Protection Agency, National Environmental  Research Center, Analytical
    Quality Control Laboratory, Cincinnati, Ohio, 45268, 1973.

7.  Goerlitz, D.  F. and Law, L. M., "Note on Removal of Sulfur Interferences
    from Sediment Extracts for Pesticide Analysis", Bulletin of Environmental
    Contamination and Toxicology, £, 9 (1971).

8.  Webb, R. G. and McCall, A. C., "Quantitative PCB Standards for Electron
    Capture Gas Chromatography", Journal of Chromatographic  Science, 11, 366
    (1973).
                                     82

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             METHOD FOR TRIAZINE PESTICIDES IN WATER AND WASTEWATER
1.  Scope and Application
    1.1  This method covers the determination of various symmetrical triazine
         pesticides in water and wastewaters.
    1.2  The following pesticides may be determined individually by this
         method:
                    Parameter                 Storet No.
                    Ametryn                      —
                    Altraton                     —
                    Atrazine                    39033
                    Prometon                    39056
                    Prometryn                   39057
                    Propazine                   39024
                    Secbumeton                   —
                    Simazine                    39055
                    Terbuthylazine               —
2.  Summary
    2.1  The method describes an efficient sample extraction procedure
         and provides, through use of column chromatography, a method
         for the elimination of non-pesticide interferences and the
         pre-separation of pesticide mixtures.  Identification is made
         by selective gas chromatographic separation, and measurement
         is accomplished by the use of an electroytic conductivity
         detector (CCD) in the nitrogen mode or a nitrogen  specific
         thermionic detector.  Results are reported in micrograms per
         liter.
                                      83

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    2.2  This method is recommended for use only by experienced
         pesticide analysts or under the close supervision of such
         qualified persons.
3.  Interferences
    3.1  Solvents, reagents, glassware, and other sample processing
         hardware may yield discrete artifacts and/or elevated
         baselines causing misinterpretation of gas chromatograms.
         All of these materials must be demonstrated to be free from
         interferences under the conditions of the analysis.  Specific
         selection of reagents and purification of solvents by
         distillation in all-glass systems may be required.  Refer to
         Appendix I.
    3.2  The interferences in industrial effluents are high and varied
         and often pose great difficulty in obtaining accurate and
         precise measurement of triazine pesticides.  The use of a
         specific detector supported by an optional column cleanup
         procedure will eliminate many of these interferences.
    3.3  Nitrogen containing compounds other than the triazines may
         interfere.
4.  Apparatus and Materials
    4.1  Gas Chromatograph - Equipped with glass lined injection port.
    4.2  Detector Options
         4.2.1  Electrolytic Conductivity.
         4.2.2  Nitrogen specific thermionic
    4.3  Recorder - Potentiometric strip chart (10 in.) compatible
         with the detector.
                                      84

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4.4  Gas Chromatographic Column Materials:
     4.4.1  Tubing - Pyrex (180 cm long x 4 mm ID)
     4.4.2  Glass Wool - Silanized
     4.4.3  Solid Support - Gas Chrom Q (100-120 mesh)
     4.4.4  Liquid Phases - Expressed as weight percent coated on
            solid support.
            4.4.4.1  Carbowax 20M, IX
4.5  Kuderna-Danish (K-D) Glassware
     4.5.1  Snyder Column - three ball (macro) and two ball  (micro)
     4.5.2  Evaporative Flasks - 500 ml
     4.5.3  Receiver Ampuls - 10 ml, graduated
     4.5.4  Ampul Stoppers
4.6  Chromatographic Column - Chromaflex  (400 mm x 19 mm  ID) with
     coarse fritted plate and Teflon stopcock on bottom;  250 ml
     reservoir bulb at top of column with flared out funnel  shape
     at top of bulb - a special order (Kontes K-420540-9011).
4.7  Chromatographic Column - Pyrex  (approximately 400 mm long x
     20 mm ID) with coarse fritted plate  on bottom.
4.8  Micro Syringes - 10, 25, 50  and  100 ;u1.
4.9  Separatory  funnels - 2000 ml with Teflon stopcock.
4.10 Blender  - High speed, glass  or  stainless steel cup.
4.11 Graduated Cylinders  - 1000 ml.
4.12 Florisil -  PR Grade  (60-100  mesh); purchase  activated at
     1250°F and  store in  the dark  in  glass  containers with glass
     stoppers or foil-lined screw caps.   Before use,  activate  each
                                   85

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         batch overnight at 130°C in foil-covered glass container.
         Determine lauric acid value (See Appendix II).
5.  Reagents, Solvents, and Standards
    5.1  Sodium Hydroxide - (ACS) 10 N in distilled water.
    5.2  Sodium Sulfate - (ACS) Granular, anhydrous (conditioned  at
         400 C for 4 hrs.).
    5.3  Sulfuric Acid - (ACS) Mix equal volumes of cone. H2S04
         with distilled water.
    5.4  Diethyl Ether - Pesticide Quality, redistilled in glass,  if
         necessary
         5.4.1  Must be free of peroxides as indicated by EM Quant
                Test strips.  (Test strips are available from EM
                Laboratories, Inc., 500 Executive Blvd., Elmsford,
                N.Y. 10523.)
         5.4.2  Procedures recommended for removal of peroxides are
                provided with the test strips.
    5.5  Hexane, Methanol, Methylene Chloride, Petroleum Ether
         (boiling range 30-60°C) - pesticide quality, redistill in
         glass if necessary.
    5.6  Pesticide Standards - Reference grade.
6.  Calibration
    6.1  Gas chromatographic operating conditions are considered
         optimum when  an injection of ^ 20 ng of each triazine will
         yield a peak  at least 50% of full scale deflection with  the
         modified Coulson detector (1).  For all quantitative
                                       86

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         measurements, the detector must be operated within its  linear
         response range and the detector noise level should be less
         than 2% of full scale.
    »
    6.2  Inject standards frequently as a check on the stability of
         operating conditions.  A chromatogram of a mixture of several
         pesticides is shown in Figure 1 and provides reference
         operating conditions for the recommended column.
    6.3  The elution order and retention ratios of various
         organophosphorus pesticides are provided in Table 1, as a
         guide.
7.  QualityControl
    7.1  Duplicate and spiked sample analyses are recommended as
         quality control checks.  Quality control charts  (2) should be
         developed and used as a check on the analytical  system.
         Quality control check samples and performance evaluation
         samples should be analyzed on a regular basis.
    7.2  Each time a set of samples is extracted, a method blank is
         determined on a volume of distilled water equivalent to that
         used to dilute the sample.
8.  Sample Preparation
    8.1  Blend the sample if suspended matter is present  and adjust pH
         to near neutral (pH 6.5-7.5) with 50% sulfuric  acid or  ION
         sodium hydroxide.
    8.2  Quantitatively transfer a 1000 ml aliquot  into  a two-liter
         separatory funnel.
                                      87

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                            6         8        10

                         RETENTION TIME IN MINUTES
14
Figure 1. Column Packing: 1% Carbowax  20M on Gas-Chrom Q (100/120 mesh),
        Column Temperature:  155 C, Carrier Gas: Helium at 80 ml/min,
        Detector: Electrolytic  Conductivity.

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                                 TABLE 1
                   RETENTION RATIOS OF VARIOUS TRIAZINE
                     PESTICIDES RELATIVE TO ATRAZINE
Pesticide
Prometon
Atraton
Propazine
Terbuthylazirie
Secbumeton
Atrazine
Prometryne
Simazine
Ametryne
Retention Ratio
0.52
0.67
0.71
0.78
0.88
1.00
1.10
1.35
1.48
Absolute retention time of atrazine = 10.1 minutes
                                       89

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9.  Extraction
    9.1  Add 60 ml methylene chloride to the sample in the  separatory
         funnel and shake vigorously for two minutes.
    9.2  Allow the solvent to separate from the sample, draw the
         organic layer into a 100-ml beaker, then pass the  organic
         layer through a chromatographic column containing  3-4  inches
         anhydrous sodium sulfate, and collect it in a 500-ml K-D
         flask equipped with a 10 ml ampul.  Add a second 60-ml volume
         of solvent to the separatory funnel and complete the
         extraction procedure a second time.  Perform a third
         extraction in the same manner.
    9.3  Concentrate the extract to 10 ml  in a K-D evaporator on a hot
         water bath.  Disconnect the Snyder column just long enough to
         add 10 ml hexane to the K-D flask and then continue the
         concentration to about 5-6 ml.  This operation is  to displace
         methylene chloride and give a final hexane solution.   If the
         need for cleanup is indicated, continue to Florisil Column
         Cleanup (10 below).
    9.4  If further cleanup is not required, replace the Snyder column
         and flask with a micro-Snyder column and continue  the
         concentration to 0.5-1.0 ml.  Analyze this final concentrate
         by gas chromatography.
10. Florisil Column Adsorption Chromatography
    10.1 Adjust the sample extract volume  to 10 ml.
                                       90

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10.2  Place a charge of activated Florisil (weight determined by
      lauric acid value, see Appendix II) in a Chromaflex column.
      After settling the Florisil by tapping the column, add about
      one-half inch layer of anhydrous granular sodium sulfate to
      the top.
10.3  Pre-elute the column,  after cooling, with 50-60 ml of
      petroleum ether.   Discard the eluate and just prior to
      exposure of the sulfate layer to air, quantitatively
      transfer the sample extract into the column by decantation
      and subsequent petroleum ether washings.  Adjust the elution
      rate to about 5 ml per minute and, separately, collect up to
      four eluates in 500-ml K-D flasks equipped with 10-ml
      ampuls.  (See Eluate Composition, 10.4.)  Perform the first
      elution with 200 ml of 6% ethyl ether in petroleum ether,
      and the second elution with 200 ml of 15% ethyl ether in
      petroleum ether.   Perform the third elution with 200 ml of
      50% ethyl ether - petroleum ether and the fourth elution
      with 200 ml of 100% ethyl ether.
10.4  Eluate Composition - By using an equivalent quantity of any
      batch of Florisil as determined by its  lauric acid value,
      the pesticides will be separated into the eluates indicated
      as follows:
                                  91

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             15% Eluate            50% Equate         100% Eluate
           Propazine (90%)       Propazine (10%)      Atraton
           Terbuthylazine (30%)   Terbuthylazine(70%)  Secbumeton
           Atrazine (20%)        Atrazine (80%)       Prometon
                                 Ametryne
                                 Prometryne
                                 Slmazine
    10.5 Concentrate the eluates to 6-10 ml in the K-D evaporator in a
         hot water bath.  Change to the micro-Snyder column and continue
         concentration to 0.5-1.0 ml.
    10.6 Analyze by gas chromatography.
11.  Calculation of Results
    11.1 Determine the pesticide concentration by using the absolute
         calibration procedure described below or the relative
         calibration procedure described in Appendix III.
         (1)   Micrograms/liter  = (A)   (B)   (V>1
                                              )
                                           (Vs
         A = ng standard
             Standard area
         B = Sample aliquot area
         Vj = Volume of extract injected
         Vt = Volume of total extract
         Vs = Volume of water extracted (ml)
12.  Reporting Results
    12.1 Report results in micrograms per liter without correction for
         recovery data.  When duplicate and spiked samples are analyzed
         all data obtained should be reported.
                                       92

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REFERENCES:
1.   Patchett, G.  G., "Evaluation of the Electrolytic Conductivity Detector
    for Residue Analyses of Nitrogen-Containing Pesticides",  Journal  of
    Chroma tog raphic Science. 8.,  155 (1970).

2.   "Handbook for Analytical Quality Control  in Water and Wastewater
    Laboratories", Chapter 6, Section 6.4,  U.  S. Environmental  Protection
    Agency, National Environmental  Research Center,  Analytical  Quality
    Control Laboratory, Cincinnati, Ohio, 45268, 1972.   (Revised edition
    to be available soon.)
                                     93

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       METHOD FOR 0-ARYL CARBAMATE PESTICIDES IN WATER AND WASTEWATER
1.  Scope and Application
    1.1   This method covers the determination of various 0-aryl carbamate
          pesticides in water and wastewater.
    1.2   The following, pesticides may be determined individually by this
          method:
                      Parameter                Storet No.
                      Aminocarb                   —
                      Carbaryl                   39750
                      Methiocarb                  —
                      Mexacarbate                 —
                      Propoxur                    —
2.  Summary
    2.1   A measured volume of water is extracted with methylene
          chloride.   The concentrated extract is cleaned up with a
          Florisil column.  Appropriate fractions from the column are
          concentrated and portions are separated by thin-layer
          chromatography.  The carbamates are hydrolyzed on the layer and
          the hydrolysis products are reacted with 2,6-dibromoquinone
          chlorimide to yield specific colored products.  Quantitative
          measurement is achieved by visually comparing the responses of
          sample extracts to the responses of standards on the same
          thin-layer.  Identifications are confirmed by changing the pH
          of the layer and observing color changes of the reaction
          products.   Results are reported in micrograms per liter.
                                     94

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    2.2  • This method is recommended for use only by experienced
          pesticide analysts or under the close supervision of such
          qualified persons.
3.  Interferences
    3.1   Direct interferences may be encountered from phenols that may
          be present in the sample.  These materials react with the
          chromogenic reagent and yield reaction products similar to
          those of the carbamates.  In cases where phenols are suspected
          of interfering with a determination, a different solvent system
          should be used to attempt to isolate the carbamates.
    3.2   Indirect interferences may be encountered from naturally
          colored materials whose presence masks the chromogenic reaction.
4.  Apparatus and Materials
    4.1   Thin-layer plates - Glass plates (200 x 200 mm) coated with
          0.25 mm layer of  Silica Gel G (gypsum binder).
    4.2   Spotting Template
    4.3   Developing Chamber
    4.4   Sprayer - 20 ml capacity
    4.5   Kuderna-Danish (K-D) Glassware  (Kontes)
          4.5.1  Snyder Column - three ball  (K-503000)
          4.5.2  Micro-Snyder Column - two ball (K-569001)
          4.5.3  Evaporative Flasks - 500 ml  (K-570001)
          4.5.4  Receiver Ampuls -  10 ml  graduated  (K-570050)
          4.5.5  Ampul  Stoppers
                                      95

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    4.6   Chromatographic Column - Chromaflex (400 mm  long x  19 mm  ID) with
          coarse fritted plate on bottom and Teflon stopcock; 250 ml
          reservoir bulb at top of column with flared  out funnel shape at
          top of bulb - a special order (Kontes K-420540-9011).
    4.7   Chromatographic Column - Pyrex (approximately 400 mm long x 20 mm
          ID) with coarse fritted plate on bottom.
    4.8   Micro Syringes - 10, 25, 50 and 100 ;ul.
    4.9   Separatory Funnel - 2000 ml, with Teflon stopcock.
    4.10  Blender - High speed, glass or stainless steel cup.
    4.11  Florisil - PR Grade (60-80 mesh); purchase activated at 1250°F
          and store in the dark in glass containers with glass stoppers or
          foil-lined screw caps.  Before use activate  each batch overnight
          at 130°C in foil-covered glass container.  Determine lauric
          acid value (see Appendix II).
5.  Reagents, Solvents, and Standards
    5.1   Sodium Hydroxide - (ACS) 10 N in distilled water.
    5.2   Sodium Sulfate - (ACS) Granular, anhydrous.
    5.3   Sulfuric Acid - (ACS) Mix equal volumes of cone. H2S04 with
          distilled water.
    5.4   Diethyl Ether - Nanograde, redistilled  in glass, if necessary.
          5.4.1  Must be free of peroxides as indicated by EM Quant test
                 strips.  (Test strips are available from EM  Laboratories,
                 Inc., 500 Executive Blvd., Elmsford,  N.Y. 10523.)
          5.4.2  Procedures recommended for removal of peroxides are
                 provided with the test strips.
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    5.5   Hexane, Methanol, Methylene Chloride, Petroleum Ether -
          nanograde, redistill in glass if necessary.
    5.6   Pesticide Standards - Reference grade.
          5.8.1  TLC Standards - 0.100^g/ul in chloroform.
    5.7   Chromogenic agent - Dissolve 0.2 g 2,6-dibromoquinone chlorimide
          in 20 ml chloroform.
    5.8   Buffer solution - 0.1 N sodium borate in water.
6.  Calibration
    6.1   To insure even solvent travel up the  layer, the tank used for
          layer development must be thoroughly  saturated with developing
          solvent before it is used.  This may  be achieved by lining the
          inner walls of the tank with chromatography paper and introducing
          the solvent 1-2 hours before use.
    6.2   Samples and standards should be introduced to the layer using a
          syringe, micropipet or other suitable device that permits all the
          spots to be about the same size and as small as possible.  An air
          stream directed on the layer during spotting will speed solvent
          evaporation and help to maintain small spots.
    6.3   For qualitative and quantitative work, spot a series representing
          0.1-1.0 pg of a pesticide.  Tables 1  and 2 present color
          responses and R.f values for several solvent systems.
7.  Quality Control
    7.1   Duplicate and spiked sample analyses  are recommended as quality
          control checks.  Quality control charts  should  be  developed
          and used  as a check on the analytical system.  Quality control
                                     97

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                                    Table 1

         Values of 0-Aryl Carbamate Pesticides in Several Solvent Systems

Carbaryl
Aminocarb
Mexacarbate
Methiocarb
Propoxur
A
0.26
0.26
0.34
0.31
0.27
B
0.22
0.02
0.22
0.31
0.10
C
0.48
0.46
0.54
0.55
0.53
D
0.41
0.52
0.53
0.55
0.59
E
0.58
0.54
0.60
0.59
0.60
F
0.24
0.04
0.24
0.28
0.13
Solvent Systems:

A.  Hexane/acetone (3:1)
B.  Methylene chloride
C.  Benzene/acetone (4:1)
D.  Benzene/cyclohexane/diethylamine (5:2:2)
E.  Ethyl acetate
F.  Chloroform
                                     98

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                               Table 2

      Color Responses and Detection Limit for 0-Aryl Carbamates


                                    Colors:Detection
                           Before            After             Limit
                           Buffer	Buffer	(ug)
Carbaryl                   Brown            Red-Purple          0.1
Aminocarb                  Gray             Green               0.1
Mexacarbate                Gray             Green               0.1
Methiocarb                 Brown            Tan                 0.2
Propoxur                   Blue             Blue                0.1
                                99

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          check samples and performance evaluation  samples  should  be
          analyzed on a regular basis.
    7.2   Each time a set of samples  is extracted,  a method  blank  is
          determined on a volume of distilled water equivalent  to  that  used
          to dilute the sample.
8.  Sample Preparation
    8.1   Blend the sample if suspended matter  is present and adjust pH to
          near neutral (pH 6.5-7.5) with 5Q% sulfuric acid or 10 N sodium
          hydroxide.
    8.2   Quantitatively transfer a one-liter aliquot into a two-liter
          separatory funnel.
9.  Extraction
    9.1   Add 60 ml of methylene chloride to the sample  in the  separatory
          funnel and shake vigorously for two minutes.
    9.2   Allow the solvent to separate from the sample, draw the  organic
          layer into a 100-ml beaker, then pass the organic  layer  through a
          chromatographic column containing 3-4 inches anhydrous sodium
          sulfate, and collect it in a 500-ml K-D flask  equipped with a
          10-ml ampul.  Add a second 60-ml volume of solvent to the
          separatory funnel and complete the extraction  procedure  a second
          time.  Perform a third extraction in the  same  manner.
    9.3   Concentrate the extract to 10 ml in a K-D evaporator  on  a hot
          water bath.   Disconnect the Snyder column just long enough to add
          10 ml of hexane to the K-D flask and then continue the
          concentration to about 5-6 ml.  If the need for cleanup  is
          indicated, continue to Florisil Column Cleanup (10 below).

                                     100

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    9.4   If further cleanup is not required, replace the Snyder column and
          t
          flask with a micro-Snyder column and continue the concentration
          to 0.5-1.0 ml.   Analyze this final concentrate by thin-layer
          chromatography (Section 11).
10.  Florisil Column Cleanup
    10.1  Adjust the sample extract to 10 ml with hexane.
    10.2  Place a charge of activated Florisil (weight determined by
          lauric-acid value, see Appendix II) in a Chromaflex column.
          After settling the Florisil by tapping the column, add about
          one-half inch layer of anhydrous granular sodium sulfate to the
          top.
    10.3  Pre-elute the column, after cooling, with 50-60 ml of petroleum
          ether.  Discard the eluate  and just prior to exposure of the
          sulfate layer to air, quantitatively transfer the sample extract
          into the column by decantation and subsequent petroleum ether
          washings.  Adjust the elution rate to about 5 ml per minute and,
          separately collect the four eluates in 500-ml K-D flasks equipped
          with  10-ml ampuls.  Perform the first elution with 200 ml  of 6%
          ethyl ether  in petroleum ether, and the second elution with 200
          ml  of 15% ethyl ether  in petroleum ether.  Perform the third
          elution with 200 ml of 50%  ethyl  ether - petroleum ether and the
          fourth elution with 200 ml  of  100% ethyl ether.
          10.3.1 Eluate Composition  - By using an equivalent quantity of
                 any batch  of Florisil as determined by  its  lauric acid
                 value, the pesticides will  be separated  into  the eluates
                 indicated  as  follows:
                                      101

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                         50% Eluate            100% Eluate
                         Carbaryl (70%)        Carbaryl (30%)
                         Mexacarbate           Aminocarb
                                               Propoxur
    10.4 Concentrate the eluates to 6 - 10 ml in the K-D evaporator in a
         hot water bath.  Change to the micro-Snyder column and continue
         concentration to 0.5-1.0 ml.
    10.5 Analyze according to 11. below.
11.  Separation and Detection
    11.1 Carefully spot 10% of the extract on a thin layer.  On the same
         plate spot several pesticides or mixtures for screening
         purposes, or a series of 1, 2, 4, 6, 8 and 10 ^1 of specific
         standards for quantitative analysis.
    11.2 Develop the layers 10 cm in a tank saturated with solvent
         vapors.  Remove the plate and allow it to dry.
    11.3 Spray the layer rapidly and evenly with about 10-15 ml
                                                               £
         chromogenic reagent.  Heat the layer in an oven at 110 C for 15
         minutes.   The pesticides will appear with colors as indicated in
         Table 2.   Make quantitative estimates by visually comparing the
         intensity and size of the spots with those of the series of
         standards.
    11.4 Spray the layer with sodium borate reagent and observe the color
         shift of the reaction products.  The color shift must be the
         same for sample and standard for identification to be confirmed.
                                     102

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12.  Calculation of Results



    12.1  Determine the concentration of pesticide in a sample by



         comparing the response in a sample to that of a quantity Of
                                          f


         standard treated on the same layer.  Divide the result, in



         micrograms, by the fraction of extract spotted to convert to



         micrograms per liter.



13.  Reporting Results



    13.1  Report results in micrograms per liter without correction for



         recovery data.  When duplicate and spiked samples are analyzed



         all data obtained should be reported.
                                     103

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  METHOD FOR N-ARYL CARBAMATE AND UREA PESTICIDES IN WATER AND WASTEWATER
1.  Scope and Application
    1.1   This method covers the determination of various N-aryl carbamate
          and urea pesticides in water and wastewater.
    1.2   The following pesticides may be determined individually by this
          method:
                     Parameter                  Storet No.
                     Barban                        —
                     Chlorpropham                  —
                     Diuron                       39650
                     Fenuron                       —
                     Fenuron-TCA                   —
                     Linuron                       —
                     Monuron                       —
                     Monuron-TCA                   —
                     Neburon                       —
                     Propham                      39052
                     Siduron                       —
                     Swep                          —
2.  Summary
    2.1  A measured volume of water is extracted with methylene chloride
         and the concentrated extract is cleaned up with A Florisil
         column.  Appropriate fractions from the column are concentrated
         and portions are separated by thin-layer chromatography.  The
         pesticides are hydrolyzed to primary amines, which in turn are
         chemically converted to diazonium salts.  The layer is sprayed
         with 1-naphthol and the products appear as colored spots.
         Quantitative measurement is achieved by visually comparing the
                                      104

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         responses of sample extracts to the responses of standards on the
         same thin layer.   Results are reported in micrograms per liter.
    2.2  This method is recommended for use only by experienced pesticide
         analysts or under the close supervision of such qualified persons.
3.  Interferences
    3.1  Direct interferences may be encountered from aromatic amines that
         may be present in the sample.  These materials react with the
         chromogenic reagent and yield reaction products similar to those
         of the pesticides.  In cases where amines are suspected of
         interfering with a determination, a different solvent system
         should be used to attempt to isolate the pesticides on the layer.
    3.2  Indirect interferences may be encountered from naturally colored
         materials whose presence masks the chromogenic reaction.
4.  Apparatus and Materials
    4.1  Thin-layer plates - Glass plates (200 x 200 mm) coated with 0.25
         mm layer of Silica Gel G (gypsum binder).
    4.2  Spotting Template
    4.3  Developing Chamber
    4.4  Sprayer - 20 ml capacity
    4.5  Kuderna-Danish (K-D) Glassware (Kontes)
         4.5.1  Snyder Column - three ball (K-503000)
         4.5.2  Micro-Snyder Column - two ball (K-569001)
         4.5.3  Evaporative Flasks - 500 ml (K-570001)
         4.5.4  Receiver Ampuls - 10 ml graduated (K-570050)
         4.5.5  Ampul Stoppers
                                      105

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    4.6  Chromatographic Column - Chromaflex (400 mm  long x  19 mm  ID) with
         coarse fritted plate on bottom and Teflon stopcock; 250 ml
         reservoir bulb at top of column with flared  out funnel shape at
         top of bulb - a special order (Kontes K-420540-9011).
    4.7  Chromatographic Column - Pyrex (approximately 400 mm long x 20 mm
         ID) with coarse fritted plate on bottom.
    4.8  Micro Syringes - 10, 25, 50 and 100 jjl.
    4.9  Separatory Funnel - 2000 ml, with Teflon stopcock.
    4.10 Blender - High speed, glass or stainless steel cup.
    4.11 Florisil - PR Grade (60-80 mesh); purchase activated at 1250°F
         and store in the dark in glass containers with glass stoppers or
         foil-lined screw caps.  Before use activate  each batch overnight
         at 130°C in foil-covered glass container.  Determine lauric acid
         value (see Appendix II).
5.  Reagents, Solvents, and Standards
    5.1  Sodium Chloride - (ACS) Saturated solution in distilled water
         (pre-rinse NaCl with hexane).
    5.2  Sodium Hydroxide - (ACS) 10 N in distilled water.
    5.3  Sodium Sulfate - (ACS) Granular, anhydrous (conditioned at 400 C
         for 4 hrs.).
    5.4  Sulfuric Acid - (ACS) Mix equal volumes of cone. H^SO* with
         distilled water.
    5.5  Diethyl Ether - Nanograde, redistilled in glass, if necessary.
         5.5.1  Must be free of peroxides as indicated by EM Quant test
                strips.  (Test strips are available from EM Laboratories,
                Inc., 500 Executive Blvd., Elmsford,   N.Y. 10523.)
                                      106

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         5.5.'2  Procedures recommended for removal of peroxides are
                provided with the test strips.
    5.6  Hexane, Methanol, Methylene Chloride, Petroleum Ether - nanograde,
         redistill in glass if necessary.
    5.7  Pesticide Standards - Reference grade.
         5.9.1  TLC Standards - O.lOOjug/jul in chloroform.
    5.8  Nitrous acid - prepare just before use by mixing 1 g NaNC^ with
         20 ml 0.2 N HC1.
    5.9  Chromogenic agent - dissolve 1.0 g 1-Naphthol in 20 ml ethanol.
         Prepare fresh daily.
6.  Calibration
    6.1  To insure even solvent travel up the  layer, the tank used for
         layer development must be thoroughly  saturated with developing
         solvent before  it is used.  This may  be  achieved by lining the
         inner walls of the tank with chromatography paper and introducing
         the solvent 1-2 hours before use.
    6.2  Samples and standards should be introduced to the layer using a
         syringe, micropipet or other suitable device that permits all the
         spots to be about the same size and as small as possible.  An air
         stream directed on the layer during spotting will speed solvent
         evaporation and help to maintain small spots.
    6.3  For qualitative and quantitative work, spot a series representing
         0.1-l.Ojjg of a pesticide.  Tables 1  and 2 present color responses
         and R~ values for. several solvent systems.
                                      107

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                                    TABLE  1

               Rf VALUES OF N-ARYL  CARBAMATE AND  UREA  PESTICIDES
                           IN SEVERAL SOLVENT  SYSTEMS
Carbamates
Propham
Chloropropham
Barban
Swep
Urea
Fenuron
Fenuron-TCA
Monuron
Monuron-TCA
Diuron
Linuron
Neburon
Siduron
A
0.49
0.57
0.61
0.48

0.03
0.03
0.04
0.04
0.05
0.40
0.21
0.02
B
0.54
0.60
0.59
0.44

0.04
0.04
0.05
0.06
0.09
0.43
0.28
0.07
C
0.73
0.73
0.72
0.70

0.38
0.36
0.37
0.34
0.38
0.62
0.64
0.68
D
0.48
0.49
0.41
0.41

0.22
0.22
0.24
0.24
0.28
0.39
0.41
0.39
E
0.36
0.37
0.28
0.28

0.10
0.10
0.10
0.10
a. 13
0.24
0.26
0.25
F
0.68
0.70
0.70
0.67

0.41
0.41
0.47
0.46
0.54
0.66
0.68
0.62
G
0.69
0.73
0.74
0.66

0.30
0.30
0.34
0.34
0.44
0.64
0.65
0.55
Solvent Systems:

A.  Methylene chloride
B.  Chloroform
C.  Ethyl Acetate
D.  Hexane/acetone (2:1)
E.  Hexane/acetone (4:1)
F.  Chloroform/acetonitrile (2:1)
6.  Chloroform/acetonitrile (5:1)
                                     108

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                           TABLE 2

COLOR RESPONSES AND DETECTION LIMIT FOR THE N-ARYL CARBAMATES
                          AND UREAS
Carbamates
Propham
Chlorpropham
Bar ban
Swep
Ureas
Fenuron
Fenuron-TCA
Monuron
Monuron-TCA
Diuron
Linuron
Neburon
Siduron
Color
Red-purple
Purple
Purple
Blue-purple

Red-purple
Red-purple
Pink -orange
Pink-orange
Blue-purple
Blue-purple
Blue-purple
Red-purple
Detection Limit (ug)
0.2
0.1
0.05
0.2

0.05
0.1
0.05
0.1
0.1
0.1
0.1
0.05
                              109

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7-  Quality Control
    7.1  Duplicate and spiked sample analyses are recommended as quality
         control checks.   Quality control charts (1) should be developed
         and used as a check on the analytical system.  Quality control
         check samples and performance evaluation samples should be
         analyzed on a regular basis.
    7.2  Each time a set of samples is extracted, a method blank is
         determined on a volume of distilled water equivalent to that used
         to dilute the sample.
8.  Sample Preparation
    8.1  Blend the sample if suspended matter is present and adjust pH to
         near neutral (pH 6.5-7.5) with 50% sulfuric acid or 10 N sodium
         hydroxide.
    8.2  Quantitatively transfer a one-liter aliquot into a two-liter
         separatory funnel.
9.  Extraction
    9.1  Add 60 ml of methylene chloride to the sample  in the separatory
         funnel and shake vigorously for two minutes.
    9.2  Allow the solvent to separate from the sample, draw the organic
         layer into a 100-ml beaker, then pass the organic  layer through a
         chromatographic column containing 3-4 inches anhydrous sodium
         sulfate, and collect it in a 500-ml K-D flask  equipped with a
         10-ml ampul.  Add a second 60-ml volume of solvent to the
         separatory funnel and complete the extraction  procedure a second
         time.  Perform a third extraction in the same  manner.
                                      110

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    9.3   Concentrate the extract to 10 ml in a K-D evaporator on a hot
         water bath.  Disconnect the Snyder column just long enough to add
         10-ml hexane to the K-D flask and then continue the concentration
         to about 5-6 ml.   If the need for cleanup is indicated, continue
         to Florisil Column Cleanup (10 below).
    9.4   If further cleanup is not required, replace the Snyder column and
         flask with a micro-Snyder column and continue the concentration to
         0.5-1.0 ml.  Analyze this final concentrate by thin-layer
         chromatography (Section 11).
10.  Florisil Column Cleanup
    10.1 Adjust the sample extract to 10 ml with hexane.
    10.2 Place a charge of activated Florisil (weight determined by lauric
         acid value, see Appendix II) in a Chromaflex column.  After
         settling the Florisil by tapping the column, add about one-half
         inch layer of anhydrous granular sodium sulfate to the top.
    10.3 Pre-elute the column, after cooling, with 50-60 ml of petroleum
         ether.  Discard the eluate and just prior to exposure of the
         sulfate layer to air, quantitatively transfer the sample extract
         into the column by decantation and subsequent petroleum ether
         washings.  Adjust the elution rate to about 5 ml per minute and,
         separately, collect up to four eluates in 500-ml K-D flasks
         equipped with 10-ml ampuls.  (See Eluate Composition,  10.3.1.)
         Perform the first elution with 200 ml of 6% ethyl ether in
         petroleum ether, and the second elution with 200 ml of 15% ethyl
         ether in petroleum ether.  Perform the third elution with 200 ml
                                      111

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         of 50% ethyl ether - petroleum ether and the fourth elution with
         200 ml of 100% ethyl ether.
         10.3.1 Eluate Composition - By using an equivalent quantity of any
                batch of Florisil as determined by its lauric acid value,
                the pesticides will be separated into the eluates indicated
                below:
                        15% Eluate          50% Eluate        100% Eluate
                        Chlorpropham        Barban (5%)       Neburon (92%)
                        Propham             Linuron           Diuron
                        Barban (95%)        Neburon (8%)      Monuron
                                                              Siduron
                CAUTION:  Fenuron and Fenuron-TCA are not recovered from
                the Florisil column.
    10.4  Concentrate the eluates to 6-10 ml in the K-D evaporator in a hot
         water bath.  Change to the micro-Snyder column and continue
         concentration to 0.5-1.0 ml.
    10.5  Analyze according to 11. below.
11.  Separation and Detection
    11.1  Carefully spot 10% of the extract on a thin layer.  On the same
         plate spot several pesticides or mixtures for screening purposes,
         or a series of 1, 2, 4, 6, 8 and 10 ;jl of specific standards for
         quantitative analysis.
    11.2  Develop the layers 10 cm in a tank saturated with solvent vapors.
         Remove the plate and allow it to dry.
    11.3  Spray the layer rapidly and evenly with about 10-15 ml sulfuric
         acid solution.  Heat the layer in an oven at 110°C for 15
         minutes.
                                      112

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    11.4 When the layer is cool,  spray it with nitrous acid reagent and
         allow it to dry.   Spray the layer with 1-naphthol reagent and
         allow it to dry again.   The pesticides will appear as purple spots
         (see Table 2).  Identifications are made by comparison of colors
         and Rf values.  Quantitative estimates are made by visually
         comparing the intensity and size of the spots with those of the
         series of standard.
12.  Calculation of Results
    12.1 Determine the concentration of pesticide in a sample by comparing
         the response in a sample to that of a quantity of standard treated
         on the same layer.  Divide the result, in micrograms, by the
         fraction of extract spotted to convert to micrograms per liter.
13.  Reporting Results
    13.1 Report results in micrograms per liter without correction for
         recovery data.  When duplicate and spiked samples are analyzed all
         data obtained should be reported.
                                      113

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REFERENCES:
1.  "Handbook for Analytical  Quality Control  in Water and Wastewater
    Laboratories", Chapter 6, Section 6.4,   U.  S.  Environmental  Protection
    Agency, National  Environmental  Research Center,  Analytical Quality
    Control Laboratory,  Cincinnati, Ohio,  45268, 1972.
                                     114

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     METHOD FOR CHLOROPHENOXY ACID PESTICIDES IN WATER AND WASTEWATERS
1.   Scope and Application
    1.1   This method covers the determination of various chlorinated
          phenoxy acid pesticides in water and wastewater.
    1.2   The following pesticides may be determined individually by this
          method:
                 Parameter                       Storet No.
                2,4-D
                Dicamba                             —
                Silvex                             39760
                2,4,5-T
    1.3   Since these compounds may occur in water in various forms
          (i.e., acid, salt, ester, etc.) a hydrolysis step is included
          to permit the determination of the active part of the herbicide.
2.   Summary
    2.1   Chlorinated phenoxy acids and their esters are extracted from
          the acidified water sample with ethyl ether.  The esters are
          hydrolyzed to acids and extraneous organic material is removed
          by a solvent wash.  The acids are converted to methyl esters
          which are extracted from the aqueous phase.  The extract is
          cleaned by passing it through a micro-adsorption column.
          Identification of the esters is made by selective gas
          chromatographic separations and may be corroborated through the
          use of two or more unlike columns.  Detection and measurement
          is accomplished by electron capture, microcoulometric or
                                      115

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          electrolytic conductivity gas chromatography (1).  Results are
          reported in micrograms per liter.
    2.2   This method is recommended for use only by experienced
          pesticide analysts or under the close supervision of such
          qualified persons.
3.   Interferences
    3.1   Solvents, reagents, glassware, and other sample processing
          hardware may yield discrete artifacts and/or elevated baselines
          causing misinterpretation of gas chromatograms.  All of these
          materials must be demonstrated to be free from interference
          under the conditions of the analysis.  Specific selection of
          reagents and purification of solvents by distillation in
          all-glass systems may be required.  Refer to Appendix I.
    3.2   The interferences in industrial effluents are high and varied
          and often pose great difficulty in obtaining accurate and
          precise measurement of chlorinated phenoxy acid herbicides.
          Sample clean-up procedures are generally required and may
          result in loss of certain of these herbicides.  It is not
          possible to describe procedures for overcoming all of the
          interferences that may be encountered in industrial effluents.
    3.3   Organic acids, especially chlorinated acids, cause the most
          direct interference with the determination.  Phenols including
          chlorophenols will also interfere with this procedure.
    3.4   Alkaline hydrolysis and subsequent extraction eliminates many
          of the predominant chlorinated insecticides which might
          otherwise interfere with the test.
                                     116

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    3.5   The herbicides, being strong organic acids, react readily with
          alkaline substances and may be lost during analysis.  Glassware
          and glass wool should be acid-rinsed and sodium sulfate should
          be acidified with sulfuric acid to avoid this possibility.
4.  Apparatus and Materials
    4.1   Gas Chromatograph - Equipped with glass lined injection port.
    4.2   Detector Options:
          4.2.1  Electron Capture - Radioactive  (tritium or nickel-63)
          4.2.2  Microcoulometric Titration
          4.2.3  Electrolytic Conductivity
    4.3   Recorder - Potentiometric strip chart  (10  in.) compatible with
          the detector.
    4.4   Gas Chromatographic Column Materials:
          4.4.1  Tubing  - Pyrex (180 cm  long X 4 mm  ID)
          4.4.2  Glass Wool - Silanized
          4.4.3  Solid Support - Gas-Chrom-Q (100-120 mesh)
          4.4.4  Liquid  Phases - Expressed  as weight percent  coated on
                    solid support.
                  4.4.4.1  OV-210, 5%
                  4.4.4  2  OV-17,  1.5% plus QF-1 or  OV-210,  1.95%
    4.5   Kuderna-Danish (K-D) Glassware
          4.5.1   Snyder Column -  three  ball (macro) and  two  ball
                  (micro)
          4.5.2  Evaporative  Flasks  - 250 ml
                                      117

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          4.5.3  Receiver Ampuls - 10 ml, graduated
          4.5.4  Ampul Stoppers
    4.6   Blender - High speed, glass or stainless steel cup.
    4.7   Graduated cylinders - 100 and 250 ml.
    4.8   Erlenmeyer flasks - 125 ml, 250 ml ground glass * 24/40
    4.9   Microsyringes - 10, 25, 50 and 100  1.
    4.10  Pipets - Pasteur, glass disposable (140 mm long X 5 mm ID).
    4.11  Separatory Funnels - 60 ml and 2000 ml with Teflon stopcock.
    4.12  Glass wool - Filtering grade, acid washed.
    4.13  Diazald Kit - Recommended for the generation of diazomethane
          (available from Aldrich Chemical Co., Cat. #210,025-2).
5.  Reagents, Solvents and Standards
    5.1   Boron Trifluoride-Methanol-esterification-reagent, 14 percent
          boron trifluoride by weight.
    5.2   N-methyl-N-nitroso-p-toluenesulfonamide (Diazald) - High
          purity, melting point range 60-62°C.  Precursor for the
          generation of diazomethane (see Appendix IV).
    5.3   Potassium Hydroxide Solution - A 37 percent aqueous solution
          prepared from reagent grade potassium hydroxide pellets and
          reagent water.
    5.4   Sodium Chloride - (ACS) Saturated solution (pre-rinse NaCl with
          hexane) in distilled water.
    5.5   Sodium Hydroxide - (ACS) 10 N in distilled water.
                                      118

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5.6   Sodium Sulfate, Acidified - (ACS) granular sodium sulfate,
      treated as follows:  Add 0.1 ml of cone, sulfuric acid to lOOg
      of sodium sulfate slurrled with enough ethyl ether to just
      cover the solid.  Remove the ether with the vacuum.  Mix  1 g of
      the resulting solid with 5 ml of reagent water and ensure the
      mixture to have a pH below 4.  Store at 130CC.
5.7   Sulfuric add - (ACS) concentrated, Sp. Gr. 1.84.
5.8   Flor1s1l - PR grade (60-100 mesh) purchased activated at  1250°F
      and stored at 130°C.
5.9   Carbltol (dlethylene glycol monoethyl ether).
5.10  Dlethyl Ether - Nanograde, redistilled  1n glass,  1f necessary.
      5.1,0.1 Must be free of peroxides as Indicated by  EM Quant test
             strips.  (Test strips are available from EM
             Laboratories, Inc., 500 Executive Blvd., Elmsford, N.Y.
             10523.)
      5.10.2 Procedures recommended for removal of peroxides are
             provided with the test strips.
5.11  Benzene Hexane  - Nanograde, redistilled 1n glass,  if  necessary.
5.12  Pesticide Standards  - Adds and  Methyl  Esters, reference  grade.
      5.12.1 Stock;  standard solutions  - Dissolve  100 mg of  each
             herbicide in  60 ml  ethyl  ether;  then make  to  100 ml with
             redistilled  hexane.  Solution contains  1 mg/ml.
      5.12.2 Working  standard  -  Pipet  1.0 ml  of each stock  solution
              Into  a single 100 ml volumetric  flask.  Make  to  volume
             with  a mixture of ethyl  ether and  hexane  (1:1).
              Solution contains  10 /ig/ml  of each  standard.
                                   119

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          5.12.3 Standard for Chromatography (Diazomethane Procedure) -
                 Pipet 1.0 ml of the working standard into a glass
                 stoppered test tube and evaporate the solvent using a
                 steam bath.  Add 2 ml diazomethane to the residue.  Let
                 stand 10 minutes with occasional shaking, then allow the
                 solvent to evaporate spontaneously.  Dissolve the
                 residue in 200 ^il of hexane for gas chromatography.
          5.12.4 Standard for Chromatgraphy (Boron Trifluoride Proce-
                 dure) - Pipet 1.0 ml of the working standard into a
                 glass stoppered test tube.  Add 0.5 ml of benzene and
                 evaporate to 0.4 ml using a two-ball Snyder microcolumn
                 and a steam bath.  Proceed as in 11.3.1.  Esters are
                 then ready for gas chromatography.
6.  Calibration
    6.1   Gas chromatographic operating conditions are considered
          acceptable if the response to dicapthon is at least 50% of full
          scale when < 0.06 ng is injected for electron capture detection
          and < 100 ng is injected for microcoulometric or electrolytic
          conductivity detection.  For all quantitative measurements, the
          detector must be operated within its linear response range and
          the detector noise level should be less than 2% of full scale.
    6.2   Standards, prepared from methyl esters of phenoxy acid
          herbicides calculated as the acid equivalent, are injected
          frequently as a check on the stability of operating
          conditions.  Gas chromatograms of several chlorophenoxys are
          shown in Figure 1.

                                      120

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    6        4
     RETENTION
TIME
2
IN
      0
MINUTES
Fig. I Column: 1.5% 0V -17 + 1.95% QF- I,
Carrier Gas : Argon (5%) / Methane: 70ml/min.,
Column Temp. 185 C, Detector: Electron Capture .
                           121

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    6.3   The elution order and retention ratios of methyl  esters  of
          chlorinated phenoxy acid herbicides are provided  in  Table  1,  as
          a guide.
7.  Quality Control
    7.1   Duplicate and spiked sample analyses are recommended as  quality
          control checks.  Quality control charts (2) should be developed
          and used as a check on the analytical system.  Quality control
          check samples and performance evaluation samples  should  be
          analyzed on a regular basis.
    7.2   Each time a set of samples is extracted, a method blank  is
          determined on a volume of distilled water equivalent to  that
          used to dilute the sample.
8.  Sample Preparation
    8.1   The sample size taken for analysis is dependent on the type of
          sample and the sensitivity required for the purpose  at hand.
          Background information on the pesticide levels previously
          detected at a given sampling site will assist in  determining
          the sample size required, as well as the final volume to which
          the extract needs to be concentrated,  A 1-liter  sample  is
          usually taken for drinking water and ambient water analysis to
          provide a detection limit of 0.050 to O.lOOjug/1.  One-hundred
          milliliters is usually adequate to provide a detection limit  of
          1 >jg/l for industrial effluents.
                                      122

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                        Table 1

 RETENTION RATIOS FOR METHYL ESTERS OF SOME CHLORINATED
       PHENOXY ACID HERBICIDES RELATIVE TO 2,4-D
Liquid Phase1

Column Temp.
Argon /Methane
Carrier Flow
Herbicide
dicamba
2,4-D
sllvex
2,4, 5-T
2,4-D
(minutes absolute)
1.5% OV-17
1.95% OF-12
185°C
70 ml/min
RR
0.60
1.00
1.34
1.72
2.00

5% OV-210
185°C
70 ml/min
RR
0.61
1.00
1.22
1.51
1.62
     columns glass, 180 cm x 4 mm ID, solid support
 Gas Chrom Q (100/120 mesh)

2OV-210 may be substituted
                             123

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    8.2   Quantitatively transfer the proper aliquot of sample from  the
          sample container into a two-liter separatory funnel.   If less
          than 800 ml is analyzed, dilute to one  liter with  interference
          free distilled water.
9.  Extraction
    9.1   Add 150 ml of ether to the sample in the separatory funnel and
          shake vigorously for one minute.
    9.2   Allow the contents to separate for at least ten minutes.   After
          the layers have separated, drain the water phase into  a 1-liter
          Erlenmeyer flask.  Then collect the extract in a 250-ml
          ground-glass Erlenmeyer flask containing 2 ml of 37 percent
          aqueous potassium hydroxide.
    9.3   Extract the sample two more times using 50 ml of ether each
          time, and combine the extracts in the Erlenmeyer flask.  (Rinse
          the 1-liter flask with each additional  aliquot of  extracting
          solvent.)
10.  Hydrolysis
    10.1  Add 15 ml of distilled water and a small boiling stone to  the
          flask containing the ether extract, and fit the flask with a
          3-ball Snyder column.  Evaporate the ether on a steam bath and
          continue heating for a total of 60 minutes.
    10.2  Transfer the concentrate to a 60-ml separatory funnel.  Extract
          the basic solution two times with 20 ml of ether and discard
          the ether layers.  The herbicides remain in the aqueous phase.
                                      124

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    10.3   Acidify the contents of the separatory funnel by adding 2 ml of
          cold (4°C)  25  percent sulfuric acid (5.9).   Extract the
          herbicides  once with 20 ml  of ether and twice with 10 ml of
          ether.   Collect the extracts in a 125-ml Frlenmeyer flask
          containing  about 0.5 g of acidified anhydrous sodium sulfate
          (5.8).   Allow  the extract to remain in contact the the sodium
          sulfate for approximately two hours.
11.  Esterification (3.4)
    11.1   Transfer the ether extract, through a funnel plugged with glass
          wool,  into  a Kuderna-Danish flask equipped with a 10-ml
          graduated ampul.  Use liberal washings of ether.  Using a glass
          rod, crush  any caked sodium sulfate during the transfer.
          11.1.1  If esterification is to be done with diazomethane,
                 evaporate to approximately 4 ml on a steam bath (do not
                 immerse the ampul in water) and proceed as directed  in
                 Section 11.2.  Prepare diazomethane as directed in
                 Appendix IV.
          11.1.2  If esterification is to be done with boron trifluoride,
                 add 0.5 ml benzene and evaporate to about 5 ml on a
                 steam bath.  Remove the ampul from the flask  and further
                 concentrate the extract to 0.4 ml using a two-ball
                 Snyder microcolumn and proceed as in  11.3.
    11.2 Diazomethane Esterification
          11.2.1  Disconnect the ampul from the K-D flask and place  in  a
                 hood, away from steam bath.  Adjust volume to  4 ml with
                                      125

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             ether,  add 2 ml diazomethane, and let stand 10 minutes
             with occasional swirling.
      11.2.2 Rinse inside wall of ampul with several hundred
             micro liters of ethyl ether.  Take sample to
             approximately 2 ml to remove excess diazomethane by
             allowing solvent to evaporate spontaneously (room
             temperature.
      11.2.3 Dissolve residue in.5 ml of hexane.  Analyze by gas
             chromatography.
      11.2.4 If further clean-up of the sample is required, proceed
             as in 11.3.4 substituting hexane for benzene.
11.3  Boron Trifluoride Ester ification
      11.3.1 After the benzene solution in the ampul has cooled, add
             0.5 ml  of borontrifluoride-methanol reagent.  Use the
             two-ball Snyder microcolumn as an air-cooled condenser
             and hold the contents of the ampul at 50°C for 30
             minutes on the steam bath.
      11.3.2 Cool and add about 4.5 ml of a neutral 5 percent aqueous
             sodium sulfate solution so that the benzene-water
             interface is in +he neck of the Kuderna-Danish ampul.
             Seal the flask with a ground glass stopper and shake
             vigorously for about one minute.  Allow to stand for
             three minutes for phase separation.
      11.3.4 Pipet the solvent layer from the ampul to the top of a
             small column prepared by plugging a disposable Pasteur
                                 126

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                 pipet with glass  wool  and packing with 2.0 cm of sodium
                 sulfate over  1.5  cm of Florisil  adsorbent.   Collect the
                 eluate in a graduated  ampul.   Complete the transfer by
                 repeatedly rinsing the ampul  with small quantities of
                 benzene and passing the rinses through the column until
                 a final volume of 5.0  ml  of eluate is obtained.   Analyze
                 by gas chromatography.
12.  Calculation of Results
    12.1  Determine the methyl ester concentration by using the absolute
          calibration procedure described below or the relative calibra-
          tion procedure described in Appendix III.
         (1)       Micrograms/liter = lALJll
                                       (V-j)  (Vs)
                  A = ng standard
                      standard area
                  B = Sample aliquot area
                  V]= Volume of extract injected
                  Vt= Volume of total extract QJ!)
                  Vs= Volume of water extracted (ml)
    12.2  Molecular weights for the calculation of methyl esters as the
          acid equivalents.
         2,4-D                 222.0      Dicamba                 221.0
         2,4-D methyl ester    236.0      Dicamba methyl ester    236.1
         Silvex                269.5      2,4,5-T                 255.5
         Silvex methyl ester   283.5      2,4,5-T methyl ester    269.5
                                      127

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13.  Reporting Results
    13.1   Report results in micrograms per liter as the acid equivalent
          without correction for recovery data.  When duplicate and
          spiked samples are analyzed all data obtained should be
          reported.
                                      128

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REFERENCES:
1.   Goerlitz, D.  6., and Lamar,  W.  L.,  "Determination of Phenoxy and
    Herbicides in Water by Electron-Capture and Microcoulometric Gas
    Chromatography", U.  S. Geol.  Survey Water-Supply Paper 1817-C (1967).

2.   "Handbook for Analytical  Quality Control  in Water and Wastewater
    Laboratories" (1972), U.  S.  Environmental  Protection Agency, National
    Environmental Research Center,  Analytical  Quality Control  Laboratory,
    Cincinnati, Ohio, 45268.

3.   Metcalf, L. D. and Schmitz,  A.  A.,  "The Rapid Preparation  of Fatty Acid
    Esters for Gas Chromatographic  Analysis",  Analytical Chemistry, 33,
    363 (1961).

4.   Schlenk, H. and Gellerman, J. L., "Esterification of Fatty Acids with
    Diazomethane on a Small Scale", Analytical Chemistry. 32,  1412 (1960).
                                     129

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  METHOD FOR VOLATILE CHLORINATED ORGANIC COMPOUNDS IN WATER AND WASTEWATERS

1.   Scope and Application

    1.1  This method covers the determination of various chlorinated organic

         compounds in water and wastewater.

    1.2  The following chlorinated organic compounds may be determined

         individually by this method:

                   Parameter                 Storet No.
                   Benzylchloride               —
                   Carbon tetrachloride        32102
                   Chlorobenzene               34301
                   Chloroform                  32106
                   Epichlorohydrin              —
                   Methylene Chloride          34423
                   1,1,2,2-Tetrachloroethane    —
                   Tetrachloroethylene         34475
                   1,2,4-Trichlorobenzene       —
                   1,1,2-Trichloroethane        —

2.   Summary

    2.1  If the sample is turbid, it is initially centrifuged or filtered

         through a fiber glass filter in order to remove suspended matter.

         A three to ten microliter aliquot of the sample is injected into

         the gas chromatograph equipped with a halogen specific detector.

         The resulting chromatogram is used to identify and quantitate

         specific components in the sample.  Results are reported in

         micrograms per liter.  Confirmation of qualitative identifications

         are made using two or more dissimilar columns.
                                     130

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3.  Interferences
    3,1  The use of a halogen specific detector minimizes the possibility of
         interference from compounds not containing chlorine, bromine, or
         iodine.  Compounds containing bromine or iodine will interfere with
         the determination of organochlorine compounds.  The use of two
         dissimilar chromatographic columns helps to eliminate this
         interference and, in addition, this procedure helps to verify all
         qualitative identifications.  When concentrations are sufficiently
         high, unequivocal identifications can be made using infrared or
         mass spectroscopy.  Though non-specific, the flame  ionization
         detector may be used for known systems where interferences are not
         a problem.
    3.2  Ghosting is usually attributed to the history of the
         chromatographic system.  Each time a sample is  injected, small
         amounts of various compounds  are adsorbed on active sites  in the
         inlet and at the head of the  column.  Subsequent injections of
         water tend to steam clean these sites resulting in
         non-representative peaks or displacement of the baseline.  This
         phenomenon normally occurs when an analysis of  a series of highly
         concentrated samples is followed by a low level analysis.  The
         system  should be checked for  ghost peaks prior  to each quantitative
         analysis by injecting distilled water in a manner identical  to the
         sample  analysis (1).   If excessive ghosting occurs, the following
         corrective measures should be applied,  as required, in the order
         listed:
         1)  Multiple flushes with distilled water
                                       131

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        2)   Clean or replace the glass injector liner
        3)   Replace the chromatographic column.
4.  Apparatus and Materials
   4.1  Gas Chromatograph - Equipped with programmed oven temperature
        controls and glass-lined injection port.  The oven should be
        equipped with a column exit port and heated transfer line for
        convenient attachment to the halogen specific detector.
   4.2  Detector Options:
        4.2.1  Microcoulometric Titration
        4.2.2  Electrolytic Conductivity
        4.2.3  Flame lonization
   4.3  Recorder - Potentiometric strip chart recorder (10 in) compatible
        with the detector.
   4.4  Syringes - 1 ^il, 10>jl, and 50 jul.
   4.5  BOD type bottle or 40 ml screw cap vials sealed with Teflon faced
        silicone septa.
   4.6  Volumetric Flasks - 500 ml, 1000 ml.
   4.7  Syringe - Hypodermic Lur-lock type (30 ml).
   4.8  Filter glass fiber filter - Type A (13 mm).
   4.9  Filter holder - Swinny-type hypodermic adapter (13 mm).
   4.10 Glass stoppered ampuls - 10 ml
   4.11 Chromatographic columns
        4.11.1    Moderately-Polar Column - 23 ft x 0.1 in ID x 0.125 in 00
                  stainless steel column #304 packed with 5% Carbowax 20 M
                  on Chromosorb-W (60-80 mesh).
                                      132

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         4.11.2    Highly-Polar Column - 23 ft x 0.1  in ID x 0.125 in OD
                   stainless steel  #304 packed with 5% l,2,3-Tris-(2-cyano-
                   ethoxy)  propane  on Chromosorb-W (60-80 mesh).
         4.11.3    Porous Polymer Column - 6 ft x 0.1 in ID x 0.125 in OD
                   stainless steel  #304 packed with Chromosorb-101 (60-80
                   mesh).
         4.11.4    Carbopack Column - 8 ft x 0.1 in ID x 0.125 in OD
                   stainless steel  #304 packed with Carbopack-C (80-100
                   mesh)  + 0.2% Carbowax 1500.
5.  Reagents
    5.1  Chlorinated hydrocarbon reference standards
         5.1.1          Prepare standard mixtures in volumetric flasks using
                        contaminant-free distilled water as solvent.  Add a
                        known amount of the chlorinated compounds with a
                        microliter syringe.  Calculate the concentration of
                        each component as follows:
        mg/1 = (Density of Compound) (^il injected) K - -^- - '
                                                  (Dilution Volume (ml))
6.  Quality Control
    6.1  Duplicate quantitative analysis on dissimilar columns should be
         performed.  The duplicate quantitative data should agree within
         experimental error (+6 percent).  If not,  analysis on a third
         dissimilar column should be performed.  Spiked sample analyses
         should be routinely performed to insure the integrity of the method.
                                      133

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7.  Selection Gas Chromatographic Column
    7.1  No single column can efficiently resolve all chlorinated
         hydrocarbons.  Therefore, a specific column must be selected to
         perform a given analysis.  Columns providing only partially or
         non-resolved peaks are useful only for confirmatory
         identifications.  If the qualitative nature of the sample  is known>
         an efficient column selection can be made by reviewing the
         literature (2).  In doing this, one must remember that injection of
         large volumes of water can cause two serious problems not normally
         noted using common gas Chromatographic techniques:
         1)  Water can cause early column failure due to liquid phase
             displacement.
         2)  Water passing through the column causes retention times and
             orders to change when compared to common sample solvent media,
             i.e., hexane or air.
         For these reasons, column life and the separations obtained by
         direct aqueous injection may not be identical to those suggested in
         literature.
8.  Sample Collection and Handling
    8.1  The sample containers should have a total volume in excess of 25 to
         40 ml , although  larger  narrow-mouth bottles may be used.

         8.1.1  Narrow mouth screw cap bottles with the TFE fluorocarbon
                                                    t
                face silicone septa cap liners are strongly recommended.
                Crimp-seal serum vials with TFE fluorocarbon faced septa or
                                       134

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           ground glass stoppered bottles are acceptable if the seal  is
           properly made and maintained during shipment.
8.2  Sample Bottle Preparation
     8.2.1  Wash all sample bottles and TFE seals  in detergent.  Rinse
            with tap water and finally with distilled water.
     8.2.2  Allow the bottles and seals to air dry at room temperature.
     8.2.3  Place the bottle in a 200°C oven for one hour, then allow
            to cool in an area known to be free of organics.
     8.2.4  When cool, seal the bottles using the TFE seals that will be
            used for sealing the samples.
8.3  The sample is best preserved by protecting  it from phase
     separation.  Since the majority of the chlorinated solvents are
     volatile and relatively insoluble  in water, it  is  important that
     the sample bottle be filled completely to minimize air space  over
     the sample.  Acidification will minimize the  formation of
     nonvolatile salts formed from chloroorganic acids  and certain
     chlorophenols.  However, it may interfere with  the detection  of
     acid  degradable compounds such as  chloroesters.  Therefore, the
     sample history must be known before  any chemical or physical
     preservation steps can be applied.   To insure sample  integrity,  it
     1s best to analyze the sample within 1 hour of  collection.
6.4  Collect all samples in duplicate.
8.5  Fill  the sample bottles in  such a  manner that no air  bubbles  pass
     through the sample as the bottle  is  filled.
8.6  Seal  the bottles  so that no  air bubbles  are entrapped in  it.
8.7  Maintain the hermetic seal  on the  sample bottle until  analysis.
                                  135

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    8.8  Sampling from a water tap.
         8.8.1 Turn on water and allow the system to flush.  When the
               temperature of the water has stabilized, adjust the flow to
               about 50Q-ml/minute and collect duplicate samples from the
               flowing stream.
    8.9  Sampling from an open body of water.
         8.9.1 Fill a 1-quart wide-mouth bottle with sample from a repre-
               sentative area.  Carefully fill duplicate 25 to 40 mi-sample
               bottles from the 1-quart bottle.
9.  Sample Preparation
    9.1  If the sample is turbid, it should be filtered or centrifuged to
         prevent syringe plugging or excessive ghosting problems.  Filtering
         the sample is accomplished by filling a 30-ml hypodermic syringe
         with sample and attaching the Swinny-type hypodermic filter adaptor
         with a glass fiber filter "Type A" installed.  Discard the first 5
         ml of sample then collect the filtered sample in a glass stoppered
         sample filled to the top.  (One should occasionally analyze the
         non-filtered sample to insure that the filtering technique does not
         adversely affect the sample).
10.  Method of Analysis
    10.1 Daily, analyze a standard containing 10.0 mg/1 of each compound to
         be analyzed as a quality check sample before any samples are
         analyzed.  Instrument status checks and lower limit of detection
         estimations based upon response factor calculations at two times
         the signal to noise ratio are obtained from these data.  In
                                      136

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         addition, response factor data obtained from this standard can be
         used to estimate the concentration of the unknowns.
    10.2 Analyze the filtered sample of unknown composition by injecting 3 to
         10 ^il into the gas chromatograph.  Record the injection volume and
         detector sensitivity.
    10.3 Prepare a standard mixture consisting of the same compounds in
         concentrations approximately equal to those detected in the sample.
         Chromatograph the standard mixture under conditions identical to the
         unknown.
11.  Calculation or Results
    11.1 Measure the area of each unknown peak and each reference standard
         peak as follows:
         Area = (Peak Height)(Width of Peak at 1/2 Height)
    11.2 Calculate the concentration of each unknown as follows:
          (Area of Sample peak)(jul of Standard Injected)(Conc'n of Standard)
  mg/1 =   (jul of Sample injected)(Area of Standard Peak)
12.  Reporting Results
    12.1 Report results in mg/1.  If a result is negative, report the minimum
         detectable limit (see 10.1).  When duplicate and spiked samples are
         analyzed, all data obtained should be reported.
                                      137

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       _l i 1  I  I  I  I  I  I  I  I  I  I I  I I
                     16
24
32
              RETENTION TIME IN MINUTES
Figure 1. Column: Chromosorb-101, Temperature Program: 125C
for 4 min  then 4C/min up to 280 C., Carrier Gas: Nitrogen at
36 ml/min,  Detector: Microcoulometric.
                            138

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REFERENCES:


1.  Dressman, R.  C., "Elimination of Memory Peaks Encountered in Aqueous-
    Injection Gas Chromatography", Journal  of Chromatographic Science, 8_,
    265 (1970).

2.  "Gas Chromatography Abstracts", Knapman, C.  E.  H., Editor, Institute of
    Petroleum, 61 New Cavendish Street, London W1M8AR, Annually 1958 to date,
    since 1970,  also includes Liquid Chromatography Abstracts.
                                    139

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             METHOD FOR PENTACHLOROPHENOL IN WATER AND WASTEWATER
1.  Scope and Application
    1.1  This method covers the determination of pentachlorophenol  (PCP)  in
         water and wastewater.
2.  Summary
    2.1  Pentachlorophenol is extracted from the acidified water sample  (pH
         3) with toluene, methylated with diazomethane, and analyzed by
         electron-capture gas chromatography, using the columns listed in
         the organochlorine pesticide method. (Page 7, this manual)
    2.2  Further identification of pentachlorophenol  is made with  a mass
         spectrometer.
3.  Interferences
    3.1  Chlorinated pesticides and other high boiling chlorinated organic
         compounds may interfere with the analysis of PCP.
    3.2  Injections of samples not treated with diazonmethane indicate, to a
         certain degree, whether interfering substances are present.
4.  Precision and Accuracy
    4.1  Single laboratory accuracy and precision reported for this method
         when analyzing five replicates of tap water  spiked with 0.05 to
         0.07 .ug/1 of PCP is as follows:
              Recovery - mean 95.9%, range 88.1 to 100.2%
              Standard Deviation - 6.0%
                                      140

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REFERENCE:

1.  "Analysis of Pentachlorophenol Residues in Soil, Water and Fish," Stark,
    A., Agricultural and Food Chemistry, J7» 871 (July/August 1969).
                                      141

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                                  APPENDIX I
     CONSIDERATIONS FOR GLASSWARE AND REAGENTS USED IN ORGANIC ANALYSIS*
1.  Glassware
    1.1  Cleaning Procedure - It is particularly important that glassware
         used in trace organic analyses be scrupulously cleaned before
         initial use as well as after each analysis.  The glassware should
         be cleaned as soon as possible after use, first rinsing with water
         or the solvent that was last used in it.  This should be followed
         by washing with hot soap water, rinsing with tap water, distilled
         water, redistilled acetone and finally with pesticide quality
         hexane.  Heavily contaminated glassware ,may require muffling at
            e
         400C for 15-to 30-minutes.  High boiling materials, such as some of
         the polychlorinated biphenyls (PCBs) may not be eliminated by such
         heat treatment.  NOTE:  Volumetric ware should not be muffled.  The
         glassware should be stored immediately after drying to prevent
         accumulation of dust or other contaminants.  Store inverted or
         cover mouth with foil.
    1.2  Calibration - Individual Kuderna-Danish concentrator tubes and/or
         centrifuge tubes used for final concentration of extracts must be
*Methods for Organic Pesticides in Water and Wastewater," 1971,
Environmental Protection Agency, National Environmental Research Center,
Cincinnati, Ohio, 45268

                                      142

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         accurately calibrated at the working volume.    This is especially
         important at volumes below 1 ml.   Calibration should be made using
         a precision microsyringe,  recording the volume required to bring
         the liquid level to the individual graduation marks.  Glass A
         volumetric ware should be used for preparing all standard solutions.
2.  Standards,  Reagents and Solvents
    2.1  Analytical Standards and Other Chemicals - Analytical reference
         grade  standards should be used whenever available.  They should be
         stored according to the manufacturer's instructions.  Standards and
         reagents sensitive to light should be stored in dark bottles and/or
         in a cool dark place.  Those requiring refrigeration should be
         allowed to come to room temperature before opening.  Storing of
         such standards under nitrogen is advisable.
         2.1.1      Stock Standards - Pesticide stock standards solutions
                   should be prepared in 1 jjg/jjl concentrations by
                   dissolving 0.100-grams of the standard in pesticide-
                   quality hexane or other appropriate solvent (Acetone
                   should not be used since some pesticides degrade on
                   standing in this solvent) and diluting to volume in a 100
                   ml ground glass stoppered volumetric flask.  The stock
                   solution is transferred to ground glass stoppered reagent
                   bottles.  These standards should be checked frequently
                   for signs of degradation and concentration, especially
                   just prior to preparing working standards from them.
                                       143

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2.1.2     Working Standards - Pesticide working standards are
          prepared from the stock solutions using a micro syringe
          preferably equipped with a Chaney adapter.  The
          concentration of the working standards will vary
          depending on the detection system employed and the level
          of pesticide in the samples to be analyzed.  A typical
          concentration (0.1 ng/jul) may be prepared by diluting 1
          jul of the 1 jug/ul stock to volume in a 10-ml ground glass
          stoppered volumetric flask.  The standard solutions
          should be transferred to ground glass stoppered reagent
          bottles.  Preparation of a fresh working standard each
          day will minimize concentration through evaporation of
          solvent.  These standards should be stored in the same
          manner as the stock solutions.
2.1.3     Identification of Reagents - All stock and working
          standards should be labeled as follows:  name of
          compound, concentration, date prepared, solvent used, and
          name of person who prepared it.
2.1.4     Anhydrous sodium sulfate used as a drying agent for
          solvent extracts should be prewashed with the solvent or
          solvents that it comes  in contact with in order to remove
          any interferences that may be present.
2.1.5     Glass wool used at the  top of the sodium sulfate column
          must be pre-extracted for about 40-hours in soxhlet using
          the appropriate solvent.
                              144

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2.2  Solvents - Organic solvents must be of pesticide quality and
     demonstrated to be free of interferences in a manner compatible
     with whatever analytical operation is to be performed.  Solvents
     can be checked by analyzing a volume equivalent to that used in the
     analysis and concentrated to the minimum final volume.
     Interferences are noted in terms of gas chromatographic response -
     relative retention time, peak geometry, peak intensity and width of
     solvent response.  Interferences noted under these conditions can
     be considered maximum.  If necessary, a solvent must be redistilled
     in glass using a high efficiency distillation system.  A 60-cm
     column packed with 1/8 inch glass helices is effective.
     2.2.1     Ethyl Ether - Hexane - It is particularly important that
               these two solvents, used for extraction of organochlorine
               pesticides from water, be checked for interferences just
               prior to use.  Ethyl ether, in particular, can produce
               troublesome interferences.  (NOTE:  The formation of
               peroxides in ethyl ether creates a potential explosion
               hazard.  Therefore it must be checked for peroxides
               before use..)  It is recommended that the solvents be
               mixed just prior to use and only in the amount required
               for immediate use since build-up of interferences often
               occurs on standing.
     2.2.2     The great sensitivity of the electron capture detector
               requires that all solvents used for the analysis be of
               pesticide quality.  Even these solvents sometimes require
                                 145

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redistillation in an all glass system prior to use.  The
quality of the solvents may vary from lot to lot and even
within the same lot, so that each bottle of solvent must
be checked before use.
                   146

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                              APPENDIX II
   STANDARDIZATION OF FLORISIL COLUMN BY WEIGHT ADJUSTMENT BASED ON
                       ADSORPTION OF LAURIC ACID
1.   Scope
    1.1  A rapid method for determining adsorptive capacity of
         Florisil is based on adsorption of lauric acid from hexane
         solution.  An excess of lauric acid  is used an'd amount not
         adsorbed is measured by alkali titration.  Weight of lauric
         acid adsorbed is used to calculate,  by simple proportion,
         equivalent quantities of Florisil for batches having
         different adsorptive capacities.
2.   Apparatus
    2.1  Buret — 25 ml with 1/10 ml graduations.
    2.2  Erlenmeyer flasks — 125 ml narrow mouth and 25 ml, glass
         stoppered.
    2.3  Pipet — 10 and 20 ml transfer.
    2.4  Volumetric flasks — 500 ml.
3.   Reagents and Solvents
    3.1  Alcohol, ethyl.  -- USP or absolute, neutralized to
         phenolphthalein.
    3.2  Hexane  -- Distilled from all glass  apparatus.
    3.3  Lauric acid -- Purified, CP.
                                      147

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    3.4  Laurie acid solution - Transfer  10.000 g  lauric  acid  to  500
         ml volumetric flask, dissolve in hexane,  and dilute to 500 ml
         (1 ml =20 mg).
    3.5  Phenolphthalein Indicator - Dissolve  1 g  in alcohol and
         dilute to 100 ml.
    3.6  Sodium hydroxide - Dissolve 20 g NaOH (pellets,  reagent
         grade) in water and dilute to 500 ml'(IN.)-  Dilute 25 ml  IN^
         NaOH to 500 ml with water (0.05J^).  Standardize  as follows:
         Weigh 100-200 mg lauric acid into 1250 ml Erlenmeyer  flask.
         Add 50 ml neutralized ethyl alcohol and 3 drops
         phenolphthalein indicator; titrate to permanent  end point.
         Calculate mg lauric acid/ml 0.05 N NaOH (about  10 mg/ml).
4.  Procedure
    4.1  Transfer 2.000 g Florisil to 25 ml glass  stoppered Erlenmeyer
         flasks.   Cover loosely with aluminum foil and heat overnight
         at 130°C.  Stopper, cool to room temperature, add 20.0 ml
         lauric acid solution (400 mg), stopper, and shake
         occasionally for 15 min.  Let adsorbent settle  and pipet  10.0
         ml of supernatant into 125 ml Erlenmeyer  flask.  Avoid
         inclusion of any Florisil.
    4.2  Add 50-ml neutral alcohol and 3 drops indicator  solution;
         titrate with 0.05N; to a permanent end point.
5.  Calculation of Lauric Acid Value and Adjustment of Column  Weight
    5.1  Calculate amount of lauric acid adsorbed  on Florisil  as
         follows:
                                      148

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         Laurie Add value * mg lauric ac1d/g Florlsil » 200 -  (ml
         required for titration X mg lauric acid/ml 0.05IN NaOH).
    5.2  To obtain an equivalent quantity of any batch of Florlsil,
         divide 110 by lauric acid value for that batch and multiply
         by 20 g.  Verify proper elution of pesticides by 6.
6.  Test for Proper Elution Pattern and Recovery of Pesticides
    6.1  Prepare a test mixture containing aldrin, heptachlor epoxide,
         p,p'-DDE, dieldrin, Parathion and malathion.  Dieldrin and
         Parathion should elute 1n the 15% eluate; all but a trace of
         malathion in the 50% eluate and others in the 6% eluate.
7.  References
    7.1  "Pesticide Analytical Manual," U.S. Department of Health,
         Education and Welfare, Food and Drug Administration,
         Washington, D.C.
    7.2  Mills, P.A., "Variation of Florisil Activity:  Simple  Method
         for Measuring Adsorbent Capacity and Its Use in Standardizing
         Florisil Columns," Journal of the Association of Official
         Analytical Chemists. 51, 29 (1968).
                                      149

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                                 APPENDIX III
                    CHROMATOGRAPHIC CALIBRATION TECHNIQUE
Relative Calibration (Internal Standardization);
A relative calibration curve is prepared by simultaneously chromatographing
mixtures of the previously identified sample constituent and a reference
standard in known weight ratios and plotting the weight ratios against area
ratios.  An accurately known amount of the reference material is then added
to the sample and the mixture chromatographed.  The area ratios are
calculated and the weight ratio is read from the curve.  Since the amount of
reference material added is known, the amount of the sample consitituent can
be calculated as follows:
                                           Rw x Us.
                        micrograms/liter =    ys
                        Rw = Weight ratio of component to standard
                             obtained from calibration curve
                        Ws = Weight of internal standard added to
                             sample in nanograms
                        Vs = Volume of sample in mi Hi liters
Using this method, injection volumes need not be accurately measured the
detector response need not remain constant since changes in response will
not alter the ratio.  This method is preferred  when the internal standard
meets the following conditions:
         a)  we 11-resolved from other peaks
         b)  elutes close to peaks of interest

                                      150

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         c)  approximates concentration of unknown

         d)  structurally similar to unknown.
"Methods for Organic Pesticides in Water and Wastewater," U.S.
Environmental Protection Agency, National Environmental Research
Center, Cincinnati, Ohio 45268
                                      151

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                                 APPENDIX  IV
                     PREPARATION OF DIAZOMETHANE  IN ETHER
1.  Scope
    1.1  Diazomethane is prepared by reaction of  Carbitol and Diazald  in  the
         presence of KOH.  Solutions of diazomethane decompose rapidly  in
         the presence of solid material such as copper powder, calcium
         chloride, boiling stones,  etc.  These solid materials cause solid
         polymethylene and nitrogen gas to form.
2.  Apparatus
    2.1  Distilling flask with condenser,  125 ml, long neck with dropping
         funnel.
    2.2  Erlenmeyer flasks - 500 ml and 125 ml.
    2.3  Water bath.
3.  Reagents and Solvents
    3.1  Ether
    3.2  Potassium hydroxide pellets.
    3.3  Carbitol (diethylene glycol monoethyl ether).
    3.4  Diazald in ether.  Dissolve 21.5  g of Diazald in 140 ml ether.
4.  Procedure
    4.1  Use a we 11-ventilated hood and cork stoppers for all connections.
         Fit a 125-ml long-neck distilling flask  with a dropping funnel and
         an efficient condenser set downward for  distillation.  Connect the
         condenser to two receiving flasks in a series - a 500-ml Erlenmeyer

                                       152

-------
         followed by a 125-ml  Erlenmeyer containing oO ml ether.  The inlet
         to the 125-ml Erlenmeyer should dip below the ether.  Cool both
         receivers to 0°C.   As a water bath for the distilling flask, set
         up a 2-liter beaker on a stirplate (hot plate and stirrerl,
         maintaining temperature at 70°C.
    4.2  Dissolve 6-g KOH in 10 ml water in the distilling- flask (no heat).
         Ad 35 ml Carbitol  (diethylene glycol monoethyl ether), stirring
         bar, and another 10 ml ether.  Connect the distilling flask to the
         condenser and immerse distilling flask in water bath.  By means of
         the dropping funnel,  add a solution of 21.5 g Diazald in  140 ml
         ether over a period of 20 minutes.  After distillation is
         apparently complete,  add another 20 ml ether and continue
         distilling until distillate is colorless.  Combine the contents of
         the two receivers  in a glass bottle (WITHOUT ground glass neck),
         stopper with cork, and freeze overnight.  Decant the diazomethane
         from the ice crystals into a glass bottle, stopper with cork, and
         store in freezer until ready for use.  The final solution may be
         stored up to six months without marked deterioration.  The 21.5 g
         of Diazald reacted in this manner produce about 3 g of Diazomethane.
5.  Cautions
    5.1  Diazomethane is very toxic.  It can explode under certain
         conditions.  The following precautions should be observed.
         5.1.1     Use only in we 11-ventilated hood.
         5.1.2     Use safety screen.
         5.1.3     Do not pipette solution of diazomethane by mouth.
                                      153

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         5.1.4     For pouring solutions of diazomethane, use of gloves is
                   optional.
         5.1.5     Do not heat solutions at 100°C (EXPLOSIONS).
         5.1.6     Store solutions of gas at low temperatures (freezer
                   compartment of explosion-proof refrigerators).
         5.1.7     Avoid ground glass apparatus, glass stirrers and sleeve
                   bearings where grinding may occur (EXPLOSIONS).
         5.1.8     Keep solutions away from alkali metals (EXPLOSIONS).
6.  Reference
    6.1  "Pesticide Analytical Manual," U.S. Department of Health, Education
         and Welfare, Food and Drug Administration,  Washington, D.C.
                                     154

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BIBLIOGRAPHY

1.  "Analysis of Pesticide Residues in Human and Environmental
    Samples," U.S. Environmental Protection Agency, Perrine Primate
    Research Laboratories, Perrine, Florida, 33157, 1971.

2.  Mills, P.A., "Variation of Florisil Activity:  Simple Method for
    Measuring Adsorbent Capacity and Its Use in Standardizing Florisil
    Columns," Journal of the Association of Official Analytical
    Chemists. 51., 29 (1968).

3.  Goerlitz, D.F. and Brown, E., "Methods for Analysis of Organic
    Substances in Water," Techniques of Water Resources Investigations
    of the United States Geological Survey, Book 5, Chapter A3, U.S.
    Department of the Interior, Geological Survey, Washington, D.C.
    20242, 1972, pp. 24-40.

4.  Steere, N.V., editor, "Handbook of Laboratory Safety," Chemical
    Rubber Company,  18901 Cranwood Parkway, Cleveland, Ohio, 44128,
    1971, pp. 250-254.

3.  Cochrane, W. P. and Wilson, B. P., "Electrolytic conductivity
    detection of some nitrogen-containing herbicides," Journal of
    Chromatography. 63_, 364  (1971).

4.  "Standard Practice for Measuring Volatile Organic Matter in Water
    by Aqueous - Injection Gas Chromatography," D2908 Annual Book of
    ASTM Standards, Part 31, Water; American Society for Testing and
    Materials, 1916 Race Street, Philadelphia, PA, 19103.

5.  Gas-liquid Chromatographic Techniques for Petro Chemical
    Wastewater Analysis, Sugar, J.W. and Conway, R.A., Journal of
    WPCF. 40, (Annual Conference Issue) 1622 (1968).

6.  "Handbook of Chemistry and Physics," 48th Edition, the Chemical
    Rubber Company,  18901 Cranwood Parkway, Cleveland, Ohio, 44128.
    (1967-1968).
                                      155

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               APPENDIX IV






GUIDELINES ESTABLISHING TEST PROCEDURES




     FOR THE ANALYSIS OF POLLUTANTS;




          PROPOSED REGULATIONS

-------
Monday
December 3, 1979
Part 111



Environmental

Protection  Agency

Guidelines Establishing Test Procedures
for the Analysis of Pollutants; Proposed
Regulations

-------
69468
Federal  Register / Vol. 44, No. 233 / Monday,  December 3,  1979 /  Proposed Rules
                                          CMoraetlwM ---------- ....................... „.
                                          2-Chlofo«thylvmyl «rw ..... . .........
                                          OibromocWoromcmin* ..
                                          f.3-Ok*iloroMnzm._
                                          OtaMoredMuoronwttww,
                                          i.i-OteNoro«marw_
                                          1,2-OicWoro«h»n«...
                                          1,1-OlcMonMttwn*	
                                          tran»-l.2-0td
                                          nra-1,3-OBtDofopnipcrw.
                                          Mwhylww cWonoa	
                                          1.1.2.2-TetracfltonMttww....
                                          T«ncMoro«h«n*	
                                          1,1.1 -TncMorocman*	-.
                                          1. l,/2-TrfeMaro*ei«rM	
                                          Tnctilorofluorom«ttian«
                                          Vinyl eWorld*
 Appendix I—-Gas Chromatographic and
 HPLC Methods—Methods 601 through
 612

 Purgeable Halocarbon$—Method601

   1. Scope and Application.
   1.1  This method covers the
 determination of 29 purgeable
 halocarbons. The following parameters
 may be determined by this method:
 PvanwMr                       STORETNo.
                                  32104
                                  32101
                                  34413
                                  32102
                                  34301
                                  34311
                                  34578
                                  32108
                                  34418
                                  34105
                                  34538
                                  34566
                                  34571
                                  34688
                                  34498
                                  34531
                                  34501
                                  34S48
                                  34541
                                  34S6t
                                  34561
                                  34423
                                  34518
                                  34473
                                  34508
                                  34511
                                  39180
                                  34488
                                  39175

   1.2  This method is applicable to the
 determination of these compounds in
 municipal and industrial discharges. It is
 designed to be used to meet the
 monitoring requirements of the National
 Pollutant Discharge Elimination System
 (NPDES). As such, it presupposes a high
 expectation of finding the specific
 compounds of interest. If the user is
 attempting to screen samples for any or
 all of the compounds above, he must
 develop independent protocols for the
 verification of identity.
   1.3  The sensitivity of this method is
 usually dependent upon the level of
 interferences rathe_r than instrumental
 limitations. The limits of detection listed
 in Table 1 represent sensitivities that
 can be achieved in wastewaters under
 optimum operating conditions.
   1.4  This method is recommended for
 use only by experienced residue
 analysts or under the close  supervision
 of. such qualified persons.
   2.  Summary of Method.
  2.1  An inert gas is bubbled through a
5 ml water sample  contained in a
 specially-designed purging chamber.
The halocarbons are efficiently
 transferred from the aqueous phase to
 the vapor phase. The vapor is swept
 through a short sorbent tube where the
halocarbons are trapped. After the purge
is completed, the trap  is heated and
backflushed with gas to desorb the
halocarbons into a gas chromatographic
system. A temperature program is used
                                                                  in the GC system to separate the
                                                                  halocarbons before detection with a
                                                                  halide-specific detector.
                                                                    2.2  If interferences are encountered,
                                                                  the method provides an optional gas
                                                                  chromatographic column that may be
                                                                  helpful in resolving the compounds of
                                                                  interest from the interferences.
                                                                    3.  Interferences.
                                                                   ' 3.1  Impurities in the purge gas and
                                                                  organic compounds out-gasing from the
                                                                  plumbing ahead of the trap account for
                                                                  the majority of contamination problems.
                                                                  The analytical system must be
                                                                  demonstrated to be free from
                                                                  contamination under the conditions of
                                                                  the analysis by running method blanks.
                                                                  Method blanks are run by charging the
                                                                  purging device with organic-free water
                                                                  and analyzing it  in a normal manner.
                                                                  The use of non-TFE plastic tubing, non-
                                                                  TFE thread sealants, or flow controllers
                                                                  with rubber components in the purging
                                                                  device should be avoided.
                                                                   3.2  Samples can be contaminated by
                                                                  diffusion of volatile organics
                                                                  (particularly freons and methylene
                                                                  chloride) through the septum seal into
                                                                  the sample during shipment and storage.
                                                                  A sample blank prepared from organic-
                                                                  free water and carried through the
                                                                  sampling and handling protocol can
                                                                  serve as a check on such contamination.
                                                                   3.3  Cross contamination can occur
                                                                  whenever high level and low level
                                                                  samples are sequentially analyzed. To
                                                                  reduce the likelihood of this, the purging
                                                                  device and sample syringe should be
                                                                  rinsed out twice  between samples with
                                                                  organic-free water. Whenever an
                                                                  unusually concentrated sample is
                                                                  encountered, it should be followed  by an
                                                                  analysis of organic-free water to check
                                                                 -for cross contamination. For samples
                                                                  containing large  amounts of water-
                                                                  soluble materials, suspended solids,
                                                                 high boiling compounds or high
                                                                 organohalide levels, it may be necessary
                                                                  to wash out the purging device with a
                                                                  soap solution, rinse with distilled water.
                                                                 and then dry in a 105° C oven between
                                                                  analyses.
                                                                   4.   Apparatus  and Materials.
                                                                   4.1 Sampling  equipment, for discrete
                                                                 sampling.
                                                                   4.1.  Vial, with cap—40 ml capacity
                                                                 screw cap (Pierce #13075 or equivalent).
                                                                 Detergent wash and dry at 105°  C before
                                                                 use.
                                                                   4.1.2  Septum—Teflon—faced
                                                                 silicone (Pierce #12722 or equivalent).
                                                                 Detergent wash, rinse with tap and
                                                                 distilled water, and dry at 105"C for one
                                                                 hour before use.
                                                                   4.2 Purge and trap device—The
                                                                 purge and trap equipment consists of
                                                                 three separate pieces-of apparatus: the
                                                                 purging device, trap, and desorber.
                                                                 Several complete devices are now

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              Federal  Register / Vol. 44. No. 233  / Monday. December 3. 1979 / Proposed Rules
available commercially. The device
must meet the following specifications:
The unit mint be completely compatible
with the gas chromatographic system;
the purging chamber must be designed
for a 5 ml volume and be modeled after
Figure 1; the dimensions for the sorbant
portion of the trap must meet or exceed
those in Figure 2. Figures 3 and 4
illustrate the complete system in the
purge and the desorb mode.
  4.3 Gas chromatograph—Analytical
system complete with programmable gas
chromatograph suitable for on-column
injection and all required accessories
including halide-specific  detector,
column supplies, recorder,  and gases. A
data system for measuring peak areas is
recommended.
  4.4  Syringes—5-ml glass hypodermic
with lueriok tip (2 each}.
  4.5  Micro syringes—10, 25,100 /A!.
  4.6  Z-way syringe valve with Luer
ends (3 each).
  4.7 ' Syringe—5-ml gas-tight with
shut-off valve.
  4.3  Bottle—15-mi screw-cap, with
Teflon cap liner.
  5. Regents.
  5.1  Sodium thiosulfate—(ACS)
Granular.
  5.2  Trap Materials
  5.2.1  Porus polymer packing 60/80
mesh chromatographic grade Tenax GC
(2.6-diphenylene oxide).
  5.2.2  Three percent OV-l on
Chromosorb-W 60/80 mesh.
  5.2.3.  Silica gel—(35/80 mesh}—
Davison, grade-15 or equivalent
  5.2.4  Coconut charcoal  6/10 mesh
Barnaby Chaney, CA-580-28 lot #• M-
2649 or equivalent
  5.3  Activated carbon—Filtrasorb-
200 (Calgon Corp.) or equivalent
  5.4  Organic-free water
  5.4.1  Organic-free water is  defined
as water free of interference when
employed in the purge and trap
procedure described herein. It  is
generated by passing tap water through
a carbon filter bed containing about 1 Ib.
of
  5.4.2  A water purfication system
(Millipore Super-Q or equivalent) may
be used to generate organic-free
deionized water.
  5.4.3  Organic-free water may also be
prepared by boiling water for 15
minutes. Subsequently, while
maintaining the temperature at 90*  C,
bubble a contaminant-free inert gas
through the water for one hour. While
still hot, transfer the water to a narrow
mouth screw cap bottle and seal with a
Teflon line septum and cap.
  5.5  Stock standards—Prepare stock
standard solutions in methyl alcohol
using assayed liquids or gas cylinders as
appropriate. Because of the toxicity of
some of the organohalides, primary
dilutions of these materials should be
prepared in a hood. A NIOSH/MESA
approved toxic gas respirator should be
used when the analyst handles high
concentrations of such materials.
  5.5.1  Place about 9.8 ml of methyl
alcohol into a 10 ml ground glass
stoppered volumetric flask. Allow die
flask to stand, unstoppered for about 10
minutes or until all alcohol wetted
surfaces have dried. Weigh the flask to
the nearest 0.1 mg.
  5.5.2  Add the assayed reference
material:
  jui.2.1   Liquids—Using a 100 pi
syringe, immediately add 2 drops of
assayed reference material to the flask,
then reweigh. Be sure that the 2 drops
fall directly into the alcohol without
contacting the neck of the flask.
  5.5.2.2   Gases—To prepare standards
for any of the six haiocarbons that boil
below 30*  C (bromomethane,
chloroethane, chloromethane.
dichJorodifluoromethane,
trichlorodifluoromethane, vinyl
chloride), fill a 5 ml valved gas-tight
syringe with the reference standard to
the 5.0-ml  mark. Lower the needle to 5
mm above the methyl alcohol menicus.
Slowly inject the reference standard
above the  surface of the liquid (the
heavy gas will rapidly dissolve into the
methyl alcohol).
  5.5.3  Reweigh, dilute to volume,
stopper, then mix by inverting the flask
several times. Transfer die standard
solution to a 15 ml screw-cap bottle with
a Teflon cap liner.
  5.5.4  Calculate the concentration in
micrograms per microliter from the net
gain in weight
  5.5.5  Store stock standards at 4* C
Prepare fresh standards weekly for the
six gases and 2-chloroethylvinyl ether.
All other standards must be replaced
with fresh standard each month.
  8.  Calibration.
  8.1   Using stock standards, prepare
secondary dilution standards in methyl
alcohol that contain the compounds of
interest either singly or mixed together.
The standards shoud be prepared at
concentrations such that the aqueous
standards prepared in 6.2 will
completely bracket the working range of
the analytical system.
  6.2   Using secondary dilution
standards, prepare calibration
standards by carefully adding 20.0 p.1 of
standard in methyl alcohol to 100, 500,
or 1000 ml of organic-free water. A 25 ul
syringe (Hamilton 702N or equivalent)
should be  used for this operation. These
aqueous standards must be prepared
fresh daily.
  6.3   Assemble the necessary gas
chromatographic apparatus and
establish operating parameters
equivalent to those indicated in Table 1.
By injecting secondary dilution
standards, establish, the sensitivity limit
and the linear range of the analytical
system for each compound..
  8.4  Assemble die necessary purge
and trap device. The trap must meet the
minimum specifications as shown in
Figure 2 to achieve satisfactory results.
Condition the trap overnight at 180* C
by backflushing with an inert gas flow
of at least 20 ml/min. Prior to use, daily
condition, traps 10 minutes while
backflushing at 180* C Analyze aqueous
calibration standards (6,2) according to
the purge and trap procedure in Section
8. Compare the responses to those
obtained by injection of standards (8.3).
to determine purging efficiency and also
calculate analytical precision. The
purging efficiencies and analytical
precision of die analysis of aqueous
standards must be comparable to data
presented by Bellar and Lichtenberg
(1978) before reliable sample analysis
may begin.
  6.5  By analyzing calibration
standards, establish the sensitivity limit
and linear range of the entire analytical
system for each compound.
  7.   Quality Control.
  7.1  Before processing any samples,
the analyst should daily demonstrate
through the analysis of an organic-free
water method blank that the entire-
analytical system is interference-free.
  7.2  Standard quality assurance
practices should be used with this
method. Field replicates should be
collected to validate the precision of the
sampling technique. Laboratory
replicates should be analyzed to
validate the precision of the analysis.
Fortified samples should be analyzed to
validate the accuracy of the analysis.
Where doubt exists over the
identification of a peak on the gas
chromatogram, confirmatory techniques
such as mass spectroscopy should be
used.
  7.3  The analyst should maintain
constant surveillance of both the
performance, of the analytical system
and the effectiveness of the method in
dealing with each sample matrix by
spiking each sample, standard and
blank with  surrogate haiocarbons. A
combination of bromochloromethane, 2-
bromo-1-chloropropane, and 1,4-
dichlorobutane is recommended to
encompass the boiling range covered by
this method. From stock standard
solutions prepared as above, add a
volume to give 1000 jxg of each surrogate
to 45 ml of organic-free water contained
in a 50-ml volumetric flask, mix and
dilute to volume (20 ng/ul). Dose 5.0 pi
of this surrogate spiking solution

-------
69470
Federal Register / Vol.  44,  No.  233 / Monday, December 3,  1979  / Proposed Rules
directly Into the 5 ml syringe with every
sample and reference standard
analyzed. Prepare a fresh surrogate
spiking solution on a weekly basis.
  8. Sampb Collection, Preservation,
and Handling.
  8.1  Grab samples must be collected
in glass containers having a total
volume in excess of 40 ml. Fill the
sample bottles in such a manner that no
air  bubbles pass through the sample as
the bottle is being filled. Seal the bottle
so that no air bubbles are entrapped in
it. Maintain the hermetic seal on the
sample bottle until time of analysis.
  8.2.  The samples must be iced or
refrigerated from the time of collection
until extraction. If the sample contains
free or combined chlorine, add sodium
thiosulfate preservative (10 mg/40 mi
will suffice for up to 5 ppm CU) to the
empty sample bottles just prior to
shipping to the sampling site,  fill with
sample just to overflowing, seal the
bottle, and shake vigorously for 1
minute.
  8.3   All samples must be analyzed
within 14 days of collection.
  9. Sampb Extraction and Gca
Chromatograph,
  9.1   Ad)ust the purge gas (nitrogen or
helium) flow rate to 40 ml/min. Attach
the trap Inlet to the purging device, and
set  the device to purge. Open the syringe
valve located on the purging device
sample introduction needle.
  9.2   Remove the plunger from a 5 ml
syringe and attach a closed syringe
valve. Open the sample bottle (or
standard) and carefully pour the water
into the syringe barrel until it overflows.
Replace-the syringe plunger and
compress the sample. Open the syringe
valve and vent any residual air while
adjusting the samples volume to 5.0 ml
Since this process of taking an aliquot
destroys  the validity of the sample for
future analysis, the analyst should fill  a
second syringe at this time to protect
against possible loss of data. Add 5.0 ul
of the surrogate spiking solution (7.3)
through the valve bore, then close the
valve.
  9.3   Attach the syringe-syringe  valve
assembly to the syringe valve on the
purging device. Open the syringe valves
and inject the sample into the purging
chamber.
  9.4   Close both valves and purge the
sample for 11.0 ± .05 minutes.
  9.5   After the 11 minute purge time,
attach the trap to the chromatograph,
and adjust the device to the desorb
mode. Introduce the trapped materials to
the  GC column by rapidly heating the
trap to 180'C while back-flushing the
trap with an inert gas between 20  and 60
ml/min for 4 minutes. If rapid heating
cannot be achieved, the gas
                           chromatographic column must be used
                           as a secondary trap by cooling it to 30* C
                           (or sub/ambient if problems persist)
                           instead of the initial program
                           temperature of 45*C
                             9.6   While the trap is being desorbed
                           into the gas chromatograph, empty the
                           purging chamber using the sample
                           introduction syringe. Wash the chamber
                           with two 5 ml flushes of organic-free
                           water.
                             9.7   After desorbing the sample for
                           approximately four minutes recondition
                           the trap by returning the purge and trap
                           device to the purge mode. Wait 15
                           seconds then dose the syringe valve on
                           the purging device to begin gas flow
                           through the trap. Maintain the trap
                           temperature at 180'C. After
                           approximately seven minutes turn off
                           the trap heater and open the syringe
                           valve to stop the gas flow through the
                           trap. When cool the trap is ready for the
                           next sample.
                             9.8   Table 1 summarizes some
                           recommended gas  chromatographic
                           column material and operating
                           conditions for the instrument. Included
                           in this table are estimated retention
                           times and sensitivities that should bt>
                           achieved by-this method. An example of
                           the separation achieved by column 1 is
                           shown in Figure 5. Calibrate  the system
                           daily by analysis of a minimum of three
                           concentration levels of calibration
                           standards.
                             10. Calculations.
                             10.1  Determine the concentration of
                           individual compounds directly from
                           calibrations plots of concentration (ju.g/1)
                           vs. peak height or area units.
                             10.2  Reports results in micrograras
                           per liter. When duplicate and spiked
                           samples are sadples are analyzed, all
                           data obtained should be reported.
                             11. Accuracy and Precision. The U.S.
                           EPA Environmental Monitoring and
                           Support Laboratory in  Cincinnati is in
                           the process of conducting an inter-
                           laboratory method study to determine
                           the accuracy and precision of this test
                           procedure.
                           Bibliography
                            1. Bellar, T. A., and J. ]. Uchtenberg, journal
                           American Water Works Astociatioa Vol. 96.
                           No. 12. Dec. 1974, pp. 730-744.
                            2. Bellar, T. A., and J. J. Uchtenberg, "Semi-
                           Automated Headspace Analysis of Drinking
                           Waters and Industrial Waters for Purgeable
                           Volatile Organic Compounds," Proceeding
                           from ASTM Symposium on Measurement of
                           Organic Pollutants in Water and Wastewater.
                           June 1978 (In Press).
                            3. "Development and Application of Test
                           Procedures for Specific Organic Toxic
                           Substances in Wastewaters. Category 11—
                           Purgeables and Category 12—Acrolein,
                           Acrylonitrile, and Dichlorodifluoromethane."
                           Report for EPA Contract 68-03-2635 (In
                           preparation).
  Tabto l—Orytnotmtidt* TMMrf Using Purgt tnd
                        (mln.)
                                 0»t«rton
                     COI.1 «  Col 2 »
CntOroflWlneWsj". ,„ _. «_. »n.» ™
OtehlorodMuoromMniM-
Vinyl cntond*		
CnloroHnmi...	..»
Mothyton* oMorld*	
Trientoranuoremitfwrai..
1,1 -Oiehleraetnino	.._
1.M
tran»1;i
CMorotomfs.
1,1,1-TrlchloroolfMno.	
Cirbontm
BromodlehloromMMM	
TneMonMihi
Obron
1,1,2-TrtonlorocttMn*.....
Cl*' 1,34lohloraprop«M.
1,1,2^-T«t«ohtoro«N
TcmohloroMnini.._
l.S-Otei
1,44tonlerebonxirM	
1.50
2.17
2.82
2.87
3.33
US
7.18
7.93
9.30
10.1
10.7
11.4
12.8
13.0
13.7
14.g
1J.2
ISJ
18.S
16.S
184
18.0

2l!s
21.7
24.2
34.0
34.9
3S.4
US
7.0S
 (1
US
S.SS
10.1
 (1
7.72
12.8
9.38
12.1
1S.4
13.1
14.4
14.8
18.8
18.8
13.1
16.8
18,1
18.0
 (1
19.2
 (1
18.0
18.9
22.4
23J
22.3
0.0009
 0.03
 0.03
 0.01
 0.01
 0.01

 0.008
 0.004
 0.008
 0.008
 0.008
 O.OOS
 0.007
 0.008
 0.004
 0.008
 0.008
 0.01
 0.008
 0.008
 0.08
 0.02
 0.008
 0.007
 0.03
 0.04
 044
 0.04
         limit ii eueuand (ram ttw minimum
QC ruponM Mng *qu* to flv« am* tt» QC HwKgreuM
n«M. wing • Hi* Mod* 700-A OoMOler.
  'CtfbopMk. S-80/80 m*h OMMd wttfl 1*  SP-tOOO
pMlud In in 8 tt x 0.1 in ID iMnMw MM or glMt column
with nHhm earn* gw tl 40 ml/mm flow nm. Column two-
ptritur* h*« *! tt'C tor 3 irtn. thin programmed II S'C/
mm. to 220* thm nMd tor 18 irtn.
  •PorW-C 100/120 mud ooeMd wnh nooun* peekod m i
8 (I x 0.1 In 10 MMM8 Meet or glaw ootumn wttti heUom
oirrlor QH M 40 ml/mtn now tut. Ootumn t«nnp«nUuri n*W
II WC (or 3 mln ttwn pnjgrimm»a it e'C/mto to 170* lhw>
hold (or 4 mtn.
  •Not doMrmlnid

 SltUrM COM SSCB-ei-M

-------
             Federal Register / Vol. 44, No. 233 / Monday, December 3,1979 /  Proposed Rules
                                                                                        68471
   OPTIONAL
    FOAM
    TRAP
                  •EXIT '/• IN.
                       0. 0.
                  —14MM 0. 0.
                   INLET '/4 IN.
                        0. 0.
 '/« IN.
 0. 0. EXIT
                             INLET

                  3—2-WAY SYRINGE VALVE
                 j[——17CM. 20 GAUGE SYRINGE NEEDLE

                         .  0. D. RUBBER SEPTUM

                                       1/16 IN. O.D.
                                     \SSTAINLESS STEEL
                                        13X MOLECULAR
                                        SIEVE PURGE
                                            RLTER
                                          PURGE GAS
                                          FLOW
                                          CONTROL
   10MM GLASS FRIT
   MEDIUM POROSITY
             Figure 1.  Purging device
     PACKING PROCEDURE
                            CONSTRUCTION
                „      7 A/FOOT
                2    RESISTANCE
ACTIVATED    I ^   W1RE wRAppE3
CHARCOAL7.7ai^i       SOLJD<
CHARCOAL     p (DOUBLE LAYER)
                                       COMPRESSION
GRADE 15
SILICA
            t
          7.7CT'
   TEN AX 7.7 Oft \
3?'- OV-1       j p-j
GLASS WOOL100 * -
                         15CM
                     7-^/FOOT.,
                    RESISTANCE
                  WIRE WRAPPED
                        SOUD
                  (SINGLE LAYER)
                          8 CM-
^
/-
^^.
—.
c
c;

. <.





_J
•—
^*

r^-
— •
•M>
--





»«
^__<
•)
4

7

k
:>
•••ii
;j

Mill
AND

niu IMU i
FERRULES

THERMOCOUPLE/
CONTROLLER
SENSOR
ELECTRONIC
JTEMPERATURE
< ^AND
^^

PYROMETER

TUBING 25CM
0.105 IN. I.D.
0.125 IN. O.D.
STAINLESS STEEL
'i
•»'
      Figure 2.  Trap packings and construction to include
                desorb capability

-------
69472
             Federal Register / Vol. 44. No. 233 / Monday. December 3. 1979 / Proposed Rules
         CARRIER GAS
         FLOW CONTROL  LIQUID INJECTION PORTS
   PRESSURE
   REGULATOR
PURGE GAS  ,
FLOW CONTROL  ,L
  13X MOLECULAR
  SIEVE FILTER   &
                                          COLUMN OVEN
                                       1    CONFIRMATORY COLUMN
                                            ANALYTICAL COLUMN
                              OPTIONAL 4-PORT COLUMN.
                              SRECTION VALVE
                         e-PORT  TRAP INI ET
                         VALVE  J RESISTANCE WIRE
                                  PURGING
                                  DEVICE
                                             Note:
                                             ALL LINES BETWEEN
                                             TRAP AND GC
                                             SHOULD BE HEATED
                                             TO 80°C.
 Figure 3. Schematic of purge and trap device - purge mode
         CARRIER GAS
         FLOW CONTROL  LIQUID INJECTION PORTS
   PRESSURE
   REGULATOR
PURGE GAS
FLOW CONTROL
  13X MOLECULAR
  SIEVE FILTER
                                           COLUMN OVEN
                                         	CONFIRMATORY  COLUMN
                                             DETECTOR
                                            ANALYTICAL COLUMN
                              ^ OPTIONAL 4-PORT COLUMN
                               SELECTION VALVE
                         S-PORT  TRAP INLET
                         VALVE  j RESISTANCE WIRE   HEATgH

                           "jHApji"     """"  '       CONTROL
                                   PURGING
                                   DEVICE
                                              Note:
                                              ALL LINES BETWEEN
                                              TRAP AND GC
                                              SHOULD SE HEATED
                                              TO 80° C.
Figure 4. Schematic of purge and trap device • desorb mode

-------
    Federal Register / Vol. 44. No. 233 / Monday. December 3, 1979 / Proposed Rules
                                                                              89473

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-------
 69474	Federal Register / Vol. 44, No. 233 / Monday. December 3, 1979  /  Proposed Rules
Purgeable Afomatics—Method 602
  1. Scope and Application.
  1.1  This method covers the
determination of various purgeable
aromatics. The following parameters
may be determined by this method:
   Straw,.
      obi
   u-oia
   1,3-Ofcl
   Town*
34030
34301
34S36
34S86
3*571
34371
34010
  1.2  This method is applicable to the
 determination of these compounds in
 municipal and industrial discharges. It is
 designed to be used to meet the
 monitoring requirements of the National
 Pollutant Discharge Elimination System
 (NPDES). As such, it presupposes a high
 expectation of finding the specific
 compounds of interest If the user is
 attempting to screen samples for any or
 all of the compounds  above, he must
 develop independent protocols for the
 verification of identity.
  1.3  The sensitivity of this method is
 usually dependent upon the level of
 interferences rather than instrumental
 limitations. The limits of detection listed
 in Table 1 represent sensitivities that
 can be achieved in wastewaters  under
 optimum operating conditions.
  1.4  This method is recommended for
 use only by experienced  residue
 analysts or under the dose supervision
 of such qualified persons.
  2. Summary of Method.
  2.1  An inert gas is bubbled through a
 5 ml water sample contained in a
 specially-designed purging chamber.
 The aromatics are efficiently transferred
 from the aqueous phase to the vapor
 phase. The vapor is swept through a
 short sorbent tube where the aromatics
 are trapped. After the purge is
 completed, the trap is heated and
 backflushed with gas to desorb the
 aromatic compounds  into a gas
 chromatographic system. A temperature
 program is used in the GC system to
 separate the aromatics before'detection
 with a photoionization detector.
  3. Interferences.
  3.1  Impurities in the purge gas and
 organic compounds out-gasing from the
plumbing ahead of the trap account for
 the majority of contamination problems.
The analytical system must be
 demonstrated to be free from
 interferences under the conditions of the
 analysis by running method blanks.
Method blanks are run by charging the
purging device with organic-free  water
 and analyzing it in a normal manner.
 The use of non-TFE plastic tubing, non-
TFE thread sealants or How controllers
with rubber components in the purging
device should be avoided.
  3.2  Samples can be contaminated by
diffusion of volatile organics through the
septum seal into the sample during
shipment and storage. A sample blank
prepared from organic free water and
carried through the sampling and
handling protocol can serve as a check
on such contamination.
  3.3  Cross contamination can occur
whenever high level and low level
samples are sequentially analyzed. To
reduce the Likelihood of this, the purging
device and sample syringe should be
rinsed out twice between samples with
organic-free water. Whenever an
unusually concentrated sample is
encountered, it should be followed by an
analysis of organic-free water to check
for cross contamination. For samples
containing large amounts of water
soluble materials, suspended solids,
high boiling compounds, or high levels of
aromatics, it may be necessary to wash
out the purging device with a soap
solution, rinse with distilled water, and
then dry in a 105* C oven between
analyses.
* 4. Apparatus and Materials.
  4.1   Sampling equipment for discrete
sampling.
  4.1.1  Vial, with cap—40 ml capacity
screw cap (Pierce #13075 or equivalent).
Detergent wash and dry at 105* C before
use,
  4.1.2  Septum-Teflon-faced silicons
(Pierce §12722 or equivalent). Detergent
wash, rinse, with tap and distilled
water, and dry at 105* C for one hour
before use.
  4.2  Purge and trap device—The
purge and trap equipment consists of-
three separate pieces of apparatus: the
purging device, trap, and desorber.
Several complete devices are available
commercially. The device must meet the
following specifications: The unit must
be completely compatible with the gas
chromatograhpic system: the purging
chamber must be designed for a  5 ml
volume and be modeled after Figure 1;
the dimensions for the sorbant portion
of the trap most meet or exceed those in
Figure 2. Figures 3 and 4 illustrate the
complete system in the purge and the
desorb mode.
  4.3  Gas chromatograph—Analytical
system complete with programmable gas
chromatograph suitable for on-column
injection and all required accessories
including Model PI-51-02
photoionization detector fh-nu Systems,
Inc.), column supplies, recorder,  and
gases. A data system for measuring
peak areas is recommended
  4.4  Syringes—5-ml glass hyodennic
with luerlok tip (2 each).
  4.5  Micro syringes—10. 25,100 jil
  4.8  2-way syringe value with Luer
ends (3 each).
  4.7  Bottle—15-ml screw-cap, with
Teflon cap liner.
  5. Reagents.
  5.1  Solium thiosulfate—(ACS)
Granular.
  5.2  Trap Materials
  5.2.1  Porous polymer packing 60/80
mesh chromatographic grade Tenax GC
(2,8-diphenylene oxide).
  5.2.2  Three percent OV-1 on
Chromosorb-W 80/80 mesh.
  5.3  Activated carbon—Filtrasorb-200
(Calgon Corp.) or, equivalent
  5.4  Organic-free water
  5.4.1  Organic-free water is defined
as water free of interference when
employed in die purge and trap
procedure described herein. It is
generated by passing tap water through
a carbon filter bed containing about 1 Ib.
of activated carbon.
  5.4.2  A water purification system
(millipore Super-Q or equivalent) may
be used to generate organic-free
deioniaed water.
  5.4.3  Organic-free water may also be
prepared by boiling water for 15
minutes. Subsequently, while
maintaining the temperature at 90" C,
bubble a contaminant-free inert gas
through the water for one hour. While
still hot, transfer the water to a narrow
mouth screw cap bottle and seal with a
Teflon lined septum and cap.
  5.5  Stock standards—Prepare stock
standard solutions in methyl alcohol
using assayed liquids. Because benzene
an 1,4-dichlorobenzene are suspected
carcinogens, primary dilutions of these
compounds should be prepared in a
hood.
  5.5.1  Place about 9.8 ml of methyl
alcoftol into a 10 ml ground glass
stoppered volumetric flask. Allow the
flask to stand, unstoppered. for about 10
minutes or until all alcohol wetted
surfaces have dried. Weigh the flask to
the nearest 0.1 mg.
  5.5.2  Using a 100 fii syringe,
immediately add 2^drops of assayed
reference material to the flask, then
reweigh. Be sure that the 2 drops fall
directly into the alcohol without
contacting the neck of the flask.
  5.5.3  Dilute to volume, stopper, then
mix by inverting the flask several times.
Transfer the standard solution to a 15 ml
screw-cap bottle with a Teflon cap liner.
  5.5.4  Calculate the concentration in
mircograms per microliter from the net
gain in weight
  5.5.5  Store stock standards at 4*C.
All standards must be replaced with
fresh standard each month.
  8. Calibration.
  6.1  Using stock standards, prepare
secondary dilution standards in methyl

-------
              Federal Register / Vol.  44. No. 233 / Monday. December 3. 1979 / Proposed  Rules	69475
 alcohol that contain the compounds of
 interest either singly or mixed together.
 The standards should be prepared at
 concentrations such that the aqueous
 standards prepared in 0.2 will
 completely bracket the working range of
 the analytical system.
  6.2  Using secondary dilution
 standards, prepare calibration
 standards by carefully adding 20.0 (d of
 standard in methyl alcohol to 100, 500,
 or 1000 ml of organic-free water. A 25 jil
 syringe (Hamilton 702N or equivalent)
 should be used for this operation. These
 aqueous standards must be prepared
 fresh daily.
  8.3  Assemble the necessary gas
 chromatographic apparatus and
 establish operating parameters
 equivalent to those indicated in Table 1.
 By injecting secondary dilution
 standards, establish the sensitivity limit
 and the linear range of the analytical
 system for each compound.
  6.4  Assemble th necessary purge and
 trap device. The Trap must meet the
 minimum specifications shown hi Figure
 2 to achieve satisfactory results.
 Condition the trap overnight at ISO'C by
 backflushing with an inert gas flow of at
 least 20 ml/min. Prior to use, daily
 condition traps 10 minutes while
 backflushing at 180'C. Analyze aqueous
 calibration standards (8.2) according to
 the purge and trap procedure in Section
 8. Compare the responses to those
 obtained by injection of standards (6.3),
 to determine purging efficiency and also
 to calculate analytical precision. The
purging efficiencies and analytical
precision of the analysis of aqueous
 standards must be comparable to data
presented by Bellar and Uchtenberg
 (1978) before reliable sample analysis
may begin.
  6.S  By analyzing calibration
standards, establish the sensitivity limit
and linear range of the entire analytical
system for each compound.
  7. Quality Control.
  7.1  Before processing any samples,
 the analyst should demonstrate daily
 through the analysis of an organic-free
water method blank that the entire
 analytical system is interference-free.
  7.2  Standard quality assurance
practices should be used with this
 method. Field replicates should be
 collected to validate the precision of the
 sampling technique. Laboratory
replicates should be analyzed to
validate the precision of the analysis.
Fortified samples should be analyzed to
validate the accuracy of the analysis.
Where doubt exists over the
identification of a peak on the gas
chromatogram, confirmatory techniques
such a» mass spectroscopy should be
used.
  74  The analyst should maintain
constant surveillance of both the
performance of the analytical system
and the effectiveness of the method in
dealing with each sample matrix by
spiking each sample, standard and
blank with surrogate compounds (e.g.
aact-trifluorotoluene).
  8. Sample Collection, Preservation,
and Handling.
  8.1  Collect about 500 ml sample in a
clean container. Adjust the pH of the
sample to about 2 by adding 1:1  diluted
HC1 while stirring vigorously. If  the
sample contains free or combined
chlorine, add 35 mg of sodium
thiosulfate per part per million of free
chlorine per liter of sample. Fill a 40 ml
sample bottle in such a manner that no
air bubbles pass through the sample as
the bottle is being filled. Seal the bottle
so that no air bubbles are entrapped in
it Maintain the hermetic seal on the
sample bottle until time of analysis.
  8.2  The samples must be iced or
refrigerated from the time of collection
until extraction.
  8.3  All samples must be analyzed
within 7 days of collection.
  9. Sample Extraction and Gas        »
Chromatography.
  9.1  Adjust the purge gas (nitrogen or
helium) flow rate to 40 ml/min. Attach
the trap inlet to the purging device, and
set the device to purge. Open the syringe
valve located on the purging device
sample introduction needle.
  9.2  Remove the plunger from a  5 ml
syringe and attach a dosed syringe
valve. Open the sample bottle (or
standard) and carefully pour the water
into the syringe barrel until it overflows.
Replace the syringe plunger and
compress the sample. Open the syringe
valve and vent any residual air while
adjusting the sample volume to 5.0 ml.
Since this process of taking an aliquot
destroys the validity of the sample for
future analysis, the analyst should fill a
second syringe at this time to protect
against possible loss of data. Add the
surrogate spiking solution (7.3) through
the valve bore, then close the valve.
  9.3  Attach the syringe-syringe valve
assembly to the syringe valve on the
purging device. Open the syringe valves
and inject the sample into the purging
chamber.
  9.4  Close both valves and purge the
sample for 12.0 ± .05 minutes.
  9.5  After the 12 minute purge time.
disconnect the purge chamber from the
trap. Dry the trap by maintaining a flow
rate  of 40 cc/min dry purge gas for 6
min. Attach the trap to the
chromatograph, and adjust the device to
the desorb mode. Introduce the trapped
materials to the GC column by rapidly
heating the trap to 180'C while
backflushing die trap with an inert gas
between 20 and 60 ml/min for 4 minutes.
If rapid heating cannot be achieved, the
gas chromatographic column must be
used as a secondary trap by cooling it to
30'C (or subambient, if problems persist)
instead of the initial program
temperature of 50'C.
  9.6   While the trap is being desorbed
into the gas chromatograph, empty the
purging chamber using the sample
introduction syringe. Wash the chamber
with two 5 ml flushes of organic-fine
water.
  9.7   After desorbing the sample for
approximately four minutes recondition
the trap by returning, the purge and trap
device to the purge mode. Wait 15
seconds then close the syringe valve on
the purging device to begin gas flow
through the trap. Maintain the trap
temperature at 180'C. After
approximately seven minutes turn off
the trap heater and open the syringe
valve to stop the gas flow through the
trap. When cool the trap is ready for the
next sample.
  9.8   Table 1 summarized the
recommended gas chromatographic
column material and operating
conditions for the instrument. Included
in this table are estimated retention
times and sensitivities that should be
achieved by this method. An example of
the separation achieved by this column
is shown in Figure 5. Calibrate the
system daily by analysis of a minimi^
of three concentration levels of
calibration standards.
  10. Calculations.
  10.1 Determine the concentration of
individual compounds directly from
calibrations plots of concentration (/xg/1)
vs. peak height or area units.
  10.2 Report results in micrograms per
liter. When duplicate and spiked
samples are analyzed, all data obtained
should be reported.
  11. Accuracy and Precision. The U.S.
EPA Environmental Monitoring and
Support Laboratory in Cincinnati is in
the process of conducting an
interlaboratory method study  to
determine the accuracy and precision of
this test procedure.
Bibliography
  1. Bellar, T. A., and J. I. Uchtenberg. Journal
American Water Works Association, VoL 86,
No. 12, Dec. 1974, pp. 739-744.
  2. Bellar, T. A., and J. J. Uchtenberg, "Semi-
Automated Headspace Analysis of Drinking
Waters and Industrial Waters for Purgeable
Volatile Organic Compounds," Proceeding
from ASTM Symposium on Measurement of
Organic Pollutants in Water and Wastewater.
June 1978 (In Press).
  3. Bellar. T. A., and J. J. Uchtenberg, "The
Determination of Purgeable Aromatic

-------
 69478         Federal Register  / VoL 44. No.  233  / Monday, December 3, 1979  / Proposed Rules
Compounds in Drinking Waters and
Industrial Wattes," (In preparation).
  4. "Development and Application of Test
Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 11—
Purgeabies and Category 12—Acrolein,
Acrylonitnle", and Dicnlorodifluoromethane."
Report for EPA Contract 68-03-2635 (In
preparation).

   Table l.—Cttromatognpfiy ofAromsUcs Using
            Purg* arxi Trap Mfthod
GofnpouAQ
3f«tnt 	 .»«... 	 ,.,.—..
ToHitw* 	 « —
Ethyl tMnzen* 	




Retention
«m»(min.)
Cot i '
..._. ... 3 33
	 	 	 5.75
.................. 8.2S
9 17




OMcttan
limit
rt/'1
<^
O
(1
(t
«
(I
«
  '•Suptteoport 100/120 nwin eo*Md wild 5% SP-Z100 and
1.75% B*nton*-34 pvlwd in a < ft x 0.085 m 10 stanta*
SIM) eekmn wtti nMum can** g»* at 38 ee/mn (tow rat*.
Column Mmpcmura n*U at WC (or 2 mm. -
grafflnwd at 6'C/fnin. 10 90*C for * Hn« hoM.
  :OMwt»n IMt is eatauMMd from ttw mnimwn iMMctaM*
OC iMponw P*mg tqutl to DM Mm tM QC backgraund
noM. using a h-nu MocM W-51-02 photonnxatton oanetor
wftna 10.2 av lamp;
  'NolotMnnnad.
8IUINO CODE ISSO-01-M

-------
 Federal Register / Vol. 44. No. 233 / Monday. December 3, 1979 / Propoaed Rules
                                                                                        69477
  [OPTIONAL
  1FOAM
   TRAP
'/4 IN.
0. 0. EXIT
       -EXIT 1/« IN.
            0. D.
                  -—14MM 0. D.
                  INLET % IN.
                       0.0.
             < /
             I I
             I I
           -SAMPLE INLET

           •2-WAlf SYRINGE VALVE
           -17QL 20 GAUGE SYRINGE NEEDLE

               .0.0. RUBBER SEPTUM

                            1/16 IN. O.D.-
                          \ySTAINLESSSTEEL
                                       13* MOLECULAR
                                       SIEVE PURGE
                                       GAS FILTER
                                          PURGE GAS
                                          FLOW
                                          CONTROL
   10MM GLASS FRIT
   MEDIUM POROSm
             Figure 1.  Purging device
       PACKING PROCEDURE
                         CONSTRUCTION
      WOOL
    TENAX 23CM
    3T. OV-1
GLASS WOOL
101)
           5UU
              TRAP INLET
                     COMPRESSION FITTING
                     NUT AND FERRULES
                       14FT.7A/FOOT RESISTANCE
                       WIRE WRAPPED SOUO
                                  THERMOCOUPLE/
                                  CONTROLLER
                                  SENSOR
! TUBING 25QI.
-0.105 IN. I.D.
 0.125 IN. 0.0.
 STAINLESS STEEL
 Rgure 2. Trap packings and construction to include
          desorb capability

-------
69478
         Federal Register / Vol. 44. No. 233 / Monday, December 3,1979 / Proposed Rules
         CARRIER GAS
         ROW CONTROL  LIQUID INJECTION PORTS
   PRESSURE
   REGULATOR
PURGE GAS
           .
FLOW CONTROL
  13X MOLECULAR
  SIEVE FILTER"
                                      COLUMN OVEN
                                        CONFIRMATORY COLUMN
                                        ^ T° DETECTOR
                                         —ANALYTICAL COLUMN
                           OPTIONAL 4-PORT COLUMN
                           SELECTION VAIVE
                     6-PORT TRAP INLET
                     VALVE J RESISTANCE WIRE
                                  PURGING
                                  DEVICE
                                                HEATER
                                                CONTROL
                                         Note:
                                         ALL LINES BETWEEN
                                         TRAP AND GC
                                         SHOULD BE HEATED
                                         TO 80° C.
 Figure 3. Schematic of purge and trap device - purge mode
       CARRIER GAS
       FLOW CONTROL
PRESSORE
REGULATOR.
 PURGE GAS
 FLOW
  13X MOLECULAR^
  SIEVE FILTER	&
                        UQU10 INJECTION PORTS

                                            COLUMN OVEN
                                              CONFIRMATORT COLUMN
                                             -ANALYTICAL COLUMN
                           ^OPTIONAL 4^>OHT COLUMN
                             SELECTION VALVE
                       6-PORT TRAP INLET
                       VALVE J RESISTANCE WIRE
                                    TRAP ( QN >
                                   180«C ^°N'
                                                   HEATER
                                                   CONTROL
                                    PURGING
                                    DEVICE
                                            Note:
                                            ALL LINES BETWEEN
                                            TRAP AND GC
                                            SHOULD BE HEATED
                                            TO 80° C.
Figure 4.  Schematic of purge and trap device - desorb mode
WLUNO COM «MO-«1-C

-------
             Federal Register  /  Vol. 44. No.  233 / Monday, December 3. 1979 / Proposed Rules        69479
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Ud UJ
2 2
SUJ
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A . .

      2   4    6    8    10  12   14  16   18  20   22  24   25   28
                       RETENTION TIME-MINUTES

 Figure 5.  Gas chromatogram of purgeable aromatics
Acrolein and Acrylonitrile—Method 803

  1. Scope and Application.
  1.1  This method covers the
determination of acrolein and
acrylonitrile. The following parameters
may be determined by this method:
Parameter                       Slant No.
   Acrolan   	   	-	    3*210
   AcrykxWnl.		-	-	    32415
  1.2  This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used to meet the
monitoring requirements of the National
Pollutant Discharge Elimination System
(NPDES). As such, it presupposes a high
expectation of finding the specific
compounds of interest. If the user is
attempting to screen samples for any or
all of the compounds above,  he must
develop independent protocols for the
verification of identity.
  1.3  The sensitivity of this method is
usually dependent upon the level of
interferences rather than instrumental
limitations. The limits of detection listed
in Table 1 represent sensitivities that
can be achieved in  wastewaters under
optimum operating conditions.
   1.4 This method is recommended for
use only by experienced residue
analysts or under the close supervision
of such qualified persons.
  2. Summary of Method.
  2.1  An inert gas is bubbled through a
5 ml water sample contained in a
specially-designed heated purging
chamber. Acrolein and acrylonitrile are
transferred from the aqueous phase to
the vapor phase. The vapor is passed
through a short sorbent rube where the
compounds are trapped. After the
extraction is completed, the trap is
heated and backflushed with gas to
desorb the compounds into a gas
chromatographic system. A temperature
program is used in the GC system to
separate  the compounds before
detection with a flame ionization
detector.
  3. Interferences.
  3.1   Impurities in the purge gas and
organic compounds out-gasing from the
plumbing ahead of the trap account for
the majority of contamination problems.
The analytical system must be
demonstrated to be free from
interferences under the conditions of the
analysis  by running method blanks.
Method blanks  are run by charging the
purging device with organic-free water
and analyzing it in a normal manner.
The use of non-TFE plastic tubing, non-
TFE thread sealants, or flow controllers
with rubber components in the purging
device should be avoided.

-------
 69480	Federal Register /  Vol.  44. No. 233 /  Monday. December  3. 1979 / Proposed Rules
   3.2  Samples can be contaminated by
 diffusion of volatile organics
 (particularly methylene chloride)
 through the septum seal into the sample
 during shipment and storage. A sample
 blank prepared from organic-free water
 and carried through the sampling and
 handling protocol can serve as a check
 on such contamination.
   3.3  Cross contamination can occur
 whenever high level and low level
 samples are sequentially analyzed. To
 reduce the likelihood of this, the purging
 device and sample syringe should be
 rinsed out twice between samples with
 organic-free water. Whenever an
 unusually concentrated sample is
 encountered, it should be followed by an
 analysis of organic-free water to check
 for cross-contamination. For samples
 containing large amounts of water
 soluble materials, suspended solids,
 high boiling compounds or high
 organohalide levels it may be necessary
 to wash out the purging device with a
 soap solution, rinse with distilled water,
 and then dry in a 105* C oven between
 analyses.
   3.4 Interferences are sometimes
 reduced or eliminated by first purging
 the water samples for 5 minutes at room
 temperature in 9.4. Then the purge
 device is rapidly heated to 85* C and
 purged as in 9.4. With such a
 modification, approximately 5 to 10% of
 the acrylonitrile and a trace of the
 acrolein in  the sample will be lost
 Therefore, calibration must be
 established for the compounds under the
 conditions of this modified procedure.
  4. Apparatus and Materials.
  4.1 Sampling equipment, for discrete
 sampling.
  4.1.1  Vial, with cap—40 ml capacity
 screw cap (Pierce #13075 or equivalent).
 Detergent wash and dry at 105* C before -
 use.
  4.1.2  Septum-Teflon-faced silicons
 (Pierce #12722 or equivalent). Detergent
 wash, rinse with tap and distilled water,
 and dry at 105* C for one hour before
 use.
  4.2 Purge and trap device—The
purge and trap equipment consists of
 three separate pieces of apparatus: the
 purging device, trap, and desorber. The
 purging device should be equipped for
 heating in the same manner as the trap
 (electrically) or with a circulating water
jacket. If electrical heating is used the
 electrical parts must be protected so
 that water will not drip on the
conductors, causing dangerous electrical
shock or shorts. All temperature
parameters must be carefully controlled.
Several complete devices are available
 commercially although most are not
 equipped to heat the purging chamber.
The device must meet the following
 specifications: die unit must be
 completely compatible with'the gas
 chromatographic system the purging
 chamber must be designed for a 5 ml
 volume and be modeled after Figure 1;
 the dimensions for the sorbant portion
 of the trap must meet or exceed those in
 figure 2. Figures 3 and 4 illustrate the
 complete system in die purge and the
 desorb mode.
  4.3  Gas chromatograph—Analytical
 system  complete with programmable gas
 chromatograph suitable for on-column
 injection, equipped with matched
 columns for dual column analysis and a
 differential flame ionization detector. A
 nitrogen specific detector (thermionic or
 Hall) may be used if only acrylonitrile is
 to be detected. Required accessories
 include: column supplies, recorder, and
 gases. A data system for measuring
 peak areas is recommended.
  4.4 Syringes—5-ml glass hypodermic
 with luerlok tip (2 each).
  4.5 Micro syringes—10, 25,100 uL
  4.6 2-way syringe valve with Luer
 ends (3  each).
  4.7 Bottle—15-tnl  screw-cap, with
 Teflon cap liner.
  5. Reagents.
  5.1 Preservatives
  5.1.1  Sodium hydroxide—(ACS) 10 N
 in distilled water.
  5.1.2.  Sulfuric acid—(ACS). Mix
 equal volumes of cone. H*SO4 with
 distilled water.
  . 5.1.3  Sodium thiosulfate—{ACS)
 Granular.
  5.2 Trap absorbent—Porous polymer
 packing, 50/80 mesh chromatographic
 grade Porapak N.
  5.3 Activated carbon—Filtrasorb-200
 (Calgon Corp.) or equivalent
  5.4  Organic-free water.
  5.4.1  Organic-free water is denned
 as water free of interference when
 employed in the purge and trap
 procedure described herein. It is
 generated by passing tap water through
 a carbon filter bed containing about 1 Ib.
 of activated carbon.
  5.4.2  A water purification system
 (Millipore Super-Q or equivalent) may
 be used to generate organic-free
 deionized water.
  5.4.3  Organic-free water may also be
 prepared by boiling water for 15
 minutes. Subsequently, while
 maintaining the temperature at 90* C,
bubble a contaminant-free inert gas
 through  the water for one hour. While
 still hot transfer the water to a narrow
 mouth screw cap bottle and seal with a
Teflon lined septum and cap.
  5.5  Stock standards—Prepare stock
standard solutions daily in water using
 assayed standards. Because of toxicity,
 primary dilutions of these materials
 should be prepared in a hood. A
NIOSH/MESA approved toxic gas
respirator should be used when the
analyst handles high concentrations of
the materials.
  5.5.1  Place about 9.8 ml of water (pH
8.5  to 7.5) into a 10 ml ground glass
stoppered volumetric flask. Allow the
flask to stand, unstoppered, for about 10
minutes or until all water wetted
surfaces have dried. Weigh the flask to
the nearest 0.1 mg.
  5.5.2  Using a 100 ul syringe,
immediately add 2 drops of assayed
reference material to the flask, then
reweigh. Be sure that the 2 drops fall
directly into the water without
contacting the neck of the flask
  5.5.3  Dilute to volunle, stopper, then
mix by inverting the flask several times.
Transfer the standard solution to a 15 ml
screw-cap bottle with a Teflon cap liner.
  5.5.4  Calculate the concentration in
micrograms per microliter from the net
gain in weight
  6. Calibration.
  6.1  Using stock standards, prepare
secondary dilution standards in water.
The standards should be prepared at
concentrations such that the  aqueous
standards prepared in 6.2 will
completely bracket the working range of
the  chromatographic system.
  6.2  Using secondary  dilution
standards, prepare calibration
standards by carefully adding 20 ul of
stock standard to 100, 500, or 1000 ml of
organic-free water.
  6.3 Assemble the necessary gas
chromatographic apparatus and
establish operating parameters
equivalent to  those indicated hi Table 1.
By injecting secondary dilution
standards, establish the sensitivity limit
and the linear range of the analytical
system for each compound.
  6.4  Assemble the necessary purge
and trap device. The trap must meet  the
minimum specifications as shown in
Figure 2 to achieve satisfactory results.
Condition the trap overnight at 180* C
by backflushing with an  inert gas flow
of at least 20 ml/min. Prior to use, daily
condition traps 10 minutes while
backflushing at 180* C. Analyze aqueous
calibration standards (6.2) according to
the  purge and trap procedure in Section
9. Compare the responses to those
obtained by injection of standards (6.3),
to determine purging efficiency and also
to calculate analytical precision. The
purging efficiencies and analytical
precision of the analysis of aqueous
standards should be 85±5% for acrolein
and 98±5% for acrylonitrile.
  6.5  By analyzing calibration
standards, establish the sensitivity limit
and linear range of the entire analytical
system for each compound.

-------
               Federal  Register / Vol.  44. No. 233  / Monday. December  3. 1979 / Proposed Rules
  7. Quality Control.
  7.1  Before processing any samples,
 the analyst should demonstrate daily
 through the analysis of an organic-free
 water method blank that the entire
 analytical system is interference-free.
  7.2  Standard quality assurance
 practices should be used with this
 method. Field replicates should be
 collected to validate the precision of the
 sampling technique. Laboratory
 replicates should be analyzed to
 validate the precision of the analysis.
 Fortified samples should be analyzed to
 validate the accuracy of the analysis.
 Where doubt exists over the
 identification of a peak on the gas
 chromatogram, confirmatory techniques
 such as mass spectroscopy should be
 used.
  7.3  The analyst should maintain
-constant surveillance of both the
 performance of the analytical  system
 and the effectiveness of the method in
 dealing with each sample matrix by
 spiking each sample, standard and
 blank with surrogate compounds.
  8. Sample Collection, Preservation,
 and Handling.
  8.1  Collect about 500 ml sample in a
 clean container. Adjust the pH of the
 sample to 6.5 to 7.5 by adding  1:1 diluted
 HaSO« or NaOH while stirring
 vigorously. If the sample contains
 residual chlorine, add 35 mg of sodium
 thiosulfate per part per million of free
 chlorine per liter of sample. Fill a 40 ml
 sample bottle and seal the bottle so that
 no  air bubbles are entrapped in it.
 Maintain the hermetic seal on the
 sample bottle until time of analysis.
  8.2  The samples must be iced or
 refrigerated at 4*C from the time of
 collection until extraction.
  8.3  All samples must be analyzed
 within 3 days of collection.
  9. Sample Extraction and Gas
 Chromatography.
  9.1  Adjust the helium purge gas flow
 rate to 20±1 ml/min and the
 temperature  of the purge device to 85*C.
 Attach, the trap inlet to the purging
 device, and set the device to purge.
 Open the syringe valve located on the
 purging device sample introduction
 needle.
  9.2  Remove the plunger from a 5 ml
 syringe and attach a closed syringe
 valve. Open  the sample bottle (or
 standard] and carefully pour the water
 into the syringe barrel until it oveflows.
 Replace the syringe plunger and
 compress the sample. Open the syringe
 valve and vent any residual air while
 adjusting the sample volume to 5.0 ml.
  9.3  Attach the syringe-syringe valve
 assembly to  the syringe valve on the
purging device. Open the syringe valves
and inject the sample into the purging
chamber.
  9.4   Close both valves and purge the
sample for 30.0±0.1 minutes. Monitor
and control the temperature of the purge
device to obtain 85±1*C,
  9.5   After the 30-minute purge time,
attach the trap to the chromatograph.
and adjust the device to the desorb
mode. Introduce the trapped materials to
the GC column by rapidly hearing the
trap to 170'C while backflushing the trap
with helium at 45 ml/min for 5 minutes.
The backflushing time and gas flow rate
must be carefully reproduced from
sample to sample. During blackflushing
the chromatographic column is held at
100'C. Record GC retention time from
the beginning of desorption.
  9.6   While the trap is being desorbed
into the gas chromatograph, empty the
purging chamber using the sample
introduction syringe. Wash the chamber
with two 5 ml flushes of organic-free
water.
  9.7   After desorbing the sample for 5
minutes recondition the trap by
returning the purge and trap device to
the purge mode and begin the GC
progrm. Wait 15 seconds then close the
syringe valve on the purging device to
begin gas flow through the trap.
Maintain the trap temperature at 170° C.
After  approximately seven minutes turn
off the trap heater and open the syringe
valve to stop the gas flow through the
trap, when cool the trap is ready for the
next sample.
  9.8   Table 1 summarizes some
recommended gas chromatographic
column materials and operating
conditions for the instrument. Included
in this table are estimated retention
times and sensitivities that should be
achieved by this method. An example of
the separation achieved by this column
is shown hi Figure 5. Calibrate the
system daily by analysis of a minimum
of three concentrations levels of
calibration standards.
  10. Calculations.
  10.1  Determine the concentration of
individual compounds directly from
calibrations plots of concentration (ug/1)
vs. peak height or area units.
  10.2  Report results in micrograms per
liter. When duplicate and  spiked
samples are analyzed, all data obtained
should be reported.
  11. Accuracy.and precision
  The U.S. EPA Environmental
Monitoring and Support Laboratory in
Cincinnati is in the process of
conducting an interlaboratory method
study to determine the accuracy and
precision of this test procedure.
Bibliography
  1. Bellar. TA., and}.}. Lichtenbeig. Journal
American Water Works Association. VoL 66,
No. 12, Dec. 1974. pp. 739-744.
  2. Beilar. TA» and J.J. Uchtenberg, "Semi-
Automated Headspace Analysis of Drinking
Waters and Industrial Waters for Pnrgeablv
Volatile Organic Compound*," Proceeding
from ASTM Symposium on Measurement of
Organic pollutants in Water and wastewater,
June 1978 (In Press).
  3. "Development and application of Test
Procedures for Specific Organic Toxic
Substance* in Wastewaters. Category 11-
Purgeables and Category 12-Acrolein.
Acrylonitrile, and Dichiorodifluoromethane."
Report for EPA Contract 68-03-2633  (In
preparation).
  4. Going, John, et al.. "Environmental
Monitoring Near Industrial Sites-
Acrylonitrile,"  EPA Report No. 560/6-79-003,
1979.

  Table 1.—GasChromatogmpfiytjy Heated Puiy»
                ana Trap
                Retention       Oatecabn
      Compound '  Time (iMn.)      Urn* uc/4 '
Acfotem	
Acrytonitnle	
7.8
8.9
  'Column condition* • Chnxnoaorb 101  80/100
packed m a 8" x tt" 0.0. start*** Heel cotumn vyitfi heftum
earner 9a» at 46 ml/mm flow rate. Column temperature it
h«w at 100* C (or J minuMt during traD-deaorptton. then pro-
grammed at 10 • C/mn to 140 *C and held for S minute*.
  'Detection limit ts «*kna«d. baaed upon  «§ uee of r
(lam* wnizatton detector.
BILLING

-------
69482
Federal Register/Vol. 44, No. 233 / Monday. December 3,1979 / Proposed Rules
   OPTIONAL
   FOAM
   TRAP
 ',4 IN.
 0. D. EXIT
          2-WAY SYRINGE VALVE
          17CH. 20 GAUGE SYRINGE NEEDLE

              . 0.  D. RUBBER SEPTUM

                           ins IN. o.o.
                                     \SSTAINLESS STEEL
                                        13X MOLECULAR
                                        SIEVE PURGE
                                        GAS RLTEH
                                          PURGE GAS
                                          FLOW
                                          CONTROL
   10MM.GLASS FRIT
   MEDIUM POROSITY
             Figure 1.  Purging device
   PACKING PROCEDURE
  WOOL
 PORAPAK N
      24CU
GLASS WOOL I
        5MM
               CONSTRUCTION
                          COMPRESSION
                         .FITTING NUT
                          AND FERRULES
                           14FT. 7A/PQOT
                          'RESISTANCE WIRE
                           WRAPPED SOLJD
                            TriESKOCOUPLE/
                      ?     CONTROLLER
                  C'T-T""" SENSOR
           TRAP INLET
                                       TUSING 25OB
                                       0.105 IN. 1.0.
                                       '0.125 IN. 0.0.
                                       STAINLESS STEEL
Figure 2. Trap packings and construction to include
          desorb capability

-------
            Federal Register / Vol. 44. No. 233 / Monday. December 3.1979 / Propoaed Rulea        69483
         CARRIER GAS
         FLOW CONTROL  LIQUID INJECTION PORTS
   PRESSURE
   REGULATOR
PURGE GAS
FLOW CONTROL  ,
  13* MOLECULAR
  SIEVE FILTER  "
     OPTIONAL 4 PORT COLUMN
     SELECTION VALVE
6 PORT  TRAP INLH
         RESISTANCE WIRE
                                          COLUMN OVEN
            -1 1    CONFIRMATORY COLUMN
          n n FfTO DETECTOR
          "•  I'  "  ANALYTICAL COLUMN
             I RAP
             22°C
                                          I OFF
                                                 HEATER
                                                 CONTROL
                                             Nole:
                                             ALL LINES BETWEEN
                               PURGING DEVICE TRAP AND GC
                               HEATED 10 85°C SHOULD BE HEATED
                                             TO 95°C.
 Figure 3. Schematic of purge and trap device - purge mode
         CARRIER GAS
         FLOW CONTROL  LIQUID INJECTION PORTS
   PRESSURE
   REGULATOR
PURGE GAS
FLOW CONTROL
 13X MOLECULAR
 SIEVE FILTER
                                          COLUMN OVEN
       r-innn I    CONFTRIBATORY COLUMN
      JU           DETECTOR
      - '^ - L
                                            ANALY-nCAL COLUMN
    \OPT10NAL 4-PORT COLUMN
      SELECTION VALVE
       TRAP INLET
VALVE  J RESISTANCE WIRE   ...,,—.»
         _z	     HEATER
                        "CONTROL
          PURGING
          DEVICE
                                             Note:
                                             ALL LINES 3ETAEBI
                                             TRAP AND GC
                                             SHOULD 8E HEATED
                                             TO 95° C.
Figure 4.  Schematic of purge-and trap device • desorfa mode
SILU
     cooe w«o-oi-c

-------
69484	Federal Register /  Vol.  44. No. 233 / Monday, December 3.  1979 / Proposed Rules
     COLUMN: CHROIMOSOR8 101
     PROGRAM: 80*C-5 MINUTES.
                8*C/ MINUTE TO 150SC
     DETECTOR:  FLAME IONIZAT10N
                                          tu
                                          «i
                                          2

            2463
                RETENTION T11WE-.MINUTES
      10
     Figures.  Gas chromatogram oi acrolein and acrylonitrile
Phenols—Method 604
  \. Scope and Application.
  1.1  This method covers the
determination of various phenolic
compounds. The following parameters
may be determined by this method:
  1.2  This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used to meet the
monitoring requirements of the National
Pollutant Discharge Elimination System
(NPDES). As such, it presupposes a high
expectation of finding the specific
compounds of interest. If the user is
attempting to screen samples for any or
all of the compounds above, he must
develop independent protocols for the
verification of identity.
  1.3  The sensitivity of this method is
usually dependent upon the level of
 interferences rather than instrumental
 limitations. The limits of detection listed
 in Table I represent sensitivities that
 can be achieved in wastewaters with a
 flame ionization detector in the absence
 of interferences. If the darivatization
 cleanup is required, the sensitivity of the
 method is 10 ju.g/1. This concentration
 represents the minimum amount proven
 to date to give reproducible and linear
 response during derivatization.
  1.4  This method is recommended for
 use only by experienced residue
 analysts or under the close supervision
 of such qualified persons,
  2. Summary of Method.
  2.1  A 1-liter sample' of wastewater is
 acidified and extracted with methylene
 chloride using separatory funnel
 techniques. The extract is dried and
 concentrated to a  volume of 10 ml or
 less. Flame ionization gas
 chroma tographic conditions are
 described which allow for the
 measurement of the compounds in the
 extract.
  2.2 The method also provides
 for the preparation of
 pentafluorobenzylbromide (PFB)
 derivatives for electron capture gas
 chromatography with additional cleanup
 procedures to aid  the analyst in the
 elimination of interferences.
  3. Interferences.
  3.1  Solvents, reagents, glassware,
 and other sample processing hardware
 may yield discrete artifacts and/or
 elevated baselines causing
 misinterpretation of gas chromatograms.
 All of these materials must be
 demonstrated to be free from
 interferences under the conditions of the
 analysis by running method blanks.
 Specific selection of reagents and
 purification of solvents by distillation in
 all-glass systems may be required.
  3.2  Interferences coextracted from
 the samples will vary considerably from
 source to source, depending upon the
 diversity of the industrial complex or
municipality being sampled.  While
general cleanup techniques are provided
as part of this method, unique samples
may require additional cleanup
approaches to achieve the sensitivities
stated in Table I.

-------
              Federal  Register / Vol. 44. No.  233 / Monday, December 3. 1979  /  Proposed Rules	69485
  4, Apparatus and Materials.
  4.1  Sampling equipment for discrete
or composite sampling.
  4.1.1  Grab sample bottle—amber
glass, 1-liter or 1-quart volume. French
or Boston Round design is
recommended. .The container must be
washed.and solvent rinsed before use to
minimize interferences.
  4.1.2  Bottle caps—Threaded to screw
on to the sample bottles. Caps must  be
lined with Teflon.
  4.1.3  Compositing equipment—
Automatic or manual compositing
system. Must incorporate glass sample -
containers for the collection of a
minumum of 250 ml. Sample containers
must be kept refrigerated during
sampling. No tygon or rubber tubing
may be used in this system.
  4.2  Separatory funnel—2000 ml, with
Teflon stopcock.
  4.3  Drying column—20 mm ID Pyrex
chromatographic column with coarse
frit.
  4.4.  Kudema-Danish (K-D)
Apparatus
  4.4.1  Concentrator tube—10 ml
graduated (Kontes K-570050-1025 or
equivalent}. Calibration must be
checked.  Ground glass stopper (size 19/
22 joint] is used to prevent  evaporation
of extracts.
  4.4.2  Evaporative  flask—300 ml
(Kontes K-57001-0500 or equivalent).
Attach to concentrator tube with
springs. (Kontes K-662750-0012).
  4.4.3  Snyder column—three-ball
macro (Kontes K-503000-0121 or
equivalent).
  4.4.4  Snyder column—two-ball micro
(Kontes K-569001-0219 or equivalent).
  4.4.5  Boiling chips—solvent
extracted, approximately 10/40 mesh.
  4.5  Water bath—Heated, with
concentric ring cover, capable of
temperature control (±2°C). The bath
should be used in a hood.
  4.6  Gas chromatograph—Analytical
system complete with gas
chromatograph suitable for on-column
injection  and' all required accessories
Including flame ionization and electron
capture detector, column supplies,
recorder, gases, syringes. A data system
for measuring peak areas is
recommended.
  4.7  Chromatographic column—10
mm 10 by 100 mm length, with Teflon
stopcock.
  4.8  Reaction vial—20 ml, with
Teflon-lined cap.
  S. Reagents.
  5.1  Preservatives:
  5.1.1  Sodium hydroxide—(ACS) 10 N
in distilled water.
  5.1.2  Sulfuric acid—(1 + 1) Mix equal
volumes of cone. H»SO< (ACS) with
distilled water.
  5.1.3  Sodium thiosulfate—(ACS)
Granular.
  5.2  Methylene chloride, acetone, 2-
propanol, hexane, toluene—Pesticide
quality or equivalent.
  5.3  Sodium sulfate—(ACS) Granular,
anhydrous (purified by heating at 400" C
for 4 hrs. in a shallow tray).
  5.4  Stock standards—Prepare stock
standard solutions at a concentration of
1.00 jxg/^1 by dissolving 0.100 grams of
assayed reference material,in pesticide
quality 2-propanol and diluting to
volume in a 100 ml ground glass
stoppered volumetric flask. The stock
solution is transferred to ground glass
stoppered reagent bottles, stored in a
refrigerator,  and checked frequently for
signs of degradation or evaporation,
especially just prior to preparing
working standards from them.
  5.5  Sulfuric acid—(ACS) 1 N in
distilled water.
  5.6  Potassium carbonate—(ACS)
powdered.
  5.7  Pentafluorobenzyl bromide (a-
Bromopentafluoro toluene)—97%
minimum purity.
  5.8  1,4.7,10,13,16—
Hexaoxacyclooctadecane (18-crown
6)—98% minimum purity.
  5.9  Derivatization reagent—Add 1 ml
pentafluorobenzyi bromide and 1 gram
18 crown 6 to a 50 ml volumetric flask
and dilute to volume with 2-propanol.
Prepare fresh weekly.
  5.10   Silica gel—(ACSJ100/200 mesh.
grade 923; activated at 130°C and stored,
in a sesiccator.
  8. Calibration.
  8.1  Prepare calibration standards for
the flame ionization detector that
contain the compounds of interest,
either singly or mixed together. The
standards should be prepared at
concentrations covering two or more
orders of magnitude that will completely
bracket the working range of the
chromatographic system. If the
sensitivity of the detection system can
be calculated from Table I as 100 pig/1 in
the final extract, for example, prepare
standards at 10 ug/1, 50 ug/1,100 Mg/1,
500 fig/1, etc. so that injections of 1-5 ^il
of each calibration standard will define
the linearity of the detector in the
working range.
  8.2  Assemble the necessary gas
chromatographic apparatus and
establish operating parameters
equivalent to those indicated in Table L
By injecting calibration standards,
establish the sensitivity limit of the
detector and the linear range of the
analytical system for each compound.
  8.3  Before using the derivatization
clean up procedure, the analyst must
process a series of calibration standards
through the procedure to validate the
precision of the derivatization and the
absence of interferences from the
.reagents.
  7. Quality Control.
  7.1  Before processing any samples,
the analyst should demonstrate through
the analysis of a distilled water method
blank, that all glassware and-reagents
are interference-free. Each time a set of
samples is extracted or there is a change
in reagents,  a method blank should be
processed as a safeguard against
chronic laboratory contamination.
  7.2  Standard quality assurance
practices should be used with this
method. Field replicates should be
collected to  validate the precision of the
sampling technique. Laboratory
replicates should be analyzed to
validate the precision of the analysis.
Fortified samples should be analyzed to
validate the accuracy of the analysis.
Where doubt exists over the
identification of a peak on the
chromatogram, confirmatory techniques
such as mass spectroscopy should be
used.
  8. Sample Collection. Preservation,
and Handling.
  8.1  Grab  samples must be collected
in glass containers. Conventional
sampling practices should be followed.
except that the bottle must not be
prewashed with sample before
collection. Composite samples should be
collected in refrigerated glass containers
in accordance with the requirements of
the program. Automatic sampling
equipment must be free of tygon and
other potential sources of
contamination.
  8.2  The samples must be iced or
refrigerated from the time of collection
until extraction. At the sampling
location fill  the glass container with
sample. Add 35 mg of sodium thiosulfate
per part per million free chlorine per
liter. Adjust the sample pH to
approximately 2, as measured by pH
paper, using appropriate sulfuric acid

-------
 69486	Federal Register / Vol. 44, No. 233  / Monday.  December 3.  1979 / Proposed Rules
 solution or ION sodium hydroxide.
 Record the volume of acid used on the
 sample identification tag so the sample
 volume can be corrected later.
   8.3  All samples, must be extracted
 within 7 days and completely analyzed
 within 30 days of collection.
   9. Sample Extraction.
   9.1  Mark the water meniscus on the
 side of the sample bottle for later
 determination of sample volume. Pour
 the entice sample into a two-liter
 separatory funnel Adjust the sample pH
 to 12 with sodium hydroxide.
   9-2  Add 60 ml methylene chloride to
 the sample bottle, seal, and shake 30
 seconds to rinse the inner walla.
 Transfer the solvent into the. separatory
 funnel, and extract the sample by
 shaking the- funnel for one minute with
 periodic venting to release vapor
 pressure. Allow the organic layer to
 separate from the water phase for a
         of fon minutes. If the emulsion.
interface between layers is more than
one-third the size of the solvent layer,
the analyst must employ mechnical
techniques to complete the phase
separation. The optimum technique
depends upon the sample, but may
include stirring; filtration of the
emulsion through glass wool, or
centrifugation. Discard the methylene
chloride layer, and wash the sample
with an additional two 60ml portions of
methylene chloride in similar fashion.
  9.3  Adjust the aqueous- layer to a pH
of 1-4 with sulfuric add.
  9.4  Add CO ml of methylene chloride
to the sample and shake for two
minutes. Allow the solvent to separate
from the sample and collect the
methylene chloride in a 250 ml
Erlenmeyer flask.
  9.5  Add a second 60 ml volume of
methylene chloride to the sample bottle
and complete the extraction procedure a
second time, combining the extracts in
the Erlenmeyer flask.
  9.6  Perform a third extraction in the
same manner. Pour the combined
extract the through a drying column
containing 3-4 inches of anhydrous-
sodium sulfate, and collect it in a 500-ml
Kuderna-Oanish (K-D) flask equipped
with a 10 ml concentrator tube. Rinse
the Erlenmeyer flask and column with
20-30 ml methylene chloride to complete
the quantitative transfer.
  9.7  Add 1-2 clean boiling chips to
the flask and attach, a three-ball Snyder
column. Prewet the Snyder column by
adding about 1 ml methylene chloride to
the top. Place the K-D apparatus on a
hot water bath (60-65'C) so that the
concentrator tube is partially immersed
tn the hot water, and the entire lower
rounded surface of the flask is bathed in
vapor. Adjust the vertical position of the
 appartus and the water temperature as.
 required to complete the concentration
 in 15-20 minutes. At the proper rate of
 distillation the balls of tie column will
 actively chatter but the chambers will
 not flood. When the apparent volume of
 liquid reaches 1 mi remove the K-D
 apparatus and allow it to drain for at
 least 10 minutes while cooling.
  9.8  Increase the temperature of the
 hot water bath to 95-100'C. Remove the
 Snyder column, and rinse the flask and
 its lower joint into the concentrator tube
 with 1-2 ml of 2-propanoL A 5-tnl
 syringe is recommended for this
 operation. Attach a micro-Snyder
 column to the concentrator tube and
 prewet the column by adding about 0.5
 ml 2-propanol to the top. Place the
 micro-K-D apparatus on the water bath
 so that the concentrator tube is partially
 immersed in the hot water. Adjust the
 vertical position of the apparatus and
 the water temperature as required-to
 complete concentration in 5-10 minutes.
 At the proper rate of distillation, the
 balls of the column wilt actively chatter
 but the chambers will not flood. When
 the apparent volume of the liquid
 reaches 2J5 ml, remove the K-D
 apparatus and allow it to drain for at
 least 10 minutes while cooling. Add an
 additional i ml of 2-propanol through
 the top of the micro-Snyder column and
 resume concentrating as before. When
 the apparent volume of liquid reaches
 0.5 ml. remove the K-D apparatus and
 allow it to drain for at least 10 minutes
 while, cooling. Remove the micro-Snyder
 column and rinse its lower joint into the
 concentrator tube with, a minimum
 amount of 2-propanol. Adjust the extract
 volume to 1.0 ml. Stopper the
 concentrator tube and store in
 refrigerator, if further processing will not
 be performed immediately. If the- sample
 extract requires no-further cleanup,
 proceed with flame ionization gas
 chroma tographic analysis. If the sample
 requires cleanup, proceed to section 11.
  9.9   Determine the original sample
 volume by refilling the sample bottle to
 the mark and transferring the liquid to a
 1000 ml graduated cylinder. After
 correction for sulfuric acid preservative,
record the sample volume to the nearest
 5mL
  10.   Gas Chromatography-Flanie
 lonizatitm Detector.
  10.1  Table I summarizes some
recommended gas chroma tographic
 column materials and operating
 conditions for the instrument Included
 in this table are estimated retention
times and sensitivities that should be
 achieved by this method An example of
 the separation achieved by one of these
 columns is shown in Figure 1. Calibrate
 the gas chromatographic system daily
 with a minimum of three injections of
 calibration standards.
  10.2  Inject 2-5 pj of the sample
 extract using the solvent-flush
 technique. Smaller (1.0 /il) volumes can
 be injected if automatic devices are
 employed. Record the volume injected to
 the nearest 0.05 ul and the resulting
 peak size, in area units.
  10.3  If the peak area exceeds the
 linear-range of the system, dilute the
 extract and reanalyze.
  10.4  If the peak area measurement is
 prevented by the presence of
 interferences, the phenols must be
 derivatized and analyzed by electron
 capture gas chromatography.
  11.   Derivatization and Electron
 Capture Gas Chromdtography.
  11.1  Pipet a 1.0 ml aliquot of the 2-
 propanol solution of standard or sample
 extract into a glass reaction vial. Add
 1.0 ml derivatization reagent This is a
 sufficient amount of reagent to
 derivatize a solution whose total
 phenolic content does  not exceed 0.3
 mg/ml.
  11.2  Add about 3 mg of potassium
 carbonate to the solution and shake
 gently.
  11.3   Cap the mixture and heat it  for 4
 hours at 80°C in a hot water bath.
  11.4   Remove the solution from the
 hot water bath and allow  it to cool.
  11.5  Add 10 ml hexane to the
 reaction vial and snake vigorously for
 one minute. Add 3.0 ml of distilled,
 deionized water to the reaction vial and
 shake for two minutes.
  11.8   Decant organic layer into a
 concentrator tube and cap with a glass
 stopper.
  11.7   Pack a 1O mm ID
 chromatographic column with 4.0 grams
 of activated silica gel. After settling the
 silica gel by tapping the column, add
 about two grams of anhydrous sodium
 sulfate to the top.
  11.8   Pre-elute the column with 6 ml
 hexane. Discard the eluate and just prior
 to exposure of the sulfate layer to air,
 pipet onto the column 2.0 ml of the
 hexane solution (11.6) that contains the
 derivatized sample or standard. Elute
 the column with 10.0 ml of hexane
 (Fraction 1) and discard this fraction.
 Elute the column, in order, with: 10.0 mi
 15% toluene in hexane (Fraction 2); 10.0
 ml 40% toluene in hexane (Fraction 3);
 10.0 ml 75% toluene in hexane (Fraction
 4]; and 10.0 ml 15% 2-propanol in toluene
 (Fraction 5). Elution patterns for the
phenolic derivatives are shown in Table
 II. Fractions may be combined as
 desired depending upon the specific
phenols of interest or level of
 interferences.
  11.9  Analyze the fractions by
 electron capture gas chromatography.

-------
               Federal Register /  Vol. 44.  No. 233 /  Monday, December  3,  1979  / Proposed Rules
                                                                             69487
Table II summarizes some
recommended gas chromatographic
column materials and operating
conditions for the instrument. Included
in this table are estimated retention
times that should be achieved by this
method. Examples of the separation
achieved by this column is shown in
Figure 2. Calibrate the system daily with
a minimum of three  aliquots of
calibration standards, containing each
of the phenols of interest that are
derivatized according to the procedure.
  11.10  Inject 2-5 p.1 of the column
fractions  using the solvent-flush
technique. Smaller (1.0 JA!) volumes can
be injected if  automatic devices are
employed. Record the volume injected to
the nearest 0.05 pL and the resulting
peak size, in area units. If the peak area
exceeds the linear range of the  system.
dilute the extract and reanalyze.
  12.  Calculations
  12.1   Determine the concentration of
individual compounds measured by the
flame ionization procedure (without
derivatization) according to the formula:

               '*'roW
                (Vj(VJ

Where:
\ a> Calibration factor for chromatographic
    system, in nanograms material per area
    unit.
B * Peak size in injection of sample extract.
    in area units
V, — Volume of extract injected Oil)
V, - Volume of total extract Oil}
V, =» Volume of water extracted (p.1)

  12.2   Determine the  concentration of
individual compounds measured by the
derivatization and electron capture
procedure according to the following
procedure:
  12.2.1   From the concentration of the
calibration standards  that were
derivatized with the samples, calculate
the amounts, ia nanograms, of
underivatized phenols that were added
as 2-propanoi solution (11.1). From the
size of the injection  into the electron
capture gas chromatograph, determine
the nanograms of material (calculated as
the underivatized phenol) injected onto
the column. Compare the detector
responses obtained to develop a
calibration factor for the
chromatographic system, in nanograms
of material per area unit.
  12.2.2   Determine the concentration
of individual compounds according to^
the formula:
                   (VJnttrophenol 	 . 	 _ 	 .....


2.4-C4chk»opnenol 	 	 	 	
2.4.8-Trtenlorephenol 	 	 „ 	 	

Pxitauh torophenol 	 	 	 	

(2,4.Dtnrtfophenol) 	
(2-MetnyM.64Mtrophenol 	
3.3 	 	
9 1
1.8 	 _. .

SB
70 	 „ 	
48 ._
28 S 	 „...
14.0 	
»48.9 	 _ 	
»36.8 	 _ 	
90

90

	 - 	 - 	 95
.. . . 	 95
50 50 ....
	 g4
75 20

	 	 	 - 	 - 	


10

7
>1

14

> 1


90


	 —


"
90

    •Column condMom: Cftremoeore W-AW-OMCS 80/100 mean coated with 5% OV-17 pecked in a 1.8 m long x 2,0 mm 10
 glace column with 5% methane/93% argon earner gas at 30 ml/mm flow rate. Column temperature t» 200'C.
    'From: "Development and Application ol Teat Procedure! for Specific Organic Toxic Substaneea in Waatewaten. Catego-
 nea 3-Chtonnat*d Hydroottont and Category 8-Phenol»."
    •Retention ttnea included for qualitative information only. The lack ol accuracy and precision of the oenvaftation reacdoA
 preclude* the uae of thn approach for quantitative purposes.

 S1LUNG CODE 8SSO-01-M

-------
   1   s
   I   s
   cs   wu
   2rf 5
   SSQ /-\
    COLUMN:  1% SP-1240DA ON SUPELCOPORT

    PROGRAM:  80*C.-0 MINUTES 8* /MINUTE TO 15Q*C.

    DETECTOR: FLAME IONIZATION
     S
        O

        UJ
          O
             i
-Z 5  _j2
csa >:  o5

111  $-.
*" f  CT
             " 1
                2
  ^«*  i  35 ^™
  •r o  ** *•
  5 I  eg
  » O  2 m
         U
                      O.
                      O
                                  O


                                  z
0      4      8      12     16     20     24


                 RETENTION TIME-MINUTES



 Figure 1.  Gas chromatogram of phenols

 Bit-UNO CODE wM-OI-C
                   COLUMN:  5% OV-17 ON CHROMOSORB W-AW

                   TEMPERATURE: 200*C.

                   DETECTOR: ELECTRON CAPTURE
                                                                                                              O
                                                                                                              8

                                                                                                              §
                                                                                                              cr
                                                                  8     12     16     20    24    28

                                                                     RETENTION TIME-MINUTES
                                                                                                               32
Figure 2. Gas chromatogram of PFB derivatives of phenols

-------
              Federal  Register / Vol. 44. No.  233 / Monday, December 3. 1979  / Proposed Rules	69491
Phthalate Esters—Method 806
  1. Scope and Application.

  1.1  This method covers the
determination of certain phthalate
esters. The following parameters may be
determined by this method:
                              StCfttHo.
                                 34292
                                 39100
                                 34110
                                 34S98
                                 34336
                                 34341
Bmyl but* pftttuMM
OWvoetyi p«hai«t« ..._
OMhyl pMhtUM
OkD*""* phmnat*
  0    «    3  12
   RETENTION TUBE-MINUTES
 Figure 1, Liquid chromatogram of banzidinM

  1.2  This method is applicable to the
 determination of these compounds in
 municipal and industrial discharges. It is
 designed to be used to meet the
 monitoring requirements of the. National
 Pollutant Discharge Elimination System
 (NPDES). As such, it presupposes a high
 expectation of finding the specific
 compounds of interest. If the user is
 attempting to screen samples for any or
 all of the compounds above, he must
 develop independent protocols for the
 verification of identity.

  1.3  The sensitivity of this method is
 usually dependent upon the level of
 interferences rather than instrumental
 limitations. The limits of detection listed
 in Table I represent sensitivities that
 can  be achieved in waste-waters in the
 absence of interferences.
  1.4  This method is recommended for
use only by experienced residue
analysts or under the close supervision
of such qualified persons.

2. Summary of Method.

  2.1  A 1-liter sample of wastewater is
extracted with methylene chloride using
separatory funnel techniques. The
extract is dried and concentrated to a
volume of 10 ml or less.
Chromatographic  conditions are
described which allow for the accurate
measurement of the compounds in the
extract.

  2.2  If interferences are encountered,
 the method provides selected general
purpose cleanup procedures to aid the
analyst in their elimination.
  3. Interferences.
  3.1   Solvents, reagents, glassware,
and other sample processing hardware
may yield discrete artifacts and/or
elevated baselines causing
misinterpretation of gas chromatograms.
All of these materials must be
demonstrated to be free from
interferences under the conditions of the
analysis by running method blanks.
Specific selection of reagents and
purification of solvents by distillation in
all-glass systems may be required.
  3.2   Interferences coextracted from
the sample will vary considerably from
source to source, depending upon the
diversity of the industrial complex or
municipality being sampled. While
general cleanup techniques are provided
as part of this method, unique samples
may require additional cleanup
approaches to achieve the sensitivities
stated in Table I.
  3.3   Phthalate esters contaminate
many types of products commonly found
in the laboratory. The analyst must
demonstrate that no phthalate residues
contaminate the sample or solvent
extract under the conditions of the
analysis. Of particular importance is the
avoidance of plastics because
phthalates are commonly used as
piasticizers and are easily extracted
from plastic materials. Serious phthalate
contamination may result at any time if
consistent quality control is not
practiced.
  4. Apparatus and Materials.
  4.1   Sampling equipment, for discrete
or composite sampling.
  4.1.1  Grab sample bottle—amber
glass, 1-liter or l-quart volume. French
or Boston Round design is
recommended. The container must be
washed and solvent rinsed before use to
minimize interferences.
  4.1.2  Bottle caps—Threaded to screw
on to the sample bottles. Caps must be
lined with Teflon. Foil may be
substituted if sample is not corrosive.
  4.1.3  Compositing equipment—
Automatic or manual compositing
system. Must incorporate glass sample
containers for the collection of a
minimum ef 250 ml. Sample containers
must be kept refrigerated during
sampling. No tygon or rubber tubing
may be used in the system.
  4.2   Separatory funnel—2000 mi. with
Teflon stopcock.
  4.3   Drying column—20 mm ID pyrex
chromatographic column with coarse
frit.
  4.4   Kuderna-Danish (K-D)
Apparatus

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 69492	Federal Register / Vol.  44. No. 233 / Monday. December  3, 1979 / Proposed Rules
   4.4.1  Concentrator tube—10 ml,
 graduated (Kontes K-570050-1025 or
 equivalent). Calibration must be
 checked. Ground glass stopper (size 19/
 22 joint) is used to prevent evaporation
 of extracts.
   4.4.2 . Evaporative flask—500 ml
 (Kontes K-57001-0500 or equivalent).
 Attach to concentrator tube with
 springs. (Kontes  K-662750-0012).
   4.4.3  Snyder column—three-ball
 macro (Kontes K503000-0121 or
 equivalent).
   4.4.4  Snyder column—two-ball micro
 (Kontes K-569001-0219 or equivalent).
   4.4.5  Boiling chips—solvent
 extracted^ approximately 10/40 mesh.
   4.5 Water bath—Heated, with
 concentric ring cover, capable of
 temperature control (± 2°Q. The  bath
 should be used in a hood.
   4.6 Gas chromatograph—Analytical
 system complete with gas
 chromatograph suitable for on-column
 injection and all  required accessories
 including electron capture or flame
 ionization detector, column supplies,
 recorder, gases, syringes. A data system
 for measuring peak areas is
 recommended
   4.7 Chromatography column—300
 mm long x 10 mm ID with coarse fritted
 disc at bottom and Teflon stopcock
 (Kontes K-420540-0213 or equivalent).
   5. Reagents.
   5.1 Preservatives:
   5.1.1  Sodium hydroxide—(ACS) 10 N
 in distilled water.
   5.1.2  Sulfuric  acid—(ACS) Mix equal
 volumes of cone. H,SO, with distilled
 water.
   5.2 Methylene chloride—Pesticide
 quality or equivalent.
   5.3 Sodium Sulfate—(ACS) Granular,
 anhydrous (purified by heating at 400°C
 for 4 hrs. in a shallow tray).
   5.4 Stock standards—Prepare  stock
 standard solutions at a concentration of
 1.00 fig/i*l by dissolving 0.100 grams of
 assayed reference material in pesticide
 quality isooctane op-other appropriate
 solvent and diluting to volume in a 100
 ml ground glass stoppered volumetric
 flask. The stock solution is transferred
 to ground glass stoppered reagent
 bottles, stored in a refrigerator, and
 checked frequently for signs of
 degradation or evaporation. especiaOy
 just prior to preparing working
 standards from them.
   5.5 Diethyl Ether—Nanograde,
 redistilled in glass if necessary.
   5.5.1  Must be free of peroxides as
 indicated by EM Quant test strips. (Test
 strips are available from EM
 Laboratories, Inc., 500 Executive Blvd.,
 Elmsford. N.Y. 10523.)
   5.5.2  Procedures recommended for
removal of peroxides are provided with
 the test strips. After cleanup, 20 ml ethyl
 alcohol preservative must be added to
 each liter of ether.
  5.8  Florisil—PR grade (80/100 mesh);
 purchase activated at 1250*F and store
 in dark in glass container with ground
 glass stoppers or foil-lined screw caps.
  5.7  Alumina—Activity Super I,
 Neutral. W200 series, (ICN Life Sciences
 Group, No. 404583).
  5.8  Hexane—Pesticide quality.
  6. Calibration.
  6.1  Prepare calibration standards
 that contain the compounds of interest,
 either singly or mixed together. The
 standards should  be prepared at
 concentrations covering two or more
 orders of magnitudes that will
 completely bracket the working range of
 the chromatographic system. If the
 sensitivity of the detection system can
 be calculated from Table I as 100 ng/1
 in the final extract for example, prepare
 standards at 10 j*g/l, 50 fig/1,100 pg/1.
 500 fig/1, etc. so that injections of 1-5 >il
 of each calibration standard will define
 the  linearity of the detector in the
 working range.
  &2 Assemble the necessary gas
 chromatographic apparatus and
 establish operating parameters
 equivalent to those indicated in Table 1.
 By injecting calibration standards,
 establish-the sensitivity limit of the
 detector and the linear range of the
 analytical'system  for each compound.
  6.3 Before using any cleanup
procedure, the analyst must process a
 series of calibration standards through
 the  procedure to validate elution
patterns and the absence of
 interferences from the reagents.
  7. Quality Control.
  7.1 Before processing any samples.
 the  analyst should demonstrate through
 the  analysis of a distilled water method
 blank, that all glassware and reagents
 are  interference-free. Each time a set of
 samples is extracted or there is a change
in reagents, a method blank should be
 processed as a safeguard against
 chronic laboratory contamination.
  7:2 Standard quality assurance
practices should be used with this
 method. Field replicates should be
 collected to validate the precision of the
sampling technique. Laboratory
 replicates should be analyzed to
 validate the precision of the analysis.
Fortified samples  should be analyzed to
validate the accuracy of the analysis.
Where doubt exists over the
identification of a  peak on the
 chromatogram, confirmatory techniques
 such as mass spectroscopy should be
used.
  8. Sample Collection, Preservation,
and Handling.
  8.1  Grab samples must be collected
in glass containers. Conventional
sampling practices should be followed.
except that the bottle must not be
prewashed with sample before
collection. Composite samples should be
collected in refrigerated glass containers
in accordance with the requirements of
the program. Automatic sampling
equipment must be free of tygon and
other potential sources of
contamination.
  8.2  The samples must be  iced or
refrigerated from the time of  collection
until extraction. Chemical preservatives
should not be used in the field unless
more than 24 hours will elapse before
delivery to the laboratory. If  the samples
will not be extracted within 48 hours of
collection, the sample should be
adjusted to a pH range  of 6.0-8.0 with
sodium hydroxide or suifuric acid
  8.3  All samples must be extracted
within 7 days and completely analyzed
within 30 days of collection.
  9. Sample Extraction.
  9.1  Mark the water meniscus on the
side of the sample bottle for later
determination of sample volume. Pour
the  entire sample into a two-liter
separatory funnel. Check the ph of the
sample pH with wide-range paper and
adjust to within the range of  5-9 with
sodium hydroide or suifuric acid.
  9.2  Add 60 ml methylene  chloride to
the  sampje bottle, seal,  and shake 30
seconds to rinse the inner walls.
Transfer the solvent into the  separatory
funnel, and extract the sample by
shakingjhe funnel for two minutes with
periodic venting to release vapor
pressure. Allow the organic layer to
separate from the water phase for a
minimum of ten minutes. If the emulsion
interface between layers is more than
one-third the size of the solvent layer,
the  analyst must employ mechanical
techniques to complete  the phase
separation. The optimum technique
depends upon  the  sample, but may
include stirring, filtration of the
emulsion through glass  wool, or
centrifugation. Collect the methylene
chloride extract in a 250-ml Erlenmeyer
flask.
  9.3  Add a second 60-ml volume of
methylene chloride to the sample bottle
and complete the extraction procedure a
second time, combining the extracts in
the  Erlenmeyer flask.
  9.4  Perform a third extraction in the
same manner. Pour the  combined
extract through a drying column
containing 3-4 inches of anhydrous
sodium sulfate, and collect it in a 500-ml
Kudema-Danish (K-D) flask equipped
with a 10 ml concentrator tube. Rinse
the  Erlenmeyer flask and column with

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              Federal Register / Vol. 44. No.  233 / Monday. December 3, 1979  / Proposed Rules	69493
20-30 ml methylene chloride to complete
the quantitative transfer.
  9.5  Add 1-2 clean boiling chips to
the flask and attach a three-ball Snyder
column. Prewet the Snyder column, by
adding about 1 ml methylene chloride to
the top. Place the K-D apparatus on a
hot water bath (60-65'C) so that the
concentrator tube is partially immersed
in the hot water, and  the entire lower
rounded surface of the flask is bathed in
vapor. Adjust the-vertial position of the
apparatus and the water temperature as
required to complete the concentration
in 15-20 minutes. At the proper rate of
distillation the balls of the column will
activeiy chatter but the chambers will
not flood. When the apparent volume of
liquid reaches 1 ml, remove the K-D
apparatus and allow it to drain for at
least 10 minutes while cooling.
  9.6  Increase the temperature of the
hot water bath to about 80°C.
Momentarily remove  the Snyder column.
add 50 ml of hexane and a new boiling
chip and reattach the Snyder column.
Pour about 1 ml of hexane into the top of
the Snyder column and concentrate the
solvent extract as before. Elapsed time
of concentration should be 5 to 10
minutes. When the apparent volume of
liquid reaches 1 ml, remove the K-D
apparatus and allow it to drain at least
10 minutes while, cooling. Remove the
Snyder column and rinse the flask and
its lower joint into the concentrator tube
with 1-2 ml of hexane, and adjust the
volume to 10 ml A 5-ml syringe is
recommended for this operation.
Stopper the concentrator tube anchstore
refrigerated if further processing will not
tie performed immediately. If the sample
extract requires no further cleanup
proceed with gas chromatographic
analysis. If the sample requires cleanup,
proceed to Section 10.
  9.7 Determine the original sample
volume by refilling the sample bottle to
the  mark and transferring the liquid to a
1000 ml graduated cylinder. Record the
sample volume to the nearest 5 ml.
  10. Cleanup and Separaton.
  10.1   If the entire extract is to be
cleaned up by one of  the following two
procedures, it must be concentrated to
about 2 ml. To the concentrator tube in
9.6, add a clean boiling chip and attach
a two-ball micro-Snyder-column. Prewet
the  column by adding about 0.5 mi
hexane through the top. Place the K-D
apparatus on a hot water bath [80'Q so
that the concentrator  tube is partially
immersed in the hot water. Adjust the
vertical position of-the apparatus and
the  water temperature as required to
complete the concentration in 5-10
minutes. At the proper rate of
distillation the balls of the column will
activeiy chatter but the chambers will
not flood. When the apparent volume of
liquid reaches about 0.5 ml, remove the
K-D apparatus and allow it to drain for
at least 10 minutes while cooling.
Remove the micro-Snyder column, and
rinse its lower joint into the
concentrator tube with 0.2 ml of hexane.
Proceed with one of the following clean-
up procedures.
   10.2  Florisil Column Cleanup for
Phthalate Esters
  10.2.1  Place 100 g of Florisil into a
500 ml beaker and heat for
approximately 16 hours at 400'C. After
heating transfer to a 500 ml reagent
bottle. Tightly seal and cfibl to room
temperature. When cool add 3 ml of
distilled water which is free of
phthalates and interferences. Mix
thoroughly by shaking or roiling for 10
minutes and let it stand for at least 2
hours.  Keep the bottle sealed tightly.
  10.2,2  Place lOg of this Florisil
preparation into a 10 mm ID
chromatography column and tap the
column to settle the Florisil. Add 1 cm of
anhydrous sodium sulfate to  the top of
the Florisil.
  10.2.3  Preelute the column with 40 ml
of hexane. Discard this eluate and just
prior to exposure of the sodium sulfate
layer to the air transfer the 2 ml sample
extract onto the column, using -an
additional 2 ml of hexane complete, the
transfer.
  10.2.4  just prior to exposure of the
sodium sulfate layer to the air add 40 ml
hexane and continue the elution of the
column. Discard this hexane  eluate.
  10.2.5  Next elute the phthalate esters
with 100 ml of 20 percent ethyl ether/80
percent hexane (V/V) into a 500 ml K-D
flask equipped with a 10 ml concentrator
tube. Elute the column at a rate of about
2 ml per minute for all fractions.
Concentrate the collected fraction by
standard K-D technique. No solvent
exchange is necessary. After
concentration and cooling, adjust the
volume of the cleaned up extract to 10
ml in the concentrator tube and analyze
by gas chromatography.
  10.3  Alumina Column Cleanup for
Phthalate Esters
  10.3.1  Place 100 g of alumina into a
500 ml beaker and heat for
approximately 16 hours at 400* C. After
heating transfer to a 500 ml reagent
bottle. Tightly seal and cool to room
temperature. When cool add  3 ml of
distilled water which is free from
phthalates and interferences. Mix
thoroughly by shaking or rolling for 10
minutes and let it stand for at least 2
hours. Keep the bottle sealed tightly.
  10.3.2  Place 10 g of this alumina
preparation into a 10 mm ID
chromatography column and tap the
column to settle the alumina. Add 1 cm
of anhydrous sodium sulfate to the top
of the alumina.
  10.3.3  Preelute the column with 40 ml
of hexane. Discard this eluate and just
prior to exposure of the sodium sulfate
layer to the air, transfer the 2 ml sample
extract onto the column, using an
additional 2 ml of hexane to complete
the transfer.
  10.3.4  Just prior to exposure of the
sodium sulfate layer to the air add 35 ml
hexane and continue to elution of the
column. Discard this hexane eluate.
  10.3.5  Next elute the column with 140
ml of 20 percent ethyl ether/80 percent
hexane (V/V) into a 500 mi K-D flask
equipped with a 10 ml concentrator
tube. Elute the column at a rate of about
2 ml per minute for all fractions.
Concentrate the collected fraction by
standard K-D technique. No solvent
exchange is necessary. After
concentration and cooling adjust the
volume of the cleaned up extract to 10
ml in the concentrator tube and analyze
by gas chromatography.
  11.   Gas Chromatography,
  11.1  Table I summarizes some
recommended gas chromatographic
column materials and operating
conditions for the instrument. Included
in this  table are estimated retention
times and sensitivities that should be   |
achieved by this method. Examples of
the separations achieved by the primary
column are shown in Figures 1 and 2.
Calibrate the system daily with a
minimum of three injections of
calibration standards.
  11.2  Inject 2-5 >tl of the sample
extract using the solvent-flush
technique. Smaller (1.0 jil) volumes can
be injected if automatic devices are
employed. Record the volume injected to
the nearest 0.05 pi, and the resulting
peak size, in area units.
  11.3  If the peak area exceeds the
linear range of the system, dilute the
extract and reanalyze.
  11.4  If the peak area measurement is
prevented by the presence of
interferences, further cleanup is
required.
  12.   Calculations.
  12.1  Determine  the concentration of
individual compounds according to the
formula:
ConountnOan. i
               (VJ(VJ

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69494         Federal Register /  Vol.  44, No. 233 /  Monday, December  3. 1979 /  Proposed  Rules
Where:
A—Calibration factor for chroma tographic
    system, in nanograma material per area
    unit.
B-Peak size in injection of sample extract, in
    area units
V,-Volume of extract injected !jd)
V,-Volume of total extract (jil)
V,» Volumeof water extracted (ml)

  12.2  Report results in micrograms per
liter without correction for recovery
data. When duplicate and spiked
samples are analyzed, all data obtained
should be reported.
  13.   Accuracy and Precision.
  13.1  The U.S. EPA Environmental
Monitoring and Support Laboratory in
Cincinnati is in the process of
conducting a Intel-laboratory method
study to determine the accuracy  and
precision of this test procedure.

Bibliography
"Development and Application of Test
  Procedures for Specific Organic Toxic
  Substances in Wastewatera. Category 1-
  Phtaalates." Report  for EPA Contract 88-
  03-2806 (In preparation).
                   fonndon Sma
                      tn*v)     Datacton
     Compound      _____^
                   Cot1  Cot 2  EC'   FIO
Oknwft* polhalata—   2.03   0.05   Q.11     19
Diathyl pMnalatt	   2.92   1-27   9.13     31
m n tiiityl pMtiaUM       ».86   ISO   0.02     14
Bmy< buy* pnmatta—   '8.J4  "5.11   0.02     IS

                    •«.«  "io.s   ao4     20
                    •112  1"«.0   0.11     3t
  • Sxmlcoooit toonzo iMih ctnttd wtth i 5% SP-2290/
1.95% SP-2401 ptcMd in • tSO em long x 4 mm 10 glM*
cokmM Mth arrlw gw M (0 ml/mm flow r*M CoKimn wm-
!>•>•*«• I* 180X «KMP4 wt>«r» • mmn* 220-C Undw
aw** oonoWom RT. at AWrtn it S.49 mm. « iag a 10 ml dual vqfuma ol Kw t Mai aamMa «-
tract, and asaumng a GC injactton of 5 mcroMara.
8ILUMQ COOC MaO-01-K

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            Federal Register / Vol. 44, No. 233 / Monday, December 3,1979 / Proposed Rules
                                                                    69495
   COLUMN:  1.5% SP-2250*

             1.35%.SP.2401 ON SUP3.COPORT

   TEMPERATURE:  1S04C.

   DETECTOR: ELECTRON CAPTURE
     ua
   UJ *-
   — O.
   o.  ,
e


C
0   24   S    3   10  12


  RETENTION TIME-MINUTES


Figure 1.  Gas chro;matogram of phthalates
                              COLUMN:  T.5% SP-22Sa*

                                       1.35% SP-2401 ON SUPaCOPORT

                              TEMPEHATURE: 180"C.

                              DETECTOR: ELECTRON CAPTURE
                                                             UJ

a.   i—



/N*   rs
2   i£
04   a
ea
-u
»
H-
3
                                                                          O
                                                                          c
                                                                           c
                                              0      4      8     12     1618


                                                    RETByTION T1ME-411NUTES



                                              Rgure 2. Gas chromatogram of phthalates
 ULUMQ CODE M60-01-C

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               Federal Register  /  Vol. 44,  iNo. 233  / Monday. December 3; 1979 /  Proposed Rules	69501
 OrganochJorina Pesticides and PC3's—
 Method 608
   1.  Scope and Application.
   1.1  This method covers the
 determination of certain organochlorine
 pesticides and polycnlorinated
 biphenyls (PCBa). The following
 parameters may be determined-by this
 method:
                               Stontjvo.
   •4HC.
   **«-
   *8HC_
                                  30298
                                  30340
   M'-OOE-
   4,«'-OOT.
   OM
                                  39310
                              30300
   Endcwuflw!	
   EMnutaiN—
   Endnufen SuMa
   Efldm.
   gndrto AMMlyd*
      crta
   H*pttditor Sparid*.
pca-ioi»_
PC8-12Z1-
PC8-1232-
PC8-1242--
PC8-1246X.
pce-i2S4_
PC8-1«0_
                              34981
                              34360
                              34351
                              39380
                              34306
                              30410
                              30420
                              30400
                              34071
               	    30408
               	    304«0
                 : .               39600
               	    30504
               	__    30600
  \2  This method is applicable to the
 determination of these compounds in
 municipal and industrial discharges. It is
 designed to be used to meet the
.monitoring requirements of the National
 Pollutant Discharge Elimination System
 (NPDES). As such, it presupposes a high
 expectation of finding the specific
 compounds of interest If the user is
 attempting to screen samples for any or
 all of the compounds above, he most
 develop independent protocols for the
 verification of identity.
  1.3  The sensitivity of this method is
 usually dependent upon the level of
 interferences rather than instrumental
 limitations. The limits of detection listed
 in Table I represent sensitivities that
 can be achieved in wastewaters in the
 absence of interferences.
  1.4  This method is recommended for
 use only by experienced residue
 analysts or under the close supervision
 of such qualified persons.
  2.   Summary of Method.
  2.1  A 1-liter sample of waste-water is
 extracted with methylene chloride using
 separatory funnel techniques. The
 extract is dried and concentrated to a
 volume of 10 ml or less.
 Chromatographic conditions are
 described which allow for the accurate
 measurement of the compounds in the
 extract
  ZJZ  If interferences are encountered,
 the method provides selected general
 purpose cleanup procedures to aid the
 analyst in their elimination.
  3.   Interferences.
  3.1  Solvents, reagents, glassware,
 and other sample processing hardware
may yield discrete artifacts and/or
elevated baselines causing
misinterpretation of gas chroma tograma.
All of these materials must be
demonstrated to be free from
interferences under the conditions of the
analysis by running method blanks.
Specific selection of reagents and
purification of solvents by distillation in
all-glass systems may be required.
  3.2  Interferences coextraded from
the samples will vary considerably from
source to source, depending upon the
diversity of the industrial complex or
municipality being, sampled. While
general cleanup techniques are provided
as part of this method, unique samples
may require additional cleanup
approaches to achieve the sensitivities
stated in Table 1.
  3.3  Glassware must be scrupulously
clean. Clean all glassware as soon as
possible after use by rinsing-with the
last solvent used. This should be
followed by detergent washing in hot
water. Rinse with tap water, distilled
water, acetone and finally pesticide
quality hexane. Heavily contaminated
glassware may require treatment in a
muffle furnace at 400° C for 15 to 30
minutes. Some high boiling materials.
such as PCBs, may not be eliminated by
this treatment. Volumetric ware should
not be heated in a muffle furnace.
Glassware should be sealed/ stored in a
clean environment immediately after
drying or cooling to prevent any
accumulation of dust or other
contaminants. Store inverted or capped
with aluminum foil.
  3.4 Interferences by phthalate esters
can pose a  major problem in pesticide
analysis. These materials eiute in the
15% and 50% fractions of the Florisil
cleanup. They usually can be minimized
by avoiding contact with any plastic
materials. The contamination from
phthalate esters can be completely
eliminated  with the use of a
microcoulometric or electrolytic
conductivity detector.
  4. Apparatus and Materials.
  4.1 Sampling equipment, for discrete
or composite  sampling.
  4.1.1  Grab sample bottle—amber
glass, 1-liter or 1-quart volume. French
or Boston Round design is
recommended. The container must be
washed and solvent rinsed before use to
minimize interferences.
  4.1.2  Bottle caps—Threaded to screw
on to the sample bottles. Caps must be
lined with Teflon. Foil may be
substituted if sample is not corrosive.
  4.1.3  Compositing equipment-
Automatic or manual compositing
system. Must incorporate glass sample
containers for the collection of a
minimum of 250 ml. Sample containers
must be kept refrigerated during
sampling. No tygon or robber tubing
may be used in the system.
  4.2  Separatory funnel—2000 ml, with
Teflon stopcock.
  4.3  Drying column—20 mm ID pyrex
chromatographic column with coarse
frit
  4.4  Kuderna-Danish (K-D)
Apparatus
  4.4.1  Concentrator tube—10 ml,
graduated (Kontes K-570050-1025 or
equivalent). Calibration must be
checked at 1.0 and 10.0 ml level. Ground
glass stopper (size 19/22 joint) is used to
prevent evaporation oi extracts.
  4.4.2  Evaporative flask—500 ml
(Kontes K-57001-0500 or equivalent).
Attach to concentrator tube with
springs. (Kontes K-662750-0012).
  4.4.3  Snyder column—three-ball
macro (Kontea K503000-0121 or
equivalent).
  4.4.4  Boiling chips—extracted,
approximately 10/40 mesh.
  4.5  Water bath—Heated, with
concentric ring  cover, capable of
temperature control (±2"C). The bath
should be used  in a hood.
  4.3  Gas chroma tograpn—Analytical
system complete with gas
chromatograpb  suitable for on-cohimn
injection and all required acessories
including electron capture or halogen-
specific detector, column supplies,
recorder, gases, syringes. A data system
for measuring peak areas is
recommended.
  4.7  Chromatographic column—Pyrex
400 mm X 25 mm OD, with coarse
fritted plate and Teflon stopcock
(Kontes K-42054-213 or equivalent).
  5. Reagents.
  5.1 Preservatives:
  5.1.1  Sodium hydroxide—(ACS) 10 N
in distilled water.
  5.1.2  Sulfuric acid (1+1}—(ACS)  Mix
equal volumes of cone. HaSO« with
distilled water.
  5.2 Methylene chloride—Pesticide
quality or equivalent.
  5.3 Sodium Sulfate—(ACS) Granular,
anhydrous (purified by heating at 400*C
for 4 hrs. in a shallow tray).
  5.4 Stock standards—Prepare stock
standard solutions at a concentration of
1.00 Mg/Ml by dissolving 0.100 grams  of
assayed reference material in pesticide
quality isooctane or other appropriate
solvent and diluting to volume in a 100
ml ground glass stoppered volumetric
flask. The stock solution is transferred
to ground glass  stoppered reagent
bottles, stored in a refrigerator, and
checked frequently for signs of
degradation or evaporation, especially
just prior to preparing working
standards from  them.

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69502        Federal  Register / Vol. 44. No.  233 / Monday, December 3. 1979  / Proposed Rules
  5.5  Boiling chips—Hengar granules
(Hengar Co.; Fisher Co.) or equivalent
  5,6  Mercury—triple distilled.
  5.7  Aluminum oxide—basic or
neutral, active.
  5.3  Hexane—pesticide residue
analysis grade.
  5.9  Isooctane (2.2,4-trimethyl
pentane)—pesticide residue analysis
grade.
  5.10 Acetone—pesticide residue
analysis grade.
  5.11 Diethyi ether—Nanograde.
redistilled in glass if necessary.
  5.11.1  Must be free of peroxides as
indicated by EM Quant test strips (Test
strips are available from EM
Laboratories. Inc., 500 Executive Blvd..
Elmsford, N.Y., 10523).
  5.1.2  Procedures recommended for
removal of peroxides are provided with
the test strips. After~cleanup 20 ml ethyl
alcohol preservative must be added to
each liter of ether.
  5.12 Florisil—PR grade {60/100
mesh); purchase activated at 1250T and
store in glass containers with glass
stoppers or foil-lined screw caps. Before
use activate each batch at least 16 hours
at 130"C in a foil covered glass
container.
  6. Calibration.
  6.1   Prepare calibration standards
that contain the compounds of interest
either singly or mixed together. The
standards should be prepared at
concentrations covering two or more
orders of magnitude that will completely
bracket the working range of the
chromatographic system. If the
sensitivity of the detection system can.
be calculated from Table I as 100 >ig/l in
the final extract, for example, prepare.
standards at 10 ug/1. 50 /ig/1,100 jug/1.
500 pg/L eta, so that injections of 1-5 pd
of each calibration standard will define
the linearity of the detector in the
working range.
  6.2  Assemble the necessary gas
chromatographic apparatus and
establish operating parameters
equivalent to those indicated in Table L
By injecting calibration standards,
establish the sensitivity limit of the
detector and the linear range of the
analytical system for each compound.
  6.3   The cleanup procedure in Section
10 utilizes Florisil chromatography.
Florisil froni different batches or sources
may vary in absorption capacity. To
standardize the amount of Florisil which
is used, the use of lauric acid value
(Mills, 1968) is suggested. The
referenced procedure determines the
adsorption from bexane solution of
lauric acid (mg) per gram Florisil. The
amount of Florisil to be used for each
column is calculated by dividing this
factor into 110 and multiplying by 20
grams.
  6.4  Before using any cleanup
procedure, the analyst must process a
series of calibration standards through
the procedure to validate elution
patterns and the absence of
Interferences from the reagents.
  7. Quality Control.
  7.1  Before processing  any samples,
the analyst should demonstrate through
the analysis of a distilled water method
blank, that all glassware and reagents
are interference-free. Each time a set of
samples is extracted or there is a change
in reagents, a method blank should be
processed as a safeguard against
chronic laboratory contamination.
  7.2  Standard quality assurance
practices should be used with this
method. Field replicates should be
collected to validate Jhe precision of the
sampling technique. Laboratory
replicates should be analyzed to
validate the precision of the analysis.
Fortified samples should be analyzed tc
validate the accuracy of the analysis.
Where doubt exists over the
identification of a peak on the
chromatogram, confirmatory techniques
such as mass spectroscopy should be
used.
  8. Sample Collection, Preservation.
and Handling.
  8.1  Grab samples must be collected
in glass containers. Conventional
sampling practices should be followed.
except that the bottle must not be
prewashed with sample before
collection. Composite samples  should be
collected in refrigerated glass containers
in accordance with the requirements of
the program. Automatic sampling
equipment must be free of tygon and
other potential sources of
contamination.
  8.2  The samples must be  iced or
refrigerated  from the time of collection
until extraction. Chemical preservatives
should not be used in the  field unless
more than 24 hours will elapse before
delivery to the laboratory. If  the samples
will not be extracted within 48 hours of
collection, the .sample should be
adjusted to a pH range of 6.0-6.0  with
sodium hydroxide or sulfuric acid.
  8.3  All samples must be extracted
within 7 days and completely analyzed
within 30 days of collection.
  9. Sample Extraction.
  9.1  Mark the water meniscus  on the
side of the sample bottle for later
determination of sample volume. Pour
the entire sample into a two-liter
separatory funnel. Check the pH  of the
sample with wide-range pH paper and
adjust to within the range of 5-9 with
sodium hydroxide or sulfuric acid.
  9.2  Add 60 ml methylene chloride to
the sample bottle, seal, and shake 30
seconds to rinse the inner walls.
Transfer the solvent into the separatory
funnel, and extract the sample by
shaking the runnel for two minutes with
periodic venting to release vapor
pressure. Allow the organic layer to
separate from the water phase for a
minimum of ten minutes. If the emulsion
interface between layers is more than
one-third the size of the solvent layer,
the analyst must enploy mechanical
techniques to complete the phase
separation. The optimum technique
depends upon the sample, but may
include stirring, filtration of the
emulsion through glass wool, or
centrifugation. Collect the msthylene
chloride extract in a 250-ml Erlenmeyer
flask.
  9.3  Add a second 60-ml volume of
methylene chloride to the sample bottle
and complete the extraction procedure a
second time, combining the extracts in
the Erlenmeyer flask.
  9.4  Perform a third extraction in the
same manner. Pour the combined
extract through a drying column
containing 3—i inches of anhydrous
sodium sulfate.'and collect it in a 500-ml
Kudema-Danish (K-D) flask equipped
with a 10 ml concentrator tube. Rinse
the Erlenmeyer flask and column with
20-30 ml methylene chloride to complete
the quantitative transfer.
  9.5  Add 1-2 clean boiling chips to
the flask and attach a three-bail Snyder
column. Prewet the Snyder column by
adding about 1 ml methylene chloride to
the top. Place the K-D apparatus on a
hot water  bath (60-65''C) so that the
concentrator tube is partially immersed
in the hot water, and the entire lower
rounded surface of the flask is bathed in
vapor. Adjust the vertical position of the
apparatus and the water temperature as
required to complete the concentration
in 15-20 minutes. At the proper rate of
distillation the balls of the column will
actively chatter but the chambers will
not flood. When the apparent volume of
liquid reaches 1 ml, remove the K-D
apparatus-and allow it to drain for at
least 10 minutes while cooling.
  9.6  Increase the temperature of the
hot water  bath to about 80°C.
Momentarily remove the Snyder column,
add 50 ml  of hexane and a new boiling
chip and reattach the Snyder column.
Pour about 1 ml of hexane into the top of
the Snyder column and concentrate the
solvent extract as before,  the elapsed
time of concentration should be  5 to 10
minutes. When the apparent volume of
liquid reaches 1 ml, remove the K-D
apparatus and allow it to  drain at least
10 minutes while cooling. Remove the
Snyder column and rinse the flask and

-------
               Federal Register  /  Vol. 44, No. 233  /  Monday, December 3,  1979  /  Proposed  Rules	69503
 its lower joint into the concentrator tube
 with 1-2 ml of hexane, and adjust the
 volume to 10 ml. A 5-ml syringe is
 recommended for this operation.
 stopper the concentrator tube and store
 refrigerated if further processing will not
 be performed immediately. If the  sample
 extract requires no further cleanup,
 proceed with gas chromatographic
 analysis. If the  sample requires cleanup.
 proceed to Section 10.
   9.7  Determine the original sample
 volume by refilling the sample bottle to
 the mark and transferring the liquid to a
 1000 ml graduated cylinder. Record the
 sample volume to the nearest 5 ml.
   10. Cleanup and Separation.
   10.1   Cleanup procedures are used to
 extend the sensitivity of a method by
 minimizing or eliminating interferences
 that mask or otherwise disfigure the gas
 chromatographic  response to the
 pesticides and PCB's. The Florisil
 column allows for a select fractionation
 of the compounds and will eliminate
 polar materials. Elemental sulfur
 interferes with the electron capture gas
 chromatography of certain pesticides
 but can be removed by the techniques
 described below.
   10.2   Florisil Column Cleanup
   10.2.1  Add a weight of Florisil,
 (nominally 21g,) predetermined by
 calibration (6.3, 6.4), to a
 chromatographic  column. Settle the
 Florisil by tapping the column. Add
 sodium sulfate to  the top of the Florisil
 to form a layer 1-2 cm deep. Add  60 ml
 of hexane to wet and rinse the sodium
 sulfate and Florisil. Just prior to
 exposure of the sodium sulfate to  air,
 stop the elution of the hexane by closing
 the stopcock on the chromatography
 column. Discard the eluate.
  10.2.2 Adjust the sample extract
 volume to 10 ml and transfer it from the
 K-D concentrator tube to the Florisil
 column. Rinse the tube twice with 1-2'
 ml hexane, adding each rinse to the
 column.
  10.2.3 Place a 500 ml K-D flask  and
 clean concentrator tube under the
 chromatography column. Drain the
 column into  the flask until the sodium
 sulfate layer is nearly exposed. Elute the
 column with 200 ml of 6% ethyl ether in
hexane (Fraction  1) using a drip rate of
 about 5 ml/min. Remove the K-D  flask
and set aside for later concentration.
Elute the column again, using 200  mi of
15% ethyl ether in nexane  (Fraction 2),
into a second K-D flask. Perform the
 third elution using 200 ml of 50% ethyl in
hexane (Fraction 3). The elution patterns
 for the pesticides  and PCB's are shown
 in Table II.
   10.2.4 Concentrate the eluates by
 standard K-D techniques (9.5),
 substituting hexane for the glassware
 rinses and using the water bath at about
 85° C. Adjust final volume to 10 ml with
 hexane. Analyze by gas
 chromatography.
   10.3 Elemental sulfur will usually
 elute entirely in Fraction 1. To remove
 sulfur interference from  this fraction or
 the original extract pipet 1.00 ml of the
 concentrated extract into a clean
 concentrator tube or Teflon-sealed vial.
 Add 1-3 drops of mercury and seal.
 Agitate the contents of the vial for 15-30
 seconds. Place the vial hi an upright
 position on a  reciprocal laboratory
 shaker and shake for 2 hours. Analyze
 by gas chromatography.
   11. Gas Chromatography.
    11.1 Table I summarizes some
 recommended gas chromatographic
 column materials and operating
 conditions for the instrument. Included
 in this table are  estimated retention
 times and sensitivities that should be
 achieved by this method. Examples of
 the separations achieved by these
 columns are shown in Figures 1  through
 10. Calibrate the system daily with a
 minimvnn of three injections of
 calibration standards.
   11.2 Inject 2-5 /il of the sample
 extract using the solvent-Hush
 technique. Smaller (1.0 jil) volumes can
 be injected if automatic devices-are
 employed. Record the volume injected to
 the nearest 0.05 jil, and the resulting
 peak size, in area units.
   11.3 If the peak area exceeds  the
 linear range of the system, dilute the
 extract-and reanalyze.
   11.4 If the peak area measurement is
 prevented by  the presence of
 interferences, further cleanup  is
 required.
   12. Calculations.
   12.1  Determine the concentration of
 individual compounds  according to the
 formula:

     Concentraoon, ^a/l- (A)(BXV'>
                    (VJ(VJ
 Where:
A=Calibration factor for chromatographic
    system, in nanograms material per area
    unit.
 8=Peak size in injection of sample extract, in
    area units
 Vj=Volume of extract injected (>il)
 V,=Volume of total extract (u,l]
 V,=Volume of water extracted (ml)
   12.2 Report results in micrograms per
 liter without correction for recovery
 data. When duplicate and spiked
 samples are analyzed, all data obtained
 should be reported.
   13. Accuracy and Precision.
   13.1 The U.S. EPA Environmental
 Monitoring and Support Laboratory in
 Cincinnati is in the process of
 conducting an interiaboratory method
 study to determine the accuracy and
 precision of this test procedure.

 Bibliography
 1. "Development and Application of Te»t
   Procedures for Specific Organic Toxic
   Substances in Wastewaters. Category 10-
   Pesticides and PCB's." Report for EPA
   Contract 68-03-2606.
 2. Mills, P. A., "Variation of Florisil Activity:
   Simple Method for Measuring Absorbent
   Capacity and Its Use in Standardizing
   Florisil Columns," Journal of the
   Association of Official Analytical
   Chemists, 51, 29 (1968).

  lata* \.—Gas Chramatognphy of Ptstladis ana
                 PCB's
       Parameter
                    Col. 1 '  Col.2 *
                                .Detection
Ab*in-
a-8HC . 	 _._
hJlWC , ,.,.„.,„ ..,...,
*9HC 	 	 	 	 	
jjiwr.
Qil
n
o
4.10
1.82
i.sr
2JO
2.13
(«)
9.08
7.15
11.75
723
9.20
8^8
10.70
8.10
9 JO
3.35
5.00
C)
C)
C)
C)
C)
(')
C)
n
0.003
0.002
0.004
0.004
0.002
0.04
0.012
0.006
0.018
0.006
0.009
0.01
0.03
0.009
0.023
0.002
0.004
0.40
0.04
0.10
0.10
o.os
0.08
0.08
0.15
  " Supeteoport 100/120 mesh coated with 1.5% SP-22SO/
1.95% SP-2401 pocked in « 180 cm long x 4 mm IO glass
column vMtl) 5* Methane/95% Argon earner gM n 60 ml/ mm
flow raw. Column temperature is JOO'C.
  'Supetcoport 100/120 mesh coated wim3%OV-l inaieo
cm long x 4 mm 10 glass column witd 5% Mettwe/95%
Argon earner gu at 60 ml/min flow rate. Column temperature
 'Detection Kmn 'a calculated from the minimum detectable
GC response being equal to five times the GC background
nose, assuming s 10 ml final volume o« the 1 liter sample
extract and assuming a <3C injection of 5 rncrentsrs.
 • Multiple peak response. See Figures 2-10.

-------
69504         Federal  Register /  Vol. 44.  No.  233  / Monday. December 3. 1979  /  Proposed  Rules
     ft**** tnd PCBt tMng ftofM Column
              Chromftogrtpfty
                              *yr
                               2 (1*   3 (M
                        1O pet)  pet)   pet)
AWrtn	    too .
«-8HC	    100 .
6-8HC	
       	100	
CMORkM	    '00	_^~_

4,4--oof JZZZZILZIir    M .Z!"ZZ!""Z
40*'-DOT	    100	
OMdrtn	     0    TOO	
EndOflUlfin I -»«..»..Mw««H».««_nr    37    64 .T_.....Tt.....
EndotulMnll		     0     7     tl
EndowiNMi MMO.	     0     0    10t
Sndhn	     4    M	
Endrin ttfttlHffto      ri_..   ^     0    98     38
H*etteNor	„	    100 .
McplMNer •poxfcl* ™—-.	.-.    100.
ToK*oft4n»	.„...	    M .
PCd-1018.	    97 .
PC8-1221	97 .
PC8-124&.
PW-1254	
PC8-1J60—
  •From •Dottopnunt and AppDetfon o( T««t PraeMurM
tor SptcMo Orgvie Tade SubCMMM m WMMMMI*. CM»
yory iO^M«o«ta and PCS'!. Report tor EPA CenMet »-
03-280*.-

INUUNO COM MW-01-M

-------
COLUMN: 1.5% SP-2250*

         1.95% SP-2401 ON SUPELCOPORT
TEMPERATURE: 200'C.

DETECTOR: ELECTRON  CAPTURE

      iu
      o

      o
O     S3                     u;
      o=                     <
      O                     u.
        4        8        12       16

          RETENTION TIME-MINUTES
Figure 1. Gas chromatogram of pesticides
                                                                         COLUMN: 1.5% SP-2250*

                                                                                  1.95% SP-2401 ON SUPELCOPORT

                                                                         TEMPERATURE: 200*C.

                                                                         DETECTOR: ELECTRON  CAPTURE
                                                                                                                  S?

                                                                                                                  !
                                                                                                                  90
                                                                                                                  I
                                                                                                                  5
                                                                                                                  CO
                                                                                                                  o

                                                                                                                  O.
                                                                                                                  B>



                                                                                                                  O
                                                                                                                  8*
                                                                                                                   °
                                                                           4        8        12

                                                                           RETENTION TIME-MINUTES
                                                                                                        16
                                                                   Figure 2.  Gas chromatogram of chlordane
O
•a
o
(0
g
(I.
n

-------
                     COLUMN: 1.5% SP-2250+
                             1.95?'. SP-2401 ON SUPELCOPORT
                     TEMPERATURE: 200*C.
                     DETECTOR:  ELECTRON CAPTURE
                 10      14      18      22
                RETENTION TIME-MINUTES
26
Figure 3. Gas chromatogram of toxaphene
                   COLUMN: 1.5% SP-2250+ 1.95% SP-2401 ON SUPELCOPORT
                    EMPERATURE:  160*C.
                   DETECTOR:  ELECTRON CAPTURE
                      2        6       10      14       18
                               RETENTION TIME-MINUTES

                  Figure 4.  Gas chromatogram of PCB-1016
22
                                                                                                                      u»
                                                                                                                      3.

                                                                                                                      I
                                                                                                                      8
                                                                                                                      o
                                                                                                                      CJ
                                                                                                                      CO
                                                                                                                      o

                                                                                                                      IB

                                                                                                                      a
                                                                                                                      CO

                                                                                                                      I
                                                                                                                      a
                                                                                                                      i
                                                                                                                      01
                                                                                                                      M
                                                                                                                      (O
o
•o
o
a>
A
a.
                                                                                                                      E.
                                                                                                                      (D
                                                                                                                      (O

-------
  COLUMN:  1.5% SP-2250* 1.95% SP-2401 ON SUPELCOPORT

  TEMPERATURE:  160*C.

  DETECTOR: aECTRON CAPTURE
            6       10      14       18

              RETENTION TIME-MINUTES
                    COLUMN: 1.5% SP-2250. 1.95'; SP-2401 ON SUPELCOPORT

                    TEMPERATURE: 160'C.

                    DETECTOR: ELECTRON CAPTURE
                                                                                                                      z

                                                                                                                      o
                                                                                                                      9
                                                                                                                      IX
                                                                                                                      to
                                                                                                                      (D
                                                                                                                      3
                                                                                                                      cr
                                                                         6       10       14       18

                                                                             RETENTION TIME-MINUTES
                                                             22
24
22
                                                             Figure 6. Gas chromatogram of PCB-1232
Figure 5. Gas chromatogram of PC8-1221
                                                                         O
                                                                         CO
                                                                         (ft
                                                                         Q-


                                                                         I
                                                                         a>
                                                                         ce
                                                                                                                      O>
                                                                                                                      CO

-------
    COLUMN:  1.SK SP-2250+ 1.95?'. SP-2401 ON SUPELCOPORT
    TEMPERATURE:  160*C.
    DETECTOR: ELECTRON CAPTURE
    2       6        10       14       18
               RETENTION TIME-MINUTES

Figure 7.  Gas chromatogram of PCS-1242
22
                       COLUMN:  1.5% SP-2250* 1.9S?/. SP-2401 ON SUPaCOPORT
                       TEMPERATURE:  160*C.
                       DETECTOR:  ELECTRON CAPTURE
                       2        6       10      14      18
                                    RETENTION TIME-MINUTES

                   Figure 8.  Gas chromatogram of PCB-1248
22
26
                                                                                                                             9-
                                                                                                                             I
                I
55
to

I
ID
2.
E.
2

-------
COLUMN: 1.5% SP-2250 +
TEMPERATURE:  200*C.
DETECTOR:  ELECTRON CAPTURE
                               SP-2401 ON SUPELCOPORT
               COLUMN: 1.5% SP-2250* 1.95X SP-2401 ON SUPELCOPORT
               TEMPERATURE:  200*C.
               DETECTOR: ELECTRON CAPTURE
                                                                                                                        2.
                                                                                                                        90
                                                                                                                        "2
                                                                                                                        o
                                                                                                                        o>
                                                                                                                        I
                                                                                                                        3
                                                                                                                        cr
                                                                                                                        a
                                                                                    _L
                                                                                       -L
                                                                                           JL
                                                                                                  _L
                                                                                10      14      18      22
                                                                                 RETENTION TIME-MINUTES
                                                                                                         26
                                                              Figure 10. Gas chromatogram of PCB-1260
               6         10        14

                 RETENTION TIME-MINUTES
                                       18
22
Figure 9. Gas chromatogram of PCB-1254
BILLING CODE *MO-Ot-C
                                                                                                                    o.
                                                                                                                    ya
                                                                                                                    a>
                                                                                                                    
-------
69510
Federal  Register / Vol. 44, No.  233 /  Monday,  December 3,  1979 /  Proposed Rules
Nitroaromatics and Isophorone—
Method 609
  1, Scope and Application.
  1.1  This method covers the
determination of certain nitroaromatics
and isophorone. The/following
parameters may be determined by this
method:
                               Slorsl No.
Parameter
   Isophorone
   Nitrobenzene
   2.4-Omrtrotoluene.
   2.6-OinttrotokMne.
                   SAW
                   34S(1
                   34826
   1.2  This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used;to meet the
monitoring requirements of the National
Pollutant Discharege Elimination System
(NPDES). As such, it presupposes a high
expectation of finding the specific
compunds of interest. If the user is
attempting to screen samples for any or
all of the compounds above, he must
develop independent protocols for the
verification of identity.
   1.3  The sensitivity of this method is
usually dependent upon the leve! of
interferences rather than instrumental
limitations. The limits of detection listed
in Table I represent sensitivities that
can be achieved in wastewaters in the
absence of interferences.
   1.4  This method is recommended for
use only by experienced residue
analysts or under the close supervision
of such qualified persons.
   2. Summary of Method.
   2.1  A 1-liter sample of wastewater is
extracted with methylene chloride using
separatory funnel techniques. The
extract is dried and exchanged to
toluene while being concentrated to 1.0
ml. Isophorone and nitrobenzene are
measured by flame ionization gas
chromatography. The dinitrotoluenes
are measured by electron capture GC.
  2.2  If interferences are encountered.
the method provides a general purpose
cleanup procedure to aid the  analyst in
their elimination.
  3. Interferences.
  3.1  Solvents, reagents, glassware,
and other sample processing hardware
may yield discrete artifacts and/or
elevated baselines causing
misinterpretation of gas chromatograms.
All of these materials must be
demonstrated to be free from
interferences under the conditions of the
analysis by running method blanks.
Specific selection of reagents and
purification of solvents by distillation in
all-glass systems may be required.
  3.2  Interferences coextracted from
the samples will vary considerably from
source to source, depending upon the
diversity of the industrial complex r
municipality being sampled. While
general clean-up techniques are
provided as part of this method, unique
samples may require additional-cleanup
approaches to achieve the sensitivities
stated in Table I.
  4. Apparatus and Materials.
  4.1   Sampling equipment, for discrete
or composite sampling.
  4.1.1  Grab sample bottle—amber
glass, 1-liter or 1-quart volume. French
or Boston Round design is •
recommended. The container  must be
washed and solvent rinsed before use to
minimize interferences.
  4.1.2  Bottle caps—Threaded to screw
on to the sample bottles. Caps must be
lined with Teflon. Foil may be
substituted if sample is not corrosive.
  4.1.3  Compositing equipment—
Automatic or manual compositing
system. Must incorporate glass sample
containers for the collection of a
minimum of 250 ml. Sample containers
must be kept refrigerated during_
sampling. No tygon or rubber  tubing
may be used in the system.
  4,2   Separatory funnel—2000 ml, with
Teflon stopcock.
  4,3   Drying column—20 mm ID pyrex
chromatographic column with coarse
frit.
  4,4   Kuderna-Danish (K-D)
Apparatus
  4,4.1  Concentrator tube—10 ml.
graduated (Kontes K-570050-1025 or
equivalent). Calibration must  be
checked. Ground glass stopper (size 19/
22 joint) is used to prevent evaporation
of extracts.
  4 4.2  Evaporative flask—500 ml
(Kontes K-57001-0500 or equivalent).
Attach to concentrator tube with
springs. (Kontes K-662750-0012).
  4,4.3  Snyder column—three-ball
macro  (Kontes K503000-0121 or
equivalent).
  4,4.4  Snyder column—two-ball micro
(Kontes K-569001-0219 or equivalent).
  4.4.5  Boiling chips-solvent extracted.
approximately 10/40 mesh.
  4,5   Water bath—Heated; with
concentric ring cover, capable of
temperaWe control (±2"C). The bath
should be used in a hood.
  4,6   Gas chromatograph—AnalyticaJ
system complete with gas
chromatograph suitable for on-column
injection and all required accessories
including both electron capture and
flame ionization detectors, column
supplies, recorder, gases, syringes. A
data system for measuring peak areas is
recommended.
  4.7   Chromatography column—400
mm long x 10 mm ID, with coarse fritted
plate on bottom and Teflon stopcock.
  5. Reagents.
  5.1   Preservatives:
   5.1.1   Sodium hydroxide—(ACS) 10 N
 in distilled water.
   5.1.2   Sulfuric acid (1 + 1)—(ACS) Mix
 equal volumes of cone. HiSO* with
 distilled water
   5.2  Methylene chloride—Pesticide
 quality or equivalent.
   5.3  Sodium sulfate—(ACS) Granular,
^anhydrous (purified by heating at 400°C
 for 4 hrs. in a shallow tray).
   5.4  Stock standards—Prepare stock
 standard solutions at a concentration of
 1.00 p.g/ul by dissolving 0.100 grams of
 assayed reference material in pesticide
 quality isooctane or other appropriate
 solvent and diluting to volume in a 100
 ml ground glass stoppered volumetric
 flask. The stock solution is  transferred
 to ground glass stoppered reagent
 bottles, stored in  a refrigerator, and
 checked frequently for signs of
 degradation or evaporation, especially
 just prior to preparing working
 standards from them.
  ^5.5  Acetone. Haxane, Methanol,
 Toluene—pesticide quality or
 equivalent.
   5.6  Florisil—PR grade (60/100 mesh);
 purchase activated at 1250T and store
 in glass containers with glass stoppers
 or foil-lined screw caps. Before use,
 activate each batch overnight at 200"C~
 in glass containers loosely covered with
 foil.
   6. Calibration.
   6.1  Prepare calibration standards
 that contain the compounds of interest.
 either singly or mixed together. The
 standards should be prepared at
 concentrations covering two or more
 orders of magnitude that will completely
 bracket the  working range of the
 chromatographic  system. If the
 sensitivity of the detection system can
 be calculated from Table I as 100 ;±g/l
 in the final extract, for example, prepare
 standards at 10 u-g/T, 50 u.g/1,100 jig/1.
 500 u.g/1, etc. so that injections of 1-5 ^1
 of each calibration standard will define
 the linearity of the detector in the
 working range.
   6.2  Assemble  the necessary gas
 chromatographic apparatus and
 establish operating parameters
 equivalent to those indicated in Table I.
 By injecting calibration standards.
 establish the sensitivity limit of the
 detector and the linear range of the
 analytical system for each compound.
  6.3  Before using any cleanup
 procedure, the analyst must process a
 series of calibration standards through
 the procedure to validate elution
 patterns and the absence of
 interferences from the reagents.
  7. Quality Control.
  7.1  Before processing any samples,
 the analyst should demonstrate through
 the analysis of a distilled water method

-------
               Federal Register  /  Vol. 44.  No. 233  / Monday. December 3.  1979 /  Proposed Rules    ~   69511
 blank, that ail glassware and reagents
 are interference-free. Each time a set of
 samples is extracted or there is a change
 in reagents, a method blank should be
 processed as a safeguard against
 chronic laboratory contamination.
  7.2 .Standard quality assurance
 practices should be used with this
 method. Field replicates should be
 collected to validate the precision of the
 sampling technique. Laboratory
 replicates should be analyzed to
 validate the precision of the analysis.
 Fortified samples should be analyzed to
 validate the accuracy of the analysis.
 Where doubt exists over the
 identification of a peak on the
 chromatogram. confirmatory techniques
 such as mass spectroscopy should be
 used.
  8. Sample Collection, Preservation.
 and Handling.
  8.1   Crab samples must be collected
 in glass containers. Conventional
 sampling practices should be followed,
 except that the bottle must not be
 prewashed with sample before
 collection. Composite samples should be
 collected in refrigerated glass containers
 in accordance with the requirements of
 the program. Automatic sampling
 equipment must be free of tygon and
 other potential sources of
 contamination.
  8.2  The samples must be-iced or
 refrigerated from the time of collection
 until extraction. Chemical preservatives
 should not be used in the field unless
 more than 24 hours will elapse before
 delivery to the laboratory. If the samples
 will not be extracted within 48 hours of
 collection, the sample should be
 adjusted to a pH range of 6.0-6.0 with
 sodium hydroxide or sulfuric acid.
  8.3  All samples must be extracted
 within 7 days and completely analyzed
 within 30 days of collection.
  9. Sample Extraction.
  9.1  Mark the water meniscus on the
side of the sample bottle for later
determination of sample volume. Pour
 the entire sample into a two-liter
separatory funnel. Check the pH of the
sample with wide-range pH paper and
adjust to within the range of 5-9 with
sodium hydroxide or sulfuric acid.
  9.2  Add 60 ml methylene chloride to
 the sample bottle, seal, and shake 30
seconds to rinse the inner walls.
Transfer tl}e solvent into the separatory
 funnel, and extract the sample by
shaking the funnel for two minutes with
periodic venting to release vapor
pressure. Allow the organic layer to
separate from the water phase for a
minimum of ten minutes. If the emulsion
interface between layers is more, than
one-third the size of the solvent layer,
the analyst must employ mechanical
 techiques to complete the phase
 separation. The optimum technique
 depends upon the sample, but may
 include stirring, filtration of the
 emulsion through glass wool, or
 centrifugation. Collect the methylene
 chloride extract in a 250-ml Erlenmeyer
 flask.
   9.3  Add a second 60-ml volume of
 methylene chloride to the sample bottle
 and complete the extraction procedure a
 second time, combining the extracts in
 the Erlenmeyer flask.
   9,4  Perform a  third extraction in the
 same manner. Pour the combined
 extract through a  drying column
 containing 3-4 inches of anhydrous
 sodium sulfate, and collect it in a 500-ml
 Kuderna-Danish (K-D) flask equipped
 with a 10 ml concentrator tube. Rinse
 the Erlenmeyer flask and column with
 20-30 ml methylene chloride to complete
 the quantitative transfer.
   9.5  Add 1-2 dean boiling chips to
 the flask and attach a three-ball Snyder
 column. Prewet the Snyder column by
 adding about 1 ml methylene chloride to
 the top. Place the  K-D apparatus on a
 hot water bath (60-65°C) so that the
 concentrator tube is partially immersed
 in the hot water, and the entire lower
 rounded surface of the flask is bathed in
 vapor. Adjust the  vertical position of the
 apparatus and the water temperature as
 required to complete the concentration
 in 15-20 minutes'. At the proper rate of
 distillation the balls of the column will
 actively chatter but the chambers will
 not flood. When the apparent volume of
 liquid reaches 1 ml, remove the K-D
 apparatus and allow it to drain for at
 least 10 minutes while cooling. Remove
 the Snyder column and rinse the flask
 and its lower joint.into the concentrator
 tube with 1-2 ml of methylene chloride.
 A 5-ml syringe is recommended for this
 operation.
  9.8  Add 1.0 ml toluene to the
 concentrator tube, and a clean boiling
 chip. Attach a two-ball micro-Snyder
 column. Prewet the micro-Snyder
 column by adding about 0.5 ml of
 methylene chloride to the.top. Place this
 micro-K-D  apparatus on a water bath
 (60-65°C) so that the concentrator tube
is partially  immersed in the hot water.
 Adjust the vertical position of the
 apparatus and water temperature as
 required to complete the concentration
 in 5 to 10 minutes. At the proper rate of
 distillation  the balls will actively chatter
 but the chambers  will not flood. When
the apparent volume of liquid reaches
0.5 ml. remove the K-D apparatus and
allow it to drain for at least 10 minutes
while cooling. Remove the micro-Snyder
column and rinse its lower joint into the
concentrator tube  with a small volume
of toluene. Adjust the final volume to 1.0
 ml and stopper the concentrator tube.
 and store refrigerated if further
 processing will not be performed
 immediately. Unless the sample is
 known to require cleanup, proceed with
 gas chromatographic analysis.
   9.7  Determine the original sample
 volume by refilling the sample bottle to
 the mark and transferring the liquid to a
 1000 ml graduated cylinder. Record the
 sample volume to the nearest 5 ml.
   10. Cleanup and Separation.
   10.1  Prepare a slurry of lOg of
 activated Florisil  in 10% methylene
 chloride in hexane (V/V). Ose it to pack
 a 10 mm ID chroma tographyl column.
 gently  tapping the column toisettle the
 Florisil. Add 1 cm anhydrous'sodium
 sulfate to  the top  of the Florisil.
   10.1.1  Just prior to exposure of the
 sodium sulfate layer to the air transfer
 the 1 ml sample extract onto the column
 using an additional 2 ml of toluene to
 complete the transfer.
   10.1.2  Just prior to exposure of the
 sodium sulfate layer to the air, add 30 ml
 10% methylene chloride in hexane and
 continue  the elution of the column.
 Elution of the column should be at a rate
 of about 2 ml per minute. Discard the
 eluate from this fraction.
   10.1.3  Next elute the column with 30
 ml of 10%  acetone/90% methylene
 chloride (V/V) into a 500 ml K-D flask
 equipped with a 10 ml concentrator
 tube. Concentrate the collected fraction
 by the  K-D technique prescribed in 9.5
 and 9.6, including the solvent exchange
 to 1 ml toluene. This fraction should
 contain the nitroaromatics and
 isophorone.
  10.1.4 Analyze by gas
 chromatography.
  11. Gas  Chromatography.
  11.1  Isophorone and nitrobenzene are
 analyzed by injection of a portion of the
 extract into a gas  chromatograph with a
 flame ionization detector. The
 dinitrotoluenes are analyzed oy a
 separate injection into an electron
 capture gas chromatograph. Table I
 summarizes some recommended gas
chromatographic column materials and
 operating conditions for the instruments.
Included in this table are  estimated
retention times and sensitivities that
 should be achieved by this method.
Examples of the separations achieved
 by the primary column are shown in
Figures 1  and 2. Calibrate the system
 daily with a minimum of three injections
of calibration standards.
  11.2  Inject 2-5 p.1  of the sample
extract using the solvent-flush
technique. Smaller (1.0 /il) volumes can
be injected if automatic devices are
employed. Record the volume injected to
the nearest 0.05 pi, and the resulting
peak size, in area  units.

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69512         Federal Register /  Vol.  44, No. 233 /  Monday,  December  3,  1979 / Proposed Rules
   11.3  If the peak area exceeds the
linear range of the system, dilute the
extract and reanalyze.
   11.4  If the peak area measurement is
prevented by the presence of
interferences, further cle'anup is
required.
   12. Calculations.
   12.1  Determine the concentration of
individual compounds according to the
formula:.
Where;
A =»Calibration factor for chromatographic
    system, in nanograms material per area
    unit.
B» Peak size in injection of sample extract, in
    area units.
V,» Volume of extract injected (p.1).
Vt=Volume of total extract (jil).
V,»Volume of water extracted (ml).

  12.2  Report results in micrograms per
liter without correction for recovery
data. When duplicate and spiked
samples are analyzed, all data obtained
should be reported.
  13. Accuracy and Precision.
  The U.S. EPA Environmental
Monitoring and  Support Laboratory in
Cincinnati is in  the process of
conducting an in terla bora lory method
study to determine the accuracy  and
precision of this test procedure.

Bibliography
"Development and Application of Test
  Procedures for Specific Organic Toxic
  Substances in Wastewaters. Category 4-
  Nitroaromaties-and Isophorone," Report for
  EPA Contract No. 68-03-2624 (In
  preparation).

 Tabte L —Gas Chtomatognphy ol NitroaromaOcs
               and laophtmno
                     Reunion Sma Detection torn.
       Compound'         (mm.)      (jig/1)'
                     Coi 1' Cot 2»  EC   FID
laopnorona.	   4 49  5.72	     5
                       3.31   4.31 	     S
                       5.35   «.54  0.0«	
ZWDtnilroioluana	   3.52   4.75  0.06	


  'GaaOvom Q 80/100 maar) coatad witn 1.99% OF-1/
1.5% OV-17 packad in a 1 x V4" 00 glaaa column. FIO
«na)y»» for» and NB raquna nitrogan c«w gas *t 44 rat/mio
and SVC column Mmpmnun. EC vnlyra tar ft* ONT«
nqum 10% McttwiM/90% Argon earner ga« «t 44 ml/mm
flew r*l» and 14S*C column Mmpwaiuni.
  'G^Chrom Q SO/100 m**n ocwtwj with 3% OV-101
p*ck«dlnilO> x 14" OO glas* column. FIO tntiysm o< IP and
NB raquna ntrogtn carrw ga» at 44 mt/mn flow raw and
100*C column Mmparatunt. EC anarywa for tna ONTj require*
10% Methana/fM% Argon camar- gas at 44 ml/mm flow rata
and 150'C column Mmparatuni.
  •Oataetton limit • calcuMad from th* minimum datactabM
QC nnponaa bamg aqual to fiv* wnaa *• GC background
nma, assuming a 10 ml final votum* of tna 1 Mar Mmpta
axtraot. and aaaummg a GC irnaction of 5 microtWara.
BMXMO COM  «fMO-01-M

-------
     COLUMN:  I.Sfi OV-17 + 1.95% QF-1 ON GAS CHROM Q
     TEMPERATURE:  85°C.
     DETECTOR: FUME ION12AT10N
           L
02468
   RETENTION TIME-MINUTES

Figure 1. Gas chromatogram of nitrobenzene and
           isophorone
BILLING CODE S5SO-01-C
 COLUMN: 1.5% OV-17+ 1.95% QF-1 ON GAS CHROM Q
 TEMPERATURE: 14S'C.
 DETECTOR: aECTRON CAPTURE
     2     46    8   10
   RETENTION TIME-MINUTES
                                                                                                                *
                                                                                                                iz
                                                                                                                o
                                                                                                               I
                                                                                                               s?
                                                                                                                CO
                                                 I
                                                 •o
D.


I
Figure 2.  Gas chromatogram of dinitrotoluenes

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69514
Federal  Register / Vol. 44, No. 233  / Monday, December 3,  1979 / Proposed Rules
Poiynudaar Aromatic Hydrocarbons-
Method 610
  1. Scope and Application.
  1.1  This method covers the
determination of certain polynuclear
aromatic hydrocarbons (PAH). The
following parameters may be
determined by this method:
   8«nzoyran«
   8mo
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              Federal Register / Vol.  44. No. 233 / Monday. December  3. 1979 / Proposed Rules	69515
 solvent and diluting to volume in a 100
 ml ground glass stoppered volumetric
 flask. The stock solution is transferred
 to ground glass stoppered reagent
 bottles, stored in a refrigerator, and
 checked frequently for signs of
 degradation or evaporation, especially
 just prior to preparing working
 standards from them.
  5.5  Acetonitrile—Spectral quality.
  5.6  Silica gel—100/120 mesh
 desiccant (Davison Chemical grade 923
 or equivalent). Before use, activate for at
 least 16 hours at 130* C in a foil covered
 glass container.
  6. Calibration.
  6.1  Prepare calibration standards
 that contain the compounds of interest,
 either singly or mixed together. The
 standards should be prepared at
 concentrations covering two or more
 orders of magnitude that will completely
 bracket the working range of the
 chromatographic system. If the
 sensitivity of the detection system can
 be calculated from Table I as 100 fig/1 in
 the final extract for example, prepare
 standards at 10 p.g/1 50 fig/1,100 fig/1,
 500 fig/1, etc. so that injections of 1-5 >il
 of each calibration standard will define
 the linearity of the detector in the
 working range.
  6.2  Assemble the necessary HPLC or
 gas chromatographic apparatus and
 establish operating parameters
 equivalent to those indicated in Table I
 or II. By injecting calibration standards,
 establish the sensitivity limit of the
 detectors and the linear range of the
 analytical systems for each compound.
  6.3   Before using'any cleanup
 procedure, the  analyst must process a
 series of calibration standards through
 the procedure to validate elution
 patterns and the absence of
 interferences from the reagents.
  7. Quality Control.
  7.1   Before processing any samples,
 the analyst should demonstrate through
 the analysis of a distilled water method
 blank, that all glassware and reagents
 are interference-free. Each time a set of
 samples is extracted or there is  a change
 in reagents, a method blank should be
 processed as a safeguard against
 laboratory contamination.
  7.2   Standard quality assurance
 practices should be used with this
 method. Field replicates should be
 collected to validate the precision of the
 sampling technique. Laboratory
replicates should be analyzed to
 validate the precision of the analysis.
Fortified samples should be analyzed to
validate the accuracy of the analysis.
Where doubt extists over the
 identification of a peak on the
 chromatogram, confirmatory techniques
 such as fraction collection and GC-mass
 spectroscopy should be used.
   8.  Sample Collection, Preservation,
 and Handling.
   8.1  Grab sample's must be collected
 in glass containers. Conventional
 sampling practices should be followed,
 except that the bottle must not be
 prewashed with sample before
 collection. Composite samples should be
 collected in refrigerated glass containers
 in accordance with the requirements of
 the program. Automatic sampling
 equipment must be free of tygon and
 other potential sources of
 contamination.
   8.2  The samples must be iced or
 refrigerated from the time of collection
 until extraction. Chemical preservatives
 should not be used in the field unless
 more than  24 hours will elapse before
 delivery to the laboratory. If the samples
 will not be extracted within 48 hours of
 collection,  adjust the sample to a pH
 range of 6.0-8.0 with sodium hydroxide
 or sulfuric  acid and add 35 mg sodium
 thiosulfate per part per million of free
 chlorine  per liter.
  8.3  All  samples must be extracted
 within 7  days and completely analyzed
 within 30 days of collection.
  9.  Sample Extraction.
  9.1  Mark the water meniscus on the
 side of the  sample bottle for later
 determination of sample volume. Pour
 the entire sample into a two-liter
 separatory funnel. Check the pH of the
 sample with wide-range pH paper and
 adjust to within the range of 5-9 with
 sodium hydroxide or sulfuric acid.
  9.2  Add 60 ml methylene chloride to
 the sample bottle, seal, and shake 30
 seconds to rinse the inner walls.
 Transfer the solvent into the separatory
 funnel, and extract the sample by
 shaking the funnel for two minutes with
 periodic venting^to release vapor
 pressure. Allow the organic layer to
 separate from the water phase for a
 munimum of ten minutes. If the emulsion
 inteface between layers is more than
 one-third the size1 of the solvent layer,
"the analyst must employ mechanical
 techniques to complete the phase
 separation. The optimum technique
 depends  upon the sample, but may
 include stirring, filtration of the
 emulsion through glass wool, or
 centrifugation. Collect the methylene
 chloride extract in a 250-ml Erlenmeyer
 flask.
  9.3  Add a second 60-rnl volume of
 methylene  chloride to the sample bottle
 and complete the extraction procedure a
 second time, combining the extracts in
 the Erlenmeyer flask.
  9.4  Perform  a third extraction in the
 same manner. Pour the combined
 extract through a drying column
containing 3-4 inches of anhydrous
sodium sulfate, and collect it in a 500-ml
Kuderna-Oanish (K-D) flask equipped
with a 10-ml concentrator tube. Rinse
the Erlenmeyer flask and column with
20-30-ml methylene chloride to complete
the quantitative transfer.
  9.5  Add 1-2 clean boiling chips to
the flask and attach a three-ball Snyder
column. Prewet the Snyder column by
adding about 1-ml methylene chloride to
the top. Place the K-D apparatus on a
hot water bath (60-85* C) so that the
concentrator tube is partially immersed
in the hot water, and the entire lower
rounded surface of the flask is  bathed hi
vapor. Adjust the vertical position of the
apparatus and the water temperature as
required to complete the concentration
in 15-20 minutes. At the proper rate of
distillation the balls of the column will
actively chatter but the chambers will
not flood. When the apparatus  volumn
of liquid reaches 1-ml, remove the K-D
apparatus and allow it to drain for at
least 10 minutes while cooling.  Remove
the Snyder column and rinse the flask
and its lower joint into the concentrator
tube with 1-2-ml of methylene chloride.
A 5-ml syringe is recommended for this
operation. Stopper the concentrator tube
and store refrigerated if further
processing will not be performed
immediately.
  9.6   Determine the original sample
volume by refilling the sample bottle to
the  mark and transferring the liquid to a
1000-ml graduated cylinder. Record the
sample volume to the nearest 5-mL
  9.7   If the sample requires cleanup
before chromatographic analysis,
proceed to Section 10. If the sample does
not require cleanup, or if the need for
cleanup is unkown, analyze an  aliquot
of the extract according to Section 11 or
Section 12.
  10.   Cleanup and Separation.
  10.1   Before the silica gel cleanup
technique can be utilized, the extract
solvent must be exchanged to
cyclohexane. Add a 1-10-ml aliquot of
sample extract (in methylene chloride)
and a boiling chip to a clean K-D
concentrator tube. Add 4-ml
cyclohexane and attach a micro-Snyder
column. Prewet the micro-Snyder
column by adding 0.5-ml methylene
chloride to the top. Place the micro-K-D
apparatus on a boiling (100° C)  water
bath so that the concentrator tube is
partially immersed in the hot water.
Adjust the vertical position of the
apparatus and the water temperature as
required to complete concentration in 5-
10 minutes. At the proper rate of
distillation the balls of the column will
actively chatter but the chambers will
not  flood. When the apparent volume of
the  liquid reaches 0,5-ml, remove K-D

-------
69516	Federal Register  /  Vol. 44. No.  233 / Monday.  December 3. 1979  /  Proposed Rules
apparatus and allow it to drain for at
least 10 minutes while cooling. Remove
the micro-Snyder column and rinse its
lower joint into the concentrator tube
with a minimum of cyclohexane. Adjust
the extract volume to about 2-ml.
  10.2   Silica Gel Column Cleanup for
PAHs.
  10-2.1  Prepare a slurry of lOg
activated silical gel in methylene
chloride and place this in a 10 mm ID
chromatography column. Gently tap the
column to settle the silica gel and elute
the methylene chloride. Add 1-2 cm of
anhydrous sodium sulfate to the top of
the silica gel.
  10.2.2  Preelute the column with 40-ml
pentane. Discard the eluate and just
prior to exposure of the sodium  sulfate
layer to the air, transfer the 2-ml
cyclohexane sample extract onto the
column, using an additional 2-ml of
cyclohexane to complete the transfer.
  10L2.3  Just prior to exposure  of the
sodium sulfate layer to the air, add 25-
ml pentane and continue elution of the
column. Discard the pentane eluate.
  10.2.4  Elute the column with 25-ml of
40% methylene chloride/60% pentane
and collect the eluate in a 500-ml K-D
flask equipped with a  10-ml
concentrator tube. Elution of the column
should be at a rate of about 2 ml/min.
  10.2,5  Concentrate the collected
fraction to less than 10-ml by K-D
techniques as in 9.5, using pentane to
rinse the walls of the glassware. Proceed
with HPLC or gas chromatographic
analysis.
  11.  High Performance Liquid
Chromatography HPLC.
  11.1   To the extract in the
concentrator tube, add 4 ml acetonitrile
and a new boiling chip, then attach a
micro-Snyder column. Increase the
temperature of the hot water bath to 95-
100* C. Concentrate the solvent  as
above. After cooling, remove  the micro-
Snyder column and rinse its lower joint
into the concentrator tube with about 0.2
ml acetonitrile. Adjust the extract
volume to 1.0 ml.
  11.2   Table I summarizes the
recommended HPLC column materials
and operating conditions for the
instrument. Included in this table are
estimated retention times and
sensitivities that should be achieved by
this method. An example of the
separation achieved by this column is
shown in Figure 1. Calibrate the system
daily with a minimum of three injections
of calibration standards.
  11.3   Inject 2-5 ui of the sample
extract with a high pressure syringe or
sample injection loop. Record the
volume injected to the nearest 0.05 jil,
and the resulting peak size, in area
units.
  11.4   If the peak area exceeds the
linear range of the system, dilute the
extract and reanalyze.
  11.5   If the peak area measurement is
prevented by the pressure of
interference, further cleanup is required.
  11.8   The UV detector is
recommended for the determination of
napthalene and acenaphthylene and the
fluorescene detector is recommended for
the remaining PAHs.
  12.  Gas Chromatography.
  12.1   The gas chromatographic
procedure will not resolve certain
isomeric pairs as indicated in Table DL
The liquid chromatographic procedure
(Section 11] must be used for these
materials.
  12.2   To achieve maximum sensitivity
with this method, the extract must be
concentrated to 1.0 ml. Add a clean
boiling^chip to the methylene chloride
extract in the concentrator tube. Attach
a two-ball micro-Snyder column. Prewet
the micro-Snyder column by adding
about 0.5 ml of methylene chloride to the
top, Place this micro-K-D apparatus on a
hot water bath [60-65* C) so that the
concentrator tube is partially immersed
in the hot water. Adjust the vertical
position of the apparatus and water
temperature as required to complete the
concentration in 5 to 10 minutes. At the
proper rate of distillation the balls will
actively chatter but the chambers will
not flood. When the apparent volume of
liquid reaches 0.5 ml, remove the K-D
apparatus and allow it to drain for at
least 10 minutes while cooling. Remove
the micro-Snyder column and rinse its
lower joint into the concentrator tube
with a small volume of methylene
chloride. Adjust the final volume to 1.0
ml and stopper the concentrator tube.
  12.3   Table H describes the
recommended gas chromatographic
column material and operating
conditions for the instrument. Included
in this table are estimated retention
times that should be achieved by this
method. Calibrate the gas
chromatographic system daily with a
minimum of three injections of
calibration standards.
  12.4  Inject 2-5 ul of the sample
extract using the solvent-flush
technique. Smaller (1.0 >il} volumes can
be Injected if automatic devices are
employed. Record the volume injected  to
the nearest 0.05 u-1, and the resulting
peak size, in ara units.
  12.5  If the peak area exceeds the
linear range of the system, dilute the
extract and reanalyze.
  12.6  If the peak ara measurement is
prevented by the presence of
interferences, further cleanup is
required.
  13.  Calculations.
  13.1   Determine the concentration of
individual compounds according to the
formula:

    Concentration, ug/1 —
                    (VJ(VJ
Where:
A=Calibration factor for chromatographic
    system, in nanograms material per area
    unit
B=-Peak size in injection of sample extract in
    area units
V) =a Volume of extract injected (pi)
Vt=Volume of total extract foil)
V,=Volume of water extracted (ml)
  13.2   Report results in micrograms per
liter without correction for recovery
data. When duplicate and spiked
samples are analyzed, all data obtained
should be reported.
  14.   Accuracy and Precision,
  14.1-  The U.S. EPA Environmental
Monitoring and Support Laboratory in
Cincinnati is in the process of
conducting an interlaboratory method
study to determine the accuracy and
precision of this test procedure.

Bibliography
  "Development and Application of Test
Procedures for Specific Organic Toxic
Substances in Wastewaters, Category 9-
PAHs." Report for EPA Contract 8S-03-26Z4
(In preparation).
 Tabta \.—High Performance Liquid Chromatography
                otPAH's
    Compound '     Retention  Detection Hfnt (pg/l)'
                time (mint
                         UV
N«phm«U>n»
Acenaphthylene 	
Acenapnthene 	
PIlMVMOA .
Phenanthrene 	
Anthracene 	
Ruoraflthene. 	 „, 	 	
Pyrene......... 	 ™.™
SenZO(a)aiiUWACOnem...
Chrysene 	 *.__ 	
Benzo(b)fluoranthene ._
Senzo(kjfluoranthene._
Benzo(a)pyrene ..._ 	
Dibenzce
1 liter sample extract, and assuming  an HPLC injection of
     Table IL— Gas Chromatography of PAHs
            Compound1
                                Retention
                               Time (mm)
Naphthalene..
Acenapnthytene..
Acanaphthene	
Ruor«ne_____
 4.5
10.4
10.3
12.6

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             Federal Register 7 Vol. 44. No.  233  /  Monday. December 3,  1979 / Proposed Rules
                                                                                                         69517
TaM* It—Ota Chromatograpty
           Compound'
                             FMwtfon
                             •nm*(irin)
Phenanthrene,
Aiwv
FtuaranOMM.
Pyran*	—
CXryMM
OiM
                                 1SJ
                                 194
                                 20.»
                                 ».e
                                 24.7
                                 29.4
                                364
                                3M
 'QC oondWonc QmmMorta W-AW-OCM* 100/120 nwMl
CMMd «Wi 3% OV-17. pKted in « V x 2 mm 10 gtew
column, «Mt nttogwi cwMr ga «  40 ml/mbr tow n«.
Cotann Kmptnkirt IM* n*u a 100* C far 4 n*Mm Him
programmed « r/mlnuM to > Ik* how « 280- 0.

Haloethen—Method 611

  1. Scope and Application
  1.1 This method covers the
determination of certain haloethen. The
                                      following parameters may be
                                      determined by this method:
                                         Bfe<2-cNanMfty« Vim.
                                         -8rameplMnyl
                                        4-CNo
                            STOfVTHot
                    	    34273
                    	    3427S
                    	    34213
                    	    34638
                    	    34641

  1.2 This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used to meet the
monitoring requirements of the National
Pollutant Discharge Elimination System
(NPDES). As such, it presupposes a high
expectation of finding the specific
compounds of interest If the user is
attempting to screen samples for any or
ail of the4 compounds above, he must
develop independent protocols for the
verification of identity.
  1.3 The sensitivity of this method is
usually dependent upon the level of
interferences rather than instrumental
limitations. The limits of detection listed
in Table I represent sensitivities, that
can be achieved in wastewaters in the
absence of interferences.
  1.4 This method is recommended for
use only by experienced residue
analysts or under the close supervision
of such qualified persons.
  2.  Summary of Method
  2.1 A 1-liter sample of wastewater is
extracted with methylene chloride using
sepaxatory funnel techniques. The
extract is dried and concentrated to a
volume of 10 ml or less.
Chromatographic conditions utilizing a
halide specific detector are described
which allow for the accurate
measurement of the compounds in the
extract.
  12 If interferences are encountered,
the method provides a selected general
COLUMN:  HC-OOS S1L-X                                  g
MOBILE PHASE'  40% TO 100% ACETONITR1LE IN VKATEB  3
DETECTOR: FLUORESCBICS                              S
             8    12     16    20    24     28    32    38     40
                         RETENTION TIME-MINUTES

 Rgure 1.  Liquid chromatogram of polynuclear aromatics

-------
69518	Federal  Register / Vol. 44. No.  233 / Monday, December 3. 1979  /Proposed Rules
purpose cleanup procedure to aid the
analyst in their elimination.
  3.  Interferences.
  3.1 Solvents, reagents, glassware, and
other sample processing hardware may
yield discrete artificats and/or elevated
baselines causing misinterpretation of
gas chromatograms. All of these
materials must be demonstrated to be
free from interferences under the
conditions of the analysis by running
method blanks. Specific selection of
reagents and purification of solvents by
distillation in all-glass systems may be
required.
  3.2   Interferences coextracted from
the samples  will vary considerably from
source to source, depending upon the
diversity of the industrial complex or
municipality being sampled. While
general clean-up techniques are
provided as part of this method,  unique
samples may require additional cleanup
approaches to achieve the sensitivities
stated in Table I.
  3.3   Oichlorobenzenes are known to
coelute with haloethers under some gas
chromatographic conditions. If these
materials are present together in a
Sample, it  may be necessary to analyze
the extract with two different column
packings to completely resolve all of the
compounds.
  4. Apparatus and Materials.
  4.1   Sampling equipment, for discrete
or composite sampling.
  4.1.1  Grab sample bottle—amber
glass, 1-liter or 1-quart volume. French
or Boston Round design is
recommended. The container must be
washed and solvent rinsed before tise to
minimize interferences.
  4.1.2  Bottle caps—Threaded to screw
on to the sample bottles. Caps must be
lined with Teflon. Foil may be
substituted if sample in not corrosive.
  4.1.3  Compositing equipment—
Automatic or manual compositing
system. Must incorporate glass sample
containers for the collection of a
minimum of 250 ml. Sample containers
must be kept refrigerated during
sampling. No tygon or rubber tubing
may be used in the  system.
  4.2   Separatory funnel—2000 ml, with
Teflon stopcock.
  4.3   Drying column—20 mm ID pyrex
chromatographic column with coarse
frit.
  4.4   Kuderna-Danish (K-D)
Apparatus
  4.4.1  Concentrator tube—10 ml,
graduated (Kontes K-570050-1025 or
equivalent).  Calibration must be
checked. Ground glass stopper (size l%z
joint) is used to prevent ecaporation of
extracts.
  4.4.2  Evaporative flask—500 ml
(Kontes K-57001-0500 or equivalent).
Attach to concentrator tube with
springs. (Kontes K-662750-O012).
  4.4.3  Snyder column—three ball
macro (Kontes K503000-0121 or
equivalent).
  4.4.4  Snyder column—two-ball micro
(Kontes K-569001-0219 or equivalent).
  4.4.S  Boiling chips—solvent
extracted, approximately *%o mesh.
  4.5  Water bath—Heated, with
concentric ring cover, capable of
temperature control (±Z'C], The bath
should be used in a hood.
  4.0  Gas chromatograph—Analytical
system complete with gas
chromatograph suitable for on-column
injection and all required accessories
including haiide specific detector,
column supplies, recorder, gases,
syringes. A data system for measuring
peak areas is recommended.
  4.7  Chromatographic Column—400
mm long x 19 mm ID with coarse fritted
plate on bottom and Teflon stopcock
(Kontes K-420540-0224 or equivalent).
  5. Reagents.
  5.1  Preservatives:
  5.1.1  Sodium hydroxide—{ACS) 10 N
in distilled water.
  5.1.2  Sulfuric acid (1 +1}—(ACS) Mix
equal volumes of cone. H,SO< with
distilled water.
  5.2  Methylene chloride—Pesticide
quality or equivalent
 . 5.3  Sodium Sulfate—(ACS) Granular^
anhydrous (purified by heating at 400*C
for 4 hrs. in a shallow tray).
  5°A  Stock standards—Prepare stock
standard solutions at a concentration of
1.00 ;ig/ud by dissolving 0.100 grams of
assayed reference material in pesticide
quality acetone or other appropriate
solvent and diluting to volume in a 100
ml ground glass stoppered volumetric
flask. The stock solution is transferred
to ground glass stoppered reagent
bottles, stored in a refrigerator, and
checked frequently for signs of
degradation or evaporation, especially
just prior to preparing working
standards from them.
  5.5  Florisil—PR Grade (60/100
mesh); purchase activated at 1250T and
store in the dark in glass containers with
glass stoppers or foil-lined screw caps.
Before use, activate each batch
overnight at 130*C in a foil-covered glass
container.
  5.6  Hexane, Petroleum ether (boiling
range 30-60°C)—pesticide quality or
equivalent.
  5.7  Diethyl Ether—Nanograde,
redistilled in glass, if necessary.
  5.7.1  Must be free of peroxides as
indicated by EM Quant test strips. (Test
strips are available from EM
Laboratories, Inc., 500 Executive Blvd.,
Elmsford, N.Y. 10523.)
  5.7.2  Procedures recommended for
removal of peroxides are provided with
the test strips. After cleanup 20 ml ethyl
alcohol preservative must be added to
each liter of ether.
  6. Calibration.
  8.1   Prepare calibration standards
that contain the compounds of interest,
either singly or mixed together. The
standards should be prepared at
concentrations covering two or more
orders of magnitude that will completely
bracket the working range of the
chromatographic system. If the
sensitivity of the detection system can
be calculated from Table I as 100 pg/1 in
the final extract for example, prepare
standards at 10 fig/1, 50 fig/l 100 jtg/1.
SCO ju.g/1. etc.  so that injections of 1-5  
-------
               Federal Register  /  Vol. 44. No.  233 / Monday. December  3. 1979 / Proposed Rules	69519
 identification of a peak on the
 chromatogram, confirmatory techniques
 such as mass spectroscopy should be
 used.
   8. Sample Collection, Preservation.
 and Handling.
   8.1  Crab samples must be collected
 in glass containers. Conventional
 sampling practices should be followed,
 except that the bottle must not be
 prewashed with sample before
 collection. Composite samples should be
 collected in refrigerated glass containers
 in accordance with the requirements of
 the program. Automatic sampling
 equipment must be free of tygon and
 other potential sources of
 contamination.
   8.2  The samples must be  iced or
 refrigerated from the time of collection
 until extraction. Chemical preservatives
 should not be used in the field unless
 more than 24 hours will elapse before
 delivery to the laboratory. If the samples
 will not be extracted within 48 hours of
 collection, the sample should be
 adjusted to a pH^nge of 6.0-8.0 with
 sodium hydroxide or sulfuric acid.
   8.3  All samples; must be extracted
 within 7 days and completely analyzed
 within 30 days of collection.
   9. Sample Extraction.
   9.1  Mark the water meniscus on the
 side of the sample bottle for later
 determination  of sample volume. Pour
 the entire sample into a two-liter
 separatory funnel. Check the pH of the
 sample with wide-range pH paper and
 adjust to within the range of S-Q with
 sodium hydroxide or sulfuric acid.
  9.2  Add 60 ml methylene chloride to
 (he-sample bottle, seal, and shake 30
seconds to rinse the inner walls.
Transfer the solvent into the  separatory
 funnel, and extract the sample by
shaking the funnel for two minutes with
periodic venting to release vapor
pressure. Allow the organic layer to
separate from the water phase for a
minimum, of ten minutes. If the emulsion
interface between layers is more than
one-third the size of the solvent layer,
the analyst must employ mechanical
techniques to complete the phase
separation. The optimum technique
depends upon the sample, but may
include stirring, filtration of the
emulsion through glass wool, or
centrifugation. Collect the methylene
chloride extract in a 250-ml Erlenmeyer
flask.
  9.3   Add a second 60-ml volume of
methylene chloride to the sample bottle
and complete the extraction procedure  a
second time, combining the extracts in
the Erlenmeyer flask.
  9.4   Perform a third extraction in the
same manner. Pour the combined
extract through a drying column
 containing 3-4 inches of anhydrous
 sodium sulfate, and collect it in a 500-ml
 Kuderna-Oanish (K-D) flask equipped
 with a. 10 ml concentrator tube. Rinse
 the Erlenmeyer flask and column with
 20-30 ml methylene chloride to complete
 the quantitative transfer.
  9.5   Add 1-2 clean boiling chips to
 the flask and attach a three-ball Snyder
 column. Prewet the Snyder column by
 adding about 1 ml methylene chloride to
 the top. Place the K-D apparatus on a
 hot water bath (60-65'C) so that the
 concentrator tube is partially immersed
 in the hot water, and the entire lower
 rounded surface of the flask is bathed in
 vapor. Adjust the vertical position of the
 apparatus and the water temperature as
 required to complete the concentration
 in 15-20 minutes.  At the proper rate  of
 distillation the balls of the column will
 actively chatter but the chambers will
 not flood. When the apparent volume of
 liquid reaches 1-2 ml, remove the K-D
 apparatus and allow it to drain for at
 least 10 minutes while cooling.
  Note.—Haloethers have a sufficiently high
 volatility that significant losses will occur in
 concentration steps if care is not exercised. It
 is important to maintain a constant gentie
 evaporation rate and not to allow the liquid
 volume to fall below 1-2 ml before removing
 the K-D from the hot water bath.
  9.6   Momentarily remove the Snyder
 column, add 50 ml hexane and  a new
 boiling chip and replace the column.
 Raise the temperature of the water bath
 to 85-90°C. Concentrate  thr extract as in
 9.5 except use hexane to prewet the
 column. Remove the Snyder column  and
 rinse the flask and its lower joint into
 the concentrator tube with 1-2  ml
 hexane. Stopper the concentrator tube
 and store refrigerated jf further
 processing will not be performed
 immediately.
  9.7   Determine  the original sample
 volume by refilling the sample bottle to
 the mark and transferring the liquid  to a
1000 ml graduated cylinder. Record the
 sample volume to the nearest 5 ml.
  9.8   Unless the sample is known to
 require cleanup, proceed to analysis by
 gas chroma tography.
  10. Cleanup and Separation.
  10.1   Florisil Column Cleanup for
 Haloethers.
  10.1.1  Adjust the sample extract
 volume to 10 ml.
  10.1.2  Place a charge (nominally  20 g
but determined in Section 6.3) of
 activated Florisil in a 19 mm ID
chroma tography column. After settling
 the Florisil  by tapping column,  add
about one-half inch layer of anhydrous
granular sodium sulfate to the top.
  10.1.3  Pre-elute the column, after
cooling, with 50-60 ml of petroleum
ether. Discard the eluate and just prior
 to exposure of the sulfate layer to air,
 quantitatively transfer the sample
 extract into the column by decantation
 and subsequent petroleum ether
 washings. Discard the eluate. Just prior
 to exposure of the sodium sulfate layer
 to the air, begin eluting the column with
 300 ml of 6% ethyl ether/94% petroleum
 ether. Adjust the elution rate to
 approximately 5 ml/min and collect the
 eluate in a 500 ml K-D flask equipped
 with- a 10 ml concentrator tube. This
 fraction should contain all of the
 haloethers.
  10.1.4  Concentrate the fraction by K-
 D as in 9.5 except prewet the Snyder
 column with hexane. When the
 apparatus is cqpl, remove the column
 and rinse the flask and its lower joint
 into the concentrator tube with 1-2 ml
 hexane. Analyze by gas
 chromatography.
  11.   Gas Chromatography.
  11.1   Table I summarizes some
 recommended gas chromatographic
 column materials and operating
 conditions for the instrument. Included
 in this table are estimated retention
 times and sensitivities that should be
 achieved by this method.,Examples of
 the separations achieved by these
 columns are shown in Figures 1 and 2.
 Calibrate the system daily with a
 minimum- of three injections of
 calibration standards.
  11.2   Inject 2-5 uJ of ths sample
 extract using the solvent-flush
 technique. Smaller (1.0 fil) volumes can
 be injected if automatic devices are
 employed. Record  the volume injected to
 the nearest 0.05 p,l, and the.resulting
 peak size, in area units.
  11.3  If the peak area exceeds the
 linear range of the system, dilute the
 extract and reanalyze.
  11.4 ' If the peak area measurement is
 prevented by the presence of
interferences, further cleanup is
 required.
  12.   Calculations.
  12.1  Determine the concentration of
 individual compounds according to the
 formula:

     Concentrate.^/'- W™™

Where:
A = Calibration factor for chromatographic
    system, in nanograms material per area-
    unit.
 B = Peak size tn injection of sample extract, in
    area units
 V, = volume of extract injected (jxl)
 V, = volume of total extract (^1)
 V, = volume of water extracted (ml)

-------
69520	Federal  Register / Vol. 44. No.  233  /  Monday. December 3,  1979 /  Proposed Rules


  12.2  Report results in micrograms per
liter without correction for recovery
data. When duplicate and spiked
samples are analyzed, all data obtained
should be reported, •
  13.  Accuracy and Precision. The U.S.
EPA Environmental Monitoring and
Support Laboratory in Cincinnati is in
the process of conducting an
interiaboratory method study to
determine the accuracy and precision of
this test procedure.

Bibliography
  1. "Development and Application of Test
Procedures for Specific Organic Toxic
Substances in Wastewaters. Category 2-
Haloethers." Report for EPA Contract 88-03-
2833 (In preparation).
  2. Mills, P. AM "Variation of Florisil
Activity. Simple Method for Measuring
Absorbent Capacity and Its Use in
Standardizing Florisil Columns." Journal of
the Association of Official Analytical
Chemists. SI. 29 (1968).

   Tub* I—Gt$ Chfomuognphy ofH»to9th*»
                          (mm.)      OMKdon
       Compound       	  fen*
                                   (ug/L)'
                      Cot i'   CoU2'


Stl(2-GhloioMpR]py4 «nv..»    8.41    9.70     0.9
a*e-cNom**iQ torn	    9J2    9.08     0.5
Blxa 2.1 mm O gttn column wtti unn>
Ngn purity Mkm camir/gH 
-------
COLUMN:  3!i SP-1000 ON SUPELCOPORT
PROGRAM: 60*C-2 MINUTES 8"/MINUTE TO  230*C.
DETECTOR: HALL ELECTROLYTIC CONDUCTIVITY
COLUMN: TENAX GC
PROGRAM:  150*C.-4 MINUTES IS'/MINUTE TO 310*C.
DETECTOR: HALL ELECTROLYTIC CONDUCTIVITY

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                     RETENTION TIME-MINUTES

Figure 1. Gas chromatogram of haloethers
                                                                                                                         p
                                                          I
                                                         s
                                                          i?
                                                          8
                                                          I
     _1_
                                                             04s        12        16       20

                                                                                 RETENTION TIME-MINUTES

                                                              Figure 2.  Gas chromatogram of haloethers
                                                  24

-------
69522	Federal Register / Vol. 44, No. 233 / Monday, December 3,  1979 / Proposed  Rules
Chlorinated Hydrocarbons—Method 612

  \. Scope and Application.
  1.1   This method covers the
determination of certain chlorinated
hydrocarbons. The following parameters
may be determined by this method.
                             STOnETNo.
                        	    34388
   HotachlorocyclopwiUiMn*...
   VMxKMonXwnm*
   HoxacMaroDutadiwi*..
   1 .2-OfchkyoMnzwM .....
   \ ,3-OteNorolMremw -----------
   1 , 4-OJcWorob«n»n» --------------
   2-cntoron»pMh»)«n« -------------
39700
34391
34396-
34636
34551
34566
94571
1*561
  1.2  This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used to meet the
monitoring requirements of the National
Pollutant Discharge Elimination System
(NPDES). As such, it presupposes a high
expectation of rinding the specific
compounds of interest. If the user is
attempting to screen samples for any or
ail of the compounds above, he must
develop independent protocols for the
verification of identity.
  1.3  The sensitivity of this method is
ususally dependent upon the level of
interferences rather than instrumental
limitations. The limits of detection li-ted
in Table I represent sensitivities that
can be achieved in waste-waters ir  the
absence of inteferences.
  1.4  This methodis recommended for
use only by experienced resid- c.
analysts or under the close f pervision
of such qualified persons.
  2. Summary of Method.
  2.1  A 1-liter sample of wastewater is
extracted with methylene chloride using
separatory funnel techniques. The
extract is dried by passing through a
sodium sulfate column and concentrated
to a volume of l&ml or less.
Chromatographic conditions are
described which allow-for the accurate
measurement of the compounds in the
extract.
  2.2  If inteferences are encountered
or expected, the method provides a
selected general purpose cleanup
procedure to aid the analyst in their
elimination.
  3.  Interferences.
  3.1  Solvents, reagents, glassware,
and  other sample processing hardware
may yield discrete artifacts and/or
elevated baselines causing
misinterpretation of gas chromatograms.
All of these materials must be
demonstrated to be free from
inteferences under the conditions of the
analysis by running method blanks.
Specific selection of reagents and
purification of solvents by distillation in
all-glass systems may be required.
  3.2  Interferences coextracted from
the samples will vary considerably from
source to source, depending upon the
diversity of the industrial complex or
municipality being sampled. While
general clean-up techniques are
provided as part of this method, unique
samples-may require, additional cleanup
approaches to achieve the sensitivities
states in Table 1.
  4, Apparatus and-Materials.
  4.1   Sampling equipment, for discrete
or composite sampling.
  4.1.1  Grab  sample bottle—amber
glass, 1-liter or 1-quart volume. French
or Boston Round design is
recommended. The container must be
washed and solvent rinsed before use to
minimize interferences.
  4.1 2  Bottle caps—Threaded to screw
on to the sample bottles. Caps must be
lined with Teflon. Foil may be
substituted if sample is not corrosive
and the foil is  found to be interference
free.
  4.1.3  Compositing equipment—
Automatic or manual compositing
system. Must incorporate glass sample
containers for the collection of a
minimum of 250 ml. Sample containers
must be kept refrigerated during
sampling. No tygon or. rubber tubing
may be used in the system.
  4.2   Separatory funnel—2000 ml, with
Teflon stopcock.
  4.3   Drying column—20 mm  ID pyrex
chromatographic column with coarse
frit.
  4.4   Kuderna-Danish (K-D)
Apparatus
•  4.4.1  Concentrator tube—10 ml,
graduated (Kontes K-570050-1025 or
equivalent). Calibration must be
checked. Ground glass  stopper (size 19/
22 joint) is used to prevent evaporation
of extracts.
  4.4.2  Evaporative flask—500 ml
(Kontes K-57001-0500 or equivalent).
Attach to concentrator tube with
springs. (Kontes K-662750-0012).
  4.4.3  Snyder column—three-ball
macro (Kontes K503000-0121 or
equivalent);
  4.4.4  Snyder column—two-ball micro
(Kontes K-569001-0219 or equivalent).
  4.4.5  Boiling chips—solvent
extracted, approximately 10/40 mesh.
  4.5   Water  bath—Heated, with
concentric ring cover, capable  of
temperature control (±2° C). The bath
should be used in a hood.
  4.8   Gas chrqmatograph—Analytical
system complete with gas
chromatograph suitable for on-column
injection and all required accessories
including electron capture detector,
column supplies, recorder, gases,
syringes. A data system for measuring
peak areas is recommended.
  4.7   Chromatography column—300
mm long x 10 mm ID with coarse fritted
disc at bottom and Teflon stopcock.
  5. Reagents.
  5.1   Preservatives:
  5.1.1  Sodium hydroxide—(ACS) 10 N
in distilled water.
  5.1.2  Sulfuric acid—(ACS) Mix equal
volumes-of cone. H,SO» with distilled
water.
  5.2   Methylene chloride, Hexane and
Petroleum ether (boiling range 30-
80°C)—Pesticide quality orequivalenL
  5.3   Sodium sulfate—(ACS) Granular,
anhydrous (purified by heating at 400*C
for4 hrs. in a shallow tray).
  5.4   Stock standards—Prepare stock
standard solutions at a concentration of
1.00 /ig/ul by dissolving 0.100 grams of
assayed reference material in pesticide
quality isooctane or other appropriate
solvent and  diluting to volume in a 100
ml ground glass stoppered volumetric
flask. The stock solution is transferred
to ground glass stoppered reagent
bottles, stored in a refrigerator, and
checked frequently for signs of
degradation or evaporation, especially
just prior to  preparing working
standards from them.
  5.5   Florisil—PR grade (60/100 mesh);
purchase activated at 1250T and store
in the dark in glass containers with glass
stoppers or foil-lined screw caps. Before
use, activate each batch at 130'C in foil-
covered glass containers.
  8. Calibration.
  6.1   Prepare calibration standards
that contain the compounds of interest,
either singly or mixed together. The
standards should be prepared at
concentrations covering two or more
orders of magnitude that  will completely
bracket the working range of the
chromatographic system. If the
sensitivity of the detection system can
be calculated from Table I as 100 fxg/1
in the final extract, for example, prepare
standards at 10 jig/1. 50 /ig/1,100 jxg/1.
500 fig/1, etc. so that injections of 1-5 p.1
of each calibration standard will define
the linearity of the detector in the
working range.
  6.2  Assemble the necessary gas
chromatographic apparatus and
establish operating parameters
equivalent to those indicated in Table I.
By  injecting calibration standards,
establish the sensitivity limit of the
detector and the linear range of the
analytical system for each compound.
  8.3  The cleanup procedure in Section
10 utilizes Florisil chromatography.
Florisil from different batches or sources
may vary in absorption capacity. To
standardize the amount of Florisil which
is used, the  use of lauric acid value
(Mills, 1968) is suggested. The
referenced procedure determines the

-------
              Federal Register / Vol. 44. No.  233 / Monday, December 3. 1979  /  Proposed Rules	69523
adsorption from hexane solution of
lauric acid (mgj per gram Florisil. The
amount of Florisil to be used for each
column is calculated by dividing this
ratio by 110 and multiplying by 20
grams.
  6.4   Before using any cleanup
procedure, the analyst must process a
series of calibration standards through
the procedure to validate elution
patterns and the absence of
interferences from the reagents.
  7. Quality Control.
  7.1    Before processing any samples,
the analyst should demonstrate through
the analysis of a distilled water method
blank, that all glassware and reagents
are interference-free.  Each time a set of
samples is extracted or there is a change
in reagents, a method blank should be
processed as a safeguard against
chronic laboratory contamination.
  7.2   Standard quality assurance
practices should be used with this
method. Field replicates should be
collected to validate the precision of the
sampling technique. Laboratory
replicates should be analyzed to
validate the precision of the analysis.
Fortified samples should be analyzed to
validate the accuracy of the analysis.
Where doubt exists over the
identification of a peak on the
chromatogram, confirmatory techniques
such as mass spectroscopy should be
used.
  8. Sample Collection. Preservation.
and Handling.
  8.1  Grab samples must be collected
in glass containers, leaving a minimum
headspace. Conventional sampling
practices should be followed, except
that the bottle must not be prewashed
with sample before collection.
Composite samples should be collected
in refrigerated glass containers in
accordance with the requirements of the
program. Automatic sampling equipment
must be free of tygon  and other potential
sources of contamination.
  8.2  The samples must be iced or
refrigerated from the time of collection
until extraction. Chemical preservatives
should not be used in the field unless
more than 24 hours will elapse before
delivery to the  laboratory. If the samples
will not be extracted within 48 hours of
collection, the sample should be
adjusted to a pH range of 6.0-8.0 -with
sodium hydroxide or sulfuric acid.
  8.3  All  samples should be extracted
immediately and must be extracted
within 7 days and completely analyzed
within 30 days  of collection.
  9. Sample Extraction.
  9.1  Mark the water meniscus on the
side of the sample bottle for later
determination of sample volume. Pour
the entire sample into a two-liter
separatory runnel. Check the pH of the
sample with wide-range pH paper and
adjust to within the range of 5-9 with
sodium hydroxide or sulfuric acid.
  9.2  Add 60 ml methylene chloride to
the sample bottle, seal, and shake 30
seconds to rinse the inner walls.
Transfer the solvent into the separatory
funnel, and extract the sample by
shaking the funnel for two minutes with
periodic venting to release vapor
pressure. Allow the organic layer to
separate from the water phase for a
minimum of ten minutes. If the emulsion
interface between layers is more than
one-third the  size of the solvent layer,
the analyst must employ mechanical
techniques.to complete the phase
separation. The optimum technique
depends upon the sample, but may
include stirring, filtration of the
emulsion through glass wool, or
centrifugation. Collect the methylene
chloride extract in a 250-ml Erlenmeyer
flask.
  9.3 Add a second 60-ml volume of
methylene chloride to the sample bottle
and complete the extraction procedure a
second time, combining the extracts in
the Erlenmeyer flask.
  9.4 Perform a third extraction in the
same manner. Pour the combined
extract through a drying column
containing 3-4 inches of anhydrous
sodium suifate, and collect it in a 500-ml
Kuderna-Danish (K-D) flask equipped
with a 10 ml concentrator tube. Rinse
the Erlenmeyer flask and column with
20-30 ml methylene chloride to complete
the quantitative transfer.
  9.5 Add 1-2 clean boiling chips to the
flask and attach a three-ball Snyder
column. Prewet the Snyder column by
adding about 1 ml methylene chloride to
the top. Place the K-D apparatus on a
hot water bath (60-65* C) so that the
concentrator tube is partially immersed
in the hot water, and the entire lower
rounded surface of the flask is bathed in
vapor. Adjust the vertical position of the
apparatus and the water temperature as
required to complete the concentration
in 15-20 minutes. At the proper rate of
distillation the balls of the column will
actively chatter but the chambers will
not flood. When the apparent volume of
liquid reaches 1-2 ml, remove the K-D
apparatus and allow it to drain for at
least 10 minutes while cooling.
  Note.—The dichlorobenzenes have a
sufficiently high volatility that significant
losses may occur in concentration steps if
care is not exercised. It is important to
maintain a constant gentle evaporation rate
and not to allow the liquid volume to fall
below 1-2 ml before removing the K-D from
the hot water bath.
  9.6 Momentarily remove the Snyder
column, add 50 ml hexane and a new
boiling chip and -jplace the column.
Raise the temperature of the water bath
to 85-90" C. Concentrate the extract as
in 9.5, except using hexane to prewet the
column. Remove the Snyder column and
rinse.the flask and its lower joint into
the concentrator tube with 1-2 ml of
hexanei A 5-ml syringe is recommended
for  this operation. Stopper the
concentrator tube and store refrigerated
if further processing will not be
performed immediately.
  9.7  Determine the original sample-
volume by refilling the sample bottle to
the  mark and transferring the liquid to a
1000 ml graduated cylinder. Record the
sample volume to the nearest 5 ml.
  9.8  Unless the sample is known to
require cleanup, proceed to  analysis by
gas chroma tography.
  10.  Cleanup and Separation.
  10.1  Florisil column cleanup for
chlorinated Hydro-carbons.
  10.1.1  Adjust the sample extract to
10ml.
  10.1.2  Place a 12 gram charge of
activated Florisil (see 6.3) in a 10 mm ID
chromatography column. After settling
the  Florisil by tapping the column, add a
1-2 cm layer of anhydrous granular
sodium suifate to the top.
  10.1.3  Pre-elute the column, after
cooling, with 100 ml of petroleum ether.
Discard the eluate and just prior to
exposure of the suifate layer to air,
quantitatively transfer the sample
extract into the column'by decantation
and subsequent petroleum ether
washings. Discard the eluate. Just prior
to exposure of the sodium suifate layer
to the air, begin eluting the  column with
200 ml petroleum ether and collect the
eluate hi a 500 ml K-D flask equipped
with a 10 ml concentrator tube. This
fraction should contain all of the
chlorinated hydrocarbons.
  10.1.4  Concentrate the fraction by K-
D as in 9.5 except prewet the column
with hexane. When the apparatus is
cool, remove the Snyder column and
rinse the flask and its lower joint into
the  concentrator tube with 1-2 ml
hexane. Analyze by gas
chromatography.
  11.  Gas Chromatography.
  11.1  Table I summarizes the
recommended gas chromatographic
column materials and operating
conditions for the instrument. Included
in this table are estimated retention
times and sensitivities that should be
achieved by this method. Examples of
the  separations- achieved by this column
are  shown in Figures 1 and 2. Calibrate
the  system daily with a minimum of
three injections of calibration standards.
  11.2  Inject 2-5 ul of the sample
extract using the solvent-flush
technique. Smaller (1.0 ul) volumes can

-------
69524	Federal Register  /  Vol.  44.  No. 233./ Monday, December 3.  1979 / Proposed Rules
be injected if automatic devices are
employed. Record the volume injected to
the nearest 0.05 ul, and the resulting
peak size, in area units.
   11.3   If the peak area exceeds the
linear range of the system, dilute the
extract and reanalyze.
   11.4   If the peak area measurement is
prevented by the presence of
interferences, further cleanup is
required.
   12.  Calculations.
   12.1   Determine the concentration  of
individual compounds according to the
formula:

      Concentrwon, «/..  'AMBi'V')
                      (VJ(VJ
Where:
A = Calibration factor for chromatographic
    system, in nanograms material per area
    unit.
8 = Peak size in injection of sample extract, in
    area units
V, = Volume of extract injected (ul)
V,=Volume of total extract (ul]
V, = Volume of water extracted (ml]

   12.2   Report results in micrograms  per
liter without correction, for recovery
data. When duplicate and spiked
samples are analyzed, all data obtained
should be reported.
   13.  Accuracy and Precision. The U.S.
EPA Environmental Monitoring and
Support Laboratory in Cincinnati is in
the process of conducting an
interlaboratory method study to
determine the accuracy and precision of
this test procedure.

Bibliography
  1. "Development and Application of Test
Procedures for Specific Organic Toxic
Substances in Wastewaters. Category  3—
Chlorinated Hydrocarbons and Category 8—
Phenols." Report  for EPA Contract 63-03-
2625 (In preparation).
  2. Mills. P. A., "Variation of Flonsil
Activity; Simple Method for Measuring
Absorbent Capacity and Its Use in\
Standardizing Florisil Columns," Journal of
the Association of Official Analytical
Chemists, 51.29 (1968).
   Tatoto L—Gas Chromatograptty of Cfilormatad
               Hydrocarbons
Retention
time (mm.) Detection
Compound col 1 ' limit (ng/0 *
1 ,3-dKhkxoberttene 	
1 ,4^Jn:hlorooenzene 	 	
1 ,2-dichlorobenzene 	
Hexachkxobutadiens 	
1 ,2.4-«tehtorceeraene 	 „ 	

2-chloronapnthalena 	 	
Hexacnlorobenzene 	 	
4.0
4.3
48
5J
11 8
12.4
•1.5
•2.5
•70
O.OOA
0.01 a
0.001
0012
0.001
0.006
O.OOT
0.015
0001
  'Ow CtifonrQ 30/100 meed coated vnlri 1.5% OV-1/
1 5% OV-22S packed m a 1 3 m long x 2 mm !O gfus
column with 5V Methane/95% Argon earner gat at 30 ml/
mm flow rate. Column temperature a 75" C  except where '
indicate*. 160* C. Under these condmone R.T. of Alarm a 18.8
minutes at 160* C.
  ' Detection limit is calculated from the minimum detectaola
GC response of the electron capture detector being, equal to
five om«  the GC background none, assuming a 10 TH final
volume of  the 1  liter sample extract,  and assuming a QC «v
lection of 5 microttters.
BILLING COOE  SWO-01-M

-------
          COLUMN: 1.5%OV-1

          TEMPERATURE: 75*C.

          DETECTOR:  aECTRON CAPTURE
1.5% OV-225 ON GAS CHROM Q
                                    03
                                    i
                                    o
                                    CM
                                         2
                                         Q
                                                                       0.

                                                                       §
                                                                       O
                                                                       O

                                                                       x
COLUMN:  1.5%OV-H

         1.5% OV-225 ON GAS CHROM Q

TEMPERATURE: 160°C.

DETECTOR:  ELECTRON CAPTURE
                                                                                                                           II
                                                             LU


                                                             LU
                                                                                          o
                                                                                          §
                                                                                          <
                                                                                          X
                                                                                          LU
                                                                                   J.
                                                                    I    1
                  8       12       16

                 RETENTION TIME-MINUTES
               20
                                                                                    8       12      16

                                                                               RETENTION TIME-MINUTES
                                                                                                I
                                                                                                SO
                                                                                                                             o
                                                                                                i
                                     Figure 2.  Gas chromatogram of chlorinated hydrocarbons
Figure 1.  Gas chromatogram of chlorinated hydrocarbons
                                                                                                                             s
                                                                                                                             Qu
                                                                                                                             0)
                                                                                                                             a
                                                                                                                             a>
                                                                                                                             o
                                                                                                                             (D
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                                                 (B
                                                 a.
                                                                                                                              to"
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                                                                                                                              en
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-------
69532
Federal  Register /  Vol. 44, No. 233  /  Monday,  December 3,  1979 / Proposed  Rules
Purgeables—Method 624
  \.  Scope and Application.
  l.l  This method is designed to
determine volatile organic materi-als that
are amenable to the purge and trap
method. The parameters listed in'Table
1 may be determined by this method.
  1.2  This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used to meet the
monitoring requirements of the National
Pollutants Discharge Elimination System
(NPDES).
  1.3  The detection limit of this method
is usually dependent upon the level_of
interferences rather than instrumental
limitations. The limits listed in Table 2
represent sensitivities that can be
achieved in wastewaters.
  1.4  The GC/MS parts of this method
are recommended for use only by
persons experienced in GC/MS analysis
or under the close supervision of such
qualified persons.
  1.5  The trapping and chromatographic
procedures described do not apply to
the very volatile pollutant,
dichlorodifluoromethane. An  alternative
three  stage trap containing charcoal is to
be used if this compound is to be
analyzed. See EPA Method 601 and
Reference 1. Primary ion for quantitative
analysis of this compound is 101. The
secondary ions are 85,  87, and 103.
  1.6  Although this method can be
used for measuring acrolein and
acrylonitrile, the purging efficiencies are
low and erratic. For  a more reliable
quantitative analysis of these
compounds, use direct aqueous injection
(Ref. 4-6) or EPA Method 603, Acrolein
and Acrylonitrile, EMSL, Cincinnati,
Ohio.
  2. Summary of Method.
  21.  A sample of wastewater is
purged with a stream of inert  gas. The
gas is bubbled through a 5 ml water
sample contained in a specially
designed purging chamber. The volatile
organics are efficiently transferred from
the aqueous phase into the gaseous
phase where they are passed  through a
sorbent bed designed to trap out the
organic volatiles. After purging is
complete, the trap is backflushed while
being rapidly heated in order  to
thermally desorb the components into
the inlet of a gas chromatograph. The
components are separated via the gas
chromatograph and detected using a
mass spectrometer which is used to
provide both qualitative and
quantitative information. The
chromatographic conditions as well as
typical mass spectrometer operating
parameters are given.
  3. Interferences.
                           3.1  Interferences coextracted from
                         the samples will vary considerably from
                         source to source, depending upon the
                         diversity of the industrial complex or
                         municipality being sampled. Impurities
                         in the purge gas and organic compounds
                         out-gassing from the plumbing ahead of
                         the trap account for the majority of
                         contamination problems. The analytical
                         system must be  demonstrated to be free
                         from interferences under the conditions
                         of the analysis by running method
                         blanks. Method  blanks are run by
                         charging the purging device with
                         organic-free water and analyzing it in a
                         normal manner. The use of non-TFE
                         plastic tubing, non-TFE thread sealants.
                         or flow controllers"with rubber
                         components in the purging device should
                         be avoided.
                           3.2  Samples  can be contaminated by
                         diffusion of volatile organics
                         (particularly methylene chloride)
                         through  the septum seal into the sample
                         during shipment and storage. A field
                         blank prepared from organic-free water
                         and carried through the sampling and
                         handling protocol can serve as a check
                         on such  contamination.
                           3.3  Cross contamination can occur
                         whenever high level and low level
                         samples are sequentially analyzed. To
                         reduce cross contamination, it is
                         recommended that the purging device
                         and sample syringe be rinsed out twice,
                         between samples, with organic-free
                         water. Whenever an. unusually
                         concentrated sample is encountered,  it
                         should be followed by an analysis of
                         organic-free water to check for cross-
                         contamination. For samples containing
                         Urge amounts of water'soluble
                         materials, suspended solids,'high boiling
                         compounds, or high organohalide levels,
                         it may be necessary  to wash out the
                         purging device with a soap solution,
                         rinse with distilled water, and then dry
                         in a 105°C oven  between analyses.
                           4, Apparatus and Materials.
                           4.1.  Sampling equipment, for discrete
                         sampling.
                           4.1.1  Vial, with cap—40 ml capacity
                         screw cap (Pierce #13075 or equivalent).
                         Detergent wash  and dry vial at 105°C for
                         one hour before use.
                           4.1.2  Septum—Teflon-faced silicone
                         (Pierce #12722 or equivalent). Detergent
                         wash and dry at 105°C for one hour
                         before use.
                           4.2  Purge and trap device—The
                         purge and trap equipment consists of
                         three  separate pieces of apparatus: a
                         purging device, a trap, and a desorber.
                         The complete device is available
                         commercially from several vendors or
                         can be constructed in the laboratory
                         according to the specifications of Bellar
                         and Lichtenberg (Ref. 2,3). The sorbent
                         trap consists of  V» in. O.D. (0.105 in. ID.)
x 25 cm long stainless steel tubing
packed with 15 cm of Tenax-GC (60-80
mesh) and 8 cm of Davison Type-15
silica gel (36-60 mesh). See figures 1
through 4. Ten centimeter traps may be
used providing that the recoveries are
comparable to the 25 cm traps.
  4.3   Gas chromatograph—Analytical
system complete with a temperature
programmable gas chromatograph
suitable for on-column injection and all
required accessories including an
analytical column.
  4.3.1  Column 1—An 8 ft. stainless
steel column (Vs in. OD.x 0.90 to 0.105 in.
ID) packed with 1% SP-1000 coated on
60/80 mesh Carbopack B preceded by a
5-cm precolumn packed with 155 SP-1000
coated on 60/80 mesh Chromosorb W. A
glass column (1A in OD x 2 mm  IDT may
be substituted. The precolumn is
necessary only during conditioning.
  4.3.2  Column 2—An 8 ft. stainless
steel column (Vs in OD x 0.09 to 0.105 in.
ID) packed with 0.2% Carbowax 1500
coated on 80/80 mesh Carbopack C
preceded by a 1 ft. stainless steel
column (Va  in. OD x 0.09 to 0.105 in. ID)
packed with 3% Carbowax 1500 coated
on 60/80 mesh Chromosorb W.  A glass
column (V*  in. OD x 2 mm ID) may be
substituted. The precolumn is necessary
only during conditioning.
  4.4   Syringes—glass, 5-ml hypodermic
with Luer-Lok tip (3 each).
  4.5   Micro syringes—10, 25,100 /j.1.
  4.6   2-way syringe valve with Luer
ends (3 each; Teflon or Kel-F).
  4.7   Syringe—5 ml gas-tight with shut-
off valve.
  4.8   8-inch, 20-gauge syringe  needle—
One per each 5-ml syringe.
  4.9   Mass Spectrometer—capable of
scanning from 20-260 in  six seconds or
less at 70 volts (nominal), and producing
a recognizable mass spectrum at unit
resolution from 50 ng of DFTPP when
injected through the GC  inlet. The mass
spectrometer must-be interfaced with a
gas chromatograph equipped with an
all-glass, on-column injector system
designed for packed column analysis.
All sections of the transfer lines must be
glass or glass-lined and deactivated. Use
Sylon-CT, Supelco, (or equivalent) to
deactivate. The GC/MS interface can
utilize any separator  that gives
recognizable mass spectra (background
corrected) and acceptable calibration
points at the limit of detection specified
for each compound in Table 2.
  4.10 A computer system should be
interfaced to the mass spectrometer to
allow acquisition of continuous mass
scans for the duration of the
chromatographic program. The  computer
system should also be equipped with
mass storage devices for saving all data
from GC-MS runs. There must be

-------
               Federal Register / Vol. 44. No.  233 / Monday. December 3.  1979 /Proposed Rules	69533
 computer software available to allow
 searching any GC/MS run for specific
 ions and plotting the intensity of the
 ions with respect to time or scan
 number. The ability to integrate the area
 under a specific ion plot peak is
 essential for quantification.
   5. Reagents.
   5.1  Sodium thiosulfate—(ACS)
 Granular.
   5.2  Trap Materials
   5.2.1  Porous polymer packing 60/80
 mesh chromatographic grade Tenax GC
 (2,6-diphenylene oxide).
   5.2.3  Silica gel-(35-60 mesh)—
   5.2.2  Three percent OV-1 on
 Chromosorb-W 60/80 mesh. Davison,
 grade-15 or equivalent.
   5.3   Activated carbon—Filtrasorb-200
 (Calgon Corp.) or equivalent.
   5.4   Organic-free water
   5.4.1  Organic-free water is defined
 as water free of interference when
 employed in the purge and trap
 procedure described herein. It is
 generated by passing tap water or well
 water through a carbon filter bed
 containing about 1 ib. of activated
 carbon.
   5.4.2  A water system (Millipore
 Super-Q or equivalent) may be used to
 generate organic-free deionized water.
   5.4.3 • Organic-free water may also be
 prepared by boiling water for 15
 minutes. Subsequently, while
 maintaining the temperature at 90°C,
 bubble a contaminant-free inert gas
 through the water for one hour. While
 still hot, transfer the water to a narrow
 mouth screw cap bottle equipped with  a
 Teflon seal.
   5.5  Stock standards (2 mg/ml)—
 Prepare stock standard solutions in
 methanol using assayed liquids or gases
 as appropriate. Because of the toxicity
 of some of the organohalides, primary
 dilutions of these materials should be
 prepared in a hood. A NIQSH/MESA
 approved toxic gas respirator should be
 worn when the analyst handles high
 concentrations of such materials.
  5.5.1  Place about 9.8 ml of methanol
 into a 10 ml ground glass stoppered
volumetric flask. Allow the flask to
 stand, unstoppered, for about 10 minutes
or until all alcohol wetted surfaces have
dried. Tare the flask to the nearest 0.1
mg.
  5.5.2  Add the assayed reference
 material:
  5.5.2.1  Liquids—using a 100 jil
syringe, immediately add 2 to 3 drops of
assayed reference material to the flask,
 then reweigh. Be sure that the drops fall
directly into the alcohol without
 contacting the neck of the flask.
  5.5.2.2 Gases—To prepare standards
of bromomethane, chioroethane,
chloromethane, and vinyl chloride, fill a
 5-ml valved gas-tight syringe with the
 reference standard to the 5.0-ml mark:
 Lower the needle to 5 mm above the
 methyl alcohol menicus. Slowly inject
 the reference standard into the neck of
 the flask (the heavy gas will rapidly
 dissolve into the methyl alcohol).
   5.5.3  Reweigh the flask, dilute to
 volume, stopper, then mix by inverting
 the flask several times. Transfer the
 standard solution to a 15-ml screw-cap
 bottle equipped with a Teflon cap liner.
   5.5.4  Calculate the concentration in
 mg per ml (equivalent to jxg per )d) from
 the net gain in weight.
   5.5.5  Store stock standards  at 4° C.
 Prepare fresh standards every  second
 day for the four gases and 2-
 chloroethylvinyl ether. All other
 standards must be replaced with fresh
 standards each week.
   5.6 Surrogate Standard Dosing
 Solution—From stock standard solutions
 prepared as above, add a volume to give
 1000 jug each of bromochloromethane,
 2-bromo-l-chloropropane, and  1,4-
 dichlorobutane to 40 ml  of organic-free
 water contained in a 50-ml volumetric
 flask, mix and dilute to volume. Prepare
 a fresh surrogate standard dosing
 solution weekly. Dose the surrogate
 standard mixture into every 5-ml sample
 and reference standard analyzed.
   6. Calibration.
   6.1 Using, the stock standards,
 prepare secondary dilution standards of
 the compounds of interest, either singly
 or mixed together in methanoi. The
 standards should be at concentrations.
 such that the aqueous standards
 prepared in 6.2 will bracket the working
 range of the chromatographic system. If
 the limit of detection listed in Table 2 is
 10 fig/1, for example, prepare secondary
 methanolic standards at 100 fj.g/1, and
 500 fig/1, so that aqueous standards
 prepared from thee secondary
 calibration standards, and the primary
 standards, will define the linearity of the
 detector in the working range.
  6.2 Using both the primary and
 secondary dilution standards, prepare
 calibration standards,by carefully
 adding 20.0 ^il of the standard in
 methanol to 100, 500, or 1000 ml of
 organic-free water. A 25 fil syringe
 (Hamilton 7JD2N or equivalent) should be
 used for this operation. These aqueous
 standards must be prepared fresh daily.
  6.3 Assemble the necessary gas
 chromatographic and mass spectrometer
 apparatus and establish operating
parameters equivalent to those
indicated in Table 2. By injecting
secondary dilution standards, establish
 the linear range of the analytical system
for each compound and demonstrate
 that  the analytical system meets the
 limit of detection requirements in Table
 2.
   8.4  Assemble the necessary purge
 and trap device. Pack the trap as shown
 in Figure 2 and condition overnight at a
 nominal 180° C by backflushing with an
 inert gas flow of at least 20 ml/min.
 Daily, prior to use, condition the traps
 for 10 minutes by backflushing at 180° C.
 Analyze aqueous calibration standards
 (6.2) according to the purge and trap
 procedure in Section 9. Compare the
 responses to those obtained by injection
 of standards (6.3), to determine the
 analytical precision. The analytical
 precision of the analysis of aqueous
 standards must be comparable to data
 presented by Bellar and Lichtenberg
 (1978, Ref. 1) before reliable sample
 analysis may begin.
  6.5  Internal Standard Method — The
 internal standard approach is
 acceptable for the purgeable organics.
 The utilization of the internal standard
 method requires the periodic
 determination of response factors (RF)
 which are defined in equation  1.
Eq. (1) RF
Where:
  A, is (he integrated area or peak height of
the characteristic ion for the priority pollutant
standard.
  Au is the integrated area or peak height of
the characteristic ion for the internal
standard.
  Cu is the amount of the internal standard in
W
  C, is the amount of the pollutant standard
in fig.

  The relative response ratio for each
pollutant should be known for at least
two  concentration values — 50 ng
injected to approximate 10 ^ig/1 and 500
ng to approximate the 100 ug/1 level.
Those compounds that do not respond
at either of these levels may be run at
concentrations appropriate to their
response. The response factor (RF) must
be determined over all concentration
ranges of standard (C,) which are being
determined. (Generally, the amount of
internal standard added to each extract
is the same so that C& remains
constant.) This should be done by
preparing a calibration curve where the
response factor (RF) is plotted against
the standard concentration (C,). Use a
minimum of three concentrations over
the range of interest. Once this
calibration curve has been determined,
it should be verified daily by injecting at
least one standard solution containing
internal standard. If significant drift has
occurred, a new calibration curve must
be constructed.
  Note. — EPA, through its contractors and
certain of its Regional Laboratories, is
currently evaluating selected compounds for

-------
69534
Federal  Register /  Vol. 44,  No. 233  /  Monday,  December 3, 1979 / Proposed Rules
use as internal standards in the analysis of
organic* by purge and trap.
  6.6  The external standard method
can also be used at the discretion of the
analyst. Prepare a master calibration
curve using a ipjniHum* of three
standard solutions of each of the
compounds that are to be measured. Plot
concentrations versus integrated areas
or peak heights  (selected characteristic
ion for GC/MS). One point on each.
curve should approach the method
detection limit After the master set of
instrument calibration curves have been
established, they should be verified
daily by injecting at least one standard
solution. If significant drift has occurred.
a new calibration curve must be
constructed.
  7. Quality Control.
  7.1  Before'processing any samples,
the analyst should daily demonstrate,
through the analysis of an organic-free
water method blank,  that the entire
analytical system is interference-free.
  72  Standard quality assurance
practices should be used with this
method. Field replicates should be
collected to validate the precision of the
sampling technique. Laboratory
replicates should be  analyzed to
validate the precision of the-analysis.
Fortified samples should be analyzed to
validate the  accuracy of the  analysis.
  7.3 The analyst should maintain
constant surveillance of both the
performance of the analytical system
and the effectiveness of the method in
dealing with each sample matrix by
determining the precision of the method
in blank water and spiking each 5-ml
sample, standard,  and blank with
surrogate halocarbons.
  7.3.1 Determine the precision of the
method by dosing blank water with the
compounds selected as surrogate
standards—bromochlorome thane, 2-
bromo-1-chloropropane, and 1,4-
dichlorobutane—and running replicate
analyses. Calculate the recovery and its
standard deviation. These compounds
represent early, middle, and late eluters
over the range of the pollutant
compounds.
  7.3.2 The sample matrix can affect.
the purging efficiencies of individual
compounds; therefore, each sample.must
be dosed with the surrogate standards
and analyzed in a  manner identical to
the internal standards in blank water. If
the recovery of the surrogate standard
shows a deviation greater than two
standard deviations  (7.3.1), repeat the
dosed sample analyses. If the deviation
is again greater .than two standard
deviations, dose another aliquot of the
same sample with the compounds of
interest at approximately two times the
                         measured values and analyze. Calculate
                         the recovery for the individual
                         compounds using these data.
                           8. Sample Collection. Preservation,
                         and Handling.
                           8.1  Grab samples must be collected
                         hi glass-containers having a total
                         volume greater than 20 ml Fill the
                         sample bottles in such a manner that no
                         air bubbles pass through the sample as
                         the bottle is being filled. Seal the bottle*
                         so that no air bubbles are entrapped in
                         it Maintain the hermetic seal on the
                         sample bottle until time of analysis.
                           8.2  The sample must be iced or
                         refrigerated from the time of collection
                         until extraction. If the sample contains
                         residual chlorine, add sodium:
                         thiosulfate- preservative (10 ^g/40 ml]  to
                         the empty sample bottles just prior to
                         shipping to the sample site, fill with
                         sample just to overflowing, seal the
                         bottle, and shake vigorously for 1
                         minute.
                           8.3  All samples must be  analyzed
                         within 7 days of collection.
                           9.   Sample Extraction and Gas
                         Chromatography.
                           9.1  Remove standards and samples
                         from cold storage (approximately an
                         hour prior to an analysis) and bring to
                         room temperature by placing in a warm
                         water bath at 20-25'C.
                           9.2  Adjust the purge gas (nitrogen or
                         helium) flow rate to 40 ml/min. Attach
                         the trap inlet to the purging device, and
                         set the device to the purge mode. Open
                         the syringe valve located on the purging
                         device sample introduction needle.
                           9.3  Remove the plunger from a 5 ml
                         syringe and attach a closed syringe
                         valve. Open the sample bottle (or
                         standard) and carefully pour the sample
                         into the syringe barrel until it overflows.
                         Replace the syringe plunger and
                         compress the sample. Open the syringe
                         valve and vent any residual air while
                         adjusting the sample volume to 5.0 ml.
                         Since this process of taking an-aliquot
                         destroys  the validity of the sample for
                         future analysis, the analyst should fill a
                         second syringe at this, time to protect
                         against possible loss of data. Add 5.0 p.1
                         of the surrogate spiking solution (7.3)
                         through the valve bore, then close the
                         valve.
                           9.4 Attach the syringe-valve
                         assembly to-the syringe valve on the
                         purging device. Open the syringe valve
                         and inject the sample into the purging
                         chamber.
                           9.5 Close both valves and purge the
                         sample for 12.0 ±.05 minutes.
                           9.8 After the 12-minute purge time,
                         attach the trap to the'chromatograph,
                         and adjust the device to the desorb
                         mode. Introduce the trapped materials to
                         the GC column by rapidly heating the
                         trap  to 180'C while backflushing the
trap, with an inert gas, at 20 to 60 ml/
min for 4 minutes. If rapid heating
cannot be achieved, the gas
chromatographic column must be used
as a secondary trap by cooling it to 30'C
(or subambient if problems persist)
instead of the initial program
temperature of 45'C.
  9.7  While the trap is being desorbed
into the gas chromatograph, empty the
purging chamber using the sample
introduction syringe. Wash the chamber
with two 5-ml flushes of organic-free
water. After the purging device has been
emptied,  continue to allow the purge gas
to vent through the chamber until the frit
is dry, and ready for the next sample.
  9.8  After desorbing the sample for
four minutes, recondition the trap by
returning the purge and trap device to
the purge mode. Watt 15 seconds then
close the syringe valve on the purging
device to begin gas flow through the
trap. Maintain the trap temperature at
180'C. After approximately seven
minutes,  turn off the trap heater and
open the  syringe valve to stop the gas
flow through the trap. When cool the
trap is ready for the next sample. (Note:
If this bake out step is omitted, the
amount of water entering the GC/MS
system will progressively increase
causing deterioration of and potential
shut down' of the system.)
   9.9  The  analysis of blanks is most
important in the purge and trap
technique since the purging device and
the trap can be contaminated by
residues  from very concentrated
samples or  by vapors in the laboratory.
Prepare blanks by filling a sample bottle
with organic-free water that has been
prepared by passing distilled water
through a pretested activated carbon
column. Blanks should be sealed, stored
at 4'C, and analyzed with each group of
samples.
   10. Gas Chromatography—Mass
Spectrometry.
   10.1 Table 2 summarizes the
recommended gas chromatographic
column materials and operting
conditions for the instrument. Included
in this tab.e are estimated retention
times and sensitivities that should be
achieved by this method. An example of
the separation achieved by Column 1 is
shown hi Figure 5.
   10.2 GC-MS Determination—
Suggested analytical conditions for
determination of the pollutants
amenable to purge and trap, using the
Tekmar LCS-1 and GC/MS are given
below. Operating conditions vary from
one system to another; therefore, each
analyst must optimize the conditions for
each purge  and trap and GC/MS system.
   10.3 Purge Parameters.

-------
               Federal  Register / Vol.  44, No.  233 / Monday,  December 3, 1979  / Proposed Rules
                                                                         69535
Sample size—S.O ml.
Purge gas—Helium, high purity grade.
Purge time—12 minutes.
Purge flow—40 ml/rain.
Trap dimensions—V4 in. O.D. (0.105 in.
  I.D.)x25 on long.
Trap sorbent—Tenax-GC. 60/80 mesh (15
  cm), plus Type 15 silica gel, 35/60 mesh (8
  cm).
Desorption flow—20 ml/min.
Desorption time—4 min.
Desorption temperature—180* C-
  10.4   Mass Spectrometer Parameters.
Electron energy—70 volts (nominaj).
Mass range—20*27, 33-260 amu.
Scan time—6 seconds or less.
  10.5   Calibration of the gas-
chroma tography-mass spectrometry
(GC-MS system—Evaluate the system
performance each day that it is to be
used for the analysis of samples or
blanks by examining the mass spectrum
ofDFTPPorSFB.
  10.5.1  To use DFTPP, remove the
analytical column and substitute a
column more appropriate to the boiling
point of the reference compound (e.g. 3%
SP-2250 on Supelcoport). Inject a
solution containing 50 ng DFTPP and
check to insure that the performance
criteria listed in Table 3 are met
  10.5.2  To use BFB, infect a solution
containing 20 ng BFB and check to
insure that the performance criteria
listed in Table 4 are met.
  10.5.3  If the system performance
criteria are not met for either test, the
analyst must retune the spectrometer
and repeat the performance check. The
performance criteria must lie met before
any samples or standards may be
analyzed.
  10.8   Analyze an internal or external
calibration standard to develop
response factors for each compound.
  11. Qualitative and Quantitative
Determination.
  11.1   To qualitatively identify a
compound, obtain an Extracted Ion
Current Profile (EICP] for the primary
ion and at least two other ions (if
available) listed in Table 5. The criteria
below must be met for a qualitative
identification.
  11.1.1  The characteristic ions for the
compound must be found to maximize in
the same or within one spectrum of each
other.
  11.1.2  The retention time at the
experimental mass spectrum must be
within ±60 seconds of the retention
time of the authentic compound.
  11.1.3 The ratios  of the three EICP
peak heights must agree within ±20%
with the ratios of the relative intensities
for these ions in a reference mass
spectrum. The reference mass spectrum
can be  obtained from either a standard
analyzed through the GC-MS system or
from a reference library.
  11.1.4  Structural isomers that have
very similar mass spectra can be
explicitly identified only if the resolution
between the isomers in a standard mix
is acceptable. Acceptable resolution is
achieved if the valley height between
isomers is less than 25% of the sum of
the two peak heights. Otherwise,
structural isomers are identified as
isomeric pairs.
  11.2 The primary ion listed in Table 5
is to be used to quantify each
compound. If the sample produces an
interference for the primary ion, use a
secondary ion to quantify.
  11.3 For low concentrations, or direct
aqueous injection of acryionitrile and
acrolein, the characteristic masses listed
for the compounds in Table 5 may be
used for selected ion monitoring (SIM).
SIM is the use of a mass spectrometer as
a substance selective detector by
measuring the mass spectrometric
response at one or several characteristic
masses in real time.
  11.4 Internal Standard Method
Calculations—By adding a constant
known amount of internal standard (C*
in fig) to every sample extract the
concentration of the pollutant (C0) in
fig/1 in the sample is calculated using
equation 2,
     Eq. «C,- _
             (AJ(F»F)(VJ
Where:
V, is the volume of the original sample in
    liters, and the other terms are defined as
    in Section 6 .5. To quantify, add the
    internal standard to the 5.0-ml sample no
    more than a few minutes before purging
    to minimize the possibility of losses due
    to evaporation, adsorption, or chemical
    reaction. Calculate the concentration by
    using the previous equations with the
    appropriate response factor taken from
    the calibration curve.
  11.5  Extenral Standard Method
Calculations—The concentration of the
unknown can be calculated from the
slope and intercept of the multiple point
calibration curve. The unknown
concentration can be determined using
equation 3.
                             (A)
Eq. (3) mlcroorarna per liter »ng/ml- -—
                            (VJ

•Where:
A—Mass of compound from calibration curve
    (ng/5 ml).
V.» volume of water purged (5 ml).

  11.6 An alternate external standard
approach for purgeables utilizes a single
point calibration. Prepare and analyze a
reference standard that closely
approximates the response for each
component in a sample. Calculate the
concentration in the sample using
Equation 4.
                          (AKB)
    Eq. 4 microgram* per liter— 	
                           
Where:
A=»area of the unknown
B=»concentration of standard 0*g/l)
C«area of the standard.
  11.7 Report ail results to two
significant figures. When duplicate and
spiked samples are analyzed, all data
obtained should be reported. Report
results in micrograms per liter without
correction for recovery data.
  12. References.
  1. "The Analysis of Haiogenated Chemical
Indicators of Industrial Contamination in
Water by the Purge and Trap Method." U.S.
EPA. Environmental Monitoring and Support
Laboratory, Cincinnati, OH. 45268, Dec. 1978.
  2. "Symposium on Measurement of Organic
Pollutants in Water and Wastewater," ASTM
Special Publication. 1979 (In Press).
  3. "Determining Volatile Organics at
Microgram-per-Uter Levels by Gas
Chromatography," T. A. Bellar and J. J.
Lichtenberg, Jour. AWWA, 88. 739-744, Dec.
1974.
  4. ASTM Annual Standards—Water, part
31, Method 02908 "Standard Recommended
Practice for Measuring Water by Aqueous-
Injection Gas Chromatography."
  5. ASTM Annual Standards—Water, part
31, Method D3371 "Tentative Method of Teat
for Nitriles in Aqueous Solution of Gas Liquid
Chroma tograph."
  6. "Direct Analysis of Water Samples for
Organic Pollutants-with Gas
Chroma tography-Mass Spectrometry,"
Harris. L. E., Budde, W. L, and Eichelberger,
J. W. Aaal. Chem^ 46,1912 (1974).
Bibliography
  1. "Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority
Pollutants," March 1977 (revised April 1977).
USEPA. Effluent Guidelines Division.
Washington, D.C. 20460.
  2. "Proceedings: Seminar on Analytical
Methods for Priority Pollutants," Volume 1—
Denver, Colorado. November 1977; Volume
2—Savannah, Georgia, May 1978: Volume 3—
Norfolk. Virginia. March 1979; USEPA.
Effluent Guidelines Division. Washington.
D.C. 20460.
                                                     PmnwMr
                                                                       STORETNo.
                                         AcroMrt	
                                         Aerytonrtri*.
                                         eromonwtMn
                                         C*rt>on Tmd
                                         CDk
                                         2-CMoroctfiyMnyl «txr
                                         DlbromocMoronwthtn*—
                                         1.1-OlcNeraMMM.
                                  34210
                                  34215
                                  34238
                                  34413
                                  32101
                                  32104
                                  32102
                                  34301
                                  34311
                                  34879
                                  32108
                                  34418
                                  34106
                                  34488

-------
     S953S


•••1-^-M.i
TaW« 1 — Continued
1 ,2-Ochloroathana 	
1.1-OicniOfO«man» 	
tran»- 1 ,2-D»cftioro«man
' .2-Oicflloropnipana ...
co- 1 .3-Otalilofoorop«o«
tran». 1 ,3-Ocrtcfopropai
£thyl_«n.ana 	 	
MathyMrw chtorida 	

• 	
na 	

	 	 	
	
	
1 . 1 .22-T«trachk>K_Mh-r-»
Tetrachlofetnana 	
1,1.1-TnchlonMIIWM
1 . 1 -Mnchttroatfian*
Trtcnloroathana 	
TncNoroouoromelhana'.
Tafc-B_»
vln^H chlunda — r— I.HW...L

	


	


•«••••-•

cuiuer o, ia
/» / WO]
sosea Rule
S

^^-OrrpPK^^tnatonAbundv>ca ^.i.-BFBKwttonaarttoAtonOincvCrit**
34531
34501
34546
34541
34561
34561
34371
34423
34516
34475
34508
34511
39180
34488
34010
38175
Tabto 2.— Gas Chromatograpty of Organic* 6?
Putyeantt Trap-
Compound
cttorammhana 	
Qromom«nan« 	
wyl emend* _____
cnlofoemana 	
nwthylan* crtcnda.
inehJaofluoromeiftana..
1.1-tfcNorootnana 	
Sromocntoromatnana
(Ss>
U-<»chloro«in*i« 	
traos-l.2-
*CftlorO«tn«n» _____
chtofofofm ....,„_._„...._
1 .2-dhXkiR.Htww 	
1 . 1 . i -tncttoroflttun* _
cartxjn i«tncnK>n» 	
IxonxxlicNaranwman*.
i.2-<*chkxopropane 	
Wna-1,3-
Oicftlofopropane
MchlomMhjn-. ,
1.1--Wchloro«thana_.
oa-1 .3-dBhlonjpiepana'
2-chkxoathylvinvl «har
2^Nuiiiu»|.
cftoreprapvi* (SS}_
bromolorm 	 ...... 	
1.1A2-
UHracnionoatnana 	
1,*-*cftloroout-n»(SS» _
tokMna 	 .... _
cNorooanzvna '""
atnyibanzBoa
•emwn
•crvtonitnl.
Rwandan HIM
(mautta)
Cot.1'
150
2.17
2.67
3.33
525
7.18
7.92
1.46
0-30
10.08
10.68
11.40
1260
13.02
13.65
14.92
15.22
1580
16.46
16_52
16.53
16.00
19-23
21.6Z
2147
iiTi"

Cot.2'
210
2.50
2.57
2-S2-
4.03
5.14
5.25
8.31 _
6.48
6.81
7.70
8.2»-
9.28
9.4S
10.36
11.30
11.7O
11JW
1288
1266
12.68
^95
13.71
1182 _
15.41
17.70
17.4*
18.13 _
18.53
20.57
25.08

Urn. of
-atac-on'
IPO/I)
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
"1 1 1.1
10
10
10
to
10
10
•100
MOO
M*»» ton abundttwtt crttartt
51 	 30 to 60 pet o< mtst 1S
'0 	 __, U»» than 2 pet o« m«ii
127 	 40 to ao pet at man is
• su
18. 75
16*. 95
l«9.
«. 98
Mau


97 	 Laattnanl po of maw 1S8. 173 	
is» 	 8a»« pMk. too pet ralakv* 17* 	
199 ., **_"*"? 175"~ -
iw. — . 	 5io9oeto
-------
             Federal Register / Vol. 44. No. 233 / Monday, December 3, 1979 / Proposed Rules
                                                                            69537
   OPTIONAL
   FOAIU
   (TRAP
V4 IN.
0. 0. EXIT
         c
         d
         1
      -EXIT '/a IN.
           0. 0.

      ~-14MM 0. D.

      INLET 5i IN.
            0. D.
                       SAMPLE INLET

                       2-WAY SYRINGE VALVE
                       •17O.1. 20 GAUGE SYRINGE NEEDLE
              . 0. D. RUBBER SEPTUM
   IQfiMfl GLASS FRIT
   MEDIUM POROSITY


1
^_10MM. 0. D.
•"*)

j V.


5
S
H
7
—INLET
'/i IN. 0. D.
cr
/
/
1/16 IN. O.D.
y'STAJIVLtii iltt1

i

^PSI




13X MOLECULAR
SIEVE PURGE
GAS FILTER

' PURGE GAS
* FLOW
fc CONTROL
             Figure 1. Purging device
     PACKING PROCEDURE
    GLASS KUM
    WOOL 5MM
GRADE 15
SILICA GEL
         8 CM
  TENAX 15 CM
  3% OV-1 1CIW
  GLASS  5MM
  WOOL
TRAP INLET
                 CONSTRUCTION
                             COMPRESSION
                             FITTING NUT
                             ANO FERRULES
                              14FT. 7-n/FOOT
                              RESISTANCE WIRE
                              WRAPPED SOLID
                              THERMOCOUPLE/
                              CONTROLLER
                              SENSOR
                    CJL   / TUBING 25CM
                             0.105 IN. I.O.
                                CL
                                J-£
                                         0.125 IN. O.D.
                                         STAINLESS STEEL

  Figure 2. Trap packings and construction to include
           deaorb capability

-------
63538       Federal Register / Vol. 44. No. 233  / Monday. December 3. 1979 / Proposed Rules
         CARRIER GAS
         FLOW CONTROL
   PRESSURE
   REGULATOR
PURGE GAS   .    .
FLOW CONTROL '
LIQUID INJECTION PORTS
 13X MOLECULAR
 SIEVE FILTER   %
/,
                  -COLUMN OVEN
       \ nnnn I    CONFIRMATORY COLUMN
       jti U LI U^-y-^Q OETECTOR
       pJ¥irir-f ^-ANALYTICAL COLUMN
       * OPTIONAL 4-PORT COLUMN
       SaECTlON VALVE
 SB-PORT TRAP INLET
                    WIRE  CHEATER
                         " CONTROL
           PURGING
           DEVICE
                                             Note:
                                             ALL LINES BETWEEN
                                             TRAP AND GC
                                             SHOULD BE HEATED
                                             TO 80° C.
 Figure 3. Schematic of purge and trap device - purge mode
         CARRIER GAS
         FLOW CONTROL
   PRESSURE
   REGULATOR
LIQUID INJECTION-PORTS
PURGE GAS
FLOW CONTROL^
 13X MOLECULAR
 SIEVE FILTER
                  -COLUMN OVEN
        n n n n  I    CONFIRMATORY COLUMN
                  TO DETECTOR
                    -ANALYTICAL COLUMN
       OPTIONAL 4-PORT COLUMN
       SaECTlON VALVE
  6-PORT TRAP INLET
  VALVE J RESISTANCE WIRE  H£ATER

                      ^ CONTROL
                                            Note:
                                            ALL LINES BETWEEN
                                            TRAP AND GC
                                            SHOULD BE HEATED
                                            TO 80°C.
           PURGING
           DEVICE
Figure 4. Schematic of purge and trap device - desorfr mode

-------
                                                   LU
-COLUMN: 1% SP-1000 ON CARBOPACK-B

PROGRAM: 45'C-3 MINUTES, 8VMINUTE TO 220°C
                                                                                                          3?
                                                                                                          8-
                                                                                                          2.
                                                                          UJ
                      8    10   12    14
                                      RETENTION TIME - MINUTES



Figure 5. Gas chromatogram of volatile organics by purge and trap
               28'   30
                                                                                                          I
                                                                                                          B-
                                                                                                          a
                                             I
                                             8
BIU-INQ CODE 65VO-01-C
                                                                                                          n
                                                                                                          (B
                                                                                                          a.


                                                                                                          I
                                                                                                          (D

-------
60540
Federal  Register / Vol. 44,  No. 233  /  Monday,  December 3,  1979 / Proposed  Rules
Base/Neutrals. Acids, and Pesticides—
Method 625
  1. Scope and Application.
  1.1 This method covers the
determination of a number of organic
compounds that are solvent extractable
and amenable to gas chroma tography.
The parameters listed hi Tables 1, 2 and
3 may be determined by this method.
  1.2 This method is applicable to the
determination of these compounds in
municipal and industrial discharges. It is
designed to be used to meet the
monitoring requirements of the National
Pollutants Discharge Elimination System
(NPDES].
  ,1.3 The detection limit of this method
is usually dependent upon the level of
interferences rather than instrumental
limitations. The limits listed in Tables 4,
5, and 6 represent the minimum quantity
that must be injected into the system to
get confirmation by the  mass
spectrometric method described below.
  1.4 The GC/MS parts of this method
are recommended for use  only by
analysts experienced with GC/MS or
under the close supervision of such
qualified persons.
  2. Summary of Method.
  2.1 A1 to 2 liter sample of
wastewater is extracted with methylene
chloride using separatory  funnel or
continuous extraction techniques. If
emulsions are a problem, continuous
extraction techniques should be used.
The extract is dried over sodium sulfate
and concentrated to a volume of 1 ml
using a Kuderna-Danish (K-D)
evaporator. Chromatographic conditions
are described which allow for the
separation of the compounds in the
extract.
  2.2 Quantitative analysis is performed
by GC/MS using either the internal
standard or external standard
technique.
  3. Interferences.
  3.1 Solvents, reagents, glassware, and
other sample processing hardware may
yield discrete artifacts and/or elevated
baselines causing misinterpretation of
chromatograms. All of these materials
must be demonstrated to be free from
interferences under the conditions of the
analysis by running method blanks.
Specific selection of reagents and
purification of solvents by distillation in
all-glass systems may be required.
  3.2 Interferences coextracted from the
samples will vary considerably  from
source to source, depending upon the
diversity of the industrial  complex or
municipality being sampled.
  3.3 The recommended analytical
procedure may not have sufficient
resolution to differentiate between
certain isomeric pairs. These are
                         anthracene and phenanthrene, chrysene
                         and benzo(a)anthracene, and
                         benzo(b)fluoranthene and
                         benzo(k)fluoranthene. The GC retention
                         time and mass spectral data are not
                         sufficiently unique to make an
                         unambiguous distinction between these
                         compounds. Alternative techniques
                         should be used to identify and quantify
                         these specific compounds. See
                         Reference 1.
                           4. Apparatus and Materials.
                           4.1  Sampling equipment, for discrete
                         or composite sampling.
                           4.1.1  Grab sample bottle—amber
                         glass, 1-liter to 1-gallon volume. French
                         or Boston Round design is
                         recommended. The container must be
                         washed and solvent rinsed before use to
                         minimize interferences.
                           4.1.2  Bottle caps—Threaded to fit
                         sample bottles. Caps must be lined with
                         Teflon. Aluminum foil may be
                         substituted if sample is not corrosive.
                           4.1.3  Compositing equipment—
                         Automatic or manual compositing
                         system. Must incorporate glass sample
                         containers for the collection of a
                         minimum of 1000 ml. Sample containers
                         must be kept refrigerated during
                         sampling. No plastic or rubber tubing
                         other than Teflon may be used in the
                         system.
                           4.2  Separatory funnel—2000 ml, with
                         Teflon stopcock (Ace Glass 7228-T-72
                         or equivalent).
                           4.3  Drying column—A 20 mm ID
                         pyrex chromatographic column
                         equipped with coarse glass frit or glass
                         wool plug.
                           4.4  Kuderna-Danish (K-D)
                         Apparatus
                           4.4,1  Concentrator tube—10 ml,
                         graduated (Kontes K-570050-1025 or
                         equivalent). Calibration must be
                         checked. Ground glass stopper (size 19/
                         22 joint) is used to prevent evaporation
                         of extracts.
                           4.4.2  Evaporative flask—500 ml
                         (Kontes K-STOOl-^SOO or equivalent).
                         Attach to concentrator tube with
                         springs.. {Kontes K-662750-0012).
                           4.4.3  Snyder column—three-ball
                         macro (Kontes K503000-0232 or
                         equivalent).
                           4.4.4  Snyder,column—two-ball micro
                         (Kontes K-569002-0219 or equivalent).
                           4.4.5  Boiling chips-extracted,
                         approximately 10/40 mesh.
                           4.5  Water bath—Heated, with
                         concentric ring cover, capable of
                         temperature control (±2' C). The bath
                         shouhi be used in a hood.
                           4,8  Gas chromatograph—Analytical
                         system complete with gas
                         chromatograph capable of on-column
                         injection and all required accessories'
                         including column supplies, gases, etc.
  4.8.1  Column 1—For Base/Neutral
and Pesticides a 8-foot glass column (V*
in OD x 2 mm ID) packed with 3% SP-
2250 coated on 100/120 Supelcoport (or
equivalent).
  4.6.2  Column 2—For Acids, a 6-foot
glass column (Vi in OD x 2 mm ID)
packed with 1% SP-1240 DA coated on
100/120 mesh Supelcoport (or
equivalent).
  4.7 Mass Spectrometers-Capable of
scanning from 35 to 450 a.m.u. every 7
seconds or less at 70 volts (nominal) and
producing a recognizable mass spectrum
at unit resolution from 50 ng of DFTPP
when the sample is introduced through
the GC inlet (Reference 2).  The mass
spectrometer must be interfaced with a
gas chromatograph equipped with an
injector system designed for splitless
injection and glass  capillary columns or
an injector system designed for on-
column injection with all-glass packed
columns. All sections of the transfer
lines must be glass or glass-lined and
must be deactivated. (Use Sylon-CT,
Supelco, Inc., or eqviivalent to
deactivate.)
  Note.—Systems utilizing a jet separator for
the GC effluent are recommended since
membrane separators may lose sensitivity for
light  molecules and glass fnt separators may
inhibit the elution of polynuclear aromatics.
Any of these separators may be used
provided that it gives recognizable mass
spectra and acceptable calibration points at
the limit of detection specified for each
individual compound listed in Tables 4, 5,
and 8.
  4.8 A computer system must be
interfaced to the mass spectrometer to
allow acquisition of continuous mass
scans for the duration  of the
chromatographic program.  The computer
system should also be equipped with
mass storage devices for saving all data
from GC-MS runs. There must be
computer software available to allow
searching  any GC-MS run  for specific
ions and plotting the int'ehsity of the
ions with respect to time or scan
number. The ability to integrate  the area
under any specific ion plot peak is
essential for quantification.
  4.9 Continuous  liquid-liquid
extractors—Teflon or glass connecting
joints and stopcocks, no lubrication.
(Hershberg-Wolf Extractor—Ace Glass
Co.,  Vineland, N.J. P/N 6841-10 or
equivalent).
  5. Reagents.
  5.1 Sodium hydroxide—(ACS) 6N in
distilled water.
  5.2 Sulfuric acid—(ACS) 6N in
distilled water.
  5.3 Sodium sulfate—(ACS) granular
anhydrous (rinsed with methylene
chloride (20 ml/g) and conditioned at
400°  C for 4 hrs.).

-------
               Federal Register  / Vol. 44, No.  233 / Monday. December  3. 1979 / Proposed  Rules	69541
   5.4  Methylene chloride—Pesticide
 quality or equivalent.
   5.5  Stock standards—Obtain stock
 standard solutions at a concentration of
 1.00 fig/p.1. For example, dissolve 0.100
 grams of assayed reference material in
 pesticide quality isooctane or other
 appropriate solvent and dilute to volume
 in a 100 ml ground glass stoppered
 volumetric flask. The stock solution is
 transferred to 15 ml Teflon lined screw
 cap vials, stored in a refrigerator, and
 checked frequently for signs of
 degradation or evaporation, especially
 just prior to preparing working
 standards from them. Protect PNA
 standards from light.
  6t Calibration.
  6.1  Prepare calibration standards
 that contain the compounds of interest,
 either singly, or mixed together. The
 standards should be prepared at
 concentrations that will bracket the
 working range of the chromatographic
 system (two or more orders of
 magnitude  are suggested). If the limit of
 detection (Tables 4, 5, or 6) can be
 calculated as 20 ng injected, for
 example, prepare standards at 1
 10 Aig/nd- 100 MJ/nd- etc. so that
 injections of 1-5 /U of the calibration
 standards will define the linearity of the
 detector in  the working range.
  6.2  Assemble the necessary gas
 chromatographic apparatus  and'
 establish operating parameters
 equivalent to those indicated in Tables
 4, 5, and 6. By injecting calibration
 standards, establish the linear range of
 the analytical system and demonstrate
 that the analytical system meets the
 limits of detection requirements  of
 Tables 4, 5, and 6.. If the sample gives
 peak areas  above the working range,
 dilute and reanalyze.
  6.3  Internal Standard Method—The'
 internal standard approach is
 acceptable  for all of the semivolatile
organics. The utilization of the internal
 standard method requires the periodic
 determination of response factors (RF)
 which are defined in equation 1.
 Eq. 1 RF=(A,Ci,)/(Al.C,)
Where:
 A, is the integrated area or peak height of the
    characteristic ion for the pollutant
    standard.
At, is the integrated area or peak height of the
    characteristic ion for the internal
    standard.
 Ci, is the amount (jtg) of the internal
    standard.
C, is the amount (jug) of the pollutant
    standard.
  6.3  The  relative response ratio for
 the pollutants should be known for at
least two concentration values—20 ng
injected to approximate 10 ^g/1 and 200
ng injected  to approximate the 100 fj.g/1
 level. (Assuming 1 ml final volume and a
 2 pi injection). Those compounds that 'do
 not respond at either of these levels may
 be run at concentrations appropriate to
 their response.
   The response factor (RF) should be
 determined over all concentration
 ranges of standard (C,) which are being
 determined. (Generally, the amount of
 internal standard added to each extract
 is the same (20 fig) so that Q, remains
 constant.) This should be done by
 preparing a calibration curve where the
 response factor (RE) is plotted against
 the standard concentration (C,), using a
 minimum of three concentrations over
 the range of interest Once this
 calibration-curve has been determined,
 it should be verified) daily by injecting at
 least one standard solution containing
 internal standard. If significant  drift has
 occurred, a new calibration curve must
 be constructed. To quantify, add the
 internal standard to the concentrated
 sample extract no more-than a few
 minutes before injecting into the GC/MS
 to minimize the possibility of losses due
 to evaporation, adsorption, or chemical
 reaction. Calculate the concentration by
 using the previous equations with the
 appropriate response factor taken from
 the calibration curve. Either deuterated
 or fluorinated compounds can be used
 as internal standards and surrogate
 standards. Naphthalene-cU, anthracene-
 dio, pyridine-dg, aniline-dj, nitrobenzene-
 ds. 1-fluoronaphthalene, 2-
 fluoronaphthalene, 2-fluorobiphenyl,
 2,2'-difluorobiphenyl, and 1,2,3,4,5-
 pentafluorobiphenyl have been used or
 suggested as appropriate internal
 standards /surrogates for the base-
 neutral compounds. Phenol-d«,
 pentafluorophenol, 2-perfluoromethyl
 phenol, and 2-fluorophenol have been
 used or suggested for the acid
 compounds. Compounds used as
 internal standards are not to be  used as
 surrogate standards. The internal
 standard must be different from the
 surrogate standards.
  6.5  The external standard method
 can also be used at the discretion of the
 analyst. Prepare a master calibration
 curve using a minimum of three
standard solutions of each of the
 compounds that are to be measured. Plot
 concentrations versus integrated areas
or peak heights (selected characteristic
ion for GC/MS). One point on each
curve should approach the limit  of
detection (Tables 4, 5, and 6). After the
master set of instrument calibration
curves have been established, they
should be verified daily by injecting at
least-one standard solution. If significant
drift has occurred, a new calibration
curve must be constructed.
   7. Quality Control.
   7.1  Before processing any samples,
 demonstrate through the analysis of a
 method blank, that all glassware and
 reagents are interference-free. Each time
 a set of samples is extracted or there is
 a change in reagents, a method blank
 should be processed as a safeguard
 against chronic laboratory
 contamination.
   7.2 . Standard quality assurance
 practices should be used with this
 method. Field replicates should be
 collected and analyzed to determine the
 precision of the sampling technique.
 Laboratory replicates should be
 analyzed to determine the precision of
 the analysis. Fortified samples should be
 analyzed to determine the accuracy of
 the analysis. Field blanks should be
 analyzed to check for contamination
 introduced during sampling and
 transportation.
   8. Sample Collection, Preservation,
 and Handling,
   8.1 Grab samples must be collected in
 glass containers. Conventional sampling
 practices should be followed, except
 that the bottle must not be prerinsed
 with sample before collection.
 Composite samples should be collected
 in refrigerated glass containers in
 accordance with" the requirements of the
 program. Automatic sampling equipment
 must be ffee of tygon and other potential
 sources of contamination.
  8.2 The samples must be iced or
 refrigerated from the time of collection
 until extraction. Chemical preservatives
 should not be used in the field unless
 more than 24 hours will elapse before
 delivery to the laboratory. If the samples
 will not be extracted within 48 hours of
 collection, they must be preserved as
 follows:
  8.2.1 If the sample contains residual
 chlorine, add 35 mg of sodium
 thiosulfate per 1 ppm of free  chlorine per
 liter of sample.
  8.2.2 Adjust the pH of the water
 sample to a pH of 7 to 10 using sodium
 hydroxide or sulfuric acid. Record the
 volume of acid or base used.
  8.3  All samples must be extracted
 within 7 days and completely analyzed
 within 30 days of collection.
  9. Sample Extraction (Base/Neutrals.
Acids, and Pesticides).
  9.1  Samples may be extracted by
 separatory funnel techniques or with a
 continuous extractor as described in
 Section 10. Where emulsions prevent
 acceptable solvent recovery with the
separatory funnel technique, the analyst
 must use the continuous extractor.
  9.2  The details of the extraction
 technique should be adjusted according
 to the sample volume. The technique
described below assumes a sample

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69542	Federal Register / Vol.  44. No. 233 / Monday, December 3.  1979 / Proposed  Rules
volume of 1000 ml. For volumes
approximating 2-liters, the volume of
extraction solvent should be adjusted to
250,100, and 100 ml for the serial
extraction of the base neutrals, and 200,
100, and 100 ml for the acids.
  9.3 Mark the water meniscus on the
side of the sample bottle for later
determination of sample volume. Pour
the entire sample into a  two-liter
separatory funnel. Adjust the pH of the
sample with 6N NaOH to 11 or greater.
Use multirange pH paper for the
measurements. Proceed to Section 10 if
continuous extraction is used.
  9.4 Add 60 ml methylene chloride to
the sample bottle, cap, and shake 30
seconds to rinse the walls. Transfer the
solvent into the  separatory funnel, and
extract the sample by shaking the funnel
for two minutes with periodic venting to
release excess vapor pressure.  Allow
the organic  layer to separate from the
water phase for a minimum of ten
minutes. If the emulsion interface
between layers is more than one-third
the size of the solvent layer, the analyst
must employ mechanical techniques to
complete the phase separation. The
optimum technique depends upon the
sample, but may include stirring,
filtration of the emulsion through glass
wool, or centrifugation. (If the emulsion
cannot be broken, that is, recovery is
less than 80% of the added solvent
corrected for the water solubility of
methylene chloride, transfer the sample,
solvent and emulsion into a continuous
extractor and proceed as described in
Section 10). Collect the methylene
chloride extract in a-250-ml Erlemneyer
flask.
  9.5 Add a second 60-ml volume of
methylene chloride to the sample bottle
and complete the extraction procedure a
second time, combining  the extracts in
the Erlenmeyer flask.
  9.6 Perform a third extraction in the
same manner. Pour the combined
extract through  a drying column
containing 3-4 inches of anhydrous
sodium sulfate, and collect it in a 500 ml
K-D flask equipped with 10 ml
concentrator tube. Rinse the Erlenmeyer
with 20 to 40 ml of methylene chloride.
Pour this through the drying column.
Seal, label as base/neutral fraction, and
proceed with the acid extraction. If the
extract must be stored overnight before
analysis by GC/MS, it may be
transferred to a 2 ml serum vial
equipped with a Teflon-lined rubber
septum and crimp cap.
  9.7 Acid (Phenols) Extraction—Adjust
the pH of the water, previously
extracted for base-neutrals, with 6N
H»SO« to 2 or below. Serially extract
with 60, 60 and 60 ml portions of
distilled-m-glass methylene chloride.
Collect and combine the extracts in a
250-ml Erlenmeyer flask then dry by
passing through a column of anhydrous
sodium sulfate. Rinse the Erlenmeyer
with 20 to 40 ml of methylene chloride
and pour through the drying column.
Seal, label acid fraction and prepare for
concentration.
  9.8  Concentrate the extracts (Base/
Neutrals and Acids) in a 500 ml K-D
flask equipped with a 10 ml concentrator
tube.
  9.9  Add 1 to 2 clean boiling chips  to
the flask and attach a three-ball macro-
Snyder column. Prewet the Snyder
column by adding about 1 ml methylene
chloride through the top. Place the K-D
apparatus on a warm water bath (60 to
65° C | so that the concentrator tube is
partially immersed in the water, and the
entire lower rounded surface of the flask
is bathed with water vapor. Adjust the
vertical position of the apparatus and
the water temperature as required to
complete the concentration in 15 to 20
minutes. At the proper rate of
distillation the balls of the column
actively chatter but the chambers do not
flood. When the liquid has reached an
apparent volume 1 ml. remove the K-D
apparatus and allow the solvent to drain
for at least 10 minutes while cooling.
Remove the Snyder column and rinse
the flask and its lower joint into the
concentrator tube with 1 to 2 ml of
methylene chloride. A 5-ml syringe is
recommended for this operation.
  9.10 Add a dean boiling chip and
attach a two-ball micro-Snyder column
to the concentrator tube in 9.8. Prewet
the column by adding about 0.5 ml
methylene chloride through the top.
Place the K-D apparatus on a warm
water bath (60 to 65°C) so that the
conceintrator tube is partially immersed
in the water. Adjust the vertical position
of the apparatus and the water
temperature as required to complete the
concentration in 5-10 minutes. At the
proper rate of distillation the balls of the
column actively chatter but the
chambers do not flood. When the  liquid
reaches an apparent volume of about 0.5
ml, remove the K-D from the water bath
and allow the solvent to drain and cool
for at least 10 minutes. Remove the
micro-Snyder column and rinse its lower
joint into the concentrator tube with
approximately 0.2 ml of methylene
chloride. Adjust the final volume to 1.0
ml, seal, and label as acid fraction.
  9.11 Determine the original sample
volume by refilling the sample bottle  to
the mark and transferring the liquid to a
1,000-ml graduated cylinder. Record the
sample volume to the nearest 5 ml
  10. Emulsions/Continuous Extraction.
  10.1  Place 100 to 150 ml of methylene
chloride in the extractor'and 200-500 ml
methylene chloride in the distilling flask.
  10.2  Add the aqueous sample (pH 11
or greater) to the extractor. Add blank
water as necessary to operate the
extractor and extract for 24 hours.
Remove the distilling flask and pour the
contents through a drying column
containing 7 to 10 cm of anhydrous
sodium sulfate. Collect the methylene
chloride in a 500 ml K-D evaporator
flask quipped with a 10 ml concentrator
tube. Seal, label as the base/neutral
fraction, and concentrate as per sections
9.8 to 9.10.
  10.3  Adjust the pH of the sample in
the continuous extractor to 2 or below
using 6N sulfuric acid. Charge a clean
distilling flask with 500 ml of methylene
chloride. Extract for 24 hours. Remove
the distilling flask and pour the  contents
through  a drying column containing 7 to
10 cm of anhydrous sodium sulfate.
Collect the methylene chloride layer on
a K-D evaporator flask equipped with a,
10 ml concentrator tube. Label as the
acid fraction. Concentrate as per
sections 9.8 to 9.10.
  11. Calibration of the GC-MS System.
  11.1  At the beginning of each day,
the mass calibration of the GC-MS
system must be checked and adjusted if
necessary to meet DFTPP specifications
(11.3). Each day base-neutrals are
measured, the column performance
specification (12.1) with benzidine must
be met Each day the acids are
measured, the column performance
specification (13.1) with          	
pentachlorophenol must be met DFTPP
can be mixed in solution with either of
these compounds to complete two
specifications with one injection, if
desired.
  11.2   To perform the mass calibration
test of the GC-MS system,  the following
instrumental parameters are required:
  Electron energy—70 volts (nominal).
  Mass range—35 to 450 a.m.u.
  Scan time—7 seconds or less.

  11.3   GC-MS system calibration-
Evaluate the system performance each
day that it is to be used for the analysis
of samples or blanks by examining the
mass spectrum of DFTPP. Inject a
solution containing 50 ug DFTPP and
check to insure that performance criteria
listed in Table 10 are met. If the system
performance criteria are not met, the
analyst must retune the spectrometer
and repeat the performance check. The
performance criteria must be met before
any samples or standards may be
analyzed.
  12. Gas Chromatography-Mass
Spectrometry of Base/Neutral Fraction.

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              Federal Register / Vol. 44, No.  233 / Monday, December 3. 1979 /  Proposed Rules	69543
  12.1  At the beginning of each day
that base/neutral analyses are to be
performed, inject 100 nanograms of
benzidine either separately or as part of
a standard mixture that may also
contain 50 ng of DFTPP. The tailing
factor for oenzidine should be less than
3. Calculation of the tailing factor is
given in Reference 2 and described in
Figures.
  12.2  Establish chromatographic
conditions equivalent to those in Tables
4 and 5. Included in these tables are
estimated retention times and
sensitivities that can be achieved by this
method. Examples of the separations
achieved by these columns are shown in
Figures 1 and 3 through 7.
  12.3  Program the GC/MS to  operate
in the Extracted Ion Current Profile
(EICP) mode,  and collect EICP for the
three  ions listed in Tables 7 and 8 for
each compound being measured.
Operating in this mode, calibrate the
system response for each compound as
described in Section 6, using either the
internal or external standard procedure.
  12.4  If the internal standard
approach is being used, the analyst may
not add the standard to sample  extracts
until immediately before  injection into
the instrument Mix thoroughly.
  12.5  Inject 2 to 5 jil of the sample
extract. The solvent-flush technique is
preferred. If external calibration is
employed, record the volume injected to
the nearest 0.05 pi. If the  response for
any ion exceeds the linear range of the
system, dilute the extract and reanalyze.
  12.6  Qualitative and quantitative
measurements are made as described in
Section 14. When the extracts are not
being  used for analysis, store them in
vials with unpierced septa in the dark at
14°  C.
  13. Cas Chromatography/Mass
Spectromatry of Acid Fraction.
  13.1  At the beginning of each day
that acid fraction analyses are to be
performed, inject 50 nanograms  of
pentachlorophenoi either separately or
as part of a standard mixture that may
also contain DFTPP. The  tailing factor
for pentachlorophenoi should be less
than 5. Calculation of the tailing factor is
given  hi Reference 2 and  described in
Figure 8.
  13.2  Establish chromatographic
conditions equivalent to those in Table
6. Included in this table are estimated
retention times and sensitivities that can
be achieved by this method. An example
of the separation achieved by the
column is shown in Figure 2.
  13.3  Program the GC/MS to  operate
in the Extracted Ion Current Profile
mode, and collect EICP for the three ions
listed  in Table 9 for each phenol being
measured. Operating in this mode,
calibrate the system response for each
compound as described in Section 8
using either the internal or external
standard procedure.
  13.4  If the internal standard
approach is being used, the analyst may
not add the standard to sample extracts
until immediately before injection into
the instrument. Mix thoroughly.
  13.5  Inject 2. to 5 jul of the sample
extract. The solvent-flush technique is
preferred. If external  standard
calibration is employed, record the
volume injected to the nearest 0.05 pi. If
the response for any ion exceeds the
linear range of the system, dilute the
extract and reanalyze.
  13.6  Qualitative and quantitative
measurements are made as described in
Section 14. When the extracts are not
being used for analysis, store them in
vials with unpierced septa in the dark at
4'C.
  14.  Qualitative and Quantitative
Determination.
  14.1 To qualitatively identify a
compound, obtain an Extracted Ion
Current Profile (EICP) for the primary
ion and the two other ions listed in
Tables 7, 8, or 9. The  criteria below must
be met for a qualitative identification.
  14.1.1  The characteristic ions for the
compound must be found to maximize in
the same or within one spectrum of each
other."
  14.1.2  The retention time at the
experimental  mass spectrum must be
within ±60 seconds of the retention
time of the authentic compound.
  14.1.3  The ratios of the three EICP
peak heights must agree within ±20%
with the ratios of the  relative intensities-
for these ions in a reference mass
spectrum. The reference mass spectrum
can be obtained from either a  standard
analyzed through  the GC-MS system or
from a reference library.
  14.1.4  Structural isomers that have
very similar mass spectra can be
explicitly identified only if the resolution
between the isomers in a "standard mix .
is acceptable. Acceptable resolution is
achieved if the valley height between
isomers is less than 25% of the sum of
the two peak heights. Otherwise,
structural isomers are identified as
isomeric pairs.
  14.2 In samples that contain an
inordinate number of interferences the
chemical ionization (CI) mass spectrum
may make identification easier. In
Tables 7 and 8 characteristic CI ions for
most of the compounds are given. The
use of Chemical ionization MS to support
El is encouraged but not required.
  14.3 When a compound has been
identified, the quantification of that
compound will be based on the
integrated area from the specific ion plot
of the first listed characteristic ion in
Tables 7, 8 and 9. If the sample produces
an interference for the first listed ion,
use a secondary  ion to quantify.
Quantification will be done by the
external or internal standard method.
  14.4   Internal  Standard—By adding a
constant known  amount of internal
standard (Q, in fig) to every sample
extract, the concentration of pollutant
(C0) is pg/1 in the sample is calculated
using equation 2.
   Eq. 2
                       (A,) (CJ
(Au)
                              (Vo)
Where: V. is the volume of the original
    sample in liters, and the other terms are
    denned as in Section 6.3.

  14.5  External Standard—The
concentration of the unknown can be
calculated from the slope and intercept
of the calibration curve. The unknown
concentration can be determined using
equation 3.
               Eq. 3
Micrograms/liter  = ng/ml
                             (A)(Vt)
where:
A=mass of compound from calibration curve
    (ng).
Y!=volume of extract injected (/il).
Vt» volume of total extract (jil).
V,« volume of water extracted (ml).
  14.6  Report all results to two
significant figures.  Report results in
micrograms per liter (Base/Neutrals and
Acids) without correction for recovery
data. When duplicate and spiked
samples are analyzed, all data obtained
should be reported.
  14.7  In order to minimize
unnecessary GC-MS analysis of method
blanks and field blanks, the field blank
may be screened on a FID-GC equipped
with the appropriate SP-2250 or SP-1240
DA columns.
  15.  References

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69544	Federal Register / Vol. 44. No. 233 /  Monday. December 3. 1979 / Proposed Rules
1. Method 610, Polynuclear Aromatic
Hydrocarbons, EMSL, Cincinnati, Ohio
45288, 1979.
2. "Reference Compound to Calibrate Ion
Abundance Measurement in Cas
Chromatography — Mass Spectrometry
Systems." }. W, Eicheiberger, L. E. Harris
and W. L Budda, Anal. Cheat. 47, 995-1000
(1975).
Bibliography
1. "Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority
Pollutants," March 1977 (revised April
1977). USEPA, Effluent Guidelines Division.
Washington, D.C. 20460.
2. "Proceedings.— Seminar on Analytical
Methods for Priority Pollutants":
Volume 1 — Denver, Colorado, November
1977
Volume 2 — Savannah, Georgia. May 1978
Volume 3 — Norfolk, Virginia, March 1979
USEPA, Effluent Guidelines Division.
Washington. D.C. 20460.
T»»il*A.—uasa-NeutralExtractati/es
Compound STORET
No.
Acenaphthene 	 ..... .. - • . 	 ,. - , 34205
AcannpntfiyWne. 	 , 34200
Anlhrac«n«. . 	 ........ 	 ,.., , ,.. 345?O
Benzo(a)anthracana 	 34526
8erzo(l()fluorantnene 	 34242
Ctan7o(g,n i)p*ry*tr» ?4f?1
3***tfcjiri* 39120
«^2^NQfO«tiy<)«ih«r •U77t
8m<2-chloroethoxy)melhane 	 	 34278
8o<2-ettiylhexyl)phthalate 	 _ 	 _ 	 39100
Bw(2-chloroiaopropyl)ether 	 	 	 	 34283
4-Bromophenyl phenyl ether. 	 _._„._ 	 	 	 34636
Butyl benzyl phthalate 	 34292
2-CNoronaphdlalene _... 	 	 	 .. 34581
4OHorophenyt phenyl ether 	 _. 	 	 34641
0*enzo-n-r'"C>Vl*™~« tUM
N-NitroaodlpnenyuuiMW ._ 	 	 - ,-m, ,„..-- 344.1$
Phenantnrene 	 34461
2.3.7,8-Tetrachlorodibenzo^dioxin 	 34675
1 ,2.4-Tnchlorobenzene 	 	 	 34551
Table) i-Aca Bmctatles
Compound STORET
No.
4-CMoro-3-melhylphenol 	 	 . . 34452

2.4-Otahlorophenol 	 34601
Table t— Ada Extractabtos— Continued
Compound STORET
Na
2 4-Otmethylphenol ... 34606
2,4-OWtwpfienol 	 34619
2-MethyM,64Mlrophenol. 	 	 	 34657



Z4.6-Titahtoroprienol 	 34621
Table *.— Pesticide Extractablea
Compound STOH6T
Na
Aldrm___ . _ _ 	 .... _ 39330
a-8HC 	 _. 	 , , ,„._ 39337

d-BHC 39340
g-SHC . 	 .__ _._ 34259

4,4'-OOO....-_. 	 —.. 	 _._._. 	 ... 	 „._ 	 . 39310
44-npr ........... „ . 	 -men


Endoaulfan 9 	 _ - 34359
Cnrt0ftulfan Surfatt V351
Ervjrtn • 19300
En*nAJdehyde 	 34366
HeptacNor Epoiode 	 39420
PTB.inm iuj7i
PCS-1221 	 	 	 - .. . 39488
PCB.1M? .,. , „ „ 34497
pea. 1242 39494

PCB-12S4 	 39504

Table 4— Gas Chromatography of Base/ Neutral
ExtractatHes
Reten- Unit of detection
Compound don ##
(Ma) ng injected w/1
1,3-Oichkxobenzene 	 74 20 10
1 4^*4t4yc£ianz9n4 73 20 10
Hexachloroethane 	 	 8.4 20 to
as<2-cMoro«inyl)etrier 	 8.4' 20 10
1.2-Ocnlorobertzene 	 	 „ 8.4 20 10
Nitrobenzene 	 	 	 	 11.1 20 10
1.2,4-TricrHorobenzene 	 11.6 20 10
laophorone 	 	 	 119 20 10
Naphthalene 	 12.1 20 10
BislZ-chloroethoxy) methane 	 12-2 20 10
Hexachlorocyclopentadiene 	 13.9 20 10
2-Chloroniphtnajene 	 	 15.9 20 10
AcanaphWene 	 „. 	 	 178 20 10
Dimethyl phtfiatate 	 	 _ 183 20 10
Fluorene.... 	 	 ....,,,_ 19.5 20 10
4-CNoropnenyl phenyl ether ._ 	 _ 19.5 20 10"
2,4-Oinrtrotohjene 	 	 	 19 fl 20 10
1,2-Oiphenyl hydrazme' . 20.1 20 10
Dlethyl phthalate 	 	 	 	 	 20.1 20 10

4.8romoptwnyl pheny* «th«r._ 	 „ 21 2 20 10
Anthracene 	 .. ._ 22.8 20 10
Di-n-butyl phthalate ..._ 	 _ 24 7 20 10
Ruorantnene 	 _ 	 „ _ 28.5 20 10
Pyrene 	 	 	 	 273 20 10
Senzidine,.... 	 	 . . 28.8 20 10
Butyl benzyl phthalaie 	 	 29.9 20 10
Sis(2-ethythaxy() pnthalate.. .306 20 10
Chryaena 	 	 	 	 „„ 31.5 20 10
Table 4— Gas Chromatography of Base/Neutral
Extractabtes — Continued
Reten- Limit of detection
Compound ton ##
time # 	
(mm.) ng intected i>9/1
Senzofalanthrecene 	 	 31 5 20 to
nu 3rt . 	 	
Toxaphene . _ 	 ... 25 to 34 ... 	 . 	
PT.fJ.1J49 ,,, . JO !(>.•?? .....„, ,
•6 toot glass column (V, m. OO x 2 mm IO) packed with
3% SP-2250 coated on 100/120 mesh Supelcoport Camer
gas: hetum at 30 ml per nun. Temperature program: Isother-
mal for 4 minutes at 50* C, then a* per minute to 270* HoM
at 270* C for 30 minutes. If desired, capillary or SCOT col-
umns may be used.
#This is a minimum level at which the entire analytical
system must give mass spectral confirmation. (Nanograms in-
lected is based on a 4 jj" injection of a one-Mar sample that
has been extracted and concentrated to a volume ol 1.0 mL
Table 6.— Gas Chromatography of Acid Extractables
Reten- Unit of
Compound ten time* detection*
(mm) — — —
ng injected ng/l
2-Chkxophenol 59 50 25
2-Nitrophenol 64 50 25
Phenol 80 50 25
2.4-OlmettrytptienoL _ 9.4 50 25
2,4-Dichlorophenol 98 50 25
2.4.6-Trlchlorophenof 	 	 11.8 50 25
2,4-Omitrophenol 	 _ 	 „ 159 500 250

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           Federal Register / Vol.  44.  No.  233 / Monday,  December  3.. 1979 /  Proposed Rules         69545
Tabl» 6.— Gas Ctirom'atography of Acid
ExtractaUes— Continued
Reien- Limit of
Compound tion lime* detection*
ng injected ng/l
2-MethyM 6-dmrtrophenol 	 162 500
Pentachlorophenol 	 	 175 50
4-Nltropnenol . — 	 20.3 50

250
25
25
•6 foot^glass column (V* m. OO x 2 mm ID) Packed with
1% SP-1240 DA coated on 100/120 mesh Supelcoport Cam-
ar gas: helium at 30 ml per min. Temperature program: 2 mm
isothermal at 70', then 8' per mm to 200' C.Jf desired, capil-
lary or SCOT columns may be used.
#Thw is a minimum level at which the entire analytical
system must give mass spectral confirmation. (Nanograms in-
lected is based on a 2 nl miection of a one liter sample that
has been extracted and concentrated to 1.0 ml.)
Table 1.— Base/Neutral Sxtractables Characteristic Ions






1 2-Dichiorobenzene 	 - 	




HexaChtOTObUtadlene 	 „ 	 „ 	 „.,.
Naphthalene 	 —> 	 • 	

Hexachlorocyclopentadiene 	 	
2-Chloronaphthalene 	 	




Fluorine

2,4-Oinitrotoluane . 	 	 	 	
1 2'0iphenylhydrazine l . « 	 ....
Dietnylphthalate 	 	 • 	 	 -...— 	
N-Nitrosodlptwiylamirw' 	 	 	


Anthracene i ... 	 	
Ottxityt phthalata .... .... 	 •« 	 	 	 ...

Pyrene ...
Banzidine . .- 	


ChfVSene . ._. „ „ 	














Characteristic ions
Electron impact
146
146
117
93
146
45
130
92
77
225
180
128
93
237
162
152
154
63
165
168
204
165
77
149
168
284
243
178
178
149
202
202
184
149
149
228
223
252
149
252
252
252
276
278
276
42
45
188
148
148
201
S3
148
77
42
95
123
223
182
129
95
235
164
151
153
194
63
16S
206
69
93
177
168
142
250
179
179
ISO
101
101
92.
91 . .
167
228
229
254
253
253
253
139
139
138
74
49
322
94
113
113
199
95
113
79
101
138
65
227
145
127
123
272
127
153
152
164
121
167
141 . ....
163
105
150
167
249
141
178
176
104
100
100
185
279
229
226
126

125
125
125
277
279
277
44.
51
320
80
Chemical lonczation
(methane)
148
148
199
S3
146
77
139
124
223
181
129
65
235
163
152
154
151
33
166
183
185
177
169
284
249
178
178
149
203
203
185
149
149 	
228
228

252
252
252
27B
278
276

59 	
189
143
148
201
1 07
148
135
167
152
225
183
157
107
237
191
153
155
163
211
167
211
213
223
170
286
251
179
179
205
231
231
213
299
229
229

253
253
253
277
279
277


217 ...
150
150
203
109
150
137
178
164
227
209
169
137
239
203
181
183
164
223
195
223
225
251
198
288
277
207
207
279
243
243
225
327
257
257

281
281
281
305
307
305




1 Detected as azobenzene.
'Detected as diphenytamine.
'Suggested internal standard.

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  69546
Federal Register /  Vol. 44. No. 233  /  Monday. December  3.1979 / Proposed Rules
                                 T«bt« •.-**«#**•«•
                                                                font
                Compound
                                                                      CtwraoMMto ien* •MeMn knpwt
  a-8HC_
  9-8HC..
  d-SHC-
  andoaultinl_
 andoaulfan !)„
 4,4'-OOT	
 «nd
-------
                                                  COLUMN: 3% SP-2250 ON SUPELCOPORT

                                                  PROGRAM: BO°C, 4 MIN. 8'PER MIN TO 270*C

                                                  DETECTOR: MASS SPECTROMETER
     2,4-DINITROTOLUENE-'  N NITBOSO OIPHENVIAMINE
10
15
20         25          30

   RETENTION TIME-MINUTES
35
40
4$
                                                                                         I

                                                                                         <
                                                                                         r-
                                                                                         •z
                                                                                         o
                                                                                         o

                                                                                         I
                                                                              o
                                                                              
                                                                              •i

                                                                              to
      Figure 1. Gas chromatogram of base/neutral fraction
                                                                                         •o
                                                                                         o
                                                                                         I
                                                                                         a
                                                                                         a

-------
COLUMN: IK SP-1240DA ON SUPELCOPORT
PROGRAM: 70°C-2 MIN. 8*/MIN TO 200°C.
DETECTOR: MASS SPECTROMETER.
                                                                                            £
                                                                                            (B
                                                                                            s.
                                                                                            I
                                                                                            CL
                                                                                            to
                                                                                            a
                                                                                            (D
                                                                                            O
                                                                                            (D
                                                                                            g
                                                                                            cr
                                                            co
                                                            t-»
                                                            CO
 8       10      12      14
RETENTION TIME-MINUTES
16
18
20'
22
                         Figure 2.  Gas chromatogram of acid fraction
                                                                                            CO
                                                                                            OB
                                                                                            CL
                                                                                            CD
                                                                                            CO

-------
    Federal Register / Vol. 44, No. 233 / Monday, December 3. 1979 / Proposed Rules	69549
COLUMN: 3% SP-2250 ON SUP&COPORT
PROGRAM: 50'C-4 MIN, 8«/MlNUTE TO 270'C
DETECTOR: MASS SPECTROMETER
                    10            15            20
                        RETENTION TIME-MINUTES
25
30
                  Figure 3. Gas chromatogram of pesticide fraction

-------
69550
Federal Register / Vol. 44, No. 233 / Monday, December 3, 1979 / Proposed Rules
  COLUMN: 3% SP-2250 ON SUPELCOPORT
  PROGRAM: 50*C, 4 WIN. 8"PER WIN TO 270*C
  DETECTOR: MASS SPECTROMETER
                                     PEAKS GIVING THE THREE
                                      CHARACTERISTIC IONS
          20
               25
30
                 RETENTION TIME-MINUTES

 Figure 4. Gas chromatogram of chlordane

-------
  COLUMN: 354 SP-2250 ON SUPELCOPORT
  PROGRAM: 50*C. 4 MIN. 8°PER WIN TO 270*C
  DETECTOR: MASS SPECTROMETER
                    COLUMN: 3% SP-2250 ON SUPaCOPORT
                    PROGRAM: 50°C. 4 MIN, 8*PER MIN TO 27CPC
                    DETECTOR: MASS SPECTROMETER
           25             3d
                  RETENTION TIME-MINUTES
35
Figure 5. Gas chromatogram of toxaphene
                                                                                                A ffl/e 224 PRESENT
                                                                                                B m/e 260 PRESENT
                                                                                                C m/e 294 PRESENT
                                             25           3T
                                          RETENTION TIME-MINUTES
35
                                                              Figure 6. Gas chromatogram of Arochlor 1248
S
a.
I
n>

-------
  COLUMWc 3X SP-2250 ON SUPaCOPERT
  PROGRAM: 50*0. 4 WIN, 8* PER MIN TO 270"C
  DETECTOR: MASS SPECTROMETER
    A m/e 294 PRESENT
    B rn/e 330 PRESENT
    C m/e 362 PRESENT
             20             25            30
                  RETENTION TlME-MINUTtS
Figure 7. Gas chromatogram of Arochlor 1254
BILLING CODE 6560-01-C
                                                                                      TAILING FACTOR
                                                                     Example calculation: Peak Height = DE = 100mm
                                                                                       10% Peak Height = BD = 10 mm
                                                                                       Peak Width at 105; Peak Height - AC = 23 mm
                                                                                             AB=tT! mm
                              12
        Therefore: Tailing Factor- — =1.1
                              11
Figure 1 . Tailing factor calculation

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-------