xvEPA
             United States
             Environmental Protection
             Agency
             Municipal Environmental Research
             Laboratory
             Cincinnati OH 45268
EPA-600/2-80-018
January 1980
             Research and Development
Samplers and
Sampling
Procedures for
Hazardous Waste
Streams

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology.  Elimination of traditional grouping was* consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:             !

      1.  Environmental  Health Effects Research
      2.  Environmental  Protectiop Technology
      3.  Ecological Research  }
      4.  Environmental  Monitorinig
      5.  Socioeconomic Environmental Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports     I
      9.  Miscellaneous Reports t

This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
 NOLOGY series. This series describes research performed to develop and dem-
 onstrate instrumentation, equipment, and methodology to repair or prevent en-
 vironmental degradation from poirjt and non-point sources of pollution. This work
 provides the new or improved technology required for the control and treatment
 of pollution sources to meet environmental quality standards.
 This document is available to the public through the National Technical Informa-
 tion Service, Springfield, Virginia! 22161.

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                                               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

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                               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 foir use.
                                   ii

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                               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

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                                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.  IThe 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

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                               CONTENTS
Foreword	    ill
Abstract		     iv
Figures   	.	     vi
Tables	    vii

  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       ...	     £6
        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        	     46
  8.  Preservation and Storage of Samples  	     48

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
                                   v

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                               FIGURES

Number                       j                                  Page
 1           Composite liquid waste sampler (Coliwasa) . ." .     6
 2           Grain sampler	    10
 3           Sampling trier  ;....•	    11
 4           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
          Basic Parts and Costs of a Veihmeyer Soil Sampler
17
  1
  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 develop 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 undet the sponsorship of the U.S. Environ-
mental Protection Agency (EPA)2  i In this sampling program, approxi-
mately 400 waste samples were collected.  These samples varied greatly
in composition and in physical characteristics.
                                 j
     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 Ion a development program to establish
recommended procedures and equipnient 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 jthe 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 operatiqn, 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.
  1.
  3.

  4.
  7.
Uses
The sampler is assembled as shown in Figure 1 and as follows:

 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.

 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.

 Install the stopper and stopper rod assembly in the sampling tube.

 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.

 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.

 Attach the upper end of the stopper rod to the swivel of the
 T-handle.                        ;

 Place the  sampler in the close position and adjust the tension  on
 the stopper by screwing the T-handle in or out.
     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 (h 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.        I

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")
                              X
                               \
                           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 trierj  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.
                                i
   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.
                                j
   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  1  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—                          i

     An ordinary  zinc-plated gar|den trowel can be  used in some cases  for
sampling  dry granular or  powderejd 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 o£ 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.

  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                   j
                                 j
     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 nonj-soi'l 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).
                    101.6 cm (40")
                               5o08  cm (2")
                        Figure 5.   Soil auger.
                                   15

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A.  Drive hammer
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
    Parta
  Costc
   Tube, 1.5 m (5 ft.)

   Tube, 3m (10 ft.)

   Tip, type A, general use

   Drive head

   Drop hammer, 6.8 kg (15 Ib.)

   Puller jack and gripc

       Total
 $   50.40

     84.75

     25.80

     29.05

     71.85

    161.90

$   433.75
  a Only one of each part is needed.  They are manufactured by
    Hansen Machine Works, 334 N. 12th Street, Sacramento, CA
    95815.

  b 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 from 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.  Specificatiojis  for  the various parts  of  the Veihmeyer
sampler are given as follows:    j
                                 I
     Points 	 Chrome-molly steel, heat-treated.  Includes  a
                      standard polint for general use, a  constricted
                      point for deep sampling in heavy clay  (keeps
                      core from hieing sucked out of the  tube) , a
                      bulge point for shallow sampling in  heavy clay,
                      and a special  point for dry sand.  (See Figure
                      6D).       i
     Drive hammer
     Tubes

     Head
     Puller jack

     Grip
.  Standard weight is 6.8 kg (15 lb.).  (See Figure 6A)
.  Chrome-molljy steel.  Maximum length is 4.9 m
  (16 ft.).  i(See Figure 6C) .
.  Chrome-molly steel, heat-treated.   (See Figure 6B).
.  Cast aluminum frame with steel roller assembly
  and handle.!
             i
.  Chrome-molljy steel, heat-treated.
Uses—
     The Veihmeyer sampler is recommended for core sampling of most types
of soil.  It may not be applicablfe to sampling stony, rocky, or very wet
soil.                            !

Procedure for Use—
                                 i
  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.                   i
                                 i
  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 hot drive the tube further than the
      tip of the hammer's drive gjjide.
                                 i
  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 the1drive head.  In this position, the ham-
      mer serves as a handle for the sampler.
                                    18

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                                                                                        I
    7.  Rotate the sampler at least two revolutions to shear off the sample
       at the bottom.

       Lower the sampler handle  (hammer) until it just clears the two ear-
       like protrusions on the drive head and rotate about 90°.

       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.

       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.

       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 (1-qt.  or %-gal) sample container
       (see Section 6) to store the sample.

  12.  Collect additional core samples at different points (see Section 6).
 8.
 9.
10.
11.
  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(lJz; in.) I.D.  by 0.32 cm(l/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 ajsuitable container (see Section 6) with
      the aid of a spatula and/or brush.
                                i
  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).
                                                        1
                        122-183 bm
                         (48-72"!)
•it
                                                            5.08-7o62 cm
                                                            (2-3") I.D.
Pond Sampler
                    Figure 7.  Waste pile sampler.
     The pond sampler (Figure 8)1 consists of an adjustable clamp attached
to the end of a two or three piepe 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.
                                                  -Varigrip clamp
               -/A
                                                         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-
   1


   4


   4
 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 cm(l% in.) I.D.

 Beaker, polypropylene,
 250-ml(%  pt.)

 Bolts,  6.35 by 0.64 cm(2%.by
 Vin.)  NC

 Nuts, 0.64 cm(%  in.) NC

. Total
                                       Laboratory supply
                                       houses
Olympic Swimming
Pool Co. 807 Buena
Vista Street, Alameda,
Calif. 94501 or other
general swimming pool
supply houses.

Laboratory supply
houses.

Hardware stores

Hardware stores
                       $7.00
                                                               16.24
  1.00

   .20

   .20
$24.64
                                  21

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Uses—

     The pond sampler is used toi 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 sepure the clamp to the pole are tightened
      properly.                 |
                                I
  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).
                                I
  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
                                                   Cork
                                                    Washer
                                          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 t:he necessary apparatus for such tests
should also be included in the preparation for sampling.

CLEANING AND STORAGE OF SAMPLER     j

     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 Colxwasa is a bottle brush that fits tight-
ly the inside diameter of the tube, j 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-ifeinforced 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
                                   i
                           SAMPLING PROCEDURES
 PURPOSES AND GENERAL CONSIDERATIONS
                                   i

      Sampling of hazardous wastes i 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.
                                   i
                                   i
      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 r'equest 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,1^ 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 almostiall 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.
RrviMrf D*««mMr 1f74
CALIFORNIA LIQUID WASTE HAULER RECORD
       STATE WATER RESOURCES CONTROL BOARD
                                                               009-000928
STATE JDEPAHTM
PRODUCER Of* WASTI 0*** be. fitted by producer* |
I H
(*..*T •• T"*l I <=«•« "">•
P'kk i*a Addta**: '
(•UMB>H| (•TH»T) (CITT)

|
wttUhPradurwIWMfiB' 	 ____ 	 _ 	 1 	 1 	 1 	 1 	 1
(Examples: metal pitting, equipment cleaning, oil drilling — coon NO.
wettewater treatment, pickling bath, petroleum refining)
OC9Cn!PTK>N OF WAXTE (MiMCtefUMbvpraduQcri |
Ch««k type •* wMtni

3 O AtKelir* eelutlBn 7. G Chemlca* toilet westee 2. D Cannery watt*


OotrteriSoeetrvl 1 1 1 1
C*m*«Aentt; i "*"*" "™*
t««*m oin; Hydf Khlor k acM. Urn*, caustic wd*. Concentration:
»ft«n«)!K%, *oh«nia (Ititl. mMala (tin). Upper Lower % ; ppm
«teanwa (U«J, cvanUe)
n n
3,
3,
___—_———_ — =, ( _
4.
»,
«^
ruiwtMut rr«pente« or wactai
OH D n«ne D toxic D flammable D eorrotlv* D explosive
_„ __ __ barrels __ i
Rwlfc Vclwme? _ Q eel U ton* U {42 gal.) D otner.. ^ A j.v,

rhyHe^Sut., O wild D liquid O ilud0e D otn.f_T___T_


j
The MMt« H deeef ib*d to th« beet of my ability and It wee de*Iye*ed to • IleertMd liquid wane heoter (if
*a*ltca^ai; j
1 tantfV (•* d«cl»r«) vnd *r penalty of perjury '
th*t lhaj fMeoaln« to tn*e arx) correct. 1
*1«H*TUH« Of AUTHOMIIBa ABBHT «NO TTTt«

HAULER OF WASTE (Mu« t» f iUed by hauler) |
1 1 1. 1
COOK HO.
a am
Plf.li lip; TIm«: 	 nom
State IJqilMWKTt Mt»'-''« H-gl«r-t!nn No. (if applicable) :.,., 	 __9 . ......
l«h Mn r Mo. of Lflarf- nr Trip.- „ Unit No.

(•PCCIFY)
facilitv named below and w« accepted.
1 certify (or declare) under penalty of perjury
lieMATURB O^ *OTHOBII«O AO««T AND TITt.*
DISPOSER- OF WASTE (Mutt be filled by dhpOMrt 1
Nem*{pr- 	 1 1 1 1

The hauler above delivered the described watte to thl« dlipoial facilitv and ft was an acceptable
local restrictions.
Handling Method(t):
D recovery 	
n trurm.ot (u^clfvl- __ 1 	 1 	 1
D dltpoeel (specify}: D Pond D epreeding D landfill D injection well . 	 . 	 .


1 certify (or declare) under penalty of perjury
that the foregoing Is true and correct.
The site operator shell submit a legible copy of each completed Record to the S tat e'O apartment of





FOR INFORMATION RILATEDTO SPILLS OB OTHER EMERGENCIES INVOLVING
HAZARDOUS WASTE OR OTHER MATERIALS CALL (BOO) 424-93OO.
O.O.T. Proper Shipping Name) 	 	 	
                     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          , x „..
                    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
Pond
 a) Grain
    sampler
 b) Sampling
    trier
Trowel or
scoop
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 cm(h 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.
Waste piles
Soil deeper
than 8 cm(3 in.)
Wastes in
storage .tanks
Waste pile
sampler
 a) Soil auger
 b) Veihmeyer
    sampler

Weighted
bottle sampler
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 pettoleum residues that are mostly incom-
patible with plastic containers.  JFor all other types of samples, 1000-and
2000-ml(l-qt and %-gal.) wide-mouth LPE bottles are recommended.
                                  i
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.
                                  i
SAMPLING PLAN

     The sampling plan should be •sjrell 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.       j

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
      Re commende d

       container
 Recommended

   closure
Oil wastes except
pesticides, HC,
chlorinated HC, and
photosensitive
wastes
Linear polyethylene  (LPE)
bottles,3 1000-and 2000-
ml(l-qt. and %-gal.),
wide mouth
 LPE caps
Pesticides, HC,
and chlorinated
HC
Glass bottles,b wide-
mouth, 1000-and 2000-ml
(1-qt. and %-gal.).
Bakelite caps
with Teflon
liner0
Photosensitive
wastes
Amber LPE or brown
glassd 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.

bScientific 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.
     I
Withdraw samples through the top of barrels,
fiberdrums, buckets, and similar containers.
Withdraw samples through fill openings of
bags land sacks.  Withdraw samples through
the center of the containers and to different
point's diagonally opposite the point of entry.

Withdraw sample through open hatch.  Sample
all other hatches.

Divide surface area into an imaginary grid.a
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.
     I
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.
aThe 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
 (h 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.13
 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 SABLES TO BE COLLECTED
Case
 No.
Information
  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
              Liquid   Drum, vacuum truck,
                       and similar
                       containers
              Liquid   Pond, pit, lagoon
                       Bag5  drum, bin
Solid
(powder
or gran-
ular)

Waste
pile
Soil
              Liquid   Drum,  vacuum truck,
                               tank
         storage
              Liquid   Ponds,   pit,  lagoon
              Solid
              (powder
              or gran-
              ular)
              Waste
               pile
              Soil
             All
             types
         Bag,  drum,  bin
         All; containers
                               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
12

13

Average
concentration
Average
concentration
Liquid

Liquid

Storage tank

Stotage tank


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 case|s, gas-masks or chemical cartridge-type
respirators with filters will suffice.  Table 7 may be used to select the
proper protective respiratory devijce.

     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
                                  t
     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 tha|t 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 sampljed 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.                             ''
                                  i
                                  s
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).
                                  i
2.  Allow the contents of the drum to settle.
                                  i
3.  Slowly loosen the bung with a Ibung 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, and 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 3.5m(llig 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(llJg ft.)  from the bank.
                                   i
 1.  Collect a composite sample with pond sampler, as directed  in Section
     4.

 Sampling Soil
                                   I
      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 deternjiine the amount of hazardous  material
 deposited on a particular area ofiland 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.
                                   I
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  jthat, 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
Department of Health Services
Collected by_
Date Collected__
Place Collected
                    (signature)
          Public Health  Division
       Hazardous Materials Laboratory
   Collector's Sample No._

   Time 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).    i

      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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                                                                                     1
 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 jfollowing 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:        j

     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 ana3.ysis 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    	  Disposal Site

                       	 Other:	.	

Company's Name	

Address
                        Telephone  (    )
         number  street

Collector's Name	

Date Sampled	
        city
signature
 state        zip

Telephone (	)	
          Time Sampled_
Type of Process Producing Waste_

Waste Type Code	 Other
Field Information
          hours
Sample Allocation:

1.

2.

3.


Chi

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
                                  i
                                  [
                    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 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.

SAMPLE INSPECTION
                                 i
     The sample custodian should inspect the sample for any leakage from
the container.  A-leaky containericontaining 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 gasesi   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 oni the sample analysis request sheet and
on the laboratory sample log bookl
                                 I
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 sampl^ 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 18,19 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
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 Zn(AC)2/£
Cool to 4° C
Add 4 ml cone. HC1/&
Storage time
24 hr
24 hr
24 hr
6 months
24 hr
24 hr
24 hr

7 days

6 months

6 months
6 months

38 days
38 days
6 hr

24 hr
7 days
6 months
24 hr

24 hr
24 hr
—
aSource:  References18»19'and
                             20
                                  49

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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.
                                 I
 3.  Merck Index, An Encyclopedia! of Chemicals and Drugs.  1968.   9th Ed.
     Merck & Co., Rahway.        j

 4.  Chemical Resistance of Excelpn R-4000.   1977.  Thermoplastic Process,
     Inc., Stirling, N.J.        i

 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.      i

 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.
                                 i
 7.  Veihmeyer, F. J. 1929.  An Improved Soil-Sampling Tube.  Soil Science
     217(2): 147-152.             \
                                 I
 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.         j

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, B.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,
     Washing ton, 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

                                   i
  APPENDIX A.  DEVELOPMENT OF THE COMPOSITE LIQUID WASTE SAMPLER (COLIWASA)
                                   I
     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.
                                   I
     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 sitjss in Los Angeles County.  In the prep-
aration  of this study, the Department of Health Services personnel designed
and constructed a simple tube samplbr 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 necessarly 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 p'roof.   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

-------
      charge of hazardous waste, it must not discharge until properly inside
      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.
                                V
                   183 cm (72")
            152 cm (60")
                              \
                                         Rod, WC, 0.95 cm (3/8") O.D.
                                         Pipe, WC, 4.13 cm (1 5/8") I.D.,
                                          4.78 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

-------
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 ne.oprene 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.              j

     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.
                                      54

-------
    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.
    l\
      152 cm (60"
      \/
    \f
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Figure A-2. Coliwasa, Model 2.
                                                          0.95 cm (3/8")  O.D.
                                                            rod,  PVC
                                                          4.13 cm (1 5/8")
                                                            I.D. pipe,  PVC
Stopper, neoprene,
 #9, with PVC nut
 and washer
                                     55

-------
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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
stopper1 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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 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  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

 % by volume collected
      19
      22
        81
         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 tihe previous experiment, the starting
 heights of the liquid phases for :each trial were measured.  The mixture
 was sampled with the Coliwasa.  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

 % by volume collected

Trial II:
 % by height of
 phases in tank

 % by volume collected

Average:
 % by height of
 phases in tank

 % by volume collected
 9.3

10 i. 2
  i


 8.8

 9.8
77.4

79.6



75.0

79.0



76.0

79.0
14.7

10.8



15.0

10.7



15.0

11.0
                                    60

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                                                                                        1
     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.

     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'."

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 cm(l% in.) O.D. X 10.2 cm(4 ifr.)
long with l.ll-cm(7/16 in.) hole ;
drilled through center.

Sleeve, PVC, 4.13 cm(l 5/8 in.) ll.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(% ih.)
square X 3.8 cm(l% in.)long with i
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 h 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. '


Laboratory supply
                       $18.00 each
                       $ 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 ft)
ware stores.


Plastic supply houses   $ .03 each

Plastic supply houses   $ .03 each

Hardware stores         $ .10 each

Hardware stores         $ .10 each

Hardware stores         $ .10 each

Hardware stores         $ .03 each

Hardware stores         $ .03 each
  1977 prices
                                    62

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                                                                                         I
   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(3/8~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 j auger
          (Section 4)


          Grain
          sampler
          (Section 4)

          Scoop,
          stainless
          steel blade
          (Section 4)
                       Fabricate^ Parts
                       can be purchased
                       from hardware
                       stores (see
                       Section 4)
To sample liquid       Fabricate^ Parts   $ 16.00
wastes, except
ketones, nitro-
benzene, dimethyl-
foramide, tetra-
hydrofuran and
pesticides
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, K.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
Approximate
    Cost
          Veihmeyer
          soil samp-
          ler
          (Section 4)
          Pond samp-
          ler
          (Section 4)
             To collect soil core
             samples
             To sample ponds, pits,
             etc.    I
          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 chlor-
          polyethylene  inated\hydrocarbons
                               i
          Coverall,    Protective garment
          long-                i
          sleeved,
          cotton
          Suit,
          neoprene
          rubber, long"-
          sleeved
             Protective garment
Hansen Machine,    $ 200.00
334 N. 125h St.,
Sacramento,Calif.
95815

Fabricate (see     $   9.00
Section 4).Clamps
available at
Cole-Parmer
Instrument
3060 Gibraltar Ave.
Costa Mesa,Calif.
92626

Telescoping handle $  16.24
available at
swimming pool
supply houses
Curtin-Matheson
Scientific
470 Valley Drive
P.O.Box 386
Brisbane,Calif.
94005

Fabricate. PVC
pipe available at
hardware stores
(see Section 4)

Laboratory supply
houses
 $  25.00
 $   3.00
                                                          11.OO/
                                                          pkg.6
    1
  pair
Gloves, neo- Protective garment
prene rubber
                                    Clothing stores    $  14.00
MSA,Catalog #33496 $ 210.00
Laboratory supply  $   4.20
houses
                                    64

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                                                                                         I
                         APPENDIX C (continued).
Quantity
    Item
Use
                                        Supplier
Approximate
    Cost
   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,
         chemical
         cartridge
         type

         Cartridges for
         respirator
               For use in atmospheres Comfo 11 Respir-
               not immediately        ator, MSA,Catalog
               dangerous to life      #460968
                                      or equivalent
               For use in atmospheres CMC Cartridge,MSA
               not immediately        Cat.#459317 & GMD
               dangerous to life      Cartridge, MSA
                                      Cat.#459318 or
                                      equivalent
1
pair
1
1
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
Usje
To keep isample records

To sample storage
tanks or similar
containers
To clean sampling
equipment


To store' waste papers ,
rags, etc.
To store sample
containers
i
To complete records
and labels
To clean samplers



Protective garment


Protective garment



i
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. OO/
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
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
              column are 12 and 04.  So far you have chosen only three
                                   67

-------
               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
                                 j

     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 tfci 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 neajr 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).
                                 i
     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 relajte the geometry of the sample tube to
the geometry of the tank truck.  |

                       % A (tank) t= (9-Sin 9)
                                 j     2ir

                       % A(sample) = 1-Cos % 9
                                 '        2
                                                         Vacuum truck
                                                     Sample tube
                                    68

-------
           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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                                                                                               I
                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
   EPA-600/2-80-018
                             2.
                                                           3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
   Samplers and Sampling Procedures fori Hazardous
   Waste Streams                         !
              5. REPORT DATE
                January 1980  (Issuing Date)
              6. PERFORMING ORGANIZATION CODE
7< AUTHOR|mil R.  deVera,  Bart P.  Simmons, Robert D.
        Stephens and David L. Storm.    [
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
        Hazardous Materials  Laboratory  [
        California Department of HealthjServices
        2151 Berkeley Way
        Berkeley, CA 94704              j
              10. PROGRAM ELEMENT NO.
                C73D1C, SOS #1, Task  32
              11. CONTRACT/GRANT NO.
                  R 804692010
12, SPONSORING AGENCY NAME AND ADDRESS        \        (Jin . , UtL
        Municipal Environmental Research Laboratory—
        Office of Research and Development
        U.S. Environmental Protection Agency
        Cincinnati,  Ohio 45268  	I	
               13. TYPE OF REPORT AND PERIOD COVERED
                  Final
              14. SPONSORING AGENCY CODE
                  EPA/600/14
15. SUPPLEMENTARY NOTES
        Richard A. Carries, 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 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-jliquid 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 procedures for develop-
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 tihis area are given.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                            c. COSAT1 Field/Group
  Samplers
  Lagoons  (ponds)—waste disposal
  Hazardous materials
 Representative sampling
 Composite  sampling
 Sampling plans
 Sampling procedures
 Hazardous  waste
 Composite  liquid waste
   sampler
68C
18. DISTRIBUTION STATEMENT
    Release unlimited
                                              19. SECURITY CLASS (ThisReport)
                                                unclassified	
                            21. NO. OF PAGES
                                78
                                              20. SECURITY CLASS (Thispage)
                                                unclassified
                                                                         22. PRICE
EPA Form 2220-1 (9-73)
70
                                                                    * U.S. GOVERNMENT PRINTING OFFICE: 1960-657-165/0005

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