EPA-600/4-76-052
October 1976
Environmental Monitoring Series

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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  five series. These  five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:

     1.    Environmental Health Effects Research
     2.    Environmental Protection Technology
     3.    Ecological  Research
     4.    Environmental Monitoring
     5.    Socioeconomic  Environmental Studies

This report has  been assigned to the ENVIRONMENTAL MONITORING series.
This series describes research conducted to develop new or improved methods
and  instrumentation for the identification and  quantification of environmental
pollutants at the lowest conceivably significant  concentrations. It also includes
studies to determine the ambient concentrations of pollutants in the environment
and/or the variance of pollutants as a function of time or meteorological factors.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                                EPA-600A-76-052
                                                October 1976
    DEVELOPMENT OF SUSPENDED SOLIDS QUALITY
   CONTROL AND PERFORMANCE EVALUATION SAMPLES
                       by
                 Enos L. Stover
                 Peter J. Marks
              Roy F. Weston, Inc.
       West Chester, Pennsylvania  19380
            Contract No. 68-03-2333
                Project Officer

                 Edward L. Berg
            Quality Assurance Branch
Environmental Monitoring and Support Laboratory
             Cincinnati, Ohio  45268
 ENVIRONMENTAL MONITORING AND SUPPORT 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 Environmental  Monitoring and
Support Laboratory-Cincinnati,  U.S. Environmental  Protection Agency,  and
approved for publication.  Mention of trade names  or commercial  products
does not constitute endorsement or recommendation  for use.
                                   i i

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                                  FOREWORD
     Environmental measurements are required to determine the quality of
ambient waters and the character of waste effluents.  The Environmental
Monitoring and Support Laboratory-Cincinnati:

     1.  Develops and evaluates techniques to measure the presence
         and concentration of physical, chemical, and radiological
         pollutants in water, wastewater, bottom sediments, and
         sol id waste.

     2.  Investigates methods for the concentration, recovery, and
         identification of viruses, bacteria, and other microbiological
         organisms in water.  Conducts studies to determine the responses
         of aquatic organisms to water quality.

     3.  Conducts an Agency~wide quality assurance program to assure
         standardization and quality control of systems for monitoring
         water and wastewater.

     Commensurate with an Agency-wide quality assurance program, the
latest report on the development of synthetic suspended solids samples
contains the results of a feasibility study to determine compounds that
exhibit the optimum physical and chemical properties for production of
large number of samples.  Consideration of such factors as solubility,
wettability, dispersion, flocculation, abrasion, biodegradabi1ity,
stability,  and sub-sampling recovery resulted in the selection of
anthracite coal, Fuller's earth, and rayon fibers as solids materials
for suspended solids quality control samples.  A total  of 10,000
quality control samples, each consisting of one of three specified weights
of one of these three compounds, were packaged in individual containers.
                                      Dwight G. Ballinger, Director
                                      Environmental Monitoring and Support
                                      Laboratory-C i nc i nnat i
                                    i i i

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                                  ABSTRACT
     A two-phase study was conducted to develop a synthetic suspended solids
sample for use in quality control checks and performance evaluation in
environmental monitoring laboratories.  The first phase consisted of a
feasibility study to determine compounds that exhibit the optimum physical
and chemical properties for synthetic suspended solids samples; the second
phase involved production of suspended solids samples in individual con-
tainers.

     Compounds investigated that met all the design criteria included rayon
fibers and Fuller's earth.  A total of 10,000 quality control samples
consisting of rayon fibers, Fuller's earth, and anthracite coal were pack-
aged for completion of the project.  Anthracite coal was packaged to demon-
strate the variability shown by certain types of solids in the sub-sampling
step of the suspended solids test method.

     This report was submitted in fulfillment of Contract Number 68-03-2333
by Roy F. Weston, Inc. under the sponsorship of the Office of Research and
Development, U.S. Environmental Protection Agency.  Work was completed in
April, 1976.
                                     IV

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                             CONTENTS

Foreword	i I i
Abstract	   iv
Figures	vi i
Tables	viii
Acknowledgments  	   ix

     I .  Introduction	1
              Background 	  1
              Objectives 	  2
              Development Criteria .  .  •	2
    I I.  Conclusions	4
   111.  Recommendations 	  5
    IV.  Development and Feasibility  Study - Phase I  	  6
              Literature Survey  	  6
                 Scope and Methodology	6
                 Compounds Meeting Initial Design Criteria ....  7
              Technical  Approach 	  7
                 Statistical  Treatment  of Data 	  7
                 Analytical  Method for  Suspended Solids	13
                 Solubility  Testing	13
                 Wettability and Dispersion Testing	18
                 Flocculation Testing	18
                 Abrasion Testing	19
                 Evaluation  of Sub-Sampling	19
                    Mixing Technique	19
                    Recovery Tests (Analytical Method)	21
                 Selection of Compounds for Packaging	21
                 Biodegradabi1ity Testing	27
                 Stability Testing	27
                 Percent Recovery Tests on Mixture of
                 Fuller's Earth, Anthracite Coal, and
                 Rayon Fibers	29
     V.  Packaging of Compounds - Phase II	31
              Preparation of  Compounds  for Packaging  	31
              Packaging  Requirements	31
                 Number  and  Type of Samples	31
                 Packaging Technique	32
                 Instrument  Packaging Precision	32
                 Quality Control	32

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                          CONTENTS
                          continued

 VI.  Discussion	3k
           Statistical Evaluation of Data	34
           Synthetic Suspended Solids Analysis	36
              Preparation of Quality Assurance Samples
              for Suspended Solids Analysis	36
              Analytical  Method for Quality Assurance
              Suspended Solids (Non-Filterable Residue) .  .  .  .36
VII.  References	38
                               VI

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                                  FIGURES

Number                                                                  Page

  1    Percent Recovery Versus Particle Size for Fuller's Earth	 25

  2    Standard Deviations of Analytical  Method Versus
         Concentration 	 35
                                     VI I

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                                   TABLES

Number                                                                  Page
                                                                        — -3	

   1    Compounds Meeting Specific Gravity and Solubility
         Requirements 	   8

   2   Compounds Selected for the Initial Developmental
         Investigations 	  11

   3   Compounds Failing Initial  Developmental  Tests	Ik

   k   Compounds Passing Initial  Developmental  Tests	15

   5   Percent Recovery Tests for Compounds Passing the  Initial
         Screening Tests (250 mg/1)  at 6 Repetitions	16

   6   Percent Recovery Tests for Compounds Passing the  Initial
         Screening Tests (25 mg/1) at 6 Repetitions 	  17

   7   Abrasion Testing Results 	  20

   8   Evaluation of Mixing Techniques Using One-Liter Volumetric
         Flasks (Vigorous Shaking and Mixing with Magnetic
         Stirring Bars) 250 mg/1	22

   9   Mixing Test Results (Shake & Pour) with  Graduated Cylinder .  .  .  2k

  10   Results of Biodegradability Tests (Five-Day BOD Tests)  	  28

  11    Compound Mixing Tests Results	30
                                    VI I I

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                              ACKNOWLEDGEMENTS
     The support of this effort by the Environmental Monitoring and Support
Laboratory, Office of Research and Development, Cincinnati, Ohio  (especially
Mr. Edward L. Berg, Project Officer, and the other manuscript reviewers)  is
acknowledged with gratitude.
                                      IX

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                                 SECTION I

                               INTRODUCTION

     The success of the environmental protection efforts to a large degree
rests on the reliability of the information provided by the data collection
activities.  Quality control and performance evaluation samples become a
requirement to insure confidence in the precision and accuracy of selected
methods used by participating laboratories; an evaluation of the results
provides a sound basis for judgment of the  relative capabilities of those
laboratories performing the analyses.  The  Environmental Monitoring Support
Laboratory has prepared various water quality parameters as a quality control
service to laboratories and analysts.

     To date, no water quality control sample for measuring suspended solids
has been developed to assist in gathering water quality data, to aid in
determining compliance with established environmental standards, or to aid
in the determination of the effectiveness of pollution abatement methods and
procedures.  A research effort and a feasibility study were required to
determine the optimum physical and chemical properties for such a synthetic
suspended solid or series of suspended solid samples for use in quality con-
trol checks and performance evaluation in environmental monitoring labora-
tories, because information pertaining to this subject was not available.

BACKGROUND

     Industrial and municipal effluents contain suspended solids that vary
widely in both physical and chemical composition, including size and specific
gravity.   Information on solids characteristics has not been researched to
an appreciable degree, especially for the various types of industrial waste-
watsrs.

     Ths results of a literature review conducted to characterize sanitary
sewage, combined sewer overflows, and stormwater runoff in terms of their
suspended solids content and physical and chemical characteristics were
reported by Beak Consultants Limited of Rexdale, Ontario, Canada.   These
results  indicated  that these wastewaters could not be characterized by single
average concentrations of  suspended  solids or by a single particle size
distribution.  A wide range of individual chemical and  physical parameters
would be required  to characterize the suspended  solids  contained  in sanitary
sewage, combined sewer overflows, and stormwater runoff.

     The solids properties of sanitary sewage are  influenced by factors  such
as  range of  flow rate, time of day,  and contribution of  industrial waste-
waters to  the  total flow.   Industrial wastewaters can add suspended solids

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with a variety of particle  sizes,  specific gravities,  and  chemical charac-
teristics, depending on  the types  of wastewaters added.   In  addition  to
those solids normally  found in  sanitary  sewage, combined  sewer overflows
contain  solids washed  into  the  sewer systems from  land areas and  roadways.
There also is wide variation  in  the solids characteristics of separate
stormwater runoff, because  of  land use and varying  soil and  topographical
features.

     The characteristics of the  grit in  wastewater  depend  on many factors,
including:  soil; type of ground cover;  urban street conditions;  age  and
condition of the sewer pipe and  its joints, pipe slope, and  catch basins;
street cleaning practices;  and whether the collection  system consists of
separate or combined sewers.  Available  data from existing wastewater treat-
ment plants concerning grit removed were compared to establish criteria for
grit character izat ion.2,3 ,**   Based on these data, a "typical grit" for the
purpose of investigation ranges  in size  from 0.2 millimeter  (mm)  to 2.0
millimeter, with a gradation  corresponding to a straight  line on  a mechanical
analysis graph.  The specific gravity of the typical grit  is assumed  to be
2.65.  Normal grit concentrations  in sewage have been defined as  those
between 20 and 360 milligrams per  liter  (mg/l).^

     Both the velocity and  the concentration of suspended  solids  in sewers
vary with position in  the sewer  cross-sect ion.5  Suspended solids heavier
than water have their  lowest  concentration near the surface, and  the  concen-
tration  increases with depth  below the surface.  Suspended solids lighter
than water float on the  surface  of the water.  The manner  in which the veloc-
ity is distributed in  the sewer  section  will affect the distribution  of the
suspended solids in the  flowing water.    Therefore,  the distribution of
suspended solids in the  sewer may  affect the accuracy of the suspended
solids results because of inadequacies in the sample collection or in the
methods themselves.   However,  evaluation of the effects of sampling equipment
and sampling procedures on the determination of suspended  solids  in water
and wastewater streams is beyond the scope of this project for the develop-
ment and packaging of quality control  samples of synthetic suspended  solids.

OBJECTIVES

     The overall  objectives of this two-phase contract were:  1) the develop-
ment of a synthetic  suspended solids sample(s) for use as quality control and
performance evaluation samples  (Phase  l); and 2) production and delivery to
the U.S. Environmental  Protection Agency (EPA) of 10,000 containers (vials)
of suspended  solids  samples (Phase II).   This report presents the results of
the development program and feasibility  study, along with the packaging in-
formation and requirements.

DEVELOPMENT CRITERIA

The synthetic suspended solid  samples  selected from the research effort should
be representative of the types of suspended solids in industrial  and municipal

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wastewaters.  The suspended solids present in these types of wastewaters can
generally be characterized as falling within the following specific gravity
and particle size ranges:

                    Specific Gravity - 0.8 to 2.65

                    Particle Size    - 0.01 to k.S mm

The following design criteria were established for consideration during the
feasibility study for the development of the synthetic suspended solids:

     1.  The weight of synthetic material shall not change during the
         analytical procedure.  Therefore, the material  shall be non-
         volatile and shall not have any other property which will
         adversely affect the weight during any step of the analytical
         procedure.

     2.  Based upon the standard glass fiber filter, 100 percent of the
         solids should be retained on the filter.

     3.  The synthetic solids material shall  be relatively non-hygroscopic
         and non-clinging to the sides of the container.

     k.  The synthetic solids shall be non-flocculating, thereby providing
         the flexibility to mix several homogenous materials to produce a
         heterogeneous synthetic solids sample containing fractions of
         varying size and with varying specific gravities.  In addition,
         the charge on the solid particles shall be delineated.  The
         synthetic solid must be easily wettable and dispersable in water.

     5.  The synthetic solid samples shall remain constant in weight and
         character over a long period of time.  As such, the solids shall be:

         a.  Non-biodegradable
         b.  Non-adsorbent
         c.  Insoluble in water

     6.  The synthetic suspended solids shall have high abrasion and impact
         resistance, to minimize breaking up into smaller particles which
         would subsequently affect the percent retention on the fiber-glass
         filter.

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                                 SECTION II

                                CONCLUSIONS

1.  During the research investigation, Fuller's earth and rayon fibers were
    found to be acceptable compounds for packaging as synthetic suspended
    solids quality control and performance evaluation samples.

2.  The precision and accuracy obtainable  in the suspended solids test
    depend within certain limits on the specific gravity and particle size
    of the suspended solids.  These characteristics can affect the accuracy
    and precision of sub-sampling in the analytical method.

3.  Anthracite coal was also selected for packaging primarily to demonstrate
    error associated with sub-sampling in the analytical method for certain
    types of suspended solids.

k.  Fuller's earth, rayon fibers, and anthracite coal were selected for
    packaging to obtain the 10,000 vials of quality control samples.

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                                SECTION III

                              RECOMMENDATIONS

1.  Preparation of the suspended solids samples and execution of the
    analytical method should be in accordance with the instructions
    specified in Section VI  of this report, to minimize variability in
    the suspended solids quality assurance data obtained.

2.  The sub-sampling step of the suspended solids analytical test method
    should be evaluated, to minimize error in the results.  Results from
    this study indicated that the accuracy of the sub-sampling step is
    dependent to some degree upon the dispersion characteristics of the
    suspended solids in the sample.

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                                 SECTION  IV

                DEVELOPMENT AND FEASIBILITY STUDY - PHASE  I
 LITERATURE SURVEY

 Scope and Methodology

     The first step  in the developmental and feasibility portion of the study
 consisted of a literature survey to develop a  list of synthetic and natural
 compounds with the desired specific gravity and solubility specifications.
 Particle size of the compounds was not considered as an  initial selection
 criterion.   (For most of the compounds, the particle size could be changed
 to meet the particle size specifications.)  Additional  information was also
 solicited by personal communications  (both verbal and written) from manu-
 facturers and chemical processors as  to the availability of various types of
 compounds and their  recommendations for additional compounds meeting the
 initial developmental criteria.

     The second step was a literature survey to gather  information which
would characterize natural, municipal, and industrial wastewaters with
 respect to specific gravities and particle sizes of the solids in these types
of wastewaters.  The information characterizing sanitary wastewaters, storm-
water, and combined sewer overflow was presented in Section I  of this report.
 However, no information pertaining to the characterization of suspended
 solids in the various types of industrial wastewaters was found.

     The third step was a literature survey to define acceptable develop-
mental test methods for the proposed compounds with respect to the previously
mentioned design criteria.  There were no acceptable test methods found in
the literature for testing the proposed compounds.  Therefore, developmental
testing procedures were developed for the feasibility investigation of the
selected compounds.

     Specific tests for each of the following  investigation requirements were
developed and will  be presented in later sections of this report:

                    Solubi1ity Testing
                    Wettability and Dispersion Testing
                    Abrasion Testing
                    Flocculation Testing
                    Sub-sampling Recovery Tests
                    Biodegradabi1ity Testing
                    Stabi1ity Testing

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     Particle size measurements were conducted according to the ASTM Test
Method No. E-20 Analysis by Microscopical Methods for Particle Substances of
Subsieve Sizes.   The analytical procedure employed for suspended solids
testing was the method stated in the current EPA manual "Methods for Chemical
Analysis of Water and Wastes."7

Compounds Meeting Initial Design Criteria

     A list of compounds which have specific gravities within the range
specified (0.8 - 2.65) and which possibly meet all the other requirements
for synthetic suspended sol ids quality control samples was developed, and
is presented in Table 1.'»2»3>^»5,B

     From this initial list, the compounds listed in Table 2 were selected
for the developmental studies, based on established design criteria, avail-
ability of compounds, and manufacturers' recommendations.

     The compounds listed  in Table 2 were categorized into four groups, by
specific gravity:

                                      Specific Gravities
                                         0.80 - 1.00
                                         1.01 - 1.50

                                         1.51 - 1.99
                                         2.00 - 2.65

     Two compounds (wood fibers and gilsonite) were eliminated before the
initial developmental testing.  Research and Development personnel  in the
wood pulp industry recommended elimination of wood fibers for the following
reasons:

     1.  Variability of fiber size.  Even after fractionating and passing a
         pulp slurry through various mesh screens, the thickness of fibers
         is extremely variable.

     2.  Even if it were possible to pulp a single tree, the fibers would
         not be uniform, because of great difference in wood growth during
         the spring and growth during the summer.

     Gilsonite is a very soft hydrocarbon compound that is subject to con-
siderable abrasion and subsequent change in particle size.  Gilsonite is
extremely friable; it has very little impact resistance and is easily reduced
to a fine powder.

TECHNICAL APPROACH

Statistical  Treatment of Data

     When a sample or a finite number of observations from a population are
selected appropriately, one is able to make precise statements concerning

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                           Table 1

Compounds meeting Specific Gravity and Solubility Requirements


Name                                        Specific Gravity

Aluminum diethyl malonate                        1.084

Aluminum Oxide                                2.42 - 2.53
(gibbsite, hydra-argi11ite,
bayerite)

Aluminum orthophosphate                          2.566

Bismuth tartrate                                 2.595

Boron  (tetra) carbide                            2.5

Calcium boride                                2.3 - 2.45

Cobalt orthophosphate                            2.58?

Carbon                                        1.8 - 2.25

Iron orthophosphate  (vivianite)                  2.58

Lanthanum hexaboride                             2.61

Magnesium ortho-arsenate                         1.788

Silicon                                       2.00-2.42

Silicon dioxide (cristobalite,                2.1 - 2.66
lechatelierite, quartz, tridymite,
amorphous-opal)

Sulfur                                        1.92 - 2.07

2, 4, 6, tribromoaniline                         2.35

Anthracene                                       1.25

Hexachlorobenzene                                2.044

4, 41 -dibromo-biphenyl                          1.897

4, 4' -dichloro-biphenyl                          1.439

Cellulose                                     1.27 - 1.6

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                           Table 1
                         (Continued)
Name

Methyl Cellulose

2-Naphthylamine

Triphenyl carbinol

2, 2' -dithiobisbenzothiozole

2-Benzothiozolethiol

p-Benzotoluide

Zinc salt of carbamic acid

Ethyl ether cellulose

Crystopine

Benzene-c i s-hexach1 or i de

Indigotin (Indigo Blue)

di-l-naphthy 1-mercury

Tetraphenyl

Triphenylamine

Dinaphthylmercury (a)

Tetraphenyl  urea

Wood Fibers

Natural Clays
  Kaolinite
  Bentonite
Specific Gravity

     1.02

     1.061

     1.188

     1.50

     1.00

     1.202

     1.24



     1.315

     1.89

     1.35

     2.318

     1.49

     0.774

     1.929

     1.222

  0.4 - 1.0
  2.60 - 2.63
  2.13 - 2.18

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                           Table 1
                         (Continued)
Name

Plastics
  Nylon
  Acetyt
  Polyethylene
  Teflon
  Lucite

Dowex An ion Exchange
  Resin 2lK

Gilsonite (natural hydrocarbon)

Polystyrene

'Petrothene

Polythene particles

Alathon

Bakelite

Arizona Road Dust

Amberlite Anion Exchange
  Resin  IRA-93
  (Based on polystyrene)

Non-ionic Resin
  XAD-2

Infusorial Earth

Pumice

Bituminous Coal

Anthracite Coal

Fuller's Earth

Rayon Fibers

Styrene Divinyl Benzene
Copolymer Latexes
Specific Gravity




  0.9 - 1.45




     1.06

     1.06

     1.05

     1.01

     0.92

     0.96

     1.42

     2.65
     1.03


     2.33

     1.35

  1.12 - 1.35

     1.6

  2.2 - 2.4

     1.52

     1.14
                            10

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                           Table 2

Compounds Selected for the Initial Developmental  Investigations


           Group I  - Specific Gravity 0.80 - 1.00

Name                                        Specific Gravity

Triphenylamine                                   0.774
Polythene                                        0.92
Alathon                                          0.96


            Group II  - Specific Gravity 1.01 - 1.50

Petrothene                                       1.01
Methyl Cellulose                                 1.02
Non-ionic Resin  XAD-2                           1.03
Amberlite Exchange Resin  IRC-50                 1.04
Amberlite Anion Exchange Resin  IRA-93           1.04
Polystyrene                                      1.05
Styrene Divinyl Benzene Copolymer Latexes        1.05
Gilsonite                                        1.06
Bituminous Coal                              1.12 - 1.35
Nylon Fibers                                     1.14
Anthracene                                       1.25
Pumice                                           1.35
Tetraphenyl                                      1.49


          Group III  - Specific Gravity 1.51  - 1.99

Rayon Fibers                                     1.52
Anthracite Coal                                  1.6
Magnesium arsenate                               1.788
4, 41 - dibromo-biphenyl                         1.897


           Group IV - Specific Gravity 2.00 - 2.65

Hexachlorobenzene                                2.044
Silicon dioxide (Sand, Glass Beads)            2.1 - 2.66
Fuller's Earth                                2.2 - 2.4
Infusorial Earth                                 2.33
Aluminum Oxide                                2.42  - 2.53
Arizona Road Dust                                2.65
                               11

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 the  population.   Statements  concerning the mean,  variance, and confidence
 limits  of  the  population  can be  made from the sample by including a
 sufficient  number of  observations.   The minimum acceptable for such calcu-
 lations is  30  individual  observations.°»

     Variance  and/or  standard deviation can be calculated to represent the
 measures of variability  in  the samples from the populations investigated.
 The  sample  variance  is generally denoted by S^, and its defining formula is:
                                      n- 1
                                i= 1
where   Xj  = Xj ,  Y-2,  •  •  .,  Xn

                              n
        X = Arithmetic Mean =
                              n

        n  = The  number  of  sets of  values  reported in each study.

     The  standard deviation, S,  is  defined  to be the positive square root of
 the variance, S .   Its defining formula  is:
                               'V(X-X)2
                               /_-*
                               i  = 1
     To calculate the confidence  interval  for  the  mean  of  a normal  distribu-
tion with unknown variance,  the sample  variance  S   must be used as  an  estima-
tion of the population variance.

     The quantity t =  (X - fi ) / (S/^rf), which  is not the  standard normal
distribution, but is known  as "Student's  t"  or !'t" distribution,  is used.
Since the "t" distribution  is symmetric about  zero,  a 1- a level  confidence
interval for /x  (the population mean) can  be  constructed as shown:
                                                =  1 — oc
     or
where  P = Probability
                                      12

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Analytical Method for Suspended Solids

     The analytical method used in this study for the determination of
suspended solids was the method described in the current EPA manual, Methods
for Chemical Analysis of Water and Wastes, 197^, specifying a drying temper-
ature of 103-105°C and requiring a vacuum during filtration to remove excess
water.7  Reeve Angel Type 93^-A, 2.4-cm glass fiber filters and 40-ml Coors
Number 27007 Gooch crucibles were used for the solids analyses.  Sample sizes
were 100 ml and 200 ml, depending on the concentration of suspended solids
in the samples.

SolubN ity Testing

     The first test procedure applied to the compounds being evaluated in-
volved percent recovery of the compounds after dilution in distilled water
and completion of the analytical procedure.   Results included solubility,
retention of the compounds on the standard glass fiber filters, and change
of weight during the analytical procedure.  The testing procedure involved
the following steps:

     1.  Specific amounts of each of the test compounds were weighed on a
         Mettler analytical balance, which was certified on a periodic
         basis during the project.

     2.  The specific weights of compounds were diluted to volume in a
         250-ml volumetric flask with distilled water.

     3.  The volumetric flask was shaken vigorously by hand for at least
         30 seconds.

     k.  The total volume of sample (250 ml) was then filtered through a
         previously dried and tared Gooch crucible with a fiber-glass
         filter pad in place.  The flask was thoroughly rinsed with distilled
         water to make certain that all of the test compound was removed
         from the flask.

     5.  The Gooch crucible containing the sample was dried at 103°C to 105°C
         for one hour, and then desiccated and re-weighed to determine the
         percent recovery of the test compound.

     Results from the initial solubility testing (six repetitions) are pre-
sented as percent recovery in Tables 3 and 4.  A 97 percent recovery value
was selected for determining acceptance or rejection for the solubility
criterion.  Percent recovery characteristics of the compounds which passed
the initial solubility tests are shown in Tables 5 and 6; Table 5 presents
the results from 30 repetitions at 250 mg/1 suspended solids, and Table 6
the results from six repetitions at 25 mg/1 suspended solids.
                                     13

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                   Table 3




Compounds Failing Initial Developmental Tests
Compound
Triphenylarnine
Petrothene
Methyl Cellulose
Amber lite Exchange
Resin IRA-93
Amber lite Exchange
Resin IRC-50
Nylon Fibers
Anthracene
Tetraphenyl
Magnesium Arsenate
4, 4' - dibromo-
biphenyl
Hexachlorobenzene
Aluminum oxide
*Minimum of one or
Specific
Gravity
0.774
1.01
1.02
1.04
1.04
1.14
1.25
1.49
1.788
1.897
2.044
2.42-2.53
two percent recovery
Wettabi li ty
1
1
1
5
5
1
1
2
5
2
2
5
observations.
%
Dl spersion Recovery
1 58.7*
1
1
5 92.7
5 79.2
1 103.1
1 67.3*
2 91.6*
5 90.3
2 82.2*
2 88.3*
1 93.5

Comments
Floats & clings to sides
of container.
Particles agglomerate
in groups and do not
wet or disperse well.
Methyl cellulose
dissolves in water.
Unacceptable recovery.
Unacceptable recovery.
Nylon fibers swel 1
significantly when wetted.
Some fibers agglomerate
and cannot be separated
by vigorous shaking.
These agglomerations pour
out with the sub-sample
and yield percent re-
coveries greater than 100.
Floats and clings to
sides of container.
Floats and settles in
clumps .
Unacceptable recovery,
clogs f i Iter pad.
Particles agglomerate
into large clumps.
Some floats and clings
to sides of container.
Unacceptable recovery.
Difficult to disperse
because of high specific
gravity.


-------
                   Table k




Compounds Passing Initial Developmental Tests
Compound
Rayon
Non- ionic Resin
XAD-2
Bituminous Coal
Anthracite Coal
Infusorial Earth
Sand
Glass Beads
Polythene
Alathon
Polystyrene
Pumice
Ful ler 's Earth
Arizona Road
Dust
Specific
Gravity
1.52
1.04
1.12-1.35
1.6
2.33
2.1-2.66
2.1-2.66
0.92
0.96
1.05
1.35
2. 2-2.it
2.65
Wettabi lity
5
3
5
k
5
5
5
4
3
k
5
5
5
Di spersion
5
k
3
3
5
3
3
3
3
4
5
5
k
%
Recovery
97.1
98.1
98.7
99.9
100.5
99.9
99.6
99.4
~~
100.1

99.3
100.5
Comments
Looks excel lent.
Floats, but will disperse
with vigorous shaking,
some cl ingage.
Dispersion characteristics
depend on particle size.
Dispersion characteristics
depend on particle size.
Looks excel lent.
Dispersion characteristics
depend on particle size.
Dispersion characteristics
depend on particle size.
Floats, but will disperse
with vigorous shaking,
some cl ingage.
Floats in groups but wi 11
disperse with vigorous
shaking.
Particles settle and
disperse with vigorous
shaking.
Particles settle and
disperse with vigorous
shaking.
Looks excel lent.
Looks excel lent.

-------
                                 Table 5
            Percent Recovery Tests for Compounds Passing the
                         Initial Screening Tests
                      (250 mg/1) at 30 Repetitions
    Compound
Polythene
XAD-2
Polystyrene
Bituminous Coal
Pumice
Rayon
Anthracite Coal
Infusorial Earth
Sand
Glass Beads
Arizona Road Dust
Fuller's Earth*

*6 repetitions at 250 mg/1
Specific Gravity
     0.92
     1.03
     1.05
   1.12 - 1.35
     1.35
     1.52
     1.6
     2.33
   2.1  - 2.66
   2.1  - 2.66
     2.65
   2.2  - 2.k
% Recovered
    99.4
    98.3
   100.1
    98.3
    99.5
    98.6
    99.9
    99.7
   100.1
    99.4
   100.5
    99.3
                              16

-------
                                 Table  6
              Percent Recovery  Tests  for  Compounds  Passing
                      the Initial  Screening Tests
                       (25 mg/1)  at  6 Repetitions
    Compound

Polythene

XAD-2

Polystyrene

Bituminous Coal

Pumice

Rayon

Anthracite Coal

Infusorial Earth

Sand

Glass Beads

Arizona Road Dust
Specific Gravity

     0.92

     1.03

     1.05

   1.12 - 1.35

     1.35

     1.52

     1.6

     2.33

   2.1  - 2.66

   2.1  - 2.66

     2.65
% Recovered

   102.9

    98.8

    99.4

    99.1

   100.6

    95.7

    99.0

    99.8

   102.0

    98.7

   100.8
                                17

-------
Wettability and Dispersion Testing

     The  second test procedure applied  to each compound  involved wettability
and dispersion tests to determine  if  the compounds were  hygroscopic,  showed
any tendency to cling to the  sides of the sample containers, or floated or
settled to the extent that good dispersion could not be  obtained with vigorous
shaking in distilled water.   Visual observations using empirical scales of
measurement were employed to  check the  degree of clinging of the compounds
to the sides of the containers, the degree of wettability, and the degree of
dispersion of the compounds  in water.   The scales of one through five in the
following tabulation were used to determine  the degree to which the com-
pounds were wetted and dispersed  in water:
          1 - Poor Wettabi1ity
          2 - Fair Wettabi1ity
          3 - Acceptable Wettability
          k - Good Wettability
          5 - Excellent Wettability
1 - Poor Dispersion
2 - Fair Dispersion
3 - Acceptable Dispersion
k - Good Dispersion
5 - Excellent Dispersion
     Results of the wettability and dispersion observations are presented  in
Tables 3 and k.  A scale measurement of 3  (acceptable wettability and
dispersion) or better was selected for acceptance.  Scale measurements of
1 and 2  indicated rejection of the test compounds.

Flocculation Testing

     Compounds meeting the previously-defined design criteria were subjected
to mixing tests with other compounds to evaluate the flocculation character-
istics of various combinations of the compounds under investigation.  Visual
observations using the following empirical scales of measurement were used
to check the flocculation characteristics of the various mixtures:

     1.  POOR.  Particles agglomerate readily and remain in groups.

     2.  FAIR.  Particles agglomerate readily and tend to remain in groups.

     3.  ACCEPTABLE.  Particles agglomerate to a small degree but break
         apart with shaking.

     4.  GOOD.  Particles agglomerate to a very small degree but break
         apart very easily.

     5.  EXCELLENT.   No agglomeration of particles.

     All compounds passed the flocculation testing when mixed with other com-
pounds, with the exception of XAD-2 and polythene, which flocculated when
mixed (rating 2).

     Rayon fibers tended to entrap other particles, especially XAD-2, coal,
and pumice.   Rayon entrapped air bubbles and floated when vigorously mixed,
but would settle with gentle agitation.
                                      18

-------
Abrasion Testing

     No acceptable method for measuring the abrasion and impact resistance of
the compounds to breaking up into smaller particles was found in the litera-
ture.  However, a test procedure involving a Burrell Wrist-Action Shaker
(made by Burrell Corporation of Pittsburgh, PA) seemed appropriate for
abrasion and impact resistance testing.  The procedure for simulation of a
"worst case" was as follows:

     1.  Initial particle size was determined by the previously-mentioned
         ASTM method.

     2.  For each compound, three 10-gram samples and six 500-mg samples
         were weighed out on the balance.

     3.  The weighted compounds were transferred to nine 250-ml volumetric
         flasks.

     k.  The nine volumetric flasks were placed on the Burrell Wrist-Action
         Shaker for a 24-hour period at a scale setting of k  (on a scale of
         0-10,  with 10 being the most vigorous shaking obtainable).

     5.  The six flasks containing 500-mg samples were diluted to volume
         with distilled water and filtered to determine the percent
         recovery of the compounds under investigation.

     6.  Particle size was again determined for the compounds in the three
         flasks with the 10-gram samples, for comparison with the initial
         particle size.

     The test compounds were vigorously shaken in the dry state to simulate
conditions of storage and shipping, because it was anticipated that the
compounds would be packaged in the dry state and that the impact and abrasion
forces would be greater in that condition.  The results of the abrasion
testing are presented in Table 7.  No compounds subjected to abrasion testing
were rejected on the basis of abrasion and impact resistance.

Evaluation of Sub-Sampling

Mixing Technique—
     Mixing techniques for sub-sampling stated in the contract to be investi-
gated included the following:

     1.  Shaking the samples vigorously by hand.
     2.  Magnetic stirring of samples.
     3.  Blade agitation stirring of samples.
     k.  Blending of samples.

However, the last two mixing techniques were eliminated because they would
introduce physical constraints in the subsequent requirement to dilute the
sample to volume in a volumetric flask.

-------
                                   Table 7

                          Abrasion Testing Results
Compound

Arizona Road
Dust
Glass Beads
Sand
Anthraci te
Coal
Biluminous
Coal
Pumi ce
Rayon
Percent Recovery After
   Abrasion  Testing

          99.8
          99.9
          99.9
          98.4
          99.0
         99.5
          98.9
Uniformity Coefficient (Cu)
Before               After
 1.50
 1.53
 1.72
 2.95
 4.04
 1.88
1
.45
.45
.45

.44
.53
.62

.76
.72
.75
2.83
3.66
3.46

3.53
4.00
4.16
2.02
2.11
2.06
 Particle Size Before
 Mean = 1.63 mm
 St. Dev. - 0.573
 Var. = 0.328
                         Rayon  Particle Size After Shaking
           #1  Sample

           Mean = 1.19
           St. Dev.  = 0.430
           Var. = 0.185
                                       #2 Sample

                                       Mean = 1.214
                                       St. Dev. = 0.458
                                       Var. = 0.210
Rayon fibers form small  tight balls when  shaken  in the abrasion test.  These balls
are extremely difficult  to re-suspend  by  shaking.  A blender was used to re-
suspend the rayon fibers.


              Rayon Particle  Size After Shaking and Blending Approx. 60 sec.

                                 Mean =  0.963
                                 St.  Dev. = 0.468
                                 Var. =  0.219

              Random samples  were taken for particle sizing with a micro-
              scope.  100  particles were  counted.
                                        20

-------
     The evaluation of mixing techniques and subsequent recovery  involved
withdrawing 100 ml sub-samples from one-liter volumetric flasks.  The com-
pounds in the flasks were mixed vigorously by hand and by magnetic stirrer
for comparison.  The sub-sample volumes of 100 ml were poured  into a
graduated cylinder or withdrawn with a volumetric pipet.  The  results of
the mixing tests are presented in Table 8.

Recovery Tests  (Analytical Method)—
     Precision and accuracy data for the analytical method were determined
by withdrawing appropriate sample volumes  (100 ml or 200 ml) from the
full-volume diluted solids samples into one-liter volumetric flasks  in
conformance with the EPA method for determining suspended sol ids.1  The
volumetric flasks were shaken vigorously by hand, and the subsequent sub-
samples were poured into graduated cylinders as contrasted to mixing with
magnetic stirring bars and withdrawing the sample with a pipet.  The average
percent recovery was higher, and the range of percent recovery and therefore
the standard deviation were less for shake-and-pour with graduated cylinders
than for magnetic stirring and pipeting.

     Extensive tests were performed on the compounds that appeared to be
acceptable for packaging (pumice, rayon fibers, and Fuller's earth).  The
results of the mixing tests and sub-sample recovery for these compounds
and for anthracite coal are presented in Table 9.  The percent recovery of
sub-sampling appeared to be a function, to some extent, of particle size
because the dispersion characteristics were somewhat dependent on particle
size as exhibited in Tables 8 and 9.

     An experiment was conducted to determine the effects of particle size
on the percent recoveries obtainable on Fuller's earth.  Fuller's earth was
screened at specific particle sizes, weighed, and diluted with distilled
water to one liter in volumetric flasks, and the sub-samples were removed
by pouring into graduated cylinders for percent recovery analyses.  The re-
sults of these particle-size investigations are presented graphically in
Figure 1.

Selection of Compounds for Packaging

     The results of the feasibility testing and the observations of the
specific compounds indicated two possible alternative methods available for
sample handling without modifying the 197^ EPA solids analysis procedure.
One alternative was to package compounds over the full range of specific
gravities (0.8-2.65)  and particle sizes (0.01-4.5 mm) and to filter the total
sample for the solids analysis.   Compounds suitable for this procedure in-
cluded the following:

     1.  Pum i ce
     2.  Rayon Fibers
     3.  Infusorial  Earth
     k.  Fuller's Earth
     5.  Sand
     6.  Glass Beads
     7.  Arizona Road Dust


                                     21

-------
                                                      Table 8

                         Evaluation of Mixing Techniques Using One-Liter Volumetric  Flasks
                          (Vigorous Shaking and Mixing with Magnetic Stirring  Bars) 250 mg/1
Compound
XAD-2

Polystyrene
Bi turn! nous
Coal

Pum i ce


Rayon
Fibers

Anthracite
Coal

Mixing
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder)
Shake & Pour
(Graduated Cylinder)
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder)
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cyl inder)
Pi pet
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder)
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder)
Repetitions
6
6
6
6
6
6
3
3
6
6
6
6
Specific Average %
Gravity Particle Size Recovery
1.03 100-200 microns 102.1
91.0
1.05 1.7 mm Zk.3
1.12-1.35 <150 microns 83. k
96.2
1.35 <75 microns 90.8
92.2
82.3
1.5-2 1.6 mm 93.6
92.3
1 .6 <150 microns 60.8
163.1
Range /
79.7
28.5
0
77.6
85.5
88.6
89.7
76.8
91.**
89.9
1*8.8
68.3
'0 Recovery
- H*5.7
- 106.7
- 80.8
- 90.5
- 107.5
- 92.0
- 95.7
- 91.9
- 95.0
- 93.5
- 78.5
- 290.5
to

-------
  Table 8
(continued)

Compound
Fuller's
Earth


Fuller's
Earth



Infusorial
Earth



Glass Beads


Arizona Road
Dust
Arizona Road
Dust
All sub-samples

Mixing
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder)
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder
Pi pet
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
(Graduated Cylinder)
Pi pet
Shake & Pour
(Graduated Cylinder)
Magnetic Stirring
Shake & Pour
(Graduated Cylinder)
Shake & Pour
(Graduated Cylinder)
were 100 ml samples.

Repetitions
6

6

3

3

3
6

6

6
6

6
6

6


Specific Average %
Gravity Particle Size Recovery
2.2 - 2.4 <150 microns 81.9

87.3

2.2 - Z.k <45 microns 92.9

9L8

94.3
2.33 8 microns 93.1

102.3

91.7
2.61 - 2.65 0.9 - 1.23 mm 0

1.0
2.65 100-200 microns 7.1

2.65 20-40 microns 77.9



Range °/
78.2

83.9

92.6

89.4

92.7
88.5

99.7

89.1


0
5.2

73.9



3 Recovery
- 84.4

- 90.6

- 93.3

- 94.7

- 97.3
- 97.4

- 103.7

- 95.2
0

- 2.0
- 9.9

- 79.6



-------
                         Table 9



Mixing Test Results (Shake & Pour) with Graduated Cylinder
Concentration
ma/L
Sub-Sample Actual Particle
Compound Size (ml) Proposed Av«r«g« Size
Pumice* 100 100 104.8 < 45 microns
Pumice*
Pumice*
Rayon**
Rayon**
Rayon**
Rayon**
Rayon**
Rayon*
Fuller's Earth**
Fuller's Earth**
Fuller's Earth**
Fuller's Earth**
Fuller's Earth**
Fuller's Earth*
Nylon Fibers***
Anthracite Coal**
Anthracite Coal**
Anthracite Coal**
Anthracite Coal****
* 3 repetitions
** 30 repetitions
*** 12 repetitions
**** 6 repetitions
100
100
200
200
100
ICO
100
100
200
200
100
100
100
100
100
200
100
100
100




250
1000
27
50
100
250
855
1000
27
50
100
250
855
1000
250
27
250
855
250




257.3
1007.8
27.4
52.1
102.0
251.9
854.9
1011.8
27.5
52.6
111.7
254.2
855.5
1007.9
250.8
28.5
253.4
861.5
251.3




< 45 microns
< 45 microns
0.5 «m
0.5 rm,
0.5 irni
0.5 irni
0.5 mm
0.5 out
< 45 microns
< 45 microns
< 45 microns
< 45 microns
< 45 microns
< 45 microns
0.5 mm
£ ISO microns
< 150 microns
< 150 microns
44 - 150 microns




Average %
Recovery
90.7
92.4
90.3
98.3
97.3
97.4
97.5
99.1
98.8
99.6
94.5
96.4
96.7
96.0
95.3
103.1
92.3
77.4
74.4
69.1




Range %
Recovery
88.8 - 92.6
91.3 - 93.1
89.3 - 90.3
85.3 -107.5
90.0 -102.5
93.9 -101.4
95.1 -100.0
97.1 -101.5
97.8 - 99.7
93.8 -105.6
88.4 -101.4
92.3 - 99.1
93.4 - 99.2
93.0 - 98.5
94.8 - 95.6
98.7 -109.0
76.6 - 106.0
66.9 - 85.1
65.7 - 81.9
63.9 - 72.5




Standard
Deviation
(Percent)
1.90
0.96
1.05
4.69
3.47
2.12
1.23
1.31
0.95
3.80
2.91
1.88
1.63
1.67
0.46
2.57
7.88
4.21
4.26
3.65




Variance
3.61
0.93
1.10
22.01
12.05
4.51
1.52
1.71
0.91
14.48
8.47
3.55
2.65
2.80
0.21
6.61
62.03
17.74
18.11
13.29




•Standard
Deviation
(IM)
0.23
0.26
1.06
0.18
0.32
0.18
0.29
0.67
1.00
0.10
0.28
0.22
0.46
1.39
O.SI
0.56
0.42
2.94
3.77
1.07




Variance
0.05
0.07
l.ll
0.03
0.10
0.03
0.08
0.46
1.00
0.01
0.08
0.05
0.2)
1.93
0.26
0.32
0.18
8.66
14.25
1.13




Standard
Deviation
(M/L)
1.99
2.47
10.58
1.29
1.81
2.16
3.10
11.20
9.61
1.05
1.53
2.10
4.14
14.29
4.67
6.45
2.25
10.67
36.70
9.17




. Variance
3.96
6.10
111.96
1.65
3.27
4.68
9.60
125.42
92.39
1.09
2.34
4.41
17.17
204.10
21.50
41.55
5.04
113.81
1346.88
84.13





-------
                                                                 PERCENT RECOVERY


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-------
However, this procedure would yield information only on the analytical
technique, with no regard to sub-sampling technique and procedure.  The
second and best alternative would be to package one or a few compounds in
the very small particle-size fractions that would allow accurate sub-sampling.

     The compounds indicated as acceptable for the second alternative were:

     1 .  Pum i ce
     2.  Rayon Fibers
     3.  Fuller's Earth

     The second alternative was chosen for selecting the compounds to be
packaged as quality control and performance evaluation samples.  Since pumice
and rayon fibers were close in specific gravity and since the particle size
of each can be varied, the rayon fibers were chosen because of higher percent
recoveries during sub-sampling.  Consequently, the following compounds shown
as compounds passing the initial developmental tests in Table k were rejected
for packaging:

               Compound                          Comments

     1.  Non-ionic Resin, XAD-2       Erratic sub-sampling recovery.

     2.  Bituminous Coal              Low sub-sampling recovery.

     3.  Infusorial Earth             Low sub-sampling recovery.  Same
                                      specific gravity as Fuller's Earth.

     4.  Sand                         Low sub-sampling recovery.

     5.  Glass Beads                  Low sub-sampling recovery.
     6.  Polythene                    Floats, yielding erratic sub-sampling.

     7.  Alathon                      Floats, yielding erratic sub-sampling.
     8.  Polystyrene                  Low sub-sampling recovery.
     9.  Pumice                       Approximately same specific gravity
                                      as rayon fibers.
    10.  Arizona Road Dust            Low sub-sampling recovery.

     Styrene di vinyl benzene (specific gravity - 1.05) was also rejected for
packaging because of initial cost (approximately $45 per 15 ml) and handling
problems.  It is packaged in liquid form and cannot be dried without changing
properties.

     The compounds selected for packaging included the following:
         Fuller's Earth - particle size <^5 microns
         Rayon Fibers   - 1.5 denier*, 0.5 mm long
         Anthracite Coal- particle size <150 microns

*A measure  of  the  fineness of  rayon yarn.   1.5 denier yarn weighs  1.5  grams
  per  9,000  meters.


                                      26

-------
     Fuller's earth and  rayon  fibers met  all  the design criteria established
 for  the  synthetic  suspended  solids  quality control  and performance evalua-
 tion samples.  The reason for  packaging anthracite  coal as a  suspended  solids
 quality  control  sample was to  show  some of the  problems  involved  in  the
 suspended  solids determination procedure.

 Biodegradabi1ity Testing

     The biodegradabi1ity tests were conducted  by measuring biochemical
 oxygen demand (BOD) in BOD bottles  according  to the procedure described in
 the  13th Edition of Standard Methods for  the  Examination of Water and
 Wastewater.  '  The distilled water, phosphate buffer  solution, magnesium
 sulfate  solution, calcium chloride  solution,  ferric chloride  solution,  sodium
 sulfite  solution, and dilution water were prepared  according  to the  instruc-
 tions.  Therefore, adequate nutrients were supplied by the prepared  solutions
 added to the dilution water.

     Each bottle was  seeded with microorganisms from  a standard house seed
 taken from the West Chester, PA municipal sewage treatment plant.  The  BOD
 bottles were  incubated at 20°C for  a five-day period.  The dissolved oxygen
 (DO) was determined with a membrane electrode DO meter, which was checked
 and  standardized before use.

     Each of the three compounds selected for packaging was tested at three
 concentrations for the five-day BOD analyses.   Standards of glucose/glutamic
 acid were also incubated for the five-day period.   Five mi 11 Miters of  the
 standard were placed  in each bottle yielding  five-day BOD's of 180 to 20k
 mg/1.  Each condition of compounds  and standard was repeated  six times.

     Fuller's earth and anthracite  coal showed  no biodegradation in the
 6005 test procedures, but the  rayon fibers showed slight biodegradation at
 the  two highest concentrations.  The results  of the biodegradabi1ity investi-
 gations are presented in Table 10.

 Stability Testing

     Fuller's earth and anthracite coal were  packaged mechanically at three
 weights for the stability testing;  the rayon  fibers were hand weighed and
 packaged at the same three weights.

     The weights of the packaged compounds were then checked at 30, 60, and
 90 days for comparison with the packaged weights at zero time to evaluate any
 possible problems associated with biodegradabi1ity, volatility, or any
 change of any other characteristics during storage  of the packaged compounds.

     Comparison of the 30-, 60-, and 90-day data to time zero weights dis-
 closed no significant evidence of increasing weight loss with time.  Weight
 loss of rayon fibers during both the 60-day and 90-day investigation periods
was  less than the weight loss  during the 30-day period.  Weight loss of
 Fuller's earth during the 90-day period was less than the weight loss during
                                      27

-------
                                                     Table 10
                                        Results of Biodegradabi1ity Tests

                        (Five-Day BOD Tests) for Rayon, Fuller's Earth, and Anthracite Coal
Sample Description Date
Glucose/Glutamfc Acid Standard (5 mJ/bottle) 11/6/75
Rayon-Low Concentration
Rayon-'Medium Concentration
Rayon^Hlgh Concentration
Fuller's Earth-Low Concentration
Fuller's Earth-Medium Concentration
Fuller's Earth-High Concentration
Glucose/Glutamic Acid Standard (5 ml/bottle) 11/7/75
Anthracite-Low Concentration
Anthracite-Medium Concentration
Anthracite-High Concentration
All Tests conducted at 6 Repetitions.
Avg. D.O. Range D.C.
Depletion Depletion Avg. BOD Range BOD,.
(mq/L) (mq/L) (mq/L) 5 (mq/L) '
3.2 3.0 - 3.3 189 180 - 198
< 0.1
0.8 0.7 - 1.0 2.4 2.1 - 3.0
3.1 2.9 - 3.5 9.3 8.7 - 10.5
< 0.1
< 0.1
< 0.1
3.3 3.2 - 3.4 196 192 - 204
< 0.1
< 0.1
0.2 0.2 0.6 0.6
to
00

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the 60-day period.  Weight loss of anthracite coal was random over the 30-,
60-, and 90-day investigation periods and exhibited no trends or patterns  in
any of the data.

     Statistical analyses were performed to test the significance of the
difference of the weights observed at SO days compared to weights at zero
time by the t test.'^  The difference in the weights observed did not prove
to be significant atOC = 0.01, with one exception, Fuller's earth at the
lowest weight packaged.

Percent Recovery Tests on Mixtures of Fuller's
Earth, Anthracite Coal, and Rayon Fibers

     Rayon fibers and Fuller's Earth, rayon fibers and anthracite coal, and
Fuller's earth and anthracite coal were each mixed at a 50:50 weight ratio
at a total concentration of 250 mg/1 per sample.  In addition, rayon fibers,
Fuller's earth, and anthracite coal were mixed at a 33.3:33.3:33.3 weight
ratio at a total concentration of 250 mg/1 per sample.  Each of these mix-
tures was added to a one-liter volumetric flask and brought to volume with
distilled water.  The samples were then shaken vigorously by hand, and a
sub-sample of 100 ml was poured into a graduated cylinder for suspended
solids analysis to determine the percent recovery.  The results of these
mixing and percent recovery investigations are presented in Table 11.

     The percent recovery obtainable by the analytical method for the mixture
of rayon fibers and Fuller's earth was excellent (average 99.5 percent).
However, the percent recoveries for the other mixtures containing anthracite
coal were all less than 90 percent.  The percent recoveries obtained were
as would be expected without flocculation reactions.  Very good percent
recoveries were obtainable with rayon fibers and Fuller's earth alone,
whereas very poor recoveries were obtainable with anthracite coal alone.

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           Table 11




Compound Mixing Tests Results

Compound
Rayon Fibers*
Fuller's Earth
Rayon Fibers*
Anthracite Coal
Fuller's Earth*
Anthracite Coal
Rayon Fibers*
Fuller's Earth*
Anthracite Coal
Rayon Fibers at 0.
Fuller's Earth at
Anthracite Coal at
6 repetitions
Total Standard
Ratio Size (ml) (mq/L) Recovery Recovery (Percent) Variance
50:50 100 250 99.5 99.0 - 100. 1 0.50 0.25
50:50 100 250 87.4 85.5 - 91.7 2.28 5.19
50:50 100 250 79.2 77.3 - 82.1 1.67 2.80
33.3:33-3:33.3 100 250 84.1 82.8 - 85.2 0.79 0.62
5 mm particle size
< 45 micron particle size
< 150 micron particle size
Standard Standard
(ma) Variance (ma/L) Variance
0.12 0.015 1.20 1.44
0.55 0.31 5.50 30.25
0.47 0.22 4.70 22.09
0.45 0.20 4,50 20.25


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                                 SECTION V

                     PACKAGING OF COMPOUNDS - PHASE  II
PREPARATION OF COMPOUNDS FOR PACKAGING

     Fuller's earth, rayon fibers, and anthracite  coal were carefully pre-
pared for packaging.  These compounds were purchased  in a pure state and
washed several times in distilled water to remove any soluble impurities
that might have been present.  These compounds were then dried overnight at
103-105°C to remove moisture.  The rayon fibers were  then ready for pack-
aging, because they were previously sized.  The Fuller's earth and anthracite
coal were ground or milled and sized to the correct sizes.  These compounds
were then dried again to remove any moisture that might have been picked up
during the sizing operations.  These compounds were then ready for packaging.

PACKAGING REQUIREMENTS

Number and Type of Samples

     The numbers and types of packages of the compounds (rayon fibers, anthra-
cite coal, and Fuller's earth) chosen for packaging by EPA are presented
be 1ow:
             Compound
          Rayon Fibers
          Fuller's Earth
          Anthracite Coal
Weight (mg)

 Low
 Med ium
 High

 Sub-Total

 Low
 Medium
 High

 Sub-Total

 Low
 Med ium
 High

 Sub-Total
No. of Vials

   1,111
   1,111
   1 ,111
   3,333

   2,711
   1,111
   1,111
   ^,933

   1,111
     311
     311
   1,733
                                      31

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     This combination of weights and number of vials at each weight was
chosen for two principal reasons:

     1.  To obtain variety in the packaged weights.

     2.  To package fewer vials of anthracite coal, because the main purpose
         of this compound is simply to indicate some of the problems of the
         test procedure.

Packaging Technique

     Weston used a semi-automatic packaging instrument (Perry Model LM-14
Accofil Portable Powder Filling Machine)  to package the anthracite coal and
Fuller's earth.  However, the instrument  could not be used to package the
rayon fibers accurately, because of their fluffy physical nature.  Therefore,
the rayon fibers were hand weighed and packaged.  The actual packaged weights
of rayon fibers were recorded for each vial.

     Strict quality control procedures were employed during preparation of
the compounds and the packaging vials and caps, and during the actual pack-
aging operations.  Rigid laboratory standards concerning equipment, vials
and caps, and housekeeping practices were enforced.  Vials were thoroughly
washed in dilute hydrochloric acid solution, rinsed, dried at 103-105°C, and
desiccated before being used for packaging.  All the packaging operations
were conducted in a temperature- and humidity-controlled balance room.  Cali-
bration of the packaging instrument and quality control checks on the
instrument and hand-packaged vials were performed on a routine basis, as
described in the sub-section on quality control.

Instrument Packaging Precision

     Anthracite coal and Fuller's earth were employed  in packaging operations
with the packaging instrument to determine the precision of packaging at
specified weights.  As the Fuller's earth and anthracite coal were final
packaged, approximately five percent of the packaged vials were checked for
packaging precision.  Quality control spot checks of each type of package
combination were made, and these quality control checks were included  in the
precision measurements of the instrument.  Packaging precision was shown to
be within ±3 percent of the average packaged weights.

Quali ty Control

     Rigid quality control procedures were utilized throughout the packaging
operations to  insure confidence  in the precision and accuracy of the pack-
aged compounds weights.  The packaging instrument was calibrated on a daily
basis, and approximately five percent of the packaged vials were checked
for packaging precision at the time of packaging.  The hand-packaged weights
were also checked by re-drying approximately five percent of the packaged
vials and determining the packaged weights for comparison with the initial
recorded weights.
                                      32

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     Additional vials of rayon fibers, anthracite coal, and Fuller's earth
were packaged at each weight combination for quality control spot checks
of the packaged weights by a senior chemist who had not been associated with
the packaging of the vials.  The samples for quality control checks were
randomly selected from each packaged combination of compounds and weights.
These quality control checks again established that the packaged weights were
within i3 percent of the average packaged weights.
                                      33

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                                 SECTION VI

                                 DISCUSSION
STATISTICAL EVALUATION OF DATA

     Calculations were conducted to determine the precision of the analytical
results that could be expected by an analyst performing the suspended solids
test from the packaged compounds (rayon fibers, Fuller's earth, and anthra-
c i te coa1).

     With the concurrence of the EPA statistician, the packaging precision
data for Fuller's earth and anthracite coal, and the analytical method
precision data were combined into a single precision statement.  To develop
this precision statement for each compound weight, it was necessary to com-
pare the results of the packaging and the analytical method at the same
weights; however, the packaged weights and those used in the analytical
method evaluation were different.  To put the data on the same basis, a plot
of  the standard deviations of the analytical method for each compound versus
the corresponding weights was made.  These plots  (Figure 2) indicated
straight-line relationships.  Consequently, the standard deviations for
analytical method at the packaged weights of the compounds were read
directly from these graphs.

     The combined standard deviation of the analytical method and packaging
was then calculated as follows:
            •K
S12  •+   S22
where     S = Combined standard deviation
          S-j = Standard deviation of analytical method
          $2 = Standard deviation of packaging

     The percent recovery of the analytical method was also determined for
the actual packaged weights of compounds by plotting the average percent
recovery versus average concentration.  The combined precision of analytical
method and packaging was then determined around the sample mean, which was
taken to be the average packaged weight multiplied by its respective average
percent recovery.

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O
p
O
EC
36


34

32


30


28


26


24


22


20

18


16


14




10


 8


 6


 4


 2
                                                                                  Anthracite Coal
                                                                                                    Fuller's Earth

                                                                                                    Rayon Fibers
                                                                    I
                                                                             I
              100      200     300      400      500      600      700      800

                                                AVERAGE CONCENTRATION. mg/L
                                                                                900
1,000
1,100     1,200
                         Figure 2. Standard deviations of analytical method versus concentration.

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SYNTHETIC SUSPENDED SOLIDS ANALYSIS

     Recent  investigations by EPA's Environmental Monitoring and Support
Laboratory  (EMSL), Cincinnati, OH, and an independent study by the National
Council of  the Paper Industry for Air and Stream  Improvement,  Inc. were
undertaken  to examine the effects of procedural differences on measured
presence of non-filterable residue (suspended solids)."  Significant
variations  in non-filterable solids capture were found to result from the
following:  type of filtering medium used; type of filter holder apparatus
used to support the medium; volume of sample filtered (volume to filter
area); and  post-washing procedure.

     These  findings led to the recommendation that a uniform test procedure
be developed and employed for measuring non-filterable residue or suspended
sol ids.

     Standard procedures for transferring the pckaged compounds to one-liter
sample containers (volumetric flasks) and for performing the suspended  solids
analysis are recommended in the following paragraphs.

Preparation of Quality Assurance Samples
for Suspended Solids Analysis

     The following procedure is recommended for preparation of the quality
assurance samples for suspended solids analysis:

     1.  Tap contents (compounds) to bottom of vial.

     2.  Remove rubber-lined seal from vial (being careful to avoid losing
         any particles that may be clinging to the rubber lining).

     3.  Clean the rubber lining by flushing thoroughly with distilled water
         into a one-liter volumetric flask (Class A glassware); with anthra-
         cite coal, rubbing the lining with a glass rod may be required for
         complete removal.  Clean until no particles remain attached to
         1 in ing.

     k.  Pour contents of the vial into the volumetric flask through a
         glass funnel.

     5.  Continually rinse and transfer remaining contents of the vial  into
         the volumetric flask until no particles remain in vial.

     6.  Dilute to one-liter mark.

Analytical Method for duality Assurance Suspended
Solids (Non-Filterable Residue)

     The procedure and the apparatus recommended for performing the suspended
solids analysis are as stated in the EPA Manual of Methods for Chemical
                                      36

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Analysis of Water and Wastes.7  The procedure for determining suspended
solids concentrations is as follows:

     1.   Insert  recommended glass fiber filter disc  into bottom of suitable
         Gooch crucible  (4.7 cm or 2.2 cm), with the wrinkled surface of
         the disc facing upward.1^

     2.  Apply vacuum to the assembled filtration Gooch crucible  in the
         f i 1 ter  apparatus.

     3.  While vacuum is applied, wash the disc with three successive 20-ml
         volumes of distilled water.  Remove all traces of water  by con-
         tinuing to apply vacuum after water has passed through.

     4.  Disconnect the vacuum, remove the Gooch crucible with the filter
         paper in place, and dry it in an oven at 103-105°C for one hour.

     5.  Remove  the Gooch crucible from the oven, and place it in a
         desiccator until cooled to room temperature.  The Gooch  crucible
         can be  stored  in the desiccator until needed, but should be
         weighted immediately before use.

     6.  Place the previously dried, desiccated, and tared Gooch  crucible
         with the glass fiber filter disc  into the filtering apparatus,
         and begin suction.

     7.  Shake the sample diluted to 1-liter volume vigorously by hand for
         at least 30 seconds.

     8.  Rapidly transfer the 100-ml or 200-ml subsample by means of a
         graduated cylinder to the Gooch crucible.

     9.  Rinse the graduated cylinder thoroughly with distilled water,
       ,  pouring the water through the Gooch crucible (minimum of three
         successive 20-ml volumes of distilled water).

    10.  Carefully remove the Gooch crucible from the crucible adaptor.

    11.  Dry in the drying oven at 103-105°C for one hour.

    12.  Cool  in a desiccator for 30 minutes.

    13.  Weigh the Gooch crucible after the 30-minute desiccation period.

     The suspended solids (non-filterable residue) concentration of the
quality assurance sample can then be calculated as follows:

         Suspended Solids,  mg/1 = (A"B) * 1>000

where    A = Weight of Gooch crucible plus solids (residue)
         B = Weight of Gooch crucible
         C = ml  of sample filtered


                                      37

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                                 SECTION VII

                                 REFERENCES

 1.  Dalrymple, R.J., S.L. Hodd, and O.C. Morin.   Physical  and Settling
     Characteristics of Particulates in Storm and Sanitary  Wastewaters.
     Environmental Protection Technology Series EPA-670/2-75-011.
     April 1975.  33 P.

 2.  Sullivan, R.H., M.M. Cohn, J.E. Ure, and F.E. Parkinson.   The Swirl
     Concentrator as a Grit Separator Device.  Environmental  Protection
     Technology Series EPA-670/2-74-026.  June 1974.   93 p.

 3.  Sullivan, R.H., M.M. Cohn, J.E. Ure, F.E. Parkinson, and  G.  Galiana.
     Relationship Between Diameter and Height for the Design of a Swirl
     Concentrator as a Combined Sewer Overflow Regulator.  Environmental
     Protection Technology Series EPA-670/2-74-039.   July 1974.  44 p.

 4.  The Swirl Concentrator as a Combined Sewer Overflow Regulator Facility.
     Environmental Protection Technology Series.   EPA-R2-72-008.
     September 1972.  179 p.

 5.  Shelley, P.E., and G.A. Kirkpatrick.  Sewer Flow Measurement-A State-
     of-the-Art Assessment.  Environmental Protection Technology  Series
     EPA-600/2-75-027.  November 1975.  424 p.

 6.  American Society for Testing and Materials Standards (General Test
     Methods).  Philadelphia, American Society for Testing  and Materials,
     1969.  Part 30, p. 106-118.

 7.  Manual of Methods for Chemical  Analysis  of Water and Wastes.   U.S.
     Environmental Protection Agency Technology Transfer EPA-625/6-74-003.
     197**.  p. 268-269.

 8.  Handbook of Chemistry and Physics.  Cleveland, The Chemical  Rubber
     Company, Forty-Seventh Edition.  1966.

 9.  Snedecor, G.W., and W.G. Cochran.  Statistical Methods.   6th ed.
     Iowa State University Press.  1967.  p.  60.

10.  Arkin, H., and R.R. Col ton.  Statistical Methods as Applied  to Economics,
     Business, Psychology, Education, and Biology. 4th Ed. Revised, Barnes
     and Nobel, Inc.  1956.  p.
                                      38

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11.  Standard Methods for the Examination of Water and Wastewater.   13th  Ed.
     Washington,  APHA, AWWA and WPCF,  1971.   p.  489-^95.

12.  Yamane,  T.,  Statistics - An Introductory Analysis.   3rd  Ed.,  Harper  and
     Row, Publishers  1973.  p. 659-669,  1080.

13.  A Preliminary Review of Analytical Methods  for the Determination  of
     Suspended Solids in Paper Industry Effluents for Compliance with
     EPA-NPDES Permit Terms.  NCASI  Special  Report No. 75-01.   1975. 20 p.

14.  Analytical  Quality Control Newsletter.   U.S. Environmental  Protection
     Agency,  Environmental Monitoring  and Support Laboratory,  Cincinnati,
     Ohio.   January 1976.  p. k.
                                     39

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
   EPA-600M-76-052
                              2.
                                                            3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
  Development of Suspended Solids  Quality Control and
  Performance Evaluation Samples
             5. REPORT DATE
              October  1976  (Issuing date)
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)

  Enos  L.  Stover and Peter J. Marks
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORG'\NIZATION NAME AND ADDRESS
  Roy  F. Weston,  Inc.
  Weston Way
  West Chester,  Pennsylvania  19380
             10. PROGRAM ELEMENT NO.
                 1H0621
             11. CONTRACT/GRANT NO.

                 68-03-2333
12. SPONSORING AGENCY NAME AND ADDRESS
  Environmental  Monitoring and Support  Laboratory
  Office of Research and Development
  U.S. Environmental Protection Agency
  Cincinnati, Ohio  45268
             13. TYPE OF REPORT AND PERIOD COVERED
                 Final   6/30/75  - 5/20/76
             14. SPONSORING AGENCY CODE

                        EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
  A two phase  study was conducted to develop  a  synthetic suspended  solids sample
  for use as quality control check and performance evaluation within  environmental
  monitoring laboratories.  The first phase consisted of a feasibility study to
  determine compounds that exhibited the optimum physical and chemical properties
  for synthetic  suspended solids samples, and the second phase  involved production of
  suspended solids  samples in individual containers.

  Compounds investigated that met all the design criteria included  rayon fibers and
  Fuller's earth.   A total of 10,000 quality  control  samples consisting of rayon
  fibers, Fuller's  earth and anthracite coal  were packaged for  completion of the
  project.  Anthracite coal  was packaged to demonstrate the variability in the sub-
  sampling step  of  the suspended solids test  method with certain types of solids.

  This report was submitted  in fulfillment of Contract Number 68-03-2333 by Roy F.
  Weston, Inc. under the sponsorship of the Office of Research and Development, U.S.
  Environmental  Protection Agency.   Work was  completed in April 1976.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED TERMS
                           c.  COSATI Field/Group
  Quality Assurance
  Standards
  Accuracy
  Calibrating
  Quality Control
  Performance tests
  Validity
                               07D
18. DISTRIBUTION STATEMENT

    RELEASE  TO  PUBLIC
19. SECURITY CLASS (ThisReport)
    UNCLASSIFIED
21. NO. OF PAGES

           SO
                                               20. SECURITY CLASS (Thispage)
                                                   UNCLASSIFIED
                                                                          22. PRICE
EPA Form 2220-1 (9-73)
                                                     ;(U.S GOVERNMENT PRINTING OFFICE: 1976-757-056/5'i25 Region No. 5-11

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