Environmental Protection Technology Series
	
Environmental Applications of

Advanced Instrumental Analyses:

Assistance Projects,  FY 72
                                National Environmental Research Center
                                Office of Research and Development

                                U.S. Environmental Protection Agency

                                Corvallis, Oregon 97330

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            RESEARCH REPORTING SERIES
Research reports of the  Office  of  Research  and
Monitoring,  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
   H.  Environmental Monitoring
   5.  Socioeconomic Environmental Studies

This report has been assigned to the ENVIRONMENTAL
PROTECTION   TECHNOLOGY   series.    This    series
describes   research   performed  to  develop  and
demonstrate   instrumentation,    equipment    and
methodology  to  repair  or  prevent environmental
degradation from point 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.

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                                               EPA-660/2-73-013
                                               September 1973
 ENVIRONMENTAL APPLICATIONS OF ADVANCED  INSTRUMENTAL

           ANALYSES:   ASSISTANCE  PROJECTS,  FY 72
                            By
                     Ann L. Alford
     Southeast Environmental Research Laboratory
                 College Station  Road
                Athens,  Georgia   30601
                   Project #16020  GHZ
                Program Element  1BA027
       NATIONAL ENVIRONMENTAL RESEARCH CENTER
         OFFICE OF RESEARCH AND DEVELOPMENT
        U. S.  ENVIRONMENTAL PROTECTION AGENCY
               CORVALLIS,  OREGON   97330
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, B.C. 20402 - Price 85 cents

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                       ABSTRACT

Identification and measurement of aquatic pollutants
are discussed under 13 project categories.  In most
cases these analyses helped to solve, or at least to
understand more clearly, the related pollution incident
and in some cases provided evidence for enforcement
of regulatory legislation.

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                         CONTENTS

                                                  Page

Abstract                                           ii

List of Figures                                    v

List of Tables                                     vii

Acknowledgments                                    viii

Sections

I      Conclusions                                 1

II     Recommendations                             2

III    Introduction                                3

IV     Projects                                    4

       1.  Excess Color in Municipal Wastes        4

       2.  Organic Pollutants Associated with
           Power Plant Cooling Water               7

       3.  Western Louisiana Industrial Waste
           Survey                                  18

       4.  Polychlorinated Biphenyls in
           Industrial Effluent                     22

       5.  Organic Pollutants in Industrialized
           Shipping Channel                        25

       6.  Taste and Odor Problems in Municipal
           Water Supply                            27

       7.  Organic Components of Laboratory
           Waste Water                             31

       8.  Polychlorinated Biphenyls in Poultry
           Fat                                     32
                           111

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Sections                                          Page

       9.  Titanium in Paint Manufacturing
           Plant Effluent                           33

      10.  Zinc in Metal Finishing Plant
           Effluent                                 33

      11.  Transition Elements in Clay Minerals     34

      12.  Cadmium and Nicke.L in Battery Manu-
           facturing Plant Effluent                 35

      13.  Arsenic in Gold Mine Tailings and
           Waste Water                              37

V     References                                    44

VI    Glossary of Abbreviations                     46
                            IV

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                           FIGURES

 No.
                                       X
 1    Mass Spectrum of Suspect Blue Pigment,
      Identified as Copper Phthalocyanine            8

 2    Map of Texas Power Generating Plant
      Sampling Area                                  °

 3    Computer Reconstructed Gas Chromatograms
      of Neutral Fractions of Samples #8, #17,
      and Blank                                      12

 4    Computer Reconstructed Gas Chromatograms
      of Acidic Fractions of Samples #8, #17,
      and Blank                                      13

 5    Computer Reconstructed Gas Chromatograms
      of Basic Fractions of Samples #8, #17,
      and Blank                                      -^

 6    Gas Chromatograms  (FID) of Neutral Fractions
      of Samples #6, #7, and #8.                     16

 7    Gas Chromatograms  (FID) of Neutral Fractions
      of Samples #1, #18, and #23                    17

 8    Chemically Characterized Gas Chromatogram of
      Petrochemical Company Effluent                 -*-°

 9    Computer Reconstructed Gas Chromatogram of
      the Chloroform Extract of a Petrochemical
      Company Effluent                               20

10    Computer Reconstructed Gas Chromatogram of
      a Manufacturing Plant Effluent                 23

11    Computer Reconstructed Gas Chromatogram of
      the Hexachlorobiphenyl Molecular Ion
      Region of a Manufacturing Plant Effluent       2^

12    Computer Reconstructed Gas Chromatogram of
      Houston Channel Water Sample                   26
                            v

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                      FIGURES  (cont.)

No.                                               Page

13   Gas Chromatogram of New Orleans Drinking
     Water Extract                                  30

14   Map of Sampling Area for
     Arsenic from Gold Mine Tailings and Waste
     Waters                                         39
                           VI

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                          TABLES

No.                                              Page
1    Analyzed Samples from Texas Power
     Generating Plant Area                         10

2    Compounds Identified in Petrochemical
     Company Effluent                              21

3    GC and GC-MS Analyses of Terpenes             29

4    Cadmium Content of Foundry Cove Water and
     Sediment Samples                              36

5    Nickel Content of Foundry Cove Sediment
     Samples                                       37

6    Arsenic Content of Water Samples              40

7    Arsenic Content of Sediment Samples           43
                           VI1

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                    ACKNOWLEDGMENTS

The following Southeast Environmental Research
Laboratory staff were the principal investigators of
the projects listed in Section IV:
Project

   1.
   2.
   3.
   4.
   5.
   6.
   7.
   8.
   9.
  10.
  11.
  12.
  13.
A. W. Garrison
A. W. Garrison
L. H. Keith
J. M. McGuire
L. H. Keith
R. G. Webb
R. G. Webb
A. D. Thruston, Jr.
T. B. Hoover
T. B. Hoover
C. E. Taylor
C. E. Taylor and R. V. Moore
R. V. Moore
The assistance of F. R. Allen, M. H. Carter, T. L.
Floyd, A. C. McCall, 0. W. Propheter, and G. D. Yager
in preparing samples for analysis, performing data
acquisition procedures, and interpreting analytical
data is gratefully acknowledged.
                         vixi

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                       SECTION I

                      CONCLUSIONS

The identification and quantification of specific
chemicals responsible for a wide variety of pollution
incidents helped to solve, or at least to understand
more clearly, the problems associated with the incidents.
In some cases evidence was provided for enforcement of
regulatory legislation.  These projects illustrate the
need for many different analytical techniques to identify
pollution sources.  Continued development of new methods
and improvement of existing techniques are required.

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                      SECTION II

                    RECOMMENDATIONS

Analytical data about specific past and present pollu-
tant sources should be used to establish and enforce
effluent water quality standards for the industrial
permit program and to update these standards as infor-
mation is obtained.  More laboratories concerned with
environmental quality should be equipped to perform
analyses such as those described in this report.
Existing analytical .techniques should be continually
improved, and new techniques should be investigated for
applicability to pollutant analyses.  Information about
specific pollution incidents should be widely dissemi-
nated to help solve and perhaps prevent future environ-
mental problems.

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                      SECTION III

                     INTRODUCTION

The National Water Contaminants Characterization
Research Program  (NWCCRP) at the Southeast Environ-
mental Research Laboratory  (SERL) develops techniques
for identifying and quantifying chemical pollutants
and identifies specific compounds associated with
various pollution sources.  The NWCCRP has analyzed
many samples related to a variety of specific pollution
problems.  Analytical results were reported only to the
persons who requested the analyses and therefore had
limited distribution.  The problems studied by the
NWCCRP are briefly summarized in annual reports to
acquaint other researchers and administrators with the
type of information that can be obtained and to inform
environmental chemists of technique applications and
developments.  This report summarizes fiscal year 1972
projects.

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                      SECTION IV

                       PROJECTS

EXCESS COLOR IN MUNICIPAL WASTES

A variety of analytical techniques were used to identify
colored components of municipal waste treatment plant
influent.  In July 1971, the city of Springfield,
Missouri, requested  assistance with a recurring problem
of excess red color  in their sewage treatment plant
influent.  On several occasions from spring through
fall during a ten-year period, the treatment plant
influent contained a red material that traveled appar-
ently unchanged through the primary clarifiers and the
activated sludge  secondary treatment.  This red material
seemed to lower the  effluent's dissolved oxygen content
and interfered with  settling of the sludge solids, some
of which passed through the treatment system along with
the absorbed red  color.  Treatment efficiency recovered
rapidly when the  colored slug passed.

Periodic sampling of area industrial wastes showed none
containing reddish materials.  Then, quite by accident,
treatment plant personnel allowed a sample from a large
cheese manufacturing plant to stand in sunlight for
several hours.  The  color changed from the original
milkish white to  a red similar to that observed at the
treatment plant.  Cheese company officials had no idea
what had caused the  coloration.  Treatment plant offi-
cials suspected the  color might be caused by a disin-
fectant or cleaner used in the cheese plant.

A turbid, reddish sample of treatment plant influent
was sent to the SERL for analysis in early August.  The
influent chloroform  extract was separated into three
colored components (two orange and one green)  by thin-
layer chromatography (TLC).   The two orange compounds
were suspected to be coloring materials used in the
cheese plant.   Their chemical and physical behavior,
including visible absorption spectra obtained after
elution from the TLC adsorbent,  indicated they were
carotenoids but probably not alpha and beta-carotene.

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In mid-August a different red influent appeared at the
treatment plant; i:t was bright pink and not very
turbid.  The pink sample.was extracted with chloroform
and chromatographed on a thin layer plate.  The single
intense pink spot matched a Ehodamine B standard spot
in both retention time and the brilliant orange fluo-
rescence observed under ultraviolet light.  After
elution from the TLC adsorbent, the pink material was
examined by ultraviolet (UV) and infrared (IR) spectro-
scopy; these spectra were identical with standard
spectra.  The influent sample contained approximately
1 mg Rhodamine B/&, calculated from UV measurements.

Rhodamine B is a common dye for a variety of materials:
textiles, paper, leather, China clay, crayons, feathers,
inks, lacquers, drugs, cosmetics, and various food-
stuffs.  Three possible sources in the Springfield area
were a pharmaceutical firm, a paint and lacquer firm,
and a paper cup manufacturer.  The paper cup manufac-
turing plant was the suspected source because the
company began using a particular red ink about the time
the treatment plant began experiencing occasional
difficulties.

When a third red color incident occurred in April 1972
treatment plant officials obtained another influent
sample and a red ink sample from the paper cup manu-
facturing plant.  The ink trade name was not available,
but manufacturing plant officials stated that it did
not contain Rhodamine B.

Methanol solutions were prepared for the red material
filtered from influent sample  (SR-1) and for the red
paper cup ink  (PCI).  After concentration to a low
volume, each methanol solution was examined with TLC.
The PCI chromatogram produced five spots after develop-
ment with ethanol.  Sample SR-1 also produced five
spots, but most of them were different from the PCI
spots.  Sample SR-l's major component, an orange-brown
spot with no fluorescence, matched in retention time,
color, and lack of fluorescence a medium intensity
spot in Sample PCI.  Some orange-brown material from
each sample was separated with preparative TLC,
dissolved in methanol, and analyzed with visible
spectrophotometry.  The visible spectra matched
perfectly, both absorbing between 450 and 510 nm with

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 a broad maximum  from  480  to  410 nm.  Another SR-1
 component,  a visible  peach-colored spot  (brilliant
 greenish yellow  fluorescence in ultraviolet light)
 matched in  color,  fluorescence, and  TLC  retention time
 a less intense spot in  PCI.   This evidence indicated
 that  two of the  main  components in the red sewage
 sample, SR-1, could have  originated  from the paper  cup
 ink,  PCI.   Sample  differences shown  by TLC could have
 been  caused by biological or chemical degradation of
 PCI to SR-1.

 Apparently  there was  no connection between any  of the
 three occurrences  of  red  treatment plant influent
 (cheese coloring,  Rhodamine  B,  and paper cup ink).  The
 source of Rhodamine B was never determined.  Paper  cup
 manufacturing plant officials were given the evidence
 that  the paper cup ink  had some of the same properties
 as the last red  material  in  the treatment plant
 influent.   Since then no  operational problems have  been
 caused by red materials in the Springfield treatment
 plant influent.

 Later in April 1972,  another color problem occurred at
 the Springfield  municipal treatment  plant; this time
 the influent was blue.  The  color was non-extractable
 with  organic solvents and appeared to be due to floc-
 culent material  that  gradually settled out and  deposited
 on the sides of  the plastic  sample container.   The
 colored solid was  removed from the sides  of the
 container with concentrated  sulfuric acid, the  only
 liquid found to  dissolve  the solid.  These properties
 suggested that the material  might be a phthalocyanine
 pigment, which is often used as the blue pigment in
 paints.  After receiving  this information, treatment
 plant officials  obtained  a sample from a paint manu-
 facturer that was suspected  to be the source of the
 blue  colored material.

 Both  suspect and sewage pigments dissolved only in
 concentrated sulfuric acid, produced an olive color in
 solution, and precipitated upon dilution  with water.
According to the Color  Index1, copper phthalocyanine
has all of these properties.   Spark source mass  spectro-
metry showed that the influent pigment contained copper.
Analysis of the suspect blue  pigment  by low resolution
electron impact mass  spectrometry  (MS)  produced  a mass

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spectrum  (Figure 1) corresponding to that expected for
copper phthalocyanine; its unique feature was the
parent ion cluster with molecular ions at m/e 575 and
577 in the ratio of 2:1, the natural abundance of "cu
to °->Cu.  The mass spectrum of the suspect blue pigment
matched that of the blue pigment from the sewage plant
influent.

A sample of copper phthalocyanine was synthesized in
the laboratory by reacting phthalonitrile with copper.
The mass spectrum of the synthetic sample matched those
of the suspect and influent pigments.

Treatment plant officials presented this information
to the paint manufacturing company officials, who
admitted their use of copper phthalocyanine.  No more
blue material has appeared in treatment plant influent.

ORGANIC POLLUTANTS ASSOCIATED WITH POWER PLANT COOLING
WATER

The Houston Ship Channel, which receives many industrial
discharges, is the source of cooling water for a large
power generating plant.  Cooling water flows through a
canal to the oil-fired power generating plant and is
discharged into a nearby bay adjacent to important
shrimp-producing estuaries (Figure 2).  Present dis-
charges may be detrimental to receiving water quality,
and even larger volumes of cooling water will be required
for planned power plant expansion.  The Environmental
Protection Agency  (EPA) needed data to evaluate biologic
and hydrologic studies prepared by power plant officials.
The NWCCRP was requested by the EPA1s Office of Standards
and Enforcement, Washington, B.C. to identify specific
organic contaminants by combined gas chromatography-
mass spectrometry  (GC-MS) and to qualitatively compare
samples by gas chromatographic (GC)  fingerprinting to
establish relative degrees of pollution.

Samples were collected from nine sites  (Table 1) during
a four day period, stored in 5-gal.  plastic containers
on ice until received at a mobile laboratory, and kept
frozen until extracted.  A blank sample (10 & distilled
water) was also stored frozen in a 5-gal. plastic
container for six days and extracted and analyzed by
the same procedure used for the samples.  Each sample

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00
» *
                                    wilf»pTsn»T«""u
   Figure 1.  Mass Spectrum of Suspect Blue Pigment, Identified as  Copper
             Phthalocyanine

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                         POWER PLANT SAMPLING AREA
                                                   PROPOSED COOLING POND
                                 COOLING WATER
                                 DISCHARGE CANAL
                                                  18
COOLING
WATER
INTAKE
                                                      COOLING WATER
                                                      DISCHARGE
                                                                   23
                                                       21
                                                 TRINITY BAY
                            \
                              \
                              V HOUSTON SHIP CHANNEL

                                \
                                 \
                                            t
                                                                                 N
                                                                        O  1  2  3 4  5
Figure  2.   Map of  Texas Power Generating Plant  Sampling Area

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                          Table  1

           Collection Sites  for  Samples  Analyzed
                        at the SERL
Sample #                   Collection Site

    1       Dredged shipping channel  water  collected at
            center of channel near  dredged  intake
            canal

    4       Water collected at mouth  of dredged cooling
            system intake  canal

    6       Bayou water collected 50  ft downstream
            (south)  from intersection of bayou and
            cooling system intake canal

    7       Bayou water collected 50  ft upstream (north)
            from intersection of bayou and  cooling
            system intake  canal

    8       Bayou water collected 50  ft downstream of
            power plant cooling system intake

   17       Bay water collected 0.5 mi due  south of
            cooling water  canal discharge point

   18       Bay water collected 1 mi  due south of
            cooling water  canal discharge point

   21       Bay water collected from  center of bay
            approximately  5 mi southeast of cooling
            water canal discharge point

   23       Bay water collected near  river  mouth
            approximately  5 mi northeast of site 21
                           10

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was made acidic and extracted with chloroform to obtain
neutral and acidic materials; the water layer from this
extraction was made basic and extracted again with
chloroform to obtain basic materials.  Each extract
(3200 ml total) was concentrated to about 3 ml, stored
in a vial, and shipped on dry ice to the SEEL.  A
second extraction procedure^ was used to separate
acidic and neutral organics.  To allow GC analyses,
acidic materials were converted to methyl esters or
ethers with diazomethane.3  The volume of each extract
was reduced to 50 y£, and a 2-y£ aliquot was injected
into the GC to be separated on a 50-ft Carbowax 20M-TPA
SCOT column.  For GC-MS analyses sample volumes were
reduced as necessary for sensitivity requirements.

Few organic compounds were specifically identified.
Computer reconstructed gas chromatograms (RGC) of
neutral, acidic, and basic fractions of cooling system
influent (sample #8), bay water collected 0.5 mi south
of cooling water discharge point (sample #17), and the
blank are shown in Figures 3-5.  The blank fractions
contained several organic compounds; peaks corres-
ponding to blank compounds are shaded in each sample
RGC.  Some of these organics were identified from their
mass spectra.  In the blank fractions most of the wide
peaks with longer retention times are plasticizers
(phthalate and adipate esters) that were probably
introduced during laboratory procedures.  Other peaks
are due to solvent impurities and artifacts produced
during methylation of the acid fractions.

Comparison of mass spectra and GC retention times
showed that several compounds were present in the
samples that were not present in the blank.  Mass
spectra of compounds unique to sample fractions were
compared with mass spectra in data collections that
contained spectra of approximately 17,000 compounds.

In the neutral fraction of the cooling system influent
(sample #8, Figure 3) triethyl phosphate and benzo-
thiazole were identified; they were not found in
neutral fractions of either the blank or the bay sample
(#17)  collected 0.5 mi from the discharge point.
Comparison of sample and standard GC peak heights
indicated the concentration of each was approximately
         Azulene and 1- and 2-methylnaphthalene were

                           11

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 8-N
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                                                              pe^ona^suooaa
                                                      • ACYCLIC ALIPHATIC
                                                                      I 90 S10 'SB fcb &W ESS SBB 5» SBB S3) SCO 610 KO
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               i» no 13 isn i
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                     iw 160 110 100 iso

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     >' '..'
          ' U' L W U1 !.'
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    ftiL
     17-A
                                                       tw W «o w V™ '«> '
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   17-B
  BLANK-B
                        ISB ao zia aai an » si a» z» » 230 »
Figure 5.   Computer Reconstructed Gas Chromatograras of Basic Fractions  of
           Samples  #8,  #17,  and Blank.   (Shaded Peaks Were in Blank.)

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identified in the bay sample neutral fraction  (Figure
3).  No spectral matches were found for the other
neutral water pollutants represented by unshaded peaks.
Several acyclic aliphatics  (peaks indicated in Figure
6) were probably alkanes- or oxygenated alkanes but were
not specifically identified.  The neutral fraction of
a bay water sample collected 1 mi South of cooling
water canal discharge point  (#18) contained triethyl
phosphate  (a compound also identified in the influent
sample), two dichloro biphenyl isomers, and two ethyl
esters of long chain saturated acids.  Exact structures
of the latter four compounds were not determined.

Although water pollutants in acid fractions of the
influent and bay water sample #17 (Figure 4) were not
specifically identified, the chromatograms show that
the bay sample  (#17) contained fewer organics in lower
concentrations than the cooling system influent  (#8).

The basic fraction of the influent  (sample #8) contained
few organic compounds not present in the blank (Figure
5) ; bay sample #17 contained more organic compounds
than the influent sample.  The basic pollutants were
not identified.

Comparison of flame ionization gas chromatograms of
neutral fractions of samples #1, #6, #7, #8, #18, and
#23 indicated the relative organic content of waters
from different areas (collection sites in Figure 2).
Peaks also found in the blank are shaded in the sample
chromatograms (Figures 6 and 7).

This organic pollutant information was reported to the
EPA Region VI Enforcement Division for inclusion with
other analytical data (such as dissolved oxygen, total
organic carbon, metals, total residue, total and
Kjeldahl nitrogen, sulfates, salinity, pH, temperature,
chlorides, chlorinated hydrocarbons, and various
biological parameters), which were obtained from other
EPA laboratories.

A report was prepared to support litigation.  However,
in January 1973 the issue was settled out of court
when power plant officials agreed to monitor chemical
and biological parameters of discharged cooling water
and Trinity Bay water.

                            15

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                                                   r~ r
Figure 6.   Gas Chromatograms  (FID) of Neutral Fractions
           of Samples #6, #7, and #8.  Shaded Peaks
           Were Also in Blank Chromatogram.
                            16

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  23-N
Figure 7.
Gas Chromatograms  (FID) of Neutral Fractions
of Samples #1,  #18,  and #23.   (Shaded Peaks
Were Also in Blank.)

                 17

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WESTERN LOUISIANA INDUSTRIAL WASTE SURVEY

In April  1971, the EPA Division of Field Investigations,
Denver, Colorado, requested the NWCCRP to characterize
chemically  a number of industrial effluents from an
industrialized area in western Louisiana.  One liter
of each effluent sample was extracted with chloroform,
and  an aliquot of each concentrated extract was injec-
ted  into  a  gas chromatograph to establish optimum  GC
conditions.  Analyses with the Hitachi-Perkin-Elmer
RMU-7 GC-MS, a non-computer-controlled system, provided
50 identifications  for compounds  in seven different
industrial  effluents.4  Some compounds occurred in more
than one  effluent.

The  most  complex mixture  of organic compounds was
found in  the effluent from a petrochemical company that
produces  olefins and  oxygenated hydrocarbons.  Plant
effluent, estimated to be 4,000,000 gal/day, flows
through three treatment ponds connected in series  and
is discharged into a  bayou.  Samples were collected
where the treated effluent entered the bayou.  Initial
analysis  of this effluent with the non-computer-
controlled  GC-MS system provided  identifications of
14 compounds (Figure  8).

After the NWCCRP obtained a Finnigan 1015 GC-MS-
computer  system, the  sample was analyzed again in
February  1972.  As GC peaks eluted, mass spectra were
collected continuously and stored in the computer  for
later output in tabular or plotted form.  Appropriate
spectra from the RGC  (Figure 9)  provided fragmentation
patterns of compounds not previously identified.
Computer matching of  these unknown spectra with stan-
dard spectra in a central data bank located in a large
computer  at the Battelle  Research Institute, Columbus,
Ohio,^ provided identifications for 15 additional
components.  The improved data handling capability of
the computer-controlled system allowed the chemist to
identify  another eight components.  A total of 37
different compounds were  identified in the treated
effluent of this one point (Table 2).  All major
components  and more than  70% of all peaks and shoulders
in the chromatogram were  specifically identified.   ine
impact of each of these compounds on water quality  has
not yet been determined,  but polycyclic aromatics such

                           18

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          93.9  CITIES SERVICE PETROCHEMICAL
          50' S.C.O.T CARBOWAX 20M-TPA
          70° ISO. / 2 MIN.; PROGRAM -» 200° AT &°/ MIN.
                             10   12
                           MINUTES
14
Figure 8.  Chemically  Characterized Gas Chromatogram
           of Petrochemical Company Effluent
                             19

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  P_
     102030189068108030
                             140 195 160 170 1BO 190 200 210 220 230 210
Figure 9.   Computer  Reconstructed Gas Chromatogram of the  Chloroform
            Extract of  Petrochemical Company Effluent

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                          Table 2

         Compounds Identified in Petrochemical
                    Company Effluent
RGC Spectrum ia
     Compound Name
       2
       4
      10
      16
      29
      36
      47
      65
      70
      75
      86
      89
     109
     121
     129
     140
     145
     156
     160
     168
     177
     193
     202
     206
     210
     221
     233
     233
     244
     249
     256
     265
     278
     287
     292
     296
     356
m-xylene*k
p-xylene*k
1, 5-cyclopctadiene
o-xylene*
isopropylbenzene  (cumene)
styrene*b
o-ethyltoluene
o-methylstyrene*
diacetone alcohol
indan*b
2-butoxyethanol
3-methylstyrene
indene*^
dimethylfuran isomer
n-pentadecane
1-methylindene*
3-methylindene
acetophenone
n-hexadecane
a-tepineol
naphthalene*
a-methylbenzyl alcohol
2-me thyInaphthalene *k
benzyl alcohol
1-me thyInaphthalene*
ethylnaphthalene isomer
2,6-dimethylnaphthalene*b
phenol*
methylethylnaphthalene isomer
eresol isomer
acenaphthene
acenaphthalene
methylbiphenyl isomer
fluorene
phthalate diester
3 ,3-diphenylpropanol
phthalate diester
     aFrom Figure 9
     "Compounds identified with mass spectra from non-
computer-controlled GC-MS system.
                           21

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 as  indenes and naphthalenes are known to be odor
 sources^  and could cause odor problems  in drinking
 water.

 At  an EPA water quality enforcement conference these
 identifications provided specific information about
 the effectiveness of the petrochemical  company's
 waste water treatment.

 POLYCHLORINATED BIPHENYLS IN INDUSTRIAL EFFLUENT

 An  Alabama plant that manufactures organophosphorus
 pesticides, PCB's, and chlorinated hydrocarbons used
 as  intermediates in the chemical industry was suspected
 to  be a source of polychlorinated biphenyl  (PCB)
 contamination.  Effluent samples were collected and
 analyzed  by electron capture gas chromatography;
 retention times of the observed GC peaks indicated the
 presence  of PCB's.  To confirm this identification,
 the EPA Region IV Surveillance and Analysis Division
 requested the NWCCRP to analyze a sample by combined
 GC-MS.

 An  initial run of the computer-controlled GC-MS system
 gave the  RGC shown in Figure 10.  Major peaks eluting
 before the peak represented by spectrum #15 were
 readily identified as chlorobenzenes and monochloro-
 biphenyls.  Mass spectra of peaks with  longer retention
 times suggested the presence of chlorinated biphenyls.
 However,  ions from column bleed and from non-PCB
 sample components prevented the acquisition of an RGC
 comparable to the electron capture chromatogram.

 To  circumvent this interference, blank  scans were made
 at  highest instrument sensitivity to determine any
 significant column bleed and instrument background ions
 in  the hexachlorobiphenyl molecular ion region.  In a
 second data acquisition run, the computer was instructed
 to monitor only ions in the hexachlorobiphenyl molecular
 ion region but to ignore all significant masses noted
 in  the blank scans.  The RGC obtained from the second
 data run  (Figure 11)  was comparable to  the electron
 capture chromatogram.  This comparison  and the
 chromatographic data indicated the effluent PCB content
was approximately 0.5 ygA.

                           22

-------
       INDUSTRIAL  PLANT  EFFLUENT
  8
  »•*-•

  8.

  8_
s8-
1?.
        102030^9060708090

      SPECTRUM NUMBER
                           100 110  120 130  110 193  160 170  180 193  200 210 220 230 2
-------
NJ
       0    10   20   30   40
            SPECTRUM NIM?€R
   Figure 11.   Computer Reconstructed Gas Chromatogram of the Hexachloro-
               biphenyl Molecular Ion Region of a Manufacturing Plant Effluent

-------
During toxicity studies conducted by the Region IV
Surveillance and Analysis Division, caged catfish
that were placed in the plant effluent died within 24
hours.  The plant effluent flowed into Snow Creek and
on into Choccolocco Creek; catfish survived in Chocco-
locco Creek but tissue analyses showed that PCB's had
been absorbed from the water.

The manufacturer has voluntarily limited production
and use of PCB's.

ORGANIC POLLUTANTS IN INDUSTRIALIZED SHIPPING CHANNEL

The EPA's National Field Investigations Center, Denver,
Colorado, requested identifications of major organic
pollutants in the Houston Ship Channel for an enforce-
ment conference concerning pollution of the Channel
and Calveston Bay.  The Houston Ship Channel probably
contains the largest concentration of industrial
effluents of any small channel in the United States;
250 major industries dump their effluents there.
Channel waters flow into Galveston Bay, an important
shrimp nursery and oyster bed along the Gulf of Mexico.
The Channel was suspected to be the source of several
polyaromatic compounds that had been isolated and
identified in Galveston Bay oysters by workers at the
Woods Hole Institute.

A 0.5-gal. water sample was collected at each of four
sites along the Channel, frozen, and shipped to SERL.
A 1-H aliquot of each sample was extracted with a
total of 600 ml chloroform, and the extract was concen-
trated in a Kuderna-Danish apparatus to about 0.1 ml.
Gas chromatographic analysis showed that all four
samples contained essentially the same compounds, but
their concentrations increased as distance upstream
from the Channel mouth increased.

The most concentrated sample (#97.4), which was taken
18 miles upstream from the Channel mouth, was analyzed
by computer-controlled GC-MS.  The RGC (Figure 12)
indicates the large number of organic compounds
contained in this sample.  A limited mass RGC that
enhanced peaks containing aromatic compounds showed
that only mass spectra 111, 177, 195, 219, 295, and
340 contained mass fragments characteristic of phenyl

                           25

-------
          HOUSTON SHIP CHANNEL SAMPLE EXTRACT
     18 30  38 10 SO  SO
     SPECTRUM NUMBER
                        93 183  118 120 138 1« 138 ISO 178 190 138 208 218 228 Z30 210 S3 Z60 ZKS 2B8 230 383 310 328 33} 3*3 338 360 370 380 338 *O 118
Figure 12.   Computer Reconstructed Gas:Chromatogram of  Houston  Ship
              Channel Water  Sample

-------
compounds  (m/e 77 and 78).  The very minor sample
component represented by  spectrum 111 was acetophenone,
the only aromatic compound identified.  Spectra 177,
195, and 219 represented  small amounts of mixtures of
aliphatic and aromatic compounds.  None of the poly-
aromatic compounds identified in Galveston Bay oysters
was found in the Channel  sample.

Most of the organic compounds extracted from Sample
#97.4 were aliphatic hydrocarbons (spectra 18, 28, 43,
54, 66, 82, 108, 117, 130, 136, 157, 162, and 170).
Their GC retention times  did not correspond to those of
n-alkane standards, and no attempt was made to speci-
fically identify them as  branched isomers.  Spectra
187 and 211 were due to unresolved alkane mixtures.
Spectrum 411 was possibly due to caffeine, and spectrum
204 was due to an unsaturated hydrocarbon that was not
specifically identified.

In another attempt to find aromatic compounds, liquid
chromatographic analysis  of the most concentrated
sample  (#97.4) showed- four peaks whose retention times
did not match any of the  polyaromatic compounds
previously identified in  Galveston Bay oysters.

Although no link was found between the oyster contami-
nants and Channel pollutants, this characterization
information was used as background material for an
Enforcement Conference held in November 1971.  The
conference led to a clean-up schedule and allocation
of industrial waste loads to be dumped into the
Houston Ship Channel.

TASTE AND ODOR PROBLEMS IN MUNICIPAL WATER SUPPLY

The EPA's Lower Mississippi River Field Facility
(LMRFF)  requested assistance with correlation of
drinking water contaminants and industrial effluent
components.  Taste and problems have long been
associated with the drinking water of New Orleans
and other municipalities  that use the Lower Mississippi
River as their water source.  Several manufacturing
plants along the river were suspected to be sources of
organic compounds causing these problems.  The NWCCRP's
GC-MS system had proven to be a powerful tool for

                           27

-------
studying this type problem, but such a system was not
available at the LMEFF laboratory.

GC-MS analysis of the carbon-chloroform extract of a
New Orleans finished water sample produced identifi-
cations of five compounds:  2-benzothiazole, 2-ethyl-
hexanol, veratrole, camphor, and isoborneol (Figure 13).
2-Benzothiazole is often used in the synthetic rubber
industry and has a strong odor very similar to that of
rubber cement used to patch holes in rubber tires.
This compound could cause a significant taste and odor
problem.  2-Ethylhexanol probably does not cause
taste and odor problems but was one of the extract's
major components.  Veratrole, camphor, and isoborneol
are terpenes, common components of paper mill waste
effluent, and could have contributed to the taste and
odor problem.

Ether extracts of effluents from two upriver paper
mills were also examined by GC and GC-MS to learn if
chemicals from these mills were contributing to the
taste and odor problems in the New Orleans drinking
water.  Veratrole was identified and confirmed in both
paper mill effluents.  Camphor was found in one paper
mill effluent; it was believed to be present in the
other effluent but was present in such small quantity
that it could not be identified with certainty.
Although an isoborneol standard had the same GC
retention time as a small peak in one paper mill
effluent, the mass spectra did not match.  Isoborneol
was not found in either plant effluent.

This project emphasized that GC identifications of
compounds from complex mixtures should always be
confirmed by MS or some other physical/chemical method.
GC evidence indicated that the finished water contained
three terpenes that had been identified by GC-MS in
one or both paper mill effluents.

     •  GC retention times of these three terpenes
        (guaiacol, a-terpineol, and borneol) matched
        retention times of three peaks in the paper
        mill effluents (Table 3).

     •  Drinking water extracts spiked with small
        amounts of these three terpene standards

                           28

-------
       Table 3.  GC AND GC-MS ANALYSES OF TERPENES
                Carbon Chloroform Extract
                    of Finished Water
                Presence Indicated             Presence
   Chemical     	by GCa	            Confirmed
              Carbowax 20-M&SE-30b          by GC-MS
Camphor              +          +                 +c
Veratrole            +          +                 +
Guaiacol             -          +
a-Terpineol          +          +                 -
Borneol              +          +
Isoborneol           +          +                 +c
                  Paper Mill "A" Effluent
Camphor
Veratrole
Guaiacol
a-Terpineol
Borneol
Isoborneol
                  Paper Mill "B" Effluent
Camphor              +          +                 +c
Veratrole            +                            +
Guaiacol             +          +                 +
a-Terpineol          +          +
Borneol                         ~                 ~
Isoborneol           -                            ~

aRetention times were not relied on alone—sample was
 spiked with small amounts of-standards to produce
 superimposed peaks.
b50' Support coated open tubular column
GSample peak very small—major fragmentations of stan-
 dard were present along with extraneous fragment ions
 from an unknown contaminant.  Background was subtracted
 from the spectrum.
                            29

-------
024
24   26
MINUTES
Figure 13.  Gas Chromatogram of New Orleans Drinking  Water Extract

-------
        produced chromatograms containing super-
        imposed peaks.

     •  On two different 50-ft. SCOT columns  (Carbowax
        20M and SE-30) retention times of two of
        these terpenes matched retention times of
        extract peaks.

However, comparison of mass spectra showed that none of
these three terpenes was present in the finished water
extract.

ORGANIC COMPONENTS OF LABORATORY WASTE WATER

As part of an investigation of the content of the SERL's
waste effluent, the NWCCRP analyzed laboratory sewage
samples for organic content.  The chloroform extract of
a 1500-ml sample of filtered raw sewage was concentrated
and analyzed by GC-MS.  One laboratory sewage sample
contained 2-ethyl-l-hexanol as a major component and
phenol as a minor component.  A sample taken on a
different day contained isopentyl alcohol and a trace
of 2-ethyl-l-hexanol.  Mass spectra also indicated the
presence of several long-chain hydrocarbons, but
specific compounds were not identified.  About a dozen
other peaks were observed in each sample but were not
identified either by the computerized mass spectral
library or by manual inspection.

In addition to the sewage samples and a tap water blank,
a sample of tap water spiked with several common labora-
tory solvents and chemicals (1 mg/2.) was analyzed.
Solvents, such as carbon tetrachloride, hexane, benzene,
acetone and isooctane, that are known to be discharged
into the laboratory waste lines were not detected in
the spiked water.  Less volatile materials, such as
chlorobenzene, para-dichlorobenzene (a common toilet
bowl odor masking agent), 2-chloroaniline and meta-
cresol, were easily detected at this level.

Organic contaminant data were reported to the Region
IV Surveillance and Analysis Division for inclusion in
a summary of the SERL's waste effluent content.
                            31

-------
POLYCHLORINATED BIPHENYLS IN POULTRY FAT

The U. S. Department of Agriculture requested analyses
of poultry fat for contamination by polychlorinated
biphenyls (PCB's).  Fish meal that is used for poultry
feed was contaminated when PCB's used as heat exchange
material leaked from a corroded coil in the fish meal
processing plant.  The leakage occurred over a rela-
tively long period of time and was not noticed until
a poultry grower noted a reduction from 90% to 2% in
the hatch rate of his eggs after his breeder fowl were
fed contaminated fish meal.  The Department of Agricul-
ture estimated that 60 million animals (fowl and pigs)
had been exposed to contaminated feed and obtained 1400
samples from poultry growers and processing plants in
the southeastern United States.  The NWCCRP was
requested to assist with analyses to determine if a
5 yg/g permissible limit of PCB content in the fat had
been exceeded.

Using a gas chromatographic method, ^ SERL personnel
analyzed 85 samples in two weeks in August and
September 1971.  Results were reported directly to
the U. S. Department of Agriculture for compilation
with analyses from other laboratories.

To assure comparable results, all participating labs
used the same method.  Each sample was dissolved in
petroleum ether and extracted with acetonitrile.  Each
acetonitrile extract was diluted with water to
partition PCB's into petroleum ether.  After each
extract was purified by Florisil column chromatography,
gas chromatography was used to quantitatively determine
the extract's PCB content.

In September 1972, the U. S. Department of Agriculture
issued a press release stating results of the testing
in the Southeast.  High levels of PCB's reported by
SERL and other cooperating laboratories caused
condemnation and destruction of 165,000 hens and
broilers, 250,000 Ib of turkey product, and 75,000 Ib
of chicken product.  Other poultry was judged accepta-
ble only for salvage; it could be used only after fat
and bone were removed.  However, in many cases
processing costs made the salvaged product so expensive
that no buyers could be found, and little of the

                            32

-------
salvaged poultry was actually used.  No figures were
available to show the total poultry loss due to PCB
contamination.

TITANIUM IN PAINT MANUFACTURING PLANT EFFLUENT

Titanium in a Florida paint manufacturing plant
effluent was quantitatively measured by polarography.
This analysis was requested by the EPA's Region IV
Surveillance and Analysis Division and was part of a
survey of 36 industrial wastes.  Since titanium salts,
primarily the oxides, are used as paint pigments,
titanium was suspected to be discharged in the plant
effluent.

Each day the paint plant discharged 630 gallons of
effluent into a septic tank from which pollutants could
enter the ground water via a drainfield.  The murky,
liquid sample that was taken from the septic tank con-
tained a large proportion of dense, white sediment.
Specimens of the well-mixed sample were ashed, fused
with potassium bisulfate, and leached with 0.5 M sul-
furic acid.  Titanium was determined by DC polarography
at the dropping mercury electrode in 1 M phosphoric acid
supporting electrolyte.  The total sample contained
1439 mg/£ titanium calculated as titanium oxide (2350
mg/£).  With a water discharge rate of 630 gal/day,
the plant was discharging titanium at a rate of 7.5 lb/
day.  The plant effluent also contained significant
amounts of mercury (3.9 mg/£, determined by another
EPA laboratory).

These analyses were included in the "Industrial Waste
Survey of Dade County, Florida,"^ and in information
presented at an enforcement conference concerning the
pollution of navigable waters of Dade County, Florida,
in November 1971.  After being informed of the results
of the survey, plant officials agreed to recycle waste
waters to recover the metal salts to eliminate the
use of mercury as a fungicide in their paint.

ZINC IN METAL FINISHING PLANT EFFLUENT

Polarographic determination of the zinc content of a
metal finishing plant effluent helped resolve

                            33

-------
analytical discrepancies between the-plant's labora-
tory methods and Tennessee State Pollution Control
methods.  The plant's polarographic analyses indicated
that little or no zinc was discharged in the effluent.
Tennessee state officials requested the EPA's Region IV
Surveillance and Analysis Division to determine the
effluent's zinc content.  Analysis by atomic absorption
spectrophotometry showed zinc content of 0.6 mg/£.  To
check this analysis/ the NWCCRP was requested to
determine zinc content by polarography, since this
method was used by the plant's laboratory.

In six samples, polarographic data showed that zinc
concentration ranged from 0.002 to 0.2 mg/£, signifi-
cantly lower than atomic absorption data.  However,
after the samples were wet-ashed with HNC>3-HC104,
polarographic analysis showed zinc content of 0.54 mg/5,
(standard deviation of 0.03 mg/&), a value comparable
to that obtained with atomic absorption.  The EPA
chemists concluded that zinc in the effluent existed
as organic complexes, which could not be determined
polarographically without special analytical procedures.
The plant revised its laboratory methods to produce
accurate values for evaluation of its water treatment
system.

TRANSITION ELEMENTS IN CLAY MINERALS

Transition element qualitative analysis aided the
SERL's Agricultural and Industrial Pollution Control
Research Program scientists to interpret electronic
absorption spectra of clay minerals.  These spectra
were being used to elucidate structural, physical,
and chemical properties of clay minerals.

In the ultraviolet-visible range (195-800 nm), clay
mineral spectra contain absorption bands that are due
to the presence of transition metal cations.  Observed
adsorption bands had been assigned to iron-associated
electronic transitions.  Since other transition metals
interfere with iron-induced bands, the NWCCRP was
requested to analyze samples of two clay minerals,
Wyoming bentonite and nontronite, to determine if
transition elements other than iron were present.
Spark source mass spectrometric analysis showed impuri-
ties of nickel, chromium, titanium and zinc.

                            34

-------
CADMIUM AND NICKEL IN BATTERY MANUFACTURING PLANT
EFFLUENT

For 12 years a battery manufacturing plant had dumped
its untreated effluent into New York's Foundry Cove,
whose waters flow into the Hudson River.  After
receiving the EPA's notification to discontinue
discharge, the company began treating its waste water
but resisted the EPA1s demands to dredge Foundry Cove
to remove sediments containing cadmium and nickel.  In
a legal hearing the company argued that any inorganic
materials left in sediments were highly insoluble in
water and would not affect biota.  Although no obvious
damage had been done to flora and fauna, the EPA con-
tended that many cadmium and nickel salts are soluble
in water and that even insoluble compounds could be
resuspended by water agitation or could degrade and
enter the aquatic system.  The judge ruled that the
EPA had insufficient evidence to force dredging.

The EPA Region II Enforcement Division sought proof that
cadmium and nickel were present in dangerous quantities
in the water and sediment.  Analyses performed by the
EPA's Edison Water Quality Laboratory, Edison, New
Jersey, showed the presence of cadmium residues in fish
tissue and aquatic plants from the area.  Atomic
absorption analyses showed that water and sediment
samples contained unacceptable amounts of cadmium.
To have irrefutable evidence for the appeal hearing,
the Edison laboratory requested confirmatory analyses
by the NWCCRP.

The cadmium content of two water samples was determined
by four unrelated analytical techniques:  neutron
activation, spark source mass spectrometry, polaro-
graphy, and atomic absorption spectrophotometry  (Table
4).  Atomic absorption data agreed well with those
reported by the Edison laboratory.  Neutron activation
and spark source mass spectrometry confirmed atomic
absorption analyses for sample #20039 but produced
different values for sample #20046.  These differences
and the polarographic data suggested that interfering
substances might be present in sample #20046 or that
sample preparation techniques might require revision.
                            35

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          Table  4.   CADMIUM CONTENT  OF  FOUNDRY  COVE WATER AND SEDIMENT SAMPLES
                                      Water  Samples
                 Sediment Samples
CO
Sample No.

Atomic Absorption
  Edison Lab.
  NWCCRP

Polarography
  acid-digested
  fine-filtered
                                   20039
                                   230  yg/Ji
                                   180  yg/£
                                   22
                                   15  yg/£
   Neutron Activation              180  yg/Jl

   Spark Source Mass Spectrometry  180  yg/£
20046
23 yg/Ji
20 yg/£
15004
not detect.*

67 yg/£       <10 mg/kg

5 yg/£        0.06 mg/kg
15043
0.8 mgAg    17000 mg/kg
             2000 mg/kg

             1000
   "detection limit:  1 yg/£

-------
Two sediment samples that had been analyzed by atomic
absorption spectrophotometry at the Edison laboratory
were also analyzed for nickel and cadmium content by
the NWCCRP with spark source mass spectrometry-   Atomic
absorption nickel were confirmed  (Table 5), but lower
cadmium concentrations (Table 4) were found with spark
source than with atomic absorption.

                        Table 5

            Nickel Content of Foundry Cove
                   Sediment Samples

Sample                     15004           15043

Atomic Absorption        100 rag/kg       8800 mg/kg
   (Edison Lab.)

Spark Source             140 mg/kg       4000 mg/kg
  Mass Spectrometry

Even the lower values indicated that cadmium and
nickel concentrations in sediment and water samples
were unacceptable.  In humans, heavy metals concentrate
in the liver, kidneys, and pancreas and are not
normally excreted after ingestion.  Quantitative data
on cadmium toxicity indicate that the lethal concen-
tration for fish varies from 0.01 to 10 mg/a, depending
on fish species, water type, temperature, and exposure
time.^  Much less toxicity data exists for nickel than
for cadmium, but nickel toxicity to man is believed to
be very low- 0

The data were presented at an appeal hearing, which
produced a court order to force the manufacturer to
dredge certain areas of Foundry Cove.  Dredged sediment
was piled on the ground, and cadmium and nickel were
extracted.  Dredging was completed in September 1972.

ARSENIC IN GOLD MINE TAILINGS AND WASTE WATER

Since the early 1900's, mine tailings and waste waters
from North America's largest gold mine, located in
South Dakota, were discharged into Whitewood Creek.
After flowing through the Belle Fourche and Cheyenne

                            37

-------
River, water from Whitewood Creek eventually reaches
the Oahe Reservoir about 150 miles away (Figure 14).

Because of the type of ore being processed, the EPA's
Denver National Field Investigation Center suspected
that large amounts of arsenic were being released into
these waters.  However, they did not have adequate
facilities for arsenic analyses and requested neutron
activation analyses by the NWCCRP.  One sample of
pulverized mine ore and four well water samples were
included with 21 water samples and 13 sediment samples
collected from various locations on Whitewood Creek,
Belle Fourche River, Cheyenne River, Oahe Reservoir,
and various small tributaries.

Water samples that contained suspended matter were
filtered to allow analyses of water and residue
separately.  Each water .sample and a standard arsenic
solution were irradiated in a 1-Mw nuclear reactor with
a thermal neutron flux of about 1 x 10^^ neutrons/sec/
cm^ for 30 min.  When 24jja background radiation had
decreased to tolerable levels (usually 1-3 days), the
level of 559-keV gamma photon radiation from each
sample and its corresponding standard was measured
with a Ge(Li) detector.  From these measurements
arsenic concentrations were calculated (Table 6).  The
arsenic content of six water samples was confirmed by
spark source mass spectrometry (Table 6).

Solids filtered from water samples were left at room
temperature on the filter papers until dry.  Aliquots
of sediment samples with uniform texture were analyzed
without treatment.  Two sediment samples with varying
particle size  (dust to rocks) were sieved, and only
particles with diameter less than 0.026 in. were
irradiated.

Subsequent analytical procedures were identical for
water residues and sediment samples.  Each weighed
solid sample and its corresponding standard solution
were irradiated and counted under the same conditions
as used for water samples.  Each of the solid samples
and liquid standards was placed at the detector center
to minimize counting errors caused by sample geometry.

                            38

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                    SAMPLING AREA FOR ARSENIC FROM

                          SOUTH DAKOTA GOLD MINE
                                                                OAHE
                                                                RESERVOIR
Figure 14.   Map of Sampling Area for Arsenic from Gold Mine Tailings
            and Waste Waters

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Table 6.  ARSENIC CONTENT OF WATER SAMPLES
Sample
Number
1425
1435
1424
1431
1419
1433
1436
1437
1438
1422
1429
1423
1421
Sampling
Site
Gold Run below Sand Dam
Gold Run below Sand Dam
Slime Plant
Slime Plant
Whitewood Creek
Whitewood Creek
Whitewood Creek
Whitewood Creek
Whitewood Creek
Elk Creek
Box Elder Creek
Horse Creek
Bear Beetle Creek
Liquid Portion
yg As/£a
NAA SSMS
138
420
27
910
300
1510
1900
970
13
ND
7
ND
ND
143
340
ND
952
230
1420
1270
880
12
ND
ND
ND
ND

321
28

230





ND








900


ND



Solid Portion
mg As/g
NAA SSMS
1
no res
2.72
2.93
—
no res
2.38
2.49
3.67
idue
2.44
2.88
—
>idue
2.52
2.45
3.90
no residue
0.01
—
0.01
—
0.01
--
0.01
—






3.00


0.01




-------
Table 6 (continued).  ARSENIC CONTENT OF WATER SAMPLES
Sample
Number
1418
1420
1432
1427
1428
1434
1426
1430
Sampling
Site
Spearfish Creek
Deadwood Creek
Deadwood Creek
Belle Fourche River
Belle Fourche River
Belle Fourche River
Cheyenne River
Cheyenne River
Liquid Portion
yg As/£a
NAA SSMS
5
8
ND
500
ND
560
210
ND
6
12
ND
425
ND
571
190
ND



450




ND

ND

0.1

100.0

Solid Portion
mg As/g
NAA SSMS
no res.
Ldue
no residue
no residue
0.14
0.01
0.13
0.07
0.12
0.12
0.01
0.12
0.06
0.10




0.08

0.02

dND - not detected

-------
Results of arsenic analyses of the filtered solids
are shown in Table 6, and sediment arsenic analyses in
Table 7.

The four well water samples collected in the vicinity
of Whitewood Creek were also analyzed for arsenic by
neutron activation, but arsenic was not present above
the detection limit of 1 mg/£%

Data from these arsenic analyses and the previous
mercury analyses were presented at a legal hearing in
late 1971, at which the mining company was ordered
to improve waste treatment.  The mine is building a
waste water treatment plant.
                            42

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        Table 7.   ARSENIC CONTENT OF SEDIMENT SAMPLES BY NEUTRON ACTIVATION
Sample
Number
1602
1610a
1617
1611
1608
1621
*> 1609a
U)
1613
1618
1619
1614
1616
1612
1615
Sampling Site
Homestake Mill Feed (pulverized ore)
Whitewood Creek, Gold Run
Whitewood Creek at Rodeo Car
Whitewood Creek near Bell Fourche River
Whitewood Creek at mouth of Belle Fourche River
Whitewood Creek at mouth of Belle Fourche River
Deadwood Creek at mouth of Whitewood Creek
Elk Creek
Box Elder Creek
Bear Beetle
Belle Fourche River
Belle Fourche River
Cheyenne River
Cheyenne River
mg As/g sediment
3.65
0.82
2.20
2.93
4.35
1.19
0.62
0.02
0.02
0.02
3.99
2.36
0.01
0.70
3.32
0.69
2.07
3.27
4.02
1.23
0.79
0.02
0.02
0.02
3.60
2.23
0.01
0.71
4.01
0.83
2.11
4.26
3.73
1.29
0.67
0.02
0.02
0.02
3.98
2.88
0.01
0.73
aSample particle size varied from dust to rocks.   Only particles with
 diameter of less than 0.026 in. were irradiated.

-------
                        SECTION V

                       REFERENCES

1.   Colour Index.   2nd ed.  The Society of'Dyers and
    Colourists and The American Association of Textile
    Chemists and Colorists.   London, Percy Lund,
    Humphries and Co., Ltd., 1956.  Vol. 2, p. 2773.
    Vol. 3, p. 3570.

2.   Braus, H., F.  M.  Middleton, and W.  Walton, Organic
    Chemical Compounds in Raw and Filtered Surface
    Waters.  Anal. Chem. 23:1160-1164,  August 1951.

3.   Webb,-R. G., A. W. Garrison, L. H.  Keith, and J. M.
    McGuire.  Current Practices in GC-MS Analysis of
    Organics in Water.  Environmental Protection Agency,
    Athens, Georgia.   Publication Number EPA-R2-73-277.
    In Press.

4.   Keith, L. H. and S. H. Hercules.  Environmental
    Applications of Advanced Instrumental Analyses:
    Assistance Projects, FY 69-71.  Environmental
    Protection Agency, Athens, Georgia.  Publication
    Number EPA-R2-73-155.  May 1973. pp. 35-50.

5.   Hoyland, J. R. and M. B. Neher.  Implementation of
    a Computer-Based Information System for Mass
    Spectral Identification of Pesticides.  Battelle
    Columbus Laboratories, Columbus, Ohio.  EPA Grant
    #16020 HGD.  Quarterly Report.  January 1972.

6.   Zoeteman, B. C. J., A. J. A. Kraayeveld, and G. J.
    Piet.  Oil Pollution and Drinking Water Odor,
    H20  (Rotterdam).   4 (16)  :367-371.  1971.

7.   Methods for Multiple Residues.  In:  Pesticide
    Analytical Manual.  Vol. 1.  Food and Drug Admini-
    stration, Washington, D. C.  1968.

8.   Industrial Waste Survey of Dade County, Florida.
    Environmental Protection Agency, Athens, Georgia.
    Publication Number EPA-TS03-71-208-03.1.
    September 1971.
                          44

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 9.   Water Quality Criteria.  2nd ed.   California State
     Water Resources Control Board, Sacramento,
     California.  Publication Number 3-A.   April 1971.
     p. 150.

10.   Ibid.  pp. 222-223.
                            45

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                        SECTION VI

                 GLOSSARY OF ABBREVIATIONS


EPA - Environmental Protection Agency

FID - flame ionization detector for gas chromatograph

GC - gas chromatography

GC-MS - combined gas chromatography and mass spectro-
metry

IR - infrared spectroscopy

LMRFF - Lower Mississippi River Field Facility of the
Environmental Protection Agency

MS - mass spectrometry

ND - not detected

NWCCRP - National Water Contaminants Characterization
Research Program at the Southeast Environmental Research
Laboratory

PCB - polychlorinated biphenyls

RGC - computer reconstructed gas chromatogram

SCOT - support coated open tubular columns for gas
chromatography

SERL - Southeast Environmental Research Laboratory

TLC - thin-layer chromatography
                            46

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SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
                                     /. Report No.
                                                      w
.  r...   ENVIRONMENTAL APPLICATIONS OF  ADVANCED         *•
INSTRUMENTAL ANALYSES:  ASSISTANCE PROJECTS, FY 72,  6.
                                                       8.
ALFORD,  A.  L.
National Contaminants Characterization Research
Program, Southeast Environmental  Research
Laboratory
                                                         Report No.
                                                       16020 GHZ
                                                      1.'  Typt ' / Repo , and
                                                         Period Covered
12,
        n. organ; -*tion Environmental  Protection Agency
 Environmental Protection Agency  report number ,
 EPA-660/2-73-013. September 1973.	
 Identification and measurement  of aquatic pollutants are discussed
 under 13 project categories.  In most cases these analyses helped
 to solve, or at least to understand more clearly, the related
 pollution incident and in  some  cases provided evidence for enforcement
 of regulatory legislation.
 173.Descriptors  *Water pollution  sources, *pollutant identification,
 *analytical techniques,  industrial wastes, mine wastes, gas chromato-
 graphy, mass spectrometry, polarographic analysis, neutron activation
 analysis, metals, polychlorinated biphenyls


 irb.  udders atomic absorption  spectrophotometry, infrared spectroscopy,
 ultraviolet spectroscopy, organoleptic compounds
   CO WRR Field £ G :\
                    05A
",• M'-I/I/I •/!•*• 19- Securit v Cl»ss.
(Repot )
~0. Sa -itity d- a.
(Page)
21. No.'of
Pages
Send To :
WATER RESOURCES SCIENTIFIC INFORMATION CENTER
US DEPARTMENT OF THE INTERIOR
WASHINGTON D C. 2O24O
A. L. Alford S.E. Environmental Research Lab.

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