United States
Environmental Protection
Agency
Roberts Kerr Environmental Research  EPA 600 2-79-175
Laboratory               August 1979
Ada OK 74820
Research end Development
Indicatory Fate
Study

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                RESEARCH REPORTING SERIES

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

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

This report has been assigned  to the  ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from 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.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia  22161.

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                                            EPA-600/2-79-175
                                            August 1979
              INDICATORY FATE STUDY
                        by
                  Leon H. Myers
              Thomas E. Short, Jr.
                Bill L. DePrater
                 Fred M. Pfeffer
               Donald H. Kampbell
                John E. Matthews
            Source Management Branch
Robert S. Kerr Environmental Research Laboratory
              Ada, Oklahoma  74820
ROBERT S. KERR ENVIRONMENTAL  RESEARCH LABORATORY
       OFFICE OF RESEARCH AND DEVELOPMENT
      U.S. ENVIRONMENTAL PROTECTION  AGENCY
              ADA, OKLAHOMA   74820

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                           DISCLAIMER


     This report has been reviewed by the Robert S. Kerr Environ-
mental Research Laboratory, U.S. Environmental Protection Agency,
and approved for publication.  Mention of trade names or com-
mercial products does not constitute endorsement or recommenda-
tion for use.
                                ii

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                            FOREWORD
     The Environmental Protection Agency was established to
coordinate administration of the major Federal programs designed
to protect the quality of our environment.

     An important part of the Agency's effort involves the search
for information about environmental problems, management tech-
niques and new technologies through which optimum use of the
nation's land and water resources can be assured and the threat
pollution poses to the welfare of the American people can be
minimized.

     EPA's Office of Research and Development conducts this
search through a nationwide network of research facilities.

     As one of these facilities, the Robert S. Kerr Environmental
Research Laboratory is responsible for the management of programs
to: (a) investigate the nature, transport,  fate and management of
pollutants in ground water; (b) develop and demonstrate methods
for treating wastewaters with soil and other natural systems;
(c) develop and demonstrate pollution control technologies for
irrigation return flows; (d) develop and demonstrate pollution
control technologies for animal production wastes; (e) develop
and demonstrate technologies to prevent, control, or abate pollu-
tion from the petroleum refining and petrochemical industries;
and (f) develop and demonstrate technologies to manage pollution
resulting from combinations of industrial wastewaters or indus-
trial/municipal wastewaters.

     This report contributes to the knowledge essential if the
EPA is to meet the requirements of environmental laws that it
establish and enforce pollution control standards which are
reasonable, cost effective and provide adequate protection for
the American public.
                                 W. C. Galegar
                                   Director
               Robert S. Kerr Environmental Research Laboratory
                                iii

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                            ABSTRACT


     This report is concerned with media disposition of specific
priority pollutants.   Composite samples were obtained from'the
influent, effluent, residuals, and air from 12 industrial biologi-
cal treatment systems.  These samples were extracted and analyzed
by gas chromatography for organic constituents, by atomic absorp-
tion for metals, and by EPA methodology for phenolics,  cyanide,
and mercury.

     Participating industries include:  (1) organics and plastics,
(2) Pharmaceuticals,   (3) pesticides, (4) rubber, (5) wood preserv-
ative, and  (6) petroleum refining.  Each of the 12 cooperating
companies reviewed and commented on the draft report for descrip-
tion of its biological treatment system, accuracy of the study
conditions as well as comments on the completed analytical data.
The data in this report represent potential disposition of spe-
cific priority pollutants during 3-day study periods and should
not be construed to represent a mass balance study.

     This work covers a period from May, 1978, to February, 1979,
and work was completed as of March, 1979.
                                iv

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                       CONTENTS
Foreword	ill
Abstract	.	   iv
Figures. .  . „	   vi
Tables	„....„...„	vii
Abbreviations and Symbols  ............. viii
Acknowledgments  .»..<>.. =	   ix

     1.  Introduction	    1

     2.  Sampling Program	    2

     3.  Plant Studies 	    7
              Organics and Plastics Industries
                   Plant 1	    7
                   Plant 2 .............   15
                   Plant 3	   22
              Pharmaceuticals Industry
                   Plant 4	   29
                   Plant 5	   35
              Pesticides Industry
                   Plant 6	   41
                   Plant 7	   48
              Rubber Industry
                   Plant 8	   55
                   Plant 9	„....„   61
              Wood-preservatives  Industry
                   Plant 10	   68
                   Plant 11.  ............   76
              Petroleum Refining  Industry
                   Plant 12.  ............   83

     4.  Observations	   91

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                        FIGURES



Number                                               Page



  1       Activated sludge sampling points 	   3



  2       Aerated lagoon sampling points 	   3



  3       Air-stripper sampler 	   5



  4       Wastewater treatment system - Plant 1. .   .   8



  5       Wastewater treatment system - Plant 2. .   .  16



  6       Wastewater treatment system - Plant 3. .   .  23



  7       Wastewater treatment system - Plant 4. .   .  30



  8       Wastewater treatment sys'tem - Plant 5. .   .  36



  9       Wastewater treatment system - Plant 6. .   .  42



 10       Wastewater treatment system - Plant 7. .   .  49



 11       Wastewater treatment system - Plant 8. .   .  56



 12       Wastewater treatment system - Plant 9. .   .  62



 13       Wastewater treatment system - Plant 10 .   .  69



 14       Wastewater treatment system - Plant 11 .   .  77



 15       Wastewater treatment system - Plant 12 .   .  84
                          VI

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                             TABLES

Number                                                       Page

   1      Biological Treatment Plant Material Balance
          (Plant 1)	    9
   2      Sampling Schedule  (Plant 1)  	   11
   3      Daily Flow Data  (Plant 1)	11
   4      Analytical Data  (Plant 1)	12
   5      Sampling Schedule  (Plant 2)  	   17
   6      Daily Flow Data  (Plant 2)	18
   7      Analytical Data  (Plant 2)	19
   8      Sampling Schedule  (Plant 3)  	   24
   9      Daily Flow Data  (Plant 3)	25
  10      Analytical Data  (Plant 3)	26
  11      Sampling Schedule  (Plant 4)  	   32
  12      Daily Flow Data  (Plant 4)	32
  13      Analytical Data  (Plant 4)	33
  14      Sampling Schedule  (Plant 5)  	   37
  15      Daily Flow Data  (Plant 5)	38
  16      Analytical Data  (Plant 5)	39
  17      Average Flow Data  (Plant 6)	43
  18      Sampling Schedule  (Plant 6)  	   44
  19      Analytical Data  (Plant 6)	45
  20      Sampling Schedule  (Plant 7)  	   50
  21      Daily Flow Data  (Plant 7)	51
  22      Analytical Data  (Plant 7)	52
  23      Sampling Schedule  (Plant 8)  	   57
  24      Analytical Data  (Plant 8)	59
  25      Sampling Schedule  (Plant 9)  	   63
  26      Daily Flow Data  (Plant 9)	64
  27      Analytical Data  (Plant 9)	65
  28      Sampling Schedule  (Plant 10)	   72
  29      Daily Flow Data  (Plant 10)	71
  30      Analytical Data  (Plant 10)	73
  31      Sampling Schedule  (Plant 11)	78
  32      Daily Flow Data  (Plant 11)	79
  33      Analytical Data  (Plant 11)	80
  34      Sampling Schedule  (Plant 12)	86
  35      Daily Flow Data  (Plant 12)	86
  36      Analytical Data  (Plant 12)	87
  37      Metric Conversion Table  	   90
                               vii

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                       ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
cfh
EGD
EPA
gpm
1C
mg
mgd
mg/1
ml
mm
pac
RSKERL
TOG
VOA
SYMBOLS
u
Mg/1
cubic feet per hour*
Effluent Guidelines Division
Environmental Protection Agency
gallons per minute*
inorganic carbon
million gallons*
million gallons per day*
milligrams per liter
milliliter
million
powdered activated carbon
Robert S. Kerr Environmental Research Laboratory
total organic carbon
volatile organics analysis

micron
micrograms per liter
micrograms per kilogram
*See Table 37, Metric Conversion Table, on page 90,
                               viii

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                       ACKNOWLEDGMENTS


     To successfully complete any applied research study, the
research team needs the full cooperation of all interested
parties.  Our sincere appreciation is extended to EPA's Office
of Research and Development (OEMI and OALWU) and Office of Water
and Hazardous Materials (EGD) for participation in planning and
administrative tasks associated with the study.  A special
acknowledgement is due the industrial plants—their executives,
supervisors, and operators—for the excellent cooperation ex-
tended to the RSKERL teams during this study.
                               IX

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                            SECTION 1

                          INTRODUCTION
     In June 1978, the Robert S. Kerr Environmental Research
Laboratory (RSKERL) began an applied research study at the re-
quest of EPA's Effluent Guidelines Division (EGD).   The purpose
of the study was to determine what happens to specific priority
pollutants as they pass through a biological treatment system.
A mass balance study on a biological treatment system would con-
sume considerable time, manpower, and resources.  It was there-
fore decided that an indication of the fate of specific priority
pollutants would be conducted in lieu of a mass balance study.
This "Indicatory Fate Study," planned and conducted by RSKERL,
represents a screening study to view the removal of specific
priority pollutants via air, water, or residuals routes.

     Specific organic pollutants were analyzed by gas chroma-
tography using methodology supplied by EGD.  Quality control for
the specific organic priority pollutants was provided by gas
chromatograph/mass spectrometer analysis on one sample obtained
from each plant site visited.  Total metals, phenol, and cyanide
analyses were conducted in accordance with EPA's April, 1977,
Protocol.

     Twelve industrial participants representing six industrial
categories were selected by Effluent Guidelines:  (1) organic
chemicals, (2) petroleum refining, (3) Pharmaceuticals, (4) wood
preserving, (5) pesticides, and (6) rubber.  Based on analytical
data generated during previous screening studies, EGD requested
sampling for specific priority pollutants from each participant.

     Responsible company officials for each plant selected were
notified by a letter from the Director, RSKERL, explaining the
purpose of the proposed study and requesting their participation,
Each of the plants visited cooperated fully in completing the
field sampling portion of the study.

     The data in this report provide only an indication of the
route of removal of specific priority pollutants and are not
intended to represent a mass balance across a biological treat-
ment system.

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                            SECTION 2

                        SAMPLING PROGRAM
                                             \.

     The sampling program was designed to examine three possible
removal routes for each type of treatment system:  (1) air,
(2) water, and (3) residuals.

SAMPLE LOCATIONS

     Two basic types of biological treatment systems were studied:
(1) activated sludge and (2) aerated lagoons.

     Sampling points established to examine removal routes from
activated sludge treatment systems were:  (Figure 1)

     Sample Location     Sample Type         Media

 1.  Primary Effluent    72-hr Composite,    Water
                         VOA Grab

 2.  Final Effluent      72-hr Composite        "
                         VOA Grab

 3.  Aeration Basin      Stripper Sampler    Air
                         Composite

 4.  Return Sludge       72-hr Composite     Residuals


     Sampling points established for aerated lagoon treatment
systems were;  (Figure 2)

     Sample Location     Sample Type         Media

 1.  Inlet to First      72-hr Composite     Water
      Lagoon             VOA Grab

 2.  Outlet from Last    72-hr Composite       "
     Lagoon              VOA Grab

 3.  Near first Lagoon   Stripper Sampler    Air
     Inlet               Composite

 4.  Bottom Deposits     72-hr Composite     Residuals

                                2

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Primary
Clarifier
                        Aeration Basin
                           Return Sludge
                Figure  I .    Activated  Sludge  Sampling Points
              Figure  2 .  Aerated  Lagoon Sampling  Points

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SAMPLE COLLECTION

Air (Figure 3)

     At the beginning of the sampling program, an air sampler was
installed in the aeration basin (mixed liquor) of the activated
sludge treatment system or in the first lagoon of the aerated
lagoon treatment system.  The air sampler was designed at RSKERL
for this study and is a combination stripper/adsorber.   A 20-
gallon/minute submersible pump continuously supplied a fresh
sample of water to the stripper, while a carbon-filtered air sup-
ply was used to sparge volatile organic compounds from the water
sample-v The sparged air was fed to a slurry pot containing
XAD-2^ ' resin for adsorption of the air strippable polynuclear
aromatic and phenolic compounds.  The sparged air was also fed/Rx
intermittently to a gas chromatograph column packed with Tenax^ '
for adsorption of purgeable organic compounds.

Water

     Water samples were collected at the inlet and effluent
points of the biological treatment system.  A 3-day composite
sample was prepared at each sample point by collecting 24
aliquots at specified times during the 72-hour sampling period.

     In addition, VGA grab samples were collected at the influ-
ent and effluent sampling points.  These samples were collected
in previously prepared 30-ml sample vials.  Blank VOA vials con-
taining Super Q water were uncapped prior to, and resealed fol-
lowing, collection of VOA samples at each location.  The VOA
samples were used to supplement samples collected using the air-
stripper sampler.

Residuals

     At plants employing an activated sludge system, the return
sludge was sampled in the same mode as the water samples.  At
those plants where an aerated lagoon was being studied, a single
dredge  sample was obtained near the inlet to the first lagoon.

SAMPLE HANDLING

     Samples were preserved in accordance with the April, 1977,
Protocol.  Water and residual samples were kept iced for the du-
ration  of the sampling program.  In addition, metal samples were
 (R) Registered trademark  - Rohm & Haas (XAD-2)

 (R) Registered trademark  - ENKA N.V., Holland (Tenax)

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                                                        Vent
                             Stripper Air
Float
          Glass pipe
          Section
        Water
        Meter
Sparger
               ,—iSub. Pump for
              -I  I mixed-liquor
                  recirculation
w &


 it-——c
leaned Compressed
Air
                                      Foam
                                      Knock-out
                                      Trap
                                                              Tenas Column

                                                                i	SB- To vacuum
                                                            XAD-2 Resin
                                                            Slurry
                                                                                             Rota meter
                                                                                     r~] Filter
                                                                                     T

                                                                                     j  [Activated
                                                                                     j   Carbon
A
                                                                                                         Comp.Air
                            Figure   3 -  AIR - STRIPPER  SAMPLER

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preserved with redistilled nitric acid;  phenol samples were
preserved with phosphoric acid; and cyanide samples were pre-
served with sodium hydroxide.  No additional preservative was
used for the organics samples.

     After the sampling study was complete, sample chests,
filled with ice, were transported to RSKERL, where they were
transferred to a 4 C walk-in constant-temperature box.  The sam-
ples remained in this environment until they were ready to be
extracted and/or analyzed.

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                           SECTION 3,

                         PLANT STUDIES
ORGANICS AND PLASTICS INDUSTRY

Plant 1

Wastewater Treatment System--
     A flow diagram of Plant 1's wastewater treatment system is
shown in Figure 4.  Wastewater generated by the manufacturing of
organic chemicals and plastics is treated by a series of proc-
esses that generally consist of (1) neutralization, (2) denitri-
fication, (3) aeration, and (4) nitrification.  Sludge produced
by the wastewater treatment process is digested aerobically,
filtered in a dual-cell gravity unit, and landfilled.   An approx-
imate material balance for the treatment system is shown in
Table 1.

     Raw wastewater from the manufacturing process is first
neutralized in a limestone reactor.   Here the  pH of the raw
wastewater is increased from about 1.5 to about 4.8.  From the
neutralization pit, the wastewater flows to a 1-million-gallon
denitrification pond.  Here the wastewater is mixed with a por-
tion of the return sludge.  A single 75-horsepower (hp) aerator
is used to mix the contents of the denitrification pond.  Some
aeration does occur; however, the amount of oxygen transferred
is low enough that the pond remains essentially anaerobic.

     From the denitrification section, the wastewater flows to a
1.1-million-gallon aeration basin, where another portion of the
return sludge is added to the wastes, and is aerated using three
mechanical aerators.  One aerator is a variable speed, 150-hp
aerator and is fixed mounted.  The other two aerators are float-
ing, high-speed, 50-hp aerators.  From the aeration section, the
wastewater flows to a 1.1-million-gallon nitrification pond,
where the final portion of return sludge is added to the waste-
water, and is aerated with three mechanical aerators.   One
aerator is a fixed speed, 150-hp aerator and is fixed mounted.
The other two aerators are floating, high-speed, 50-hp aerators.

     The wastewater is then clarified, and the effluent is dis-
charged into a local river.  The total retention time of the
treatment system is 1.48 days at 1,500 gallons per minute  (gpm),
and it has a total volume of 3.2 million gallons.

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 SAMPLE POINTS

0- INFLUENT

©-EFFLUENT

©-SLUDGE

(?)- AIR STRIPPER
         LANDFILL
                         WASTEWATER
                              U
                        LIMESTONE
                         REACTOR
                               B
DENITRIFICATION
   AERATION
                        NITRIFICATION
                               H
                         CLARIFICATION
                             l<
                             TO
                           RIVER
                      E
    Figure 4 - WASTEWATER TREATMENT SYSTEM-PLANT

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	TABLE   1.  BIOLOGICAL  TREATMENT  PLANT MATERIAL  BALANCE—PLANT  1

                     Stream  Flow    TOG    1C   NH -N   NO^-N    TSS         09
	#     #/hr.  #/hr. #/hr. #/Kr.   #/nr.   #/hr. pH   #/hr.

Total Influent          A   952,000   490     9    84      350     180  1.5

Limestone Reactor      B   952,700   490    85    84      350     180  4.8

Clarifler Recycle      C   605,000    24  163     9        36   9,070  8.0

Denitrification         D  1,545,700   190  480    93        42   9,250  8.2

Clairfier Recycle      E   305,000    12    82     5        18   4,570  8.0

Aeration                F  1,850,700    74  594    65        77   7,570  8.1    230

Clarifler Recycle      G   460,000    18  124     7        28   6,900  8.0

Nitrification           H  2,310,700    92    62    35      139 20,914  8.0    150

Effluent                I   937,700    37  250    14        56      60  8.0

Wasted  Sludge           J     15,000    -     -    -               211  8.0

Aerobic Digestor        K     15,000    -     -    -         -      211  7.5

Land-Fill               L     3,000    -                          210  7.5

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Sample Collection--
     Based on previous screening conducted at Plant 1 under the
direction of EPA's Effluent Guidelines Division, a list of pri-
ority pollutants was compiled for investigation in this study
(Table 4).   This list represents the priority pollutants which
have been identified in Plant 1's influent to the treatment sys-
tem.  From this list, it was determined that six 1-gallon samples
of composite were required for specific organic compound analysis

     The sampling point locations are shown in Figure 4.  The
influent sample was taken immediately following the limestone
reaction pit.  The effluent sample was taken out of the clarifier
overflow channel.  The return sludge sample was taken off the
discharge side of the recycle pump.  The air-stripper sampler
was placed just off the walkway in the denitrification pond.

     Samples of the influent, effluent, and return sludge were
composited.  Every 3 hours, beginning at 9 pm on July 10, 1978,
six 130-milliliter (ml) aliquots were taken at each sample point
for specific organic analysis.  In addition, three 40-ml aliquots
were taken for cyanide, phenolics, and metals.  Each metals,
cyanide, and phenolics sample was "preserved" at 10:30 am on
July 11, by adding 5 ml of nitric acid to the metals samples,
1 ml of  sodium hydroxide to the cyanide, and 2 ml of phosphoric
acid to  the phenolics samples.  At all times each of the samples
taken was kept on ice.  At 5 pm on July 13, 1978, VGA grab sam-
ples were taken from the influent and effluent.   A detailed sam-
pling schedule is presented in Table 2.

     The air-stripper sampler was placed into operation at 9:30
pm on July 10, 1978, and operations were concluded at 6 pm on
July 13, 1978, for a total operating time of 68 1/2 hours.  Air
charged  to the stripper averaged 60 cubic feet per hour (cfh),
and the  quantity of air to the XAD-2 scrubber was 30 cfh.
Stripped air was collected on the Tenax columns for 10 minutes
each day.  At this plant two Tenax columns were used.  On the
first day one column was used; for the second and third days an-
other column was used.

     Table 3 contains flow data for this plant's treatment sys-
tem on the days sampled.

Analytical Results--
     Priority pollutants for which samples were collected and
analyzed are presented in Table 4.  All extractions and analyses
of samples were conducted at RSKERL.
                               10

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              TABLE 2.  SAMPLING SCHEDULE  (PLANT  1)
 Date
 7/10/78
  Time
               Samples taken
                            Remarks
 7/11/78
    11
    it
 7/12/78
    M

    M

    II

    II

    II

    II
 7/13/78
 9:00 pm
12:00 Midnight
 3:00 am
 6:00 am
 9:00 am
               Composites*
10:30
12:00
 3:00
 6:00
 9:00
12:00

 3:00
 6:00
 9:00
12:00
 3
 6
  :00
  :00
 9:00
12:00
am
Noon
pm
pm
pm
Midnight

am
am
am
Noon
pm
pm
pm
Midnight
                            Composites
                                11
                                          Added 5 ml HNOs,  2 ml
                                          NaOH, 2 ml H3P04  to
                                          metals, cyanide,  and
                                          phenolics composites
                                          Tenax  col.  5,  10 min.
Tenax col. 6, 10 min.
 3:00 am
 6:00 am
 9:00 am
12:00 Noon
 3:00 pm
 5:00 pm
 6:00 pm
                            VOA
                            Composites
                             Tenax col.  6, 10 min.
^Composites consist of six
 40-ml aliquots for metals,
              130-ml aliquots for organics,three
               cyanide, and phenols.
               TABLE 3.  DAILY FLOW DATA  (PLANT 1)
          Date
            Time
                                             Flow
7/10/78
7/11/78
7/12/78
7/13/78 »
7/13/78
7/13/78
Daily average
8 am
12 Noon
4 pm
1,623
1,404
1,698
1,590
2,340
2,280
                                 11

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                         TABLE  4.   ANALYTICAL  DATA (PLANT 1)
    Priority Pollutant
 Sparged  Air,  XAD-2
	(ue)
            Sparged Air, Tenax
                   (ug)
POLYNUCLEAR AROMATICS
     Naphthalene
     2-Chloronaphthane
     Acenaphthalene
     Acenaphthene
     Fluorene
     Phenanthrene/Anthracene
     Fluoranthene
     Pyrene
     1,2-Benzanthracene
     Chrysene
     3,4-Benzopyrene
     1,2:5,6-Dibenzanthracene

PHENOLICS
     2-Chlorophenol
     2-Nitrophenol
     Phenol
     2,4-Dimethylphenol
     2,4-Dichlorophenol
     2,4,6-Trichlorophenol
     4-Chloro-m-cresol
     2,4-Dinitrophenol
     4,6-Dinitro-o-cresol
     Pent achlor opheno1
     4-Nitrophenol

PURGEABLES
     Methylene chloride
     1,1-Dichloroethane
     1,2-Trans-dichloroethylene
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene	
        5,910
        4,410
        4.
        7.
890
590
 <7
 <6
 10
 57
 <3
 <3
          <38

        1,060
          360
        2,400
          304
       13,300
          530
        1,880
          366
          507
          225
                         1
                         .7

                          8

                         .7
                       <.05
                        380
                         .6
                         .4
                      <.025
                       <.05
                       <.25
                         17
                        1.1
                        .06
                        .08
                          2
                          .7
                          14
                        <.25
                          48

                        <.05
                        <.08
                       <.025
                        <.05
                        <.25
                           2
                       <-025
                          .4

                         .07
                         .03
                                      12

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                            TABLE  4.   (Continued)

Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Ant imony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGE ABLE S
1 , 4-Dichlorobenzene
Benzene
1 , 3-Dichlorobenzene
Chloroform
1 , 2-Dichloropropane
Methylene chloride
Ethylbenzene
Trans-dichloroethylene
Influent
(ug/D

.62
21

12
<10
3
<3
160
650
81
770
<10
<10
10
<1.0


<10
405
<10
<10
<10
<10
<10
<10
Return Sludge
(ug/D

.16
<50

200
<10
48
11
4,000
18,000
3,900
15,000
13
<10
530
<5.0


N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
Effluent
(ug/D

<.08
<20

<10
<10
1
<3
17
50
65
89
<10
<10
<10
<.05


<10
<40
<10
<10
<10
<10
<10
<10
DINITROTOLUENE
     Nitrobenzene

HALOETHER
     2-Chloroethyl vinyl ether

POLYNUCLEAR AROMATICS
     Phenanthr ene/Anthracene
     Fluorene
     Naphthalene
N.P.
<49
<50
<64
<22
N.P.
<43
 <50
 <64
 <22
N.P.
<47
<50
<64
<22
(Continued)
                                      13

-------
     Priority Pollutant
Influent
 0*8/1)
                                                      Return Sludge  Effluent
PHENOLICS
     Phenol
     4-Nitrophenol
     2-Nitrophenol
     2,4,6-Trichlorophenol
     Pentachlorophenol

PHTHALATE ESTERS
     Bis(2-ethylhexyl) phthalate
     25
     40
  1,780
    N.D.
     53
    <49
 20
N.D.
N.D.
 44
115
<43
   2
   5
 566
N.D.
41.2
 <47
  *Note:  Total Cyanides expressed in mg/1.
 **Key:   N.D. - Not Detectable, or less than detectable limits
          N.A. - Not Applicable
          N.S. - No Standard Available
          N.P. - No Procedure Available
                                       14

-------
Plant 2

Wastewater Treatment System--
     A flow diagram of Plant 2's biological wastewater treatment
system is shown in Figure 5.  The biological system has been in
operation since August, 1971, and has incorporated powdered
carbon in the mixed liquor  since May, 1977.  Stormwater meeting
permit limits is  combined with  final effluent, both of which
ultimately enter  an estuary.

     Specifically, Plant 2  process wastewater receives primary
clarification in  a separator, is neutralized, and is then
fed to an equalization basin having a volume of 2.1 million gal-
lons (mg) and a retention time  of approximately 2 days.  Waste-
water in the equalization basin is lifted to two identical
activated sludge  bays employing surface-type extended aeration
and incorporating PAG added on  a batch basis to maintain an
estimated 1,800 pounds of PAC in both basins.  The operational
result is 3,500 milligrams  per  liter (mg/1) of mixed-liquor
volatile suspended solids (MLVSS), of which approximately 5-6
percent is PAC.

     The total volume of the aeration basins is 1.1 million gal-
lons, and the retention time is 31 hours.  Mixed liquor flows by
gravity to one final clarifier  having a diameter of 50 feet and
a retention time  of 3.4 hours.

Sample Collection--
     The study period at Plant  2 was from July 31-August 3, 1978.
Based on screening conducted under the direction of EPA's Efflu-
ent Guidelines Division, a  list of priority pollutants and two
common wastewater parameters (total cyanide and total phenols)
was compiled for  investigation  in this study (Table 7).  Three-
liter samples were composited in 1-gallon glass bottles for
analyses of specific organic compounds (no preservative added).
Samples of approximately 1-liter volume were composited for the
total metals (acid preservation), total cyanide (alkaline preser-
vation) , and total phenols  (acid preservation).

     Referring to Figure 5, the bioinfluent (point 1) was collec-
ted from a tap on the discharge side of the lift pump transfer-
ring equalization pond wastewater to the aeration basins.
Return sludge (point 2) was sampled from a tap on the discharge
side of the return sludge pump.  Final effluent (point 3) was
sampled at the weir used in monitoring for permit parameters
(prior to introduction of Stormwater).  An air-stripper sampler
equipped with both XAD and  Tenax traps was floated in a corner
of the south aeration bay adjacent to the point where bioinfluent
and return sludge are introduced.  Volatile organics were sampled
in the bioinfluent and final effluent using the standard 28-ml
VGA (volatile organics analysis) septum vials.
                                15

-------
       PLANT
   API
SEPARATOR
CHEMICAL
 SUMPS
  CAUSTIC
RETENTION
   PLANT
   DITCHES
                  EMERGENCY
                  RETENTION
                                         NEUTRALIZATION
STORMWATER
   BASIN
                            SLUDGE
                           DIGESTER
                  ACTIVATED
                   SLUDGE
                 ACTIVATED
                   SLUDGE
                                                  TO LAND.
                                                    FILL
           INFLUENT                    PLANT FE
          I SLUDGE SAMPLE            	
          I EFFLUENT
          I AIR STRIPPER

           Figure 5 - WASTEWATER TREATMENT SYSTEM - PLANT" 2
                             16

-------
     Samples of bioinfluent, return sludge, and final effluent
were composited every 3 hours, beginning at 6 pm on July 31, 1978,
and ending at 3 pm on August 3, 1978.  Preservatives were added
at the initiation of sampling.  Preservatives used were concen-
trated phosphoric acid to achieve a final pH£ 4 (total phenols),
50-percent sodium hydroxide solution to pH->12 (total cyanide),
and glass-redistilled nitric acid to pH£ 2 (total metals).  The
compositing procedure for each of these parameters was 40 ml of
grab sample every 3 hours to obtain 1 liter of composite.  For
organics, no preservative was used, and final sample of 3 liters
was obtained by compositing 125 ml every 3 hours.  All sample
containers were iced throughout the period of compositing.  A
detailed sampling schedule  is presented in Table 5.
              TABLE 5.  SAMPLING SCHEDULE (PLANT 2)

Date
7/31/78
Time Sample taken
3:30 pm
6 pm Composite
9 pm
12 Midnight
Remarks
Air stripper on
8/1/78








8/2/78








8/3/78





3 am
6 am
9 am
12 Noon
2 pm Tenax
3 pm Composite
6 pm
9 pm
12 Midnight
3 am
6 am
9 am
12 Noon
2 pm Tenax
3 pm Composite
6 pm "
9 pm
12 Midnight
2 am
3 am Composite
6 am
9 am
12 Noon Composite;
3 pm Composite


Forward flow stopped
Forward flow resumed














Air stripper off



VOA

                               17

-------
     The air-stripper sampler was placed in operation at 3:30 pm,
July 31, and continued uninterrupted until 2 am on August 3, for
a total operating time of 58 hours.   Air charged to the stripper
averaged 60 cfh, and the quantity of air to the XAD-2 scrubber
was 30 cfh.  Duplicate Tenax traps each received a slipstream
from the stripper sampler for 15 minutes on two of the three
sampling days, at 2 pm on August 1 and at 2 pm on August 2.  One
of the Tenax traps was left with Plant 2.  The VGA samples were
collected at 12 noon on August 3.

     Two operational anomalies were noted which could result in
atypical results for Plant 2.  At 9 am on August 1, the forward
feed pumps to the aeration basins were shut down, resulting in
noticeable reduction in final effluent flow.  The pumps resumed
in 2 hours, and final flow was "normal" by 12 noon.  During the
morning of August 2, wastewater containing a high concentration
of aniline was diverted to the emergency retention basin and
bled slowly to the equalization basin.  The normal 24-hour com-
posite value for aniline in the discharge from the equalization
basin is 0-5 mg/1 as C^-HcNI^.  The value for the last 24-hour
period of the study (August 3) was 86 mg/1, as determined by the
Plant 2 laboratory.

     The daily average flows for this period are found in
Table 6.  Sludge wastage is not normal at this facility and did
not occur during the study; therefore, the forward flow to the
aeration basins equals the effluent flow.
TABLE 6.
DAILY FLOW DATA
(PLANT 2)

Date
7/31/78
8/01/78
8/02/78
8/03/78
Return Sludge
(mgd)
0.3283
0.3283
0.3283
0.3010
Effluent
(mgd)
1.3450
0.9915
0.6828
1.1199

Analytical Results--
     Priority pollutants, total cyanide, and total phenolics for
which samples were collected and analyzed are presented in
Table 7.  All extractions and analyses of samples were conducted
at RSKERL.
                               18

-------
                       TABLE 7.  ANALYTICAL DATA (PLANT 2)
                                    Sparged Air, XAD-2   Sparged Air, Tenax
	Priority Pollutant	' (yg)	(yg)	

POLYNUCLEAR AROMATICS
     Naphthalene                        40
     2-Chloronaphthane                 <10
     Acenaphthalene                    <10
     Acenaphthene                      <10
     Fluorene                          <13
     Phenanthrene/Anthracene           <10
     Fluoranthene                       14
     Pyrene                            <10
     1,2-Benzanthracene                <10
     Chrysene                          <10
     3,4-Benzopyrene                   <35
     l,2:5,6-Dibenzanthracene          N.D.
PHENOLICS
     2-Chlorophenol                    <25
     2-Nitrophenol                     <25
     Phenol                             11
     2,4-Dimethylphenol                < 25
     2,4-Dichlorophenol                <50
     2,4,6-Trichlorophenol             <10
     4-Chloro-m-cresol                  60
     2,4-Dinitrophenol                 <100
     4,6-Dinitro-o-cresol               80
     Pentachlorophenol                 <25
     4-Nitrophenol                     <25

PURGEABLES
     Methylene  chloride                                  Undefinable results
     1,1-Dichloroethane                                  because of high
     1,2-Trans-dichloroethylene                          background inter-
     Chloroform                                         ference.
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon  tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl  bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene	
                                     19

-------
TABLE 7.
   (Continued)
II-T-I '- 	 -• __m— -i ._ _ IT— -1— -a- — • — I- • II
Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS

Arsenic

Selenium

Cadmium

Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
NITROTOLUENES /NITROBENZENE
Nitrobenzene
2 , 4-Dinitrotoluene
2 , 6-Dinitrotoluene
POLYNUCLEAR AROMATICS
Naphthalene
Fluorene
Phenanthrene /Anthracene
Benzo-a-pyrene
Acenaphthene
Influent

<.08
372

fin
\j\j
i n
Xly
j» 1
-1-
^q
^3
32
260
36
530
<10
<10
27
<5


N.P.
N.S.
N.S.

<10
63
<10
<70
<10
Return Sludge
Gig/1)

.43
1,300

90
*s v/
10
^, \-f
80
U \J

1,700
31,000
4,200
39,000
<10
<10
1,500
18


N.P.
N.S.
N.S.

<10
<25
320
<70
<10
Effluent
dig/1)

.23
263
f S\
60
O /^
20
,. -i

-------
                           TABLE 7.    (Continued)
     Priority Pollutant
ACRYLONITRILE
                                            Influent
Return Sludge
   (/ig/D
Effluent
PHENOLICS
2-Nitrophenol
4-Nitrophenol
Phenol
2 , 4-Dinitrophenol
2 , 4-Dimethylphenol
2-Chlorophenol
Pentachlorophenol

5
24
20
39
35
24
14

53
N.D.
8
16
11
6
36

62
N.D,
2
4
22
24
27
  -No sample-
 *Note:  Total Cyanides expressed in mg/1.
**Key:  N.D. - Not Detectables Or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                       21

-------
Plant 3

Wastewater Treatment System--
     A flow diagram of Plant 3's wastewater treatment system is
shown in Figure 6.  Wastewaters generated by the manufacturing of
organic chemicals are treated by a process consisting of (1) grit
removal, (2) primary API, (3) compositing and neutralization,
(4) secondary API, (5) aeration lagoon, (6) flocculation, and
(7) clarification.

     The typical inlet feed from the chemical sewer to the grit
chamber is 1,100 gallons per minute.  Wastewater flows from the
grit chamber through a primary API separator into a compositing
pond.  The pond has a volume of about 2.5 million gallons and con-
tains two 2-horsepower mechanical agitators.  Detention time is
about 1 day.  The wastewater then flows through a secondary API
separator before being pumped into a large aerated lagoon.   Addi-
tional lagoon loading is from waste acid transferred to the com-
positing pond, and belt press wash water, landfill pumpout, and
occasionally surface pond water transferred to the aerated lagoon.

     The aerated lagoon has a volume of 26 millio^gallons, a
depth of 22 feet, and surface area of 160,000 feet .   The lagoon
is equipped with 32 mechanical aerators,  each with a horsepower
of either 50 or 75.  The average detention time in the lagoon is
10 days.  Effluent from the aerated lagoon at the typical rate of
1,700 gallons per minute is pumped to a flocculator,  then to a
final clarifier before final discharge.  The final clarifier also
receives wastewaters from a surface sewer which have been treated
by a trickling filter.

     In addition to the described wastewater treatment system,
this facility employs an activated sludge treatment system for
treating wastewaters generated by specific process units.

Sample Collection--
     The survey of this facility was conducted during the period
August 28-31, 1978.  Composite samples were collected within a
72-hour period at three locations in the biological treatment
system (Figure 6):

     (1)  Influent to aerated lagoon (water phase)
     (2)  Effluent from aerated lagoon (water phase)
     (3)  Air-stripper samples (air phase)

     The air-stripper sampler was located in the aerated lagoon
near the influent point.  The stripper sampler was placed in opera-
tion at 11 am, August 28, and operation was concluded at 7 am,
August 31, for a total operating time of 68 hours.  Air charged to
the stripper averaged 60 cfh, and the quantity of air to the XAD-2
scrubber was 30 cfh.  Two samples were collected using the stripper
sampler.  Stripped air was collected on the Tenax column for 10
minutes on each of the three days the sampler was operated.
                                22

-------
        SAMPLE  POINTS
            INFLUENT
            EFFLUENT

            AIR STRIPPER

            SEDIMENT
                           AERATED LAGOON
CHEMICAL
 SEWER
                                                   LANDFILL
      SANITARY AND
       SURFACE
        WATER
BELT
PRESS
FILTER
      Figure  6 - WASTEWATER TREATMENT SYSTEM - PLANT  3
                             23

-------
     Twenty-four aliquots were collected manually from the
water-phase sampling points beginning at 12 noon, August 28.
Aliquots were collected at intervals of approximately 3 hours.
The final aliquot was collected at 9 am, August 31.  A detailed
sampling schedule is presented in Table 8.
              TABLE 8.  SAMPLING SCHEDULE (PLANT 3)
  Date
 8/28/78
 Time	
12:00 Noon
Sample taken	Remarks	
1st CompositeStarted stripper at 11 am.
 aliquot       Added preservative as
               needed
Composite aliquot
                 ,  10" Tenax
            3:00 pm
            6:00 pm
            9:00 pm
           12 :00 Midnight

 8/29/78    3:00 am
            6:00 am
            9:00 am
           12:00 Noon
            3:00 pm
            6:00 pm
            9:00 pm
           12:00 Midnight

 8/30/78    3:00 am
            6:00 am
            9:00 am
           12:00 Noon
            3:00 pm
            6:00 pm
            9:00 pm
           12 .- 00 Midnight
 8/31/78    3:00 am
            6:00 am
            8:00 am      24th1
                           M
                               ,  10" Tenax
                               ,  10" Tenax
                               ,  VGA grab,  bottom sample
                             Stripper sampler shut off
                             at 7:30 am.
     Samples were collected for those pr.'ority pollutants which
were found in the previous priority pollutants screening survey
or which might be expected to be found if all plant processes
were in operation (Table 10).   Samples were preserved by pre-
scribed EPA methods.  All samples were kept on ice throughout the
sample period.  Duplicate metals, cyanide, and phenolics samples
were provided to plant personnel.
                               24

-------
     At the end of the sample period, grab samples for VGA
analyses were collected from the water-phase sampling points.
At this time, a grab sample for the residual phase was collected
from the bottom of the aerated lagoon.

     Daily flow data for the sampling period are presented in
Table 9.
               TABLE 9.  DAILY FLOW DATA*  (PLANT 3)

Date
8/28/78
8/29/78
8/30/78
Influent
(gpm)
1,100
1,100
1,100
Effluent
(gpm)
1,700
1,700
1,700

•*These are typical  flow rates under normal operating conditions


Analytical Results--
     Priority pollutants  for which samples were collected and
analyzed are presented in Table 10.  All extractions and analyses
of  samples were  conducted at RSKERL.
                               25

-------
                        TABLE  10.   ANALYTICAL DATA (PLANT 3)
     Priority Pollutants
                                    Sparged Air, XAD-2
               Sparged Air,  Tenax
                      (Ug)   	
POLYNUCLEAR AROMATICS
     Naphthalene
     2-Chloronaphthane
     Acenaphthalene
     Acenaphthene
     Fluorene
     Phenanthrene/Anthracene
     Fluoranthene
     Pyrene
     1,2-Benzanthracene
     Chrysene
     3,4-Benzopyrene
     1,2:5,6-Dibenzanthracene

PHENOLICS
     2-Chlorophenol
     2-Nitrophenol
     Phenol
     2,4-Dimethylphenol
     2,4-Dichlorophenol
     2,4,6-Trichlorophenol
     4-Chloro-m-cresol
     2,4-Dinitrophenol
     4,6-Dinitro-o-cresol
     Pentachlorophenol
     4-Nitrophenol
PURGEABLES
     Methylene chloride
     1,1-Dichloroethane
     1,2-Trans-dichloroethylene
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Mchloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene	,
  70
  16
  15
  50
  40
 <35
 N.D.

 <25
 <25
  18
 <25
 <50
  12
 <25
<100
 <25
 <25
 <25
              Undefinable results
              because of extraneous
              matrix.
                                     26

-------
                           TABLE 10.
(Continued)

Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
t
ACROLEIN
ACRYLONITRILE
PURGE ABLE S
Benzene
Chloroform
1 , 2-Dichloropropane
Methylene chloride
Dichlorodibromomethane
Chlorodibromomethane
Toluene
PHENOLICS
Phenol
2-Nitrophenol
4-Nitrophenol
2,4-Nitrophenol
Influent
(^g/D

4.76*
4,730

17
11
2
<3
1,100
<10
1,400
1,600
2,000
< 10
< 10
380
<0.1


<10,000
<10,000

<40
<10
<10
26
N.D.
<10
<10

680
<10
<10
<50
Bottom Sediment
Dry Weight
(jig/kg)

N.P.
N.P.

10,000
<930
670
1,300
360,000
<970
250,000
1,400,000
420,000
<880
<880
30,000
3


N.P.
N.P.

N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.

N.P.
N.P.
N.P.
N.P.
Effluent

6.70*
<40

34
20
2
<3
960
< 10
1,400
3,300
1,900
<10
< 10
250
<0.5


<10,000
<10,000

<40
<10
<10
<10
N.D.
<10
<10

<10
<10
<10
<50
(Continued)
                                      27

-------
TABLE 10.
(Continued)





Priority Pollutant
POLYNUCLEAR AROMATICS
Benzo (a) anthracene
Benzo (a) pyrene
3 , 4-Benzof luoranthene
Benzo (k) f luoranthane
Chrvsene

Influent
teg/D

<60
<30
N.D.
N.D.
<20
Bottom Sediment
Dry Weight
(/ig/kg)

N.P.
ii
11
ii
"

Effluent
(pg/D

<60
<30
N.D.
N.D.
<20
Acenaphthylene
Benzo(g,h,i)perylene
Fluorene
Phenanthrene/Anthracene
Dibenzo( a, h) anthracene,
Indeno(1,2,3-cd)pyrene
Pyrene
Acenaphthene
Naphthalene
                                             N.D.
                                             <30
                                             N.D.
                                             126
                                             980
N.D.
<30
N.D.
 *Note: Total Cyanides expressed in mg/1.
**Key:  N.D. - Not Detectable, or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                      28

-------
PHARMACEUTICALS INDUSTRY

Plant 4

Wastewater Treatment System--
     A flow diagram of Plant 4's wastewater treatment system is
shown in Figure 7.  Wastewater generated by the manufacturing of
Pharmaceuticals is treated by a process that generally consists
of  (1) primary clarification,  (2)  equalization,  (3) activated
sludge, and (4) chlorine contact.   Sludge produced by the waste-
water treatment process is thickened, aerobically digested, and
finally landfilled.  In addition to the manufacturing wastewater,
the treatment system also handles  sanitary waste from the plant.
As part of the treatment, approximately 80-100 pounds of granular
activated carbon  are added to the  aeration basin or equalization
tanks every three to four weeks.

     Treatment of the manufacturing wastewater begins when about
90,000 gallons per day of the water flows into the primary clar-
ifier, which has  a volume of 20,000 gallons  (37.5 feet long by
9.0 feet wide by  7.9 feet deep).   From the primary clarifier, the
wastewater flows  to two parallel equalization basins, each with
a volume of 90,000 gallons.  Then  the water is combined with
about 20,000 gallons per day of sanitary wastewater and flows to
a 100,000-gallon  aeration basin (64 feet long by 22 feet wide by
9.5 feet deep).   Two-hundred twenty-five cubic feet per minute
of  air is supplied to the aeration basin through 18 helix air
diffusers.  From  the aeration basin, wastewater  then flows to two
parallel final clarifiers, each one being 26.5 feet long by 6.0
feet wide by 8.4  feet deep.  The final effluent  is treated in a
7,500-gallon chlorine contact tank (13.0 feet long by 13.0 feet
wide by 5.9 feet  deep) prior to final discharge.  The total
residence time of the treatment system is 2 to 2 1/2 days.  Both
sludges from the  primary clarifier and waste secondary sludge are
treated in an aerobic digester and then thickened.  Supernatant
from the thickener is returned to  the primary clarifier.  The
sludge is then finally disposed of in a contract or municipal
landfill.

Sample Collection--
     Based on the previous Effluent Guidelines Division screening
survey study, the list of compounds in Table 13 was compiled.
This list represents the priority  pollutants that have been
identified in Plant 4's influent to the treatment system.  From
this list, it was determined that  four 1-gallon samples of com-
posite were required for specific  organic compound analysis.

     The sampling point locations  are shown in Figure 7.  The in-
fluent sample was taken immediately preceding the primary clari-
fier.  The effluent sample was taken just prior to chlorine con-
tact.  The return sludge sample was taken at the point where it


                                29

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              SAMPLE POINTS


                - INFLUENT

                - SLUDGE

                -  EFFLUENT

              )-  AIR STRIPPER
to
O
90,000 gpd
INDUSTRIAL^
WASTEWATER


1 1

i
T>
a.
o>
0
O
^
XJX 1 1 ffi)
w -1 	 r . j
V.
, 1 1 	 '
n I
PRIMARY EQUALIZATION a AERATION
CLARIFIER BASINS Q BASIN

SLUDGE TO
CONTRACT
DISPOSAL
AEROBIC THICKENER
DIGESTER
1 1
— p l~ (3) IO3,60Ogpd

V CHLORINE
FINAL CONTACT
CLARIFIERS TANK
q 28,8OOgpd 0
INSANITARY
                                         WASTEWATER
                      Figure 7-WASTEWATER TREATMENT SYSTEM - PLANT 4

-------
returns to the aeration basin.  The air-stripper sampler was
placed in the aeration basin near the side closest to the con-
trol house.

     Samples of the influent, effluent, and return sludge were
composited every 4 hours beginning at 4 pm, November 6, 1978.
Four 170-ml aliquots were taken for cyanide, phenolics, and
metals.  Each cyanide, metals, and phenolics sample was "pre-
served" at about 4 pm on November 6, 1978.  These samples were
preserved by adding 5 ml of nitric acid to the metals samples
and 2 ml of phosphoric acid to the phenolics samples.  At all
times each of the samples taken was kept on ice.  At 8 am on
November 9, 1978, VOA grab samples were taken for the influent
and effluent.  A detailed sampling schedule is presented in
Table 11.

     The air-stripper sampler was placed into operation at 10 pm
on November 6, 1978, and operations were concluded at 10:30 am
on November 9, 1978, for a total operating time of 58 1/2 hours.
Air charged to the stripper averaged 60 cubic feet per hour, and
the quantity of air to the XAD-2 scrubber was 30 cubic feet per
hour.  Stripped air was collected on the Tenax columns for 3 1/2
hours on November 8.  Tenax sampling began at 8:40 am on
November 8, 1978, and ended at 12:10 pm that day.  Tenax column
No. 14 was used for this sampling.

     Daily flow data for the  sampling period are presented in
Table 12.

Analytical Results--
     Priority pollutants for which samples were collected and
analyzed are presented in Table 13.  All extractions and
analyses of samples were conducted at RSKERL.
                                31

-------
            TABLE 11.  SAMPLING SCHEDULE  (PLANT 4)

Date Time
11/06/78 4:00 pm
Sample taken
Composites*
Remarks
Added 5 ml HNO~ ,
          8:00 pm

         12 Midnight
11/07     4:00 am
          8:00 am
         12 Noon
          4:00 pm
          8:00 pm
         12 Midnight

11/08     4:00 am
          8:00 am
         12 Noon
          4:00 pm
          8:00 pm
         12 Midnight

11/09     4:00 am
          8:00 am
         12 Midnight
M
ii
M
ii
M
ii


n
ii
n
n
ii
n


M
ii
n
     2 ml NaOH, 2 ml H3P0

     metals, cyanide, and

     phenolics composites
                                to
& VOA
^Composites consist of four 170-ml aliquots for organics and
three 50-ml aliquots for cyanides, phenolics, and metals.
             TABLE 12.  DAILY FLOW DATA  (PLANT 4)

Date
11/6/78
11/7
11/8
11/9

Influent*
(spd)
66,910
72,450
71,830
72,490

Effluent
(*pd)
90,640
93,850
92,070
92,230

*Does not include sanitary wastes
                               32

-------
                       TABLE 13.  ANALYTICAL DATA (PLANT 4)
                                    Sparged Air, XAD-2   Sparged Air,  Tenax
     Priority Pollutant	pgrams	ugrams	
POLYNUCLEAR AROMATICS
     Naphthalene                        90
     2-Chloronaphthane                 <10
     Acenaphthalene                    <10
     Acenaphthene                      <10
     Fluorene                          <13
     Phenanthrene/Anthracene           <10
     Fluoranthene                      <10
     Pyrene                            <10
     1,2-Benzanthracene                <10
     Chrysene                          <10
     3,4-Benzopyrene                   <35
     l,2:5,6-Dibenzanthracene          N.D.

PHENOLICS
     2-Chlorophenol                    <25
     2-Nitrophenol                     <25
     Phenol                            <10
     2,4-Dimethylphenol                <25
     2,4-Dichlorophenol                 80
     2,4,6-Trichlorophenol             <10
     4-Chloro-m-cresol                 110
     2,4-Dinitrophenol                 100
     4,6-Dinitro-o-cresol              <25
     Pentachlorophenol                 <25
     4-Nitrophenol                     <25

PURGEABLES
     Methylene  chloride                                 No results - sample
     1,1-Dichloroethane                                 lost.  Analytical
     1,2-Trans-dichloroethylene                         equipment malfunction.
     Chloroform
     1,2-Mchloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene	.	.	
                                     33

-------
                  TABLE 13.     (Continued)

Influent Return Sludge
Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Ant imony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGE ABLE S
1 , 2-Dichloroethane
Toluene
Chloroform
Methylene chloride
Benzene
Ethylbenzene
Tetrachloroethylene
Trichloroethylene
PHENOLICS
Phenol
Pentachlorophenol
PHALATES
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
(ng/1)

<.05 *
350

<10
<10
2
3
120
<10
12
<10
620
<10
<10
12
<0.8


<10
<10
<10
<10
<40
<10
10
<10

17
18

<10
<10
(Mg/D

<.05*
74

<10
33
59
<3
8,300
<10
740
110
7,700
160
<10
810
62


N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.

9
38

<21
<10
Effluent
(/g/D

<.05*
18

<10
<10
<1
<3
29
<10
11
12
260
<10
<10
<10
<0.5


<10
<10
<10
48
<40
<10
<10
<10

19
26

<10
<10

*Note: Total Cyanides expressed in mg/1.
**Key: N.D. - Not Detectable, or less than

detectable

limits


N.A. - Not Applicable
N.S. - No Standard Available
N.P. - No Procedure   "
                             34

-------
Plant No. 5

Wastewater Treatment System--
     A flow diagram of Plant 5's wastewater treatment system is
shown in Figure 8.  Sanitary wastes from the plant flow into a
grinder, then into a clarifier and digester.  After treatment in
a chlorination basin, these wastes are added to the process
stream just after the neutralization basin.

     Process wastes from the manufacturing first flow into an
equalization basin, from which they enter a neutralization basin
of about 19,400 gallons.  Acid and alkali are added as needed to
adjust pH prior to the flow entering the sedimentation basin.
Wastes from the sanitary system enter between the neutralization
basin and the sedimentation basin.

     The sedimentation basin effluent is fed to a roughing trick-
ling filter, then into an activated sludge system which consists
of two tanks in series which have a combined volume of 240,000
gallons.  Biological sludge for the activated sludge unit comes
from skimmings from the dissolved air flotation unit (DAF), which
is in line just after the activated sludge tank.  At present,
none of  the skimmings are wasted.  From the DAF unit, the waste
is pumped through a lift station into two parallel final trick-
ling filters of 73,500 gallons each.  After treatment by the
trickling filters, the waste enters a splitter and from there
flows into two parallel final clarifiers.  The effluent from
these clarifiers is combined, then mixed with cooling water and
surface  runoff before discharge to the receiving stream.  The
sludge from the final clarifiers is dewatered by centrifugation,
and the  solids are incinerated.

     The flow through the treatment system averages about 1.2 to
1.4 million gallons a day.  The treatment effluent is mixed in a
ratio of approximately 1:9 with cooling water before discharge.

Sample Collection--
     The survey of Plant 5 was conducted September 11-14, 1978.
Composite samples were collected within a 72-hour period at four
points.  At the final clarifiers, the discharge was mixed under-
ground with no provision for sample-taking prior to the efflu-
ent's being mixed with surface and cooling water.  For this rea-
son, samples were taken at each final clarifier overflow, then
mixed in equal proportions prior to compositing so as to produce
one sample for the two locations.  The samples taken were from:

     (1)  The sedimentation basin effluent was sampled as bio-
influent due to the inaccessibility of effluent from the roughing
trickling filter.
     (2)  The final clarifier sludge taken from a valve on the
discharge side of the pump that lifts sludge to the sludge aera-
tion bays.

                                35

-------
FLOW FROM
EQUAL. BASIN
AND NEUT.
 BASIN
 OUGHIN
TRICKLIN
 ILTER
                                       ACTIVATED
                                        SLUDGE
                               SLUDGE/FINAL
                                      CLAR.
                                                   COOLING WATER

                                                          TO
        I-INFLUENT

        I-SLUDGE

        '-EFFLUENT
      (4)- DAF SKIMMINGS
      
-------
      (3)   The  final clarifier effluents flowing into the weir
 trough  at  each final clarifier.
      (4)   The  DAF skimmings which were taken at a valve located
 on  the  lift pump to the head end of the aeration tank.

     Due to the  inaccessibility, the air stripper was placed in
the sedimentation basin between the skimmer rail and the overflow
weir.  The  stripper was started at 12 Noon, September 11, and
operation was  concluded at  9  am on September 14, for a total op-
erating time of  69 hours.   The system was shut down 2 3/4 hours
prior to the prescribed 72-hour time period because of failure of
both the vacuum  pump and the  water meter that measured flow into
the air stripper.  Stripped air was collected on the Tenax col-
umn for 15 minutes three times while the sampler was in operation.

      Twenty-four aliquots were collected from the four
 sampling points, beginning at 12 Noon, September 11.   Aliquots
 were collected at intervals of 3 hours.  The final aliquot was
 collected at 8 am, September 14.  A detailed sampling schedule
 is presented in Table 14.
             TABLE 14.  SAMPLING SCHEDULE (PLANT 5)
 Date
Time
Sample taken
Remarks
 9/11/78
 9/12/78
 9/13/78
 9/14/78
12 Noon
3:00 pm
6:00 pm
9:00 pm
12 Midnight
3:00 am
6:00 am
9:00 am
12 Noon
3:00 pm
6:00 pm
9:00 pm
12Midnight
3:00 am
6:00 am
9:00 am
12 Noon
3:00 pm
6:00 pm
9:00 pm
12 Midnight
3:00 am
6:00 am
8:00 am
Composite aliquots
                                         " -        Tenax, 15 min.
                               Composite & VGA grab samples
                               Composite aliquots
                                         it
                                         "         Tenax, 15 min,
                                                   Tenax 15 min.
                                37

-------
     Samples were collected for the priority pollutants which
were found in the priority pollutants survey or which might be
expected to be found in plant wastewater operations.  The samples
were preserved by prescribed EPA methods.  All samples were kept
on ice throughout the sampling period.

     VGA samples were taken of the sedimentation basin effluent
and the final clarifier effluent on September 13 at 9 am.  Du-
plicate samples for cyanides and phenol analyses were taken from
the final clarifier effluent for company personnel.

     Throughout the sampling period, the underflow in the DAF
unit was approximately 1.185 to 1.275 million gallons per day,
while the skimmings or DAF sludge that was pumped varied between
151,910 to 179,940 gallons per day.  The final clarifier sludge
removed to aeration was about  .078 million gallons per day, and
the final clarifier effluent was 1.107 to 1.197 million gallons
per day.

     Daily flow data for the sampling period are presented in
Table 15.

             TABLE 15.  DAILY FLOW DATA (PLANT 5)
DAF skimmings Influent Return sludge Effluent
Date returned (mgd) (mgd) (mgd) (nigd)
9/11/78
9/12/78
9/13/78
9/14/78
.178 1.2-1.4 .078 1.11-1.20
152 " " "
.114
.118

Analytical Results--
     A list of the priority pollutants for which samples were
collected is presented in Table 16.  All extractions and analyses
were done at RSKERL.  Results of these analyses are presented in
Table 16.
                               38

-------
                     TABLE  16.  ANALYTICAL DATA  (PLANT 5)
     Priority Pollutant
Sparged Air, XAD-2
   (yg)
                                                         Sparged Air,  Tenax
POLYNUCLEAR AROMATICS
     Naphthalene                        940
     2-Chloronaphthane                5,000
     Acenaphthalene                     <60
     Acenaphthene                        60
     Fluorene                           <78
     Phenanthrene/Anthracene            150
     Fluoranthene                       <60
     Pyrene                             <60
     1,2-Benzanthracene                 <60
     Chrysene                           <60
     3,4-Benzopyrene                   <210
     l,2:5,6-Dibenzanthracene           N.D.
PHENOLICS
     2-Chlorophenol                    <150
     2-Nitrophenol                     <150
     Phenol                             <60
     2,4-Dimethylphenol                <150
     2,4-Dichlorophenol               1,500
     2,4,6-Trichlorophenol              <10
     4-Chloro-m-cresol                1,800
     2,4-Dinitrophenol                 <600
     4,6-Dinitro-o-cresol               600
     Pentachlorophenol                 <150
     4-Nitrophenol                     <150

PURGEABLES
     Methylene  chloride
     1,1-Dichloroethane
     1,2-Trans-dichloroethylene
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene    	  .	
                     Sample lost  -
                     Analytical apparatus
                     malfunction.
                                     39

-------
                              TABLE 16.    (Continued)
Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGE ABLE S
Benzene
Chloroform
Methylene chloride
Toluene
Ethylbenzene
1,1, 1-trichloroethane
1 , 2-dichloroethane
PHENOLICS
4-Nitrophenol
2-Nitrophenol
PHTHALATE ESTERS
Bis(2-ethylhexyl) phthalate

DAF Clarifier Clarifier
Influent Skimmings Effluent Sludge
(jig/1) OiB/D (»K/1) (Mg/D

.25*
945

<1 Q
<1 Q
<01
3
120
10
12
39
41
<10
<10
22
<2.0


127
<10
47
<10
150
<10
<10

N.D.
123

Matrix
removed

.22*
107

16
<10
11
<3
1,900
<10
1,500
42
5,600
17
<10
12
<10


N.A.
"
11
"
11
"
it

381
387

interferences
by procedure

.17* .23*
39 201

<10 21
<10 < 10
<1 16
<3 <3
34 2,800
< 10 < 10
34 2,100
38 32
9 7,800
<10 72
<10 56
<10 30
<2.0 <10.0
-

<40 N.A.
<10 "
<10 "
<10 "
<10 "
< 1 0 "
<10 "

N.D. N.A.
21 N.A.

not sufficiently
cleanup .
 *Note:  Total Cyanides expressed in mg/1.
**Key:  N.D. - Not Detectable,  or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                     40

-------
PESTICIDES INDUSTRY

Plant 6

Wastewater Treatment System--
     A flow diagram of Plant 6's wastewater  treatment system is
shown in Figure  9.  Wastewater generated by  the manufacturing of
pesticides and organic chemicals is  collected  centrally after
several streams  have been pretreated.  The central system con-
sists of (1) neutralization, (2) equalization,  (3) activated
sludge, (4) followed by  a polishing  lagoon.  Excess sludge
produced by the  wastewater  treatment process is disposed of in a
sludge pit with  a metal  process waste  solid.   The supernatant
from the sludge  pit is chemically  oxidized and fed to the feed
of the central organic wastewater  system at  the pump station.

     Approximately 1.7 mgd  of process  water  from the manufactur-
ing process is pumped to a  2.1-million-gallon  equalization
basin. The wastewater is mixed with  return sludge from the
activated sludge clarifier.  This  mixture is split and flows to
two parallel 2.4-million-gallon aeration basins.  Each basin has
five 50-horsepower mechanical aerators.  The mixed liquor flow
from the two aeration basins is combined and flows to a single
250,000-gallon clarifier.   This system operates with a return
sludge flow rate of about 750 gallons  per minute (gpm) and a
sludge wasting rate of about 3 gpm.  Figure  9  indicates the
average flow through the activated sludge unit for a 6-month
period in 1978.  Overflow of treated water from the clarifier
flows through the polishing lagoon for final solids removal and
then is mixed with combine  non-contact and inorganic process
water streams before discharge into  the bay.

Sample Collection--
     Based on the previous  screening survey  studies of the
Effluent Guidelines Division, the  list of 24 organic compounds
in Table 19 was  compiled.   This list represents the priority
pollutants that  were anticipated to  be in Plant 6's influent to
the treatment system.

     The locations of the sampling points are  shown in Figure 9.
The influent sample  (No. 1) was taken  from the channel leading
from the equalization basin just before the  return sludge is
mixed with the influent. The effluent sample  (No. 2) was taken
from the overflow channel of the clarifier.  The return sludge
sample (No. 3) was taken from the  sump for the recycle pump.
The air-stripper sampler (No. 4) was placed  in the southeast
corner of the south aeration basin due to inaccessibility.
                                41

-------
      PRETREATMENT
                                             CENTRAL   TREATMENT
V)
Ul
ac,
ac.
ui

I
HI
j-
M
4
3
O
st
Hi
±"£
                                       JAN 78
                                       FEB 78
                                       MAR78
                                       APR 78
                                       MAY 78
                                       JUN78
                                  CENTRAL ORGANIC WASTEWATER
                                           FLOW DATA
1.77 mm Gol./Doy
1.52
1.72
1.66
1.58
1.81
                                       AVE.  1.68
                                            EQUAUZATIO
                                            (Waste Ave.)
                                            2mm gal.
                                            4-20 Hp
                                            Floating Aer.
 AERATION
  BASIN
  24mmgal.
  5-50Hp
  Floating
  Aero tors
                                                                          CLARIFIER
                                                                          .250m gal.
          SLUDGE
          PIT
         (Solids
         Removal)
                   Super.
                    note
                                  EXCESS
MIXING and
 SPLITTING
                                   3 gpm
\
^4.^L
>JS>N>
	 ^r^T
	 	 S'
EQUAL.
a
THERMAL
BASIN


SETTLING
BASIN
1 Otf.1 U«
isoiids
Removal)

SAMPLE POINTS:
                Figure 9.  WASTEWATER TREATMENT SYSTEM - PLANT  6
                                                                            I-INFLUENT
                                                                            2-EFFLUENT
                                                                            3- RETURN SLU06E
                                                                            4-AIR STRIPPER

-------
     Samples of the influent, effluent, and return sludge were
composited over a period of about 3 days.  Every 3 hours begin-
ning at 9 am on the first day, July 25, 1978, four 130-ml ali-
quots were taken at each sample point for specific organics
analysis.  Then, beginning at 8 am on the second day, July 26,
composites were taken again every 3 hours.  Finally, beginning
at 7 am on the third day, July 27, composites were taken about
every 3 hours.  In addition, three 40-ml aliquots were taken for
metals, cyanides, and phenolics at the same time as the organic
samples were taken.  These samples were preserved by adding 5 ml
of nitric acid to the metals samples, 2 ml of sodium hydroxide
to the cyanides samples, and 2 ml of phosphoric acid to the
phenolics samples.  At all times, each of the samples was kept
on ice.  At 2 pm, July 27, VOA samples were taken for the influ-
ent and effluent.  A detailed sampling schedule is presented in
Table 18.

     The air-stripper sampler was placed into operation at 10 am
on July 25, 1978, and operations were concluded at 7:30 pm, July
27, for a total operating time of 57 hours and 20 minutes.  Air
charged to the stripper averaged 60 cfh, and the quantity of air
to the XAD-2 scrubber was 30 cfh.  Stripped air was collected
on the Tenax columns for 10 minutes on each day of sampling.   At
this plant two Tenax columns were taken.  One column was retained;
the other column was left with the company for its own separate
analysis.

     Average flow data for this plant are presented in Table 17.


            TABLE 17.  AVERAGE FLOW DATA (PLANT 6)

Date
1/78
2/78
3/78
4/78
5/78
6/78
Average
Influent
(mgd)
1.77
1.52
1.72
1.66
1.58
1.81
1.68
Return Sludge
(mgd)
750

Analytical Results--
     Priority pollutants for which samples were collected and
analyzed are presented in Table 19.  All extractions and analyses
were conducted at RSKERL.
                               43

-------
            TABLE 18.  SAMPLING SCHEDULE (PLANT 6)
  Date
  Time
Sample taken    Remarks
7/25/78
7/26/78
7/27/78
 9:00 am
12 Noon
 1:00 pm
 3:00 pm
 6:00 pm
 9:00 pm
12 Midnight
 3:00 am
 6:00 am
 8:00 am
11:00 am
 2:00 pm
 5:00 pm
 8:00 pm
11:00 pm
 2:00 am
 5:00 am
 7:00 am
10:00 am
 1:00 pm
 2:00 pm
 4:00 pm
 5:30 pm
 7:00 pm
10:00 pm
11:00 pm
12 Midnight
Composites
                        Composites
                                        Added 5 ml HN03  2 ml NaOH,

                                        2 ml H3P04 to metals,

                                        cyanides, and phenolics.
                            II

                            II
                          VGA
                        Composites
                        Effluent grabs
                        Composites
                               44

-------
                     TABLE  19..  ANALYTICAL  DATA (PLANT  6)
                                     Sparged Air, XAD-2   Sparged Air, Tenax
	Priority Pollutant	    (p g)                  (y g)

POLYNUCLEAR AROMATICS
     Naphthalene                            .12
     2-Chloronaphthane                      <5
     Acenaphthalene                           7
     Acenaphthene                           <3
     Fluorene                               <13
     Phenanthrene/Anthracene                10
     Fluoranthene                             5
     Pyrene                                 <4
     1,2-Benzanthracene                     <6
     Chrysene                               <4
     3,4-Benzopyrene                        <35
     l,2:5,6-Dibenzanthracene              N.D.
PHENOLICS
     2-Chlorophenol                      1,380
     2-Nitrophenol                          250
     Phenol                                 520
     2,4-Dimethylphenol                     500
     2,4-Dichlorophenol                     340
     2,4,6-Trichlorophenol               3,200
     4-Chloro-m-cresol                      240
     2,4-Dinitrophenol                      <.l
     4,6-Dinitro-o-cresol                  100
     Pentachlorophenol                      290
     4-Nitrophenol                         <.02
PURGEABLES
     Methylene  chloride                                  „      ,      .,  , ,
     1  , ~. i i     . i_                                     No results available
     1,1-Dichloroethane                                  ,         _ .
     i  o m      j. , i     4.1.1                             because of instru-
     1,2-Trans-dichloroethylene
     .,'     ,.                                             ment malfunction.
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenz ene
     Ethylbenzene	
                                     45

-------
TABLE 19.     (Continued)

Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGE ABLE S
Benzene
Chloroform
Methylene Chloride
Bromoform
Toluene
Trichloroethylene
Chlorobenzene
1,1, 1-tr ichloroethane
1 , 2-dichloroethane
1,1,2, 2-tetrachloroethane
POLYNUCLEAR AROMATICS
Naphthalene
2-Chloronaphthalene
Benzo (a) anthracene
Benzo (a) pyrene
3,4-Benzofluoranthene
Benzo (k) f luoranthene
Chrysene
Acenaphthylene
Anthracene /Phenanthrene
Benzo (g ,h , i) perylene
Fluorene
Dibenzo (a ,h) anthracene
Indeno (1 , 2 , 3-cd) pyrene
Pyrene
(Continued)
Influent
Qig /I)

.26*
190

20
<10
<1
<5
130
<10
88
23
130
<10
<10
<10
<2.0


<40
2,240
10,400
56
37
1,620
N.D.

-------
                        TABLE 19.     (Continued)
                                            Influent  Return Sludge  Effluent
     Priority Pollutant	Qig/1)      Qig/1)	fog/D

PHENOLICS
     Phenol                                     23           12          1.3
PESTICIDES
     Lindane                                   <10          105          <10

 *Note: Total Cyanides expressed in mg/1.
**Key:  N.D. - Not Detectable, or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                      47

-------
Plant 7

Wastewater Treatment System--
     A flow diagram of Plant 7's wastewater treatment system  is
shown in Figure 10.  Wastewaters generated by the manufacturing of
agricultural chemicals, including pesticides,  are treated by a
process consisting of  (1) lime precipitation,  (2) equalization,
(3) acid/base neutralization, (4) activated sludge treatment, and
(5) polishing in an aerated lagoon.  Normally  the activated sludge
unit is operated without wasting sludge.

     The average wastewater flow entering the  treatment  system is
200 gpm.  The flow may be split to enter two parallel equaliza-
tion basins.  Normally equalization basin No.  1 receives 134  gpm,
and equalization basin No. 2 receives 66 gpm.  The average deten-
tion time for each basin is 3 days.  Flows from the two basins
are recombined  for acid/base neutralization prior to being fed
into the aeration basin of the activated sludge unit.

     The aeration basin has a volume of 956,001) gallons, a depth
of 15 feet, and a surface area of 16,800 feet  .  The basin is
equipped with five 75-hp mechanical aerators.  Each aerator is
rated for an oxygen transfer rate of 240 pounds per hour.  The
average detention time in the basin is 3 days.

     The final  clarifier is 30 feet in diameter and 12 feet deep,
with an average detention time of 5 hours.  The treated water
flows from the  clarifier to an aerated polishing lagoon  contain-
ing five 30-hp  mechanical aerators prior to final discharge.
Little additional biological removal as measured by TOG occurs in
this lagoon.  The average detention time in the lagoon is 13  days.

     In addition to the described wastewater system, this facil-
ity employs two deep-well systems for disposal of wastewaters
from specific process units.  The plant currently produces only
two pesticide products; a third pesticide producing unit has been
idle since October, 1977.  Wastewater from only one of the oper-
ating pesticide units goes to the biological treatment system;
wastewater from the other unit goes into one of the deep-well
systems.

Sample Collection--
     The survey of this facility was conducted during the period
June 27-30, 1978.  Composite samples were collected within a
72-hour period  at four locations in the biological treatment
system (Figure  9):

     (1)  Influent to aeration basin (water phase)
     (2)  Effluent from final clarifier (water phase)
     (3)  Return sludge (residual phase)
     (4)  Air-stripper sampler (air phase)


                                48

-------
        HERBICIDE
     CONC.  WASTES
          LIME
       PRECIPITATION
TO LANDFILL
                FLUME
 CLARIFIER
               AERATION
                 BASIN
  HERBICIDE, ORGANIC  AND
   INORGANIC  WASTES
                             ACID
COLLECTION
  TANK
                             BASE
                             NEUT.
                             TANK
                             1   f
                           ACID BASE
             TO ni«r«;TPR
             T0 DIGESTER
            ^FINAL DISCHARGE
                                 (\) -INFLUENT
                                 ©-EFFLUENT
                                 ©-SLUDGE
                                 ($)- AIR STRIPPER
FLUME
                 EQUALIZATION
                  BASIN NO. I _
                                                  EQUALIZATION
                                                    BASIN NO. 2
                         J FLUME
                         LPL
           Figure 10 - WASTEWATER TREATMENT SYSTEM - PLANT  7

-------
     The air-stripper sampler was located in the aeration basin
near the influent point.  The air-stripper sampler was placed in
operation at 8:30 am, June 27, and operations concluded at
3:30 pm, June 29, for a total operating time of 55 hours. Air
charged to the stripper averaged 60 cfh, and the quantity of air
to the XAD-2 scrubber was 30 cfh.  Stripped air was collected on
the Tenax column for 10 minutes on each of the 3 days the sampler
was operating.

     Twenty-four equal aliquots were collected manually from the
water and residual phase sampling points beginning at 8:45 am,
June 27.  Aliquots were collected at intervals of approximately
3 hours.  The final aliquot was collected at 3 am, June 30.

     Samples were collected for those priority pollutants which
were found in the previous priority pollutant screening survey,
or which might be expected to be found if all plant processes
were in operation.  Samples were preserved by prescribed EPA
methods.  All samples were kept on ice throughout the sampling
period.  At the end of the sampling period, grab samples for VGA
analyses were collected from the water-phase sample points.  A
detailed sampling schedule is presented in Table 20.


	TABLE 20.  SAMPLING SCHEDULE (PLANT 7)	


Date	Time	Sample taken  	Remarks	

6/27/78        8:45 am        Composite aliquots
              12:00 Noon               "
               3:00 pm                 "          Tenax, 10 min.
               6:00 pm                 "            each
              12:00 Midnight
6/28/78        3:00 am
               6:00 am
               9:00 am
              12:00 Noon
               3:00 pm                 "          Tenax, 10 min.
               6:00 pm                 "            each
               9:00 pm
              12:00 Midnight
6/29/78        3:00 am
               6:00 am
               9:00 am
              12:00 Noon               "          Tenax, 10 min.
               3:00 pm        VGA grab samples      each
               6:00 pm        Composite aliquots
               9:00 pm'
              12:00 Midnight
6 /30 /78        2:00 am
               4:00 am
                                50

-------
     Duplicate sets of all samples, with the exception of the
XAD slurry and Tenax columns, were collected and given to plant
representatives.

     Influent and effluent flow data for the sample period are
presented in Table 21.

TABLE 21
. DAILY FLOW DATA (PLANT 7)

Date
June 27 ,
June 28,
June 29,

1978
1978
1978
Influent*
(mgd)
0.25
0.27
0.38
Return Sludge
(mgd)
Not Available
it
it
Effluent**
(mgd)
0.13
0.13
0.14
    [ows entering the bio  system before equalization.
**Flows exiting aerated lagoon (final plant discharge).

Analytical Results--
     Priority pollutants  for which  samples were collected and
analyzed are presented in Table 22.  All extractions and analyses
were conducted at RSKERL.
                                51

-------
                       TABLE 22.  ANALYTICAL DATA  (PLANT 7)
                                    Sparged Air, XAD-2    Sparged  Air,  Tenax
     Priority Pollutant                    (n.g)                  (ug)
POLYNUCLEAR AROMATICS
     Naphthalene                            <.005
     2-Chloronaphthane                      <.005
     Acenaphthalene                         <.006
     Acenaphthene                              .5
     Fluorene                               <.013
     Phenanthrene/Anthracene                   6
     Fluoranthene                              2
     Pyrene                                 <.004
     1,2-Benzanthracene                     <.006
     Chrysene                               <.005
     3,4-Benzopyrene                        <.035
     l,2:5,6-Dibenzanthracene                N.D.

PHENOLICS
     2-Chlorophenol                            74
     2-Nitrophenol                          <.02
     Phenol                                  260
     2,4-Dimethylphenol                        8
     2,4-Dichlorophenol                        39
     2,4,6-Trichlorophenol                     16
     4-Chloro-m-cresol                       <.l
     2,4-Dinitrophenol                       100
     4,6-Dinitro-o-cresol                      11
     Pentachlorophenol                         14
     4-Nitrophenol                          <.02
PURGEABLES
     Methylene chloride                                          <.02
     1,1-Dichloroethane                                          <.01
     1,2-Trans-dichloroethylene                                  <.25
     Chloroform                                                      1
     1,2-Dichloroethane                                            .01
     1,1,1-Trichloroethane                                       <.05
     Carbon tetrachloride                                          <.l
     Dichlorobromomethane                                           .3
     1,2-Dichloropropane                                         <.01
     Benzene                                                       .01
     Trichloroethylene                                           .002
     Chlorodibromomethane                                        <.01
     1,1,2-Trichloroethane                                       <.05
     Methyl bromide                                              <.25
     Bromoform                                                   <.01
     1,1,2,2-Tetrachloroethane                                   <.025
     Tetrachloroethylene                                         <.05
     Toluene                                                     .006
     Chlorobenzene                                               <.01
	Ethylbenzene	<.QI
                                     52

-------
                            TABLE 22.    (Continued)
    Priority Pollutant
                                            Influent
                                                      Return Sludge
                                                         (Mg/D
                        Effluent
CLASSICAL

TOTAL CYANIDES (mg/1)*

TOTAL PHENOL

TOTAL METALS
     Arsenic
     Selenium
     Cadmium
     Beryllium
     Copper
     Antimony
     Chromium
     Nickel
     Zinc
     Silver
     Thallium
     Lead
     Mercury

ORGANICS  (GAS CHROMATOGRAPHY)

PURGEABLES
     Benzene
     Toluene
     Ethylbenzene
     1,1,1-Trichloroethylene

PESTICIDES
     Aldrin
     Dieldrin
     Chlordane
     DDT
     4,4'-DDT
     4,4'-DDE
     4,4'-ODD
     a-endo su1f an-Alpha
     b-endosulfan-Beta
     Endosulfan  sulfate
     Endrin
     Endrinaldehyde
     Heptachlor
     Heptachlor  epoxide
                                               .04

                                            13,700


                                                10
               .25

                79
                 .04

                <100


                  10
    2
   10
   40
  220
   51
1,600
1,500
   <5
   <5
    5
 <5.0
                                               <40
     11
      1
    230
    350
    190
      2
  4,300
     <5
     <5
    110
Sample lost
               N.A.

                ii
                ii
                                                                          <5
                                                                          60
                                                                          31
                                                                         510
                                                                         830
                                                                          <5
                                                                          <5
                                                                           5
                                                                        <5.0
                 <40
(Continued)
                                     53

-------
                           TABLE 22.   (Continued)
     Priority Pollutant
Influent  Return Sludge  Effluent
 (jig/D
PESTICIDES (Continued)
     a-BHC-Alpha
     b-BHC-Beta
     r-BHC (lindane)-Gamma
     g-BHC-Delta
     Toxaphene

PHENOLICS
     Phenol
     4-Nitrophenol
     2-Nitrophenol
     2,4-Dimethylphenol
     2,4-Dichlorophenol
     2,4-Dinitrophenol
     2,4,6-Trichlorophenol
,290
 103
  17
 N.D.
   2
  36
   4
                18
               N.D.
                 2
               N.D.
                 3
                14
                 1
 24
N.D.
 71
N.D.
 20
 96
  4
NITROSAMINES
     N-nitrosodimethylamine
     N-nitrosodiphenylamine
     N-nitrosodi-N-propylamine
  A nitroso specific thermal
  detector not available
 *Note: Total Cyanides expressed in mg/1.
**Key:  N.D. - Not Detectable, or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                     54

-------
RUBBER INDUSTRY

Plant 8

Wastewater Treatment System--
     A flow diagram of Plant 8's wastewater treatment system is
shown in Figure 11.  Wastewater generated by the manufacturing
of rubber and associated products is treated by a process con-
sisting of (1) equalization, (2) neutralization, and (3) activated
sludge treatment.  Normally, the activated sludge unit is operated
without wasting of sludge.

     Treatment of the wastewater begins when process water from
the various plant units enters the equalization basin at the
design flow of 1,200 gpm.  Volume of the basin is 8.0 million
gallons with an average detention time of 110 hours at the design
flow rate of 1,200 gpm.

     From the equalization basin, wastewater is pumped to a
neutralization basin for pH adjustment and addition of nutrients.
An antifearning agent is also added here if needed.  Volume of
the neutralization basin is 138,000 gallons with an average de-
tention time of 2.0 hours at the design flow of 1,200 gpm.

     From the neutralization basin, the wastewater is split to
flow into two parallel aeration basins with a combined volume of
700,000 gallons.  The design influent flow to each basin is 600
gpm.  Each basin contains three 25-horsepower mechanical aerators.
Average detention  time in the aeration basins is 6.5 hours at
the design flow rate.

     Effluent from the aeration basins flows into a clarifier
which has a diameter of 60 feet and a volume of 300,000 gallons.
Retention time is 4 hours at the design flow of 1,200 gpm.  Ef-
fluent from the clarifier merges with chlorinated effluent from
the plant's sanitary waste treatment system for final discharge.

     The plant has a 25-million-gallon stormwater basin to retain
excess waters during heavy rainfall.  Water from the basin is
bled back through  the treatment system.

Sample Collection--
     The survey of this facility was conducted during the period
July 10-13, 1978.  Composite samples were collected within a
72-hour period at four locations in the biological treatment
system:

     1.  Influent to aeration basin (water phase)
     2.  Effluent from final clarifier (water phase)
     3.  Return sludge (residual phase)
     4.  Air-stripper (air phase)
                               55

-------
SLUDGE
           STORMWATER
             BASIN
EQUAL.



SUMP

                                            1200 GPM
              TOWER MAKE-UP
          I60OO GPD
SANITARY
WASTE
CHLORINE
_L
                                      pH  NUTRIENTS
                                                              NEUT.
                                                               ©
                                                             BASIN
                                                                FINAL DRAINAGE
                             SAMPLE POINTS
                          0 - INFLUENT
                          @ -EFFLUENT
                          (D - SLUDGE
                          f4) -AIR STRIPPER
     Figure  II - WASTE WATER TREATMENT SYSTEM - PLANT  8

-------
     The air-stripper sampler was located in one of the aeration
basins as near the influent point as possible.  The air-stripper
sampler was placed in operation at 5:30 pm, July 10, 1978, and
operation was concluded at 1:30 pm on July 13, for a total oper-
ating time of 68 hours.  Air charged to the stripper averaged
60 cfh, and the quantity of air to the XAD-2 scrubber was 30 cfh.
Stripped air was collected on the Tenax column for 15 minutes on
each of the three days the sampler was operating.

     Twenty-four equal aliquots were collected manually from the
water- and residual-phase sampling points beginning at 5:30 pm,
July 10.  Aliquots were collected at intervals of approximately
3 hours.  The final aliquot was collected at 2:30 pm, July 13.
A detailed sampling schedule is presented in Table 23.
             TABLE  23.  SAMPLING SCHEDULE  (PLANT 8)
  Date
 Time
Sample taken
Remarks
7/10/78
 7/11/78
 7/12/78
 7/13/78
 5:30 pm
 8:30 pm
11:30 pm

 2:30 pm
 5:30 am
 8:30 am
11:30 am
 2:30 pm
 5:30 pm
 8:30 pm
11:30 pm

 2:30 am
 5:30 am
 8:30 am
11:30 am
 2:30 pm
 5:30 pm
 8:30 pm
11:30 pm

 2:30 am
 5:30 am
 8:30 am
11:30 am
 2:30 pm
Composite aliquots
                                            Tenax, 15 minutes each
                                            Tenax, 15 minutes each
                                   M

                                   II

                                   II
                                          + VGA grab samples
                                            Tenax, 15 minutes each
                               57

-------
     Samples were collected for those priority pollutants which
were found in the previous priority pollutant screening survey
or which might be expected to be found if all plant processes
were in operation.  All samples were preserved by prescribed EPA
methods and kept on ice throughout the sampling period.  At the
end of the sampling period, grab samples for VGA analyses were
collected from the water-phase sample points.  Duplicate samples
from the water- and residual-phase sample points were furnished
to company personnel as requested.

     Flow measurements are not taken routinely at the points
where samples were collected; however, plant personnel estimated
that throughput during the sampling period averaged approximately
2.4 mgd with a feed rate of 1.9 mgd and return sludge rate of
0.7 mgd.

Analytical Results--
     The priority pollutants for which samples were collected and
analyzed are presented in Table 24.   All extractions and analyses
were performed at RSKERL.
                              58

-------
                        TABLE 24.   ANALYTICAL DATA (PLANT  8)
    Priority Pollutant
Sparged Air,  XAD-2
    & g)
                  Sparged  Air,  Tenax
                       (M g)
POLYNUCLEAR AROMATICS
     Naphthalene
     2-Chloronaphthane
     Acenaphthalene
     Acenaphthene
     Fluorene
     Phenanthrene/Anthracene
     Fluoranthene
     Pyrene
     1,2-Benzanthracene
     Chrysene
     3,4-Benzopyrene
     1,2:5,6-Dibenzanthracene
PHENOLICS
     2-Chlorophenol
     2-Nitrophenol
     Phenol
     2,4-Dimethylphenol
     2 ,4-Dichlorophenol
     2,4,6-Trichlorophenol
     4-Chloro-m-cresol
     2,4-Dinitrophenol
     4,6-Dinitro-o-cresol
     Pentachlorophenol
     4-Nitrophenol

PURGEABLES
     Methylene  chloride
     1,1-Dichloroethane
     1,2-Trans-dichloroethylene
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene      	
2,560
   <5
   66
   <3
  <13
   17
   <4
   <4
   <6
   <5
  <35
  N.D.

   54
1,100
7,800
2,100
  950
1,800
  660
7,000
  910
  940
1,200
                   Lost  sample  -
                   Analytical equip-
                   ment  malfunction
                                      59

-------
                  TABLE 24.     (Continued)
Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Ant imony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGEABLES
Benzene
Toluene
Ethylbenzene
PHENOLICS
Phenol
2-Nitrophenol
2,4-Dinitrophenol
4-Nitrophenol
2-Chlorophenol
2,4, 6-Trichlorophenol
NITROSAMINES
N-nitrosodiphenylamine
*Note: Total Cyanides expressed in mg/1.
**Key: N.D. - Not Detectable, or less than
Influent Return Sludge Effluent
Qig/1) (}Jg/l) (ug/1)

<.08
1,190

<10
<10
1
<3
22
<10
230
89
1,200
<10

-------
Plant 9

Wastewater Treatment System—
     A flow diagram of Plant 9's wastewater treatment system is
shown in Figure 12.  Wastewater generated by the manufacturing
of rubber and other products is treated by a process that gener-
ally consists of  (1) equalization,  (2) dissolved air flotation,
(3) cooling, and  (4) activated sludge treatment.  Normally this
activated sludge unit is operated without any wasting of sludge.
The plant has operated this system  for a number of years and has
not found a need for sludge-wasting.

     Treatment of  the wastewater begins when water from the
rubber plant is split into two 1,000-gpm streams and flows into
two parallel equalization basins.   Each basin has a 4-hour deten-
tion time at 1,250 gpm.  Wastewater from the equalization basins
is flash-mixed with cat ionic coagulant aid in a 7,500-gallon tank.
The wastewater then flows to a dissolved air flotation (DAF) unit
with anionic coagulant aid added as needed in line to the DAF.

     From the DAF  unit, a portion of the wastewater (approxi-
mately 1,500 gpm)  flows to a cooling tower for temperature con-
rol.  After cooling, caustic, acid,  and/or ammonia are added to
the wastewater as  required.  Also,  wastewaters from an oil sepa-
rator and oil-skimming basin are combined with the wastewater.

     Next, the wastewater flows into the aeration basin of the
activated sludge unit.  The aeration basin has a volume of 1.48
x  10~ gallons, a  depth of 17 feet,  and a surface area of 16,870
feet  .  The aeration basin is equipped with four 50-horsepower
mechanical aerators.  These aerators are rated for an oxygen
transfer rate of  450-500 pounds per hour.  The clarifier is about
85 feet in diameter and 18 feet deep.  Treated water (effluent)
flows from the clarifier to the bayou.

Sample Collection--
     Based on Effluent Guidelines Division's previous screening
survey studies, the list of compounds in Table 27 was compiled.
This list represents the priority pollutants that were expected
to be present in  Plant 9's influent to the treatment system.
From this list, it was determined that four 1-gallon samples of
composites were required for specific organic compound analysis.

     The locations of the sampling  points are shown in Figure 12.
The influent sample was taken just  before the wastewater flows
into the aeration  basin.  The influent sample was taken from the
plant's sample pump.  The return sludge sample was taken from the
return sludge pump.  The air-stripper sampler was placed in the
aerator basin just in front of the  point where influent enters
the basin.
                                61

-------
                                   SAMPLE POINTS
o
t-
FROM NEUTRALIZE

WASTEWATEfJ
2,000 gpm
O" INFLUENT
CATIQNIC /5\ -AIR CTRIPDPR
COAGULANT ^ AIR STRIPPER
AID @ -PFF! IIFNT
® -SLUDGE
COAGULANT AID (AN ION 1C
i
1 i /
/ '
EQUALIZATION / __
BASINS *J 	 	 - 	 	

i

~>3 i
„ FLASH [\
MIX 	 V J
OAF UNIT
PRODUCT
RECOVERY
OH
5CP£
,500 gpm max.
t'
\ /
COOLING
TOWER
1^^


flATOf T0
< BAYOU
H o 1/5\
coo 2 K^
§5 S AERATION BASIN ^L^
*^ "^ X. S /^ ^*N.
f T f «P D ( CLARIFIER)
ODD V y
c "S — T —
i ,
f ®
— ' ,000 gpm
            OIL SKIMMING
               BASIN

Figure 12 - WASTEWATER TREATMENT SYSTEM - PLANT  9
                    62

-------
     Samples of the influent, effluent, and return sludge were
composited.  Every 3 hours beginning at 3 pm on July 17, 1978,
the first day, four 130-milliliter aliquots were taken at each
sample point for specific organics analysis.  Then, beginning at
2 pm on July 18, the second day, composites were taken every 3
hours.  In addition, three 40-milliliter aliquots were taken for
cyanide, phenolics, and metals at the same time as the organics
samples were taken.  Each cyanide, phenolics, and metals sample
was preserved at 8 pm on July 17.  These samples were preserved
by adding 5 ml of nitric acid to the metals sample, 2 ml of
sodium hydroxide to the cyanides sample, and 2 ml of phosphoric
acid to the phenolics sample.  At all times, each of the samples
was kept on ice.  At 7:30 pm on July 19, VGA samples were taken
for the influent and effluent.  . / detailed sampling schedule is
presented in Table 25.

            TABLE 25.  SAMPLING SCHEDULE (PLANT 9)

Date
7/17/78
Time
3:00 pm
Sample taken
Composites*
Remarks

7/18/78
7/19/78
 6 :00 pm
 8:00 pm
 9:00 pm
12 Midnight

 3:00 am
 6:00 am
 9:00 am
12 Noon
 2:00 pm
 5:00 pm
 8 :00 pm
11:00 pm

 2:00 am
 5:00 am
 8:00 am
11:00 am
 1:00 pm
 4:00 pm
                         Composites
                              ii
                              M
               Added 5 ml HN03,  2 ml


               metals, cyanide,  and
               phenolics
                              M

                              II

                              II

                              II

                              II
            :00 pm
            :30 pm
7/20/78
10:00 pm

 1:00 am
 4:00 am
 6:00 am
 7:30 am
VOA
Composites

Composites
^Composites consist of four 130-ml aliquots for organics,
three 40-ml aliquots for cyanide, phenolics and metals.
                                63

-------
     The air-stripper sampler was placed in operation at 7 pm on
July 18, 1978, and operations were concluded at 7:40 am on July 20,
for a total operating time of 60 hours and 40 minutes.   Air
charged to the stripper averaged 60 cfh, and the quantity of air
to the XAD-2 scrubber was 30 cfh.  Stripped air was collected on
the Tenax column for 10 minutes three times while the sampler was
in operation.

     Daily flow data for the sample period are presented in
Table 26.
             TABLE 26.  DAILY FLOW DATA (PLANT 9)

Date
7/18/78
7/19/78
7/19/78
Time
9:00 am
9:00 am
6:30 pm
Influent
(gpm)
2,190
2,220
2,340

Analytical Results--
     Priority pollutants for which samples were collected and
analyzed are presented in Table 27.   All extractions and analyses
of samples were conducted at RSKERL.
                               64

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                        TABLE 27.  ANALYTICAL DATA (PLANT 9)
                                    Sparged Air, XAD-2   Sparged Air, Tenax
     Priority Pollutant	(yg)	(yg)	

POLYNUCLEAR AROMATICS
     Naphthalene                    Undefinable gas
     2-Chloronaphthane              chromatogram obtained
     Acenaphthalene                 because of matrix inter-
     Acenaphthene                   ferences
     Fluorene
     Phenanthrene/Anthracene
     Fluoranthene
     Pyrene
     1,2-Benzanthracene
     Chrysene
     3,4-Benz opyrene
     1,2:5,6-Dibenzanthracene

PHENOLICS
     2-Chlorophenol                 Undefinable gas
     2-Nitrophenol                  chromatogram obtained
     Phenol                         because of matrix inter-
     2,4-Dimethylphenol             ferences
     2,4-Dichlorophenol
     2,4,6-Trichlorophenol
     4-Chloro-m-cresol
     2,4-Dinitrophenol
     4,6-Dinitro-o-cresol
     Pentachlorophenol
     4-Nitrophenol

PURGEABLES
     Methylene  chloride                                         .01
     1,1-Dichloroethane                                          .5
     1,2-Trans-dichloroethylene                                  .2
     Chloroform                                                 .2
     1,2-Dichloroethane                                         <.l
     1,1,1-Trichloroethane                                     <.05
     Carbon  tetrachloride                                       <•!
     Dichlorobromomethane                                      <.05
     1,2-Dichloropropane                                       <.01
     Benzene                                                  <.02
     Trichloroethylene                                          -07
     Chlorodibromomethane                                      <.01
     1,1,2-Trichloroethane                                     <-05
     Methyl  bromide                                            <.25
     Bromoform                                                 <.01
     1,1,2,2-Tetrachloroethane                                 <.02
     Tetrachloroethylene                                       <.05
     Toluene                                                  <-01
     Chlorobenzene                                             <.01
     Ethylbenzene		<.Q1	
                                     65

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                           TABLE  27.     (Continued)

Priority Pollutant
CLASSICAL
TOTAL CYANIDES (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGEABLES
Chloroform
Carbon tetrachloride
Methylene chloride
Toluene
Ethylbenzene
1,1, 1-Tr ichloroethane
ACRYLONITRILE
POLYNUCLEAR AROMATICS
Phenanthrene/Anthracene
Naphthalene
Pyrene
PHENOLICS
Phenol
2-Chlorophenol
2,4, 6-Tr ichlorophenol
2 , 4-Dinitrophenol
Pentachlorophenol
4-Nitrophenol
Influent
Cug/D

<.05
778

<10
<10
1
<3
24
<10
36
<10
120
<10
<10
10
<1.2


<10
<10
<10
35
29
<10
<10,000

235
155
<10

322
7
15
183
252
70
Return Sludge
(ug/1)

<.05
<20

17
<10
2
<3
410
<10
1,300
36
250
<10
10
70
3.5


N.A.
M
ii
ii
n
ii
N.A.

110
<10
12

1,802
207
72
N.D.
N.D.
133
Effluent
(>ig/D

<.05
<20

<10
<10
1
<3
440
<10
30
<10
300
<10
<10
10
<0.5


<10
<10
<10
<10
<10
<10
<10,000

<10
<10
<10

3
3
1
.140
142
224
(Continued)
                                      66

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TABLE 27. (Continued)

Priority Pollutant
Influent
(ug/D
Return Sludge Effluent
Qig/1) (ug/1)
NIIROSAMINES
     N-riitrosodiphenylamine                A nitroso specific thermal  detector
	not available.	
 *Note:   Total  Cyanides  expressed  in mg/1.
**Key:  N.D. - Not Detectable, Or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                      67

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WOOD-PRESERVATIVES INDUSTRY

Plant No. 10

Wastewater Treatment System--
     A flow diagram of Plant 10's wastewater treatment system is
shown in Figure 13.  Wastewater generated by the wood-treating
process flows into a cooling-water pond and is recirculated from
the pond through the condenser and back to the pond.  As the
level of the pond rises as a result of the addition of waste-
water, a portion of the water is removed and treated.  The
treatment system generally consists of (1) chemical flocculation,
(2) nutrient addition, (3) aeration, (4) spray pond evaporation,
and (5) total retention.

     Treatment begins when the flocculation tank is filled with
an approximately 5,000-gallon batch of water from the pond.  A
Bentonitic clay is then mixed in a drum with water and added to
the tank.  This is well mixed into the water, and then a cationic
liquid polymer is added,  which serves only to gather the floe
particles together to increase their size and speed settling of
the floe.  The tank is allowed to settle for 1 1/2 to 3 hours,
after which the clarified water is pumped from the tank to the
aeration basin.  The tank (7 feet high) is decanted to within
only 18 inches of the bottom.  The sludge from the first batch
will all be below this point and is not removed at this time;
instead, the tank for the next batch flocculation is refilled as
needed.  The sludge will react with the new floe in the same way
as did the clay in the first mix; so no more clay is added, only
the polymers.  Again, the tank is allowed to  settle.  After-
wards it is decanted and remixed until the sludge is near the
decant level, at which time the sludge is pumped to drying beds.
The sludge has excellent drying characteristics, unlike some
others, and when dry is seemingly unaffected by rainfall.  When
dry, the sludge from 60 to 80 thousand gallons of water will be
approximately 3 cubic yards and can easily be handled for dis-
posal at a landfill.  The next step in the process is aeration
and nutrient addition.  Ammonium nitrate and phosphate fertil-
izers are added daily at the rate of approximately 20 pounds of
nitrogen and 1 pound of phosphate for each 100 pounds of COD.
Clarified water is transferred to a 1-million-gallon aerated
lagoon.

     Air is supplied by two 10-hp positive displacement blowers
with a rated capacity of 150 cfm each.  These blowers supply air
through a pipe system at a depth of 4 feet.  After the aeration
basin, the effluent flows to a smaller settling pond where most
of the biological sludge settles and is returned to the aeration
basin.  The effluent then flows to a large pond, where it is ex-
tensively sprayed into the air for evaporation and aeration
purposes.  Following the spray lagoon, the wastewater finally


                                68

-------
                                                                    SAMPLE POINTS
VD
               OH
               UJ
               I
               UJ  Ul
               I-  W
               w  o
               g  UJ
               II
                                    AERATED LAGOON
•o'
a.
                 COOLING
                 WATER
                  POND
                           ©
                           ©

                             NEW
                            POND
      LOCULATION
      TANK
0-INFLUENT
@-AIR STRIPPER
(D-SEDIMENT  I
0-SEDIMENT  2
©-EFFLUENT
                             SLUDGE
                            DRYING BED
                                'SLUDGE TO
                                 LANDFILL
                       Figure 13- WASTEWATER TREATMENT SYSTEM-PLANT 10

-------
flows to a 1-million-gallon retention pond.  One notable feature
of this plant is the fact that it does not discharge any efflu-
ent.  Normally the wastewater is disposed of entirely by evapora-
tion.

Sample Collection--
     Based on the previous Effluent Guidelines Division Screen-
ing Survey study, the list of compounds in Table 30-was compiled.
This list represents the priority pollutants that have been
identified in Plant No. 10's influent to the aerated lagoon.
From this list, it was determined that four 1-gallon samples of
composite were required for specific organic compound analysis.
The locations of the sampling points are shown in Figure 12.
The sample of the influent to the treatment system was taken
directly out of the top of the flocculation tank.  The "effluent"
sample was taken from the new pond (or retention pond) at a
point farthest from its influent.  It should be noted that this
plant does not normally discharge any effluent; however, the
"effluent" sample point represents the water that would be
discharged if an effluent were allowed.

     Two sediment samples were taken.  One sample was taken from
the aerated lagoon, and the other was taken from the final re-
tention pond.  The aerated lagoon sediment sample was taken near
the point where the wastewater flows from this lagoon to the
"quiet" lagoon."  The final lagoon sediment sample was taken near
the "effluent" sampling point.  The air-stripper sampler was set
up in the aerated lagoon just off the walkway located approxi-
mately 60 feet from the point where the influent enters the
system.

     Clarified water from the flocculation tank was added twice
daily (during daylight hours) to the aeration lagoon; thus sam-
pling times were coordinated to the operation of the floccula-
tion tank.  All liquid samples were taken during the times
influent was being added to the treatment system.  One-sixth of
the total volume of composite required was collected for each
batch of influent.  Effluent samples were collected at the same
time as were influent samples.  A detailed sampling schedule is
presented in Table 28.

     The air-stripper sampler was placed in operation at 2:58 pm
on June 20, 1978, and operation was concluded at 10:50 am on
June 22 (for a total operating time of 12 hours).  The air-
stripper sampler was operated during daylight hours to corres-
pond roughly to the liquid sampling.   Air charged to the stripper
averaged 60 cfh, and the quantity of air to the XAD-2 scrubber
was 30 cfh.  Stripped air was collected on the Tenax column for
10 minutes each day the stripper was in operation.
                                70

-------
     Daily flow data for the sample period are presented in
Table 29.
             TABLE 29.  DAILY FLOW DATA  (PLANT 10)

Date
6/20/78
6/21/78
6/22/78
Influent
(gal.)
10,000
10,000
10,000
Effluent
(sal.)
0
0
0
Analytical Results--
     Priority pollutants  for which  samples were collected and
analytical results are presented  in Table 30.  All extractions
and analyses were conducted at  RSKERL.
                                71

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            TABLE 28.  SAMPLING SCHEDULE (PLANT 1:0)
Date
Time
Sample taken
Remarks
6/20/78  10:30 am

          3:30 pm

          5:03 pm


6/21/78   9:30 am

          1:38 pm
          2:30 pm
6/22/78   9:15 am
          9:30 am
         10:20 am

          2:30 pm
         Influent— composites
         "Effluent" composites
         Influent composites
         "Effluent" composites
         Tenax (10 min)-'
         Influent composites
         "Effluent" composites
         Tenax (10 min)
         Influent composites
         "Effluent" composites

         Sediment samples
         Influent composites
         Influent VGA and Blank
         "Effluent" composites
         "Effluent" VOA and Blank
         Tenax (10 min)

         Influent composites
         "Effluent" composites
                 Added 2 ml NaOH-/
                 to cyanides;  added
                 2 ml HoPO^ to phenolics
                 samples.
]VInfluent and effluent composites consisted of 500 ml each for
three organics samples, 500 ml for metals, 150 ml for cyanides,
and 150 ml for phenolics.

2/Nitric acid was not available for metals preservation.
3/Column No.  4
                               72

-------
                        TABLE 30.   ANALYTICAL DATA (PLANT  10)
                                    Sparged Air, XAD-2   Sparged Air, Tenax
   ^Priority Pollutant	(yi;g)	fog)	

POLYNUCLEAR AROMATICS
     Naphthalene                          286
     2-Chloronaphthane                     45
     Acenaphthalene                        <3
     Acenaphthene                          54
     Fluorene                              28
     Phenanthrene/Anthracene               55
     Fluoranthene                          <4
     Pyrene                                <4
     1,2-Benzanthracene                   <28
     Chrysene                              <9
     3,4-Benzopyrene                      <15
     1,2:5,6-Dibenzanthracene             N.D.
PHENOLICS
     2-Chlorophenol                   390,000
     2-Nitrophenol                     61,000
     Phenol                            47,000
     2,4-Dimethylphenol                48,000
     2,4-Dichlorophenol                74,000
     2,4,6-Trichlorophenol             42,000
     4-Chloro-m-cresol                  4,500
     2,4-Dinitrophenol                    540
     4,6-Dinitro-o-cresol               3,000
     Pentachlorophenol                    630
     4-Nitrophenol                      5,100
PURGEABLES
     Methylene chloride                                        2
     1,1-Dichloroethane                                       .9
     1,2-Trans-dichloroethylene                               .1
     Chloroform                                               .1
     1,2-Dichloroethane                                       .5
     1,1,1-Trichloroethane                                   .06
     Carbon tetrachloride                                      3
     Dichlorobromomethane                                      2
     1,2-Dichloropropane   .                                   .2
     Benzene                                                   3
     Trichloroethylene                                      <.01
     Chlorodibromomethane                                     . 1
     1,1,2-Trichloroethane                                  <.05
     Methyl bromide                                         <.02
     Bromoform                                               -03
     1,1,2,2-Tetrachloroethane                              <.02
     Tetrachloroethylene                                       4
     Toluene                                                <.01
     Chlorobenzene                                          <.01
     Ethylbenzene         .	
-------
TABLE 30.
(Continued)
— —- ' 	 •*" 	 ™ 	 — — 	
Priority Pollutant
CLASSICAL
TOTAL CYANIDE (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
Influent
GlB/D

<.02*
170,000

60
<10
<1
<5
<10
<10
16
30
160
<5
8
<5
<.5
Bottom Sediment
Dry Weight
(^g/kg)
Aer. Lag. Final Pond

N.P.
"

9,300
<4,500
2,100
<1,900
40,000
<3,700
5,600
19,000
310,000
<2,100
6,300
<2,100
<136

N.P.
ti

7,600
<1,600
<1,300
3,200
4,300
<1,100
3,100
18,000
48,000
<690
<690
27,000
<3.4
Effluent
OiK/D

<.02*
<100

20
<10
<1
<5
<10
<10
<10
<10
<10
<5
<5
<5
<.5
ORGANICS (GAS CHROMATOGRAPHY)

PURGEABLES
     Benzene
     Chloroform
     Methylenechloride
     Ethylbenzene
     Dichlorobromomethane
     Toluene

POLYNUCLEAR AROMATICS
     Benzo(a)anthracene
     Benzo(a)pyrene
     3,4-benzofluoranthene
     Chrysene
     Acenaphthylene
     Benzo(g,h,i)perylene
     Fluorene
     Phenanthrene/Anthracene
     Dibenzo(a,h)anthracene
     Indeiio (1,2,3-cd) pyrene
     Pyrene
     Acenaphthene
     Naphthalene
               187
          N.P.
N.P.
450
300
<20
<10
N.S.
<10
<10
N.S.
<10
<10
<10
N.S.
<10
13
14,300
If
If
3,700
<310
N.S.
4,500
<100
N.S.
17,600
19,500
N.D.
N.S.
5,300
5,110
<104
"
ii
149
<310
N.S.
2,060
<100
N.S.
210
3,390
N.D.
N.S.
4,140
<250
<104
<40
                                                <20

                                               N.S.
                                               N.S.
                                               N.S.
            74

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                          TABLE 30.   (Continued)
    Priority Pollutant
            Bottom Sediment
              Dry Weight
Influent       (jig/kg)           Effluent
 (ug/1)  Aer. Lag.  Final Pond   (ug/1)
PHENOLICS
Phenol
2 , 4-dimethylphenol
2-chlorophenol
2,4, 6-tr ichlorophenol
Pentachlorophenol

47,000
N.D.
N.D.
112
1,660

9,030
4,398
396,000
N.D.
302,010

16,000
3,418
1,200
25,000
58,000

N.D.
N.D.
N.D.
116
663

 *Note: Total Cyanide expressed in mg/1.
**Key:  N.D. - Not Detectable or less than detectable limits
        N.A. - Not Applicable
        N.S. - No Standard Available
        N.P. - No Procedure Available
                                      75

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Plant 11

Wastewater Treatment System—
     A flow diagram of Plant 11's wastewater treatment system is
presented in Figure 14.  Wastewaters generated by a wood-preserv-
ing (creosote) plant are treated by a combined biological/land
irrigation process.  The process consists of (1) settling,
(2) storage, (3) aerated treatment, (4) spray irrigation, and
(5) runoff storage.  Rainfall runoff water is collected in a
storage pond, recycled through 10 spray nozzles, and then bled
into the settling basin for treatment.

     The average wastewater flow entering the treatment system is
50,000 gallons a day.  Wastewater flows from the settling basin
to a storage pond prior to entering the aerated lagoon.  Deten-
tion time in the storage pond and aerated lagoon is 40 to 60 days
each.

     The aerated lagoon contains four 7.5-hp mechanical aerators.
The wastewater is intermittently pumped from the lagoon and
sprayed through 18 spray nozzles in three sections onto an eight-
acre field growing fescue and sericea lespedeza.  Runoff from the
field is collected in a runoff storage pond.

     Water from the storage pond is recycled to the plant, where
it is treated and used as boiler feedwater, cooling water, etc.
The plant has no wastewater discharge.

Sample Collection--
     The survey of this facility was conducted during the period
August 7-10, 1978.  Samples were collected at four locations in
the treatment system (Figure 14):

     (1)  Influent to aerated treatment (water phase)
     (2)  Runoff storage pond (water phase)
     (3)  Air-stripper sampler (air phase)
     (4)  Aerated lagoon bottom sediment, grab (residual phase)

     The air-stripper sampler was located in the aerated lagoon.
The air-stripper sampler was placed into operation at 2:50 pm,
August 7, and operation was concluded at 6:50 am on August 10,
1978, for a total operating time of 64 hours.  Air charged to the
stripper averaged 60 cfh, and the quantity of air to the XAD-2
scrubber was 30 cfh.  Stripped air was collected on the Tenax
column for 10 minutes on each of the three days the sampler was
operated.

     Twenty-four aliquots were collected manually from the
water-phase sampling points, beginning at 3 pm, August 7.  Ali-
quots were collected at intervals of approximately 3 hours.  The
final aliquot was collected at 10 am, August 10.  A detailed
sampling schedule is presented in Table 31.

                              76

-------
                                  SAMPLE POINTS
                                   -SEDIMENT

                  BOILER FEEDWATER. COOLING WATER. ETC.
OIL RECYCLE
 NUTRIENT
ADDITION
EFFLUENT
BOILER f
SLOWDOWN
CONTAMINATED /
RUNOFF V
8
8
o
o
§
SETTLING
BASIN
/ '
V
L
STORAGE
NO. 2


STORAGE
NO. 3A


y
«C.I»*"% 1 t.1-/
LAGOON
®
g) N0.3B
loo
) SPF
1 o o
0 0
                                                  STORAGE
                                                   NO. 4
                                          o  o  o  o
                                      SPRAY FIELD
                                          o  o  o  o
                                          o  o o  o
                                                        RAINWATER
                                                         RUNOFF
  Figure 14 - WASTEWATER TREATMENT SYSTEM - PLANT  II

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             TABLE 31.  SAMPLING  SCHEDULE  (PLANT  11)
Date
 Time
Sample taken
Remarks
8/7/78
8/8/78
8/9/78
8/10/78
 3:00 pm
 6:00 pm
 9:00 pm
12 Midnight
 3:00 am
 6:00 am
 9:00 am
12 Noon
 3:00 pm
 6:00 pm
 9:00 pm
12 Midnight
 3:00 am
 6:00 am
 9:00 am
12 Noon
 3:00 pm
 6:00 pm
 9:00 pm
12 Midnight
 3:00 am
 6:00 am
 9:00 am

10:00 am
Composite aliquots  Rain  showers
         IT

         II

         II

         II

         II

         II

         II

         It

         If

         II

         II

         II

         II

         II

         II

         II

         II
                                                       II

                                                       II

                                                       II
                                                   No  rain
                                                   Tenax,  20 min.
                                                   Tenax,  20  min,
         11          Rain showers
         "          Tenax, 20 min,
VGA grab samples,
bottom sediment sample
Final composite aliquot
     Samples were collected for those priority pollutants which
were found in the previous priority pollutants screening survey.
Samples were preserved by prescribed EPA methods.  All  samples
were kept on ice throughout the sample period.

     At the end of the sample period, grab samples for  VGA  anal-
yses were collected from the water-phase sample points.  At this
time, a grab sample for the residual phase was collected from the
bottom of the aerated lagoon.
                                78

-------
     Daily flow data for the sample period are presented in
Table 32.
Date
8/7/78
8/8/78

8/9/78
Influent*
(mgd)
Not available
for
these
dates

Return Sludge
(mgd)
N.A.
N.A.

N.A.
Effluent
(mgd)
0.05
0.05

0.05

^Average  influent  flow:  0.05 mgd
Analytical  Results--
     Priority pollutants  for which  samples were collected and
analyzed  are presented  in Table 33.  All extractions and analyses
were conducted  at  RSKERL.
                                79

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                        TABLE  33.   ANALYTICAL  DATA (PLANT 11)
     Priority Pollutant
Sparged Air, XAD-2
     (MS)	
Sparged Air, Tenax
       (yg)	
POLYNUCLEAR AROMATICS
     Naphthalene
     2-Chloronaphthane
     Acenaphthalene
     Acenaphthene
     Fluorene
     Phenanthrene/Anthracene
     Fluoranthene
     Pyrene
     1,2-Benzanthracene
     Chrysene
     3,4-Benzopyrene
     1,2:5,6-Dibenzanthracene
PHENOLICS
     2-Chlorophenol
     2-Nitrophenol
     Phenol
     2,4-Dimethylphenol
     2,4-Dichlorophenol
     2,4,6-Trichlorophenol
     4-Chloro-m-cresol
     2,4-Dinitrophenol
     4,6-Dinitro-o-cresol
     Pentachlorophenol
     4-Nitrophenol
PURGEABLES
     Methylene  chloride
     1,1-Dichloroethane
     1,2-Trans-dichloroethylene
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
	Ethylbenzene	
    4,230
        7
       <3
        2
       <5
        7
       15
       13
       70
       24
      N.D.


      <25
    2,410
       24
        3
      <50
       <5
      <25
      <25
      <25
      <25
      <25
                    Undefinable GC results
                    because of inaccurate
                    retention time of in-
                    ternal standard
                                     80

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TABLE 33.
(Continued)

Priority Pollutant
CLASSICAL
TOTAL CYANIDE (mg/1)*
TOTAL PHENOL
TOTAL METALS
Arsenic
Selenium
Cadmium
Beryllium
Copper
Antimony
Chromium
Nickel
Zinc
Silver
Thallium
Lead
Mercury
ORGANICS (GAS CHROMATOGRAPHY)
PURGEABLES
Benzene

Chloroform
Methylene Chloride
Ethylbenzene
Dichlorodibromome thane
Toluene
POLYNUCLEAR AROMATICS
Benzo (a) anthracene
Benzo (a) pyrene
3 , 4-benzof luoranthene
Chrysene
Acenaphthylene
Benzo (g,h,i) perylene
Fluorene
Phenanthrene/Anthracene
Dibenzo (a, h) anthracene
Indeno (1,2,3-cd) pyrene
Pyrene
Acenaphthene
Naphthalene
Influent
Gug/D

<.08*
79,000

530
<10
< 1
< 5
44
<10
260
22
70
<10
<10
<10
<.5


<40
"i /^
<1U
32
156
N.S.
31

<20
<10
N.S.
67
670
N.S.
42
1900
<10
N.S.
570
400
<10
Bottom Sediment
Dry Weight
(ug/kg)

N.P.
N.P.

51,000
940
200
2,500
99,000
<990
56,000
18,000
280,000
<910
910
20,000
<20


N.P.
ii

"

"


1250
5980
N.S.
9280
1400
N.S .
547
43,700
N.D.
N.S.
4250
1840
-• s\ /
<104
Effluent
Ow/1)

<.08*
16

<50
<10
< 1
< 5
16
<10
<10
<10
100
<10
<10
15
<.5


<40
- 1 f\
*-xu
16
<10
N.S.
<10

<20
<10
N.S .
<10
N/^
.s .
<10
<10/10
<10
N.S .
10
<10
           81

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                          TABLE 33    (Continued)
     Priority Pollutants
           Bottom Sediment
Influent      Dry Weight   Effluent
 CuR/1)        (ug/kg)	Oig/1)
ORGANICS (GAS CHROMATOGRAPHY)
PHENOL I CS
Phenol
2, 4-dimethylphenol
2-chlorophenol
2,4, 6-trichlorophenol
Pentachlorophenol**

10,900
N.D.
200
420
6,820

4,500
N.D.
300
N.D.
4,800

2
26
N.D.
37
105

  *Note:  Total Cyanide expressed in mg/1.
 **Pentachlorophenol is questionable.
***Key:  N.D. - Not Detectable,  Or less than detectable limits
         N.A. - Note Applicable
         N.S. - No Standard Available
         N.P. - No Procedure Available
                                     82

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PETROLEUM REFINING INDUSTRY

Plant 12

Wastewater Treatment  System--
     A flow diagram of Plant 12's biological wastewater treatment
system including  sample points  is shown  in Figure 15.  The bio-
logical system consists of two  completely separated bays receiv-
ing overflow from two dissolved  air flotation units.  The two
bays are identical in hydraulic  characteristics and operation;
but bay A utilizes powdered activated carbon in the mixed liquor,
while bay B does  not.  At the time of the study, both bays were
operating^at steady state.  The  type of  biological treatment
utilized in each  bay  is extended aeration with surface aerators.
Waste^sludges, including wasted  return sludge, receive thickening
by filtration prior to land disposal.

     Specifically, Plant 12 process wastewater (approximately 4.0
mgd) receives primary clarification with two API separators (each
having a volume of 0.084 mg; dimensions, 80 feet long by 20 feet
wide by 7 feet deep).  The API  effluents are fed to respective
dissolved air flotation  (DAF) units (each having a volume of
0.060 mg; dimensions, 55 feet long by 20 feet wide by 7.25 feet
deep).  The DAF effluents are combined and lifted to two identical
aeration bays and split equally  between  the bays.  Each bay con-
sists of an aeration  basin and  final clarifier in concentric
configuration, the clarifier being innermost.  Each aeration
basin has a volume of 2.28 mg and dimensions of 184 feet OD, 89
feet ID, and 15 feet  deep.  Each clarifier has a volume of 0.56
mg and dimensions of  89 feet in  diameter by 12 feet deep.  The
average daily forward flow for  the study period (November 5-8,
1978) was 3.6 mgd.  The return  sludge pumping rate for each bay
was 0.72 mgd.

Sampling Program--
     Based on previous screening of the  refining industry by the
EPA's Effluent Guidelines Division, a list of priority pollutant
compounds was compiled for investigation in this study (Table 22).
In addition, two  common wastewater parameters were measured:
total cyanides and total phenol.  Three-liter samples for analyses
of specific organic compounds were composited in 1-gallon glass
containers (no preservative added).  Samples of approximately 1
liter volume were composited for T-metals (nitric acid added);
T-cyanide (sodium hydroxide added); and  T-phenols (phosphoric
acid added).

     Sample locations can be found in Figure 15.  DAF effluent
(sample point 1)  was  collected  atop the  aeration bays.  Final
clarifier effluents  (points 4 and 5) were sampled from separate
taps located beneath  the bioreactors.  Return sludge samples
(points 2 and 3)  were collected  on the discharge sides of the
                                83

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                                  RETURN SLUDGE
               PAC
  API
 	»
  EFF.
 DISSOLVED
   AIR
FLOTATION
Q) INFLUENT

© RETURN  SLUDGE

© RETURN SLUDGE  (CONTROL)
© EFFLUENT (PAC)
©  EFFLUENT (CONTROL)

© AIR STRIPPER (PAC)
Q) AIR STRIPPER (CONTROL)
 WASTE
 SLUDGE
PROCESSING
                                  RETURN  SLUDGE
             Figure 15 - WASTEWATER TREATMENT SYSTEM - PLANT  12
                                 84

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respective lift pumps.  An air-stripper sampler equipped with XAD
resin trap was placed in each aeration basin at a point after
entry of the DAF  effluent  (points  6  and 7) .  Volatile organics
were sampled in the DAF and  final  clarifier effluents using the
standard 28-ml VOA septum vials.   The VGA  grab samples were
collected at 2 pm on November 8.

     Samples of DAF effluent, return sludges, and final effluents
were composited every 4 hours beginning at 6 pm on November 5,
1978, and ending  at 2 pm on  November 8, 1978.  Preservatives were
added at the initiation of sampling.  Preservatives used were
concentrated phosphoric acid to  achieve a  final pH^4 (total
phenol); sodium hydroxide pellets  to achieve a final pH >12
(total  cyanides); and redistilled  nitric acid to achieve a final
pH ^2 (total metals).  The compositing procedure for these sam-
ples was 55 ml every 4 hours.  No  preservative was used for
organics sampling; a 170-ml  grab sample was composited every 4
hours.  All sample containers were iced throughout the sampling
period.

     The air-stripper samplers were  placed in operation at 9 am,
November 6, and performed  adequately until 2 pm, November 8,
1978, with the exception of  a 4-hour stoppage on November 7
(i.e.,  49 hours total operational  time).   Air charged to the
strippers averaged 60 cfh, and the quantity of air to the XAD-2
scrubber was 30 cfh.  A detailed sampling  schedule is presented
in Table 34.  Flow data are  found  in Table 35.

Analytical Results--
     Pollutants for which  samples  were collected and analyzed are
presented in Table 36.  All  extractions and analyses of samples
were conducted at RSKERL.
                                85

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                  TABLE 34.   SAMPLING SCHEDULE (PLANT 12)
 Date
  Time    Sample taken
                      Remarks
11/5/78   6:00 pm   Composite

         10:00 pm
11/6/78
11/7/78
11/8/78
 2:00 am
 6:00 am
 9:00 am
10:00 am
 2:00 pm
 6:00 pm
10:00 pm

 2:00 am
 6:00 am
10:00 am
 2:00 pm
 6:00 pm
10:00 pm

 2:00 am
 6:00 am
10:00 am
 2:00 pm
ii
ii
                          Preservatives added for T-met-
                          als,  T-cyanide, and T-phenols.
                                   Air-stripper on at 9 am.
                                   Air-stripper off at 6:00 am.
                                   Air-stripper on at 10:00 am.
                                   Air-stripper off at 2:00 pm;
                                   VOA grabs collected at 2:00 pm.
                  TABLE 35.  DAILY FLOW DATA (PLANT 2)
        Date
            Return Sludge
                (PAC)
                (gpm)
                             Combined
             Return Sludge Final Effluent
                (gpm)          (mgd)
11/4-5/78*
11/5-6/78
11/6-7/78
11/7-3/78
500
500
500
500
500
500
500
500
2.9
4.2
3.5
3.4

^Twenty-four hour period, from 6:00 am to 6:00 am.

Note:  Sludge wasteage was-VZS gpm, meaning that combined FE
       flows approximated bioinfluent (DAF) flow during the
       s tudy.
                               86

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                     TABLE 36.  ANALYTICAL DATA (PLANT 12)
     Priority Pollutant
Sparged Air,  XAD-2
      (Mg)
                 Sparged Air, Tenax
                      (Vtg)
POLYNUCLEAR AROMATICS
     Naphthalene
     2-Chloronaphthane
     Acenaphthalene
     Acenaphthene
     Fluorene
     Phenanthrene/Anthracene
     Fluoranthene
     Pyrene
     1,2-Benzanthracene
     Chrysene
     3,4-Benzopyrene
     1,2:5,6-Dibenzanthracene

PHENOLICS
     2-Chlorophenol
     2-Nitrophenol
     Phenol
     2,4-Dimethylphenol
     2,4-Dichlorophenol
     2,4,6-Trichlorophenol
     4-Chloro-m-cresol
     2,4-Dinitrophenol
     4,6-Dinitro-o-cresol
     Pentachlorophenol
     4-Nitrophenol

PURGEABLES
     Methylene  chloride
     1,1-Dichloroethane
     1,2-Trans-dichloroethylene
     Chloroform
     1,2-Dichloroethane
     1,1,1-Trichloroethane
     Carbon  tetrachloride
     Dichlorobromomethane
     1,2-Dichloropropane
     Benzene
     Trichloroethylene
     Chlorodibromomethane
     1,1,2-Trichloroethane
     Methyl  bromide
     Bromoform
     1,1,2,2-Tetrachloroethane
     Tetrachloroethylene
     Toluene
     Chlorobenzene
     Ethylbenzene   	
    PAC
    N.D.
     30
         Control
         N.D.
         220
     20
     20
    <35
    N.D.
    <25
    <25
          <35
          N.D.


          <25
          <25
    <25
    <50
          <25
          <50
          200
  80       30
<100     <100
 <25      <25
 <25      <25
 <25      <25
                    No  samples taken
                    due to equipment
                    malfunction.
                                      87

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                            TABLE 36.    (Continued)

Influent
Priority Pollutant (>*g/l)
CLASSICAL
TOTAL CYANIDES (mg/1)* <.05
TOTAL PHENOL 417
TOTAL METALS
Arsenic <10
Selenium <10
Cadmium <1
Beryllium <3
Copper 45
Antimony <10
Chromium 280
Nickel 17
Zinc 390
Silver <10
Thallium <10
Lead 40
Mercury <0 . 6
ORGANICS (GAS CHROMATOGRAPHY)
PURGEABLES
Methylene chloride <1Q
Chloroform ^-in
PAC Return Return PAC
Sludge Sludge Effluent
(ug/1) (>ig/l) (fig/1)

<.05
386

260
400
31
20
5,800
<10
64,000
1,200
37,000
22
<10
12,000
<10


N.A.
ii

<.05 <.05
67 42

150 <10
280 <10
24 <1
9 < 3
4,900 18
<10 <10
60,000 100
1,100 14
28,000 140
22 <10
<-^Q <1Q
11,000 18
<10 <1.0


N.A. <10
Final
Effluent
Oug/D

<.05
29

<10
<10
<1
<3
16
<10
72
17
130
<10
<10
14
<0.8


<10
     Benzene                     320
     1,1,2,2-Tetrachloroethylene <10
     Toluene                     695
     Ethylbenzene                 55

POLYNUCLEAR AROMATICS
     Pyrene
     Benzo-a-pyrene
     Chrysene
     Fluoranthrene
     Phenanthrene/Anthracene <10/<10
     Naphthalene                 282
     Acenaphthene                 24
     Fluorene
<44
                                           <106
                                                               <40
                                        <40
                                            <39
PHENOLS
     2,4-dimethylphenol

(Continued)
                                142
            10
N.D.
                                                              N.D.
                                        N.D.
                                      88

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                            TABLE 36.   (Continued)
                                       PAC Return  Return    PAC      Final
                              Influent     Sludge    Sludge  Effluent  Effluent
     Priority Pollutant        (ug/1)      Qig/1)    (yg/1)    (jxg/1)    (jig/1)


EHTHALATE ESTERS
     Dimethyl phthalate
     Diethyl phthalate
     Di-n-butyl phthalate
     Bis(2-ethylhexyl)
        phthalate


  *Note:   Total Cyanides expressed in mg/1.
 **Key:    N.D.  - Not Detectable, or less than detectable limits
          N.A.  - Not Applicable
          N.S.  - No Standard Available
          N.P.  - No Procedure Available
                                       89

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TABLE  37.   ENGLISH-TO-METRIC UNIT  CONVERSIONS
Multiply
This
Ibs
short tons
short tons
inches
feet
statute miles
gallons
barrels
Btu
SCF
Btu/lb
Btu/CF
Btu/SCF
109 Btu/day
106 Btu/day
MM Btu/hr
SCFD
MM SCFD

SCF/MM Btu
Ibs/MM Btu
Ibs/CF
psi
gpm
acre-ft/year
horsepower
nautical miles
knot
By
This
0.4536
0.9072
907.2
2.54
0.3048
1.609
3.785
0.1590
0.252
0.02679
0.5556
8.899
9.406
252
252
252
0.02679
0.02679

0.1063
1.8
16.02
0.07031
0.227
0.1408
745.7
1.852
1.852
To Obtain
This
kg
metric tons
kg
cm
m
km
1
m3
kcal
nm
kcal/kg
kcal/m3
3
kcal/nm
Gcal/day
Meal/day
Mcal/hr
nm /day
106 nm3/day
(Mnm3/day)
nm /Gcal
kg/Gcal
kg/m3
2
kg/cm
m /hr
m /hr
W
km
km/hr
                             kilograms
                             metric tons (1000 kg)
                             kilograms
                             centimetres
                             metres
                             kilometres
                             litres (1000 litres =  1 m3)
                             cubic metres
                             kilocalories
                             normal cubic metres
                             kilocalories/kilogram
                             kilocalories/cubic metre
                             kilocalories/normal cubic metre
                             gigacalories/day
                             megacalories/day
                             megacalories/hour
                             normal cubic metres/day
                             million normal cubic metres/day
                             (mega normal cubic metres/day)
                             normal cubic metres/gigacalorie
                             kilograms/gigacalorie
                             kilograms/cubic metre
                             kilograms/square centimetre
                             cubic metres/hour
                             cubic metres/hour
                             watts
                             kilometres
                             kilometres/hour
                        90

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                            SECTION 4

                          OBSERVATIONS


     1.  There are five metals that tend to concentrate in the
residuals samples.  These metals are: (1) copper, (2) chromium,
(3) zinc, (4) nickel, and (5) lead.

     2.  For samples showing the presence of phenols by the
4-aminoantipyrine procedure, individual phenolic compounds were
identified by the gas chromatographic procedure.  However, min-
imal correlation was found between the sum of the concentrations
of individual phenolics determined by gas chromatograms and the
concentration of total phenols by the 4-aminoantipyrine method.

     3.  The study required strict adherence to a clearly defined
set of analytical procedures.  These procedures did not have
provisions for eliminating matrix interferences.  This resulted
in difficulty in quantitating individual compounds identified in
the gas chromatograms.

     4.  Priority pollutants of the polynuclear aromatics and
phenolics groups are subject to air stripping in biological
treatment systems under the sampling conditions employed in the
study.

     5.  There is an indication that many of the nonvolatile
organics concentrate in bottom sediment samples.

     6.  The chromatographic procedures showed the presence of
many unidentified organic compounds in addition to the priority
pollutants specified for each industrial category.

     7.  The study conditions implemented for 3 days did not
account for process variations and do not represent a mass bal-
ance across a biological treatment system.  It appears necessary
to conduct a long-term study, perhaps incorporating additional
techniques,  to obtain a mass balance.

     8.  A surprisingly large number of industrial activated
sludge treatment systems studied did not waste excess sludge.

     9.  One of the plants studied employed parallel activated
sludge systems, one of which was "enhanced" by the use of powdered


                               91

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activated carbon.   The analytical results showed no significant
differences between the control and bioenhanced systems.

    10.   The experimental Tenax column used during the study
shows promise in adsorbing volatile compounds.   There does need
to be additional research to alleviate the mechanical problems
associated with this system.
                               92

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
 REPORT NO.
  EPA-600/2-79-175
2.
                              3. RECIPIENT'S ACCESSION>NO.
 TITLE AND SUBTITLE

         Indicatory  Fate Study
                              5. REPORT DATE
                                August 1979 issuing date
                                                            6. PERFORMING ORGANIZATION CODE
 , AUTHOR(S)
          L. H. Myers,  T. E. Short,  Jr.,  B. L. DePrater,
 F.  M.  Pfeffer, D.  H. Kampbell,  J.  E. Matthews
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 R.  S.  Kerr Environmental Research  Laboratory
 U.S.  Environmental Protection Agency
 P.  0.  Box 1198
 Ada,  Oklahoma   74820
                              10. PROGRAM ELEMENT NO.

                                1BB610
                              11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
 Effluent Guidelines Division  (WH-552)
 U.S.  Environmental Protection Agency
 401 "M" Street,  S.W.
 Washington, D.C.   20460
                              13. TYPE OF REPORT AND PERIOD COVERED
                               Final—May 1978  to  Feb.  1979
                              14. SPONSORING AGENCY CODE
                                EPA/600/15
 15. SUPPLEMENTARY NOTES
 16. ABSTRACT
 This report is  concerned with media  disposition of specific  priority pollutants.
 Composite samples  were obtained from the influent, effluent,  residuals, and air from
 12 industrial biological treatment systems.  These samples were  extracted and
 analyzed by gas chromatography for organic constituents, by  atomic absorption for
 metals, and by  EPA methodology for phenolics, cyanide, and mercury.

 Participating industries included:  (1)  organics and plastics,  (2)  Pharmaceuticals,
 (3) pesticides, (4) rubber,  (5) wood preservative, and (6) petroleum refining.
 The data in this report represent potential disposition of specific priority
 pollutants during 3-day study periods and should not be construed  to represent
 a mass balance  study.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.lDENTIFIERS/OPEN ENDED TERMS
                                                                            COS AT I Field/Group
                                                                            13B
          Activated sludge process
          Plastics Industry
          Petroleum Refining
          Pharmaceuticals
          Pesticides
          Rubber
                  Priority pollutants
                  Aerated Lagoons
                  Organic Chemicals  Industry
                  Wood Preservatives
                  Air stripping
13. DISTRIBUTION STATEMENT

          Release to Public
                 19. SECURITY CLASS (This Report)
                   Unclassified
103
                 20. SECURITY CLASS (This page)
                   Unclassified
                                            22. PRICE
EPA Form 2220-1 (9-73)
                                            93
                                                                     ft U.S. GOVERNMENT PRINTING OFFICt 1979 -657-060/5390

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