ROBERT S.  KERR
ENVIRONMENTAL RESEARCH
        LABORATORY
                UJ
                O
        PRELIMINARY SURVEY OF TOXIC POLLUTANTS
       AT THE MUSKEGON WASTEWATER MANAGEMENT SYSTEM
           ADA, OKLAHOMA

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   PRELIMINARY SURVEY OF TOXIC POLLUTANTS
AT THE MUSKEGON WASTEWATER MANAGEMENT SYSTEM

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     PRELIMINARY SURVEY OF TOXIC POLLUTANTS

  AT THE MUSKEGON WASTEWATER MANAGEMENT SYSTEM
                   Prepared by
          Ground Water Research Branch
Robert S. Kerr Environmental Research Laboratory
              Post Office Box 1198
              Ada, Oklahoma  74820
                  Contributors

          Ground Water Research Branch
          Wastewater Management Branch
Robert S. Kerr Environmental Research Laboratory
              Post Office Box 1198
              Ada, Oklahoma  74820

           Analytical Chemistry Branch
    Athens Environmental  Research Laboratory
              College Station Road
             Athens, Georgia  30601

  Muskegon County Wastewater Management System
                 8301 White Road
            Muskegon, Michigan  49442
                    May 1977

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                                       SUMMARY


     A preliminary survey of toxic pollutants was conducted at the Muskegon  County,
Michigan, Wastewater Management System to determine the presence and fate of
selected toxic pollutants in the System and to provide information needed for a
possible National survey of toxic pollutants in municipal  treatment systems.

     The Muskegon System is a land treatment operation in  which wastewater is
ultimately treated by spray irrigation of 5500 acres of farmland after receiving
preliminary treatment in eight-acre aerated lagoons and 850-acre storage lagoons.
At the time of this study an average of 28 mgd of combined domestic and municipal
waste was being treated, including 16 mgd from a pulp paper manufacturer and at
least 1.5 mgd from several chemical plants.  Reductions in total organic carbon,
chemical oxygen demand, and total suspended solids across  the system were 96, 97,
and 99 percent, respectively.

     A minimum of five daily samples each of raw influent  wastewater, aerated
lagoon effluent, holding lagoon effluent, and final effluent leaving the site via
a drainage tile lying 5-12 feet below an irrigated area (20 samples total) were
specifically analyzed for the following toxic pollutants:   arsenic, beryllium,
cadmium, cyanide, mercury, benzene, chloroform, trichloroethylene, vinyl chloride,
benzidine, endrin, toxaphene, and polychlorinated biphenyls.  In addition, selected
samples were surveyed for other toxic metals, and additional organic compounds
observed to be present during specific analyses for selected toxic organics  were
identified.

     No significant levels of arsenic, beryllium, cadmium, cyanide, or mercury
were found in any wastewater sample, nor were significant  quantities of other
toxic metals noted.  No detectable levels of benzidine, endrin, toxaphene, poly-
chlorinated biphenyls, and vinyl chloride were observed.   However, benzene,  chloro-
form, and trichloroethylene were present in the influent wastewater in concentration
ranges of 6-53, 360-2645, and 6-120 pg/1, respectively. Concentrations of these
compounds were significantly reduced in the treatment sequence, but low levels of
chloroform (1-13 yg/1) and trichloroethylene (2-10 pg/1) were present in all  final
effluent samples analyzed, and benzene (8 yg/1) was detected in one such sample.

     Fifty-six additional organic pollutants, including eight on EPA's "List of
Dangerous Pollutants" (dichloromethane; 1,2-dichloroethane; 1,2-dichloroethylene;
toulene; dichlorobenzidine; phenol; ethylbenzene; and trichlorobenzene), were
identified as constituents of influent wastewater.  Low levels of only five  of
these (dichloromethane, acetone, hexadecanoic acid, dodecanol, and tetradecanol),
plus trimethylisocyanurate (origin unknown) and atrazine (from herbicide used on
the irrigated farmland) were detected in the final effluent in addition to benzene,
chloroform, and trichloroethylene.  Hence, the Muskegon System appeared to be
relatively quite effective in removing organic pollutants  of possible concern
from the wastewater it was treating.  However, the presence of low levels of
organics in the final effluent indicates the need for definitive information
concerning the movement and fate of organic pollutants in  the subsurface.

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     This study clearly emphasizes the need for careful  development  of  a  compre-
hensive and feasible protocol  based on a realistic  conception  of  analytical  capa-
bilities and limitations, particularly in regard to organics,  before initiation of
a National survey of toxic pollutants in municipal  wastewater.  This could  best be
achieved through a coordinated effort of ORD personnel  experienced in GC/MS
analysis of wastewaters and in municipal treatment  technology  with Office of
Water and Hazardous Material personnel authorized to make decisions  concerning
the scope and sensitivity required of analytical methods.

     The time required for the specific analysis portion of this  work,  involving
analysis of 13 toxic pollutants plus TOC, COD,  and  TSS  in 20 samples, was approxi-
mately 113 man-days, excluding preliminary preparation  and administration.   Total
cost, based on $30,000 per man-year, was approximately  $14,330, or $716 per sample,
including extraordinary transportation costs for sampling.


                                     INTRODUCTION


     In March, 1976, the Assistant Administrator for Water and Hazardous Materials
requested the assistance of ORD in developing information on toxic materials in
municipal sewage treatment plant influents and  effluents.  As  a result  of this
request, the Municipal Environmental Research Laboratory, Cincinnati, was directed
in May, 1976 to initiate studies of selected toxic  pollutants  at  two municipal waste-
water treatment plants.  The plants chosen were Dayton, Ohio,  a trickling filter
plant with substantial industrial waste contributions;  and Muddy  Creek, Ohio, an
activated sludge system receiving primarily domestic sewage.  In  July,  1976, it
was decided that the Robert S. Kerr Environmental Research Laboratory should
supplement the work of MERL by conducting a preliminary survey of toxic pollutants
in wastewater at the Muskegon County, Michigan, Wastewater Management System, thus
extending the scope of the program to include a municipal system  employing  land
application for wastewater treatment.  Those studies conducted by RSKERL personnel
to elucidate the presence and fate of potentially toxic pollutants  in wastewaters
at the Muskegon System are described in this report.

     The primary purposes of the Muskegon studies were:  to determine if selected
toxic pollutants were present in the wastewater being treated  by  this system and,
if so, to evaluate the effectiveness of the treatment system in removing these
substances; and, to provide information, in terms of procedural  and  resource
requirements, needed in developing a protocol for a possible National survey of
toxic pollutants in municipal treatment systems.  The scope of work  was severely
limited by time restrictions, since experimental efforts could not be initiated
until early August, 1976 and a report of results was expected by late September.
The principal thrust of the investigation was,  therefore, directed toward detec-
tion and quantisation of 13 pollutants  selected from a  "List of Dangerous Pollutants"
which first appeared in an  EPA document entitled "Action Program to Control the
Discharge of Dangerous Pollutants  from  Industrial Point Sources."  These pollutants
were:  cyanide, mercury, arsenic,  cadmium, beryllium, benzene, chloroform, trichloro-
ethylene, vinyl chloride, benzidine, endrin, toxaphene, and polychlorinated biphenyls
 (PCB's).

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     The Muskegon studies and resulting data for the  13  selected  toxic  pollutants,
as well as for several  additional  pollutants of possible interest, were described
in very abbreviated form in early  October,  1976, by means of  a  brief, summary  report
entitled "Preliminary Toxic Pollutants Survey,  Muskegon  County, Michigan Wastewater
Management System."  A more detailed accounting of the information contained in  that
summary report as well  as additional data developed in limited  further  studies of
the organic fractions previously obtained from  wastewater samples from  Muskegon
are presented below.


                     DESCRIPTION OF THE MUSKEGON TREATMENT SYSTEM


     The Muskegon County Wastewater Management  System is a land application opera-
tion which occupies approximately  11,000 acres  (4450  hectares)  about 10 miles  (16
km) east of the city of Muskegon.   The essentials of  this System, which treats
wastewaters from both domestic and industrial sources, are shown in  Figure 1.
Incoming wastewater receives initial treatment  in eight-acre  aerated lagoons and
then enters 850-acre (344 hectare) storage lagoons where it is  held  until applied
to the land.  Final treatment is achieved by spray irrigating,  as necessary, 5500
acres  (2230 hectares) of farmland  with effluent from  the storage lagoons, using
54 center-pivot irrigation rigs.  Drainage tiles, ditches, and, in.a few cases,
wells  collect the renovated water leaving the system  and carry  it into  nearby
surface waters.  Operation of the System is seasonal  to the extent  that essen-
tially no irrigation is done in the winter.  During this time effluent  wastewater
from the aerated lagoons is accumulated in the  storage lagoons.  Irrigation at
rates  considerably exceeding the daily input to the System in the warm  months
results in depletion of the accumulated wastewater in the storage lagoons before
the succeeding winter.

     During the period of this investigation, the Muskegon System was treating an
average of 28 mgd  (105,980 m3/day), including approximately 16 mgd (60,560 m3/dav)
of industrial waste from a pulp paper manufacturer and at least 1.5 mgd  (5,680 m3/day)
of wastewater from several chemical manufacturers producing such products as phar-
meceutical intermediates, pesticides, detergents, chemical Intermediates, waxes,
specialty chemicals, and high purity solvents.   Raw wastewater was receiving an
estimated 36 hr of treatment in a single aerated  lagoon  and then was being passed
through the west storage lagoon prior to application to  the land.


                                       SAMPLING


     Samples were  obtained daily at each of  four  sampling points indicated by
number in Figure 1 and  shown schematically  in  Figure 2.  The sampled waters were:
influent wastewater just before it  entered  the  aerated  lagoon  (sampling  point #
effluent  emerging  from  the aerated  lagoon and  entering  the west  storage  lagoon
 (sampling point  #2); effluent from  the storage  lagoon as it entered the  spray
irrigation  system  at the north  pumping station  (sampling point #3); and,  final
effluent  as  it emerged  from  a drainage tile  underlying  the north irrigated area
at a depth  of  5-12 ft  (1.52-3.66 m, sampling point #4).

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Mosquito Creek
                                   West
                                 Storage
                                  Lagoon
  East
Storage
 Lagoon
               Drainage Ditch                • Irrigation  Pumping  Stations

               Drainage Tile                 • Submerged  Drainage  Pumps

                               XSamp!ing Points
            Figure 1.   Muskegon County Wastewater Management System.

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               RAW WASTEWATER
               AERATED LAGOON
               STORAGE LAGOON
                               SAMPLING  POINT #1
                               (INFLUENT)
               SPRAY-IRRIGATED
               SOIL DRAINED BY
               SUBSURFACE TILE
                               SAMPLING  POINT #2
                               (AERATED  LAGOON EFFLUENT)
                               SAMPLING  POINT #3
                               (STORAGE  LAGOON EFFLUENT)
                               SAMPLING  POINT #
                               (FINAL  EFFLUENT)
            RENOVATED (SUBSURFACE
          DRAINAGE) WATER-TO CREEK
Figure 2.  Sampling points for preliminary toxics survey,
     Muskegon County Wastewater Management System

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     Sampling was conducted principally during  a  period  of  five  consecutive  days
•jpginning Sunday, August 8, 1976,  and ending  on Thursday, August 12.   Limited
supplemental sampling was done on  Tuesday and Wednesday, September  7  and  8.  During
the principal sampling period, nine samples were  collected  at  each  sampling  point
each day, as shown in Table 1, to  permit analysis of several parameters of interest.
Only samples for highly volatile and extractable  organics were obtained during  the
supplemental period, since the main purpose was to augment  data  for volatile
organics.

     As soon as each day of sampling was completed, the  samples  obtained  were
packed in ice and shipped by scheduled and chartered air service to the Kerr
laboratory for analysis at the earliest possible  time.   Most samples  arrived at
the Laboratory less than 16 hr after sampling.  The logistics  involved in rapid
shipment of samples to the Laboratory required  that sampling at  Muskegon  generally
be conducted between 7:00 and 9:00 a.m. daily.  Except  for  raw influent wastewater,
this procedure probably entailed no significant disadvantage in  comparison to
sampling on a more varied temporal basis, since effluents from the  lagoons and
soil would not be expected to vary significantly  in composition  over  short time
ppriods due to high mixing volumes and relatively long  retention times encountered
by wastewater in these components  of the System.

     In addition to the daily samples, composite  samples for metals and extract-
able organic analyses were collected at sampling  points  #1, #3,  and #4 during  the
initial five-day sampling period.   For extractable organics, total  volumes of
composite samples were approximately one, four, and four gallons (3.8, 15.1, and
15.1 1) at sampling points #1, #3, and #4, respectively. These  were  collected  by
placing 750 ml of sample daily in the appropriate number of one-gallon (3.8  1)
jugs, each containing 100 ml of chloroform as preservative. For metals,  a  total  of
750 ml of sample was collected at each sampling point by placing 150  ml daily  in  a
one-liter cubitainer.  All composited samples were maintained  at 4° C during the
sampling period and shipped by air to the Athens  Environmental Research Laboratory
for analysis upon completion of sampling.


                                 ANALYTICAL PROCEDURES


     Samples obtained daily from each of the four sampling  points during  the prin-
cipal five-day sampling period were specifically analyzed for arsenic, cadmium,
beryllium, mercury, cyanide, benzidine, endrin, toxaphene,  polychlorinated biphenyls,
benzene, chloroform, trichloroethylene, and vinyl chloride, except that the latter
four compounds were not determined for the first two sampling  days because samples
for volatile organics analysis  (VOA) were lost by freezing in an improperly oper-
ating refrigerator.  Total organic carbon (TOC), chemical  oxygen demand  (COD), and
total suspended  solids  (TSS) were also determined in order to provide an indication
of the conventional treatment efficiency of the System.  In addition, daily influent
and final effluent  samples were surveyed for the presence of metals other than
those specifically  analyzed,  and  identification was attempted of a number of addi-
tional organic compounds  noted  during  analysis of the eight specified toxic organics
to be present  in the sampled wastewaters.

     Daily  samples  obtained in  the two-day supplemental sampling period were speci-
fically  analyzed for benzene, chloroform, trichloroethylene,  and vinyl chloride and
were subjected to limited study of additional  organic constituents.

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               Table 1.   SAMPLES OBTAINED  DAILY AT EACH
                   SAMPLING POINT AT MUSKEGON  SYSTEM
      Sample
Analysis
  Preservative
1-one liter cubitalner
3-one liter cubitainers
1-one liter cubitainer
1-one liter cubitainer
2-125 ml serum bottles,
   crimp-sealed w/TefIon-
   lined septum
1-one gallon (3.8 liter)  jug
   w/TefIon-lined screw cap
Cyanide
Metals
COD, TOC
TSS
Volatile
Organics
Extractable
Organics
2 ml 10 N NaOH/1
5 ml Redistilled HNtyi
2 ml Cone H2S04/1
None (packed in ice)
None (packed in ice)

None (packed in ice)

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     Total suspended solids (1), total  organic carbon (2),  chemical  oxygen demand (3),
arsenic (4), mercury (5), cyanide (6),  and cadmium and beryllium (7, 8)  were deter-
mined by standard procedures for wastewater analysis, except that a  graphite furnace
was utilized in the determinative step  for cadmium and beryllium.

     Surveying of influent and final  effluent samples for additional toxic metals
was achieved by emission spectroscopy.   Samples were first concentrated  fifty-fold
by evaporation and then were analyzed by a Jarrell-Ash Mark IV emission  spectro-
graph.  Spectra were recorded on photographic plates which were scanned  on a
comparator densitometer to detect spectral lines indicating the presence in the
wastewaters of potentially harmful metals other than those specifically  analyzed
in this study.

     Benzene, chloroform, trichloroethylene, and vinyl chloride were analyzed by
the volatile organic analysis (VOA) method developed by Bellar and Lichtenberg (9),
utilizing a commercially available purging instrument equipped with  a 25 ml purging
chamber (Tekmar Company, P. 0. Box 37202, Cincinnati, Ohio  45222).   A Finnigan
1015 C gas chromatograph-mass spectrometer (GC/MS) equipped with a Systems
Industries System 150 data system was employed for detection, confirmation of
identification, and quantisation of the specifically-analyzed volatile pollutants.
Limited mass search techniques were utilized when appropriate, and quantisation
was usually achieved by computerized comparison of mass spectrometer ion currents
produced by unknowns with those produced by standards carried through the same
analytical procedures.

     Benzidine, endrin, toxaphene, and PCB's were analyzed in the wastewater samples
by the analytical sequence presented below.

     1.   One-gallon (3.8 1) samples of wastewater were extracted with
          glass-distilled dichloromethane according to a procedure,
          shown in Figure 3, designed to separate the organic components
          into acidic, basic, and neutral fractions.

     2.   Extracted fractions were dried with anhydrous sodium sulfate,
          concentrated to 0.5-1 ml volumes with rotary evaporators and
          Kuderna-Danish concentrators, and subjected to preliminary
          examination by gas chromatography.

     3.   The neutral and basic fractions were analyzed by GC/MS,
          utilizing limited mass search and, in some cases, specific
          ion monitoring techniques  (10) to search for the presence of
          the four specific compounds of interest.

     One-gallon samples of influent wastewater and storage lagoon effluent from
the Muskegon System and of essentially organic-free laboratory water were spiked
with known quantities of benzidine, endrin, toxaphene, and Arochlor 1016 and
carried through this analytical sequence in order to establish detection limits
for these compounds.

     Identification of additional organic pollutants in the wastewaters was achieved
by GC/MS, utilizing the EPA computerized library of mass spectra and standard mass
spectral  interpretative procedures.  In the case of highly volatile components and
basic and neutral extractable compounds, this usually entailed further examination
of selected GC/MS data obtained during analyses for the eight specifically-analyzed

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 organic pollutants.   Selected acidic extracts,  which had  been  prepared  but  not
 analyzed in the specific analysis portion of this  work, were methylated with  diazo-
 methane (11) and then analyzed by 6C/MS for identification  of  extractable acidic
 pollutants as the methyl esters.   Time limitations precluded quantitative deter-
 minations of most of the additional  organic pollutants identified  by  these
 procedures.

      Five-day composite samples were subjected  to  comprehensive metals  analysis
 and limited qualitative analysis  for extractable organics at the Athens Environ-
 mental  Research Laboratory.   Metals  were determined by both plasma emission spec-
 troscopy and neutron activation.   Organic pollutants were extracted from the  waste-
 water samples by a procedure similar to that shown in Figure 3, and GC/MS was
 utilized for identification  of individual  compounds.  Because  of heavy  commitment
 to other projects, only limited investigation of acidic and basic  pollutants  from
 the composited samples could be achieved at Athens within the  time frame of this
 study.

      During all  analytical operations,  stringent efforts were  exerted to assure
 the validity of data produced.  Recommended quality assurance  programs  were utilized
 where applicable (12).   Methods and  techniques  generally accepted for quality con-
 trol  in trace organic analyses  were  employed  in identification and quantisation of
 organic pollutants.


                                RESULTS  AND DISCUSSION


      Table  2 presents  data obtained  for  TOC,  COD,  TSS, and  the five toxic inorganic
 pollutants  specifically analyzed  in  this  study.

      The TOC,  COD, and  TSS data indicate  that, by  conventional  standards, the
 Muskegon System  was  doing an  effective job  of treating the wastewater passing
 through it  during  the  period  of this study.   TOC concentrations of the  influent
 wastewater  during  the  five-day  principal sampling  period averaged 159 mg/1, while
 final effluent concentrations averaged 6.5 mg/1 during this time.   Similarly,
 average influent and final effluent values were 510 and 15.6 mg/1  for COD and 299
 and 3 mg/1  for TSS.

     As shown  in Table  2, significant levels  of the five toxic  inorganic chemicals
 analyzed did not occur  in any of the wastewater samples obtained at the four sampling
 points  during the  five-day sampling period.  Arsenic and beryllium were not present
 in detectable concentrations  (10 and 2 yg/1,  respectively) in any of the wastewater
 samples.  Cadmium, cyanide, and mercury were not present in detectable concentrations
 (2, 10, and 0.2 yg/1, respectively) in any of the final  effluent samples.   Low levels
of cadmium  (2-5 yg/1) were detected in two influent, two  aerated lagoon effluent,  and
one holding lagoon effluent samples.   Mercury appeared in  detectable concentrations
only in one influent sample (0.9 yg/1) and one aerated lagoon effluent (0.2 yg/1)
These values compare quite favorably with drinking  water  standards  of 10 yg/1,
200 yg/1, and 2 yg/1, respectively, for cadmium, cyanide,  and mercury.

     No significant concentrations of any additional toxic metals were noted in  the
daily influent and final effluent  samples which were examined by emission spectro-
scopy, or in the composite samples analyzed by plasma emission  spectroscopy and
"•••utron activation at AERL (see Appendix).

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                       WASTEWATER SAMPLE
       CHCi_2 EXTRACTS
       (NEUTRALS/ACIDS)
                                  pH 2
                                  1 x 125 ML CH2CL2
                                  2 x 75 ML CH2CL2
       I
 AQUEOUS LAYER
    (BASES)
CL2 LAYER
EUTRALS
                  3  x 50 ML 5% NAOH
        I
AQUEOUS EXTRACTS
    (Ac IDS)
                                          I
          pH 11
          3 x 75 ML CH2CL2
                     I
I  EXTRACTS    AQUEOUS LAYER
USES                I
                 DISCARD
                         pH 2
                         3 x 50 ML CH2CL2
                               I
       CH2CL2 EXTRACTS   AQUEOUS  LAYER
             ACIDS             I
                            DISCARD
   Figure 3.  Extraction procedure for organics in Muskegon wastewater
                                10

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                Table 2.  TOC, COD, TSS, AND SPECIFICALLY ANALYZED TOXIC
                   INORGANIC POLLUTANTS IN MUSKEGON SYSTEM WASTEWATER
Sampling 8-8-76
Pollutant Point (a) Sun.
Total Organic Carbon
(mg/1)


Chemical Oxygen Demand
(mg/1 )


Total Suspended Solids
(mg/1)


Arsenic (pg/1)



Beryllium (yg/1)



Cadmium (ug/1)



Cyanide (ug/1)



Mercury (ug/1)



1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4
160
125
43
9
532
390
127
17
156
250
11
4
<10
<10
<10
<10
< 2
< 2
< 2
< 2
3
< 2
< 2
< 2
<10
14
20
<10
< 0.2
< 0.2
< 0.2
< 0.2
8-9-76
Mon.
165
110
45
6
758
374
128
16
584
282
14
4
<10
<10
<10
<10
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
<10
<10
<10
<10
< 0.2
< 0.2
< 0.2
< 0.2
8-10-76
Tue.
170
110
56
7
790
373
153
16
205
236
12
2
<10
<10
<10
<10
< 2
< 2
< 2
< 2
4
2
3
< 2
<10
<10
<10
<10
< 0.2
< 0.2
< 0.2
< 0.2
8-11-76
Wed.
150
115
56
5
534
380
160
12
424
214
15
2
<10
<10
<10
<10
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
18
18
<10
<10
< 0.2
< 0.2
< 0.2
< 0.2
8-12-76
Thu.
148
124
49
6
438
422
154
17
126
220
21
3
<10
<10
<10
<10
< 2
< 2
< 2
< 2
< 2
5
< 2
< 2
14
10
<10
<10
0.9
0.2
< 0.2
< 0.2
(a)   Sampling Point 1  -  Influent
     Sampling Point 2  -  Aerated Lagoon  Effluent
     Sampling Point 3  -  Storage Lagoon  Effluent
     Sampling Point 4  -  Final  Effluent
                                           11

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     As Table 3 shows, chloroform and trichloroethylene  were  found  in  all  20 waste-
water samples analyzed for these constituents.   Influent wastewater concentrations
ranged from 360 to 2645 yg/1  for chloroform and from 6-120  yg/1  for trichloro-
ethylene.  Concentrations of these pollutants were successively  less in  the waste-
waters emerging from each operation in the treatment sequence, with final  effluent
concentrations being 1-13 yg/1  for chloroform and  2-10 yg/1 for  trichloroethylene.

     Benzene was present in all five influent wastewater samples analyzed  at con-
centrations ranging from 6-53 yg/1, and was also present in four of five aerated
lagoon effluents in concentrations of 2-8 yg/1. This pollutant  was present above
the minimum detectable limit of 1 yg/1 in two holding lagoon  effluent  samples
(2 and 3 yg/1) and in only one final effluent sample (8  yg/1).

     As Table 3 clearly shows, concentrations of benzene, chloroform,  and  tri-
chloroethylene were generally higher in the wastewater samples obtained  during
the two-day supplementary sampling period in September than in samples obtained
in the initial period in August.  For influent  and aerated  lagoon effluent samples
this may simply reflect variation in the incoming  wastewater  stream.   Decreased
retention time of wastewater in the holding lagoon due to very heavy usage of  its
effluent for irrigation may at least partially  explain the  increased levels of the
three volatile organics noted in water from this source  in  September.  This possi-
bility is supported by the fact that gas chromatography  indicated the  presence of
higher concentrations of extractable organics  in holding lagoon  effluent in
September than in August.  Due to probable long retention times  of  organic pollut-
ants in the soil profile because of sorption on earth solids, the variations in
concentrations of benzene, chloroform, and trichloroethylene  in  the final  effluent
in August and September probably cannot be explained by  similar  variations in  the
composition of the wastewater concurrently applied to the soil.   However,  these
final effluent variations may well reflect compositional differences of  wastewaters
applied at earlier dates.

     No vinyl chloride was detected in any of  the  wastewater  samples analyzed.
The minimum detectable level for this compound  was 1 yg/1.  Likewise,  benzidine,
endrin, toxaphene, and PCB's were not present during this study  in  detectable
concentrations in the wastewater entering the Muskegon System or in any  of the
effluents from the various treatment steps. Based on spiked  samples carried
through the entire analytical sequence, respective minimum  detectable  limits for
the four compounds were estimated to be:  5, 5, 100, and 25 yg/1 in influent and
aerated lagoon effluent samples; 2, 4, 80, and  25  yg/1  in storage lagoon effluent;
and 1, 1, 50, and 10 yg/1 in final effluent.

     Sixty-one organic compounds which were identified  in addition  to  benzene,
chloroform, and trichloroethylene in the influent  and various effluent wastewater
samples obtained at Muskegon are listed in Table 4.  Only those  compounds  identified
in a majority of the daily samples obtained at  a given  sampling  point  or in a  com-
posite sample for that sampling point are presented as  positive  in  this  table.
Although no quantitative data were obtained in  most cases,  the  identified  compounds
were probably present in concentrations of at  least 1 yg/1, the  estimated  minimum
level of detectability for the analytical procedures employed.   A number of compounds,
including toluene, 1,2-dichloroethane, xylene,  diazobenzene,  dichlorobenzophenone,
chloroaniline, hexadecanoic acid, octadecanoic  acid, dodecanol,  and tetradecanol,
appeared to be present in relatively high concentrations, possibly  several hundred
micrograms per liter or more, in the influent  wastewater.


                                          12

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Table 3.  BENZENE, CHLOROFORM,  AND TRICHLOROETHYLENE
            IN MUSKEGON SYSTEM  WASTEWATER


Concentration in yg/1 (b)
Sampling 8-10-76 8-11-76
Pollutant
Benzene



Chloroform



Tn'chloroethylene



(a) Sampling Point 1
Sampling Point 2
Sampling Point 3
Sampling Point 4
(b) Average for dupl
Point (a) Tue
1 6
2 7
3 < 1
4 < 1
1 425
2 105
3 12
4 3
1 13
2 16
3 7
4 6
- Influent
- Aerated Lagoon
- Storage Lagoon
- Final Effluent
icate samples.
Wed.
53
2
< 1
< 1
440
61
9
3
6
3
4
3

Effluent
Effluent


8-12-76
Thu.
6
< 1
< 1
< 1
480
81
4
1
10
5
1
2





9-7-76
Tue.
41
8
3
< 1
360
365
100
13
110
35
11
10





9-8-76
Wed.
32
5
2
8
2645
610
75
10
120
33
6
8





                         13

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             Table 4.  ADDITIONAL ORGANIC COMPOUNDS IDENTIFIED IN
                             MUSKEGON SYSTEM WASTEWATER

Pollutant (b)
Wastewater Sampled (a)
Aerated Holding
Lagoon Lagoon
Influent Effluent Effluent

Final
Effluent
Dichloromethane (c)
1,2-Dichloroethane (c)
1,2-Dichloroethylene (c)
Toluene
Xylene (d)
Acetone
Dimethyl Sulfide
3-Pentanone
Dimethyl Disulfide
Dichlorobenzidine (c)
Phenol (c)(d)
Ethyl benzene (c)
Trichlorobenzene (c)
Diazobenzene
Di chlorobenzophenone
Aniline (d)
N-Ethyl aniline
N,N-Diethylaniline
N,N-Dimethyl aniline (d)
Chloroaniline (d)
Benzothiazole
Benzyl Alcohol (d)
Cresol (d)
Methoxy Phenol (d)
Hydroxymethoxyacetophenone
Di methoxyacetophenone
Chloropropiophenone
Hexanoic Acid (d)
Decanoic Acid (d)
Dodecanoic Acid
Tetradecanoic Acid
Hexadecanoic Acid
Heptadecanoic Acid
Octadecanoic Acid
a-Pinene
B-Pinene
a-Terpineol
Trithiapentane (d)
Tetrathiahexane (d)
2-Ethyl-l-hexanol
Isoborneol
Decanol
Dodecanol
Tetradecanol
                                        14

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      Table 4 (continued).   Additional  Organic  Compounds  Identified  In
                           Muskegon  System  Wastewater
                                          Uastewater  Sampled  (a)
Pollutant (b)
Influent
Aerated
Lagoon
Effluent
Holding
Lagoon
Effluent
Final
Effluent
2-(2-(2-ethoxyethoxy)ethoxy)ethanol +
Tetradecene
Tri methyl 1 socyanurate
Atrazine
Heptanoic Acid (e)
Octanoic Acid (e) +
Nonanoic Acid (e) +
Pentadecanoic Acid (e)
0-Phenyl Phenol (e) +
Benzoic Acid (e) +
Phenylacetic Acid (e) +
Salicylic Acid (e) +
Phenylpropionic Acid (e) +
Vanillin (e) +
Acetovanillin (e) +
Homovanillin (e) +
2-(4-Chlorophenoxy)2-Methyl +
Propionic Acid (e)
-
+
+
_ -
(f) +
(f) +
(f)
(f) +
(f)
(f) +
(f)
(f)
(f)
(f)
(f)
(f)
(f) +

-
-
+
+
-
_
_
-
_
-
-
-
_
-
_
-

(a) Presence or absence of pollutant in wastewater  is  indicated by + or  -.
    "?"  indicates presence suspected but  not  confirmed beyond  reasonable
    doubt.

(b) Unless  noted otherwise, listed  compounds  were identified in daily  samples
    at RSKERL.

(c) Compounds appearing on the EPA  "List  of Dangerous  Pollutants."

(d) Identified in both daily samples at RSKERL  and  composite samples at  AERL.
(e) Identified in composite samples at AERL.

(f) Composite samples  of aerated  lagoon effluent were  not obtained.
                                         15

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     As Table 4 shows, 56 of the 61  additional  organic  compounds  identified were
present in the influent wastewater.   The other  five  compounds  (tetradecene,
pentadecanoic acid, heptanoic acid,  trimethylisocyanurate,  and atrazine) were
present in various effluent wastewaters  but were  not detected  in  the  influent
during this study.  In some cases this may have resulted  from  production of
compounds not in the influent by biochemical  processes  occurring  in the lagoons or
soil.  Temporal changes in influent  wastewater  composition, amplified by the rela-
tively long residence times of water and pollutants  in  the  last stages of  the
System, may also have been involved.  For example, trimethylisocyanurate,  which
was detected only in storage lagoon  and  final effluent  samples, has been observed
to be an intermittent contaminant of selected river  waters, possibly  originating
from a seasonally active source such as  pesticide manufacture  (13).   Hence, the
trimethylisocyanurate found in the storage lagoon and final effluents at Muskegon
may reflect the presence of this compound in the  influent wastewater  at an earlier
date, even though it was not detected in any influent sample obtained during this
study.  The source of atrazine, which was found only in the final  effluent in
concentrations of 5-7 pg/1, was almost certainly  herbicide  which  was  being used
to treat the spray-irrigated farmland.

     Seventeen of the 56 additional  organic pollutants  identified in  the influent
wastewater were present in detectable concentrations in the storage lagoon effluent
being applied to the land, while only five (dichloromethane, acetone, hexadecanoic
acid, dodecanol, and tetradecanol) were  detected  in  the final  effluent.  It is
interesting to note that, while dodecanol and tetradecanol  were present in the
influent and final effluent, neither was detected in the  storage  lagoon effluent
and only dodecanol was detected in the aerated  lagoon effluent during this study.
This may indicate temporal variation of  incoming  wastewater, increased degradative
activity in the lagoons, or effects of biochemical  processes in the soil profile.

     Eight of the organic pollutants identified in  influent wastewater, in addition
to the specifically analyzed benzene, chloroform, and trichloroethylene, appeared
on the EPA "List of Dangerous Pollutants."  These were:  dichloromethane;  1,2-dichloro-
ethane; 1,2-dichloroethylene; toluene; dichlorobenzidine; phenol; ethylbenzene;  and
trichlorobenzene.  Of these compounds, only dichloromethane was detected in the  final
effluent.  Two other compounds appearing on the "List," namely,  1,1-dichloroethylene
and tetrachloroethylene, were each detected in  low concentration  in  single influent
samples, but were not included in Table  4 because of their limited occurrence.

     In assessing the information obtained in this  study  concerning  organic pollut-
ants in the Muskegon Wastewater Treatment System, it must be emphasized that  this
was a preliminary survey conducted within a restricted  time frame which consider-
ably limited both sampling and analytical efforts.   In  particular, sampling over
a much wider time span would have been highly desirable because  of the relatively
long retention times for wastewater in the Muskegon System, and  quantitation  of
many more of the organic compounds  identified in the study would  have added much
to the value of the work.  Nevertheless, the data presented in Tables 3 and 4 are
sufficient to clearly indicate that the Muskegon County Wastewater Treatment  System
was receiving for treatment wastewaters  consistently containing  a great many  organic
pollutants of possible concern, including at least 11 compounds  appearing  on  the
EPA "List of Dangerous Pollutants."   It is further apparent from Tables  3  and 4
that, even though low levels of eight organic pollutants,  including  four  toxic
compounds, were indicated  to survive  the treatment sequence, the Muskegon  System
was relatively quite effective in removing organic pollutants from the wastewater
                                          16

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v/hich it was treating.  This is emphasized by Figure 4,  which presents  a  comparison
by gas chromatography of neutral extracts prepared from  influent,  aerated lagoon
effluent, storage lagoon effluent, and final  effluent samples.   These chromatograms,
which were obtained by chromatographing quantities of extract equivalent  to 7.5 ml
of each wastewater, clearly show the very significant attenuation  of organic
pollutants across the System.  It is very doubtful if any other types of  treatment
systems, with the possible exception of those utilizing  heroic and very costly
measures for polishing of final effluents, would have been more effective than the
Muskegon System in removing the organic pollutants occurring in the wastewater
being treated, especially since more than 60  percent of  this wastewater was com-
prised of industrial components.  The presence in the final effluent of atrazine,
trimethylisocyanurate, and those eight compounds which survived the entire treat-
ment sequence is significant primarily because these substances necessarily
traversed 5-12 ft (1.5-3.66 m) of sandy soil  to reach the tile carrying the final
effluent from the site.  This comprises further evidence that organic pollutants,
including chlorinated compounds of suspected  toxicity, may survive and  move signif-
icantly in the subsurface under proper conditions.  Hence, the need is  reiterated
for developing definitive information concerning the movement and  fate  of organic
pollutants in the subsurface environment in order that waste disposal methods
which employ the subsurface as a pollutant receptor may  be utilized to  their full
potential with minimum impact on ground water.

     The experience gained in this study emphasizes that the major problems in
conducting a large-scale National survey of toxic pollutants in municipal waste-
waters would be concerned with the analysis of organics.  Of the 65 pollutants or
groups of pollutants on the "List of Dangerous Pollutants," 50 are organic substances.
Furthermore, these 50 substances actually comprise more  than 200 individual organic
compounds, since 22 represent either groups of isomers or whole classes of compounds.
Obviously, inclusion in a toxics survey of all of the individual compounds implied
by the "List of Dangerous Pollutants" would be an overwhelming task.  In  toxics
survey work currently being conducted in an effort to fulfill the  mandates of the
"65 Toxic Pollutants Consent Decree Agreement" of 1976,  a list of  109 organic
pollutants developed from the original "list  of 65" is being used.  However,
analysis for 109 organic compounds in a survey of many complex effluents  still
poses problems of considerable magnitude, particularly if the quality of  the
analytical work is maintained at a high level.

     Analytical procedures based on computerized gas chromatography-mass  spectrom-
etry similar to those used for organic analysis in this  study are  probably the best
available methods for survey work involving organic pollutants.  However, some of
the compounds which appear on the "List of Dangerous Pollutants" probably cannot
be analyzed by GC/MS, and methods adaptation  and testing are needed for many others.
Also, the sensitivity of GC/MS methods for some compounds may be less than desired,
particularly if relatively extensive clean-up of extracts of complex samples is
not employed before the GC/MS step.  For example, the minimum limits of detection
for toxaphene and PCB's which were achieved in this study were relatively high,
particularly for influent and aerated lagoon  effluent samples which contained
complex arrays of organic substances that impeded specific analyses for individual
compounds.

     From the above considerations, it is apparent that  planning for a  possible
survey of toxic pollutants in municipal wastewaters should be very thorough, with
careful development of a comprehensive and feasible protocol based on a realistic


                                          17

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                                        SAMPLE;  EQUIVALENT TO 7,5 ML
                                                OF WASTEWATER.
                                        COLUMN:  32 OV-1 ON 100/200 GAS CHROM.
                                                Q, 1.8 M x 2 MM,
                                        TEMP:    70-210°. 6"/niN.
                                           AERATED LAGOON EFFLUENT
                                          STORAGE LAGOON E FLUENT
Figure  4.   Comparison  by gas chromatography of  neutral  extracts
     of wastewaters from Muskegon  System,  August  10, 1976.

                                     18

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conception of analytical  capabilities and limitations  being  an  absolute  necessity.
This could best be achieved through a coordinated effort  of  ORD personnel  exper-
ienced in GC/MS analysis  of wastewaters and in municipal  treatment  technology  with
Office of Water and Hazardous Materials personnel authorized to make  policy  deci-
sions concerning the scope of the survey and the sensitivity required of analytical
procedures.

     The time and cost for the specific analysis portion  of  this study,  involving
analysis of 13 selected toxic pollutants plus TOC, COD, and  TSS in  20 samples,
are presented in Table 5.  Analytical work required 99 man-days and an estimated
expenditure of $11,385, based on a cost rate of $30,000 per  man-year.  Sampling
required 14 man-days and  $2,945; relatively high sampling costs were  incurred
because of the wide separation of the Laboratory and sampling site, but  may  be
indicative of what should be expected in a National survey.   The total time
required for both sampling and analysis was 113 man-days  at  a cost  of $14,330, or
$716.50 per sample, excluding preliminary preparation, administration, and equipment.
                                          19

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     Table 5.  TIME AND COST REQUIRED FOR SURVEY FOR 13 TOXIC POLLUTANTS
               AT MUSKEGON COUNTY WASTEWATER MANAGEMENT SYSTEM
	Operation	Man-Days    Cost.  $  (a)

ANALYSIS

   General and Inorganic Analysis                             32          3,680
     (8 parameters/sample, 20 samples—160 analyses)

   Volatile Organic Analysis                                  20          2,300
     (4 compounds/sample, 20 duplicate samples—
     160 analyses)

   Extractable Organic Analysis
Extraction (4/sample, 20 samples— 80 extractions)
Preliminary GC (20 basic, 20 neutral extracts—
40 analyses)
GC/MS, Neutrals (3 compounds/extract, 20 extracts—
60 analyses)
GC/MS, Bases (1 compound/extract, 20 extracts—
20 analyses)
Total , Analysis
SAMPLING
Personnel (2 men, 5 days at remote sampling site
plus 2 days in transit)
Transportation for Personnel (auto and air)
Transportation for Samples (air)
Total , Sampling
TOTAL TIME AND COST (b)
TIME AND COST PER SAMPLE (b)

18
6
15
8
99
14
14
113
5.65
2,070
690
1,725
920
11,385
1,610
625
710
2,945
14,330
716.50
(a)  Based on $30,000/man-year  or  $115/man-day.
(b)  Excluding preliminary preparation, administration, and equipment.
                                         20

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                                     REFERENCES


 1.  Standard Methods for the Examination of Water and  Wastewater,  Fourteenth
     Edition.  American Public Health Association, Washington,  D.C.,  1976.   p.  94.

 2.  Ibid., pp. 532-534.

 3.  Ibid., pp. 550-554.

 4.  Ibid., pp. 159-162.

 5.  Ibid., pp. 156-159.

 6.  Ibid., pp. 370-372.

 7.  Manual of Methods for Chemical  Analysis of Water and Wastes.   EPA-625/6-74-003,
     U.S.  Environmental Protection Agency, Cincinnati,  Ohio,  1974.   pp.  99-102.

 8.  Analytical Methods for Atomic Absorption Spectroscopy Using  the H  G A  Graphite
     Furnace.  The Perkin Elmer Corporation, Norwalk, Connecticut,  1974.

 9.  Bellar, T. A. and J. J. Lichtenberg.  Determining  Volatile Organics at Microgram-
     per-Litre Levels by Gas Chromatography.  J.  Amer.  Water  Works  Assn.  66(12):739-
     744,  1974.

10.  Eichelberger, J. W., L. E. Harris,  and W.  L.  Budde.   Application of Gas Chroma-
     tography-Mass Spectrometry with Computer Controlled  Repetitive Data Acquisition
     from  Selected Specific Ions.   Anal.  Chem.   46:227-232, 1974.

11.  Webb,  R. G., A.  W. Garrison,  L.  H.  Keith,  and J. M.  McGuire.   Current  Practice
     in GC-MS Analysis of Organics in Water.  EPA-R2-73-277,  U.S. Environmental
     Protection Agency, Corvallis, Oregon, 1973.   pp. 88-89.

12.  Analytical Quality Control Laboratory.  Handbook for Analytical  Quality Control
     in Water and Wastewater Laboratories.  U.S.  Environmental  Protection Agency,
     Cincinnati, Ohio, 1972.  98 p.

13.  Eichelberger, J. W.  and W. L. Budde.  Trimethylisocyanurate:   An Unusual
     Organic Pollutant.  Analytical  Quality Control  News  Letter,  No.  32.  U.S.
     Environmental Protection Agency, Cincinnati,  Ohio, January 1977.   pp.  5-6.
                                          21

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Appendix.  Elemental Analyses of Composited Samples of Muskegon
           Wastewater by Plasma Emission and Neutron Activation
Elements
Al
AM
Au
B
Ba

Be
Br
Ca
Cd

Ce
Cl
Co
Cr
Cu

Bu
F«
Hg
K
La
Lu
Kg
Mn
Mo
Ma
Nd
Ni
Pb
Rb
Sb
Sc
Sa
Sm
Sn
Sr
Th
Ti
U
V
«>
Zn
Plawna Emission (ppm)
tl(a) |3(b) t4(c)
1.3
<5.0xl(T2

6.3*10~l
7.U10"2
— q
< 1.0x10

5.6X101
<2.0xlO"3



4.0xlO"3
5.9xlO"2
S.OxlO"3


7.3X10"1
1.2xlO"2



1.2X101
S.lxlO"1
4.0xlO~3


l.OxlO"2
< S.OxlO"2

<5.0xiO"3

< S.OxlO"2

< S.OxlO"2
1.4X10"1

2.5X10"1

2.0xlO"3

3.5X10"1
l.OxlO"1
<5.0xlO"2

5.2X10"1
4.8xlO"2
_i
<1.0xlO J

7 . 2X101
<2.0xlO"3



7.0xlO"3
S.lxlO"2
4.0xlO"3


7.5X10"1
l.lxlO"2



1.4X101
2.5xlO~l
l.SxlO"2


2.3xlO"2
<5.0xlO"2

< S.OxlO"3

<5.0xlO"2

<5.0xlO"2
l.SxlO"1

5.6xlO"2

l.OxlO"3

2.1X10"1
4.0xlO"2
<5.0xlO"2

3.4X10"1
S.SxlO"2
— a
<1.0xlO J

S.2X101
<2.0xlO"3



2.0xlO"3
4.0xlO"3
2.0xlO"3


9.1xlO"2
S.OxlO"3



l.SxlO1
2.9xlO"2
l.SxlO"2


6.0xlO"3
< S.OxlO"2

< S.OxlO"3

<5.0xlO"2

<5.0xlO"2
6.4xlO"2

2.0xlO"3

2.0xlO"3

l.lxlO"2
Neutron Activation (ppm)
ll(a) I3(b) f4(c)
5.9

<1.0xlO"3

7.4xlO~2


2.1X10"1
1.2xl02

_•>
2.0x10 J
1.7xl02
l.OxlO"3
4.7xlO"2

_3
< 1.0x10 J
6.6X10"1
2.0xlO"3
1.9X101
l.OxlO"3

1.2xlOX
3.4X10"1
6.0xlO"3
1.4xl02



1.0X10"2
4.0xlO"3

<1.0xlO J

l.OxlO"3

3.0xlO~3
a.oxio"3
1.2X101
3.3xlO~2

5.3X101
1.6xlO~2



7.0xlO"3
el.OxlO"3

l.OxlO"3




l.OxlO"3

a.oxio"3
8.2xlO~2
(a)  Sampling Site //I - Influent.
(b)  Sampling Site #3 - Storage Lagoon Effluent.
(c)  Sampling Site 14 - Final Effluent.
                                  22

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