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