ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
E PA-330/2-78-019
NPDES COMPLIANCE MONITORING
AND
WATER/WASTE CHARACTERIZATION
SALSBURY LABORATORIES/CHARLES CITY, IOWA
(JUNE 1 9-30, 1 97 8)
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER, COLORADO
AND
REGION VII, KANSAS CITY. MISSOURI
NOVEMBER 1978
S7^
132/
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PRO^ ^
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Environmental Protection Agency
Office of Enforcement
EPA-330/2-78-019
NPDES COMPLIANCE MONITORING
AND
WATER/WASTE CHARACTERIZATION
SALSBURY LABORATORIES/CHARLES CITY, IOWA
[June 19 - 30, 1978]
Thomas 0. Dahl
November 1978
National Enforcement Investigations Center - Denver
and
Region VII - Kansas City
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ACKNOWLEDGMENTS
The Project Coordinator wishes to thank the staff members of the
NEIC and Region VII for their cooperation and assistance in the plan-
ning and conduct of the Salsbury/Laboratory/Charles City, Iowa study
and in the preparation of this report.
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TABLE OF CONTENTS
I INTRODUCTION 1
II SUMMARY AND CONCLUSIONS 5
NPDES EFFLUENT LIMITATIONS COMPLIANCE 5
WASTEWATER AND WATER QUALITY CHARACTERIZATION 6
PERFORMANCE AUDIT 13
BIOLOGICAL STUDIES 18
TOXICITY AND HEALTH EFFECTS OF POLLUTANTS IDENTIFIED DURING
NEIC STUDY 21
III BACKGROUND 23
SALSBURY LABORATORIES 23
CHARLES CITY, IOWA WWTP 36
IV SURVEY METHODS 41
COMPLIANCE MONITORING AND WASTEWATER/WATER CHARACTERIZATION . 41
BIOLOGICAL STUDIES 51
V SURVEY FINDINGS 61
NPDES EFFLUENT LIMITATIONS COMPLIANCE 61
WASTEWATER AND WATER QUALITY CHARACTERIZATION 66
PERFORMANCE AUDIT 106
BIOLOGICAL STUDIES 114
VI TOXICITY AND HEALTH EFFECTS OF POLLUTANTS IDENTIFIED DURING
NEIC STUDY 151
REFERENCES 166
APPENDICES
A SALSBURY LABORATORIES NPDES PERMIT NUMBER IA0003557
B PRIORITY POLLUTANTS LISTING
C FLOW MONITORING TECHNIQUES
D METHODS, ANALYTICAL PROCEDURES AND QUALITY CONTROL
E JUNE 1978 SELF-MONITORING DATA, CHARLES CITY, IOWA WWTP
AND SALSBURY LABORATORIES
F PERFORMANCE AUDITS, SALSBURY LABORATORIES AND CHARLES CITY,
IOWA WWTP
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TABLES
LISTING OF RAW MATERIALS, INTERMEDIATES AND SPECIALTY PRODUCTS .
SELF-MONITORING DATA
SALSBURY LABORATORIES' COMPOUNDS PRESENT "X"% OF TIME
HISTORY OF WASTE PRODUCTION AT SALSBURY LABORATORIES
SELF-MONITORING DATA
BIOLOGICAL SAMPLING STATIONS
NPDES COMPLIANCE MONITORING
METALS SAMPLING DATA
pH AND TEMPERATURE DATA
BOD, COD, TOC, TSS SAMPLING DATA
PHENOLIC COMPOUNDS AND AMMONIA-NITROGEN SAMPLING DATA
VOLATILE ORGANICS SAMPLING DATA
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SELECTED ORGANIC PRIORITY POLLUTANTS SAMPLING DATA
COMPARISON OF FLOWS
SUMMARY OF MUTAGEN TESTS (AMES BACTERIAL ASSAY)
MUTAGENIC ACTIVITY OF SALSBURY LABORATORIES/CHARLES CITY . . . .
96-HOUR FLOW-THROUGH SURVIVAL DATA
PROBIT ANALYSIS ON DOSE SALSBURY PROCESS WASTEWATER
96-HOUR FLOW-THROUGH SURVIVAL DATA
PROBIT ANALYSIS ON DOSE GROUNDWATER FROM LA BOUNTY DUMP SITE . .
96-HOUR FLOW-THROUGH SURVIVAL DATA
96-HOUR FLOW-THROUGH SURVIVAL DATA
PROBIT ANALYSIS ON DOSE
PROBIT ANALYSIS ON DOSE
IN SITU FISH EXPOSURE DATA
FISH PALATABILITY DATA
FISH POPULATION DATA
CEDAR RIVER PERIPHYTIC ALGAL POPULATIONS
CEDAR RIVER PERIPHYTIC CHLOROPHYLL a, ASH-FREE WEIGHT AND
AUTOTROPHIC INDEX 7
BENTHOS
TOXICITY OF COMPOUNDS IDENTIFIED
FIGURES
CHARLES CITY, IOWA AND VICINITY
IOWA - CEDAR RIVER BASIN
WASTEWATER TREATMENT SYSTEM '
PLOT DIAGRAM AND SAMPLING STATION LOCATIONS
CHARLES CITY WWTP AND SAMPLING STATIONS
SAMPLING STATION LOCATIONS
BIOLOGICAL STUDIES STATION LOCATIONS
CEDAR RIVER ARSENIC PROFILE UPSTREAM OF (STATION 11) AND
DOWNSTREAM FROM (STATION 12) LA BOUNTY DUMP SITE
MUTAGEN TESTING DOSE RESPONSE CURVE
PROBIT ANALYSIS ON DOSE SALSBURY PROCESS WASTEWATER
PROBIT ANALYSIS ON DOSE GROUNDWATER FROM LA BOUNTY DUMP SITE . .
PROBIT ANALYSIS ON DOSE CHARLES CITY WWTP PRIMARY CLARIFIER
OVERFLOW
PROBIT ANALYSIS ON DOSE CHARLES CITY WWTP EFFLUENT
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I. INTRODUCTION
On September 12, 1975, NPDES Permit No. IA0022039 was issued to the
northern Iowa community of Charles City to limit discharges from its
wastewater treatment plant (WWTP) to the Cedar River [Figure 1]. The
major industrial contributor to the Charles City sewerage system is
Salsbury Laboratories, a manufacturer of veterinary biological and
pharmaceutical preparations and feed additives and intermediate organic
chemicals. In addition to discharging process wastewaters to the Charles
City WWTP, Salsbury discharges noncontact cooling waters and surface
runoff to an unnamed drainage which discharges to Wildwood Creek, a
tributary of the Cedar River. The noncontact cooling water discharges
are limited by National Pollutant Discharge Elimination System (NPDES)
Permit IA0003557. Beginning in 1953, solid wastes, primarily arsenic
and gypsum sludges, were deposited by Salsbury Laboratories in the
La Bounty Dump [Figure 1] within the Cedar River floodplain. This con-
tinued until December 14, 1977, when the Iowa Department of Environmental
Quality (IDEQ) issued order 77-DQ-01 requiring Salsbury to cease dis-
posing of wastes at that site. This order was issued following studies
by the Iowa Department of Environmental Quality (DEQ) and Iowa Geological
Survey, and the EPA Region VII discovery of orthonitroani1ine (ONA), one
of the compounds used by Salsbury in manufacturing growth stimulant
products, in shallow wells in Waterloo, Iowa, approximately 105 km (65
mi) downstream by river from Charles City [Figure 2].
In December 1977, EPA Region VII requested technical assistance
from the National Enforcement Investigations Center (NEIC) in assessing
the Salsbury Laboratories/Charles City situation. From January 9 to 12,
1978, NEIC conducted reconnaissance inspections in the Charles City
area. Region VII subsequently requested that NEIC conduct technical
studies to ascertain compliance with applicable Federal regulations and
characterize waste sources and water quality. Further reconnaissance
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Figure l. Charles City, Iowa and Vicinity
Scale 1:24000
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3
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inspections for study planning purposes were conducted by NEIC from
April 25 to 27, 1978. From June 19 to 30, 1978, the NEIC conducted
the requested studies.
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II. SUMMARY AND CONCLUSIONS
During June 19 to 30, 1978, the National Enforcement Investigations
Center (NEIC) conducted an NPDES compliance monitoring and wastewater/
water quality study in the Charles City, Iowa area. The study deter-
mined that environmental contamination from Salsbury Laboratories is
widespread, affecting the Charles City WWTP, the Cedar River and ground-
water in the Charles City area. The findings and conclusions of the
study are discussed below.
NPDES EFFLUENT LIMITATIONS COMPLIANCE
Charles City, Iowa WWTP
Effluent data collected during June 19 to 30, 1978, indicated that
the Charles City WWTP was in compliance with NPDES permit limits for
BOD, TSS, NH3-N and total heavy metals. The daily average arsenic
concentration was 1.9 mg/1 which exceeded the permit limit of 1.6
mg/1. The daily maximum arsenic limitation of 2.5 mg/1 was exceeded
on 3 of the 11 days of sampling, with concentrations ranging from
2.7 to 3.6 mg/1. Twelve hourly pH measurements were outside the pre-
scribed range of 6.5 to 9.0 standard units.
Salsbury Laboratories
Salsbury Laboratories was in compliance with NPDES permitted
limits for its cooling water discharges. However, the permitted moni-
toring site does not include process contaminated discharges which
enter the storm sewer system downstream from the monitoring site, and
hence does not represent all discharges from Salsbury.
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WASTEWATER AND WATER QUALITY CHARACTERIZATION
Salsbury Process Wastewaters
1. Average BOD and phenols concentrations during the NEIC study of
140 and 0.31 mg/1 were atypically low in comparison to the pre-
vious year's self-monitoring averages of 621 and 27.2 mg/1, res-
pectively.
2. Average ammonia as nitrogen and TSS concentrations of 67.9 and
19 mg/1 were consistent with past self-monitoring data.
3. Although BOD analyses did not indicate toxicity, COD and TOC
analyses provided a better assessment of the strength of the
wastewaters. C0D:T0C:B0D ratio, based on loadings, averaged
4.3:1.4:1.0.
4. With the exception of mercury, zinc and arsenic, metals concen-
trations in the process wastewaters were generally less than
detectable. Average mercury concentrations were low, 1.8 pg/1,
and consistent with the self-monitoring average for the past
year, 3.6 pg/1. Zinc averaged 0.12 mg/1 during the study. Arsenic,
resulting from the production of organic arsenicals averaged 6.0
mg/1, which was consistent with the average for the past year,
5.05 mg/1.
5. Characterization of the process wastewaters resulted in the identi-
fication of 26 organic compounds and tentative identification of
an additional 4 compounds. Average concentrations of the compounds
identified ranged from low level detection of approximately 1
pg/1 to 11,000 pg/1 for orthonitroani1ine, which is the compound
that has previously been identified in the Waterloo, Iowa water
supply. Seven compounds were found in concentrations of 1,000
pg/1 or greater. Of the 26 compounds identified, 17 are priority
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pollutants, compounds of environmental concern as defined by the
June 7, 1976 Natural Resources Defense Council (NRDC) vs. Russell
Train (USEPA) Settlement Agreement. In addition to the daily
organics characterization data, three days of composite samples
were combined into one sample proportional to daily flows and
analyzed by priority pollutant methodology. These data indicated
the presence of an additional 5 priority pollutant organic compounds,
6. A comparison between the process wastewater flows measured by
Salsbury Laboratories and those measured by NEIC indicated the
former are inaccurate and yield consistently low values. The
Salsbury flows averaged 77% of those measured by NEIC.
Salsbury Cooling Waters
Data collected from combined cooling waters and plant runoff in-
dicated process contamination.
1. Average concentrations of phenols, 0.34 mg/1, were approximately
the same as those found in the process wastewater, 0.31 mg/1.
2. Metals concentrations were generally low or undetectable with
the notable exception of arsenic which averaged 1.9 mg/1.
3. Organics characterization of combined cooling waters and plant
runoff resulted in the identification of 15 organic compounds.
Average concentrations of the compounds identified ranged from
low level detection at approximately 1 ng/1 to 300 pg/l for 1,
1, 2-Trichloroethane. Of the 15 organic compounds 14 were also
present in the Salsbury process wastewaters and 11 of the 15 are
priority pollutants. As with the process wastewaters, three 24-hour
composite samples were combined into one sample for separate
priority pollutant analyses. These data indicated the presence
of one additional priority pollutant organic compound.
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4. No organic compounds were identified in the sample collected
June 28 from the NPDES monitoring site, the cooling tower discharge,
thus indicating that this NPDES monitoring site is not representa-
tive of possible contamination from plant surface runoff, plant
drains, process sewer connections or sewer leaks.
Charles City WWTP
Data collected at the Charles City WWTP reflected the effects of
discharges to the system by Salsbury Laboratories.
1. Average influent BOD and phenols concentrations of 92 mg/1 and
0.15 mg/1 were atypically low in comparison to the past year's
self-monitoring data averages of 245 and 5.63 mg/1 respectively.
These low values reflected concurrent atypically low concentra-
tions found in the Salsbury process wastewaters.
2. TSS, BOD, COD, TOC and phenols removal efficiencies averaged
approximately 71, 76, 50, 46 and 70% respectively. Although the
TSS and BOD removals were not as high as might be expected from
a well-operated trickling filter plant, they were at least in
part affected by the low influent concentrations, 78 and 92 mg/1,
respectively. They may also be affected by toxic compounds from
Salsbury. The lower COD and TOC removals indicate the WWTP was
considerably less successful in removing other more complex and
refractory organic matter.
3. The average influent and effluent arsenic concentrations during
June 19 to 26 were 2.3 and 2.4 mg/1, respectively, indicating
the ineffectiveness of the treatment process in removing the
arsenic.
4. Organics characterization of the Charles City WWTP influent
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resulted in the identification of 24 compounds and the tentative
identification of an additional 2 compounds. Twenty-two of the
24 were also identified in the Salsbury process wastewaters.
Average concentrations ranged from low-level detection at approxi-
mately 1 |jg/l to a high of 3,000 pg/1 for orthonitroanil ine. Of
the 24 compounds, 15 are priority pollutants. In addition to
the characterization data, three 24-hour influent composite samples
were combined proportional to daily flow into one sample and
analyzed by priority pollutant methodology. An additional 4
priority pollutant organic compounds were identified in this
sample.
5. Organics characterization of the effluent resulted in the identifi-
cation of 22 compounds and the tentative identification of an
additional 2 compounds. Tv/enty-one of the 22 were also identified
in the Salsbury process wastewaters. Average concentrations
ranged from low level detection at approximately 1 pg/1 to a
high of 2,600 pg/1 for orthonitroaniline. Of the 22 compounds
identified, 14 are priority pollutants. Separate characteriza-
tion for selected organic priority pollutant analyses was con-
ducted as described above for the influent. Three additional
priority pollutant organic compounds were identified in this
sample.
6. The ability of the Charles City WWTP to remove organic compounds
varied considerably. Removal efficiencies for neutral extractable
organics were as follows:
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Removal
Efficiency
Chemical Name %
p-chloronitrobenzene
17
chloroni trotoluene*
38
4-chloro-3-nitrobenzamide
37
2,6-dichlorobenzamide
63
1,2-dichloro-3-nitrobenzene
79
2-phenylbenzimidzole
55
orthonitroani1ine
4
paranitroaniline
83
nitrobenzene
59
orthonitrophenol
99
1,2,4-trichlorobenzene
68
^Compound was tentatively identified but isomer
structure could not be confirmed.
As noted above, the treatment process was 99% effective in removing
orthonitrophenol. However, the process was only able to remove 17%
of the p-chloronitrobenzene and orthonitroaniline passed through
the plant with only 4% removal. All of the above compounds were
also found in the Salsbury process wastewaters.
La Bounty Dump Site Groundwater
Samples of groundwater drawn from a well located between the
La Bounty Dump and the Cedar River contained considerable concentra-
tions of pollutants, resulting from leachate contamination from the
dump.
1. Average BOD, COD and TOC concentrations averaged 2,000, 7,100
and 2,300 mg/1, respectively.
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2. Average Ammonia as nitrogen and phenols concentrations were also
significant, averaging 130 and 18 mg/1, respectively.
3. As was the case with the Salsbury process wastewaters, most metals
concentrations were low, with the exception of arsenic, which
was considerably higher at 590 mg/1. Present in the groundwater
samples, but not in the process wastewaters, was barium at 0.6
mg/1.
4. Organics characterization of the leachate-contaminated ground-
water resulted in the identification of 24 compounds and the
tentative identification of one additional compound. Eighteen
of the 24 were also present in the Salsbury process wastewaters
during the study. Conversely 18 of the 26 compounds identified
in the process wastewaters were also identified in the ground-
water samples. Average concentrations of the compounds identi-
fied in the groundwater ranged from low level detection of approxi-
mately 1 pg/1 to a high of 180,000 (jg/1 for orthonitroaniline.
Eight compounds were identified in concentrations of 1,000 pg/1
or greater. Of the 24 compounds identified, 14 are priority
pollutants. Separate analyses by priority pollutant methodology
was also conducted on an equal volume composite comprised of
three daily grab samples. An additional 6 priority pollutant
organic compounds were identified.
Groundwater Seep/Spring
Samples collected from the groundwater seep and spring on the
south bank of the Cedar River in downtown Charles City indicated that
wastewaters from Salsbury Laboratories have entered the groundwater
and subsequently the Cedar River, and are indicators of the widespread
presence of pollutants from Salsbury:
1. Arsenic averaged 0.36 mg/1 in the seep and 0.69 mg/1 in the spring.
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2. Organics characterization of the groundwater seep and spring re-
sulted in the identification of 14 and 16 compounds, respectively,
and the tentative identification of one additional compound. Of
the 14 and 16 compounds identified, 13 and 15 respectively were
also identified in the Salsbury process wastewaters. Average
concentrations of the compounds identified ranged from low-level
detection of approximately 1 pg/1 to a high of 330 pg/1 in the
spring for 1,1, 2-Trichloroethane. Of the 14 organic compounds
identified in the seep and 16 in the spring, 10 and 12, respect-
ively, are priority pollutants.
Cedar River Quality-LaBounty Dump Site
Flow proportional samples collected upstream of and downstream
from the La Bounty dump site demonstrated that the site is leaching
pollutants to the Cedar River.
1. Based on the difference in concentrations between the upstream
and downstream stations and flow recorded at the USGS gaging
station, the average pollutant loadings to the Cedar River from
leachate in the vicinity of the LaBounty dump were:
2. There were two direct discharges to the Cedar River in the vicinity
of the La Bounty dump. The first is a 42-inch city storm sewer
carrying wastewaters from White Farm Equipment and the second a
small overland discharge at the downstream end of the La Bounty
site carrying surface runoff, truck washings from Allied Construc-
tion Company and seepage from the La Bounty site. Data collected
kg(lb)/day
Arsenic
1,1,2-Trichloroethane
Orthonitroaniline
Aniline
52.2 (115)
8.2 (18)
11 (25)
1 (2.2)
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during the NEIC study indicated these sources were insignificant
in comparison to leachate contributions.
3. An arsenic profile at 10-foot intervals across the Cedar River
downstream from the La Bounty site indicated the highest concentra-
tions near the dump side of the river (approximately 0.09 mg/1),
tapering off toward the other side (to approximatley 0.02 mg/1).
PERFORMANCE AUDIT
The NEIC evaluation of the Salsbury Laboratories and Charles
City WWTP self-monitoring practices indicated the following proce-
dures deviated from USEPA prescribed/recommended techniques:
Salsbury Laboratories
Sampling Techniques
1. Twenty-four-hour composite samples of process wastewaters
were not flow proportional as prescribed by the Iowa DEQ
Operation Permit No. 5-34-05-0-01. Furthermore, composite
samples for BOD, TSS and phenols were not maintained at 4°C
during collection as prescribed by 304h regulations promul-
gated pursuant to the Federal Water Pollution Control Act
(FWPC).
2. The pH and color values reported to the Iowa DEQ were deter-
mined on the 24-hour composite samples, not a grab sample
as required by the Iowa DEQ Operation Permit. According to
Salsbury Laboratories, this procedure had been reported to
the DEQ, and the Company received no response.
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3. Phenolic compounds samples were taken from the composite
referenced in #1 above, which was collected in a plastic
container. 304h regulations require glass sampling con-
tainers. Samples should also be preserved with phosphoric
acid and copper sulfate during collection of a composite
sample.
4. BOD composite samples collected on Monday through Tuesday
were refrigerated after collection and held until Friday
for analysis. 304h regulations require that holding time
not exceed 6 hours.
Flow Monitoring
Salsbury Laboratories measures process wastewater flows to
the Charles City sewerage system with a magnetic flow meter and
recorder installed on the influent line to the equalization basin.
As noted previously, NEIC measurements during the study indicated
these flows are consistently low (77% of actual flows from 6/20 to
6/26). Hence, pollutant load data contained in self-monitoring
reports would also be low.
Analytical Procedures
The June 20, 1978, performance audit of analytical procedures
indicated a generally good understanding and performance of re-
quired analyses. There were, however, a number of practices
which were contrary to prescribed/recommended procedures:
1. No reference chemical standard such as glucose-glutamic
acid was in routine use for checking the BOD procedure.
Periodic use of such a reference material is necessary to
demonstrate the quality of the dilution water, the effec-
tiveness of the seed and the technique of the analyst.
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2. Examination of the Company's BOD data indicated poor agree-
ment between different dilutions of the same sample. Further
investigation indicated that sample aliquots for the test
were being taken from the settled supernatant of the origi-
nal samples. This procedure could produce low results; all
samples should be thoroughly mixed before aliquots are
withdrawn for analysis.
3. No required pre-washing of filters was performed in the TSS
analyses.
4. The analytical procedures for barium, chromium, copper,
lead and zinc did not include the required digestion step.
Since a small amount of suspended material is present in
the samples, omission of this step may lead to slightly low
results.
5. The total arsenic procedure performed by Salsbury included
an ashing treatment developed in-house to reduce organic
arsenic to inorganic arsenic. Although past testing has
been conducted which reportedly confirms the accuracy of
this method, as well as the acceptable results on the per-
formance sample NEIC provided (see below), this does rep-
resent an alternate procedure and requires agency approval.
6. Performance samples for a wide variety of parameters were
provided during the NEIC audit for subsequent analysis.
Results were acceptable with the exception of pH, COD sample
1, Chromium sample 1 and Lead sample 1 which were marginal;
and the Phenol sample and Selenium samples 1 and 2 which
were unacceptable.
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Charles City, Iowa WWTP
Sampling Techniques
1. Twenty-four hour composite samples were not flow proportional
as required by the NPDES permit. Furthermore, BOD, TSS and
ammonia samples were not maintained at 4°C as required by
304h regulations of the FWPC Act. Once the plant personnel
were informed of this they immediately began refrigerating
their automatic samplers with ice.
2. Phenolic compound samples were collected in plastic, not
glass as required and were not preserved during collection
with phosphoric acid and copper sulfate.
3. pH was determined on composites samples, not grabs as required
by the NPDES Permit.
Flow Monitoring
1. When the NEIC study commenced there was no flow accuracy
verification procedure in use at the Charles City WWTP.
Operators were instructed by NEIC in performing flow calcu-
lations by taking head measurements at the primary device
and verifying accuracy and making minor adjustments at the
transmitter and recorder.
Analytical Procedures
1. Dilution water for BOD analyses was prepared once-per-week.
It must be prepared prior to each test or at least the phos-
phate buffer has to be omitted until just prior to testing.
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2. Blank samples of dilution water often had a BOD of 1-2 mg/1,
most likely a result of algal growth observed on the bottom
of the dilution water bottles. Blanks with a BOD as great
as 2 mg/1 were used in reporting data. Samples where the
dilution water control depletes by more than 0.2 mg/1 must
be voided for BOD testing.
3. The dissolved oxygen probe used in the BOD procedure was
calibrated every other week against the Winkler method using
PAO as the titrant. The probe must be calibrated each day
it is used.
4. No reference standard such as glucose-glutamic acid was in
routine use for checking the BOD procedure. Periodic use
of such a reference standard is necessary to demonstrate
the quality of the dilution water and the technique of the
analyst.
5. The temperature of the BOD incubator bath was 22°C, rather
than the required 20°±1°C.
6. The desiccant used for TSS analyses was non-indicating CaCl2-
An indicating desiccant is required.
7. For TSS analyses, Schleicher and Schuell 47 mm glass fiber
filters, which have an approximate thickness of 0.75 mm
were used. A Reeves Angle 934A or H or equivalent is required
rather than the thick glass fiber filter referenced above.
8. During the TSS analysis no required pre-washing of filters
was performed.
9. Reference buffer solution for pH testing was stored in an
open beaker. Although the buffer was changed weekly, it
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should be protected from evaporation and the laboratory
environment both of which could affect calibrations.
10. Performance samples for BOD and TSS were provided during
the NEIC audit for subsequent analyses. Analytical results
provided to NEIC were acceptable.
BIOLOGICAL STUDIES
Mutagen Testing
The Standard Ames Bacterial Assay Test determines bacterial muta-
genicity, an activity which correlates closely (>90% probability)
with inducement of cancer in laboratory animals by organic compounds.
Results of the Ames Test for mutagenesis conducted at the NEIC
Laboratory demonstrated that twelve of thirteen samples analyzed con-
tained mutagenic substances and potential carcinogens. Test results
show that samples collected from: 1) the Salsbury Laboratories process
wastewaters, 2) Charles City, Iowa WWTP influent and effluent, and 3)
the La Bounty dump site groundwater satisfy the Ames Test requirements
for mutagenicity. The one sample collected from Salsbury Laboratories
cooling water discharge was negative for mutagenic activity.
Biomonitoring
The Salsbury process wastewater and groundwater from the La Bounty
dump site were acutely toxic to fish. The 96-hour LC50* for the process
wastewater and groundwater were calculated to be a 18.6% and 3.8%
concentration, respectively. The Primary clarifier overflow and effluent
from the Charles City WWTP were also acutely toxic to fish. The
* LC50 indicates the concentration (actual or interpolated) at which
50% of the test organisms died or would be expected to die.
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LC5o values for the primary overflow and effluent were calculated to
be a 41.6% and 57.3% wastewater concentration, respectively. These
data indicate that the WWTP is not effective in significantly reducing
the toxicity of the combined municipal and Salsbury process wastewater.
In Situ Fish Survival and Palatability
The final effluent from the Charles City WWTP was determined to
be acutely toxic to fish within 96-hours at the discharge point in
the Cedar River. Mortality of test fish at other exposure sites did
not differ significantly from the reference fish caged at the suspen-
sion bridge near the upstream edge of Charles City. Fish from the
Cedar River adjacent to the La Bounty dump site as well as those from
200 meters downstream from the Charles City WWTP discharge, which
were exposed for approximately one week, were judged to be signifi-
cantly off-flavor and less desirable as a food product compared to
the upstream reference fish.
Indigenous Fish Population
The results of net trapping a reach of the Cedar River extending
from the suspension bridge in Charles City to Midway Bridge show a
noticeable downstream trend toward increasing numbers of coarse and
pollution-tolerant fish species. This trend was not related to any
specific effluent discharge or other input to the Cedar River occurring
at the time of the study. It did not appear that seepage from the La
Bounty dump site or effluent discharge from the Charles City WWTP were
adversely affecting the total fish population or diversity of fish
species in the Cedar River. However, atypical conditions existed
since the Cedar River was in a falling stage following near flood
conditions which would tend to mask any normally occurring physical or
chemical deficiencies.
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20
Periphyton
Periphytic algal communities changed downstream from the
reference station at the suspension bridge in Charles City, Iowa.
The concentration of chlorophyll a was considerably less in Wildwood
Creek near the confluence with the Cedar River than at the reference
station. Increases in both blue-green algae and the autotrophic
index indicated degraded water quality adjacent to the La Bounty dump
and at least 0.8 km (0.5 mi) downstream from the Charles City WWTP.
Decreased periphytic algal population densities and chlorophyll a
concentrations at these same locations indicated toxic conditions for
periphytic algae. Toxic conditions downstream from the Charles City
WWTP are especially noteworthy because treated domestic wastewaters
usually stimulate rather than inhibit algal growth.
Benthic Macroinvertebrates
Examination of Cedar River benthic macroinvertebrates in the
Charles City, Iowa area indicated a generally diverse and pollution-
sensitive community. However, adjacent to the La Bounty dump site,
the benthic population was reduced to only two forms, indicating an
adverse effect of leachate from the dump. In the plume of the Charles
City WWTP discharge, the river was degraded again.
The benthic community improved slightly downstream from the La
Bounty site, and included pollution-sensitive organisms approximately
0.8 km (0.5 mi), downstream from the WWTP. At approximatley 5 km (3
mi) downstream from the WWTP, no benthic evidence of organic or toxic
pollution was observed. The 15 benthic forms found at this site were
indicative of good water quality.
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21
TOXICITY AND HEALTH EFFECTS OF POLLUTANTS IDENTIFIED DURING NEIC STUDY
During the June 19 to 30, 1978 NEIC study, 46 organic compounds
were identified including 4 compounds tentatively identified, and 5
metals were analyzed for and identified. To assess toxicity and health
effects, all these compounds and metals were searched for in both the
Registry of Toxic Effects of Chemical Substances (RTECS) and the Toxline
data base. Health effects and toxicity information was located for
40 of the 51 organic compounds and metals.
Of the 51 compounds and metals, 39 were present in the Salsbury
Laboratories process wastewaters, and health effects and toxicity
information existed for 29 of these 39. The available information
indicates 11 have demonstrated human effects. Benzene is a known
carcinogen to humans and carbon tetrachloride, chloroform, trichloro-
ethene and phenol are known to be carcinogenic to animals.
Thirty-six of the 51 compounds and metals were found in the leachate
contaminated groundwater at the La Bounty dump site. Of these, 32
have known toxicity and health effects, and 11 have known human health
effects. One of the 36, benzene, is a known carcinogen to humans,
and chloroform, trichloroethene and phenol are known to be carcinogenic
to animals.
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22
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III. BACKGROUND
SALSBURY LABORATORIES
Plant and Process Description
Salsbury Laboratories, which was founded in the 1920's, employs
approximately 450 people in Charles City, Iowa, a community of approxi-
mately 9,500. The Salsbury plant typically operates 5 days/week, 24
hours/day and is reputed to be the world's largest animal health pharma
ceutical company. The plant complex occupies approximately 200 acres
and is divided into Biologies, Pharmaceuticals, Chemical Processing,
and Research and Administration. Principal products listed in the
Company's 1974 Iowa DEQ Operation Permit application include:
1.
Sulfonamides
2.
Organic arsenicals
3.
Nitrated aromatics
4.
Phenol sulfonates
5.
Miscellaneous organics
6.
N-nitroso-diphenyl amine
Although the bulk of Salsbury1s products are for animal use, some
sulfa drugs are manufactured for human trade. In addition, Salsbury
packages the pesticide Malathion, for retail sale.
Most products are formulated by batch chemical processes from
various organic and inorganic chemicals. A partial listing of raw
materials, chemical intermediates and specialty products are included
in Table 1. Approximately 60% of the intermediates are consumed intern
ally and 40% are sold directly. Table 1 does not, however, reflect
Salsbury's largest sales line, organic arsenicals, which are marketed
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24
Table 1
LISTING OF RAW MATERIALS, INTERMEDIATES AND SPECIALTY PRODUCTS
SALSBURY LABORATORIES - CHARLES CITY, IOWA*
A. Toluic, Isophthalic and Terephthalic Acid Derivatives
Raw Materials
m-xylene
m-toluic acid
isophthalic acid
p-xylene
p-toluic acid
terephthalic acid
Intermediates & Specialties
6-nitro-m-toluic acid
6-amino-m-toluic aid
4-nitro-m-toluic acid
4-amino-m-toluic acid
2-nitro-m-toluic acid
2-amino-m-toluic acid
4-nitroisophthalic acid
4-aminoisophthalic acid
2-nitroisophthalic acid
2-aminoisophthalic acid
5-sulfoisophthalic acid
3-nitro-p-toluic acid
3-ni tro-p-toluami de
3-amino-p-toluic acid
3-ami no-p-toluamide
nitroterephthalic acid
ni troterephthalami de
ami noterephthalami de
B. Benzoic Acid Derivatives
Raw Materials
toluene
o-chlorotoluene
p-chlorotoluene
m-ni trotoluene
o-nitrotoluene
p-ni trotoluene
2-chloro-4-ni trotoluene
benzoic acid
* Listing included in September 15, 1976 Iowa DEQ memo "Review of Salsbury
Laboratories Current Wastewater Characteristics Effect of Industrial
Wastes on City Treatment Plant and Present Status".
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Table 1 (continued)
LISTING OF RAW MATERIALS, INTERMEDIATES AND SPECIALTY PRODUCTS
SALSBURY LABORATORIES - CHARLES CITY, IOWA*
Intermediates & Specialties
p-chlorobenzoic acid
4-ch1oro-3-nitrobenzoic acid
3-amino-4-chlorobenzoic acid
4-chloro-3-nitrobenzamide
3-ami no-4-chlorobenzamide
4-amino-3-nitrobenzoic acid
3.4-diaminobenzoic acid
4-methoxy-3-nitrobenzoic acid
3-amino-4-methoxybenzoic acid
o-chlorobenzoic acid
2-chloro-3,5-dinitrobenzoic acid ~
0-nitrobenzoic acid
m-nitrobenzoic acid
m-aminobenzoic acid
m-dimethyl aminobenzoic acid
3.5-dinitrobenzoic acid
3,5-diaminobenzoic acid
p-nitrobenzoic acid
p-aminobenzoic acid
p-ami nobenzamide
2-ch1oro-4-nitrobenzoic acid
4-amino-2~chlorobenzoic acid
2-amino-4-nitrobenzoic acid
2,4-diaminobenzoic acid
4-nitrosalicy lie acid
4-aminosal icy 1ic acid
C. Acetani1 ides, Sulfonamides, Sulfonates
Raw Materials
benzene
chlorobenzene
1-chloro-4-nitrobenzene (p-nitrochlorobenzene)
1-chloro-2-nitrobenzene (o-nitrochlorobenzene)
nitrobenzene
ani1i ne
p-ni troani1i ne
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26
Table 1 (continued)
LISTING OF RAW MATERIALS. INTERMEDIATES AND SPECIALTY PRODUCTS
SALSBURY LABORATORIES - CHARLES CITY, IOWA*
Intermediates & Specialties
4-chloro-3-nitrobenzene sulfonyl chloride
4-chloro~3-nitrobenzenesulfonamide
4-amino-3-nitrobenzenesulfonamide (3-nitrosulfani1 amide)
3-nitro-N4-phenylsulfanilamide
3-nitro-Nl,N4-diphenlsulfanilamide (2-nitrodiphenylamine
4-sulfonani1ide)
acetani1ide
p-nitroacetani1ide
p-ami noacetani1ide
m-nitrobenzenesulfonic acid
ammonium m-nitrobenzenesulfonate
sodium m-nitrobenzenesulfonate
N-acetylsulfanilyl chloride
sulfanilie acid
sulfanilamide
p-methylsulfonylaniline
sulfaguanidine
sulfathiazole
sulfapyridi ne
salicylazosulfapyridine
sulfamethazine
D. Phenol sulfonates, Salicyclic Acid Derivatives
Raw Materials
phenol
sal icy lie acid
Intermediates & Specialties
p-phenolsulfonic acid
zinc phenolsulfonate
ammonium phenolsulfonate
sodium phenolsulfonate
lithium phenolsulfonate
aluminum phenolsulfonate
salicyclazosulfapyridine
3,5-dinitrosalilic acid
3,5-dinitrosalicylic acid, methyl ester
3,5-dinitrosalicylic acid, hydrazide
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27
Table 1 (continued)
LISTING OF RAW MATERIALS,INTERMEDIATES AND SPECIALTY PRODUCTS
SALSBURY LABORATORIES - CHARLES CITY, IOWA*
E. Chemicals In Tank Farm Storage
chlorosulfonic acid
phenol
nitrobenzene
recove'red HC1
NaOH
H2S04 acid
HC1 acid
arsenic acid
propane
acetic acid
ethylene glycol
1,1,2-trichloroethane
aniline
mixed acids
ammoni a
orthonitroaniline
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28
as growth stimulants for chickens, turkeys and swine, and reportedly
reduce time to market from 12 weeks to 7 weeks for chickens. These
are marketed as "3-Nitro" and "4-Nitro" and contain active ingredients
roxarsone or 3-nitro - 4 hydroxyphenylarsonic acid and nitrasone or
4-nitro-phenylarsonic acid, respectively. Reported by Company offi-
cials as essential to the manufacture of these arsenicals is the com-
pound orthonitroaniline.
On April 23, 1978, an explosion occurred in the Chemical Processing
area of Salsbury Laboratories. This resulted in temporary curtailment
of nitration facilities, principally nitrated benzoics. The nitration
compounds are Salsbury's second largest sales line and curtailment
resulted in approximately 25% to 30% reduction in total plant production.
It was anticipated that these production processes would be down until
at least late summer 1978.
Process Wastewaters
Process wastewaters generated at Salsbury Laboratories are segre-
gated into one of two sewer systems [Figure 3]. Waste acid wash water
from the nitration processes (when operating) plus other acidic centri-
fugates, totaling approximately 38 m3/d (10,000 gpd) are neutralized
with NaOH, forming a soluble compound, sodium sulfate (Na2S04). Prior
to the Iowa DEQ order of December 14, 1977, these wastewaters were
neutralized with lime, forming an insoluble gypsum sludge.
These neutralized wastes are joined with approximately 1,500
m3/d (400,000 gpd) of contact cooling waters, neutral centrifugates,
pump seal water, compressor cooling water, floor washings, spill clean-
ups and jacketed vessel drainage and further neutralized if necessary.
The co-mingled wastewaters are then discharged to a clarifier for
solids separation. According to Company officials, little, if any,
solids will be separated in the clarifier since the switch from lime
-------
Waste Acid Wash Water
(from Nitration Process)
plus other acidic centri-
fugates (10,000 qnd)
Other process wastewaters (contact coolinq,
neutral cftitrifugates, pumo seal and compressor
water, floor wash and snill cleanuD, jacket
drains from jacketed vessels - 0 4 mod)
Arsenic wastes
(30,000 gpd)
i/>
Filtrate ,
Sludge
Vacuum filter
Filtrate
Sludge'
Magnetic
Flow Meter
Vacuum Fi1*ers
Commercial
Oisnosal Site
U >1
Lift Station
R 6 A Building Discharge
Wet
Well
pH adjusment
if necessary)
Influent Basin
pll adjustment
(NaOH)
Clarifier
(150,000 gal)
Arsenic Treatment
Equalization Pond
Figure 3 VJastewater Treatment System
Salsbury Laboratories, Charles City, Iowa
June 19 -30, 1978
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30
to NaOH as a neutralizing agent. Furthermore, it is anticipated that
when nitration facilities are brought back on-line, waste acid will
be intercepted and sent to a fertilizer manufacturer.
The second sewer system collects approximately 95 to 114 m3/d (25
to 30,000 gpd) of arsenic-containing process wastewaters which orig-
inate in the manufacture of Salsbury's two arsenicals, 3-Nitro-4-Hydroxy-
phenylarsonic acid and 4-Nitrophenylarsonic acid. The manufacturing
process requires the reaction of an organic compound with inorganic
arsenic to form the organic arsenical product. Because of the reaction
equilibrium characteristics, both organic and inorganic arsenic are
present in the resulting wastewater. The waste treatment process is
operated on a batch basis and consists of two parallel lines of treat-
ment basins in series. Slaked lime and a flocculating agent are added
to each batch for pH adjustment to 11.2 - 11.4 and subsequent precipita-
tion of inorganic arsenic. The precipitate [(Ca3As04)2 and Ca3(As03)2]
is filtered on a pre-coated rotary drum vacuum filter. The filtrate
and decant liquors are combined and introduced into a second basin
for treatment with MnS04 and a flocculating agent. The pH is lowered
to 7.5 with HC1 or H2S04 to form a precipitate which is then drawn
off to a second pre-coated rotary drum vacuum filter. The filtrate
and decant liquors are discharged to a third basin from which they
are discharged to comingle with clarifier overflow [Figure 3]. Fil-
tered sludge from both the vacuum filters is stored in drums and
shipped by rail to a commercial disposal operation in Illinois.
Clarifier overflow and treated arsenic wastewaters pass through
a magnetic flow meter for flow measurement and are discharged to a
3,800 m3 (1 million gal) equalization pond having a detention time of
approximately two days at current flows. Pond effluent flows by gravity
through a manhole to the lift station wet well from which it is pumped
through a force main to the Charles City sewerage system. This line
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31
discharges to a gravity line which carries wastewaters to the Charles City
WWTP. Should the lift station be out of service, equalization pond
wastewaters can be diverted at the manhole to another plant sewer
which then carries the wastewaters to the Charles City WWTP via the
sanitary sewer lines.
Self-monitoring data, collected by Salsbury Labs from July 1977
to June 1978, which represent discharges to the city system are summar-
ized in Table 2. Compounds which can be expected to be present X% of
the time were submitted December 12, 1974, as part of the Iowa DEQ
Operation Permit application [Table 3].
Sanitary Wastewaters
Sanitary wastewaters from the Chemical Processing, Biologies and
Pharmaceuticals Buildings discharge by gravity to the Charles City
sewerage system. Floor drains in the Pharmaceutical Building also
discharge to the sanitary lines. All wastewaters from the Research
and Administration Building, which are reported by plant officials to
be primarily sanitary wastewaters and a minor amount of lab washings,
are discharged by gravity line to the wet well of the process waste-
water lift station [Figure 3].
Noncontact Cooling Waters and Surface Runoff
Noncontact cooling waters permitted for discharge by NPDES No.
IA0003557 [Appendix A] include cooling tower blowdown and excess
cooling water resulting from the use of well water to satisfy the
need for cooling water in the closed loop. These waters, in addition
to surface runoff from the Biologies, Pharmaceuticals and Chemical
Processing areas, flow by gravity through plant sewers to an unnamed
drainage from which they enter Wildwood Creek approximately one-quarter
mile away. The surface runoff is not currently limited by the NPDES
Permit.
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32
Table 2
SELF-MONITORING DATA
SALSBURY LABS' PROCESS WASTEWATER DISCHARGE
TO CHARLES CITY, IOWA WWTP
July 1977 - June 1978
Month
Flow
m-Vday
x 103
mgd
pH Range BOD
s u mg/1
TSS
mg7T
Phenols
mg/1
Hg_
mg/1
Total
Color Heavy
Range Arsenic Metals
cpu mg/1 mg/1
Jul
Aug
Sep.
Oct.
Nov
Dec.
Jan
Feb.
Mar
Apr.
May
June
Avg.
1.00
1.28
1 74
1.54
1.43
0 889
0 727
0.678
0 723
0.727
0 507
0.988
1.02
0.266
0.339
0 460
0.406
0.377
0.235
0 192
0 179
0.191
0 192
0.134
0 261
0.269
4 7-
8.9
7.4-
8 9
8.2-
8 9
6.6-
9.2
7 1-
9.2
8.2-
9 7
7 0-
9 4
6 8-
8 70
5.2-
9 0
4.5-
9.7
6 8-
9.0
6 3-
8.8
171
425
318
590
499
727
742
408
1,230
1,500
487
360
621
1977
33.5
11 0
10 8
8 4
6 6
14.0
1978
6 6
7.4
10 0
16 2
9.8
10
12 0
27.3 0 0077 2,030- 4.30 0.15
12,300
61 6 0.0017 1,250- 5 09 1.83
11,400
12.3 0 0016 2,880- 4.24 1.09
6,080
40.5 0 0011 1,700- 5.58 1.37
13,100
22.5 0 0040 2,880- 8.69 1 09
13,500
0.6 0.0011 280- 4 96 0 66
4,830
7.5 0.0108 200- ,3.77 0.64
4,990
25.3 0 0012 400- 3 52 1 66
3,875
57.1 0 0038 2,025- 4 44 1 44
13,750
24.1 0 006 2,950- 4 19 1 12
13,950
31.9 0.002 1,525- 6 23 121
3,525
15 5 0 0025 1,500- 5.53 0 52
5,000
27 2 0.0036 - 5.05 1.06
a Total Heavy Metals includes Ba, Cd, Cr (hexavalent and trivalent), Cu, Pb,
Zn, Se and Hg.
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33
Table 3
SALSBURY LABORATORIES" COMPOUNDS
PRESENT "X"% OF TIME*
Compounds present at least 80% of the time:
3-Nitro-4-Hydroxyphenylarsonic Acid
Sulfanilic Acid
Acetic Acid
Phenol
Benzoic Acid
Nitrobenzoic Acid (3 isomers)
Acetanilide
Aniline
o-Nitroaniline
Diphenylamine
Butyl Acetate
Phenolsulfonic Acid
N~Nitrosodi phenyl ami ne
1,1,2-trichloroethane
Sulfanilamide
o-Ni trophenol
Sulfuric Acid
Nitric Acid
Hydrochloric Acid
Sodium Hydroxide
Calcium Oxide (Hydroxide)
Sodium Nitrite
Manganese Sulfate
Arsenic Acid
Arsenic Trioxide
Compounds present at least 50% of the time (in addition to the above):
Zinc salt of phenolsulfonic acid p-Nitroani1ine
Sodium salt of phenosulfonic acid
Compounds present at least 30% of the time (in addition to the above):
4-Nitrophenylarsonic Acid
Nitrobenzene
Salicyclic Acid
Sulfapyri di ne
Sali cylazosulfapyri di ne
Dinitrobenzoic Acids
Methanol
Dichloronitroani 1 ine
N'4-Acetyl-N1-(4-nitrophenyl)
sulfanilamide
Ethylenediamine
N.N^Bi s(3-Ni trobenzenesul fonyl)
Ethylenedi ami ne
2-Ami no-5-Ni trophenyl Thi ocyanate
Ammonium thiocyanate
2-Amino-6~Nitrobenzothiazole
Chioro-nitroaniline
Compounds present at least 10% of the time (in addition to the above):
Lithium salt of phenosulfonic Acid Ethylene glycol
2-chloro-4-nitrotoluene Methyl Ethyl Ketone
2-chloro-4-nitrobenzoic acid Diphenyloxide
2-chloro-4-ni trobenzamide 2-Ethyl-Hexanol
2-amino-5,6-dichlorobenzothiazole Aluminum chloride
10,10'-Oxybi sphenoxarsi ne
Compounds present less than 10% of the time (in addition to the above):
3,5-Dinitrosalicylic acid
Ammonium salt Phenolsulfonic Acid
3,5-Dinitrobenzamide
*Submitted December 12, 1974 as part of Iowa DEQ Operation Permit
Application based on projected 1975 production schedule.
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34
Solid Waste Disposal
From 1953 to December 14, 1977, Salsbury Labs disposed of its
solid wastes in the LaBounty dump, leased from Mr. Duane LaBounty,
along the Cedar River in south Charles City where the river, flowing
southeasterly, turns approximately 90° and flows southwesterly [Figure 1].
Prior to 1953, solid wastes were disposed of across the river at the
municipal dump. Quantities of material discarded at this site would
have been relatively minor in comparison to those at the La Bounty
site since the chemical synthesis building was not completed until
1951. Soils at the La Bounty site include sand, gravel, loam and clay,
with combinations as well. These overlay a fractured cavernous lime-
stone which extends to a depth of approximately 67 m (220 ft) and is
underlain by dolomites and shales.*
Underlying the alluvial groundwaters at the site is the Cedar
Valley Formation, a major aquifer that provides municipal and private
water to northeastern Iowa. Present indications are that groundwater
movements at this site are upward from the Cedar Valley Formation and
through the alluvial material with discharge to the Cedar River.
Although the wastes disposed of at La Bounty dump were described
as "solid", they were in fact a combination of solids, liquids and
slurries. According to Mr. Russ Smith, Manager of Chemical Engineering
and Production for Salsbury, wastes deposited in the La Bounty site
included gypsum sludges, arsenicals, carbon cakes, reaction heels,
distillation residues, incinerator ashes and miscellaneous other waste
products, including some empty drums of orthonitroaniline and arsenic
trioxide, and possibly some full drums of 1,1,2 trichloroethane bottoms.
* "Soil Characteristics LaBounty Site"—Salsbury Laboratories, Charles
City, Iowa by Eugene A. Hickok and Associates for Iowa DEQ, August 15,
1977.
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35
The bulk of the wastes included gypsum sludges [approximately 90 m3
(120 yd3)/day in January, 1978] resulting from neutralization of waste
acids with lime, and arsenic sludges [approximately 7.5 m3 (10 yd3)/day
in January, 1978]. An approximation of solid waste production since
1953 is included in Table 4.
Studies performed by Eugene A. Hickok and Associates in 1977 for
the Iowa Department of Environmental Quality (IDEQ) resulted in the
following calculated estimates of compounds in the LaBounty dump site:
Compound Kg lb
Arsenic
2,740,000
6,044,000 lbs
1,1,2-Trichloroethane
32,000
70,000
Nitrobenzene
130,000
280,000
Orthonitroaniline
680,000
1,500,000
Phenol
12,000
27,000
This is not an all inclusive listing since pre-identified compounds
were being quantified.
On December 14, 1977, following studies by the Iowa DEQ, Iowa
Geological Survey (IGS) and USEPA Region VII, which indicated: (1) the
above quantities of contaminants perched over a major aquifer; (2)
the presence of arsenic in the alluvial groundwater; and (3) one of
the chemicals used by Salsbury, orthonitroaniline, in shallow municipal
wells 65 river miles from the site in Waterloo, Iowa, the IDEQ issued
Executive Order No. 77-DQ-01 to Salsbury Labs. This order, among
other things, required Salsbury to cease immediately the disposal of
solid, semi-solid and liquid wastes at the La Bounty site; to commit
to and implement a program for the removal of all hazardous wastes
and contaminated materials at the La Bounty site to an approved hazard-
ous waste disposal site; and to commence operation of the new site
by July 1, 1979.
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36
Salsbury Laboratories ceased using the La Bounty site as ordered,
but sought judicial relief from the removal provisions. On January
19, 1978, these provisions were stayed by the Floyd County District
Court, pending attempts to first seek administrative relief through
the Iowa DEQ. This process is continuing.
Following the DEQ order of December 14, 1977, Salsbury Laboratories
began depositing solid wastes in a temporary on-site holding basin.
However, within 24 hours leachate was detected in the underdrain system,
signifying a breakthrough, and use of the system was terminated. The
Company curtailed its large waste acid producing product lines, re-
sulting in a cutback in production of 20% to 25%, and began storing
solid wastes in drums. In early 1978, waste acid was stored for from
two to three days up to one week prior to shipping by bulk tank
truck to Illinois where some material was taken by a fertilizer manu-
facturer and the remainder delivered to a commercial disposal operation.
Arsenic sludges were stored in 55-gallon drums (approximately 25 generated/
day) and then sent by rail to a commercial disposal operation in Illinois.
The previously mentioned explosion of April 23, 1978, curtailed
the nitration processes which were the principal source of the above
waste acid. Arsenic sludges continued to be drummed and shipped by
rail to Illinois for disposal.
CHARLES CITY, IOWA WWTP
The Charles City WWTP has a design average flow of approximately
11,400 m3/day (3.0 mgd) and includes the following unit operations:
screening, flow monitoring (12-inch Parshall flume), grit removal,
lift station, two primary clarifiers in parallel, a single stage trick-
ling filter and a secondary clarifier. Approximately 190 m3 (50,000
gal)/day of secondary clarifier overflow is recycled to the wet well
following grit removal. Treated wastewaters which averaged 5,500 m3
(1.46 m. gal)/day from July 1977-June 1978 are discharged without
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37
disinfection through an outfall pipe to the Cedar River several hun-
dred feet from the plant [Figure 1]. Primary and secondary sludges
are digested aerobically with supernatant returned to the plant wet
well, downstream from grit removal. Digested settled sludge is
trucked to local farms and applied to the land. According to City
Engineer Dan Barrett, greater than 90% of the sludge is sent to a
farm owned by Mr. Wilbur Winterink. When soil conditions permit, the
sludge is injected into the soil with a "Big Wheels" owned by the
Ci ty.
On September 12, 1975, NPDES Permit IA0022039 was issued to
Charles City with an expiration date of June 30, 1977 [Appendix A].
The permit is currently being drafted for reissuance. In the interim,
USEPA Region VII has held that the previous limits will remain in
effect.
Self-monitoring data collected over the past year indicate the
Salsbury wastewaters constitute approximately 18% of the influent
flow to the WWTP [Tables 2, 5]. This figure is probably conservative
since, as will be discussed later, the Salsbury flow monitoring system
is inaccurate and provides low values. Salsbury is the only industrial
contributor of any consequence to the Charles City sewerage system.
The White Farm Equipment Company which employs approximately 2,000
people under normal conditions in the manufacturing of tractors and
other farm equipment has five connections to the sewerage system.
However, the wastewaters discharged are almost exclusively sanitary
wastes. Process wastewaters and cooling waters are discharged via
four sewers to the Charles City storm sewer system, eventually dis-
charging to the Cedar River via the Hawkins Avenue sewer.
Self-monitoring data collected from July 1977-June 1978 indicate
atypically high levels of phenols, arsenic and ammonia for domestic
wastewaters [Table 5]. These can be attributed in large part to dis-
charges from Salsbury Laboratories [Table 2]. Data collected by EPA
Region VII in August 1977, and reported in a "Corrected Final Draft
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38
Table 4
HISTORY OF WASTE PRODUCTION AT SALSBURY LABORATORIES3
Period
Total
Waste,
(cu ft)D
Gypsum
(cu ft)
Arsenical
(cu ft)
Waste
Percent
of Total
1953-57
1958-61
1962-65
1966-68
48,008
87,104
> 681,476
624,330
0
0
559,300
467,000
47,060
69,090
108,940
140,040
98
79
16
22
1953-68
1,440,918
1,026,300
373,130
26
1969-76
6,800,00
N/A
480,000
7
1977
expected
929,656
800,000
123,775
13
Estimated
total
through
mid-1977
8,700,000
>1,800,000
920,000
11
a Table 1 from "Waste Characteristics LaBounty Site" by Eugene A.
Hickok and Associates for Iowa DEQ August 29, 1977. Report
indicated information obtained from Salsbury Laboratories and
1968 report by Baumann and Schara.
b Total includes some waste which is neither gypsum nor arsenical,
c Gypsum volume for 1966-68 includes arsenic from waste treatment.
-------
Table 5
SELF-MONITORING DATA
CHARLES CITY, IOWA WASTEWATER TREATMENT PLANT
July 1977 - June 1978
Total3
Flow
BOD
TSS
Phenols
Arsenic
Ammoma Heavy metals
Color Range
Month m3/day mgd
x 103
Inf.
mg/1
Effl %
mg/1 Rem.
Infl. Effl. %
mg/1 mg/1 Rem
Infl Effl.
mg/1 mg/1
Infl. Effl.
mg/1 mg/1
Effl Infl. Effl
mg/1 mg/1 mg/1
Infl. Effl.
cpu cpu
1977
July
4
758
1 257
198
39
79
193
23
88
6.75
2.
72
0 441
0 243
32
8
0 062
0
051
150-5000
150-5000
Aug
5
889 '
1 556
220
44
79
174
19
89
14 94
0.
392
1.015
0 994
23
9
0 564
0
641
40-5000
50-4000
Sept.
5
07
1 34
240
52
77
174
25
86
4 69
0.
20
1 161
1 053
67
9
0 497
0
407
1500-3500
1500-3000
Oct
5
454
1.441
260
71
73
144
36
75
9.98
0
752
1 599
1 78
49
8
1.53
1.
69
900-5000
1500-5000
Nov.
5
848
1.545
213
53
75
199
32
84
6.83
1.
14
2 41
2 34
30
0
0.341
0
354
1500-5000
1200-5000
Dec.
4.
754
1 256
310
91
71
179
33
82
0
1 Q~7Q
0
0.875
0.961
28
8
0 371
0.
388
200-3200
150-3200
Jan
4
561
1.205
300
101
66
131
34
74
i y to
1.78
0
493
1.153
1.279
34
9
0.216
0.
.217
200-3500
200-3500
Feb.
5
235
1.383
220
66
71
153
32
80
4 14
0.
538
1 08
1.478
73
3
0 385
0.
.264
600-3000
800-3000
Mar
5
473
1 446
330
96
71
132
34
74
7 93
0
523
1 32
1.34
37
8
0 453
0.
.308
1000-5000
900-5000
Apr
6.
434
1.700
230
67
71
130
34
72
2 52
0
138
0.849
0.882
24
0
0.475
0
512
1200-5000
1500-5000
May
5.
889
1.556
232
62
74
170
29
83
4 42
0
495
1.25
1.226
37
.0
0 270
0
182
800-2500
800-2000
June
6
953
1.837
190
46
76
146
19
87
3.63
0.
.054
1.39
1.58
31
.0
0 181
0
158
1600-3500
900-3000
Avg
5
526
1 460
245
66
74
160
29
81
5.63
0
620
1 21
1.18
39
.3
0.445
0
431
a Total Heavy Metals includes Ba, Cd, Cr (hexavalent and tnvalent), Cu, Pb, Zn,
Se and Hg.
-------
40
Preliminary Report" of December 14, 1977, substantiated these atypically
high levels and also indicated the presence of a number of Priority
*
Pollutants in the WWTP influent, including arsenic, chromium, copper,
selenium, zinc, antimony, lead, nitrobenzene, orthonitrophenol, para-
nitrophenol and phenol, as well as two other organics of potential
toxicity concern, ortho- and paranitroaniline. These compounds, with
the exception of nitrobenzene and lead, were also identified in the
Salsbury Laboratories wastewaters discharges to the Charles City sewer-
age system. Removal efficiencies at the Charles City WWTP for BOD
(74%) and TSS (81%) over the past year have been atypically low for a
secondary treatment facility [Table 5]. It is probable that Salsbury
Labs was at least in part responsible for adversely affecting the
biological treatment system and producing these low removals.
* Priority Pollutants are those derived from the June 7, 1976 Natural
Resources Defense Council (NRDC) vs. Russell Train (USEPA) Settlement
Agreement. For a listing of the pollutants, see Appendix B.
-------
41
IV. SURVEY METHODS
COMPLIANCE MONITORING AND WASTEWATER/WATER CHARACTERIZATION
Salsbury Laboratories
During June 19 to 26, 1978, the NEIC conducted compliance monitoring
and wastewater characterization of the process wastewaters and cooling
water discharges of Salsbury Laboratories. Sampling and flow monitoring
locations are shown in Figure 4.
Station 01
The sampling location for characterizing process wastewater was
at Manhole E, about 5 m (16 ft) downstream from the overflow standpipe
of Salsbury1s equalization pond and about 12 m (40 ft) upstream of
the lift station wet well. Aliquots were collected manually at this
site every 2 hours and continuously composited on a flow-weighted
basis for each of the seven consecutive days. The 24-hour composite
samples were analyzed for biochemical oxygen demand (BOD), total sus-
pended solids (TSS), chemical oxygen demand (COD), total organic carbon
(TOC), ammonia as nitrogen (NH3-N), metals, organic compounds and
phenolic compounds. In addition, four grab samples for volatile organics
analysis (VOA) were collected each day, and, for three days, June
20 to 23, additional composites were collected for selected organic priority
pollutant analyses and for mutagenicity determinations.
Instantaneous flow measurements of process wastewaters were performed
every 2 hours using the tracer dilution technique with lithium as the
tracer [Appendix C]. The injection site for the concentrated lithium
chloride solution was the overflow standpipe at the southeast corner
of the equalization pond. Samples of the well mixed solution were
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42
Iowa State Highway 14
PHARMACEUTICAL
BIOLOG ICS
PRODUCTION
Parking Lot
WASTEWATER
TREATMENT BLD6
CHEMICAL
-N-
PRODUCTION I
-a.
MAINTENANCE
BLDG^J""
MH 11
COOLING TOWER
CHEMICAL PRODUCTION II
KEY
SAMPLING STATIONS
R&A BLD6
DISCHARGE
FORCE MAIN TO CHARLES CITY
SEWERAGE SYSTEM
LIFT STATION
WET WELL
Figure 4. Plot Diagram and Sampling Station Locations
Salsb u ry Laboratories, Charles City, Iowa
June J9-30, 1978
-------
43
collected for flow determinations in the effluent stream at the point
where it discharges to the lift station wet well. During the period
0700 to 1100 hours on June 19, the lift station was undergoing repairs
following flooding of the dry well, and the process wastewater was
diverted via Manhole 11 to the Charles City sewerage system. Conse-
quently, during this period the downstream diluted samples for flow
determinations were collected at this manhole. No other bypassing of
the lift station was observed during the study period. Samples for
background lithium concentration were always collected from the south-
east corner of the equalization pond.
Station 07
On June 24 a grab sample of the Salsbury Research and Administration
Building effluent was collected upstream of the discharge to the wet
well for BOD, TSS, metals and organics analyses. On June 28, another
grab sample was collected for metals and organics analyses. Flow
rates were small [approximately 0.3-0.9 1/sec (5 to 15 gpm)] and were
estimated.
Station 02
The NEIC sampling location for the Salsbury cooling water and
storm runoff discharges was at the open ditch on the southside of
Iowa Highway 14, about 3 m (10 ft) downstream from the storm sewer
opening. Hourly aliquots were collected manually at this site and
continuously composited on a flow-weighted basis from June 19 to 26.
The 24-hour composite samples were analyzed for the same parameters
as the process wastewater (Station 01), and the additional sampling
for V0A and selected organic priority pollutant analyses was also the
same. Mutagens composite sampling was conducted for one day only,
June 20 to 21.
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44
Instantaneous flow measurements were performed hourly at this
site with a 6-inch Parshall flume, installed by NEIC. On June 25,
heavy rains and the subsequent storm water runoff raised the water
level at this site above the top of the flume from 1000 to 1200 hours.
Samples were not collected at this site during this time since no
flow rates could be determined. Sampling resumed at 1305. Analyt-
ical results for this day were not included in pollutant mass calcula-
tions reported in Section V, Survey Findings.
Station 09
On June 28, grab samples for TSS, metals and organics were col-
lected from the Salsbury cooling tower discharge, which corresponds
to the NPDES permit monitoring site, at the manhole immediately down-
sewer from the cooling tower. Flow was measured by recording the
time required to fill a known volume in the manhole.
Charles City WWTP
During June 19 to 30, 1978, the NEIC conducted compliance moni-
toring and wastewater characterization at the Charles City WWTP.
Sampling and flow monitoring locations are shown in Figure 5.
Station 03
From June 19 to 26, the WWTP influent was sampled approximately
6 m (20 ft) downstream from the 12-inch Parshall flume. Hourly aliquots
were collected manually at this site and continuously composited on a
flow-weighted basis for each of the seven consecutive days. The 24-hour
composite samples were analyzed for BOD, TSS, COD, T0C, NH3-N, metals,
organic compounds and phenolic compounds. In addition to these compo-
sites, four grab V0A samples were collected each day, and, on June
-------
45
Supernatant Return Line Diqesters
Parshall Flume
Office
Influent
Wet lief 1
Lift Station
Primary
Settling
Tank
Primarv
Settlinn
Tank
Sludne lie! 1
KEY
Sewage Line
Sludge Line
Covered
Trickl inn
Fil ter
Sampling Station # (26
Final
Settling
Tank
Final £ffluent
Figure 5 Charles City WWTP and Sampling Stations
Salsbury Laboratories/Charles City, Iowa Project
June 19-30, 1978
-------
46
20 to 23, composites were collected for selected organic priority pol-
lutant analyses and mutagenicity determinations.
Flow measurement at this site was performed using the facility's
12-inch Parshall flume which was inspected by NEIC personnel and found
A
to meet the requirements for proper installation. Head was measured
with a bubbler tube, converted to flow, and transmitted to a Foxboro
continuous-flow recorder in the office building. To assure acurate
measurements, the flow monitoring system was calibrated by NEIC person-
nel before sampling started. In addition to the plant's flow recording
system, NEIC personnel installed a Manning recording flow meter at
the Parshall flume. Periodic flow checks were performed during the
seven-day monitoring period to assure that the WWTP system was measuring
and recording flow accurately.
Station 30
During the period June 26 to 30, the influent sampling station
location was changed to the primary clarifier overflow at the combina-
tion box in order to characterize the wastewater for NEIC bioassay studies.
The sampling program was the same as at Station 03, except that compos-
ite samples were collected for metals, organics and NH3-N only. The
flow measurement technique was to use the flows measured by the Parshall
flume near Station 03.
Station 04
The WWTP effluent was sampled at the discharge from the final
clarifier. The sampling program at this station was the same as at
Station 03 for June 19 to 26 and the same as at Station 30 for June
* Water Measurement Manual, U. S. Department of Interior, Bureau of
Reclamation, Second Edition, 1967, pages 43-88.
-------
47
26 to 30. Flow measurements from the Parshall flume near Station 03
were used at this site for all eleven days of the study.
La Bounty Dump Site Groundwater
Station 06
On four days, June 19 to 22, grab samples of La Bounty dump site
groundwater [Figure 6] were collected for BOD, TSS, COD, TOC, NH3-N,
metals, organics, VOA and phenolic compounds. On June 20 to 22, addi-
tional samples were collected for selected organic priority pollutant
analyses and mutagenicity determinations. The samples were collected
from a monitoring well on the south side of the sloped dike, between
the foot of the slope and the river. The well point was drilled by
personnel of USEPA Region VII prior to the NEIC study to refusal
(rock) at a depth of approximately 4 m (13 ft). The well screen was
between 2.7 m (9 ft) and 3.5 m (11.5 ft). No flow determinations
were performed on this groundwater.
Cedar River Stations
During the study period, NEIC also conducted a water quality
investigation of the Cedar River in the Charles City area. The main
objectives of this investigation were to characterize the water quality
in the vicinity of the La Bounty dump site and to determine the effects,
if any, of the La Bounty leachate on the river. A secondary objective
was to determine any effects on the river of any of the various other
discharges to the river in this vicinity. Sampling and flow monitoring
locations are shown in Figure 6.
Stations 11 and 12
Two river sampling stations were established to collect samples
upstream of and downstream from the La Bounty dump site. The upstream
-------
WHITE FARM EQUIP.
H iw ay 1 8
\
CHARLES CITY
21)—'
-N-
H Iw ay_J 4
USGS 6AQE-
STATION
Labounty Dump Site
CHARLES CITY WWTP
SALSBURYI
LABORATORIES
V
-------
49
location (Station 11) was approximately 30 m (100 ft) upstream of the
USGS gage station on the Cedar River at Charles City. The downstream
station (Station 12) was located approximately 90 m (300 ft) upstream
of the Charles City WWTP discharge. On each of three days, June 27 to
29, flow-weighted grab samples were collected at these two sites and
analyzed for metals, organics and V0A. On June 28, an additional
sample was collected for selected organic priority pollutant analyses.
The procedure followed at each site was to divide the river cross-
section into 10-foot segments, measure the flow in each segment, and
then collect and combine flow-proportional aliquots from the segments.
V0A samples were poured from the completed organics samples. The
day before startup of the three-day sampling period, average velocity
measurements were conducted by stream gaging at Stations 11 and 12
and a midway point, and a theoretical travel time was computed. The
sampling at Station 12 was scheduled by approximating the travel
time from Station 11. On June 29, additional grab samples for an
arsenic profile were collected at these two stations by collecting
a separate grab from each 10-foot segment.
Flow measurements were performed by using the USGS gage station
near Station 11.
Station 10
On June 19 to 22 and 26 to 28, grab samples were collected daily
from the Cedar River at the suspension bridge to characterize river back-
ground conditions and the dilution water used in NEIC bioassay studies.
These samples were analyzed for NH3-N, organics, metals, and V0A.
Stations 20. 21, 05 and 08
In order to characterize groundwater spring (Station 20) and seep
(Station 21) discharges to the Cedar River and determine their effect,
-------
50
if any, on the river, grab samples for metals, organics and VOA were
collected at these two sites on each of the three days, June 27 to 29.
Also sampled for the same parameters on these three days was the storm
sewer carrying the combined process and cooling water effluent from
the White Farm Equipment Company. Equal volume aliquots were manually
collected at five-minute intervals from a city storm sewer manhole at
the intersection of 5th and E streets (Station 05) and composited
over a 30-minute period. The sampling time was roughly approximated
such that the sampled stream would reach Station 12 while that station
was being sampled. Flow through the manhole was gaged using the
velocity-area method with a Marsh-McBirney electromagnetic flow meter.
During the sampling period the Company was in the process of shutting
down operations for its annual maintenance in July. Hence wastewater
characteristics would not necessarily represent normal operating condi-
tions.
On June 21 and 29, grab samples for metals and organics were
collected from a direct discharge from the LaBounty dump site (Station
08). The sampling location was on the left bank of the river on the
downstream end of the dump, approximately 30 m (100 ft) upstream of
the Iowa Terminal railroad bridge. This discharge includes surface
runoff, ready-mix truck washings from the Allied Construction Company
and groundwater seepage from the La Bounty dump site. Flow was estimated
by measuring the time required to fill a container of known volume.
Sample Handling, Analytical Procedures and Quality Control
All samples were stored at 4°C and/or preserved by techniques
promulgated by EPA pursuant to Section 304(h) of the Federal Water
Pollution Control Act (FWPCA). Samples for BOD and TSS were transported
to the NEIC mobile laboratory at the Charles City WWTP for analysis;
COD, T0C, NH3-N, organics, phenolic compounds, VOA and mutagenicity
samples were shipped daily to the NEIC laboratories in Denver. Metals
samples were accumulated until the end of the study, at which time
-------
51
they were transported to Denver. Whenever applicable, EPA-approved
procedures, as promulgated pursuant to Section 304(h) of the FWPCA,
were used in the analysis of samples. New Methods or modifications
to existing methods were documented when required. Pertinent analyti-
cal methodology and quality control statements are included in Appendix D.
Split samples were provided to Salsbury Laboratories upon
request. NEIC procedures for sample control and Chain-of-Custody
were followed throughout the course of the study.
The quality control program for the field study included the
collection of preserved blanks (distilled water) for phenols, metals
and COD, duplicate composite sampling at Stations 01 and 04 and
regular calibration of field instruments.
BIOLOGICAL STUDIES
Mutagen Testing
Analyses for mutagenic activity were performed on 13 samples
collected from five stations during the study. One grab sample of
process wastewaters at the effluent from the equalization pond was
collected on April 27, 1978 during a presurvey visit (Station 01).
Thirteen samples were collected June 21 to 23. These consisted of
three grab samples from the La Bounty dump site groundwater (Station 06)
and ten 24-hour flow-proportional composite samples; three from the
Salsbury process effluent (Station 01), one from the Salsbury cooling
water discharge (Station 02), three from the Charles City WWTP influent
(Station 03*), and three from the Charles City WWTP effluent (Station 04).
The Standard Bacterial Assay for Mutagenicity was performed on
liquid sample concentrates using the plate incorporation method, as
* The sample collected 6/22/78 from Station 03 was broken in shipment,
which precluded analyses.
-------
52
described by Ames, et al.1. This test consists of specially developed
strains of Salmonella typhimurium that are auxotrophic for the amino
acid, histidine (i.e., unable to grow without histidine supplemented
to their media). The organisms have been genetically altered so that
if they are subjected to certain mutagenic and carcinogenic substances
they will mutate and regain the natural ability to synthesize histidine.
Thus, the mutant colonies can be detected on media which does not
contain histidine.
Acidic and basic sample extracts were prescreened for mutagenic
activity using four standard Salmonella tester strains, TA 98, TA 100,
TA 1535 and TA 1537. Samples were first tested individually. If
they showed negative mutagenicity, they were then subjected to metabolic
activation by adding rat-liver homogenate (S-9 mix) [Appendix D],
The Standard Ames Test determines mutagenic activity through use
of bacteria as indicator organisms; this information correlates closely
(>90% probability) with inducement of cancer in laboratory animals by
organic compounds.2'3'4 Extrapolation of this information to higher
organisms (such as humans) is warranted because mutagens may alter
deoxyribonucleic acid (DNA) in a similar manner in other life forms.
It is the opinion of knowlegeable investigators that if a compound is
mutagenic in any organism, it should not be exposed to the human popu-
lation. Only one molecule of a mutagen is sufficient to cause a muta-
tion that is also likely to be carcinogenic. Because genetic repair
systems are not completely effective, safe doses of mutagens and carcino-
gens cannot be projected.5
Biomonitoring Techniques
Between June 19 to 30, 1978, four 96-hour continuous-flow bioassays
were conducted at Charles City, Iowa. The specific sources of materials
tested were:
-------
53
1) The process wastewater discharge from Salsbury Laboratories
(Station 01);
2) groundwater from the La Bounty dump site obtained from a
shallow well (Station 06);
3) primary clarifier overflow (Station 30) at the Charles City
WWTP;
4) final effluent from the Charles City WWTP (Station 04).
The objectives of the tests were to:
1) determine if the process wastewater discharges from Salsbury
Laboratories and groundwater from the La Bounty dump site were acutely
toxic to fish.
2) determine whether the wastewater treatment at the Charles
City WWTP had a positive effect on reducing the toxicity of the combined
municipal and Salsbury Laboratories influent. Fathead minnows (Pime
phales promelas Rafinesque) averaging approximately 5.5 cm in total
length were used as test organisms. Detailed methodology of the bio-
assay procedures are included in Appendix D.
Fish Survival and Palatability
In situ fish exposures were performed at eight sampling sites in
the Cedar River (Stations 40, 20, 42, 43, 44, 45, 46 and 47) in addition
to an upstream reference at Station 10 [Table 6, Figure 7]. Black
bullheads (Ictalurus melas) approximately 30 to 35 cm (12 to 14 inches)
in total length and weighing approximately 0.5 kg (1 pound) were used
as test organisms. The exposure period was approximately one week,
extending from June 21 to June 29, 1978. The objectives of the exposure
study were to:
1) determine if specific reaches of the Cedar River contained
pollutants acutely toxic to fish;
-------
WHITE FARM EQUIP.
H i w ay 18
CHARLES CITY
-N-
H iw ay 14
USGS GAGE
STATION
\
Labounty Dump Site
CHARLES CITY WWTP
"O
SALSBURY
LABORATORIES
KEY:
SAMPLING STATION
Figure 7a.1 Biological Studies Station Locations
Salsbury Laboratories/Charles City, Iowa Project
1 0, 8
-------
amp Chrlsti
Midway Bridge
Figure 7b. Biological Studies Station Locations
Salsb ury Laboratories/Charles City, Iowa Project
June 19-30, 1978
<_n
-------
56
Table 6
Biological Sampling Stations
Cedar River, Charles City, Iowa
June, 1978
Description
Station
10 Cedar River at suspension bridge upstream of Wildwood
Creek near right bank.
76 Midstream of Cedar River at suspension bridge upstream
of Wildwood Creek.
77 Cedar River at suspension bridge upstream of Wildwood
Creek near left bank.
83 Wildwood Creek 60 m (200 ft) upstream of unnamed drain-
age which carries Salsbury cooling water/storm runoff
di scharge
84 Unnamed drainage carrying Salsbury cooling water/storm
runoff 3 m (10 ft) upstream of discharge to Wildwood Creek
85 Wildwood Creek 230 m (250 yds) downstream from unnamed
drainage carrying Salsbury cooling water/storm runoff
40 Wildwood Creek at confluence with Cedar River
78 Cedar River 30 m (100 ft) downstream from the mouth
of Wildwood Creek near left bank
79 Cedar River 60 m (200 ft) downstream from mouth of
Wildwood Creek near right bank
20 Cedar River at spring discharge 90 m (300 ft) downstream
from Main Street bridge near left bank
42 Cedar River near left bank at groundwater seep discharge
approximately 60 m (200 ft) upstream of Highway 18 bridge
60 Cedar River 10 m (30 ft) downstream from groundwater
seep near left bank
62 Cedar River 30 m (100 ft) upstream of Highway 18 bridge
near right bank
43 Cedar River 91 m (100 yds) upstream of Iowa Terminal
Railroad bridge near left bank
65 Cedar River 91 m (100 yds) upstream of Iowa Terminal
Railroad bridge near right bank
-------
Table 6 (Cont'd.)
Description
Station
66 Cedar River 15 m (50 ft) upstream of Iowa Terminal Rail-
road bridge near left bank
67 Cedar River midstream 15 m (50 ft) upstream of Iowa
Terminal Railroad bridge
68 Cedar River 15 m (50 ft) upstream of Iowa Terminal Rail-
road bridge near right bank
44 Cedar River 9 m (30 ft) downstream from Charles City
WWTP discharge near right bank
70 Cedar River midstream 9 m (30 ft) downstream from
Charles City WWTP discharge
71 Cedar River 9 m (30 ft) downstream from Charles City
WWTP discharge near left bank
48 Cedar River 46 m (50 yds) downstream from Charles City
WWTP discharge near right bank
45 Cedar River 180 m (200 yds) downstream from Charles City
WWTP discharge near right bank
46 Cedar River 0.8 km (0.5 mi) downstream from Charles City
WWTP discharge near left bank
82 Cedar River 0.8 km (0.5 mi) downstream from Charles City
WWTP discharge from right bank to midstream
80 Cedar River 5 km (3 mi) downstream from Charles City
WWTP discharge near right bank
81 Cedar River midstream 5 km (3 mi) downstream from
Charles City WWTP discharge
72 Cedar River 46 m (50 yds) upstream of Midway bridge
near left bank 10 km (6 mi) downstream from Charles City
WWTP discharge
73 Cedar River midstream 46 m (50 yds) upstream of
Midway bridge
74 Cedar River 46 m (50 yds) upstream of Midway bridge
near right bank
47 Cedar River 15 m (50 ft) downstream from Midway bridge
near left bank
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58
2) relate any toxic conditions to specific imputs into the
Cedar River;
3) determine if imputs to the Cedar River affected the desirability
or palatability of fish.
Indigenous Fish Populations
Indigenous fish populations were collected at four locations in
the Cedar River (Stations 10, 43, 48, and 47). This encompassed a
reach of river extending from the suspension bridge in Charles City
downstream approximately 13 km (8 mi) to the Midway Bridge [Table 6,
Figure 7]. The purpose was to determine whether waste inputs, in-
cluding leachate from the La Bounty dump site and discharge from the
Charles City WWTP, adversely affect fish populations of the Cedar
River. A 24-hour net trapping effort, June 27 to 28, was used as the
standard unit of measurement.
Periphyton
Cedar River and Wildwood Creek periphyton populations in the
Charles City area were sampled by exposing floating wooden racks con-
taining microscope slides at the nine fish survival stations [Table
6, Figure 7]. Since substrates were similar, changes in periphytic
algal population compositions would indicate changing environmental
conditions. The racks were exposed for 8 days, commencing June 20 or
21, 1978, with the exception of the Midway Bridge, where the exposure
was for 5 days, commencing June 24, 1978. After exposure, slides
containing attached growths were preserved and used to determine peri-
phytic algal population densities, periphytic chlorophyll a concentra-
tions, ash-free weight, and autotrophic index [Appendix D]. The periphy-
tic algal population is a portion of the biomass of the samples.
Chlorophyll a varies with population composition and health. Ash-free
weight is used as a measure of biomass, and the ash-free weight to
-------
59
chlorophyll a ratio, known as the autotrophic index, can be determined.
Periphyton growing in surface water relatively free of pollution con-
sists largely of algae and consequently would have a low autotrophic
index. Non-chlorophyll bearing organisms may increase with increasing
pollution consequently causing the autotrophic index to increase.
Benthic Macroinvertebrates
To assess the effects of water quality on Cedar River biota,
benthic macroinvertebrates were collected from ten sites extending
from the suspension bridge at Illinois Street, in the northwest sec-
tion of Charles City, Iowa, downstream approximately 13 km (8 mi) to
the Midway Bridge [Figure 7].
Benthic macroinvertebrates were quantitatively sampled, using a
Petite Ponar grab or Ekman grab at two or three sites (cross-stream
transects) per station. In addition, qualitative samples were taken
at each location by sampling all available habitats, including the
screening of sediments and manual removal of organisms from beneath
rocks, logs and debris. Samples were preserved in a 70% solution of
alcohol, transported to the NEIC laboratory, separated from the debris,
identified and counted. Results of quantitative sampling were expressed
as numbers of organisms per square meter of stream bed.
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60
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61
V. SURVEY FINDINGS
NPDES EFFLUENT LIMITATIONS COMPLIANCE
Charles City, Iowa WWTP
Effluent data collected during June 19 to 30, 1978, indicated
the Charles City WWTP in compliance with limits for BOD, TSS, NH3-N
and total heavy metals [Table 7]. The daily average arsenic concen-
tration was 1.9 mg/1 which exceeded the permit limit of 1.6 mg/1. The
daily maximum arsenic limitation of 2.5 mg/1 was exceeded on 3 of the
11 days of sampling, with concentrations ranging from 2.7 to 3.6 mg/1
[Table 8]. Table 9 indicates 12 hourly measurements where pH values
were outside the prescribed range of 6.5 to 9.0 standard units.
The average effluent BOD during the NEIC study, 23 mg/1 [Table 10],
was atypically low when compared with self-monitoring data collec-
ted over the past year [Table 2]. As noted in the self-monitoring
data in Appendix E, approximately one week before the NEIC study com-
menced, effluent BOD levels at Salsbury began to drop, accompanied by
a drop in influent BOD levels at the Charles City WWTP. The average
BOD of the Salsbury process wastewaters during the NEIC study, 140
mg/1, was considerably lower than their last year's average, 621 mg/1,
and lower than any monthly average in the past year [Table 2].
Salsbury Laboratories
As noted previously, the only NPDES permit currently held by
Salsbury Laboratories covers cooling tower discharges. The permit
states that samples taken for determining compliance shall be collected
"before the combined flow discharges to the storm sewer." The permitted
site was sampled by NEIC at 1030 hours on June 28, 1978, at the manhole
immediately downstream from the cooling tower [Figure 6]. The wastewater
-------
cn
ro
Table 7
NPDES COMPLIANCE MONITORING
CHARLES CITY WWTP EFFLUENT LIMITATIONS
JUNE 19-30, 1978
NPDES PERMIT NEIC RESULTS
Daily Average^ Pally Maximum Other Units (specify) Average Maximum Other Units (specify)
Parameter kg/daylb/day kg/day lb/day Daily Avg Daily Max. kg/day lb/day kg/day lb/day Daily Avg. Oaily Max.
B0Dc
794 1,750
1 ,360
3,000
70 mg/1
120 mg/1
170
380
210
460
23 mg/1
29 mg/1
TSSC
"J o
340 750
1,000
2,200
30 mg/1
90 mg/1
170
380
200
450
23 mg/1
29 mg/1
Flow-m /day
-
-
-
11,355
18,925
7,620
8,250
(MGD)
(3.000)
(5.000)
(2.01)
(2.18)
PH
J
6.5-9.0
Range=5.0-8.2
Ammonia Nitrogen
Total Heavy Metals3'*'
1,000 2,200
1,360
3,000
90 mg/1
120 mg/1
210
463
264
583
29 mg/1
37/1 mg/1
-
-
-
1 5 mg/1
2.5 mg/1
-
-
-
-
0 10 mg/1
0 12 mg/1
Total Arsenic*'
— ~
~
-
1 6 mg/1
2 5 mg/1
-
-
-
-
1.9 mg/1
3 6 mg/1
a The total heavy metals group shall be determined by the sum of the individual analyses for barium, cadmium, chromium (hexavalent and trivalent),
copper, lead, zinc, selenium and mercury
b The daily average" discharge means the sum of the total daily discharges by weight, volume or concentration during the reporting period divided
by the total number of days during the reporting period when the facility was 1n operation. With respect to the monitoring requirements, the
daily average" discharge shall be determined by the summation of all the measured daily discharges by weight, volume or concentration divided
by the number of days during the reporting period when the measurements were made
c Data collected June 19-26, 1978.
d Data collected June 19-30, 1978.
-------
METALS SAMPLING DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-30, 1S78
Station Location
Date3
June
1978
b Flow
Time m3/day
x 103
mgd
AsC
mg/1 kg/day lb/day
Ba
mg/1
Cdc
mg/1
Crc
mg/1
_Cuf
mg/1
Pbc
mg/1
_Ha!
mg/1
Sec
mg/1
ZnC
mg/1
Station 01
20
2 1
0
55
7 0
15
32
NDd
ND
ND
0 09
ND
0 0040
ND
0 14
Salsbury Labs
21
1 7
0
44
5 9
10
22
ND
ND
ND
ND
ND
0.0022
NO
0 12
Process Wastewaters
22
1 5
0
39
5 0
7 3
16
ND
ND
ND
ND
ND
0 0010
NO
0 07
At Effluent From
23
1 9
0
50
8 0
15
33
ND
ND
ND
NO
ND
0 0010
NO
0 12
Equalization Pond
24
2 0
0
54
8 4
17
38
ND
ND
ND
ND
ND
0.0016
NO
0 08
25
1 9
0
51
3 9
7.7
17
ND
ND
ND
ND
ND
0 0012
ND
0 16
26
1.7
0
45
3.9
6 8
15
ND
ND
ND
ND
ND
0.0015
ND
0.18
Avg
1.8
0
48
6 0
11
25
0 0
0 0
0.0
0 01
0 0
0.0018
0 0
0 12
Station 02
20
0 87
0
23
2 6
2 3
5 0
ND
ND
ND
ND
ND
0.0008
ND
0 09
Salsbury Labs
21
0 83
0
22
2 2
1.8
4 0
ND
ND
ND
ND
ND
NO
NO
0 06
Cooling Waters at
22
1 2
0
33
0 84
1 0
2.3
ND
ND
ND
ND
ND
ND
ND
0.06
Discharge to
23
0 98
0
26
0.89
0.86
1 9
ND
ND
ND
ND
ND
ND
ND
0 04
Unnamed Drainage
24
0 49
0
13
2.0
1.0
2.2
ND
ND
ND
ND
ND
ND
ND
0 07
to Wildwood Creek
25
0.26
0
07r
2.9
0.77
1.7
ND
ND
ND
ND
ND
ND
ND
ND
26
>0 49e
>0
13
3 4d
"" f
ND
ND
ND
ND
ND
NO
ND
0 01
Avg
>0.73
>0.
.20
1.9
1.3
2 9
0 0
0 0
0 0
0.0
0.0
o.ooor
0 0
0 05(
Station 03
20
8 25
2
18
3 3
27
60
ND
ND
ND
ND
ND
0 0030
ND
0.14
Charles City WWTP
21
7.79
2
06
2.7
21
46
ND
ND
ND
ND
ND
0.0028
ND
0 11
Influent Following
22
7 26
1,
.92
2 4
17
38
ND
ND
ND
ND
ND
0 0170
ND
0 13
Bar Screen
23
7.91
2
09
2.7
21
47
ND
ND
ND
ND
ND
0 0032
ND
0 13
24
7.53
1
.99
2.7
20
45
ND
ND
ND
ND
ND
0 0020
ND
0 16
25
7 04
1
.86
1.4
10
22
ND
ND
ND
ND
ND
0 0011
ND
0 15
26
7 53
1
99
1 2
9.1
20
ND
ND
ND
ND
ND
0 0012
ND
0 15
Avg
7.62
2
.01
2.3
18
40
0.0
0.0
0 0
0.0
0 0
0.0043
0.0
0 14
Station 30
27
7 30
1
.93
1.0
7 3
16
ND
ND
ND
ND
ND
0 0011
ND
0 12
Charles City WWTP
28
6 73
1
.78
1 0
6 8
15
ND
ND
ND
ND
ND
0 0015
ND
0 10
Primary Clarifiers
29
6 77
1
79
1 2
8 2
18
ND
ND
ND
ND
ND
0 0026
ND
0 09
Overflow at
30
6.58
1
.74
1 2
7.7
17
ND
ND
ND
ND
ND
0 0045
ND
0 08
Combination Box
Avg
6.84
1
.81
1.1
7 5
17
0 0
O.O
0.0
0.0
0 0
0.0024
0 0
0.10
Detection Limits (mg/1)
0.01
0.50
0.04
0 10
0.09
0.095
0.0003
0.0
0.01
a Compositing period was 0700-0700 Date listed is day period ended,
b Grab samples. Date listed is day sample was collected,
c Metals footnoted are priority pollutants as defined by June 7, 1976 NRDC
vs USEPA settlement agreement,
d NO means not detected
e Heavy rain and resulting runoff submerged Parshall flume section Consequently no flows
were measured or sample aliquots collected at 1000, 1100, or 1200 on June 25, 1978
f Average excluding result from June 26, 1978
g Aliquot collected each time dilution water drawn for bioassay On days when
no aliquots were collected, equal volumes were combined to form composite
-------
Table 8 (Cont )
METALS SAMPLING DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-30, 1978
Station Location
Date-
June
1978
Time
Flow
m3/day
x 103
As
mgd mg/1 kg/day lb/day
Ba
mg/1
Cr
mg/1
mg/1
_Ha!
mg/1
Zn
mg/1
cn
-P*
Station 04
20
8.25
2.18
3.6
30
65
ND
ND
ND
ND
ND
0.0130
ND
0.11
Charles City WWTP
21
7.79
2.06
2.7
21
46
ND
ND
ND
ND
ND
0.0071
ND
0.08
Effluent at Discharge
22
7 26
1 92
2 3
17
37
ND
ND
ND
ND
ND
0 0058
ND
0 11
From Final Clarlfier
23
7 91
2 09
2.4
19
42
ND
ND
ND
ND
ND
0.0041
ND
0 10
24
7.53
1.99
3 0
23
50
ND
ND
ND
ND
ND
0.0022
ND
0 10
25
7.04
1.86
1.5
10
23
ND
ND
ND
ND
ND
0.0022
ND
0.11
26
7.53
1.99
1.3
10
22
ND
ND
ND
ND
ND
0.0016
ND
0.11
27
7.30
1.93
0.98
7.3
16
ND
ND
ND
ND
ND
0 0037
ND
0.12
28
6.73
1.78
0.98
6 8
15
ND
ND
ND
ND
ND
0 0015
ND
0.06
29
6.77
1 79
0 95
6 4
14
ND
ND
ND
ND
ND
0 0018
ND
0.07
30
6.58
1.74
1.2
7 7
17
ND
ND
ND
ND
ND
0.0028
ND
0 11
Avg
7.34
1.94
1 9
14
32
0 0
0.0
0.0
0.0
0.0
0.0042
0.0
0.10
Station 05
27
1440
1.85
0 49
0.6
1.1
2.5
ND
ND
ND
ND
ND
0.0003
ND
0 05
White Farm Equipment
28
1350
2.35
0.62
0.07
0 16
.36
ND
ND
ND
ND
ND
0.0006
ND
0.28
Wastewater in 42" Storm-
29
1440
1.48
0.39
0 01
0.01
03
ND
ND
ND
ND
ND
0.0008
ND
0.04
sewer at 5th & E Sts,
Avg
1.89
0.50
0.23
0.42
0.96
0.0
0 0
0.0
0.0
0.0
0.0006
0.0
0.12
Charles City, Iowa
Station 06
19
1030
680
0.5
ND
ND
0.09
ND
0.0058
ND
0.30
La Bounty Site Groundwater
20
1228
560
ND
ND
ND
ND
ND
0.0030
ND
0.10
Drawn from Well Point
21
1232
560
0.5
ND
ND
ND
ND
0 0061
ND
0 16
Between LA Bounty Dump
22
1135
550
0 9
ND
ND
ND
ND
0.0043
ND
0 12
and Cedar River
Avg
590
0.6
0.0
0.0
0.02
0.0
0.0048
ND
0.17
Station 07
24
1310
0.03
0 007
0.43
-
-
ND
ND
ND
ND
ND
0.0016
ND
0 14
Salsbury Research & Ad-
28
1015
0.08
0.02
0 59
-
-
ND
ND
ND
ND
ND
0.0022
ND
0 34
ministration Bldg Dis-
Avg
0.06
0.01
0.51
-
-
0.0
0.0
0.0
0.0
0.0
0.0019
0.0
0.24
charge to Lift Station
Wet Well
Station 08
21
0940
0 087
0.023
16
1 4
3 1
ND
ND
ND
0 10
ND
0.0005
ND
ND
La Bounty Dump Site
29
1245
0 017
0.0046
8.4
0 15
.32
ND
ND
ND
ND
ND
0 0004
ND
ND
Direct Discharge to
Avg
0.052
0.014
12
0.77
1.7
0.0
0.0
0.0
0 05
0.0
0.0004
0.0
0.0
Cedar River Approx 30 m
(100 ft) Upstream of Iowa
Terminal Railroad Bridge
Station 09
28
1030
0 61
0.16
0.17
_
_
ND
ND
ND
ND
ND
0.0004
ND
ND
Salsbury Labs Cooling
Waters at Manhold Imme-
diately Oownstream from
Cooling Tower
Detection Limits (mg/1)
-------
Table 8 (Cont.)
METALS SAMPLING DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-30, 1978
Station Location
Date3
June
1978
Flow
Ase
JBa
mg/1
Cde
mg/1
Cre
mg/1
Pbe
mg/i
Hqe
See
Zne
mg/1
Time m3/day
x 103
mgd
mg/1 kg/day lb/day
mg/1
mg/1
Station 10^
19
0600,1420
0 55
ND
ND
ND
NO
ND
0 0008
ND
0 09
Cedar River at Suspen-
20
1630
0 48
NO
ND
ND
ND
ND
0 0004
ND
ND
sion Bridge Upstream of
21
0825,2018
0.12
HO
ND
ND
NO
ND
0.0004
ND
ND
Wildwood Creek in
22
0820,1420
0 03
NO
ND
ND
ND
ND
NO
NO
ND
Charles City, Iowa
26
0735,1545
0 03
ND
ND
ND
ND
ND
0.0004
ND
0 08
27
1620
0.02
ND
ND
ND
ND
ND
0 0010
ND
ND
28
0735,1720
0 12
ND
ND
ND
ND
ND
0.0015
ND
ND
Avg
0.19
0.0
0 0
0.0
0.0
0.0
0.0006
0 0
0.02
Station 11
27
1515 1890
500
0.010
19
42
ND
ND
ND
ND
ND
0 0005
ND
ND
Cedar River 30 m (100 ft)
28
1425 1500
397
ND
0.0
0 0
NO
ND
ND
ND
ND
0 0005
ND
ND
Upstream of USGS Gage
29
1415 1300
343
0.010
13
29
ND
ND
NO
ND
ND
0 0005
ND
ND
Station in Charles
Avg
1560
413
0.007
11
24
0 0
0 0
0.0
0.0
0.0
0.0005
0.0
0.0
City, Iowa
Station 12
27
1620 1890
500
0 030
57
130
ND
ND
ND
NO
ND
0 0004
ND
ND
Cedar River 90 m (300 ft)
28
1530 1500
397
0.012
63
140
ND
ND
ND
ND
ND
0.0004
ND
ND
Upstream of Charles
29
1512 1300
343
0 055
71
160
ND
ND
ND
ND
ND
0 0007
ND
ND
City WWTP Discharge
Avg
1560
413
0 042
64
140
0.0
0.0
0 0
0 0
0.0
0.0005
0 0
0.0
Station 20
27
1310
0.59
ND
ND
ND
ND
ND
0.0003
ND
ND
Spring Discharging to
28
1240
1 0
ND
ND
ND
ND
ND
0 0004
ND
ND
Cedar River Approx. 90 m
29
1255
0.48
ND
ND
ND
ND
ND
0 0007
NO
ND
(300 ft) Downstream from
Avg
0 69
0.0
0.0
0.0
0.0
0.0
0 0005
0.0
0.0
Main St Bridge in
Charles City, Iowa
Station 21
27
1304 12
0 32
0 44
0 54
1.2
ND
ND
ND
ND
ND
0 0003
ND
ND
Groundwater Seep Dis-
28
1245 1.2
0.32
0.43
0 50
1 1
ND
NO
ND
ND
HO
0 0003
ND
ND
charging to Cedar River
29
1255 1.2
0.32
0.22
0.27
0 59
ND
ND
ND
ND
ND
0 0004
ND
ND
Approx. 60 m (200 ft)
Avg
1 2
0.32
0 36
0.44
0 96
0.0
0.0
0.0
0 0
0.0
0.0003
0 0
0 0
Upstream of Highway 18
Bridge in Charles City, Iowa
Detection Limits (mg/1)
0 01
0 50
0.04
0.10
0.09
0.095
0 0003
0 01
0.1
CT>
<_n
-------
66
temperature was 68° and the sample contained 4 mg/1 TSS which complied
with permit limits of a maximum temperature of 95°F and a maximum TSS
of 45 mg/1 [Appendix A]. As will be noted later, however, monitoring
wastewaters at this site does not characterize all wastewaters flowing
from Salsbury Laboratories to the unnamed drainage to Wildwood Creek.
WASTEWATER AND WATER QUALITY CHARACTERIZATION
Salsbury Process Wastewaters
The NEIC sampled and analyzed Salsbury process wastewaters for a
wide variety of parameters [Tables 8-14]. As noted in the previous
section, the average BOD concentration during the June 19 to 26, 1978
study, 140 mg/1 [Table 10], was atypically low in comparison to the
past year when BOD averaged 621 mg/1 (range of monthly averages from
171-1,500 mg/1). This was even more pronounced in the case of phenols.
During the NEIC study, phenols averaged 0.31 mg/1 [Table 11]; the av-
erage for the past year was 27.2 mg/1 or 88 times the June 19 to 26,
1978 average.
Ammonia as nitrogen concentrations averaged 67.9 mg/1 [Table 11].
This was similar to the 75 mg/1 projected in September 1977 by
*
Engineering Science Inc. as being representative of current conditions
for design of proposed treatment facilities. As with the ammonia as
nitrogen values, average TSS concentrations during the NEIC study, 19
mg/1 [Table 10], were consistent with the average for the past year,
12 mg/1 [Table 2].
* "Preliminary Engineering Report for Wastewater Treatment", prepared
for Salsbury Laboratories by Engineering Science Inc., September 1977.
-------
Table 9
pH AND TEMPERATURE DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19 - 30 1978
June
19-20
June
20-21
June
21-22
June
22-23
June
23-24
Stations
Stations
Stations
Stations
Stations
Time
01a
02b
03C
04d
01
02
03
04
01
02
03
04
01
02
03
04
01
02
03
04
PH
(S.U.
)
0700
6.5
7 3
7 2
7 2
6 7
6 9
6 7
7 0
6.8
7 1
7 1
7.3
7.6
7.2
7 2
7 0
7.9
7 3
7.1
6 9
0800
6 9
7.5
7 1
6 8
6 9
7 2
7.3
7 5
7.4
7.3
7 3
7.1
7 3
7.0
7 1
0900
6 6
6 8
7 4
6 9
6.7
7 0
7 1
6 8
7.0
7.1
7 3
7.3
7.6
7.1
7 5
7 3
8.0
7 6
7 5
6.9
1000
6 9
6.8
6 8
6 8
6 7
7.2
7 6
7 5
7 3
7.3
7 0
7.2
7.8
7.5
7 5
1100
6.6
6 9
7.2
7 2
7.1
-
6.6
6 9
7.2
7 7
7.3
7.1
7.8
7.4
7.1
7 2
7.8
7 8
7.5
7 6
1200
7 2
7 1
7 3
-
7 1
7 4
7.8
7 5
7 4
7.3
7.8
7 4
7 9
8.1
7.5
1300
6 4
7 2
7 1
7 3
7.0
6 9
7 6
7 5
7.3
7 9
7 3
7 6
8.1
7.4
7.6
7 5
7 6
7.6
7.6
7. 1
1400
7.3
7 2
7 1
7.2
7 6
7 4
7 4
7 6
7 3
7.2
7.5
7.3
7 1
7.3
6 9
1500
6 6
7 3
7 3
7 6
7.2
7 2
7 3
7.5
7 4
7.6
7 6
7 4
8.1
7 1
7 6
7.4
7.9
7 6
7.1
7 2
1600
7 4
7.3
7 2
6.7
7 4
7 4
7 7
7 4
7.4
7 4
7.6
6 8
7 3
8 0
7 0
1700
6 6
7.3
7 0
7 0
6.9
7 2
7 4
7 5
7.5
7 7
8.0
7 4
8 1
7 3
7 6
7.3
7.8
7.5
7.4
6 9
1800
7.4
7 5
7 3
7 3
7.2
7 3
7 8
7.3
7.0
7 3
7 3
7 2
7.3
7 1
7 0
1900
6 6
7 4
7 6
7.3
7.2
7 3
7 4
7.0
8.1
7 5
7 4
7.5
8.0
7.6
7.2
7.3
7 9
7 6
7.6
7.4
2000
7 4
7 0
7 0
7 3
7 3
7 0
7 7
7 7
7 3
7.7
7 7
7 4
7.6
7.5
7 4
2100
7.0
7 4
7.2
7 1
6.9
7 4
7 3
7.5
7.7
7.3
7.7
7 0
7.9
7.9
7.3
7.0
8.1
7.5
7 7
7 2
2200
7 4
7 2
7.2
7 4
7 3
7.7
7 5
7 5
7 5
7.5
7 3
7.0
7.2
7.4
7 4
2300
7 0
7.0
7.0
7 0
6.9
7 3
7.6
7 7
7.8
7.4
7.5
7 0
8.0
7.4
7 6
7 0
8.2
-
7 4
7 2
2400
6.9
7 0
7 2
7 3
7.5
7 5
7.4
7.7
7.3
7 4
7.5
7.1
7 5
7 4
7. 1
0100
7 0
7.2
7 5
7 0
6.8
7 4
7 4
7 4
7.9
7 4
7 7
7.4
8.0
7 5
7.4
7.2
8.2
7.4
7.4
7. 1
0200
7 3
7 7
7.2
7 4
7.2
7 5
7.7
7.6
7 2
7 5
7.7
7 2
7.3
7.6
7 1
0300
7.3
7 2
7 6
6 8
6 8
7 3
7 1
7 1
7 9
7 7
8 0
7.4
8.1
7 5
7 0
7 4
7.7
7 2
7 3
7. 1
0400
7 2
7.0
6 4
7 4
7 0
7 2
7.7
7 5
7 2
7 4
7 6
7 5
7.3
7 5
7.0
0500
6 8
6 9
7 7
6 7
6 9
7 4
7 0
7 6
7.9
7.6
7 4
7.1
8.1
7.6
7.7
7 4
7.7
-
7.5
7 2
0600
7.0
7 4
7 7
7 4
7 5
7.2
7.7
7 5
7.2
7.4
7.7
7.4
7.5
7 3
7 1
Max
7 3
7 4
7 7
7 7
7.2
7.4
7 6
7.7
8 1
7.9
8 0
7.6
8 1
7.9
7.8
7 5
8 2
7.9
8 1
7 6
Mm
6 4
6 8
6.8
6 4
6.7
6.7
6 6
6 8
6.8
7 1
7.1
7.0
7.6
7.1
7.0
6.8
7.6
7 1
7.0
6.9
Temp
(°C)
Max
27 0
22 5
19.0
19 0
25 0
21 0
19.0
20.0
27 5
19 0
19 0
21.0
28.0
21.0
20 0
22 0
25.0
23 0
20 5
21 0
Mi n
20 5
18.0
17.0
16.5
20.5
18.0
17 5
14.0
21.0
15.5
17.0
16.0
22.0
18 0
18.5
17 0
23 0
19.0
18.5
17 0
Avg
23.5
20 0
18 5
18 0
22 5
19.5
18 0
17.5
23 5
18 0
18.5
18.5
25.5
19.5
19.5
19.0
24.5
21.0
19.5
19 0
cn
-------
TABLE 9 (Cont )
pH AND TEMPERATURE DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19 - 30, 1978
June 24-25
June 25-26
June 26-27
June 27-28
June 28-29
June 29-30
Stations
Stations
Stations
Stations
Stations
Stations
Tine
01a 02b 03C 04d
01
02 03 04
30e 04
30 04
30 04
30 04
pH (S.U.)
0700
7 9
7 4
7 3
7 4
7 4
7
5
7 2
7.
4
6 5
5 9
6 0
7.3
6 9
7.1
7.2
7 1
0800
7.2
7.2
7.3
7.
7
7 4
7.
6
6.9
5 9
6 2
7.3
7.2
7 0
7.4
6.4
0900
7.6
7 4
7 5
7 1
7 5
7.
7
6 9
7.
4
6.7
6 7
7.1
7 5
7.1
7.0
6.6
6.9
1000
7 6
7 1
7 3
7 2
7
5
6.8
7 5
6.5
7.5
7 0
7 2
7 2
7 4
1100
7 6
7 5
6.8
7.2
7.1
5 2
5
8
6 6
7 6
7 4
7 5
7.2
7.2
7 3
7.2
1200
7 1
7.3
6.9
5 6
5
1
5 2
7 3
6.8
7 6
6.8
7.2
7 5
7.3
1300
7.6
7 7
7 0
7 3
7.5
7
5
7.0
7
2
7 4
7.6
7 5
7 5
7.2
7.0
7.2
7 3
1400
7 8
7.2
7.0
7
7
7.0
7
3
7.4
7.8
7 4
7.6
7.2
7.2
7.2
7.4
1500
7.4
7 4
7 1
7.1
7.5
7
9
7 2
7
0
6.2
7 7
6 9
7.6
6.9
7.2
7.1
7.3
1600
7 8
6 9
7 O
7
2
7 3
7
3
7.2
7 6
7.4
7.6
7.0
6 9
7.4
7 3
1700
7 4
7 0
6 9
' 7.0
7.3
7.
6
7 1
7
3
7.1
7.6
7.4
7.6
7.8
7.2
7.3
7.2
1800
7 6
7 2
7 2
7
5
7 1
7
3
7 5
7 6
7 4
7.5
7 0
7.0
7 2
7 3
1900
7 1
7 5
7.5
7 8
6 2
7
9
7 7
7.
3
7 0
7 4
7 4
7.6
7.0
7 5
7 0
6 8
2000
7.4
7 4
7.2
7
4
7 4
7
4
6 5
7 5
7.4
7.4
7 3
7.3
7.0
6 8
2100
7.3
7 4
7 3
7.1
7 4
7
7
7.2
8
1
7.0
7.5
7.3
7 4
7 0
7.4
6.0
5 9
2200
7 4
7.1
7 3
7
4
7 1
8
2
7 0
7.4
7.3
7 4
7.0
7.3
6.5
5 4
2300
7 4
7 4
7.2
7 2
7.1
7.
8
7 4
7.
.6
7.0
7 4
7.3
7.4
6 8
7.2
7.0
6 2
2400
7.5
7 6
7.4
7.
9
7 1
7
6
7 1
7 4
7 2
7 3
6 2
7.1
6.9
5 0
0100
7.4
7.7
7 3
7. 1
7 3
8
0
7 1
7
9
7.1
7 4
7 3
7.3
5.9
7.2
6 4
6 4
0200
7 4
7 5
7 7
7
4
7.2
8
2
6.2
7.4
7.3
7.5
5.5
7.5
6.4
6 9
0300
7.2
7.6
7 1
7.7
7.4
7
7
7 6
7
8
5 4
7 4
7.2
7 8
4 5
7 2
6 6
6.0
0400
7 4
7 7
7 6
7
4
6 9
7
4
5 6
7.4
6 9
7.8
4.5
7.6
6.6
6.9
0500
6.9
7 5
7.6
7 5
7.3
8
0
7.2
7
.7
5 5
7 7
6 3
7.7
4.4
7.2
6 8
6 9
0600
7 1
7 2
7.4
7
6
7.2
7
.6
5.4
7.8
7.4
7.8
4 5
7.3
6.5
6.8
Max
7.9
7.8
7 7
7 8
7.5
8
0
7 7
8
2
7.5
7.8
7 5
7.8
7.8
7.6
7.5
7 4
Min
6.9
7.0
6.8
6.9
6.2
7
.2
5.2
5
.1
5 2
5.9
6.0
7 3
4.4
6.9
6.0
5.0
Temp
(°C)
Max
28 0
23 0
21 0
24 0
28 5
25
0
20.0
22
5
20 0
24.5
20 0
22 5
19 0
23 0
22 0
27 0
Min
23 0
21.0
19 0
18.5
22 0
22
0
17.0
20
0
17 5
21 O
17 0
21 0
17 0
21 0
18 0
21 5
Avg
26 0
22.0
20.0
21.0
26.0
23
0
17 5
20
.5
19.0
22.0
18 0
21.5
18.5
22.0
20.5
23 0
a Salsbury Labs process wastewaters at effluent from equalization pond
b Salsbury Labs cooling waters at discharge to unnamed drainage to Wildwood Creek,
c Charles City WWTP influent following bar screen
d Charles City WWTP effluent at discharge from final clarifier
e Charles City WWTP primary clarifiers overflow at combination box.
-------
55
70
26
100
210
51
34
78
77
29
36
17
24
9.3
32(
1300
930
1100
1600
1500
930
1800
1300
400
290
340
380
380
Table 10
BOD, COD, TOC, TSS SAMPLING OATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-28, 1978
Date3 Time'5 Flow BOD COD TOC TSS
June 1978 m3/day nigd mg/1 kg/day lb/day mg/1 kg/day lb/day mg/1 kg/day lb/day mg/1 kg/day
x 103
20
2 1
0 55
120
250
550
580
1200
2700
190
400
870
12
25
21
1 7
0 44
160
270
590
670
1100
2500
220
370
810
19
32
22
1 5
0 39
300
440
980
830
1200
2700
240
350
780
8
12
23
1.9
0 50
170
320
710
780
1500
3300
260
490
1100
25
47
24
2.0
0 54
140
290
630
630
1300
2800
200
410
900
46
94
25
1.9
0 51
65
130
280
370
710
1600
120
230
510
12
23
26
1 7
0 45
39
66
150
310
530
1200
100
170
380
9
15
Avg
1 8
0.48
140
250
560
600
1100
2400
190
350
760
19
35
20
0 87
0 23
12
10
23
45
39
86
20
17
38
40
35
21
0 83
0.22
7
5 8
13
18
15
33
11
9 2
20
16
13
22
1 2
0.33
3
3.7
8 3
9
11
25
7
8 7
19
13
16
23
0 98
0.26
4
3 9
8 7
8
7 9
17
7
6 9
15
8
7 9
24
0.49
0 13
14
6.9
15
33
16
36
16
7 9
17
22
11
25
0 26
0 07
6
1.6
3.5
15c
4.0
8.8
1Zc
3 2
7.0
16c
4.2
26
>0 49
>0 13
4C
20
8
6
Avg.
>0.73
>0 20
8d
5 3d
12d
21d
15d
34d
12d
8.8d
19d
19d
15d
20
8 25
2 18
97
800
1800
310
2600
5600
91
750
1700
71
590
21
7 79
2 06
110
860
1900
450
3500
7700
93
730
1600
54
420
22
7 26
1 92
99
720
1600
360
2600
5800
110
800
1800
71
520
23
7 91
2 09
110
870
1900
380
3000
6600
120
950
2100
93
740
24
7 53
1.99
97
730
1600
370
2800
6100
110
830
1800
89
670
25
7 04
1 86
65
460
1000
240
1700
3700
74
520
1100
60
420
26
7 53
1 99
65
490
1100
290
2200
4800
70
530
1200
110
830
Avg.
7.62
2.01
92
700
1600
340
2600
5800
95
730
1600
78
600
20
8 25
2 18
21
170
380
170
1400
3100
50
410
910
22
180
21
7.79
2 06
18
140
310
130
1000
2200
40
310
690
17
130
22
7.26
1 92
24
170
380
190
1400
3000
58
420
930
21
150
23
7 91
2.09
19
150
330
180
1400
3100
56
440
980
22
170
24
7 53
1 99
20
150
330
200
1500
3300
58
440
960
23
170
25
7.04
1 86
29
200
450
190
1300
2900
55
390
850
29
200
26
7 53
1 99
28
210
460
160
1200
2700
48
360
800
26
200
Avg
7.62
2.01
23
170
380
170
1300
2900
52
400
870
23
170
-------
Table 10 (Cont )
BOD, COD, TOC, TSS SAMPLING DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-28, 1978
Station Location Date3 Time'' Flow BOD COD TOC TSS
June 1978 ma/day ingd mg/1 kg/day lb/day mg/1 kg/day lb/day mg/1 kg/day lb/day mg/1 kg/day lb/day
x 103
Station 06
19
1030
2100
7300
2400
6
La Bounty Dump Site
20
1228
2100
7100
2300
<1
Groundwater Drawn From
21
1232
2300®
7000
2300
3
Well Point Between
22
1135
1700
7000
2300
1
Dump and Cedar River
Avg
2000
7100
2300
<3
Station 07
24
1310
.03
.007
24 -
-
-
32
Salsbury Research and
Administration Bldg Dis-
charge to Littleton Wet Well
Station 09 28 1030 0.61 0.16 ... -- - - __4
Salsbury Labs
Cooling Waters at
Manhole Immediately
Downstream from
Cooling Tower
a Compositing period was 0700-0700 Date listed is day period ended
b Grab samples Date listed is day sample was collected.
c Heavy rain and resulting runoff submerged Parshall flume Consequently no flows were measured
or sample aliquots collected at 1000, 1100, 1200 on June 25, 1978.
d Average excluding result from June 26, 1978.
e Possibility of toxicity BOD was higher at greater dilutions. Results reported are conservative
-------
Table 11
PHENOLIC COMPOUNDS AND AMMONIA-NITROGEN SAMPLING DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-30, 1978
Station Location
Date3 Time'5
Flow
Phenols
NHa—N—
June 1978
m-Vday
mgd
mg/1
kg/day
lb/day
mg/1
kg/day
lb/day
xlO3
Station 01
20
2.1
0 55
0 61
1.3
2 8
35 6
74
160
Salsbury Labs Process
21
1 7
0 44
0 48
0.80
1.8
52 8
88
190
Wastewaters at Effluent
22
1.5
0 39
0 33
0.49
1 1
61 6
91
200
From Equalization Pond
23
1.9
0 50
0 26
0.49
1 1
58 0
110
240
24
2 0
0 54
0 16
0.33
0.72
89 4
180
400
25
1 9
0 51
0 14
0.27
0.60
84 4
160
360
26
1 7
0 45
0.20
0.34
0.75
93.8
160
350
Avg.
1 8
0.48
0 31
0.57
1 3
67.9
120
270
Station 02
20
0 87
0 23
0.34
0.30
0 65
1.5
1.3
2.9
Salsbury Labs Cooling
21
0.83
0 22
0.24
0 20
0.44
0 23
0.19
0 42
Waters at Discharge to
22
1 2
0 33
0.09
0 11
0.25
0 15
0 19
0 41
Unnamed Drainage to
23
0.98
0 26
0 07
0.07"
0.15
0.13
0 13
0 28
Wildwood Creek
24
0 49
0.13
0 21
0.10
0.23
0 14
0 07
0 15
25
0 26
0.07
0.29
0.08
0.17
0- 28
0.07
0 16
26
>0.49
>0.13
0.34
0. 30
Avg.
>0 73
>0.20
0 21d
0.14d
0.32d
0.40d
0.32d
0 72d
Station 03
20
8 25
2 18
0 26
2 1
4.7
14 1
116
257
Charles City WWTP
21
7.79
2 06
0.24
1.9
4.1
16 4
128
282
Influent Following
22
7 26
1 92
0.15
1 1
2 4
19.0
138
304
Bar Screen
23
7.91
2 09
0 12
0 95
2.1
20 8
165
363
24
7 53
1.99
0 08
0.60
1.3
30 8
232
511
25
7 04
1 86
0 09
0 63
1.4
30 3
213
470
26
7.53
1.99
0 09
0.68
1 5
27 3
206
453
Avg
7.62
2.01
0.15
1.1
2.5
22 7
171
377
Station 30
27
7 30
1 93
32 5
237
523
Charles City WWTP Primary
28
6 73
1 78
36 9
249
548
Clarifiers Overflow at
29
6 77
1.79
35 0
237
523
Combination Box
30
6 58
1.74
31 0
204
450
Avg
6 84
1.81
33 9
232
511
-------
Table 11 (Cont.)
PHENOLIC COMPOUNDS AND AMMONIA-NITROGEN SAMPLING DATA
SALSBURY LABS/CHARLES CITY, IOWA
June 19-30, 1978
Date3 Time Flow Phenols NH -N
Station Location June 1978 nF/day mgd rag/1 kg/day lb/day mg/1 kg/day lb/day
x 103
Station 04
20
8.25
2.18
0.032
0.26
0.58
17.1
141
311
Charles City WWTP
21
7.79
2.06
0 036
0.28
0 62
17.5
136
301
Effluent at Discharge
22
7.26
1 92
0.041
0 30
0 66
23.4
170
375
From Final Clarlfier
23
7.91
2 09
0.061
0 48
1 1
23 4
185
408
24
7.53
1.99
0 057
0.43
0 95
30.1
227
500
25
7.04
1.66
0.041
0.29
0.64
36 7
258
570
26
7.53
1.99
0.037
0.28
0.61
30 5
230
506
27
7.30
1.93
36.2
264
583
28
6.73
1.78
37.1
250
551
29
6.77
1.79
34.2
232
511
30
6.58
1.74
32.6
215
473
Avg.
7.34
1.94
0.044
0.33
0.74
29.0
210
463
Station 06
19
1030
19
133
La Bounty Dump Site
20
1228
20
132
Groundwater Drawn from Well
21
1232
17
130
Point Between Dump
22
1135
18
130
and Cedar River
Avg.
18
130
Station 10e
19
0600,1420
0.31
Cedar River at Suspension
20
1630
0.09
Bridge Upstream of Wildwood
21
2018
0.06
Creek in Charles City, Iowa
22
26
27
28
0820,1420
0735,1545
1620
0735,1720
0.08
0.22
0.09
0.14
Avg. 0.14
a Compositing period was 0700-0700 Date listed is day period ended
b Grab samples Date listed is day sample was collected
c Heavy rain and resulting runoff submerged Parshall flume section. Consequently, no
flows were measured or sample allquots collected at 1000, 1100, or 1200 on June 25, 1978.
d Average excluding result from June 26, 1978
e Aliquot collected each time dilution water drawn for bioassay On days when
two aliquots collected, equal volumes combined to form composite
-------
Cable 12
VOLATILE ORGAN ICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
Concentration (ppb or mq/1)
Chemical Name Date (June) •
20
21
22
23
24
25
26 27 28
29
30
Detection
Time (hr)
Average
Limi t
Station
01 -
Salsbury
Labs Process
Wastewaters
At
Effluent from Equilization Pond
BENZENE
3 4
ND
MS
1 5
1 4
1 5
2 9-
1
5
1 0
BR0M0DICHL0R0METHANE
NDe
ND
ND
NO
NO
ND
MS -
-
-
0
1 0
CHL0R0BENZENE
5.9
1 6
1 5
4 2
3 6
2 1
1.4 -
-
2.
9
1.0
1,2-DICHLOROETHANE (ETHYLENE DICHL0RIDE)
7.2
2 2
3 1
5 9
5 4
7 8
7 0-
-
5
5
1 0
trans-1,2-DICHLOROETHENE
ND
ND
ND
ND
ND
ND
MS -
-
0
1 0
DICHLOROMETHANE (METHYLENE CHLORIDE)
ND
ND
ND
ND
ND
ND
ND -
-
0
16
1,2-OICHLOROPROPANE
ND
ND
ND
ND
ND
ND
MS -
-
-
0
1 0
ETHYL BENZENE
ND
ND
MS
ND
ND
ND
MS -
-
-
0
1.0
1,1,2,2-TETRACHLOROETHANE
NO
ND
NO
ND
ND
ND
ND -
-
-
0
1 0
TETRACHL0R0METHANE (CARBON TETRACHLORIDE)
ND
ND
NO
ND
ND
ND
MS -
-
0
1.0
TOLUENE
ND
ND
NO
NO
ND
ND
ND -
-
0
3 6
TRIBR0M0METHANE (BR0M0F0RM)
ND
ND
NO
ND
ND
NO
MS -
-
-
0
1 0
1 ,1 ,1-TRICHLOROETHANE (METHYL CHLOROFORM)
NDf
ND
MS
ND.
ND.
ND,
. MS -
-
-
0
1 0
1,1 ,2-TRICHLOROETHANE
1300
360
380
980
970
1300
r 330 -
-
800
1 0
TRICHL0R0METHANE (CHLOROFORM)
3 3
MS
MS
1 7
ND
2.0
3 0-
-
1
4
1 0
TRICHLOROETHENE (TRICHLOROETHYLENE)
3.9
ND
MS
1.6
1.4
1.4
1.7 -
1
.4
1 0
Station 02 - Salsbury Labs Cooling Waters
At Discharge to Unnamed Drainage To Wildwood Creek
BENZENE
1.1
ND
ND
MS
MS
ND
MS
0 16
1.
0
BROMODICHLOROMETHANE
ND
ND
NO
ND
ND
ND
ND -
0
1.
0
CHLOROBENZENE
ND
ND
ND
ND
NO
ND
HS
0
1
0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIOE)
2.6
ND
3 3
2.7
5 5
MS9
2 0-
2.7
1
0
trans-1,2-DICHLOROETHENE
ND
NO
ND
ND
ND
ND
ND
0
1
0
DICHLOROMETHANE (METHYLENE CHLORIDE)
ND
ND
ND
ND
ND
ND
ND -
0
16
1 ,2-DICHLOROPROPANE
ND
ND
ND
ND
ND
ND
ND -
0
1
0
ETHYL BENZENE
ND
ND
ND
ND
ND
ND
MS
0
1
0
1,1,2,2-TETRACHLOROETHANE
ND
ND
ND
ND
ND
ND
ND -
0
1
0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
ND
ND
ND
ND
ND
ND
MS -
0
1
0
TOLUENE
ND
ND
ND
ND
ND
ND
ND
0
3
6
TR1BR0M0METHANE (BROMOFORM)
ND
ND
ND
ND
ND
ND
ND -
0
1
0
1,1,1-TRICHLOROETHANE (METHYL CHLOROFORM)
ND
ND
ND
ND
ND
N0„
MS9
MS -
0
1
0
1,1,2-TRICHLOROETHANE
450
350
190
120
470
210
300
1
0
TRICHLOROMETHANE (CHLOROFORM)
ND
ND
ND
ND
MS
MS9
ND -
0
1
0
TRICHLOROETHENE (TRICHLOROETHYLENE)
NO
NO
ND
ND
MS
ND
MS -
0
1
0
a Result corresponds to equal volume composite of up to 4 grab samples each
24-hr collected during compositing period
b Date listed is the day compositing period ended; composite period 0700-0700 hr
c Single grab sample Date listed is day sample was collected
d MS means the compound was identified by mass spectrometry but was below the
quantitation detection limit
e ND means not detected at or above the detection limit,
f quantity represents the minimum amount present
g Present in sample but problems with analyses
prevented quantitation not included in average
h ND or MS entries assumed to be 0 0, hence
averages conservative,
i NA means not analyzed.
j In these instances volatile orgamcs samples were
collected in cleaned solvent bottles Analysis
of blanks showed contamination by dichloromethane
(methylene chloride) and chloroform
-------
Table 12 (Cont )
VOLATILE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
Concentration (ppb or pg/l)a
Chemical Name Date (June) '
20
21
22
23
24
25
26
27
28
29
30
h
Detection
Time (hr) :
Average
Limit
Station 03
- Charles City WWTP Influent
Following Bar Screen
BENZENE
3 3
1 3
2 4
1 5
2 2
1 5
2.3
_
_
_
2 1
1 0
BROMODICHLOROMETHANE
NDd
ND
ND
ND
ND
ND
ND
-
-
-
0
1.0
CHLOROBENZENE
MS
ND
2 9
ND
1 6
ND
MS
*
-
-
-
0 64
1.0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE)
3 2
ND
1 3
ND
4.6
4.9
ND
-
-
2 0
1 0
trans-1,2-DICHLOROETHENE
ND
MS
ND
MS
1.7
ND
ND
-
-
-
-
0.24
1.0
OICHLOROMETHANE (METHYLENE CHLORIDE)
ND
ND
ND
28
ND
ND
ND
-
-
-
-
4.0
16.
1,2-DICHLOROPROPANE
ND
ND
ND
ND
ND
ND
ND
-
-
-
-
0
1 0
ETHYL BENZENE
ND
ND
ND
ND
ND
ND
MS
*
-
-
0
1.0
1,1,2,2-TETRACHLOROETHANE
ND
ND
ND
ND
ND
ND
ND
-
-
-
0
1 0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
ND
ND
ND
ND
ND
ND
ND
-
-
-
0
1.0
TOLUENE
ND
ND
5.1
ND
5 7
ND
7.4
-
-
-
2.6
3.6
TRIBROMOMETHANE (BROMOFORM)
ND
ND
ND
ND
ND
ND
ND
-
-
-
-
0
1 0
1,1,1-TRICHL0R0ETHANE (METHYL CHLOROFORM)
NDf
MS
3.0
MS
ND
5 3
ND
*
-
-
-
1.2
1.0
1,1,2-TRICHL0R0ETHANE
690
300
450
390
450
290
140
-
-
-
-
390
1.0
TRICHLOROMETHANE (CHLOROFORM)
12
17
9 3
16
11
9.9
ND
-
-
-
-
11
1.0
TRICHLOROETHENE (TRICHLOROETHYLENE)
1.0
MS
MS
MS
1 7
1 2
ND
"
'
"
0 56
1 0
Station 04
- Charles City WWTP Effluent
At Discharge From Final Clarifier
BENZENE
1 2
MS
MS
1 1
MS
MS
MS
MS
MS
1 1
1 7
0.46
1.0
BROMODICHLOROMETHANE
NDe
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0
1 0
CHLOROBENZENE
MS
ND
NO
2 2
1 3
ND
ND
MS
MS
MS
1.2
0 43
1.0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE)
MS
ND
ND
1.1
ND
5 6
1 4 1
2
1 2
1.1
1 1
1.2
1 0
trans-1,2-DICHLOROETHENE
MS
ND
ND
ND
MS
ND
MS
ND
ND.
ND
MS
0
1 0
OICHLOROMETHANE (METHYLENE CHLORIDE)
ND
ND
ND
ND
ND
ND
ND
ND
NA1
ND
ND
0
16.
1 ,2-DICHLOROPROPANE
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0
1 0
ETHYL BENZENE
ND
ND
ND
ND
2 9
ND
3.6
ND
ND
MS
ND
0.59
1 0
1 ,1,2,2-TETRACHLOROETHANE
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0
1.0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
NO
ND
1 4
ND
ND
ND
ND
ND
ND
ND
NO
0.13
1.0
TOLUENE
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0
3.6
TRIBROMOMETHANE (BROMOFORM)
ND
ND
MS
ND
ND
ND
ND
ND
ND
ND
ND
0
1.0
1,1,1-TRICHLOROETHANE (METHYL CHLOROFORM)
ND
ND
ND
1 3
ND
ND
ND
MS
ND
ND
NO
0.12
1 0
1,1 ,2-TRICHLOROETHANE
230
410
210
290
280
260
100
77
75
210
260
220
1.0
TRICHLOROMETHENE (CHLOROFORM)
1.3
4 3
9 3
ND
11
ND
ND
50
4 4
5 4
9 4
8 6
1.0
TRICHLOROETHENE (TRICHLOROETHYLENE)
MS
ND
MS
MS
ND
MS
ND
ND
NO
ND
MS
0
1.0
-------
Table 12 (Cont )
VOLATILE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
Chemical Name Date (June)^-
Time (hr) :
Concentration (ppb
or (jq/1 )a
20
21
ZZ
23
24
25
26
27
1432
28
1330
29
1345
30 h
Average
Detection
Limit
Station 05
- White Farm Equipment Wastewaters
At 5th and E Sts, Charles City,
in 42"
Iowa
Storm
Sewer
BENZENE
.
.
NDe
MSd
MS
0
1.
0
BROMOD1CHLOROMETHANE
-
-
-
-
-
-
-
ND
ND
MS
0
1
0
CHLOROBENZENE
-
-
-
-
-
-
-
ND
ND
MS
0
1
0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE)
-
-
-
-
-
-
-
ND
ND
ND
0
1
0
trans-1,2-DICHLOROETHENE
-
-
-
-
-
-
-
ND
ND
MS
0
1
0
OICHLOROMETHANE (METHYLENE CHLORIDE)
-
-
-
-
-
-
-
ND
ND
ND
0
16
1,2-DICHLOROPROPANE
-
-
-
-
-
-
-
ND
ND
ND
0
1
0
ETHYL BENZENE
-
-
-
-
-
-
-
ND
ND
ND
0
1
0
1 ,1 ,2,2-TETRACHLOROETHANE
-
-
-
-
-
-
-
ND
MS
ND
0
1
0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
-
-
-
-
-
-
-
ND
ND
MS
0
1
0
TOLUENE
-
-
-
-
-
-
-
ND
NO
ND
0
3
6
TRIBROMOMETHANE (BROMOFORM)
-
-
-
-
-
-
-
ND
ND
ND
0
1
0
1,1,1-TRICHI.OROETHANE (METHYL CHLOROFORM)
-
-
-
-
-
-
-
1.9
1 8
1 9
1 9
1
0
1,1 ,2-TRICHLOROETHANE
-
-
-
-
-
-
-
ND
MS
MS
0
1
.0
TRICHLOROMETHANE (CHLOROFORM)
-
-
-
-
-
-
-
MS
ND
1 1
- 0.37
1
.0
TRICHLOROETHENE (TRICHLOROETHYLENE)
""
—
~
—
MS
ND
MS
0
1
0
Station 06
- LA Bounty Dump Site Groundwater
Drawn
1
:rom Well
Point
Between
Dump
and Cedar River
Date (June)j/
19
20
21
22
23
24
25
26
27
28
29 30
Avg
Det
Lim.
Time (hr) :
1030
1228
1813
1135
BENZENE
180
230
150
200
_
_
_
190
1
0
BROMODICHLOROMETHANE
ND
ND
ND
ND
-
-
-
-
0
1.
0
CHLOROBENZENE
4 6
5 4
5 1
7 0
-
-
-
-
-
-
-
5 5
1
0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE)
310
330
270
320
-
-
-
-
-
-
-
310
1
0
trans-1,2-DICHLOROETHENE
30
25
27
31
-
-
-
-
-
28
1.
0
DICHLOROMETHANE (METHYLENE CHLORIDE)
29
130
71
96
-
-
-
-
-
82
16
1,2-DICHLOROPROPANE
NO
NO
ND
ND
-
-
-
-
-
-
0
1
0
ETHYL BENZENE
3 0
3 5
3 8
5 2
-
-
-
-
-
-
-
3 9
1
0
1,1,2,2-TETRACHLOROETHANE
ND
ND
ND
ND
-
-
-
-
-
0
1
0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
NO
ND
ND
ND
-
-
-
-
-
-
0
1
0
TOLUENE
27
28
24
34
-
-
-
-
-
-
-
28
3.
.6
TRIBROMOMETHANE (BROMOFORM)
ND
ND
ND
ND
-
-
-
-
-
0
1.
.0
1,1,1-TRICHLOROETHANE (METHYL CHLOROFORM)
5 3
4.2
5 ^f
5 6f
-
*
-
-
-
-
-
5 0
1
0
1,1,2-TRICHLOROETHANE
390
870^
510
650'
-
-
-
-
-
600
1
0
TRICHLOROMETHANE (CHLOROFORM)
220
320
190
270
-
-
"
-
-
250
1
0
TRICHLOROETHENE (TRICHLOROETHYLENE)
42
42
39
48
"
"
43
1
0
-------
Table 12 (Cont.)
VOLATILE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
CTi
Concentration (ppb or pq/l)3
Chemical Name Date
-------
Table 12 (Cont.)
VOLATILE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
h
Concentration (ppb or pg/lja
Chemical Name
Date (June)
Time (hr) •
20 21 22 23 24 25 26 27 28
1515 1425
29
1415
30 h Detection
Average Limit
Station 11 - Cedar River 30 m (100 ft) Upstream of
USGS Gage Station in Charles City, Iowa
BENZENE -
MS
MS
MS
0
1.0
BR0M0D1CHL0R0METHANE ....
NDe
ND
ND
0
1.0
CHLOROBENZENE -
ND
ND
ND
0
1 0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE) -
NO
ND
ND
0
1 0
trans-1,2-DICHL0R0ETHENE -
: : : 3:°j
MS,
ND.
1.0
1 0
DICHLOROMETHANE (METHYLENE CHLORIDE) ....
. J
- J
-
16
1,2-DICHL0R0PR0PANE ....
ND
ND
ND
0
1 0
ETHYL BENZENE -
ND
ND
ND
0
1 0
1,1,2,2-TETRACHLORETHANE ....
ND
ND
ND
0
1.0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE) -
ND
ND
ND
0
1 0
TOLUENE ....
ND
ND
ND
0
3.6
TRIBROMOMETHANE (BR0M0F0RM) ....
ND
ND
ND
0
1.0
1,1,1-TRICHLOROETHANE (METHYL CHLOROFORM) - -
ND
ND
ND
0
1.0
1,1,2-TRICHLOROETHANE -
1.3.
\3i
1 4,
1.3
1.0
TRICHLOROMETHANE (CHLOROFORM) ....
. J
.J
1.0
TRICHLOROETHENE (TRICHLOROETHYLENE) ....
ND
ND
ND
0
1.0
Station 12 - Cedar River 90 m (300 ft) Upstream Of
Charles City WWTP Discharge
Time (hr)c: 1620 1530 1512 Average'1
BENZENE ....
MS
3 2
MS
1.1
1.
0
BROMODICHLOROMETHANE -
NDe
ND
ND
0
1
0
CHLOROBENZENE ....
ND
ND
ND
0
1.
.0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE) -
ND
MS
MS
0
1
0
trans-1,2,DICHLOROETHENE -
: : : 2:3j
ND
ND,
0.77
1.
.0
DICHLOROMETHANE (METHYLENE CHLORIDE) -
ND
. J
_
16
1 ,2-DICHLOROPROPANE ....
ND
ND
ND
0
1
0
ETHYL BENZENE ....
ND
ND
MS
0
1
0
1,1 ,2,2-TETRACHLOROETHANE ....
ND
ND
ND
0
1
0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE) -
ND
ND
NO
0
1
0
TOLUENE ....
NO
ND
ND
0
3
6
TRIBROMOMETHANE (BROMOFORM) ....
ND
ND
ND
0
1
0
1,1,1-TRICHLOROETHANE (METHYL CHLOROFORM) -
ND
ND
ND
0
1
0
1,1,2-TRICHLOROETHANE ....
5.0,
7 2
8 0,
6 7
1
0
TRICHLOROMETHANE (CHLOROFORM) ....
_ J
ND
-J
1
0
TRICHLOROETHENE (TRICHLOROETHYLENE) -
ND
MS
ND
0
1.
.0
-------
Table 12 (Cont )
VOLATILE ORGANICS SAMPLING OATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
Chemical Name Date (June)''.
Time (hr) :
Concentration (ppb or gq/l)a
20
21 22
23
24
25 26 27
1505
28
1240
29
1255
30
Average'1
Detection
Limi t
Station
90 m
20 - Groundwater Spring Discharging to Cedar River Approximately
(300 ft) Downstream From Main St. Bridge in Charles City, Iowa
BENZENE
_
_
MS^
1.5
1 7
1.1
1.
0
BROMODICH LOROMETHANE
-
-
-
-
ND
MS
ND
-
0
1.
0
CHLOROBENZENE
-
-
-
-
ND
MS
ND
-
0
1.
0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE)
-
-
-
3 5
3 9
3.8
-
3.7
1.
0
trans-1,2-DICHLOROETHENE
-
-
-
MS,
MS
MS
-
0
1.
0
DICHLOROMETHANE (METHYLENE CHLORIDE)
-
-
-
. J
ND
ND
-
-
16
1,2-DICHLOROPROPANE
-
-
-
-
ND
MS
ND
-
0
1
0
ETHYL BENZENE
-
-
-
-
ND
MS
ND
-
0
1.
0
1,1,2,2-TETRACHLOROETHANE
-
-
-
-
ND
ND
ND
-
0
1.
0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
-
-
-
ND
ND
ND
-
0
1.
0
TOLUENE
-
-
-
-
ND
ND
ND
-
0
3
6
TRIBROMOMETHANE (BROMOFORM)
-
-
-
-
ND
MS
ND
-
0
1.
0
1,1 ,1-TRICHLOROETHANE (METHYL CHLOROFORM)
-
-
-
23.
23
2"f
-
23
1.
0
1,1,2-TRICHLOROETHANE
-
-
-
-
350
290
350
-
330
1
0
TRICHLOROMETHANE (CHLOROFORM)
-
-
-
-
ND
MS
MS
-
0
1
0
TRICHLOROETHENE (TRICHLOROETHYLENE)
7.5
7.5
8.4
"
7 8
1
0
Station 21 -
Groundwater
Seep Discharging to Cedar
River
Approx
60 m (200 ft)
Upstream of
Highway 18 Bridge in
Char 1
es City,
Iowa
Time (hr)c-
1505
1245
1255
Average'1
BENZENE
_
_ _
_
1 3a
1.2
1 8
1.4
1.
.0
BROMODICHLOROMETHANE
-
-
-
-
MS
NDe
ND
-
0
1
0
CHLOROBENZENE
-
-
-
-
MS
ND
ND
-
0
1
0
1,2-DICHLOROETHANE (ETHYLENE DICHLORIDE)
-
-
-
-
3 6
3 6
4 3
-
3.8
1
.0
trans-1,2-DICHLOROETHENE
-
-
-
-
MS
ND
MS
-
0
1
0
DICHLOROMETHANE (METHYLENE CHLORIDE)
-
-
-
-
ND
ND
ND
-
0
16
1,2-DICHLOROPROPANE
-
-
-
-
ND
ND
ND
-
0
1
0
ETHYL BENZENE
-
-
-
-
ND
ND
ND
-
0
1
.0
1,1,2,2-TETRACHLOROETHANE
-
-
-
-
ND
ND
ND
-
0
1
.0
TETRACHLOROMETHANE (CARBON TETRACHLORIDE)
"
-
-
-
ND
ND
ND
-
0
1
0
TOLUENE
-
-
-
-
ND
ND
ND
-
0
3
6
TRIBROMOMETHANE (BROMOFORM)
-
-
-
-
ND
ND
ND
-
0
1
0
1,1,1-TRICHLOROETHANE (METHYL CHLOROFORM)
-
-
-
-
16
18
25
-
20
1
0
1,1 ,2-TRICHLOROETHANE
-
-
-
-
300
280
370
-
320
1
0
TRICHLOROMETHANE (CHLOROFORM)
-
-
-
-
MS
MS
ND
-
0
1
.0
TRICHLOROETHENE (TRICHLOROETHYLENE)
-
-
-
6 6
6 0
8 1
-
6.9
1
0
-------
Table 12 (Cont.)
VOLATILE ORGANICS SAMPLING DATA
SALS8URY LABORATORIES/CHARLES CITY, IOWA
June 1978
Chemical Name Date (June)*! Detection
Time (hr) 20 21 22 23 24 25 26 27 28 29 30 Average Limit
Station 30 - Charles City WWTP Primary
Clarifiers Overflow at Combination Box
Concentration (ppb or |jq/l )a
BENZENE
BROMODICHLOROMETHANE
CHLOROBENZENE
1,2-DICHLOROETHANE (ETHYLENE DICHL0R1DE) -
trans-1,2-DICHLOROETHANE
DICHLOROMETHANE (METHYLENE CHLORIDE)
1,2-OICHLOROPROPANE
ETHYL BENZENE
1,1,2,2 TETRACHLOROETHANE
TETRACHLOROMETHANE (CARBON TETRACHLORIDE) -
TOLUENE
TRIBROMOMETHANE (BR0M0F0RM)
1.1.1-TRICHL0R0ETHANE (METHYL CHLOROFORM) -
1.1.2-TRICHLOROETHANE
TRICHLOROMETHANE (CHLOROFORM)
TRICHLOROETHENE (TRICHLOROETHYLENE)
1 4
1 6
2 1
5.6
2 7
1 0
NDe
ND .
NO
ND
0
1.0
1.4
MS
1 1
1 9
1.1
1.0
2.0
1 4
1 6
1.5
1.6
1 0
MS
MS
MS
MS
0
1.0
NA1
ND
ND
ND
0
16
ND
ND
MS
ND
0
1.0
MS
ND
ND
ND
0
1 0
ND
ND
ND
ND
0
1 0
ND
ND
ND
ND
0
1.0
ND
ND
4 6
4.9
2.4
3 6
ND
ND
ND
ND
0
1.0
ND
MS
1.7
4 3
1 5
1 0
150
92
230
330
200
1.0
4.8
16
14
21
14
1.0
ND
MS
1.3
1 4
0.67
1.0
-------
Table 13
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA CO
SALSBURY LABORATORIES/CHARLES CITY, IOWA <=>
Station 01 - Salsbury Labs Process Wastewaters
At Effluent From Equalization Pond
Date (Juge)a -~ 20 21 22 23 24 25 26 Avgb
Time(hr) •+
Flow m3/day (mgd) - 2.1 (0.55) 1 7 (0.44) 1.5 (0.39) 1.9 (0.50) 2.0 (0.54) 1.9 (0.51) 1.7 (0.45) 1 8 (0.48)
x 103
Chemical Name Concentration (|jg/l); Load (kg/day, lb/day)
ACETANILIDE
NDd
ND
ND
ND
ND
ND
ND
0 0
ANILINE f
MSe
MS
ND
ND
17 0.035
0.077
22 0
.043
0.094
15 0
.026
0.056
8 G
1.015
0.032
BENZ0FURAN
MS
MS
MS
MS
MS
MS
MS
0 0
O-CHL0R0ANILINE
ND
ND
ND
ND
NO
ND
ND
0 0
P-CHL0R0NITR0BENZENE ,
CHL0R0NITR0BENZ0NITBILE
CHL0R0NITR0LT0LUENE
4000
8 3
IB
3200
5.3
12
3000
4 4
9.8
2900
5.5
12
2300
4.7
10
1200
2.3
5.1
810
1.4
3 0
2500
4 5
10
ND
NO
ND
ND
960
2.0
4.3
1100
2.1
4 7
1300
2 2
4 9
480
0 87
1 9
920
1 9
4 2
1700
2 8
6.2
2600
3.8
8 5
3800
7.2
16
4800
9 8
22
5400
10
23
5200
8.9
20
3500
6 4
14
4-CHL0R0-3-NITR0BENZAMIDE
9400
20
43
5800
10
21
4900
7.2
16
2300
4 4
9.6
610
1.2
2.7
700
1 4
3 0
4300
7 3
16
4000
7 3
16
2,6-DICHLOROBENZAMIDE
DICHL0R0BENZAMIDE
ND
ND
ND
1500
2.8
6.3
820
1.7
3.7
320
0 62
1.4
610
1.0
2.3
460
0 84
1 8
ND
ND
ND
ND
270
0 55
1.2
330
0.64
1 4
ND
86
0. 16
0.34
1.2-DICHL0RO-3-NITROBENZENE
110
0.23
0 50
550
0.92
2.0
700
1.0
2.3
1500
2.8
6.3
2200
4.5
9.9
2400
4 6
10
2500
4 3
9 4
1400
2 5
5.6
2,6-DINITR0CHL0R0BENZENE
ND
ND
ND
ND
1100
2.3
5.0
1100
2.1
4.7
1400
2.4
5 3
510
0.93
2.0
2-ETHYLHEXANAL
NA9
NA
NA
NA
NA
NA
NA
NA
2-ETHYLHEXANOL
NA
NA
NA
NA
NA
NA
NA
NA
3-HEPTANONE
NA
NA
NA
NA
NA
NA
NA
NA
PHENOL
370
0.78
1 7
290
0.48
1.1
ND ¦
ND
87
0 18
0.39
60
0.12
0.26
94
0.16
0 35
130
0.24
0 52
2-PHENYLBENZIMIDAZOLE
2000
4.2
9 2
3300
5. 5
12
3100
4.6
10
1900
3 6
7 9
2700
5.5
12
2100
4 1
8.9
1400
2 4
5.3
2400
4.4
9.6
O-NITROANILINE
22000
46
100
12000
20
44
12000
18
39
13000
25
54
9700
20
44
5300
10
23
5500
9.4
21
11,000 20
44
P-NITROANILINE
290
0 6
1.3
350
0.58
1 3
190
0 28
0.62
360
0 68
1.5
200
0.41
0 90
160
0.31
0.68
18 0
.031
0 068
220 0 400
0.88
NITROBENZENE
240
0 5
1.1
180
0.30
0.66
190
0 28
0 62
150
0 28
0.63
TOO
0.20
0.45
56
0.11
0 24
49 0
.084
0.18
140
0 25
0 56
0-NITR0PHEN0L
7300
15
34
980
1.6
3.6
970
1.4
3 2
950
1 8
4.0
310
0 63
1.4
200
0 39
0.85
80
0.14
0.30
1500
2.7
6.0
1,2,4-TRICHLOROBENZENE
ND
ND
ND
¦
210
0.40
0.88
ND
NO
ND
30
0 55
0.12
a Date listed is the day compositing period ended; composite period 0700-0700.
b ND or MS entries assumed to be 0.0, hence averages conservative,
c Grab samples, date listed is day sample was collected.
d ND means not detected at or above the detection limit which is approximately 1 yg/1 for all compounds
at Stations 05, 10, 11 12, 20 and 21 and approx. 10 pg/1 for all other stations
e MS means the compound was identified by mass spectrometry but was below the quantitation detection limit,
f Compound is not confirmed and concentrations are estimated based on the response of a similar compound
at a similar GC retention time,
g NA means not analyzed for
h Heavy rain and resulting runoff submerged Parshall flume section. Consequently, no flows measured
or sample aliquot collected at 1000, 1100 or 1200 on June 25, 1978
l Average concentration and loadings excluding results from June 26, 1978
j GC peaks not resolved; quantitation based on relative response from GC/MS
-------
Table 13 (Cont. )
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
STATION 02 - SALSBURY LABS COOLING WATERS AT DISCHARGE
TO UNNAMED DRAINAGE TO WILDWOOD CREEK
Date (June) -»
Time(hr) -»
20
21
22
23
24
25
26h
* b, i
Avg '
Flow m3/day (mgd)
0
.87 (0.23)
0
83 (0.22)
1.2 (0 33)
0.98
(0.26)
0.49
(0.13) 0 26
(0.07)
O
A
cn
o
A
13)
>0
.73 (>0.20)
x 103
Chemical Name
Concentration (pg/1); Load (kg/day,
lb/day)
ACETANILIOE
18
0 016
0 035
NDd
ND
62J
ND
ND
ND
ND
3
0 0023 0 005
ANILINE f
61
0 053
0.12
ND
0 078 0.17
MS
MSe
ND
20J 0.0099
0 022
20
0.015 0.033
BENZ0FURANT
ND
ND
ND
ND
ND
ND
ND
0 0
O-CHLOROANILINE
ND
ND
ND
ND
ND
ND
ND
0 0
P-CHLORONITROBENZENE ,
ND
ND
ND
ND
ND
ND
ND
0.0
CHLORONITROBENZONITBILE
ND
ND
ND
ND
ND
ND
ND
0 0
CHLORONITROLTOLUENE
ND
ND
ND
ND
ND
ND
ND
0 0
4-CHLORO-3-N1TROBENZAMIDE
ND
ND
ND
ND
ND
ND
ND
0 0
2,6-DICHLOROBENZAMIDE
ND
ND
ND
ND
ND
ND
ND
0 0
DICHLOROBENZAMIDE
ND
ND
ND
ND
ND
ND
ND
0 0
1.2-DICHL0R0-3-NITR0BENZENE
ND
ND
ND
ND
ND
ND
ND
0 0
2,6-DINITROCHLOROBENZENE
ND
ND
ND
ND
ND
ND
ND
0.0
2-ETHYLHEXANAL
ND
ND
ND
ND
ND
ND
ND
0 0
2-ETHYLHEXANOL
ND
ND
ND
ND
ND
ND
ND
0 0
3-HEPTANONE
ND
ND
ND,
38
ND
ND.
17J
ND
ND.
0 0
PHENOL
91
0.079
0 17
100
0.083
0 18
0.048 0 10
MS
0 0084
0.018 MS
42 0.021
0 046
41
0.031 0.068
2-PHENYLBENZIMIDAZOLE
ND
ND
ND
ND
ND
ND
ND
0.0
O-NITROANILINE
490
0 43
0 94
60
0 050
0.11
26
0.033 0.072
ND
ND
10 0 0027
0.0058
MS
84
0 064 0.14
P-NITROANILINE
46
0 040
0.088
ND
ND
ND
ND
ND
ND
7
0 0053 0.012
NITROBENZENE
170
0 15
0 33
160
0.13
0 29
160
0.20 0.44
55 0.054
0.12 69
0.034
0.075 280 0.074
0.16
200 0.099
0 22
160
0.11 0.25
O-NITROPHENOL
ND
ND
ND
ND
ND
NO
ND
0 0
1,2,4-TRICHL0R0BENZENE
ND
ND
ND
ND
ND
ND
ND
0.0
-------
Table 13 (Cont.)
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA 00
SALSBURY LABORATORIES/CHARLES CITY, IOWA fvj
STATION 03 - CHARLES CITY WWTP INFLUENT
FOLLOWING BAR SCREEN
Gate (June)3 -~ 20 21 22 23 24 25 26 Avgb
Time(hr) ¦*
Flow m3/day (mgd) - 8.25 (2.18) 7.79 (2.06) 7.26 (1.92) 7 91 (2.09) 7.53 (1.99) 7 04 (1.86) 7.53 (1.99) 7.62 (2 01)
xlO3
Chemical Name Concentration (pg/1>; Load (kg/day, lb/day)
ACETANILIDE
NDh
ND
ND
ND
ND
ND
ND
0.0
ANILINE f
MS
MS
13 0
.095
0.21
ND
ND
ND
ND
2
0.015
0.034
BENZOFURAN
MS
MS
MS
MS
MS
MS
MS
0 0
0-CHL0R0AN1LINE
NO
NO
ND
ND
ND
ND
NO
0 0
P-CHLORONITROBENZENE f
600
5 0
11
640
5.0
11
590
4.3
9 5
650
5.1
11
580
4.4
9.6
170
1 2
2.6
180
1.4
3.0
490
3.7
8.2
CHLORONITROBENZONITRILE
ND
NO
ND
ND
ND
ND
22
ND
11
25
0 0
16
CHLORONITROLTOLUENE
170
1 4
3.1
380
3 0
6 5
400
2 9
6 4
1200
9 5
21
1600
12
27
1400
10
1500
950
7.2
4-CHL0R0-3-NITR08ENZAMIDE
2500
21
45
1600
12
28
2500
18
40
3000
24
52
2700
20
45
290
2.0
4 5
310
2 3
5 1
1800
14
30
2,6-DICHL0R0BENZAMlDE
D1CHLOROBENZAMIDE
320
2.6
5 8
180
1.4
3.1
330
2.4
5.3
530
4.2
9.2
380
2.9
6 3
70
0.49
1.1
350
2.6
5.8
310
2.4
5.2
ND
NO
ND
ND
ND
ND
ND
0 0
1.2-DICHL0R0-3-NITR0BENZENE
ND
92
0.72
1.6
75
0 55
1 2
100
0.79
1.7
470
3.5
7.8
510
3 6
7.9
390
2.9
6.5
230
1 8
3 9
2,6-DINITROCHLOROBENZENE
ND
ND
160
1 2
2.6
ND
ND
NO
NO
23 0
0.18
0.39
2-ETHYLHEXANAL
NA
NA
NA
NA
NA
NA
NA
NA
2-ETHYLHEXANOL
NA
NA
NA
NA
NA
NA
NA
NA
3-HEPTAN0NE
NA
NA
NA
NA
NA
NA
NA
NA
PHENOL
85
0.70
1.5
32
0 25
0.55
26
0.19
0.42
ND
ND
ND
ND
20
0 15
0.34
2-PHENYLBENZIMIDAZOLE
1000
B. 3
18
500
3.9
8 6
600
4.4
9 6
1200
9.5
21
620
4.7
10
160
1.1
2.5
270
2.0
4 5
620
4.7
10
O-NITROANILINE
3900
32
71
3200
25
55
3300
24
53
4200
33
73
3500
26
58
1400
10
22
1600
12
27
3000
23
50
P-NITROANILENE
160
1.3
2 9
140
1.1
2 4
110
0.80
1.8
13
0 10
0 23
17
0.13
0.28
MS
62
0 47
1.0
72
0 55
1.2
NITROBENZENE
57
0.47
1 0
49
0.38
0.84
47
0.34
0.75
66
0 52
1.2
41
0.31
0.68
12
0.084
0.19
12
0.090
0 20
41
0.31
0 69
O-NITROPHENOL
1900
16
35
1600
12
28
1500
11
24
2900
23
51
2700
20
45
1300
9.2
20
1400
11
23
1900
14
32
1,2,4-TRICHLOROBENZENE
ND
ND
ND
53
0.42
0.92
67
0 50
1.1
110
0.78
1.7
110
0.83
1.8
50
0 38
0.84
-------
T. 3 (C
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
STATION 04 - CHARLES CITY WTP EFFLUENT AT DISCHARGE FROM FINAL CLARIFIER
Date (June)a ¦*
20
21
22
23
24
25
Time(hr)c
Flow m3/day (mgd) -»
x 103
8
.25
(2 18)
7
.79
(2.06)
7.26 (1.92)
7.91
(2.09)
7
53
(1.99)
7
04 (1
.86)
Chemical Name
Concentrat
ion (pg/1);
Load (kg/day,
lb/day)
ACETANILIDE
NDa
ND
NO
ND
ND
ND
ANILINE f
NDb
ND
ND
ND
ND
ND
BENZOFURAN
MS
MS
MS
MS
MS
MS
O-CHLOROANILINE
41
0.34
0 75
32
0 25
0 55
43
0 31
0.69
34
0.27
0.59
ND
20
0 14
0 31
P-CHLORONITROBENZENE ,
440
3.6
8 0
470
3.7
8 1
450
3 3
7.2
490
3.9
8 5
500
3.8
8.3
290
2.0
4 5
CHLORONITROBENZONITBILE
ND
NO
ND
ND
ND
ND
CHLORONITROLTOLUENE
100
0 83
1.8
230
1 8
4.0
280
2 0
4 5
620
4 9
11
1100
8 3
18
1500
11
23
4-CHL0R0-3-NITR0BENZAMIDE
980
8 1
18
830
6 5
14
1200
8 7
19
1900
15
33
1500
11
25
530
3.7
8.2
2,6-DICHLOROBENZAMIDE
150
1.2
2.7
89
0.69
1.5
130
0.95
2.1
130
1.0
2.3
130
0 98
2.2
35
0.25
0 54
DICHLOROBENZAMIDE
NO
ND
ND
ND
ND
ND
1.2-DICHL0R0-3-NITR0BENZENE
NO
ND
26
0.19
0.42
59
0.47
1.0
120
0 90
2.0
140
0 99
2.2
2,6-DINITROCHLOROBENZENE
NO
ND
ND
ND
ND
NO
2-ETHYLHEXANAL
NA
NA
NA
NA
NA
NA
2-ETHYLHEXAN0L
NA
NA
NA
NA
NA
NA
3-HEPTANONE
NA
NA
NA
NA
NA
NA
PHENOL
ND
ND
ND
ND
ND
ND
2-PHENYLBENZIMIDAZOLE
260
2.1
4 7
370
2.9
6 4
360
2 6
5 8
370
2.9
6 5
NA
250
1 8
3.9
O-NITROANILINE
3800
31
69
2800
22
48
2900
21
46
3300
26
58
3700
28
61
2000
14
31
P-NITROANILINE
MS
29
0 23
0 50
13
0 095
0.21
26
0.21
0 45
13
0.098
0.22
ND
NITROBENZENE
38
0 31
0.69
23
0 18
0.40
24
0.17
0.38
19
0.15
0.33
MS
10
0.07
0.16
O-NITROPHENOL
100
0.83
1 8
ND
NO
ND
24
0 18
0.40
ND
1,2,4-TRICHLOROBENZENE
NO
ND
ND
ND
33
0.25
0.55
23
0 16
0 36
Date (June)3
26
27
28
29
30
Avab
Flow m3/day (mgd) -»
7.
53
(1.99)
7
30
(1 93)
6 73
(1.78)
6.
77
(179)
6.
58
(1 74)
7
34
(1.94)
x 103
ACETANILIDE
ND
ND
NA
ND
ND
0 0
ANILINE f
ND
ND
ND
ND
ND
0 0
BENZOFURAN
ND
ND
MS
MS
MS
0 0
O-CHLOROANILINE
MS
ND
ND
25
0 17
0 37
43
0 28
0 62
22
0 16
0.36
P-CHLORONITROBENZENE
170
1.3
2.8
180
1.3
2.9
190
1 3
2.8
420
2.8
6 3
510
3 4
7.4
370
2 7
6.0
CHLORONITROBENZONITBILE
ND
ND
ND
ND
ND
0 0
CHLORONITROLTOLUENE
520
3.9
8.6
1100
8 0
18
610
4 1
9 1
340
2.3
5 1
620
4 1
9 0
640
4 7
10
4-CHLORO-3-NITROBENZAMIDE
1100
8 3
18
800
5 8
13
1400
9.4
21
1300
8 8
19
1500
10
22
1200
8 8
19
2,6-DICHLOROBENZAMIDE
100
0.76
1.7
38
0.28
0.61
77
0.52
1.1
140
0.95
2.1
140
0.92
2.0
110
0 81
1 8
DICHLOROBENZAMIDE
ND
ND
NO
ND
ND
0 0
1.2-DICHLORO-3-NITROBENZENE
ND
210
1.5
3.4
59
0 40
0.88
90
0.61
1.3
100
0.66
1.5
73
0.54
1.2
2,6-DINITROCHLOROBENZENE
ND
ND
NO
ND
ND
0.0
2-ETHYLHEXANAL
NA
NA
NA
NA
NA
NA
2-ETHYLHEXANOL
NA
NA
NA
NA
NA
NA
3-HEPTANONE
NA
NA
NA
NA
NA
NA
PHENOL
ND
ND
ND
ND
ND
0 0
I
2-PHENYLBENZIMIDAZOLE
120
0.90
2 0
87
0 64
1.4
180
1 2
2 7
270
1 8
4 0
620
4.1
9 0
260
1.9
4 2 '
O-NITROANILINE
1400
11
23
1200
8.8
19
1800
12
27
2600
18
39
3600
24
52
2600
19
42.
P-NITROANILINE
ND
ND
ND
ND
32
0 21
0 46
10
0 073
0 16
NITROBENZENE
MS
11
0.080
0 18
MS
12
0 081
0.18
43
0 28
0.62
16
0.12
0 26
O-NITROPHENOL
27
0.20
0.45
23
0.17
0.37
ND
ND
ND
16
0 12
0 26
1,2,4-TRICHLOROBENZENE
62/
0.47
1 0
470
3 4
7.6
ND
ND
ND
53
0 39
0 86
-------
Table 13 (Cont )
00
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
STATION 05 - WHITE FARM EQUIPMENT WASTEWATERS STATION 06 - LA BOUNTY DUMP SITE
CHARLES CITY, IOWA GROUNDWATER DRAWN FROM WELL POINT BETWEEN DUMP AND CEDAR RIVER
Date (Juge) -»
27 28 29
a b
Avg
19
20
21
22
Avg
Time(hr)
1440 1350 1400
1030
1220
1232
1135
Flow m3/day (mgd) -»
1.85 (0 49) 2.35 (0.62) 1 48 (0.39)
1.89 (0 50)
xlO3
Chemical Name
Concentration (pg/1), Load (kg/day, lb/day)
Concentration (pg/l)
ACETANILIDE
None of the compounds listed were detected
NDa
ND
ND
ND
0 0
ANILINE f
on any sampling day.
400
220
140
870
410
BENZOFURAN
ND
ND
ND
ND
0 0
O-CHLOROANILINE
ND
180
360
ND
140
P-CHLORONITROBENZENE f
460
670
790
940
720
CHLORONITROBENZONIIRILE*
ND
ND
ND
ND
0.0
CHLORONITROTOLUENE
ND
460
ND
ND
120
4-CHL0R0-3-NITR0BENZAMIDE
8,700
6,500
1,200
440
4,200
2,6-DICHLOROBENZAMIDE
2,200
890
2,000
30,000
8,800
DICHLOROBENZAMIDE
ND
NO
ND
ND
0.0
1.2-DICHLORO-3-NITROBENZENE
ND
ND
ND
ND
0 0
2,6-DINITROCHLOROBENZENE
ND .
ND
ND
ND
0 0
2-ETHYLHEXANAL
NA
4,500
3,200
2,600
2,600
2-ETHYLHEXANOL
22,000
23,000
23,000
19,000
22,000
3-HEPTANONE
ND
1,300
670
610
640
PHENOL
17,000
16,000
12,000
12,000
14,000
2-PHENYLBENZIMIDAZOLE
ND
ND
ND
ND
0 0
O-NITROANILINE
,
180,000
170,000
180,000
170,000
180,000
P-NITROANILINE
47,000
36,000
32,000
34,000
37,000
NITROBENZENE
ND
250
740
ND
250
O-NITROPHENOL
8,600
9,600
12,000
12,000
11,000
1,2,4-TRICHLOROBENZENE
ND
ND
ND
ND
0 0
-------
Table 13 (Cont. )
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
STATION 07 - SALSBURY LABS RESEARCH AND ADMINISTRATION BUILDING STATION 08 - LA BOUNTY SITE DIRECT DISCHARGE TO CEDAR RIVER
DISCHARGE TO LIFT STATION WET WELL APPROXIMATLEY 30 m (100 FT) UPSTREAM OF IOWA TERMINAL RAILROAD BRIDGE
Date (June) •»
24
28
a b
Avg
21
29
Avg'>
Time(hr) -»
1310
1015
0940
1245
Flow m3/day (mgd) -» 0
xlO3
03 (0 007)
0
08 (0.02)
0 06 (0.01)
0.087 (0.023)
0 017 (0 0046)
0.
052
(0 014)
Chemical Name
Concentration (pg/1);
Load (kg/day,
lb/day)
Concentration (|jg/l);
Load (kg/day,
lb/day)
ACETANILIDE
NDa
ND
0 0
NDa
ND
0
0
ANILINE f
ND
NO
0.0
ND
ND
0
0
BENZOFURAN
ND
ND
0 0
ND
ND
0
0
O-CHLOROANILINE
ND
ND
0 0
NO
ND
0
0
P-CHLORONITROBENZENE f
NO
ND
0.0
ND
ND
0
0
CHLORONITROBENZONITRILE
ND.
ND
0 0
NO
ND
0
0
CHLORONITROTOLUENE
MS
ND
0 0
ND
ND
0
0
4-CHLORO-3-NITROBENZAMIDE
ND
NO
0 0
ND
ND
0
0
2,6-DICHL0R0BENZAMIDE
ND
ND
0.0
ND
ND
0
0
DICHLOROBENZAMIDE
ND
ND
0 0
ND
ND
0
0
1,2-DICHLORO-3-NITROBENZENE
MS
ND
0 0
ND
ND
0
0
2,6-DINITROCHLOROBENZENE
ND
ND
0 0
ND
ND
0
0
2-ETHYLHEXANAL
ND
ND
0 0
ND
ND
0
0
2-ETHYLHEXANOL
ND
ND
0 0
ND
ND
0
0
3-HEPTANONE
NO
ND
0 0
ND
ND
0
0
PHENOL
ND
ND
0 0
ND
ND
0
0
2-PHENYLBENZIMIDAZOLE
ND
ND
0 0
ND
ND
0
0
O-NITROANILINE
MS
MS
0.0
20. 0.0017
0.0038 12
0.00021
0.00046
16 0.00085 0.0019
P-NITR0AN1L1NE
MS
50
0.0038 0.0083 25 0.0019 0 0042
MS
ND
0
0
NITROBENZENE
ND
ND
0.0
ND
ND
0
0
O-NITROPHENOL
ND
ND
0.0
ND
ND
0
0
1,2,4-TRICHLOROBENZENE
MS
ND
0.0
ND
ND
0.0
00
en
-------
Table 13 (Cont.)
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
OO
CTl
STATION 09 - SALSBURY LABS COOLING WATERS
AT MANHOLE IMMEDIATELY DOWNSTREAM FROM COOLING WATER STATION 10 - CEDAR RIVER AT SUSPENSION BRIDGE
UPSTREAM OF WILDWOOD CREEK IN CHARLES CITY, IOWA
Date (Jupe) -»
28
19
20
21
22 26 27
28
Avgb
Time(hr) ¦+
1030
0600,1420
1630
0825,2018
0820,1420 0735,1545 1620
0735,1720
Flow m3/day (mgd) -»
0.61 (0.16)
xlO3
Chemical Name
Concentration (pg/1)
ACETANILIDE
None of the compounds
ND
ND
ND
None of the Compounds listed were
detected
0 0
ANILINE .
listed were detected on
ND
ND
ND
on these sampling days
0.0
BENZOFURAN
any sampling day.
ND
ND
ND
0 0
O-CHLOROANILINE
ND
ND
ND
0 0
0.0
0 0
0 0
P-CHLORONITROBENZENE .
ND
ND
ND
CHLORONITROBENZONITRILE
CHLORONITROTOLUENE
ND
ND
ND
ND
ND
ND
4-CHLORO-3-NITROBENZAMIDE
ND
ND
ND
0.0
0 0
2,6-DICHLOROBENZAMIDE
ND
ND
ND
DICHLOROBENZAMIDE
ND
ND
ND
0 0
1,2-DICHL0R0-3-NITR0BENZENE
ND
ND
ND
0 0
2,6-DINITROCHLOROBENZENE
ND
ND
ND
0 0
2-ETHYLHEXANAL
ND
ND
ND
0 0
0 0
0 0
0 0
2-ETHYLHEXANOL
ND
ND
ND
3-HEPTANONE
ND
ND
ND
PHENOL
ND
ND
ND
2-PHENYLBENZIMIDAZOLE
ND
ND
ND
0.0
2
O-NITROANILINE
ND
1
12
P-NITROANILINE
ND
ND
ND
0.0
NITROBENZENE
ND
1
ND
0 1
O-NITROPHENOL
ND
ND
ND
0.0
1,2,4-TRICHLOROBENZENE
ND
ND
ND
0.0
-------
Table 13 (Cont.)
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
STATION 20
STATION 11 STATION 12 GROUNDWATER SPRING DISCHARGING TO CEDAR
CEDAR RIVER 30 M (100 FT) CEDAR RIVER 90 M (300 FT) RIVER APPROXIMATELY 90 M (300 FT)
UPSTREAM OF USGS GAGE STATION UPSTREAM OF CHARLES CITY WWTP DISCHARGE DOWNSTREAM FROM MAIN ST BRIDGE IN
CHARLES CITY, IOWA CHARLES CITY, IOWA CHARLES CITY, IOWA
Date (June)8 ¦»
27 28 29
Avgb
27
28
29
A t>
Avg
27
28
29
Avg
Time(hr) -»
1515 1425 1415
1620
1530
1512
1310
1240
1255
Flow m3/day (mgd) - 1890 (500) 1500 (397) 1300 (343)
1560
(413]
1890 (500) 1500 (397) 1300 (343) 1560
(413)
xlO3
-1
Chemical Name
Concentration
(mq/i);
Load (kg/day, lb/day)
Concentrati
on (pg/1)
ACETANILIDE
0
0
NOh
ND
ND
0.0
NDa
NO
ND
0 0
ANILINE . None of
the compounds listed were detected
0
0
MS 0
0 2
3 0
6.6 MS
0.7
1.0 2.2
ND
ND
ND
0 0
BENZOFURAN
on these sampling days
0
0
ND
ND
ND
0.0
ND
ND
ND
0 0
O-CHLOROANILINE
0
0
NO
ND
ND
0 0
MS0
ND
MSd
0.0
P-CHLORONITROBENZENE f
0
0
NO
ND
ND
0.0
ND
ND
ND
0 0
CHLORONITROBENZONITRILE
0
0
ND
ND
ND
0.0
ND
ND
ND
0 0
CHLORONITROTOLUENE
0
0
ND
ND
ND
0 0
5
4
27
12
4-CHL0R0-3-NITR0BENZAMIDE
0
0
ND
ND
ND
0 0
ND
ND
ND
0 0
2,6-DICHLOROBENZAMIDE
DICHLOROBENZAMIOE'
0
0
0
0
ND
ND
ND
ND
ND
ND
0 0
0 0
ND
NO
ND
NO
ND
ND
0.0
0 0
1,2-DICHL0R0-3-NITR0BENZENE
0
0
ND
ND
ND
0 0
ND
ND
4
1
2.6-DINITR0CHL0R0BENZENE
0
0
ND
ND
ND
0 0
ND
ND
ND
0 0
2-ETHYLHEXANAL
0
0
ND
ND
ND
0 0
ND
ND
ND
0 0
2-ETHYLHEXANOL
0
0
ND
ND
ND
0 0
ND
ND
ND
0 0
3-HEPTANONE
0
0
ND
ND
ND
0 0
ND
NO
NO
0 0
PHENOL
0
0
ND
ND
ND
0 0
ND
ND
ND
0 0
2-PHENYLBENZIMIDAZOLE
0
0
ND
ND
NO
0.0
ND
ND
ND
0 0
O-NITROANILINE
0
0
6 11
25 7
11
23 9 12 26
7
11 25
27
27
29
28
P-NITROANILINE
0
0
ND
ND
ND
0 0
2
1
2
2
NITROBENZENE
0
0
ND
NO
ND
0 0
ND
ND
ND
0 0
O-NITROPHENOL
0
0
ND
NO
ND
0 0
ND
ND
ND
0 0
1,2,4-TRICHLOROBENZENE
0
0
ND
ND
ND
0.0
ND
ND
NO
0 0
00
-------
Table 13 (Cont.)
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
Date (June)3 -~ 27 28 29 Avg'5 qq
Time(hr) - 1304 1245 1255 CO
Flow m3/day (mgd) - 1.2 (0 32) 1.2 (0.32) 1.2 (0.32) 1.2 (0 32)
xlO3
STATION 21 - GROUNDWATER SEEP DISCHARGING TO CEDAR RIVER
APPROXIMATELY 60 M (200 FT UPSTREAM OF HIGHWAY 18)
BRIDGE IN CHARLES CITY, IOWA
Chemical Name Concentration (pg/l); Load (kg/day, lb/day)
ACETANILIDE
NDa
ND
ND
0.0
ANILINE
ND
ND
ND
0.0
BENZOFURANC
ND.
ND
ND
0 0
O-CHLOROANILINE
MS
MS
MS
0.0
P-CHLORONITROBENZENE
ND
ND
3
0.0036
0 008
1
0.0012
0.0027
CHLORONITROBENZONITRILE
CHLORONITROTOLUENE
ND
7
0 0085 0.019
ND
4
0.0048
0.011
ND
29
0.035
0.077
0.0
13
0.016
0.035
4-CHL0R0-3-NITR0BENZAMIDE
ND
ND
ND
0 0
2,6-DICHLOROBENZAMIDE
ND
ND
ND
0 0
DICHLOROBENZAMIDE
ND
ND
ND
0 0
1.2-DICHL0R0-3-NITR0BENZENE
ND
ND
6
0 0073
0.016
2 0
.0024
0.0053
2,6-DINITROCHLOROBENZENE
ND
ND
ND
0.0
2-ETHYLHEXANAL
ND
ND
ND
0.0
2-ETHYLHEXANOL
ND
ND
ND
0 0
3-HEPTANONE
ND
NO
ND
0 0
PHENOL
ND
ND
ND
0 0
2-PHENYLBENZIMIDAZOLE
ND
ND
ND
0.0
O-NITROANILINE
36
0.044 0.096
23
0 028
0 061
34
0.041
0.091
31
0.038
0 083
P-NITROANILINE
ND
ND
ND
0 0
NITROBENZENE
ND
ND
ND
0 0
O-NITROPHENOL
ND
NO
ND
0.0
1,2,4-TRICHLOROBENZENE
ND
ND
3
0.0036
0.008
1
0.0012
0.0027
STATION 30 - CHARLES CITY WWTP PRIMARY CLARIFIERS
OVERFLOW AT COMBINATION BOX
Date (June)
Time(hr)
Flow m3/day mgd
-~
-~
28 29 30
6 73 (1.78) 6.72 (1 79) 6 58 (1.74)
a b
Avg
6.84 (1.81)
Chemical Name
Concentration (pg/l); Load (kg/day, lb/day)
ACETANILIDE
ANILINE
BENZOFURAN
O-CHLOROANILINE
P-CHLORONITROBENZENE
CHLORONITROBENZONITRILEC
ND
ND
ND
ND
630 4.2
ND
9.4
ND
ND.
MS
ND
550
ND
3.7 8.2
ND
ND
MS
65
580
ND
0 43
3.8
0.94
8.4
0 0
0 0
0 0
22
590
0.0
0.15
4.0
0.33
8.9
-------
Table 13 (Cont )
NEUTRAL EXTRACTABLE ORGANICS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
STATION 30 - CHARLES CITY WWTP PRIMARY CLARIFIERS .
OVERFLOW AT COMBINATION BOX
Date (June)
Time(hr)
Flow m3/day mgd
-*
28 29 30
6 73 (1 78) 6.72 (1 79) 6 58 (1 74)
Avgb
6.84 (1.81)
Chemical Name
Concentration (ng/1); Load (kg/day, lb/day)
CHLORONITROTOLUENE
500
3 4
7.4
420
2 8
6.3
720
4.7
10 5
550
3 8
8 3
4-CHLORO-3-NITROBENZAMIDE
4800
32
71
2600
18
39
360
2.4
5 2
2600
18
39
2,6-DICIILOROBENZAMIDE
180
1.2
2 7
380
2 6
5.7
260
1.7
3 8
270
1 9
4.1
OICHLOROBENZAMIDE0
NO
330
2.2
4 9
ND
110
0.75
1 7
1.2-DICHL0R0-3-HITR0BENZENE
120
0.81
1.8
ND
380
2.5
5.5
170
1.2
2.6
2,6-DINITROCHLOROBENZENE
ND
ND
ND
0.0
2-ETHYLHEXANAL
NA
NA
NA
NA
2-ETHYLHEXANOL
NA
NA
NA
NA
3-HEPTANONE
NA
NA
NA
NA
PHENOL
ND
ND
ND
0 0
2-PHENYLBENZIMIDAZOLE
1200
8.1
18
340
2.3
5 1
290
1.9
4.2
610
4 2
9 2
O-NITROANILINE
3600
24
53
2900
20
43
3700
24
54
3400
23
51
P-NITROANILINE
ND
MS
ND
ND
NITROBENZENE
ND
11
0 075
0 16
18
0.12
0 26
10
0.069
0 15
O-NITROPHENOL
1300
8.8
19
1000
6.8
15
25
0.16
0 36
780
5.3
12
1 ,2,4-TRICHLOROBENZENE
ND
ND
ND
ND
-------
TABLE 14
SELECTED ORGANIC PRIORITY POLLUTANTS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
Concentration In ug/1
No.a Sta. 01b Sta 02C Sta 03d Sta 04e Sta. Q6f Sta 109 Sta. llh Sta. 121
Name 6/21"23j 6/23J 6/23j 6/23j 6/20-22k 6/28 1720 6/28 1425 6/28 1530
1
ancenaphthene
ND
ND
NO
ND
NO
ND
ND
ND
2
acrolein*
NO
ND ¦
ND
ND
ND
ND
ND
ND
3
acrylonitirile*
ND
MS
ND
ND
NO
ND
ND
ND
ND
4
benzene*
ND
2
MS
190
MS
MS
3
5
benzidine
ND
NO
ND
NO
ND
NO
ND
ND
6
carbon tetrachloride*
ND
ND
ND
MS
ND
ND
ND
ND
7
chlorobenzene*
2
ND
1
MS
6
NO
ND
ND
8
1,2,4-trichlorobenzene
45
ND
6
ND
ND
ND
ND
ND
9
hexachlorobenzene
NO
ND
ND
NO
ND
ND
ND
ND
10
1,2-dichlroethane*
4
2
MS
MS
310
ND
ND
MS
11
1,1,1-trichloroethane*
ND
ND
1
MS
5
ND
ND
ND
12
hexachloroethane
NO-
ND
ND
ND
NO
ND
ND
ND
13
1,1-dichloroethane*
NA
NA
NA
NA
NA
NA
NA
NA
14
1,1,2-trichloroethane*
570
220
380
300
680
MS
1
7
15
1,1,2,2-tetrachloroethane*
ND
ND
ND
ND
ND
ND
ND
ND
16
chloroethane*
NA
NA
NA
NA
NA
NA
NA
NA
17
bis(chloromethyl)ether*
NA
NA
NA
NA
NA
NA
NA
NA
18
bis(2-chloroethyl)ether
ND
ND
ND
NO
ND
ND
NO
ND
19
2-chloroethyl vinyl ether*
ND
ND
ND
ND
ND
ND
ND
ND
20
2-chloronaphthalene
ND
ND
ND
ND
ND
ND
ND
ND
21
2,4,6-trichlorophenol
ND
ND
ND
ND
NDP
NDq
NOq
ND
ND
22
p-chloro-m-cresol
ND
ND
NO
ND
NDP
Ng
ND
23
chloroform*
MS
ND
14
5
p
ND
ND
24
2-chlorophenol
6
ND
ND
ND
NDq
ND
ND
25
1,2-dichlorobenzene
NO
ND
ND
ND
ND
ND
ND
ND
26
1,3-dichlorobenzene
ND
ND
ND
ND
ND
ND
ND
ND
27
1,4-dichlorobenzene
ND
ND
ND„
ND
ND
ND
ND
ND
29
1,1-dichloroethylene*
MS0
MS0
MS0
MS0
MS0
ND
ND
ND
30
trans-1-2-dichloroethene*
ND
ND
ND
ND
28
ND
MS
ND
31
2,4-dichlorophenol
ND
ND
ND
NO
NDP
NDq
ND
ND
32
1,2-dichloropropane*
ND
ND
ND
ND
ND
ND
ND
NO
33
1,3-dichloropropylene*
NA
NA
NA
NA
NA
NA
NA
NA
34
2,4-dimethyl phenol
ND
ND
ND
ND
NDP
NDq
ND
ND
35
2,4-dinitrotoluene
ND
ND
ND
NO
ND
ND
ND
ND
36
2,6-dim trotoluene
ND
ND
ND
NO
ND
NO
ND
ND
37
1,2-diphenyl hydrazine
ND
ND
ND
ND
ND
ND
ND
ND
38
ethylbenzene*
ND
ND
ND
ND
4
ND
ND
ND
39
fluoranthene
ND
ND
NO
ND
NO
ND
ND
NO
* Volatile organic compound
-------
TABLE 14 (Continued)
SELECTED ORGANIC PRIORITY POLLUTANTS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
Concentration in ug/1
No.a Sta. 01b Sta. 02c Sta. 03d Sta. 04e Sta. 06f Sta. TO9 Sta. llh Sta. 121
Name 6/21-23j 6/23j 6/23J 6/23j 6/20-22k 6/28 1720 6/28 1425 6/28 1530
40
4-chlorophenyl phenyl ether
ND
ND
ND
ND
ND
ND
ND
ND
41
4-bromophenyl phenyl ether
ND
ND
ND
ND
ND
ND
ND
ND
42
bis(2-chloroisopropyl)ether
NO
ND
ND
ND
ND
ND
ND
ND
43
bis(2chloroethoxy)methane
ND
ND
ND
ND
ND
ND
Ng
ND
44
methylene chloride*
ND
ND
9
ND
99
ND
ND
45
methyl chloride*
NA
NA
NA
NA
NA
NA
NA
NA
46
methyl bromide*
NA
NA
NA
NA
NA
NA
NA
NA
47
bromoform*
ND
ND
ND
ND
ND
ND
ND
ND
48
dichlorobromomethane*
ND
ND
ND
ND
ND
ND
ND
ND
49
trichlorof1uoromethane*
NA
NA
NA
NA
NA
NA
NA
NA
50
dichlorodi fluoromethane*
NA
NA
NA
NA
NA
NA
NA
NA
51
chlorodibromomethane*
ND
ND
ND
ND
ND
ND
ND
ND
53
hexachlorocyclopentadiene
ND
ND
ND
ND
ND
ND
ND
ND
54
isophorone
ND
ND
ND
ND
ND
ND
ND
ND
55
naphthalene
ND
ND
ND
ND
ND
ND
ND
ND
56
nitrobenzene
220
110
29
15
6
ND
ND
ND
57
2-ni trophenol
960
ND
2,000
ND
11.000
NDq
ND
ND
58
4-nitrophenol
NA
NA
NA
NA
NAP
NAq
NA
NA
59
2,4-dinitrophenol
19
ND
ND
ND
99p
NDq
ND
ND
60
4,6-d1nitro-o-cresol
ND
ND
ND
ND
NDP
NDq
ND
ND
62
n-nitrosodiphenyl amine
ND
ND
ND
ND
190r
ND
ND
ND
63
n-nitrosodipropyl amine
ND
ND
ND
ND
NDp
ND
ND
ND
64
pentachlorophenol
ND
ND
ND
ND
NDP
NDq
ND
ND
65A phenol
96
44
19
ND
13,000
NDq
ND
ND
66
di-(2-ethylhexyl)phthalate
13
ND
37
28
ND
8
22
15
67
butyl benzylphthalate
ND
ND
ND
ND
ND
ND
ND
ND
68
di-n-butylphthalate
ND
ND
ND
ND
ND
9
ND
ND
69
di-octylphthalate
ND
ND
ND
ND
ND
ND
ND
ND
70
diethylphthalate
ND
ND
ND
ND
ND
ND
ND
ND
71
dimethylphthalate
ND
ND
ND
ND
ND
ND
ND
ND
72
benzo(a)anthracene
ND
ND
ND
ND
ND
ND
ND
ND
76
chrysene
ND
ND
NO
ND
ND
ND
ND
ND
77
acenaphthylene
ND
ND
ND
ND
ND
ND
ND
ND
78
anthracene
ND
ND
ND
ND
ND
ND
ND
ND
80
fluorene
ND
ND
ND
ND
ND
ND
ND
ND
81
phenanthrene
ND
ND
ND
ND
ND
ND
ND
ND
84
pyrene
ND
ND
ND
ND
ND
ND
ND
ND
85
tetrachloroethylene*
ND
ND
6
MS
23
ND
ND
ND
86
toluene*
ND
ND
2
ND
29
ND
ND
ND
87
trichloroethylene*
MS
ND
ND
ND
43
ND
ND
MS
88
vinyl chloride*
NA
NA
NA
NA
NA
NA
NA
NA
-------
Table 14 (Continued)
SELECTED ORGANIC PRIORITY POLLUTANTS SAMPLING DATA
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 1978
a Corresponds to Consent Decree or Green list number
b Salsbury Labs process wastewaters at effluent from equalization pond
c Salsbury Labs cooling waters at discharge to unnamed drainage to Wildwood Creek,
d Charles City WWTP Influent following bar screen
e Charles City WWTP Effluent at discharge from final clarifier
f Labounty dump site groundwater drawn from well point between dump and Cedar River,
g Cedar River at suspension bridge upstream of Wildwood Creek in Charles City, Iowa,
h Cedar River 30 m (100 ft) upstream of USGS gage station, Charles City, Iowa
i Cedar River 90 m (300 ft) upstream of Charles City WWTP discharge, Charles City, Iowa
j Composite prepared at laboratory from 3 daily flow proportional 24-hr. composites or 3 day's grab samples for volatile parameters(*).
Composites were combined proportional to the daily flows,
k VolatileC) composite prepared at laboratory from 3 grab samples collected 6-20, 6-21 and 6-22 Neutral and basic component composite was prepared
from 2 grab samples collected 6-21 and 6-22. Composites were combined on an equal volume basis.
1 ND means not detected at or above the detection limit
m MS means the compound was identified by mass spectrometry but was below the quantitation detection limit,
n NA means not analyzed for
o Present in sample but problems with analysis prevented quantitation
p Phenols composite weighted 1:4-1 for grab samples collected 6-20, 6-21, 6-22, respectively,
q Phenols sample was grab sample from 6-19-78.
r N-nitrosodiphenylamine decomposes to diphenylamine under the analytical conditions used The result reported is for diphenylamine.
s In these instances volatile organic samples were collected from general organic sample collected in cleaned solvent bottles. Analyses of blanks
showed contamination by dichloromethane (methylene chloride) and chloroform.
-------
93
Since past data collected had indicated the possible presence of
refractory and toxic substances in the Salsbury wastewaters, which
could influence or adversely affect characterization by BOD results
alone, COD and TOC data were also collected. Although the BOD analyses
did not indicate toxicity, the COD and TOC data provided a better
assessment of the "strength" of the wastewaters [Table 10]. As noted
below, although the TOC loadings averaged only 1.4 times the BOD, the
COD averaged 4.3 times the BOD:
Compositing Relative Loadings
Day (COD:TOC:BOD)
COD
TOC
BOD
6/19-20
4.9
1.6
1.0
20-21
4.2
1.4
1.0
21-22
2.8
0.8
1.0
22-23
4.6
1.5
1.0
23-24
4.4
1.4
1.0
24-25
5.7
1.8
1.0
25-26
8.0
2.5
1.0
Avg.
4.3
1.4
1.0
With the exception of mercury, zinc and arsenic, metals concentra-
tions in the process wastewaters were generally less than detectable.
Average mercury concentrations were low, 1.8 pg/1 [Table 8], and con-
sistent with the average for the past year, 3.6 pg/1 [Table 2]. Zinc
averaged 0.12 mg/1 during the study. Arsenic, resulting from the pro-
duction of organic arsenicals, averaged 6.0 mg/1, which was consistent
with the average for the past year, 5.05 mg/1.
Characterization of the process wastewaters resulted in the identi-
fication of 26 organic compounds and tentative identification of 4
additional ones [Tables 2-13]. Average concentrations ranged from low
level detection of approximately 1 pg/1 to 11,000 pg/1 for orthonitro-
aniline, which is the compound that has previously been identified in
the Waterloo, Iowa water supply. Seven compounds were found in con-
centrations of 1,000 pg/1 or greater.
-------
94
Of the 26 compounds identified, 17 are priority pollutants, com-
pounds of environmental concern as defined by the June 7, 1976 Natural
Resources Defense Council (NRDC) vs. Russell Train (USEPA) Settlement
Agreement [Appendix B]. In addition to the daily organics character-
ization data, three days of composite samples were combined into one
sample proportional to daily flows and analyzed by priority pollutant
methodology [Appendix D]. These data indicated the presence of 5 addi-
tional priority pollutant organic compounds [Table 14].
As discussed previously, wastewaters from the Research and Adminis-
tration area discharge to the process wastewater effluent sump downstream
from the NEIC sampling site; consequently they would not be reflected
in data discussed above. These wastewaters were assigned Station 07
and sampled on June 24 and 28 for organics and metals [Tables 11-13].
The average flow rate was small, averaging 60 m3/d (0.01 mgd) and the
data indicated the low level presence of compounds found in the Salsbury
process wastewaters. These compounds are probably indicative of on-going
research with products, lab washings and wastewater testing.
A comparison between the process wastewater flows measured by
Salsbury Laboratories and those measured by NEIC indicate the former
are inaccurate and yield consistently low values [Table 15]. The
Salsbury flows averaged 77% of those measured by NEIC. The EPA has
*
established a guideline of +10% for flow monitoring accuracy.
As noted previously, Salsbury laboratories measures flow with a
magmeter installed upstream of wastewater discharges to the equali-
zation pond. The week prior to startup of the NEIC study, plant offi-
cials reported to NEIC personnel that despite the rated capacity of 750
gpm, when flows reached approximately 500 gpm, the mag meter section
appeared unable to handle the flow. Consequently, they would open a
valve to bypass the mag meter, and sometimes an operator would forget
to close it when "flows dropped again. This situation in itself would
* NPDES Compliance Sampling Inspection Manual, June 1977 (p. 57).
-------
95
Table 15
COMPARISON OF FLOWS DURING
JUNE 19-26, 1978
NEIC VS. SALSBURY LABORATORIES
NEICb
Salsbury Labsc
Month
Day3
m^/day x 10^
mgd
m^/day x 10"^
mgd
SL:NEIC
June
19-20
2.08
0.55
_d
-
20-21
1.66
0.44
1.17
0.31
0.70
21-22
1.48
0.39
1.21
0.32
0.82
22-23
1.89
0.50
1.48
0.39
0.78
23-24
2.04
0.54
1.59
0.42
0.78
24-25
1.93
0.51
1.44
0.38
0.75
25-26
1.70
0.45
1.36
0.36
0.80
Average
(excluding 6/19-20)
1.78
0.47
1.38
0.36
0.77
a Flows were determined 0700-0700.
b NEIC flows determined every two hours and averaged for 24-hour period,
c Salsbury Laboratories flows determined from mag meter totalizer readings
recorded daily.
d No flow entered since (1) mag meter was bypassed portion of day, and
(2) recorder erroneously reading full scale until approximately
4:00 p.m.
-------
96
result in lower than actual flow readings since the mag meter recorder
would not sense all of the flow. This situation prevailed for a portion
of the startup day on June 19, 1978. However, subsequent NEIC checks
at approximately two-hour intervals, 24 hours/day, until the end
of sampling on June 26, 1978, revealed no further bypassing. Despite
this, the flows measured by Salsbury were consistently low. Prior to
the startup of the NEIC study, both the transmitter and recorder were
fed electrical signals and calibrated properly. This would tend to
indicate that erroneous signals were being generated at the mag meter
itself, yielding inaccurate results.
Salsbury Cooling Waters
Data collected from combined cooling waters and plant runoff
indicated process contamination. Concentrations of BOD, COD, TOC,
TSS and ammonia as nitrogen were low, averaging 8, 21, 12, 19 and
0.30 mg/1, respectively [Tables 10-11]. Concentrations of phenols on
the other hand, 0.34 mg/1, were approximately the same as those found
in the process wastewater, 0.31 mg/1 [Table 11]. Metals concentrations
were generally low or undetectable with the notable exception of arsenic
which averaged 1.9 mg/1 [Table 8].
Organics characterization of combined cooling waters and plant
runoff resulted in the identification of 15 organic compounds [Tables
12-13]. Average concentrations ranged from low-level detection at
approximately 1 pg/1 to 300 pg/1 for 1, 1, 2-Trichloroethane. Of the
15 organic compounds identified, 14 were also identified in the Salsbury
process wastewaters and 11 of the 15 are priority pollutants. As with
the process wastewaters, organics composites from three days were
combined into one sample for separate priority pollutant analyses.
These data indicated the presence of one additional priority pollutant
organic compound [Table 14].
-------
97
On June 28, 1978 when the NPDES monitoring site, the cooling
tower discharge, was sampled, no organic compounds were identified
[Table 13]. Other data collected at this site, including TSS and
metals, also indicate only minor contamination in comparison to the
combined cooling waters and runoff [Tables 8, 10]. A comparison be-
tween data collected at the two sites indicate the NPDES monitoring
site is not representative of possible contamination by plant surface
runoff, plant drains, process sewer connections or sewer leaks.
Charles City WWTP
Data collected at the Charles City WWTP clearly reflect the impact
of the Salsbury discharges. Influent flows during June 19 to 26 averaged
7,620 m3/day (2.01 mgd) of which Salsbury contributed 1,800 m3/day
(0.48 mgd) or 24%. As has been noted in a previous section, influent
BOD concentrations were atypically low and reflected the concurrent
low BOD concentrations in wastewater coming from Salsbury [Table 10].
Phenols, not a constituent of significance in typical domestic waste-
waters, averaged 0.15 mg/1 [Table 11]. Self-monitoring data collected
over the past year [Table 5] indicate an average of 5.63 mg/1, signifi-
cantly higher than during the NEIC study when data reflected the atypi-
cal ly low levels found in the Salsbury process wastewater. WWTP effluent
concentrations during the NEIC study averaged 0.044 mg/1 for an average
removal efficiency, based on mass, of 70.4%.
TSS, BOD, COD and T0C removal efficiencies at the WWTP averaged
70.8%, 76.2%, 50.0% and 45.6%, respectively, based on loadings. Al-
though the TSS and BOD removals were not as great as might be expected
from a well-operated trickling filter plant, they were at least in
part affected by the low influent concentrations prevailing during
the study, 78 and 92 mg/1 respectively. They may also be affected by
toxic compounds from Salsbury. The lower COD and T0C removals indicate
the WWTP was considerably less successful in removing other more complex
and refractory organic matter. This is also evidenced by the fact
-------
98
that the average COD:BOD ratio increased from 3.6 in the influent to
7.6 in the effluent. To a lesser degree the TOC data also reflect
this; the TOC:BOD ratio was 1.0 in the influent and 2.3 in the effluent.
The average arsenic concentration in the WWTP influent, 2.3 mg/1,
was atypically high for domestic wastes and indicative of Salsburys'
discharges to the system [Table 8]. The WWTP effluent concentration
during the 7-day period when the influent was sampled averaged 2.4
mg/1. No arsenic was removed in the plant, indicating the ineffec-
tiveness of the treatment process in removing the arsenic.
An examination of the arsenic data for the Salsbury process waste-
waters and the Charles City WWTP presents an unexplained anomaly.
During June 11-26, 1977, the Salsbury process wastewaters contained
an average of 11 kg (25 lb)/day of arsenic. For this same time period,
18 kg (40 lb)/day were measured in the Charles City WWTP influent, or
an increase of 7 kg (15 lb)/day. The WWTP influent values were consist-
ently higher than the process wastewater values, and WWTP effluent
values were consistent with influent values. The only possible explana-
tions include another source of arsenic discharges in the Charles
City area, which is highly unlikely, and discharges by Salsbury through
its sanitary sewer connections rather than process wastewater system.
Since orthonitroaniline (ONA) and arsenic are both used in the manu-
facture of Salsbury1s organic arsenicals, and available information
indicates ONA to be resistent to biodegredation, data collected on
ONA were also investigated. These data indicate that on 5 of 7 days
of sampling, the process wastewater contribution was less than that
monitored in the WWTP influent [Table 13]. The 7-day average for
this process wastewater (20 kg) was slightly less than that for the
WWTP influent (23 kg).
Beginning on June 25, 1978, significant periodic drops in pH
were recorded on the influent and effluent of the WWTP [Table 9] in-
cluding a low of 5.2 and 5.1 standard units, respectively. These
-------
99
periodic excursions continued throughout the remainder of the study,
June 30. Although monitoring was not being conducted for the Salsbury
process wastewater after the morning of June 26, pH data was being
collected on the first day of the pH excursions, June 25-26. As noted
in Table 9 no concurrent low pH values were recorded at Salsbury.
The reason for the low pH values is unknown.
Organics characterization of the Charles City WWTP influent re-
sulted in the identification of 24 compounds and the tentative identi-
fication of two additional ones [Tables 12-13]. Twenty-two of the 24
were also identified in the Salsbury process wastewaters. Average
concentrations ranged from low-level detection at approximately 1
pg/1 to a high of 3,000 pg/1 for orthonitroani1ine. Of the 24 compounds,
15 are priority pollutants. In addition to these characterization
data, three days of influent composite samples were combined propor-
tional to daily flow into one sample and analyzed by priority pollutant
methodology. These data indicated the presence of 4 additional priority
pollutant organic compounds [Table 14].
Organics characterization of the effluent resulted in the identifi-
cation of 22 compounds and tentative identification of 2 additional
ones [Tables 12-13]. Twenty-one of the 22 were also identified in
the Salsbury process wastewaters. Average concentrations ranged from
low-level detection at approximately 1 [jg/1 to a high of 2,600 pg/l
for orthonitroaniline. Of the 22 compounds identified, 14 are priority
pollutants. Separate characterization for selected organic priority
pollutant analyses was conducted as described above for the influent.
These data [Table 14] indicated the presence of 3 additional priority
pollutant organic compounds.
The ability of the Charles City WWTP to remove organic compounds
ranged from very effective to totally ineffective. Removal efficiencies
for neutral extractable organics (no removals calculated for volatile
-------
100
organics since series of grabs, not composites) for the period June 19
to 26 were:
Chemical Name
Removal
%
(Based on Mass)
p-chloronitrobenzene
17
A
chloronitrotoluene
38
4-chloro-3-nitrobenzamide
37
2,6-di chlorobenzami de
63
1,2-dichloro-3-nitrobenzene
79
2-phenylbenzimidazole
55
orthonitroaniline
4
paranitroaniline
83
nitrobenzene
59
orthonitrophenol
99
1,2,4-trichlorobenzene
68
As noted above, the treatment process was 99% effective in removing
orthonitrophenol. However, the process was only able to remove 17% of
the p-chloronitrobenzene, and orthonitroaniline passed through the plant
with only 4% removal. All of the above compounds were also found in the
Salsbury process wastewaters.
* Compound was tentatively identified but isomer structure could not be
confirmed.
-------
101
La Bounty Dump Site Groundwater
Groundwater collected between the LaBounty Dump and the Cedar
River [Figure 6] contained considerable concentrations of pollutants,
indicating contamination by leachate from the dump. BOD, COD and TOC
concentrations averaged 2,000, 7,100 and 2,300 mg/1, respectively
[Table 10]. BOD results for two of the three days' samples collected
indicated possible toxicity, since the BOD was consistently higher at
greater dilutions. Ammonia as nitrogen and phenols concentrations
were also significant, averaging 130 and 18 mg/1 respectively [Table 11].
As was the case with the Salsbury process wastewaters, most metals
concentrations were low, with the exception of arsenic, which was
considerably greater at 590 mg/1 [Table 8]. Present in the ground-
water samples, but not in the process wastewaters, was barium at 0.6
mg/1.
Organics characterization of the La Bounty site groundwater re-
sulted in the identification of 24 compounds, and the tentative identi-
fication of 1 additional compound [Tables 12-13]. Eighteen of the 24
were also present in the Salsbury process wastewaters during the study.
Conversely, 18 of the 26 compounds identified in the process wastewaters
were also identified in the groundwater samples. Average concentrations
ranged from low level detection of approximately 1 pg/1 to a high of
180,000 pg/1 for orthonitroani1ine. Eight compounds were identified
in concentrations of 1,000 pg/1 or greater. Of the 24 compounds identi-
fied, 14 are priority pollutants. Separate analyses by priority pol-
lutant methodology were also conducted on an equal-volume composite
comprised of three daily samples [Table 14]. These data indicated
the presence of 6 additional priority pollutant organic compounds.
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102
Groundwater Seep/Spring
Samples collected from the groundwater seep and spring sites on
the south bank of the Cedar River in downtown Charles City indicated
the presence of contamination from Salsbury Laboratories. Arsenic
averaged 0.36 mg/1 in the seep and 0.69 mg/1 in the spring [Table 8].
Organics characterization of the groundwater seep and spring resulted
in the identification of 14 and 16 compounds, respectively, and the
tentative identification of one additional compound, chloronitrotoluene
[Tables 12-13]. Of the 14 and 16 compounds identified, 13 and 15
respectively were also identified in the Salsbury process wastewaters.
Average concentrations ranged from low level detection of approximately
1 mg/1 to a high of 330 mg/1 for 1,1,2-trichloroethane in the spring.
Of the 14 organic compounds identified in the seep and 16 in the spring,
10 and 12, respectively, are priority pollutants.
Data collected from these two sites are consistent indicators of
the widespread presence of pollutants from Salsbury. Whether this
contamination consists of a continuing interchange between Salsbury
process wastewaters and the groundwaters, such as broken sewer(s) or
leaking equalization pond, or the flushing out of past contamination,
is unknown and beyond the scope of the NEIC study.
Cedar River Quality-La Bounty Dump Site
Results of samples collected upstream of and downstream from the
La Bounty dump site demonstrated that the site is leaching pollutants
to the Cedar River. Flow-proportional samples collected at Station
11, upstream of both the USGS gage station and the dump site
[Figure 6], indicated low arsenic concentrations, averaging 0.007 mg/1
or 11 kg (24 lb)/day over the three days of sampling [Table 8]. There
were two direct discharges between Station 11 and Station 12, which
was downstream from the La Bounty site and 90 m (300 ft) upstream of
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103
the Charles City WWTP discharge. The first is a 42-inch city storm
sewer carrying wastewaters from White Farm Equipment, and the second
a small overland discharge at the downstream end of the La Bounty
site carrying surface runoff, truck washings from Allied Contruction
Company and seepage from the La Bounty site [Figure 6]. Data collected
during the June 27 to 29 stream study, indicated these sources were
minor contributors of arsenic; based on flow rates at the time of
sampling, the White Farm discharge averaged 0.42 kg (0.96 lbs)/day of
arsenic, and the LaBounty discharge 0.15 kg (0.32 lbs)/day [Table 8].
The LaBounty discharge was also sampled earlier on June 21 and the
calculated arsenic load was 1.4 kg (3.1 lb)/day.
Arsenic levels at Station 12 downstream from the La Bounty site
and 90 m (300 ft) upstream of the Charles City WWTP discharge, averaged
0.042 mg/1, or 64 kg (140 lb)/day. Hence the stream picked up an
average arsenic load of 53 kg (116 lb)/day in the vicinity of the
La Bounty site, of which only approximately 1 lb/day can be attributed
to White Farm and the overland La Bounty discharge. It can also be
noted in [Table 8], that as the flow dropped over the three-day period
the arsenic loadings increased, reflecting the change in differential
head between the groundwater and the river. These data are good in-
dicators of the dynamic conditions that exist; it can be expected
that arsenic loadings both increase and decrease from those levels
found during the NEIC study.
On the last day of stream sampling (June 29) individual aliquots
from each of the 10-foot sampling segments were retained for arsenic
analysis. As can be observed in Figure 8, arsenic concentrations at
the downstream site, Station 12, were highest near the LaBounty dump
side of the river, tapering off toward the other side of the river.
These individual aliquots also served as a check against the compos-
ited value. The results for the aliquots were weighed with their
respective flows to form a composite value of 0.062 mg/1. The composite
value for that day formed by continually flow-proportioning across
the stream was 0.055 mg/1, which agrees well with the 0.062 value.
-------
1
09
oa
07
06
05
04
03
02
01
00
Stream Width, Feet
Figure 8. Cedar River Arsenic Profile Uostream of (Station 11) and Downstream from (Station 12)
LaGounty Dump Site - Charles City, Iowa - June 29, 1978
-------
105
Organics characterization data also demonstrated the leaching of
pollutants from the dump site to the Cedar River. Data collected at the
upstream control Station 11, indicated the presence of 3 organic compounds
[Tables 12-13], all 3 of which were also identified in Salsbury process
wastewaters. Although the process wastewaters enter the Charles City
WtfTP and discharge downstream from the La Bounty site and, therefore,
should not have affected the control station, Salsbury contaminants
were found in upstream sources, as previously discussed, including
the cooling water discharge and the groundwater spring and seep. In
addition to these upstream sources, data collected at the upstream
control station above these sources, the suspension bridge, indicated
the low level presence of 8 organic compounds [Tables 12-13], 7 of
which were also identified in the Salsbury process wastewaters. These
data raise the possibilities of additional upstream groundwater contri-
butions contaminated with Salsbury1s wastes and/or a minor influence
of backwater from Wildwood Creek which carries the cooling water dis-
charges [Figure 6].
Downstream from the La Bounty dump site at Station 12, 8 organic
compounds were identified [Tables 12-13], all of which were also identi-
fied in the La Bounty leachate samples. Of the 8 compounds identified,
6 are priority pollutants. Separate priority pollutant analysis on
the sample collected June 28, 1978 indicated the presence of one addi-
tional priority pollutant organic compound, di-(2 ethylhexyl)pthalate,
which was also identified in the upstream sample, but not in the La Bounty
leachate [Table 14]. It was, however, identified in the Salsbury
process wastewaters, the spring and seep and the upstream control
Station 10.
Based on the difference in concentrations between the upstream
and downstream stations and flow recorded at the USGS gage, the average
organic pollutant loadings to the Cedar River from leachate in the
-------
106
vicinity of the La Bounty dump were:
1,1,2-Trichloroethane
Orthonitroaniline
Aniline
8.2 kg/d (18 lb/d)
11 kg/d (25 lb/d)
1 kg/d (2.2 lb/d)
Characterization of the two direct discharges in the vicinity of
the La Bounty dump indicated they were insignificant in comparison to
leachate contributions. Characterization of the storm sewer discharge
identified 10 organic compounds, all of which are priority pollutants
[Tables 12-13]. Average concentrations were very low ranging approxi-
mately 1 (jg/1 to 1.9 pg/1. The LaBounty site direct discharge contained
8 organic compounds, 7 of which were also found in the La Bounty leachate
samples. Average concentrations for the two times this discharge was
sampled ranged from low level detection of approximately 1 pg/1 to a
high of 16 (jg/1 for orthonitroaniline. Organic loadings for any com-
pound from these two sources were less than 0.005 kg (0.01 lb)/day
based on flows at the time of sampling.
PERFORMANCE AUDIT
During the June 19-30 NEIC study, evaluations of self-monitoring
procedures practiced by Salsbury Laboratories and the Charles City
WWTP were conducted consisting of interviews with Salsbury and Charles
City personnel and observations of equipment and procedures.
Salsbury Laboratories
The NEIC evaluation of Salsbury Laboratories' self-monitoring
practices indicated the following procedures deviated from prescribed/
recommended techniques:
-------
107
Sampling Techniques
1. Twenty-four hour composite samples of the process wastewater
discharges to the city sewerage system were collected by automat-
ically collecting equal-volume aliquots every approximately one
minute into an unrefrigerated plastic container. Since the flow
rate is not constant, these composites were not flow proportional
as prescribed by the Iowa DEQ Operation Permit No. 5-34-05-0-01
[Appendix A]. Composite samples for BOD, TSS and phenols must
also be maintained at 4°C during collection as prescribed by
304h regulations promulgated pursuant to the Federal Water Pollu-
tion Control Act (FWPCA).
2. The pH and color values reported to the Iowa DEQ were determined
on the 24-hour composite samples, not a grab sample as required
by the Iowa DEQ Operation Permit. According to Mr. Neil Leipzig,
an engineer with Salsbury Laboratories, this procedure had been
reported to the IDEQ, and the Company received no response.
3. Phenolic compounds samples were taken from the composite referenced
in #1 above. 304h procedures of the FWPC Act require glass sampling
containers. Samples should also be preserved with phosphoric
acid and copper sulfate during collection of a composite sample.
4. BOD composite samples collected on Monday through Tuesday were
refrigerated after collection and held until Friday for analysis.
304h regulation of the FWPC Act require that holding time not
exceed six hours.
-------
108
Flow Monitoring
1. As noted previously Salsbury Laboratories measures process waste-
water flows to the Charles City sewerage system with a magnetic
flow meter and recorder installed on the influent line to the
equalization basin. NEIC measurements during the study indicated
these flows are consistently low (77% of actual flows from 6/20
to 6/26). Hence pollutant load data contained in self-monitored
reports would also be low.
Analytical Procedures
The June 20, 1978, performance audit of analytical procedures
indicated a generally good understanding and performance of required
analyses [see Appendix F for complete evaluation]. There were, however,
a number of practices which were contrary to prescribed/ recommended
procedures:
1. No reference chemical standard such as glucose-glutamic acid was
in routine use for checking the BOD procedure. Periodic use of
such a reference material is necessary to demonstrate the quality
of the dilution water, the effectiveness of the seed and the
technique of the analyst.
2. Examination of the Company's BOD data indicated poor agreement
between different dilutions of the same sample. Further investi-
gations indicated that sample aliquots for the test were being
taken from the settled supernatant of the original samples.
This procedure could produce low results; all samples should be
thoroughly mixed before aliquots are withdrawn for analysis.
-------
109
3. No required pre-washing of filters was performed in the TSS analyses.
4. The analytical procedures for barium, chromium, copper, lead and
zinc did not include the required digestion step. Since a small
amount of suspended material is present in the samples, omission
of this step may lead to slightly low results.
5. The total arsenic procedure performed by Salsbury included an
ashing treatment developed in-house to reduce organic arsenic to
inorganic arsenic. Although past testing has been conducted
which reportedly confirms the accuracy of this method, as well
as the acceptable results on the performance sample NEIC provided
[see below], this does represent an alternate procedure and re-
quires agency approval.
Though not specifically required for lab procedures, the following
were recommended to Company personnel as being desirable lab practices:
1. Calibrate the analytical balance each day it is used and make a
permanent record of the calibrations.
2. Use a thermometer calibrated against an NBS thermometer or equiva-
lent procedure.
3. Use an oil free aquarium pump to aerate dilution water.
4. Establish and document a quality control program to include:
a. Routine analysis of analysis of reference chemical materials
for those parameters where applicable;
b. 10% duplication of testing to establish precision of analyses;
c. Addition of known amounts of chemical constituents to samples on
a periodic basis to establish recovery levels;
d. Participation in a sample split program with another
reputable lab on a yearly basis.
Performance samples were provided during the NEIC audit for
subsequent analyses. Results were:
-------
110
Parameter
Reported Value
True
Value
Rating
pH Sample 1
7.60
1.9
Marginal
Non-filterable Residue-BC
910
mg/1
884
mg/1
Acceptable
Phenol
0.072
mg/1
0.13
mg/1
Unacceptable
COD Sample 1
138
mg/1
114
mg/1
Marginal
COD Sample 2
430
mg/1
419
mg/1
Acceptable
TOC Sample 1
45
mg/1
44.8
mg/1
Acceptable
TOC Sample 2
190
mg/1
165
mg/1
Acceptable
BOD* Sample 1
19
mg/1
28.7
mg/1
Acceptable
BOD* Sample 2
212
mg/1
264
mg/1
Acceptable
Arsenic Sample 1
0.037
mg/1
0.040
mg/1
Acceptable
Arsenic Sample 2
0.272
mg/1
0.300
mg/1
Acceptable
Chromium Sample 1
0.091
mg/1
0.060
mg/1
Marginal
Chromium Sample 2
0.26
mg/1
0.250
mg/1
Acceptable
Copper Sample 1
0.055
mg/1
0.040
mg/1
Acceptable
Copper Sample 2
0.38
mg/1
0.350
mg/1
Acceptable
Zinc Sample 1
0.090
mg/1
0.060
mg/1
Acceptable
Zinc Sample 2
0.40
mg/1
0.400
mg/1
Acceptable
Selenium Sample 1
1.8
mg/1
0.020
mg/1
Unacceptable
Selenium Sample 2
5.41
mg/1
0.050
mg/1
Unacceptable
Mercury Sample 1
0.0014
mg/1
0.003
mg/1
Acceptable
Mercury Sample 2
0.0036
mg/1
0.008
mg/1
Acceptable
Cadmium Sample 1
0.009
mg/1
0.010
mg/1
Acceptable
Cadmium Sample 2
0.056
mg/1
0.070
mg/1
Acceptable
Lead Sample 1
0.035
mg/1
0.080
mg/1
Marginal
Lead Sample 2
0.27
mg/1
0.400
mg/1
Acceptable
* Hach Chemical Company, Ames, Iowa.
** The acceptance criteria for pH was taken from statistical data for
EPA Laboratory Performance Evaluation WP 002; no such data exists
for the above TSS sample but results were acceptable because the
reported value was very close to the true value; limits for the
phenolic sample were set by the manufacturer, Environmental Research
Associations, at +.02 mg/1; the remainder of the above parameters
were judged on the basis of EPA Performance Evaluation Samples WP 003.
-------
Ill
Charles City, Iowa WWTP
The NEIC evaluation of the permittee's self-monitoring practices
indicated the following procedures deviated from the prescribed/reco-
mmended techniques:
Sampling Techniques
1. Composite samples were collected by automatically collecting
(ISCO 1580 Sampler) equal-volume aliquots every 20 minutes into
an unrefrigerated plastic jug. Since the flow rate is not constant,
these composites were not flow proportional as required by the
NPDES permit [Appendix A]. Furthermore, 304h regulations of the
FWPC Act require samples for BOD, TSS and ammonia nitrogen by
maintained at 4°C. Once the plant personnel were informed of
this they immediately began refrigerating their automatic samplers
with ice.
2. Although Charles City personnel collect all required NPDES and
Iowa DEQ Operating Permit samples, Salsbury Laboratories performs
the analyses for ammonia nitrogen, all required metals, and phenolic
compounds. Samples are reportedly brought over to Salsbury Labora-
tories immediately after collection and then analyzed shortly
thereafter. 304h regulations of the FWPC Act require that phenolic
compounds samples be collected in glass not plastic. They should
also be preserved during collection with phosphoric acid and
copper sulfate.
3. The pH was determined on the composites, not grabs as required
by the NPDES Permit.
-------
112
Flow Monitoring
1. When the NEIC study commenced there was no flow accuracy verifica-
tion procedure in use at the Charles City V/WTP. Operators were
instructed by NEIC in performing flow calculations by taking
head measurements at the primary device, a 12-inch Parshall flume
and verifying accuracy and making minor adjustments at the trans-
mitter and recorder.
Analytical Procedures
1. Dilution water was prepared once per week [see Appendix F for more
details of lab audit]. It must be prepared prior to each test
or at least the phosphate buffer has to be omitted until just
prior to testing.
2. Blank samples of dilution water often had a BOD of 1-2 mg/1, most
likely a result of algal growth observed on the bottom of the
dilution water bottles. Blanks with a BOD as great as 2 mg/1
were used in reporting data. Samples where the dilution water
control depletes by more than 0.2 mg/1 must be voided for BOD
testing.
3. The dissolved oxygen probe used in the BOD procedure was calibrated
every other week against the Winkler method using PAO as the
titrant. The probe must be calibrated each day it is used.
4. No reference standard such as glucose-glutamic acid was in routine
use for checking the BOD procedure. Periodic use of such a refer-
ence standard is necessary to demonstrate the quality of the
dilution water and the technique of the analyst.
-------
113
5. The temperature of the BOD incubator bath was 22°C rather than
the required 20°±1°C.
6. The desiccant used for TSS analyses was non-indicating CaCl2.
An indicating desiccant is required.
7. For TSS analyses, Schleicher and Schuell 47 mm glass fiber filters,
which have an approximate thickness of 0.75 mm, were used. A
Reeves Angle 934A or H or equivalent is required rather than the
thick glass fiber filter referenced above.
8. During the TSS analysis no required pre-washing of filters was
performed.
9. Reference buffer solution for pH testing was stored in an open
beaker. Although the buffer was changed weekly, it should be
protected from evaporation and the laboratory environment both
of which could affect calibrations.
Though not specifically required by the NPDES or IDEQ permits,
the following were recommended to plant personnel as being desirable
lab practices.
1. Calibrate the analytical balance each day it is used and make a
permanent record of the calibrations.
2. Check distilled water every three months for minerals and heavy
metals or measure conductivity.
3. Periodically clean the dilution water bottle with 10% HC1 or
equivalent and rinse thoroughly.
4. Use thermometer calibrated against NBS thermometer or equiv-
alent procedure.
-------
114
5. Establish and document a quality control program to include:
a. Routine analysis of BOD reference material.
b. At least 10% duplication of testing.
c. Annual split sample program with State or other
reputable lab.
Performance samples were provided during the NEIC audit for sub-
sequent analyses. Results were:
True Value Reported Value
Parameter mg/1 mg/1 % Deviation Rating
37 Acceptable
34 Acceptable
9
The acceptance limits used for BOD are taken from results of EPA
Performance Evaluation 003, 1976. No criteria are available for judging
the TSS sample. It is, however, reasonably close to the true value and
therefore should be considered slightly low but acceptable.
B0D5
bod5
TSS
264
28.7
957
166
19
870
BIOLOGICAL STUDIES
Mutagen Testing
As noted in the "Survey Methods" section, analyses for mutagenic
activity were performed on 13 samples collected from five stations,
including the La Bounty dump site groundwater (Station 06), the
Salsbury process wastewaters (Station 01), the Salsbury cooling water
discharge (Station 02), the Charles City WWTP influent (Station 03),
and the Charles City WWTP effluent (Station 04). The purpose of
the tests was to determine the mutagenicity and potential carcino-
genicity of the wastes. The criteria for determination of a positive
-------
115
result include: 1) the substance must demonstrate a mutagenic activity
ratio* of 2.5 or greater, and 2) the substance must show a typical
dose-response relationship, i.e., the substance causes increasing
numbers of revertants with increasing doses of material over optimum
volumes.
All samples, including the presurvey grab sample, collected from
the Salsbury Laboratories process wastewaters, (Station 01) showed
mutagenic activity ratios higher than 2.5 with Salmonella tester strain
TA 98 [Table 16]. The mutagenic activity ratio is a measure of the
tester strain mutation rate compared to control rates. A mutagenic
activity ratio of 2.5 or greater correlates closely (>90% probability)
with inducement of cancer in laboratory animals by organic compounds.2'3'4
Further testing showed a typical dose-response relationship [Table 17,
Figure 9] between the tester strain TA 98 and concentrated extracts
from samples collected at Station 01, illustrating an increasing number
of revertant colonies with increasing concentrations of sample. The
optimum concentrations, causing highest reversion rates, occurred
with the basic extract from the composite sample collected on June 22
(60 ml equivalent sample volume) and the acidic extract from the sample
collected June 23 (11 ml equivalent sample volume). Larger volumes
of extract could not be tested because they exceeded the limits of
the test or were toxic to the bacterial tester strain [Table 17].
Mutagenic substances were not detected in the single composite
sample collected from the Salsbury Laboratories cooling water dis-
charge (Station 02). Concentrated aliquots of sample did not demon-
strate elevated mutation reversion rates with any of the Salmonella
tester strains. The sample concentrates were screened individually
and in the presence of microsomal rat liver preparations [see Methods,
* The mutagenic activity ratio is defined as E-C/c, where E is the
average number of mutant colonies per test with the sample added;
C is the corresponding value for the control, and c is the
historical control value of 40 averaged over 100 or more tests.
-------
Table 16
Summary of Mutagen Tests (Ames Bacterial Assay)
Salsbury Laboratories/Charles City, Iowa
April-August, 1978
Station Number
& Description
Sample Type
Date-Tlme
Collected
Extract
pH
Mutagen Activity8
Result
Mutaqenic Activity Ratio15
Range
01
GrabC
4/27
Base
+
<1 0-4.2
Salsbury Labs Process
1100
Neutral
+
<1 0-5.0
Wastewaters at Effluent
Acid
-
From Equalization Pond
01
Composlte^
6/21
Base
+
<1.0-5 8
Salsbury Labs Process
Acid
+
<1 0-3.5
Wastewaters at Effluent
From Equalization Pond
Composi te
6/22
Base
¦fr
<1 0-3 5
Acid
+
<1 0-4 1
Composite
6/23
Base
+
<1 0-3.6
Acid
+
<1.0-8.7
02
Composite
6/21
Base
_
Salsbury Labs Cooling
Acid
-
Waters at Discharge to
Unnamed Drainage to
Wildwood Creek
03
Composite
6/21
Base
<1.0-6 5
Charles City WWTP
Acid
+
<1.0-3.4
Influent Following
Bar Screen
Composite
6/23
Base
~
<1 0-3.2
Acid
+
<1.0-5.1
04
Composite
6/21
Base
-
Charles City WWTP
Acid
-
Effluent at Discharge
From Final Clarifier
Composite
6/22
Base
+
<1 0-3 3
Acid
+
<1.0-4 4
Composite
6/23
Base
-
Acid
<1.0-3.8
06
Grab
6/20
Base
-
La Bounty Site
1228
Acid
+
<1.0-5 2
Groundwater Drawn from
Wei 1 Point Between
Grab
6/21
Base
+
<1 0-19.6
La Bounty Dump
0615
Acid
+
<1 0-8.8
and Cedar River
Grab
6/22
Base
+
<1 0-10.7
1135
Acid
+
<1 0-6.0
a Criteria for determination of positive result = 1) the substance must demonstrate a mutagenic activity
ratio of 2 5 or greater, and 2) the substance must
c _ p show a typical dose-response relationship,
b Mutagenic Activity Ratio = —;—' where E is the no. of colonies/experimental plate
c C is the no. of colonies/control plate
c is the historical control value of 40 averaged over 100 tests
c Grab samples, day listed is date sampled
d Compositing period was 0700-0700. Date listed is day period ended
-------
Act
tio
4 0
4.2
3.4
3.2
2.5
2 5
1 4
1.0
1 0
1.0
1.0
5 0
3 9
3 6
2 6
2 1
1 0
1 0
1.0
5 8
3.9
2 3
1 2
1 0
1 0
1 0
3 5
3 2
2 4
1 3
1 0
8 3
6 6
3 8
3 2
2 4
1 6
1 0
1 0
1 0
Table 17
Mutagenic Activity of Salsbury Laboratories/Charles City
Samples on Salmonella Tester Strain TA 98
Apri1, June 1978
a Volume of Sample No. of Revertant
Sample Date-Time Extract Concentrate Tested Equivalent Volume Colonies Per Plate
Type Collected pH (ul) of Sample (ml) Control'3 Experimental0
Grab 4/27 1100 Base 400 64 0 22 183
350 56 0 193
300 48 0 160
250 40 0 153
200 32 0 126
150 24 0 126
100 16 0 79
75 12 0 16
50 8 0 42
25 4 0 25
10 1.6 18
Neutral 150 24 0 22 223
100 16.0 181
- 75 12.0 168
60 10 0 128
50 8 0 107
35 6.0 45
25 4 0 47
10 1.6 37
Composite 6/21 Base 500 62.0 24 t
400 50 0 247
300 37 0 181
200 25 0 116
100 12 0 73
75 9 3 50
25 3 1 37
10 1.2 15
6/21 Acid 300 37 0 24 t
200 25 0 t
150 19 0 t
100 12 0 164
75 9 3 154
50 6 2 118
25 3 1 75
10 12 27
Composite 6/22 Base 500 60 0 24 356
400 48 0 288
300 36.0 177
200 24 0 154
100 12 0 122
75 9 0 89
50 6 0 60
25 3.0 46
10 1.2 26
-------
Actl
tio
4 1
3 3
1.5
1.0
3 6
3 6
2.3
1 7
1 0
1 0
1 0
1 0
1 0
8 7
e 4
4 2
2 4
1 9
1 2
: 1 0
:l 0
:1.0
6 5
4 6
4 3
1 8
2 1
d 0
d 0
cl.O
3 4
3 4
2.8
2 2
1 4
a 0
O 0
<1.0
Table 17 (Cont'd.)
Mutagenic Activity of Salsbury Laboratories/Charles City
Samples on Salmonella Tester Strain TA 98
April, June 1978
Volume of Sample No. of Revertant
Sample3 Oate-Time Extract Concentrate Tested Equivalent Volume Colonies Per Plate
Type Collected pH (ul) of Sample (ml) Control'1 Experimental0
Acid 300 36 0 24 t
200 24.0 t
100 12.0 t
75 9.0 187
50 6 0 155
25 3.0 85
10 1.2 58
Composite 6/23 Base 500 76.0 24 169
400 61 0 167
300 46.0 116
200 30 0 93
100 15 0 49
75 11.0 35
50 7.6 48
25 3 8 35
10 1.5 25
Acid 200 30.0 24 t
100 15.0 t
75 11.0 371
50 7 6 362.
25 3 8 194j
20 3.1 120
10 1.5 100
7 5 1.1 72
5 0 0.8 49
2 5 0 4 37
1 0 0.2 35
Composite 6/21 Base 500 72.0 24 t
400 58 0 285
300 43.0 210
200 29 0 197
100 14 0 94
75 11 0 108
50 7 2 61
25 3.6 37
10 1.4 28
Acid 500 72 0 24 161
400 58 0 159
300 43 0 137
200 29 0 113
100 14 0 82
75 11 0 57
50 7.2 46
25 3.6 37
'0 14
-------
Act
tio
3 2
2 2
1 4
1 5
1 0
1 0
1 0
1 0
1 0
5 1
3 2
2 6
2.3
1 4
1 2
1 0
1 0
3.3
2 6
1 9
1 1
1 0
1 0
1 0
1 0
1.0
4 4
4 0
2 8
2.0
1 2
1 0
:l 0
:l 0
: 1.0
3.8
3 6
2 0
1 9
:l 0
: 1 0
: 1 0
:l 0
:1 0
Table 17 (Cont'd )
Mutagenic Activity of Salsbury Laboratories/Charles City
Samples on Salmonella Tester Strain TA 98
April, June 1978
Sample
Type
Date-Time
Collected
Extract
pH
Volume of Sample
Concentrate Tested Equivalent Volume
No of Revertant
Colonies Per Plate
(Ul)
of Sample (ml)
Control''
Experimental
500
68.0
24
152
400
54.0
110
300
41 0
79
200
27 0
84
100
14 0
37
75
10 0
30
50
6 8
30
25
3.4
24
10
1.4
13
500
68 0
24
t
400
54.0
228
300
41 0
151
200
27 0
129
100
14 0
115
75
10 0
78
50
6 8
72
25
3 4
38
10
1 4
27
500
72 0
24
157
400
58 0
129
300
43 0
99
200
29 0
66
100
14.0
41
75
11 0
34
50
7.2
29
25
3 6
28
10
1.4
24
500
72.0
24
198
400
58 0
186
300
43 0
136
200
29 0
103
100
14.0
71
75
11 0
64
50
7 2
49
25
3.6
37
10
1.4
26
500
72 0
24
174
400
58 0
168
300
43 0
104
200
29 0
102
•100
14 0
57
75
11.0
55
50
7 2
38
25
3 6
33
10
1 4
25
Composite
6/23
Base
Aci d
Composite
6/22
Base
Acid
Composite
6/23
Acid
-------
u Actl
atio
5 2
3 8
2 2
1 1
<1 0
19 6
16.4
11 9
8 2
4 2
2 6
<1.0
8.8
5 6
3 1
1 8
1 5
<1 0
<1 0
10 7
7 1
4 1
3 1
3 2
1 8
1.4
<1 0
<1.0
<1.0
Table 17 (Cont'd )
Mutagenic Activity of Salsbury Laboratories/Charles City
Samples on Salmonella Tester Strain TA 98
April, June 1978
Volume of Sample No. of Revertant
Sample Date-Time Extract Concentrate Tested Equivalent Volume Colonies Per Plate
Type Collected pH (ul) of Sample (ml) Control Experimental0
Grab 6/20 1288 Acid 30 4 8 24 t
20 3.2 231
10 16 174
5 0 0 8 113
2 5 0.4 67
1.0 0.2 35
Grab 6/21 0615 Base 400 59.0 24 t
300 44 0 808
200 30 0 679
100 15.0 501
75 11.0 353
50 7 4 191
25 3.7 127
10 1.5 58
Acid
50
25
20
10
7 5
5
2.5
1
7 4
3 7
3.0
1.5
1.1
0 7
0 4
0.1
24
t
374
249.
146
94
83
60
31
Grab 6/22 1135 Base 100 16.0 24 t
75 12.0 452
50 7 8 308
25 3 9 187
20 3.1 147
15 2.3 151
10 16 96
7 5 12 81
5.0 0 8 56
2 5 0 4 42
1.0 0.2 26
-------
Table 17 (Cont1d.)
Mutagenic Activity of Salsbury Laboratories/Charles City
Samples on Salmonella Tester Strain TA 98
Apri1, June 1978
Volume of Sample
No of Revertant
J
Station Number
Sample3
Date-Time Extract
Concentrate Tested
Equivalent Volume
Colonies Per Plate
Mutagenic Activity
& Description
Type
Collected pH
-------
122
Appendix D]. In both test systems, the Ames Test protocol for presence
of mutagens was not satisfied.
Analysis of both samples collected from the Charles City Iowa
WWTP influent (Station 03) demonstrated the presence of mutagenic
material. All sample extract concentrates from these samples showed
a typical dose-response relationship [Figure 9] and a mutagenic
activity ratio of 2.5 or higher [Tables 16-17]. Greatest reversion
rates were obtained from the basic extract concentrate from the
sample collected on June 21 (mutagenic activity ratio of 6.5) and
the acidic extract of the sample collected June 23 (mutagenic activity
ratio of 5.1).
To determine if mutagenic substances were being discharged from
the Charles City, Iowa WWTP, samples were collected at the discharge
from the final clarifier (Station 04). Two of the 3 composite samples
collected displayed mutagenic activity ratios greater than 2.5 and
typical dose-response relationships [Tables 16-17, Figure 9]. The
sample collected on June 21 did not satisfy the Ames Test require-
ments for positive mutagenic activity. However, both the basic and
the acidic extract from the sample collected June 22 and the acidic
extract from the June 23 composite sample displayed elevated reversion
rates greater than 2.5 times the control. Equivalent volumes of
wastewater that showed a mutagenicity ratio of 2.5 or higher ranged
from 2 ml to 72 ml. These results indicate that mutagenic and po-
tentially carcinogenic substances were being discharged from the
Charles City, Iowa WWTP.
Three grab samples of groundwater were drawn from a well between
the La Bounty dump and the Cedar River. These were analyzed to
determine the extent of mutagenic activity in the leachate that may
find its way to the river. All three samples displayed a mutagenic
activity ratio of 2.5 or higher [Tables 16-17]. Only one aliquot
tested (the basic extract from the sample collected on June 20) failed
-------
400
100
Salsbury Process Wastewaters
6/21/78
Salsbury Process Wastewaters
4/27/78
123
300 ¦
300
200
200
100 -
100 "
70
60
80
50
40
30
20
10
70
CO
00
a
c
400
400
Salsburv Process Wastewaters
6/23/78
Salsbury Process Wastewaters
6/22/78
C
to
4_»
£ 300
a>
a
«+-
o
L.
a)
1 200.
200
100 - i
100
80
CO
70
40
50
30
20
10
70
50
60
300
300
Charles Citv WWTP Influent
6/23/78
Charles City WUTP Influent
G/21/78
250
250
200
200
150
100 -
100 -
LEGEU0 Eouivalent ml of Fflluent
q. BASE ~Figure 9 Salsbury Laboratories/Charles City, Iowa
Mutagen Testing Dose Response Curves
• ACID
• ."'FUTRAL
-------
300
2 bO -
200 •
150
100
50 -
124
Charles City Ill/TP Effluent
6/22/78
300 -
200
200
1 DO
100 "
50
Charles Citv IfllTP Tffluent
G/23/78
______ —•
10 20 30
-r
40
I
50 60
70
o400
300
200 -
100 - i
II
r
10
LaBounty Dunp Site Groundwater
6/20/78
I
20
30
T
40
T
50
T
GO
COO -»
GOO "
400 -
200 -
X
LaBountv Dunn Site Groundwater
6/21/78
70
10
20
T
30
40
50
T
GO
—P
70
LEGEND
800 -i
GOO
400 ~
200 ~
LaBounty Dump Site Groundwater
G/22/78
I
10
-I 1 I i 1 r
20 30 40 50 60 70
Eouivalent nl of fffluent
Figure 9 Salsbury Laboratories/Charles City, !owa
Mutagen Testing Dose Resnonse Curves
-------
125
to show a high dose-response. This occurred because larger volumes
of sample could not be tested due to toxicity to the tester strain.
Relatively low equivalent volumes of sample (2 ml from all samples in
both the acidic and the basic extract) caused a mutagenic activity
ratio of 2.5 or higher. In the case of samples collected from this
site on June 21 the acid extract showed a mutagenic activity ratio of
8.8 from only 4 ml equivalent sample volume. The basic extract had a
mutagenic activity ratio as high as 19.6 from only 44 ml equivalent
sample volume. All sample extracts displayed a typical dose-response
relationship, with increasing volumes of sample having increased mutation
activity [Figure 9]. The results of mutagen analyses of samples collected
from Station 06 demonstrate the presence of mutagens and potential
carcinogens in the groundwater samples.
Results of the Standard Ames Test clearly show that wastewater
and groundwater samples collected during the Salsbury Laboratories,
Charles City, Iowa Project contained mutagens and potential carcino-
gens. Concentrated extracts of the samples satisfied both require-
ments for determining if mutagenic and potential carcinogenic sub-
stances are present.
Biomonitoring
The Salsbury process wastewater and groundwater from the La Bounty
dump site were determined to be acutely toxic to fish. The 96-hour
LC50* for the Salsbury process wastewater was determined to be an
18.6% effluent concentration [Tables 18 and 19, Figure 10]. The La
Bounty dump groundwater was significantly more toxic than the Salsbury
process wastewater, having a calculated 96-hour LC5o of 3.8% [Tables 20
and 21, Figure 11]. As noted in previous sections, both of these
sources contain an extremely complex mixture of organic and inorganic
compounds. It was not within the scope of the NEIC study to define
* LC5o indicates the concentration (actual or interpolated) at which
50% of the test organisms died or would be expected to die.
-------
126
Table 18
96-HOUR FLOW-THROUGH SURVIVAL DATA
June, 1978
SALSBURY LABORATORIES PROCESS WASTEWATER
% Survival
Time Period Effluent Concentration (%)
Control 4.0
(Cedar River Water)
7.2
12.8
22.4
30.0
40.0
24-hour
100
100
100
100
100
100
20
48-hour
100
100
100
100
100
65
0
72-hour
100
100
100
95
80
0
96-hour
95
100
100
85
25
Table 20
96-HOUR FLOW-THROUGH SURVIVAL DATA
June, 1978
LA BOUNTY DUMP SITE GROUNDWATER
% Survival
Time Period Effluent Concentration (%)
Control 1.1 2.0 3.5 6.2 8.2 11.0
(Cedar River Water)
24-hour
100
100
100
100
10 0 0
48-hour
100
100
100
100
0
72-hour
95
100
100
90
96-hour
95
100
85
70
-------
Probit Analysis on Dose
Salsbury Process Wastewater
June, 1978
^USABILITY
DOSE:
9b PERCENT
fiducial limits
LOWER
UPPER
0.01
0.07261 543
-0.31943077
0.13282647
0.02
0.03536166
-0 .26208109
0.14183049
o.n?
0.094 £65^7
-0.22590312
0.14775682
0 .OA
C.100*8321
-0 .1 9883728
0.15235565
0.05
0.1 05 73CS6
-0.17692524
0.15620444
0.06
0.11010806
-0.15836436
0.15957006
0.07
0.11394601
-3.14216830
0.16259927
0.05
0.11738244
-0.1 2773 71 3
0.16538203
U.09
0.12050773
-0.11467758
0.16797786
0.10
0.12333457
-0 .1 0271 734
0.17042842
0.15
0 .1 35 <19544
-0.05 397728
0.18135293
0 . 20
0 .1 44 761 83
-0 .01 646380
0.19125895
0 .25
0.15288314
0.01445358
0.201 U2330
iJ .30
0.16017634
0.04083930
0.21 1 1 71 02
0.35
0 .1 6693457
0.06375 797
0 .22210602
U . 40
0 .1 7334747
0.08381111
0.23417671
0.4 3
0.17955202
0.10138061
0.24768738
0 . 50
0 .1 8565821
0.1167o307
0.26239233
0.55
0.1 9176439
0.13024494
0 .27999788
0.60
D • 1 9 79 68 9b
0.14213316
0.29918983
0 o 6 5
0.20433184
0.15275525
0 .32069157
0.70
0.21114008
0.16244907
0.34485143
0.7 5
0.21843327
0.17156186
0 .37227208
U .30
0.22635458
0.18047449
0.404 04116
0.85
C.23602097
0.1 89o7883
0 .44225628
0.90
0.24793185
0.20001423
0.49158550
0.91
0.2505086S
0 .20235668
0.50365386
U.92
0.253933°8
0 .20484663
0.51681928
0.93
0.i5 737040
0.20752517
0.53135467
0.94
0.26120825
0.21045106
0.54765^04
0.95
0.26553556
0.21371328
0.56631833
0*9
0.27072321
0.i1745709
0.58333535
0.97
0 o 27705044
0.22194636
0 .61 5515 2u
0 .98
0.28545475
0.22775511
0.65130630
0.99
0.29870098
0.2366184 2
0.70929669
-------
Figure 10
Probit Analysis on Dose
Salsbury Process Wastewater
Probability June, 1978
1 .T ~
~ • • •
f . J 4 « • •
• •
• •
• II
0.3
3 ~ 7
0. S
0.6
O.T
0
0.0
ro
00
• •
• • X
• •
• •
• • •
X • •
• •
011 ~ • # •
• t • •
L?01 LD05 LD10 L02S LD5G LD75 LD93 1095 L09S
0 .073 0.106 0.1 23 0 .1 53 0.166 0.213 0.243 0.266 0.299 DOSE
-------
Probit Analysis on Dose
Groundwater from La Bounty Dump Site
June, 1978
PROBABILITY
DOSE
95 PERCENT
FIDUCIAL LIMITS
LOWER
UPPFR
0.01
0.00941749
-Q.11531290
0.02273459
0.02
0 .01273567
-0.09427694
0.02504909
0.03
0.014 cJ4095
-0.08118889
0.02661270
o .ru
0.01 6 4 2 A 6 7
-0.07135576
0.02785667
0 .0 5
0.01 771291
-0.06337648
0.02892403
U .06
0.01880940
-0.05665073
0.02988136
0.07
0.01977080
-0 .05079850
0.03076571
J. 0 3
0 .U20631 63
-0.04560115
0.031o0014
0.09
0.02141451
-0.04091551
0.0324002 7
0.10
P .0221351 6
-0.03664314
0.03317737
0.15
0.02511884
-0.01952512
0.03596591
0 .20
0.02749017
-0.00694364
0.04100031
J. 25
0.02952456
0.00266573
0.0,4 5 64 5 39
0 .30
0 .0 31 3 51 51
0 .01000483
0.05110817
0.35
0 .0 3 30444 4
0 .01 555737
0.05741801
0.40
0.03461)088
0 .01 976697
0.064 4 6466
0 .45
0.03620512
0.02^02630
0.07209537
0 .50
0.03773472
0.02564020
0.03019985
0.5 5
0.03926432
0.027824 66
0.03873326
0 .60
0.04031856
0.02972818
0.09772029
0.65
0 .04 2-42499
0.0314 55 1 5
0.10724957
0.70
0.04 41 1 7 97.
0.03308451
0.11748259
U.75
0.0459^488
0 .03462427
0.12363421
0 .80
0.04797927
0.03632590
0.14129752
0.85
0 ,05035060
0.03810653
0.1 5613277
0.90
0.05333428
0 .04020521
0 .1 74 94066
0.91
0 .054 J5492
0.04069421
0.17950123
0.92
0 .05483781
0.04121894
0.13446217
0.93
0.05569864
0. 041 7888 1
0.18992409
U.9 4
0.05666004
Q.04241731
0.19603215
G.95
0.05775653
0.04312495
0.2030075 9
0.95
0 .05904477
0 .04 394528
0.21121390
0.97
0 .0 60 o2 S4 9
0.04493951
0.221316 78
0.73
0,06273377
0 .04 624052
0.23476744
0.99
0.06605195
0.04825253
0 .2550058 3
-------
130
the specific compound or group of compounds that produced toxicity.
Both the primary clarifier overflow and effluent wastewater
from the Charles City WWTP were determined to be acutely toxic
to fish. The LC50 for the primary clarifier overflow and effluent
were calculated to be 41.6% and 57.3% wastewater concentration
respectively [Tables 22, 23, 24, 25, and Figures 12 and 13]. These
data indicate that treatment by the Charles City WWTP does not
significantly reduce the toxicity of the combined municipal and
Salsbury process wastewater.
Fish Survival and Palatability
Some mortality occurred among the exposed fish at all but
two sites (Stations 40 and 45) including the reference fish at
Station 10 [Table 26]. The average survival rate for all test
sites was 69%. At Station 44, which was 9 meters downstream from
the Charles City WWTP discharge, mortality was significantly higher
than among the reference fish. None of the test fish at this site
survived a 96-hour exposure, indicating that the final effluent from
the WWTP was acutely toxic to fish at the point of discharge to the
Cedar River. The mortality observed among the reference fish and
other test sites is attributable to induced stress unrelated to
toxicity. Dissolved oxygen concentrations, pH range, and water tem-
perature were adequate for fish survival at all test sites throughout
the exposure period [Table 26]. Necropsy of dead test fish showed
the fish to be in a state of advanced sexual development. The majority
of dead fish were observed to be gravid females. It can be concluded
that mortality of test fish except at Station 44 was attributable
to a combination of stress factors resulting from containment in
the exposure cages and physical stress related to advanced sexual
development.
-------
.-re
Probit Analysis on Dose
Groundwater from La Bounty DumD Site
Probabili ty June, 1978
1.0
0,9
0."
0.7
0.6
n.*
n .4
'J. 3
0.2
rj.T
• • • •
• • •
• •
• ft
• • •
• •
• •
• ft
I I
III
X
• •
• • •
• Ml
L 001 L010 LUd5 LD30 LD75 LD90 LD95 L0V9
U *00° 0*018 0*022 U.030 0 .038 O.L'66 0.053 0.U58 0.066 UJSt
-------
132
Table 22
96-HOUR FLOW-THROUGH SURVIVAL DATA
June, 1978
CHARLES CITY VWTP
FINAL EFFLUENT
% Survival
Time Period Effluent Concentration (%)
Control 10 18 32 56 75 100
(Cedar River Water)
24-hour
100
100
100
100
90
65
0
48-hour
100
100
100
90
80
40
72-hour
100
100
100
90
75
30
96-hour
100
100
100
85
75
5
Table 23
96-HOUR FLOW-THROUGH SURVIVAL DATA
June, 1978
CHARLES CITY WWTP
PRIMARY CLARIFIER OVERFLOW
% Survival
Time Period Effluent Concentration %
Control 6.0 10.8 19.2 33.6 45.0 60.0
(Cedar River Water)
24-hour
100
100
100
100
80
65
0
48-hour
100
100
100
100
80
60
72-hour
100
100
100
100
80
50
96-hour
100
100
100
95
80
45
-------
IuuiO CH
Probit Analysis on Dose
Charles City WWTP Primary Clarifier Overflow
JUNE, 1978
PROSABILITY
uOSE
95 PERCENT
FIDUCIAL limits
LOWER
UPPER
0.01
0.16376248
-0.1490143d
0.26581364
0.02
0 .1 9771410
-Q.08391457
0.28717924
0.03
C.21608297
-0.04287392
0.30036850
0.06
0.22990116
-0 .01218594
0.3104 o 686
0.0 5
0.24114116
0.01264492
0.31381663
C .06
0 .2507US21
0.03366743
0.32603604
0.07
0.25909663
0.05200219
0.33246392
0.08
0 » Z 66607 4 5
0.06833079
0 .33330731
0 .09
0.27343324
0.00310001
0.3437G263
0.10
0.27972600
0.09661924
0 .34 374488
0.15
0.50575899
0.15163452
0.37057914
0 .20
0.32644019
0.1933L210
0.33940913
0 . 25
0.34419954
0.223o5 216
0.40703818
0 .30
0.36013990
0.25834437
U.42440200
0 .35
0.57491102
0.284 25 287
0 .44209792
0 .AO
0.3SS92736
0.30 7174 4 7
U.46055265
0.4 5
0.40243834
0.32767129
0.43008791
o,so
0.415 8 3432
0.34619333
0.50095825
0.55
0.42913029
0.36316524
0.52338872
0 . 60
0.4427412?
0.37896331
0.54762223
0 ,65
0.45675762
0.39398230
0.57393007
0.70
0.4715 2374
G.40862291
0.60294339
0.75
0.487A 6910
0.42333702
0.6352858U
0.80
0 .505 21 9A 5
0.43870157
0 .672320 37
0.R5
0.5 259 09 64
0.45560097
0.71549854
0.90
0.55194264
J. 475764 1 5
0. 7731 o43 9
0.91
0.55823039
0.48049453
0.78701600
0.92
0.565Uo119
0.43556281
0.80209226
0.93
0.57257201
0.49112236
0 .81372469
0.94
0.58096042
0.49724751
0.83736219
0.95
0.5905 2745
0,50416234
0.85368 92S
0.96
0 .6017 o7A8
0.51220125
0.63333099
0.97
0 .01 558567
0.52197496
0 . 914 84 8 6 3
C .93
0 .£>3395454
0 . 5 34 81 066
0.95 323794
0.99
0 .6629061 5
0.55475217
1 .021 761 74
-------
Probabi1ity
1 • "i ~
o. =i
O.-
0.6
e.s
C.'>
;.3
Figure 12
Probit Analysis on Dose
Charles City WWTP Primary Clarifier Overflow
June, 1978
^ •
• •
. x
CjO
.fV
0.?
• •
. X
0.1
J.o
L001
0.169
ID 0 c
0.241
ld n
0,2 SO
LO 25
0.34 4
L 050
0 .41 6
LU7S
0.487
L090
0.552
L09S
0.591
L099
C.663
-------
Probit Analysis on Dose
Charles City WWTP Effluent
June, 1978
PROBABILITY
DOSE
95 PERCENT
fiducial limits
LOWER
UPPER
0.01
0.19404 07 7
-0.25888100
0.344 39234
0.02
0 .2 38 $U?40
-0.16434314
0.37621536
0.03
0 ,26671 1 88
-0.10477444
0.39681908
0.04
0.28793277
-0.06023241
0.41258727
0.05
0.30519433
-0.0 24205793t>33Q5
1 . 15 72771 5
0.9 A
0.32706222
0.70032155
1 .18425033
0.95
0.841 754 52
0.71119725
1 .21 51304 5
0.95
0.85901607
0.72383336
1 . 25 1 55 1 5 4
0 • ?7
0.88023697
0.73918777
1 . 29.350785
0.98
0e908446 4 5
0.75933701
1.35053353
0,99
G .95 290808
0 .79061 151
1 .451 61 69U
-------
Figure 13
Probit Analysis on Dose
Charles City WWTP Effluent
Probability June, 1978
1.0 ~
d.9
0.1
0.7
0.6
0.5
0.4
0.^
0.2
0.1
O.D
X ,
• •
• •
• • •
• •
t •
• •
• •
• • •
I ..
• •
• • •
• • • •
CO
-------
26
In Situ Fish Exposure Data
Cedar River, Charles City, Iowa
22 June - 29 June, 1978
Station Number
10 40 20 42 43 44 45 46 47
22 June 1978
pH
8 0
7.6
8
0
8.0
temperature °C
20.0
19 0
20
0
20.0
Dissolved oxygen concentration mg/1
7.0
6 5
7
0
7.0
Number of surviving fish
11
6
6
6
6
6
6
6
23 June 1978
PH
8 0
7.9
8 0
7.7
*
temperature °C
21 0
17 0
21 0
17 0
21.0
21 0
22.
0
21 0
Dissolved oxygen concentration mg/1
7 0
7.0
6 5
6.5
8 0
8.5
8
5
8.0
Number of surviving fish
10
6
5
6
6
5
6
6
24 June 1978
PH
7 9
7 8
7 4
7.2
temperature °C
20.0
17 9
17 0
15 0
Dissolved oxygen concentration mg/1
6 5
7.5
6.5
7 0
Number of surviving fish
9
6
5
6
25 June 1978
pH
8 0
8 0
7 6
7 8
8 0
7 9
8
2
8 1
7.6
temperature °C
23 0
18.0
14 0
19.0
21.5
19 0
23
0
23 0
22.0
Dissolved oxygen concentration mg/1
7 0
6 5
6.5
7.0
7.0
Number of surviving fish
9
6
5
5
5
2
6
6
6
26 June 1978
pH
8 0
8 0
7 7
7 9
8 2
8 1
8
1
8 2
8 1
temperature °C
22 0
18.0
13.0
17.0
23 0
22 0
24
0
23 0
22 0
Dissolved oxygen concentration mg/1
7 0
7 0
6 5
5 0
8.0
7 5
7.
.5
8.0
7 0
Number of surviving fish
8
6
5
5
5
0
6
6
6
27 June 1978
PH
8 1
7 9
7 8
7 8
8.0
7
8
7 7
7.9
temperature °C
23 0
18 5
16 5
14.5
24.0
24
0
24.0
23 0
Dissolved oxygen concentration mg/1
6 5
6 8
6 0
5.5
7.5
7
0
7 0
6 5
Number of surviving fish
8
6
4
5
5
6
5
5
28 June 1978
pH
7.8
7.8
7 8
7 6
7 9
7 8
temperature °C
24.0
19 0
17 0
15.0
25 0
22.0
Dissolved oxygen concentration mg/1
6 5
6 5
6 5
5 5
7 5
7.0
Number of surviving fish
8
6
4
4
5
5
29 June 1978
pH
7 8
7 7
7.3
7 5
7 8
7
9
8 0
7 5
temperature °C
22 0
19 0
14 0
15 0
24 0
24
0
24 0
22 0
Dissolved oxygen concentration mg/1
4 5
6 5
6.0
6.5
7.0
6
5
7 0
7 0
Number of surviving fish
8
6
4
4
5
6
5
3
Ranqe
PH
7
8-8 1
7.
7-8 0
7 4-8 0
7
.2-7 9
7.8-8 2
7 6-8 1
7 8
-8 2
7 7-8 2
7 5-8
temperature °C
20
0-24 0
17
0-19.0
13.0-21 0
15.
.0-19.0
20 0-25.0
19.0-22 0
20.0
-24 0
20 0-24 0
22 0-2:
Dissolved oxygen concentration mg/1
4
5-7 0
6.
5-7.0
6.0-6.5
5,
.0-7.0
6.0-8 0
6 0-8 5
6.5
-8 5
7 0-8 0
6 5-7.
% of surviving fish
73
100
66
66
83
0
100
83
50
-------
138
Palatability tests were performed by an independent food science
laboratory on all fish that survived the entire exposure period. The
tests showed that flesh of fish exposed at Stations 43, adjacent
to the La Bounty dump site and Station 45, 200 meters downstream
from the Charles City WWTP discharge, were significantly off-flavored
and significantly less desirable as a food product [Table 27].
All other fish samples were judged not significantly different
from the reference fish at Station 10.
Indigenous Fish Populations
An average of 147 fish were captured per unit effort (1-day
net trap) ranging from a low of 86 at Station 43, adjacent to the
La Bounty Dump site, to a high of 200 at Station 47, approximately
10 km (6 mi) downstream from the Charles City WWTP discharge
[Tables 6 and 28]. The diversity index*, ranging from 2.2 to 2.8,
was not significantly different at any of the four study sites;
however, there was a noticeable trend toward increasing numbers
of coarse and pollution tolerant fish species (suckers and bullheads)
from the most upstream site at the suspension bridge to the most
downstream site at the Midway Bridge. This trend does not appear
related to altering habitat as all sampling sites were chosen to
reflect similar environmental characteristics. Nor does it appear
related to adverse physical and chemical conditions, since water
temperature, pH range, and dissolved oxygen concentration during
the study were adequate for all species of fish at all sampling
sites [Table 26]. However, these data represent atypical values
obtained when the Cedar River was in a falling stage following near
flood conditions which would tend to mask any normally occurring
physical or chemical deficiencies. Seasonal or intermittent dis-
solved oxygen depression, a phenomenon common to shallow water streams
receiving wastewater inputs during low flow periods, could account
* A mathematical expression pertaining to the variety of species
within a given association of organisms.
-------
Station
10 (Reference)
40
41
42
43
45
46
47
139
Table 27
Fish Palatability Data
Cedar River, Charles City, Iowa
June, 1978
Off-flavor
6.67
6.00
6.33
6.17
5.67*
5.42*
6.04
6.25
Desi rabi1ity
4.42
4.12
4.33
4.08
3.70*
3.29*
3.92
4.25
*Significantly different from reference at the five percent level.
Score Range: 7 - No off flavor - very desirable
1 - Extreme off flavor - very undesirable
-------
Table 28
FISH POPULATION DATA
CEDAR RIVER, CHARLES CITY, IOWA
27 June - 28 June, 1978
Species
No a
Station 10
Length*5
Mean Range
No
Station 43
Length''
3 Mean Range
No.
Station 48
Length*5
.a Mean Range
Station 47
Length'5
No.a Mean Range
Cyprinus carpio (Carp)
2
27 9
—
6
24.1 20.3-31.5
Nocomis biguttatas (Horny-
head chub)
1
12.5
9
13.0
7.0-16.0
10
9.3 7.0-13.5
Notemigonus crysoleucus
(Golden Shiner)
2
11.25
11.0-11.5
Notropis spilopterus
(Spotfin shiner)
15
7 7 7.0-9 0
9
10.0
8.5-12.0
42
7.8 6.5-12.5
Pimpephales promelas
(Fathead minnow)
1
7 5
—
1
8.0
Carpoides cyprinus
(Quillback carpsucker)
1
27 9
Carpoides velifer
(Carpsucker)
1
35.6
3
22.0 15.2-33 0
Ictalurus melas
(Black bullhead)
16
13.2 7.6-20.3
30
14.5 7.6-22.9
61
14.1
7.6-25.4
99
13.3 7.6-22 9
Ictalurus punctatus
(Channel catfish)
3
36.4
25.4-38 1
1
9.1
Noturus exils
(Slender madtom)
4
8.9 6 4-10.2
12
6.4 3.75-10.0
24
15 1
7.6-20 3
1
15.0
Ambloplites rupestris
(Rockbass)
3
15 4 10.2-20.3
4
14.0
12.7-15 2
Lepomis cyanellus
(Green sunfish)
64
10 2 7.6-15 2
5
8.9 5.1-12 7
16
12.6
8 9-15 2
21
11 9 7.6-14.6
-------
Table 28 (Cont'd.)
FISH POPULATION DATA
CEDAR RIVER, CHARLES CITY, IOWA
27 June - 28 June, 1978
Species
» a
No
Station
Length
Mean
10
b
Range
Station 43
Length'5
No.a Mean Range
Station 48
Length''
No.S Mean Range
Station 47
Length'5
No 3 Mean
Range
Lepomis humilis (Orange
spotted sunfish)
9
7 9
5.1-11.4
Lepomis macrochirus
(Bluegi 11)
2
10 2
--
1
5.1
1 19.1
Lepomis
(Hybrid sunfish)
30
6 8
3.7-8 7
Pomoxfs annularis
(White crappie)
23
13 9
7.6-19 1
9
17.2 7 6-22.9
10 14 4 8.9-30 5
4 16.5 15
2-17.8
Remorina albescens
(White suckerfish)
4
35 2
30.5-41 9
7
21.4 17.8-22.9
8 27.3 20.3-38.1
14 29.7 22.
.9-35 6
Crustacea (Crayfish)
17
168
170
174
Chrysemys picta
(Painted turtle)
Clemmys insculpta
(Wood turtle)
Trionyx spiniferus
(Spiny softshell turtle)
Total Taxia 11 13 14 12
Total Fish Species 9 10 13 11
Total Fish 153 86 150 200
Fish Diversity Index 24 27 28 22
a Unit Effort-1 trap day
b Total Length in CM
-------
142
for the increased numbers of tolerant fishes in the lower reach of
the study area. The Cedar River at the uppermost study site at the
suspension bridge has been physically restructured by the incorpora-
tion of overflow spillway dams and midstream channelling. This re-
structuring has created a much greater potential water reservoir
than is available downstream. This increased reservoir would be
more resistant to dissolved oxygen depression during low flow
periods, creating a local environment conducive to maintaining
a population of fishes with higher dissolved oxygen requirements.
Periphyton
The Cedar River at Station 10 at the suspension bridge was used
as a reference station, since it is upstream of known sources of
pollution in the Charles City area. Diatoms comprised about 94%
of the total periphytic algal population of 2823/cm2 with small num-
bers of filamentous green and blue-green algae [Table 29]. Periphytic
chlorophyll a concentration was 79.2 pg/cm2 with an ash-free weight
of 171 pg/cm2. The autotrophic index, a biomass-chlorophyll a ratio,
was 2.2 [Table 30].
Evaluation of periphyton at Station 40 in Wildwood creek near
the confluence with the Cedar River indicated diatoms comprised about
96% of the periphytic algal population of 2482/cm2 which was similar
to Station 10. The periphytic chlorophyll a concentration was
10.8 pg/cm2 with an ash-free weight of 112 pg/cm2 for an autotro-
phic index of 10.4. The chlorophyll a concentration was considerably
less [10.8 versus 79.2 pg/cm2] at Station 40 than at Station 10.
The only known discharge into Wildwood Creek in the Charles City
area is the combined cooling water and storm runoff from Salsbury
Laboratories.
The groundwater spring input to the Cedar River upstream from
the foot bridge (Station 20) had a periphytic algal population of
-------
Table 29
CEDAR RIVER PERIPHYTIC ALGAL POPULATIONS
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 19-30, 1978
Stati on
No.
Location
Number/cm (%)
Filamentous Other
Blue-Green Green Green
Diatoms
Pennate Centric
Total
10 Cedar River at Suspension Bridge,
upstream of Wildwood Creek, near
Right Bank 43(2)
40 Wildwood Creek at Confluence with
Cedar River 19(1)
20 Cedar River at Spring Discharge
90M (300 ft) downstream from
Main Street Bridge near Left Bank 199(2)
42 Cedar River near Left Bank, ground-
water seep discharge approximately
60M (200 ft) upstream of Highway 18
Bridge 177(4)
43 Cedar River 100M (100 yards) upstream
of Iowa Terminal Railroad Bridge
near Left Bank 272(20)
44 Cedar River 9M (30 ft) downstream
from Charles City WWTP discharge near
Right Bank 185(17)
45 Cedar River - 200M (200 yds) down-
stream from Charles City WWTP near
Right Bank 102(11)
46 Cedar River 0.8Km (0.5mi) down-
stream from Charles City WWTP
near Left Bank 38(2)
123(4)
57(2) 9(<1)
85(1)
14(<1)
7(1)
14(1)
2652(94) 5(d)
2392(96) 5(d)
8610(97) 0
3839(95) 7(d)
1077(79) 7(d)
909(83) 5(d)
832(88) 0
1425(96) 9(1)
2823
2482
8894
4037
1357
1099
941
1486
-------
144
Table 30
CEDAR RIVER PERIPHYTIC CHLOROPHYLL a^
ASH-FREE WEIGHT, AND AUTOTROPHIC INDEX
SALSBURY LABORATORIES/CHARLES CITY, IOWA
June 19-30, 1978
No.
Station Chlorophyll a
2
Location mg/cm
Ash-free
Weight
2
mg/cm
Autotrophic
Index
10
Cedar River at Suspen-
sion Bridge, upstream
of Wildwood Creek near
Right Bank
79.2
171
2.2
40
Wildwood Creek at Con-
fluence with Cedar
River
10.8
112
10.4
20
Cedar River at Spring
Discharge 90M (300 ft)
downstream from Main
Street Bridge near
Left Bank
40.9
77
1.9
42
Cedar River near Left
Bank, groundwater seep
discharge approximately
60M (200 ft) upstream at
Highway 18 Bridge
39.6
84
2.1
43
Cedar River 91M (100yds)
upstream of Iowa Terminal
Railroad Bridge near
Left Bank
8.2
178
21.7
44
Cedar River 9M (30ft)
downstream from Charles
City WWTP discharge near
Right Bank
1.1
158
143.6
45
Cedar River - 180M (200 yds)
downstream from Charles
City WWTP near Right Bank
3.6
46
12.8
46
Cedar River 0.8Km (0.5mi)
downstream from Charles
City WWTP near Left
Bank
11.2
144
12.9
-------
145
8894/cm2 with diatoms comprising 97% of this population. Periphy-
tic chlorophyll a concentration was 40.9 pg/cm2 with an ash-free weight
of 77 pg/cm2 for an autotrophic index of 1.1. Although population
density was higher, the chlorophyll a concentration was approximately
half that found at the reference station. Only one slide was avail-
able for preservation in formalin and subsequent determination of
periphytic algal density at Station 20 versus 5 or 6 slides available
at all other stations. The high population density may be an anomaly
based on differences in number of slides.
The Cedar River inlet into which groundwater seepage flowed,
Station 42, downstream from the foot bridge had a periphytic algal
population of 4032/cm2 with 95% diatoms. Periphytic chlorophyll a
concentration was 39.6 pg/cm2 with an ash-free weight of 84 pg/cm2
for an autotrophic index of 2.1. Similar to station 20, periphytic
algal population density at Station 42 was higher and the chlorophyll
a concentration was approximately half that found at reference
Station 10.
Station 43 upstream of the Iowa Terminal Bridge and adjacent to
the La Bounty dump had a periphytic algal population density of
1357/cm2 compared to 2823/cm2 at reference Station 10. Population
composition also changed with 79% versus 94% diatoms and 20% versus
2% filamentous blue-green algae at reference Station 10. Periphytic
chlorophyll a concentration was 8.2 pg/cm2 versus 79.2 pg/cm2 with an
ash-free weight of 178 pg/cm2 versus 171 pg/cm2 for an autotorphic
index of 21.7 compared to 2.2 for reference Station 10. The increase
in blue-green algae and autotrophic index indicate degraded water
quality. The decreased densities and chlorophyll a concentration
indicate toxic conditions for periphytic algae. Leachate from the La
Bounty dump vicinity appeared to affect Cedar River periphyton.
Station 44 immediately down stream from the Charles City WWTP
discharge had a periphytic algal population density of 1099/cm2 with
83% diatoms and 17% filamentous blue-green algae. Periphytic chloro-
phyll a concentration was 1.1 pg/cm2 with an ash-free weight of 158
-------
146
(jg/cm2 for an autotrophic index of 143.6. The presence of many stalked
protozoa (Vorticella) commonly associated with sewage and the low
concentration of chlorophyll a account for the high autotrophic index.
These data indicate the effluent from the Charles City WWTP adversely
affect Cedar River periphyton. Toxic conditions downstream from the
Charles City WWTP as indicated by the low periphytic algal population
desnsities and chlorophyll a concentration are especially noteworthy
because treated domestic wastewaters usually stimulate rather than
inhibit algal growth.
Periphytic algal population densities at the two downstream Stations,
45 and 46, ranged from 941 to 1486/cm2, respectively, with 88 to 97%
diatoms. The periphytic chlorophyll a concentration ranged from 3.6
to 11.2 pg/cm2, respectively, and the autotrophic index was 12.8 to
12.9. These data indicated periphytic algal populations at Stations
45 and 46 were stressed compared to reference Station 10. Although
population composition at Station 46 (96% diatoms and 2% filamentous
blue-green algae) was similar to the reference station, complete re-
covery was not evident in any river reach examined.
Periphyton results from the Cedar River at Midway Bridge approxi-
mately 10 km (6 mi) downstream from the Charles City WWTP, Station
47, were not comparable to those from upstream locations because the
periphyton racks were only exposed for 5 days versus 8 days at the
other stations. No evaluation of periphyton from this station was
made.
Benthic Macroinvertebrates
The Cedar River, from about 100 m (325 ft) upstream of the High-
way 18 bridge, is basically an impoundment formed by two dams. This
river reach is characterized by a soft mud or muck bottom-type with
an abundance of detritus and debris. Downstream from the Highway 18
bridge, the river is characterized by a well entrenched channel,
-------
147
moderate gradient, a hard compacted stream bed overlain with loose
cobble and occasionally alternative riffles and pools [Fig. 7].
Two factors extant of the June 24 to 25, 1978 benthos study ap-
peared to have a direct and substantial impact on the benthic popula-
tion. First, high water levels with concommitant amounts of debris,
scouring effects and increased silt loads occurred immediately prior
to the study. Such conditions create what Waters (1972) has termed
"catastrophic drift"6 (extreme physical disturbance of the bottom
fauna) and results in gross reduction in the aquatic invertebrate
population level. Second, by late June, most benthic invertebrates
have gone through the reproductive stage, and in the case of aquatic
insects, for example, a large part of the population have become
winged adults and are, therefore, no longer aquatic. Thus, a sub-
stantial reduction of the resident standing crop occurs.
In the impounded portion of the river from the suspension bridge
downstream to the dams near the Highway 18 bridge (Stations 10, 76 to
79) the benthos consisted of aquatic worms, crustacea, aquatic insects
and snails [Table 31]. The community structure reflected the pool
environment of the river. No benthic evidence of excessive organic
pollution or of toxic conditions was found in this river reach which
included the confluence with Wildwood Creek.
A cursory examination at Stations 83 to 85 in Wildwood Creek
revealed the benthic community included mayflies, midges and snails.
In combination with findings in the Cedar River immediately down-
stream from the Wildwood Creek confluence (Stations 78 to 79) it ap-
peared that Wildwood Creek did not adversely impact the benthic inverte-
brate community.
The next river reach examined was the riffle area near the Highway
18 bridge (Stations 60 to 62), about 200 m (650 ft) downstream of the
impounded area. The invertebrates in this reach consisted of a diverse
community of aquatic worms, crayfish, and aquatic insects. No benthic
-------
Table 31
BENTHOS
CEDAR RIVER IN CHARLES CITY, IOWA VICINITY
June, 1978
_____ 4^
(Numbers per meter2) 00
STATIONS
Organisms 10, 76-77 78 & 79 60 62 43-65 66-68 44, 70-71 82 80 & 81 72-74
Turbellaria
Tncladidia
Dugesia
13
Annelida
01igochaeta
Limnodrilus
Lumbn cuius
Hirudinea
Macrobdella
Crustacea
Amphipoda
Gammarus
Hyallella
Decopoda
Orconectes
481
156
2784
247
13
Insecta
Ephemeroptera
Baetis
Ephemerel la
Heptagenia
Hexaqenia
Isonychia
Potomanthus
Stenonema
Tricorythodes
Odonata
Coenaqri on
Plecoptera
Nemoura
Megaloptera
Corydalus
Coleoptera
Stenelmis
Trichoptera
Cheumatophysche
Hydropsyche
13
13
39
13
26
13
-------
Table 31 (Cont1d.)
BENTHOS
CEDAR RIVER IN CHARLES CITY, IOWA VICINITY
June, 1978
Organisms
10, 76-77
78 & 79
(Numbers per meter2)
STATIONS
60 62 43-65
66-68
44, 70-71
82
80 & 81
72-74
Diptera
Simul l mm
Ablabesmyia
Chironomus
Diamesa
Finfeldia
Harmschia
Kiefferulus
Polypedi1um
Tanytarsus
Mollusca
Pelecypoda
Sphaerium
Lamps111 s
Gastropoda
Goniobasi s
Helisoma
Ph.ysa
Number of kinds
Number per m2
13
26
104
26
13
65
13
8
741
13
13
13
26
6
221
12
13
39
2
52
13
26
13
6
2862
3
65
15
13
65
6
377
Q = Samples collected qualitatively only
-------
150
evidence of organic or toxic pollution was found in this portion of
the Cedar River.
About 0.5 km (0.3 mi) further downstream at the La Bounty dump
site (Station 43, 65) the benthic population was reduced to two forms,
a dipteran and a snail. Such an abrupt change in the number of taxa
and in the standing crop indicated that leachate from the dump site
vicinity had an adverse effect on the benthos. About 100 m (328 ft)
downstream (Stations 66 to 68) of the railroad bridge, immediately
downstream from the La Bounty dump, a slight recovery was noted; a
community of aquatic worms, beetles, clams, and snails were found.
Near the outfall (Stations 44, 70 to 71) of the Charles City
WWTP, the river was degraded again; only three kinds of aquatic in-
sects were found, strongly indicating that degraded conditions existed
in the Cedar River reach adjacent to the WWTP.
At Station 82, about 0.8 km (0.5 mi) downstream from the WWTP,
the benthic community included pollution sensitive organisms such as
mayfly nymphs, hellgramites and midge larvae. This community structure
indicated improved water quality conditions.
At the next sampling site, Station 80 to 81, about 5 km (3 mi)
downstream from the WWTP, the benthos community was the most diverse
of any sampling reach in the stream. The 15 benthic forms found in
this riffle were indicative of good water quality. No benthic evidence
of organic or toxic pollution was found in this portion of the river.
The most downstream site studied, at the Midway bridge (Station
72 to 74), approximately 10 km (6 mi) downstream from the WWTP, was
similar to the upstream impounded area (Station 75-79). The community
of aquatic worms, mayflies, dipterans and clams reflected no benthic
evidence of organic pollution or toxic conditions in this river reach.
-------
151
VI. TOXICITY AND HEALTH EFFECTS OF POLLUTANTS
IDENTIFIED DURING NEIC STUDY
During the June 19 to 30, 1978 NEIC study, 46 organic compounds
were identified, including four tentative identifications, and five
metals were analyzed for and identified. In order to assess toxicity
and health effects, all these compounds and metals were searched in
the Registry of Toxic Effects of Chemical Substances (RTECS), which
is an annual compilation prepared by the National Institute for Occupa-
tional Safety and Health. The Registry contains toxicity data for
approximately 21,000 substances, but does not presently include all
chemicals for which toxic effects have been found. Chemical substances
in TRECS have been selected primarily for the toxic effect produced
by single doses, some lethal and some non-lethal. It should be re-
membered that substances whose principal toxic effects are from ex-
posure over a long period of time are not presently included. Toxic
information on each chemical substance is determined by examining and
evaluating the published medical, biological, engineering, chemical
and trade information and data for each substance selected.
The 51 compounds and metals noted above were then searched in the
Toxline data base, which is a computerized bibliographic retrieval
system for toxicology containing more than 650,000 records taken from
material published in primary journals. It is part of the MEDLINE
file from the National Library of Medicine and is composed of ten
subfiles:
(1) Chemical-Biological Activities, 1965-(taken from Chemical
Abstracts, Biochemistry Sections)
(2) Toxicity Bibliography 1968-(a subset of Index Medicus)
(3) Abstracts on Health Effects of Environmental Pollutants
1971-(published by Biological Abstracts)
-------
152
(4) International Pharmaceutical Abstracts 1970-(published by
the American Society of Hospital Pharmacists)
(5) Pesticides Abstracts 1967-(complied by EPA)
(6) Environmental Mutagen Information Center 1969-(Dept. of
Energy, Oak Ridge National Lab)
(7) Environmental Teratology Information Center 1950-(Dept. of
Energy, Oak Ridge National Lab)
(8) Toxic Materials Information Center (Dept. of Energy, Oak
Ridge National Lab)
(9) Teratology file 1971-1974 (a collection of citations on
teratology complied by the National Library of Medicine)
(10) The Hayes File on Pesticides
(a collection of more than 10,000 citations on the Health
aspects of pesticides complied by Dr. W.J. Hayes, Jr., EPA)
The RTECS search yielded information on 40 of the 51 compounds and
metals. The Toxline search yielded 457 citations to human health
effects from the 40 compounds, providing support to the toxic infor-
mation from RTECS. Information on the 40 compounds is summarized in
Table 32. Twenty-eight of these 40 compounds are listed as priority
pollutants.
The 11 compounds and metals which were not located in RTECS are:
barium; benzene, l,2-dichloro-3-nitro; 2,6-dichlorobenzamide; 2-phenyl-
benzimidazole; 2-octanol; benzofuran; bromodichloromethane; benzene,
l-chloro-2-methyl-3-nitro;benzonitrile, l-chloro-6-nitro;benzamide,
4-chloro-3-nitro; and dinitrochlorobenzene isomer. All of the above,
except dinitrochlorobenzene isomer (which cannot be searched without
more information) were searched in Toxline as well. No information
was discovered on toxic and health effects to humans.
-------
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT
Chemical Other Toxicity Data
Compound Name Molecular Abstracts Aquatic Toxicity Route of _ , , Type of Exposure
Formula Service No Entry |30C es Dose Dose Duration Effects Limits
Acetani1ide
C8H9N0
103-84-4
Am 1 ine
Aniline, o-Chloro-
Aniline, o-Nitro-
Aniline, p-Nitro
Arsenic
C6H7N
62-53-3 TLm96-100-10 ppm
C6H6C1N
Cg^6^2®2
95-51-2 TLm96:100-1Oppm
88-74-4
100-01-6
As
7440-38-2
Oral-human
Oral-rat
Oral-mouse
Intraperitoneal-mouse
Oral-dog
Intravenous-dog
Oral-guinea pig
Oral-human
Unreported-human
Oral-rat
Inhalation-rat
Skin-rat
Intraperitoneal-rat
Oral-mouse
Intraperi toneal-mouse
Subcutaneous-mouse
Unreported-mouse
Oral-cat
Inhalation-cat
Skin-cat
Intraperitoneal- rabbi t
Subcutaneous-rabbit
Skin-rabbit
Skin-guinea pig
Skin-guinea pig
Oral-mouse
Subcutaneous-cat
Skin-cat
Oral-rat
Oral-mouse
Oral-human
Oral-rat
Oral-mouse
Intraperitoneal-mouse
Intramuscular-mouse
Oral-bird, wild
Intravenous-mammal
Oral-human
Intramuscular-rat
Oral-mouse
Intraperitoneal-mouse
Subcutaneous-rabbit
LDLo 50 mg/kg
LD50 800 mg/kg
LD50 1,210 mg/kg
LDLo 1,000 mg/kg
LDLo 500 mg/kg
LDLo 300 mg/kg
LDLo-200 mg/kg
LDLo 50 mg/kg
LDLo 357 mg/kg
LD50 440 mg/kg
LCLo 250 ppm
LD50 1,400 mg/kg
LD50 1 ,400 mg/kg
LD50 464 mg/kg
LD50 492 mg/kg
LDLo 480 mg/kg
LD50 572 mg/kg
LDLo 1,750 mg/kg
LDLo 180 ppm
LDLo 254 mg/kg
LDLo.200 mg/kg
LDLo 1,000 mg/kg
LD50 820 mg/kg
LDLo.1,750 mg/kg
LDLo:1,290 mg/kg
LD50-256 mg/kg
LDLo 310 mg/kg
LD50.222 mg/kg
LD50.3,564 mg/kg
LD50'1,288 mg/kg
LDLo 5 mg/kg
L050:3249 mg/kg
LD50 812 mg/kg
LD50 250 mg/kg
LD50 800 mg/kg
LD50.75 mg/kg
LDLo:40 mg/kg
LDLo 5 mg/kg
LDLo 25 mg/kg
TDLo.120 mg/kg
TDLo 40 mg/kg
LDLo 300 mg/kg
OSHA std (air)
TWA 5 ppm (skin)
4H
8H
Preg.
Preg.
Terato-
genic
Terato-
genic
OSHA std (air)
TWA 1 ppm (skin)
OSHA std (air)3
TWA 500 ug/m
NI0SH recm std
(air) CI 2 M9/"i3
-------
Table 32 (Cont)
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Compound Name
Chemical
Molecular Abstracts Aquatic Toxicity'
Formula Service No.
a
Route of
Entry
Other Toxicity Data
- Species
Type of
Dose:
Dose Duration
Effects
Exposure
Limits
-------
T 12 (<
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Chemical Other Toxicity Data^
Compound Name Molecular Abstracts Aquatic Toxicity Route of _ , . Type of Exposure
Formula Service No Entry p Dose Dose Duration Effects Limits
Benzene,1,2,4- C6H3C1;
Trichloro-
Carbon tetrachloride CC1^
(Tetrachloromethane)
120-82-1" TLm96-10-lppm
56-23-5 TLm96 100-10 ppm
Oral-dog
Intravenous-dog
Oral-cat
Skin-cat
Oral-rabbit
Skin-rabbit
Intraperitoneal-guinea pig
Subcutaneous-guinea pig
Oral-mammal
Oral-rat
Oral-mouse
Intraperitoneal-mouse
Intramuscular-hamster
Oral-human
Oral-woman
Inhalation-human
Oral-woman
Oral-man
Inhalation-human
Oral-rat
Inhalation-rat
Inhalation-rat
LDLo:750 mg/kg
LDLo-150 mg/kg
LDLo 2,000 mg/kg
LDLo:25 g/kg
LDLo-700 mg/kg
LDLo:600 mg/kg
LDLo:500 mg/kg
LDLo:500 mg/kg
LDLo:1,000 mg/kg
LD50 756 mg/kg
LD50.766 mg/kg
LDLo:500 mg/kg
LDLo.25 mg/kg
LDLo 43 mg/kg
TDLo:1,800 mg/kg
TCLo:20 ppm
TOLo:1,800 mg/kg
TDLo:1,700 mg/kg
LCLo 1,000 ppm
LD50.2,800 mg/kg
LCLo.4,000 ppm
TCLo:300 ppm
4H
(6-15D
preg)
Systemic
Central
Nervous
System
Pulmonary
Central
Nervous
System
Terato-
genic
OSHA std (air)
TWA 10 ppm;
CI 25; Pk 200/
5M/4H
NI0SH recm std (air)
CI 2 ppm/60M
Intraperitoneal-rat
Subcutaneous-rat
Oral-mouse
Oral-mouse
Inhalation-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
LD50:1,500 mg/kg
TDLo-133 gm/kg 25 WI
LD50.12,800 mg/kg
TDLo 4,800 mg/kg 88DI
LC50.9,526 ppm 8H
LD50.4,675 mg/kg
LDLo:12 gm/kg
Neoplastic
Carcinogenic
-------
Table 32 (Cont)
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
_ . u Chemical Other Toxicity Data13
Compound Name Molecular Abstracts Aquatic Toxicity Route of I Tvoe~of r
Formula S.„,c. Ho E„,ry "SP-C. Eff
-------
laDle 3^ (Lont)
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Compound Name
Molecular
Chemical
Abstracts
Aquatic Toxicity Route of
Formula Service No
Other Toxicity Data
Type of
Exposure
Entry
Copper
Diphenylamine
Dipheny1 amine,
n-nitroso-
Ethane,
1,2-Dichloro-
(Ethylene Dichloride)
Cu 7440-50-8
C12H,XN 122-39-4
C12H10N20 86-30-6d
Intraperi toneal-mouse
Oral-human
Oral-rat
Oral-rat
Oral-guinea pig
Oral-rat
Oral-mouse
Oral-mouse
Subcutaneous-mouse
C2H4C12 107-06-2 TLm96 1,000-100 ppm Inhalation-human
LD50:3,500 ug/kg
LDLo-500 mg/kg
LDLo 3,000 mg/kg
TDLo:7,500 mg/kg
LD50 300 mg/kg
LD50 1,650 mg/kg
LD50-3,850 mg/kg
TDLo 410 gm/kg
TDLo:1,000 mg/kg
TCLo.4,000 ppm
Ethane,1,1,2,2-
Tetrachloro-
C2H2C1«
79-34-5
17-22D
preg
78WI
Terato-
gemc
Neoplastic
Neoplastic
Oral -human
TDLo 428 mg/kg
Oral-man
LDLo 810 mg/kg
Oral-human
LDLo 500 mg/kg
Oral-rat
LD50-680 mg/kg
Inhalation-rat
LCLo 1,000 ppm
4H
Intraperitoneal-rat
LDLo-600 mg/kg
Subcutaneous-rat
LDLo 500 mg/kg
Oral-mouse
LDLo 600 mg/kg -
Inhalation-mouse
LCLo-5,000 mg/m
2H
Intraperitoneal-mouse
LDLo 250 mg/kg
Subcutaneous-mouse
LDLo.380 mg/kg
Oral-dog
LDLo:2,000 mg/kg
Intravenous-dog
LDLo 175 mg/kg
Oral-rabbit
LD50. 860 mg/kg
Inhalation-rabbit
LCLo 3,000 ppm
7H
Subcutaneous-rabbi t
LDLo 1,200 mg/kg
Inhalation-pig
LCLo 3,000 ppm
7H
Inhal ati on-gui nea pig
LCLo 1,500 ppm
7H
Intraperitoneal-guinea pig
LDLo-600 mg/kg
Oral-human
TDLo.30 mg/kg
4H
Inhalation-rat
LCLo 1,000 ppm
Oral-human
LDLo 50 mg/kg
Intraperitoneal-mouse
LDLo 30 mg/kg
Oral-dog
LDLo-300 mg/kg
Intravenous-dog
LDLo:50 mg/kg
Subcutaneous-rabbit
LOLo.50 mg/kg
Central 0SHA std (air)
Nervous TWA 50 ppm
System CI 100,
Pk 200/5M/3H
NI0SH recm std (air)
TWA 5 ppm,
CI 15
Central 0SHA std (air)
Nervous TWA 5 ppm (skin)
System
cn
-------
Table 32 (cont)
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT
Chemical
Compound Name
Formula
Molecular Abstracts Aguatic.Toxicity Route of
Service No. Entry Spe*i« Dose
Dose
Type of
Duration
Other Toxicity Data
Effects
Limits
Exposure ,
en
00
Ethane, 1,1,1-
Trichloro-
(Methyl Chloroform)
Ethane, 1,1,2-
Trichloro-
Ethene, 1,1-
dichloro-
C2H3CI3
C2H2 C12
Ethylene, trans-1,-2- C12C2H2
dichloro-
(trans-1,2-dichloroethene)
Ethylene, Tetrachloro- C2C14
(Tetrachloroethene)
71-55-6 TLm96 100-10 ppm
79-00-5 TLm96:100-10 ppm
75-35-4 TLm96
1,000-100 ppm
156-60-5"-
127-18-4 TLm96:100-10 ppm
Oral-human
Inhalation-man
Inhalation-man
Inhalation-human
Oral-rat
Inhalation-rat
Inhalation-mouse
Intraperitoneal-mouse
Oral-dog
Intraperitoneal-dog
Intravenous-dog
Oral-rabbit
Subcutaneous-rabbit
Oral-guinea pig
Oral-human
Oral-rat
Inhalation-rat
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Intraperitoneal-dog
Intravenous-dog
Subcutaneous-rabbi t
Inhalation-human
Inhalation-rat
Oral-dog
Intravenous-dog
Subcutaneous-rabbit
Inhalation-human
Inhalation-mouse
Inhalation-cat
Inhalation-human
Oral-human
Inhalation-man
Inhalation-man
Inhalation-rat
LDLo 500 mg/kg
LCLo 27 gm/m3 10M
TCLo.350 ppm
TCLo:920 ppm 70M
LD50:14,300 mg/kg
LCLo:1,000 ppm
LCLo 11,000 ppm 2H
LD50 4,700 mg/kg
LD50:750 mg/kg
LD50.3,100 mg/kg
LDLo-95 mg/kg
LD50 5,660 mg/kg
LDLo 500 mg/kg
LD50 9,470 mg/kg
LDLo:50 mg/kg
LD50.1,140 mg/kg
LCLo.500 ppm 8H
LD50:994 mg/kg
LD50-227 mg/kg
LDLo-500 mg/kg
LDLo 450 mg/kg
LDLo-95 mg/kg
LDLo 500 mg/kg
TCLo-25 ppm
LCLo 10,000 ppm 24H
LDLo: 5,750 mg/kg
LDLo-225 mg/kg
LDLo 3,700 mg/kg
3
TCLo:4,800 mg/m 10M
LCLo 75,000 mg/m3 2H
LCLo:43,000 mg/m3 6H
TCLo 200 ppm
LDLo 500 mg/kg
TCLo:280 ppm 2H
TCLo 600 ppm 10M
LCLo:4,000 ppm 4H
OSHA std (air)
Psycho- TWA 350 ppm
tropic
Central NI0SH recm std (air)
Nervous CI 350 ppm/15M
System
OSHA std (air)
TWA 10 ppm (skin)
Systemic
TLV (air)
10 ppm
Central
Nervous
System
Systemic
OSHA std (air)
TWA 100 ppm,
CI 200,
PK 300/5M/3H
Eye
effects
Central
nervous NI0SH recm std (air)
system TWA 50 ppm,
CI 100 ppm/15M
-------
„ - 32 (
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Compound Name
Chemical
Molecular Abstracts Aquatic Toxicity
Formula Service No.
a
Other Toxicity Data
Route of _
Entry ' SPecleS
Type of
Dose: Dose Duration
Effects
Exposure
Limits
Oral-mouse
LD50 8,850 mg/kg
Inhalation-mouse
LCLo. 23,000 mg/m3
2H
Intraperitoneal-mouse
LD50-5.671 mg/kg
Oral-dog
LDLo 4,000 mg/kg
Intraperitoneal-dog
LD50:2,100 mg/kg
Intravenous-dog
LDLo-85 mg/kg
Oral-cat
LDLo'4,000 mg/kg
Oral-rabbi t
LDLo:5,000 mg/kg
Subcutaneous-rabbit
LDLo-2,000 mg/kg
Oral-human
LDLo 250 mg/kg 3
0SHA std (air)
Inhalation-human
TCLo:6,900 mg/m
10M
Central
TWA 100 ppm;
Nervous
CI 200; Pk300/5f
System
Inhalation-human
TCLo-160 ppm
83M
Central
Nervous
System
Inhalation-man
TCLo 110 ppm
8H
Irritant
NIOSH rec'm std
Oral-rat
LD50:4,920 mg/kg
(air) TWA 100
Inhalation-rat
LCLo-8,000 ppm
4H
150/10M ppm;
Oral-mouse
TDLo 135 gm/kg
27WI
Carcinogenic
Inhalation-mouse
LCLo:3,000 ppm
2H
Pk LSO/lOm
Intravenous-mouse
LD50 34 mg/kg
Oral-dog
LDLo-5,860 mg/kg
Intraperitoneal-dog
LD50:1,900 mg/kg
Intravenous-dog
LDLo 150 mg/kg
Subcutaneous-rabbit
LDLo:1,800 mg/kg
Oral-cat
LDLo.5,864 mg/kg
Inhalation-cat
LCLo:32,500 mg/m3
2H
Inhalation-guinea pig
LCLo:37,200 ppm
40M
Oral-rat
LD50 2,760 mg/kg
0SHA std (air)
Inhalation-rat
LCLo:2,000 ppm
4H
TWA 50 ppm
Oral-rat
LDLo 3,200 mg/kg
Inhalation-rat
LCLo:4,000 ppm
4H
Oral-rat
LD50 3,200 mg/kg
Oral-mouse
LDLo.3,200 mg/kg
Skin-rabbit
LD50.2,380 mg/kg
Ethylene, Trichloro-
(Trichloroethene)
C2HCL3
79-01-6
TLm96
1,000-100 ppm
3-Heptanone
Hexanal,
2-ethyl
1-Hexanol, 2,-
ethyl-
C7H140 106-35-4
C8H160 123-05-7
C8Hl80 104-76-7
en
vo
-------
Table 32 (Cont)
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Chemical Other Toxicity Oatab
Compound Name Molecular Abstracts Aquatic Toxicity3 Route of _ <-nprlp, Type of Exposure —¦
Formula Service No Entry p Dose Dose Duration Effects Limits g
Mercury
Methane, Dichloro-
(Methylene Chloride)
Hg
CH2C12
7439-97-6
75-09-2
TLm96
1,000-100 ppm
Methane,
Tribromo-
(Bromoform)
Phenol
CHBR,
c6h6o
75-25-2
108-95-2
TLm96-
100-10 ppm
Intraperitoneal-rat
Inhalation-rabbit
Inhalation-human
Oral-human
Inhalation-human
Oral-rat
Inhalation-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Inhalation-dog
Intraperitoneal-dog
Subcutaneous-dog
Intravenous-dog
Oral-rabbit
Subcutaneous-rabbit
Inhalation-guinea pig
Subcutaneous-mouse
Subcutaneous-rabbit
Oral-human
Oral-rat
Skin-rat
Intraperitoneal-rat
Subcutaneous-rat
Oral-mouse
Skin-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
Intravenous-mouse
Oral-dog
Parenteral-dog
Oral-cat
Subcutaneous-cat
Parenteral-cat
Oral-rabbit
Skin-rabbit
TDLo:400 mg/kg
LCLo:29 mg/m3
TCLo.500 ppm
LDLo:500 mg/kg
TCLo:
LD50-
LC50:
LD50
LD50.
LOLo:
LCLo:
LOLo
LDLo:
LDLo:
LDLo-
LDLo.
LCLo:
500 ppm
945 mg/kg
14,400 ppm
1,500 mg/kg
6,460 mg/kg
3,000 mg/kg
20,000 ppm
950 mg/kg
2,700 mg/kg
200 mg/kg
1,900 mg/kg
2,700 mg/kg
5,000 ppm
LD50:1,820 mg/kg
LDLo:410 mg/kg
LDLo.140mg/kg
LD50 414 mg/kg
LD50.669 mg/kg
LD50 250 mg/kg
LOLo 650 mg/kg
LD50:300 mg/kg
TDLo:4,000 mg/kg
L050- 360 mg/kg
LD50.344 mg/kg
LD50:112 mg/kg
LOLo-500 mg/kg
LOLo.2,000 mg/kg
LDLo.80 mg/kg
LDLo.80 mg/kg
LDLo 500 mg/kg
LDLo*420 mg/kg
LD50.850 mg/kg
14DI
30H
1YI
8H
7H
7H
2H
Neoplas- 0SHA std (air)
tic CI 1 mg/10m3
NI0SH recm std (air)
TWA 50 ug (Hg)m3
Central
Nervous
System
Blood
OSHA std (air)
TWA 500 ppm; CI
1,000, Pk 2,000/
5M/2H
NI0SH recm std
(air) TWA 75
ppm, Pk 500/15M
OSHA std (air)
TWA 0.5 ppm (skin)
OSHA std (air)
TWA 5 ppm (skin)
NI0SH recm std (air)
TWA 20 mg/m3
CI 60 mg/m3/15M
20WI
Carcinogenic
-------
32 (.
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Compound Name
Molecular
Formula
Chemical
Abstracts
Service No
Aquatic Toxicity3
Route of
Entry
Species
Other Toxicity Data
Type of
Dose:
Dose Duration
Effects
Exposure
Limits
Phenol,o-Chloro-
(2-chlorophenol)
C6H5C10
95-57-8
Phenol, 2,4-dimtro-
C6H4N20s 51-28-5 TLm96.10-1 ppm
Intraperitoneal-rabbit
Subcutaneous-rabbit
Intravenous-rabbit
Parenteral-rabbit
Intraperitoneal-guinea pig
Subcutaneous-guinea pig
Subcutaneous-frog
Parenteral-frog
Oral-rat
Intraperitoneal-rat
Subcutaneous-rat
Oral-mouse
Skin-mouse
Subcutaneous-rabbit
Intravenous-rabbit
Subcutaneous-guinea pig
Subcutaneous-frog
Oral-mammal
Oral-human
Oral-rat
Intraperitoneal-rat
Subcutaneous-rat
Unreported-rat
Oral-mouse
Intraperi toneal-mouse
Oral-dog
Subcutaneous-dog
Intravenous-dog
Oral-rabbit
Subcutaneous rabbit
Oral-guinea pig
Skin-guinea pig
Subcutaneous-guinea pig
Intramuscular-pigeon
Unreported-mammal
Oral-bird, wild
LDLo-620 mg/kg
LDLo:620 mg/kg
LDLo:180 mg/kg
LDLo.300 mg/kg
LDLo:300 mg/kg
LDLo:450 mg/kg
LDLo:75 mg/kg
LDLo:290 mg/kg
LD50 670 mg/kg
L050:230 mg/kg
LD50:950 mg/kg
LD50:670 mg/kg
TDLo:4,800 mg/kg
LDLo.950 mg/kg
LDLo:120 mg/kg
LDLo 800 mg/kg
LDLo.400 mg/kg
LD50:440 mg/kg
LDLo 4,300 ug/kg
LD50:30 mg/kg
LD50.20 mg/kg
LD50-25 mg/kg
LD50 27 ug/kg
LD50-45 mg/kg
LD50 26 mg/kg
LDLo:30 mg/kg
LDLo-20 mg/kg
LDLo 15 mg/kg
LD50 30 mg/kg
LDLo 20 mg/kg
LD50 81 mg/kg
LDLo 700 mg/kg
LDLo 25 mg/kg
LDLo:7,500 ug/kg
LD50 40 gnt/kg
LD50:13 mg/kg
12WI
Neoplas-
tic
Phenol ,o-Ni tro- C,H,.NO, 88-75-5 Oral-rat
Subcutaneous-rat
Oral-mouse
LD50 2,828 mg/kg
LDLo-1,100 mg/kg
LD50-2,080 mg/kg
-------
Table 32 (Cont)
TOXICITY OF COMPOUNDS IDENTIFIED IN
SALSBURY LABORATORIES/CHARLES CITY, IOWA PROJECT (Continued)
Chemical Other Toxicity Oatab
Compound Name Molecular Abstracts Aquatic Toxicity3 Route of _ - , Type of Exposure —1
Formula Service No. Entry pec es Dose: Dose Duration Effects Limits ^
Phthalic Acid
Bis (2-Ethylhexyl)
Ester
(di-(2-ethylhexyl)
phthalate)
t-2 dKloOa
117-81-7
Phthalic Acid,
Dibutyl Ester
(di-n-butyl
phthalate)
Propane, 1,2-
Dichloro-
Intramuscular-mouse
Intravenous-dog
Subcutaneous-cat
Subcutaneous-rabbit
Subcutaneous-guinea pig
Subcutaneous-frog
Oral-man
Oral-rat
Intrapen toneal-rat
Intraperitoneal-rat
Intravenous-rat
Intraperitoneal-mouse
Oral-rabbit
Skin-rabbit
Skin-guinea pig
CieHcioOd
84-47-42 TLm96:1,000-10 ppm Oral-human
C3H6C1S
78-87-5 TLm96:100-10 ppm
Oral-human
Intraperitoneal-rat
Intraperitoneal-rat
Oral-human
Oral-rat
Inhalation-rat
Oral-mouse
Oral-dog
Ski n-rabbit
Oral-guinea pig
LDLo:600 mg/kg
LDLo.100 mg/kg
LDLo'600 mg/kg
LDLo-1,700 mg/kg
LDLo:900 mg/kg
LDLo:300 mg/kg
TDLo:143 mg/kg
LD50:31 gm/kg
LD50.30,700 mg/kg
TDLo:30 gm/kg
LDLo-300 mg/kg
LD50:14 gm/kg
LD50:34 gm/kg
LD50.25 gm/kg
LD50 10 gm/kg
LOLo: 5,000 mg/kg
TDLo-140 mg/kg
LD50:3,050 mg/kg
TDLo-874 mg/kg
LDLo 50 mg/kg
LD50 1,900 mg/kg
LCLo-2,000 ppm
LD50-860 mg/kg
LDLo 5,000 mg/kg
LD50 8,750 mg/kg
L050.2,000 mg/kg
5-15D
preg.
Gastro-
intes-
tinal
Terato-
genic
OSHA std (air)
TWA 5 mg/m3
OSHA std (air)
TWA 5 mg/m3
5-15D
preg
4H
Eye
Terato-
genic
OSHA std (air)
TWA 75 ppm
-------
163
Of the 51 compounds, 39 were found in the Salsbury process waste-
waters, including:
Arsenic2'3
Copper2,3
Mercury2 *3
Zinc2'3
Benzene1'2,3
Bromodi chloromethane2
Chlorobenzene2'3
1,2-Dichloroethane (Ethylene Dichloride)1,2 ,3
trans-l^-Dichloroethene1'2,3
1,2-Dichloropropane2,3
Ethyl Benzene1'2'3
Tetrachloromethane (Carbon Tetrachloride)1'2'3
Tribromomethane (Bromoform)2'3
1.1.1-Trichloroethane (Methyl Chloroform)1'2'3
1.1.2-Trichloroethane2'3
Trichloromethane (Chloroform)1'2'3
Trichloroethene (Trichloroethylene)1'2'3
Aniline3
Benzofuran4
p-Chloronitrobenzene3
Chloronitrobenzonitrile4
Chloroni troltoluene4
4-Chloro-3-Ni trobenzami de
2,6-Dichlorobenzamide
Di chlorobenzami de4
l,2-Dichloro-3-Nitrobenzene
2,6-Dinitrochlorogenzene
Phenol2'3
2-Phenylbenzimidazole
o-nitroaniline3
p-Nitroaniline3
Nitrobenzene1'2'3
o-Nitrophenol2'3
1,2,4-Trichlorobenzene2'3
Di-(2-ethylhexyl)phthalate1'2'3
2-Chlorophenol2'3
2-Nitrophenol2'3
2,4-Dinitrophenol2'3
1,1-Dichloroethylene1'2'3
1 Demonstrated Human Health Effects -- See Table 32.
2 Priority Pollutants
3 Toxicity and health effects located, see Table 32.
4 Compounds tentatively identified but isomer structure could
not be confirmed.
-------
164
Of these 39 compounds, toxicity and health effects information was
located for 29 of the compounds [Table 32]. The available informa-
tion indicates 11 of these have demonstrated human effects associated
with them. Benzene is a known carcinogen to man and carbon tetra-
chloride, chloroform, trichlorethene, and phenol are known to be car-
cinogenic to animals.
Thirty-six of the 51 compounds were found in the La Bounty dump
site groundwater, including:
Arsenic2'3
Barium
Copper2'3
Mercury2'3
Zinc2'3
Benzene1,2,3
Chlorobenzene2,3
1,2-Dichloroethane (Ethylene Dichloride)1'2,3
trans-l^-Dichloroethene1,2 '3
Dichloromethane (Methylene Chloride)2'3
Ethyl Benzene1'2'3
Toluene1,2'3
1.1.1-Trichloroethane (Methyl Chloroform)1'2'3
1.1.2-Trichloroethane2'3
Trichloromethane (Chloroform)1'2'3
Trichloroethene (Trichloroethylene)1'2'3
Aniline3
o-Chloroaniline3
p-Chloronitrobenzene3
Chioronitroltoluene4
4-Chloro-3-Ni trobenzami de
2,6-Dichlorobenzamide
2-Ethylhexanal3
2-Ethylhexanol3
3-Heptanone3
Phenol2'3
o-nitroaniline3
p-Nitroaniline3
Nitrobenzene1'2,3
o-Nitrophenol2'3
N-Nitrosodiphenylamine2'3
2-Chlorophenol2'3
2-Nitrophenol2'3
2,4-Di nitrophenol2,3
1,1-Dichloroethylene1'2'3
Tetrachloroehtylene1'2'3
-------
165
1 Demonstrated Human Health Effects — See Table 32.
2 Priority Pollutants
3 Toxicity and health effects located, see Table 32.
4 Compounds tentatively identified but isomer structure could
not be confirmed.
Of these 36, toxicity and health effects information was located for
32 of the compounds [Table 32]. The available information indicates
11 of these have demonstrated human effects associated with them.
Benzene is a known carcinogen to humans and chloroform, trichloro-
ethene and phenol are known to be carcinogenic to animals.
-------
166
REFERENCES
1. Ames, B.N., McCann, J., and Yamansaki, E., Methods for Detecting
Carcinogens and Mutagens with the Salmonella/Mammalian - Micro-
some Mutagenicity Test. Mutation Research, 31, (1975) 347-364.
2. Commoner, B., Chemical Carcinogens in the Environment, Presenta-
tion at the First Chemical Congress of the North American Conti-
nent, Mexico City, Mexico, Dec. 1975.
3. Commoner, B., Development of Methodology, Based on Bacterial
Mutagenesis and Hyperfine Labelling, For the Rapid Detection
and Identification of Synthetic Organic Carcinogens in Environ-
mental Samples, Research Proposal Submitted to National Science
Foundation, Feb., 1976.
4. Commoner, B., Henry, J.I., Gold, J.C. , Reading, M.J., Vithayathil
A.J., "Reliability of Bacterial Mutagenesis Techniques to Dis-
tinguish Carcinogenic and Noncarcinogenic Chemicals,1 Final Report
to the U.S. Environmental Protection Agency, EPA-600/1-76-011,
Government Printing Office, Washington, D.C. (April 197 ).
5. Hollander, A., ed., Chemical Mutagens, Principles and Methods for
their Detection, Vol. 1, New York: Plenum Press, Chap. 9,
p. 267, 1971.
6. Waters, T.F., 1972. The Drift of Stream Insects. In Annual
Review of Entomology, Ed. R.F. Smith, T.E. Miffler, and C.N.
Smith, 253-272. Annual Reviews, Inc., Palo Alto, CA.
-------
APPENDIX A
Salsbury Laboratories
NPDES Permit Number IA0003557
Salsbury Laboratories
Iowa DEQ Operation Permit Number 5-34-05-0-01
Charles City, Iowa WWTP
NPDES Permit Number IA 0022039
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Pe.mil No ^ 0003557
Vpplicition No
IA 070 0X6 3 000058
AUTHORIZATION TO DISCHARGE UNDER THE
NATIONAL POLLUTANT DISCHARGE ELIMINATION SYSTEM
In compliance with the provisions of ' je Federal Water Pollution Control Act, as amended,
(33 U.S.C. 1251 et. seq; the "Act"),
in accordance with effluent limitations, monitoring requirements and other conditions set forth
in Parts I, II, and III hereof.
This permit shall become effective on May 28, 1974
This permit and the authorization to discharge shall expire at midnight, May 27, 1979 .
Signed this 28 day of May, 1974
Salsbury Laboratories
2000 Rockford Road
Charles City, Iowa 50616
is authorized to discharge from a facility located at
2000 Rockford Road
Charles City, Iowa
to receiving waters named
Cedar River
Jerome H. Svore
Jerome H. Svore
Regional Administrator
U.S. Environmental Protection Agency
Region VII
EPA Form 3370-4 0 0-73)
-------
I
A. EFFLUENT LIMITATIONS" AND MONITORING REQUIREMENTS
with the
During the period beginning eff ective date and lasting through the date of expiration
,the permittee is authorized to discharge from outfall(s) serial number(s)
Such discharges shall be limited and monitored by the permittee as specified°below:
Effluent Characteristic
Discharge Limitations
kg/day (lbs/day) other Units (Specify)
Flow—m3/Day (MGD)
Temperature
Total Suspended Solids
Daily Avg
It/A
Daily Max
N/A
Daily Avg
N/A
*Not to exceed Iowa Water
Quality Standards
5.7(12.5) 8.5(18.8) 30 mg/1
Daily Max
ft/A
95°F
Monitoring Requirements
Measurement
Frequency
one/month
one/month
45 mg/1 one/month
Sample
Type
N/A
grab
grab
*No heat shall be added to interior streams that would cause an increase of more than 5° Fahrenheit. The
rate of temperature change shall not exceed 2° Fahrenheit per hour. In no case shall heat be added in
excess of that amount that would raise the stream temperature above 90° Fahrenheit.
The pH shall not be less than 6.5 standard units nor greater than 9.0 standard units and shall be monitored
once per three months using a grab sample.
fP I?
There shall be no discharge of floating solids or visible foam in other than trace amounts. £ i ^
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following location(s): §
33
O 2 SJ • J
o
Ln
Before the combined flow discharges to the storm sewer.
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State of Iowa
DLPAitf'MLNT OF Eh'VI RONMhNTAL QbALI iY
WATfcR QUALITY MANAGEMENT DIVISION
AJtEiJDMENT TO OPERATION PERMIT
Amendment to Iowa Operation
Pnrnit No. 5-Vt-O.'T-'J-Ol
Isauod April 25, l&^S
Date of this Amendment April 7, 1976
liaino ttiu! Mailing Aii.lress of Applicant:
City of Charles City
10!) Milwaukee Mall
Cuarles City, Iowa 50616
Identity and Location of Facility:
Cuarles City Wastewater Treatment Plant
Facility 'Jo. Vl-0r.-0-01
SocLion 7f 'i'.J.Sii, KlilV, Floyd County, Iowa
Pursuant to the authority op .'tactions 1.¦><>». V: ari l •' I- ^ 15.1 , Code of loua,
197o, aud of Rule IS. >(<»:>jB) of trie rules of the Iowa Department of
Lnvironmental Quality, ftator Quality Commission as published in the Iowa
Administrative Code, the Executive Director of the Department of
Environmental Quality has issued the above referenced permit. Said
pen lit is hereby incorporated within this amendment as if set forth in
tull, and pursuant to the above authority the executive Director does
by this amendment hereby amend said permit as set forth below:
Pa; o 6 of 5 shall he delotcd and tne attache,! fare (i of :>
inserted in lieu thereof.
The attacheJ pop.s 7 of 9 shall be inscrL-id afti/r pnae (> of V
and all subsequent pages renumbered accordingly.
For tiie i)cpartmu.it of Luviroiunontal Quality:
7 7%,wi"1 " • | i u; jt
Witter Quality Management Division
Larry L. 'Jrane, Lxccutivo Director
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State of Ibwa
DEPARTMENT OP ENVIRONMENTAL QUALITY
WATER QUALITY MANAOiMuIfT DIVISION
OPERATION PERMIT FOR DISCHARGES INTO WATERS UF T>iE STATU
Iowa Operation Permit No. S-34-05-0-01
Dato of Issuance April 25, 1975
Date of Expiration April 1, ID 78
Pursuant to the authority of Chapter 455B.32, 45S1J.45 and 4S5B.74, Cod® of Iowa,
1975, and Rule 19* 3(455B) of tho Rules of tho Iowa Department of Environiissntal
Quality (January, 1974, Supplement I.D.R.), the terms, conditions, and require-
ments of Permit Wo. 64-301-S issued on December 18, 1964, are heroby incorporated
within tliis penalt as if set forth in full, excopt where said terms, conditions and
requirements have been modified by the terms, conditions and requirements of this
pormit. Pursuant to the above authority, the Executive Director of tho Department
of Environmental Quality does hereby issue this porait for the operation of the
disposal system and the discharge of sewage, industrial waste or othor waste into
waters of the Stato for the facility described below:
Name and Mailing Address of Applicant:
City of Charles City
105 Milwaukee Mall
Charles City, Iowa 50616
Identity and Location of Facility:
Charles City Wastewater Treatment Plant
Facility Mo. 54-05-0-01
Section 7, T9SN, R15W, Pioyd County, Iowa
Receiving Watercourse:
Cedar River
The permittee is hereby authorized to operate the disposal system and to discharge
the pollutants specified herein into State wators in accordance with tne effluent
limitations, monitoring requirements and othor stipulations set forth in the
following general and special conditions:
GENERAL AND SPECIAL CONDITIONS
1. This permit shall expire at midnight on April 1, 1978. The permittee shall filo
for renewal of this permit at least 120 days prior to its expiration. Continued
oporation of said disposal 3yatea or discharge from said facility after ejqiiratiot
of this permit is prohibited.
2. Outfall description(s):
Outfall Serial Number Description
001 Outfall from trickling filter treatment plr~'
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3. EIT1UOJT LIMITATIONS AHD MDNITORIiJC REQUIREMENTS
Permit ho. 5-34-03-0-01
Page 2 of G
(a) Dur*a£ t^Q period beginning on the date of Issuance and lasting -^through April 1, 1976
authorized to discharge from outfall aerial number 001.
the permittee La
Such discharge shall be limited and monitored by the permittee &a specified:
Wastewater Parameter
Flow n^/day (MGD)
BOD (5-day)
Suspended Solids
Ammonia Nitrogen (aa H)
Total Heavy Metals***
Mercury
Total Arsenic
phenols
Pa
Color
Temperature
Settleable Solids
Dlssolvad Oxygen
EQAP**
Recirculation. Ratio
Effluent Limitations
kg/day(lbs/day) Other Units(Specify)
1-ton.ltorinx Requirements
Heaaureiaeuc
Sample
Dally Avg
Max
Dally Avg
Kax
Frequency
Type Location*
-
—
11355(3.000)
18925(5.000)
Dally
1
794(1750)
1360(3000)
70 mg/1
120 mg/1
2/week
24-nr. Composite
1.2
340 ( 750)
1000(2200)
30 mg/1
90 mg/1
2/week.
24-ur. Composite
1,2
1000(2200)
1360(3000)
90 mg/1
120 mg/1
2/week
24-hr. Composite
2
—
—
1.5 mg/1
2.5 mg/1
1/ 2 weeks
24-nr. Coupoalta
JL.^
••
—
—
—
1/week
24-ar. Composite
1,2
—
—
1.6 ms/1
2.5 mg/1
1/week
24-nr. Composite
1,2
—
-
—
-
1/week
24-hr. Composite
1»2
Proa 6.3 to 9*0
Daily
Grab
1,4
••
—
—
Daily
Crab
1,2
•
—
—
—
Daily
Grab
1,4
••
—
—
Daily
Grab
1,2,3
••
—
—
—
Daily
Grab
2,4
—
—
—
—
Monthly
Grab
2
•
—
—
-
Dolly
-
-
There shall be no discharge of floating or settleable substances in other than trace aaouncs.
•Samples taken in compliance with the monitoring requirements specified above shall be td&uu at tne following
locatioa(s);
1 — rav sewage influent to the treatment plant
2 - final effluent from tike treatment plant
3 — wastewater flow following primary clarification
4 - contents of the sludge digester
**Sample submitted for the Effluent Quality Analysis Program (£QAP) conducted in accordance uitn Chaptar lb
of the Rules of the Iowa Department of Environmental Quality (1973 I.D.R.).
***Tho total heavy metals group shall be determined by Che sum of the individual analyses for darlum, Cadmium,
Chromium (hexavalont and trlvalent), Copper, Lead, Zinc, Selenium and Mercury•
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Permit No. 5-Vt-i)')-0-t)i
Page 4 of a
4. Pursuant to Condition Number 3, the permittee shall conduct all
required monitoring in accordance with the following provisions:
(a) Samples and measurements taken as required herein shall be
representative of the volume and nature of the monitored
discharge. All samples shall be collected at the point of
discharge prior to the combination of the specified dis-
charge with any other effluent.
(b) The permittee shall record the results of all required analyst
and measurements and shall submit said records to the Department
on forms provided by the Department on a monthly basis; said
records of operation being due by the 10th day of the month
following the reporting period.
(c) The analytical and sampling methods must conform to the follov
ing reference methods or equivalents approved by the Department:
(1) Standard Methods for the Examination of Water and Waste-
waters, 13th Edition, 1971, American Public Health
Association, New York, New York 10019
(2) W.Q.O. Methods for Chemical Analysis of Water and Wastes,
April, 1971, Environmental Protection Agency, Water Quality
Office, Analytical Quality Control Laboratory, 1014 Broaden
Cincinnati, Ohio 54202
(3) A.S.T.M. Standards, Part 23, Water: Atmospheric Analysis.
1970, American Society for Testing and Materials, Phila-
delphia, Pennsylvania 19103
(d) The permittee shall maintain records of all information result i
from any monitoring activities required pursuant to this permi
Such records shall include:
(1) the date, exact place, and time of sampling;
(2) the dates analyses were performed;
(3) the identity of the analyst or analytical laboratory;
(4) the analytical techniques/methods used; and
(5) the results of such analyses.
(e) The permittee shall retain for a minimum of three (3) years an'
records of monitoring activities and results, including all
original strip chart recordings and calibration and maintenance
records for continuous monitoring instrumentation. This
period of retention shall be extended during the course of any
unresolved litigation or when requested by the Executive Direc_~:
(f) If the permittee monitors any parameter at the location (s)
designated herein more frequently than required by this
permit, using approved analytical methods as specified above,
the results of such monitoring shall be included in the
records of operation submitted to the Department.
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Permit Ko. 5-34-05-0-01
Page 3 of 6
3. LIMITATIONS AND MONITORING REQUIREMENTS FOR. SIGNIFICANT INDUSTRIAL/COHMiiRCIAL COHTEULBCTOKS
(b) During the effective period of this permit, the permittee is authorized to accept for treatsent such sewa&e,
industrial waste, or other waste as may bo contributed by the significant industrial/commercial facilities
identified belov. Tho permittee shall report to the Executive Director, in writing, at least 180 days in
advance of any ncv facility expansions, production increases, or process codifications or the connection
of any new contributor which may result in nev, different or increased discharges of sewage, industrial
waste or other waste.
"Significant Industrial/Commercial Contributor" is defined as any facility for which at least one of the
following applies:
(a)
(b)
(c)
(d)
the facility contributes at least 50,000 gallons of wastewater per day at discharge,
the facility contributes at least 5X of the organic or hydraulic loading of the treatment facility,
the facility contributes toxic materials which nay adversely affect tha treatment process, or
the facility contributes any waste which may have an adverse or deleterious impact on the treatment
facility.
The permittee shall limit and monitor said sewage, industrial waste or otner waste for eacn facility as
specified:
Industrial/Commercial
Contributor
Salsbury Laboratories
HoaitorlnR Requirements
White Farm Equipment Co.
Wastewater Limitations
Measurement
Sample
Wastewater Parameter
Daily Avg
Mas
Frequency
Type
Plow HGD
0.518
0.&20
Daily
BOD (5-day)
2500 lbs/day
5000 lbs/day
2/week
24-nr. Composite
Suspended Solids
115 lbs/day
240 lbs/day
2/week.
24-hr. Composite
Total Heavy Hatals**
-
8 mg/1
1/ 2 weeks
24-hr. Composite
Mercury
-
-
1/veek
24-hr. Composite
Total Arsenic
-
15 mg/1
1/weeic.
24-hr. Composicr
Phenols
-
40 mg/1
1/weejt
24-ar. Composite
Pa
—
—
Daily
Crab
Color
—
—
Daily
Grao
Total Heavy Metals**
-
0.75 mg/1
1/ 3 months
Grab
**The total heavy metal group shall be determined by the sum of the Individual analyses for barium, Cadraiuia, Cnromiuut
(hexavalont and trivalent), Copper, LEAD, Zinc, Selenium, Kercury.
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Permit No5-34-05-0-Ql
Page5 of#
4. (g) The following definitions shall apply:
(1) The "Daily Average" discharge means the sum of the tota
daily discharges by weight, volume or concentration dur-
ing the reporting period divided by the total number of
days during the reporting period when the facility was
in operation. With respect to the monitoring requireme..~:
the "daily average" discharge shall be determined by the
summation of all the measured daily discharges by weigh
volume or concentration divided by the number of days
during the reporting period when the measurements were
made. •
(2) The "Maximum" discharge means the total discharge by
weight, volume or concentration which cannot be exceeded
during any 24-hour period.
(3) A "Grab Sample" is a representative portion of the sewacre
industrial waste, other waste, surface water or ground-
water collected at a specific time with no regard to fli
rate.
(4) A "Composite Sample" consists of a number of grab sampL
collected at regular time intervals over a given time
period and combined in proportion to the flow rate at th"=»
time of sample collection.
(h) The permittee shall submit samples for the Effluent Quality
Analysis Program (EQAP) conducted by the Iowa Department of
Environmental Quality in accordance with Chapter 18 of the
Department (1973 I.D.R.). The Iowa Department of Environ-
mental Quality shall notify the permittee of the method and
procedure for sample collection and analysis.
5. The permittee shall employ, contract with, or otherwise maintain
an operation and maintenance staff adequately trained and know-
ledgeable in the operation of any treatment or control facilities
or systems installed or used by the permittee to achieve compliance
with the terms and conditions of this permit.
6. The discharge of any sewage, industrial waste, or other waste more
frequently than or at a level in excess of that authorized herein
shall constitute a violation of this permit. The permittee shall
report to the Executive Director, in writing, at least 120 days
in advance of any facility expansions, production increases, or
process modifications which may result in new, different or in-
creased discharges of sewage, industrial wastes or other wastes.
-------
Permit No.
P.-jge of ^
SCHEDULE OF COMPLIANCE (as amondod 4/7/76)
The permittee shall achieve compliance with the effluent limitations,
monitoring requirements and other stipulations in accordance with the
following implementation schedule:
When used below, "required facilities" noons those facilities provided by
the permittee which will achieve compliance with the following limitations:
Wastewater Parameter Daily Max
UioOhonical Oxygen Demand (5-day)** 3) :n<:/l mrj/l
Suspended Solids** 30 rug/1 'IS me/1
Fecal Coliform 200/100 inl 400/i00 ral
Ammonia Nitrogen (as N) 10 mg/1 15 mg/1
Phonol 0.01 mg/1 0.015 mg/1
Mercury 0.001 tjj/1 0.0015 mg/1
color 75 CPU* 1J0 CPU*
*chloroplatinato units
**A minimus removal of 85» is also required
Note: Certain industrial chemicals from Salsbury Laboratories may bo toxic <
ilelcLurioas to biological treatment processes and stream aquatic life
loose organic cheiricals have not been specifically addressed due to
the limited data available a3 to their possible effects. The pcrmitti
shall be cognizant of the Industrial wastes being contributed by Salsl
Laboratories and shall provide such treatment or rennJrn such jirotreal
iitent facilities .is may be nccucd to prevent any idvi:rsc- effect o:i tho
tr^HLMeut *.or!.s or receiving stream.
(a) by August 1, 1975, the permittee shall provile all the laboratory equip-
• i-... ment necessary for reporting the required tests and analyses specified
in tiie above monitoring requirements or shall contract with n rrsponsibl
agency for tho submission of tho required data.
(b) by August 15, 15)76, the permitteo shall submit to tho Ioi#a Department of
Environmental Quality (DEQ) an infiltration/inflow analysis and ir.dustri
w.istt, treatment cost effective analysis for the construction of t^-.e
requirod bacilitius.
(c) by October 1, 1076, the permittee shall S'jbnit to tho Iowa P-°partr'cnt of
Environmental Quality (dt-.Q) a complete facilities plai, cons is tan t with
all applicable State and Federal regulations, fur the construction of
the required facilities. The permittee stiall also by the sars
-------
•rmit flo. 5-M-Q')- t
F«j>e 7 of 9
4. SCilLDULi; OF CO?ITLIANCC (con't)
(e) by December 1, 1977, the permittee shall award a contract or
contracts for the construction of tho required facilities.
(f) by April 1, 1979, tho pcraittoo shall complete construction of
the required facilities, and by said dale, shall submit to the
Iowa Oilc ted in accordance
with tiia application, plans, specifications anu permit therefor.
(g) tho permittee shall subnit to the Iowa J)l:Q 180-day projjross
reports stating the progress beinn made toward completion of thi
required facilities. Tho first such roport shall bo submitted on
or before Juno 1, 1975.
-------
Permit. No. :>-34-(D-0-01
Page 6 of 8
7.
SCHEDULE OF COMPLIANCE
The permittee shall achieve compliance with the effluent limitations, monito
requirements and other stipulations in accordance with the following impleme
schedule:
tfheu used below, "required facilities'1 means those facilities provided by tb
permittee which will achieve compliance with the following limitations:
Wastewater Parameter
/
Blocliemlcal Oxygen Demand (5-day)
Suspended Solids
Fecal Coliform
Ammonia Nitrogen (ad H)
Phenol
Mercury
Color
~
/
Dally Avg /
30 tag1/!
30 ag/1
200/100 ml
,10 mg/1
,'0.01 14^/1
/O.OOI tog/1
/ 75 CPU*
*cliloroplatinatu units
liax.
45 zag/1
45 ng/1
400/1U0 ml
15 mg/1
0.015 ray/l •
U.0015 m^/l
120 CPU*
Note: Certain industrial chemicals frort Salsbury Laboratories may.be toxic o:
daleterious to biological treatment processes and stream aquatic life.
These organic chemicals have not been specifically addressed duo to t>
limited data available as to'their possible effects. Hie permittee si
be cognisant of the Industfial wastes being contributed by Salsbury
Laboratories and sltall provide such treatment or require such pretrial
facilities a3 nay be needed to prevent any adverse effect on the treat
works or receiving streiua.
by August 1, 1975, they^eraittee shall provide all the laboratory equips
necessary for reporting the required testa and analyses specified in the
above nonitoring requirements or shall contract with a responsible agent
the submission of the required data.
by December 1, 1975, the permittee shall submit to the Iowa Department c
Environmental Quality (D.E.Q.) a preliminary engineering report includlc
infiltration/inflow analysis, for the construction of the required facll
(a)
00
(c)
(d)
of the requi
facilities, and by said date, shall submit to the loua D.E.Q. certifies
by a/registered professional englnaer that the-construction thereof has
completed in accordance with tha application, plans, specifications
perhlt therefor.
(f) the permittee shall submit to the Iowa D.E.Q. 180 day progresu reports
stating the progress being made toward completion of tha required faclli
The first such report shall be submitted on or before June 1, 19 75.
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Permit No. 5-34-
-------
Permit No. ^
Page 8 of 8
15. Ho legal or finanoial responsibility arising from the operation or
maintenance of any disposal system or part thereof installed by
the permittee to achieve compliance with the conditions of this
permit shall attach to the State of Iowa or the Department of
Environmental Quality.
16. The issuance of this pemit in no way relieves the permittee of
the responsibility for complying witn all local, state, and federa
laws, ordinances, regulations or other requirements applying to
the operation of this facility.
For the Department of Environmental Quality:
Larry 12. Crane, Executive Director
Jdaeph/£. Obr, F.ii., Director
/(Jater Quality Management Division
//
11 r. •
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I'ik.ik n.. IA-0027039
Aim-' 1A-0022039
AUTHORIZATION TO DISCI I Alt (110 UNDIilt TIIIO
NATIONAL POLLUTANT DISCIIAIICK IOMMINATION SYSTI-.M
In eompluine with Ihe provisions of llu' Federal Waler Pollution Control Ai t, .is amended
(.13 lis.c. ur»1 el seep, the "Art").
City of Charles City, Iowa
is million/oil to discharge from a facility located at
Charles City Wastewater Treatment Plant
Facility No. 34-05-0-01
Charles City, Iowa 50616
Section 7, T95N, R15W, Floyd County, Iowa
to receiving waters named
Cedar River
in accordance with effluent limitations, monitoring requirements and other condition- set foilh
in Parts I, II, and III hereof. "
This permit shall become effective on October 12, 1975 unless an adjudicatory hearii
is requested pursuant to AO CFR 125.36 within 10 days following receipt of this perr
This permit and the authorisation to discharge shall expire at midnight, on june 30} 1977.
.Signed this 12 day of September, 1975
"v.l-
- . / ' '
/Jerome H. Svore
'' Reoional Administrator
U.S. Enviionmsntat Piolcction Agency
Region VU
F e a r oihi 3170-4 (i n_ 7ji
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PART I
A. EFFLUENT LIMITATIONS AND MONITORING REQUIREMENTS - FINAL
PaSe 2 of 17
Permit No. ia-0022039
1. During the period beginning on the effective date and lasting through June 30, 1977,
permittee is authorized to discharge from outfall serial number 001.
Such discharges shall be limited and monitored by the permittee as specified:
Minimum
Monitoring Requirements
Effluent Limitations
Wastewater Parameter
Biochemical Oxygen
Demand (5-day)
Suspended Solids
Flow - m^/day (MGD)
pH
Ammonia Nitrogen (as N)
***Total Heavy Metals
Total Arsenic
kg/day(lbs/day)
Daily Avg Max
Other Units(Specify)
Daily Avg Max
Measurement
Frequency
794(1750) 1360(3000) 70 rag/1 120 mg/1 2/week
340(750) 1000(2200) 30 mg/1 90 mg/1 2/week
11,355(3.000) 18,925(5.000) daily
Sample
Type*
composite
Sample
Location**
1,2
comoosite
6.5-9.0 (not to be averaged)
1000(2200) 1360(3000) 90 mg/1 120 mg/1
1.5 mg/1 2.5 mg/1
1.6 mg/1 2.5 mg/1
2/week grab
2/week composite
1/ 2 weeks composite
1/week composite
1,2
2
1,2
1,2
1,2
1,2
There shall be no discharge of floating or settleable substances in other than trace amounts.
*A11 composite samples are 24 hr composites (9 samples at 3 hr intervals).
¦ **Samples taken in compliance with the monitoring requirements specified above snail be taken at the
following location(s): (1) raw influent into wastewater treatment facility, (2) final effluent from
wastewater treatment facility.
***The total heavy metals group shall be determined by the sum of the individual analyses for Barium,
Cadmium, Chromium (hexavalent and trivalent), Copper, Lead, Zinc, Selenium and Mercury.
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PART I
Page 3 of 17
Permit No. 1^-0022039
A. EFFLUENT IJIUTA'i IONS AND MONITORING REQUIREMENTS
4. Pollutants from Industrial Users
Effluent limitations on pollutants from this municipal discharge
are listed in Part I, Section A.l, Section A.2 and Section A.3
of this permit. It is possible Lhat other pollutants attributable
to inputs from major contributing industries using the municipal
system are also present in the permittee's discharge. At such
time as sufficient information becomes available to establish
limitations for such pollutants, this permit may be revised to
specify effluent limitations for any or all-of such other polluLants
In accordance with industrial best practicable technology require-
ments or water quality standards.
It may be necessary to supplement the limitations given in Part I,
Section A.l, Section A.2 and Section A.3 with Federal Pretreatment
Standards (AO CFR 128) to ensure compliance by the permittee with
all applicable effluent limitations. In AO CFR 128, pretreatment
of wastewater is required for incompatible pollutants. In addition,
no discharge to publicly owned treatment works shall contain wastes
which create a fire or explosion hazard in the publicly owned
treatment works, wastes which will cause corrosive structural damage,
wastes with a pH lower than 5.0, wastes In amounts which would cause
obstruction to the flow in sewers or interfere with the proper
treatment operation, or wastewaters at a flow rate and/or pollutant
discharge rate which Is excessive over relatively short time periods
resulting in a loss of treatment efficiency.
Specific actions by the permittee may be necessary so that all of
the major contributing industries discharging to the municipal
system comply with applicable pretreatment standards.
Beginning on January 1, 1976 tf,e permittee shall submit
to the permit Issuing authority semi-annual reports suaunarizing the
progress of all known major contributing industries subject to the
requirements of Section 307 of the Act toward full compliance with
such requirements. Such a report shall include at least the
following information:
(1) The number of major contributing industries using the treatment
works, divided into SIC group categories;
(2) The number of major contributing industries in full compliance
with the requirements of Section 307, or not subject to these
requirements (e.g., discharge only compatible pollutants);
(3) A list identifying by name those major contributing Industries
presently in violation of the requirements of Section 307.
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PART I
Page 4 of 17
Permit No. IA-0022039
These semi-annual reports must be filed with the permitting
authority by January 1 and July 1 of each year until compliance
is achieved. Submission is required again only if a major con-
tributing industry reverts to violating the requirements of
Section 307.
Beginning on January 1, 1976 monitoring reports for each major
contributing industry will be required on basis.*
The permittee shall establish and implement a procedure to obtain
specific information on the quality and quantity of effluents intro-
duced by each major contributing industry. This information shall
be presented using the instructions and format as given in Section
IV of Standard Form A (attached). A separate set of six questions
should be completed for each major industrial user.
Information on the municipal facilities as a whole is to be
reported on the monthly NPDES Discharge Monitoring Report Form
(Form 3320-1).
Based on the information regarding industrial inputs reported by
the permittee pursuant to the preceding paragraph, the permittee
will be notified by the permitting authority of the availability of
industrial effluent guidelines on which to calculate allowable inputs
of incompatible pollutants based on best practicable technology for
each industry group. Copies of guidelines will be provided as
appropriate. Not later than 120 days following receipt of this in-
formation, the permittee shall submit to the permitting authority
calculations reflecting allowable inputs from each major contributing
industry. The permittee ehall also require all such major contrib-
uting industries to implement necessary pretreatment requirements
(as provided for in AO CFR Part 128), and provide the permitting
authority with notification of specific actions taken in this regard.
At that time, the permit may be amended to reflect the municipal
facility's effluent requirements for incompatible pollutants.
*The first industrial monitoring report is due January 1, 1976.
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PART 1
Page ^
Permit Mo. IA-0022039
1$. MONITORING AND REPORTING
]. Representative Samp]ing
Samples and measurements taken as required herein shall he repre-
sentative of the volume and nature of the monitored discharge.
2. Reporti ng
Monitoring results obtained during the previous three months
shall be summarized for each month and reported on a Discharge
Monitoring Report Form (OMB No. 158-TC0073), postmarked no later
than the 28th day of the month following the completed reporting
period. The first report shall be submitted for the period
ending December 31, 1975 . Duplicate signed copies of these,
and all other reports required herein, shall be submitted to the
Regional Administrator and the State at the following addresses:
U. S. Environmental Protection Agency
Attn: Compliance Branch
1735 Baltimore, Room 249
Kansas City, Missouri 64108
Iowa Department of Environmental Quality
P.O. Box 3326
3920 Delaware
Des Moines, Iowa 50316
3. Other Reporting Conditions
Any unforeseen or anticipated modifications in influent character-
istics or volume, waste collection systems, industrial contribu-
tions, treatment and disposal facilities, changes in operational
procedures, elimination of discharge, industry relocation, or other
significant activities which alter the nature and/or frequency
of the discharge(s), or otherwise affec.t the conditions of this
permit, shall be enumerated in a written report accompanying the
earliest subsequent monitoring report. This report shall include
information on the quantity and quality of the changes to the
influent to the treatment facility and any impact of such change
to the facility effluent.
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PART I
Pago 6 of 17
Permit No. IA-0022039
U. Test Proccduicq
Test procedures for the analysis of pollutants shall conform
to regulations published pursuant to Section 304(g) of the Act,
under which such procedures may be required.
5. Recording of Results
For each measurement or sample taken pursuant to the requirements
of this permit, the permittee shall record the following
information:
a. The exact place, date, and time of sampling;
b. The dates the analyses were performed;
c. The person(s) who performed the analyses;
d. The analytical techniques or methods used; and
e. The results of all required analyses.
6. Additional Mom' toring by Permittee
If the permittee monitors any pollutant at Lhe location(s)
designated herein more frequently than required by this
permit, using approved analytical methods as specified above,
the results of such monitoring shall be included in the cal-
culation and reporting of the values required in the Discharge
Monitoring Report Form (OMii No. 158-R0073) . Such increased
frequency shall also be indicated.
7. Records Retention
All records and information resulting from the monitoring
activities required by this permit including all records of
analyses performed and calibration and maintenance of instru-
mentation and recordings from continuous monitoring instrumentation
shall be retained for a minimum of throe (3) years, or longer if
requested by the Regional Administrator or the State water pollu-
tion control agency.
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i nt\ i i
Permit No. ^ 0022039
f tni tions
The "d,jlly average" discharge means the sum of the total daily
discharges by weight, volume or concentration during the re-
porting period divided by the total number of days during Lhe
reporting period when the facility was in operation. l.'ith
respect to the monitoring requirements, the "daily average"
discharge shall be determined by the summation of all the
measured daily discharges by weight, volume or concentration
divided by the number of days during the reporting period
when the measurements were made.
The "maximum" discharge means the total discharge by weight,
volume or concentration which cannot be exceeded during any
24-hour period.
The "weekly average", other than for fecal coliform bacteria
is the arithmetic mean of the values for effluent samples
collected in a period of seven consecutive days. The weekly
average for fecal coliform bacteria is the geometric mean of
the values for effluent samples collected in a period of seven
consecutive days.
A "grab sample" is an individual sample collected in less than
15 minutes. For fecal coliform bacteria, a grab sample consists
of one effluent portion collected during a 24-hour period.
A "composite sample" is a combination of individual samples
obtained at regular intervals over a time period. Either the
volume of each individual sample is proportional to discharge
flow rates or the sampling frequency (for constant volume
samples) is proportional to the flow rates over a time period
used to produce the composite.
A "major contributing industry" is a wastewater source that:
(a) has a flow of 50,000 gallons or more per average workday;
(b) has a flow greater than five percent of the Flow carried by
the municipal system receiving the waste; (c) has in its waste
a toxic pollutant in toxic amounts as defined in standards issued
under Section 307(a) of the Act; or (d) has significant impact,
either singly or in combination with other contributing industries
on the treatment works or the quality of its effluent.
"Compatible pollutants" are biochemical oxygen demand, suspended
solids, pH and fecal coliform bacteria, plus additional pollutants
identified in the NPDES permit if the publicly owned treatment
works was designed to treat such pollutants, and in fact docs
remove such pollutants to a substantial degree, e.g., nitrogen
and phosphorus.
An "incompatible pollutant" is any pollutant which is not a
compatible pollutant as defined above.
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PART I
PaE° 8 of 17
Permit No. ia_0022039
C. SCII1DULE or COMPLIANCE
1. The permittee shal 1 achieve compliance with thr effluent limita-
tions specified for discharges in accordance with the following
schedule:
The permittee shall submit 180-day progress reports to the
Compliance Branch, U.S. Environmental Protection Agency stating
the progress being made toward compliance with the D.E.Q.
implementation schedule specified within Part I, C-3. The
first such report shall be submitted on or before December 1, 1975.
The above schedule contains the latest possible dates to accomplish
the actions specified. Earlier compliance is encouraged.
2. No later Llian 14 calendar days following a date identified in the
above schedule of compliance, the permittee shall submit either a
report of progress, or in the case of specified actions being
required by identified dates, a written notice of compliance or
noncompliance. In the latter case, the notice shall include the
cause of noncompliance, any remedial actions taken, and the
probability of meeting the next scheduled requirement. The above
submittals shall be sent to E.P.A.
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I'AKT 1
9 of 17
Permit No. 1A-0022039
C. SCHtrJULC OF COMI'LfANCli (cont'd)
3. The permittee sh.ill achieve compliance with the ef T3 uenL limita-
tions, monitoring requirements and other stipulations in accord-
ance wi Lh the following D.E.Q. implementation schedule:
When used below, "required facilities" means those facilities
provided by the permittee which will achieve compliance with tlie
following limitations:
Wastewater Parameter
Biochemical Oxygen Demand (5-day)
Suspended Solids
Fecal Coliform
Ammonia Nitrogen (as N)
Phenol
Mercury
Color
Daily, Avg
30 mg/1
30 mg/1
200/100 ml
10 mg/1
0.01 mg/1
0.001 mg/1
75 CPU*
Max
45 mg/1
45 mg/]
400/100 ml
15 mg/1
0.015 mg/1
0.0015 ing/1
120 CPU*
*chloroplatinate units
Note: Certain industrial chemicals from Salsbury Laboratories may
be toxic or deleterious to biological treatment processes
and stream aquatic life. These organic chemicals have not
been specifically addressed due to the limiLed data available
as to their possible effects. The permittee shall be cogni-
zant of the industrial wastes being contributed by Salsbury
Laboratories and shall provide such treatment or require such
pretreatment facilities as may be needed to prevent any
adverse effect on the treatment works or receiving stream.
(a) by August 1, 1975, the permittee shall provide all the labora-
tory equipment necessary for reporting the required tests and
analyses specified in the above monitoring requirements or
shall contract with a responsible agency for the submission of
the required data.
(b) by December 1, 1975, the permittee shall submit to the Iowa
Department of Environmental Quality (D.E.Q.) a preliminary
engineering report including an infiltration/inflow analysis,
for the construction of the required facilities.
(c) by August 1, 1976, the permittee shall submit to the Iowa
D.E.Q. final plans and specifications for the construction
of the required facilities.
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PART I
Pafic 10 of 17
Permit No. jA-0022039
c. scmmuLr. ok compliance: (cont'd)
3. The permittee1 shall achieve compliance with the effluenL limiLa-
tions, monitoring requirements and oLhcr stipulations m accord-
ance with the following D.E.Q. implementation schedule:
(d) by January 1, 1977, the permittee shall award a contract or
contracts for the construction of the required facilities.
(e) the permittee shall submit to the Iowa D.E.Q. J 80-day
progress reports stating the progress being made toward
completion of the required facilities. The first such
report shall be submitted on or before June 1, 1975.
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rage 11 of 17
Term It No. ia-0022039
PAUT T1
A. MANAGI.MCNT Kl.fJUIKWII.NTS
J . Change in Discharge
All discharges authcuizcd herein shall be consistent with the terms
and conditions of this permit. The discharge of any pollutant
identified in this permit more frequently than or at a level in
excess of that authorized shall constitute a violation of the permit.
Any anticipated facility expansion, additions, or modifications, as
well as any new industrial discharge or substantial change in an
existing industrial discharge to the treatment system, which will
result in new, different, or increased discharges of pollutants
must be reported by submission of a new Nl'DES application or, if
such changes will not violate the effluent limitations specified
in this permit, by notice to the Regional Administrator and the
State water pollution control agency of such changes. Following
such notice, the permit may be modified to reflect any necessary
not previously limited. In no case are any new connections, increased
flows or major changes in influent quality permitted that will cause
violation of the stated effluent limitations.
2. Noncompliance Notification
If, for any reason, the permittee does not comply with or will be
unable to comply with any effluent limitation specified in this
permit due to an unusual or extraordinary occurrence, the permittee
shall immediately notify and provide the Regional Administrator
and the State with the following information, in writing, within
five (5) days of becoming aware of such condition:
a. A description of the discharge and cause of noncompliance; and
b. The period of noncompliance, including exact dates and times;
or if not corrected, the anticipated time the noncompliance is
expected to continue, and steps being taken Lo reduce, eliminate
and prevent recurrence of the noncomplying discharge.
3. Onshore-offshore construction
This permit doer; not authorize or approve the construction of any
onshore or offshore physical structures or facilities, or the under-
taking of any work in any navigable waters.
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PAR'] II
Page of 17
Permit No. IA-0022039
A. Adverse Impact
The permittee shall take nil reasonable steps to minimize dny
adverse impact to navigable waters resulting from noncompliance
with any effluent limitations specified in this permit, including
such accelerated or additional monitoring as necessary to determine
the nature and impact of the noncomplying discharge.
5. Bypassing
Any diversion from or bypass of facilities necessary to maintain
compliance with the terms and conditions of this permit is pro-
hibited, except (i) where unavoidable to prevent loss of life or
severe property damage, or (ii) where excessive storm drainage or
runoff would damage any facilities necessary for compliance with
the effluent limitations and prohibitions of this permit. The
permittee shall promptly notify the Regional Administrator and
the State in writing of each such diversion or bypass.
6. Removed Substances
Solids, sludges, filter backwash, or other pollutants removed
from or resulting from treatment or control of wastewaters shall
be disposed of in a manner such as to prevent any pollutant from
such materials from entering navigable waters.
7. Power Failures
In order to maintain compliance with the effluent limitations and
prohibitions of this permit, the permittee shall either:
a. In accordance with the Schedule of Compliance contained in
Part I, provide an alternative power source sufficient to
operate the wastewater control facilities;
or, if no date for implementation appears in Part I,
b. Halt, reduce or otherwise control production and/or all
discharges upon the reduction, loss, or failure of one
or more of the primary sources of power to the wastewater
control facilities.
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l'ART JI
PnC° 13 of 17
l'crnu L No. IA_0022039
8. FncLilly Operation and Quality Control
All waste collection, control, treatment and di.sposal facilities
shall be operated in a manner consistent with the following:
a. At all times, all facilities shall be operated as efficiently
as possible and in a manner which will minimize upsets and
discharges of excessive pollutants.
b. The permittee shall provide an adequate operating staff which
is duly qualified to carry out the operation, maintenance and
testing functions required to insure compliance with the con-
ditions of this permit.
c. Maintenance of treatment facilities that results in degrada-
tion of effluent quality shall be scheduled during non-critical
water quality periods and shall be carried out in a manner
approved by the permitting authority.
9. Discharge Consistency
The permittee shall maintain and operate the facilities under his
control with sufficient personnel, standby equipment, adequate
power, an inventory of replacement parts, and a satisfactory
contingency plan to assure that the quality of the discharge(s)
will meet the effluent limitation requirements.
10. Industrial Users
The permittee shall require any industrial user of the treatment
works to comply with the requirements of Sections 204(b), ^07,
and 308 of the Act. Any industrial user subject to the requirements
of Section 307 of the Act shall be required by the permittee to
prepare and transmit, to the Regional Administrator periodic notice
(over intervals not to exceed nine (9) months) of progress toward
full compliance with SecLion 307 requirements.
The permittee shall require any industrial user of stonn sewers
to comply wiLh the requirement of Section 308 of the Act.
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I'AIU II
r,,Rt' 14 of 17
Permit ho. ia_0022039
B. RESrONSIlUUTIKS
1. Right of I'liLiy
The permittee shall allow tlio head of the State water pollution
control agency, the Regional Administrator, and/or their authorized
representatives, upon the presentation of credentials:
a. To enter upon the permittee's premises where an effluent
source is located or in which any records are required
to be kept under the terms and conditions of this permit;
and
b. At reasonable times to have access to and copy any records
required to be kept under the terms and conditions of this
permit; to inspect any monitoring equipment or monitoring
method required in this permit; and to sample any discharge
of pollutants.
2. Transfer of Ownership or Control
In the event of any change in control or ownership of facilities
from which the authorized discharges emanate, the permittee shall
notify the succeeding owner or controller of tlie existence of Liiis
permit by letter, a copy of which shall be forwarded to tlie Regional
Administrator and the State water pollution control agency.
3. Availability of Reports
Except for data determined to be confidential under Section 308
of the Act; all reports prepared in accordance with the terms of
this permit shall be available for public inspection at the offices
of the State water pollution control agency and the Regional
Administrator. As required by the Act, effluent data shall not
be considered confidential. Knowingly nuking any false statement
on any such report may result in the imposition of criminal
penalties as provided for in Section 309 of the Act.
A. Permit Modification
After notice and opportunity for a hearing, this pcimit may be
modified, suspended, or revoked in whole or in part during its
term for cause including, but not limited to, the following:
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I'AKT If
P'ir.f> 15 of 17
Permit No.
1A-00220J9
a. Violations of any terms or conditions of this permit;
b. Obtaining this permit by misrepresentation or failure
to disclose fully all relevant facts; or
c. A change in any condition that requires either a temporary
or permanent reduction or elimination of the authorized
discharge.
5. Toxic Pollutants
Notwithstanding Part II, B-4 above, if a toxic effluent standard or
prohibition (including any schedule of compliance specified in such
effluent standard or prohibition) is established under Section 307(a)
of the Act for a toxic pollutant which is present in the discharge
and such pollutant in this permit, this permit shall be revised or
modified in accordance with the toxic effluent standard or prohibition
and the permittee so notified.
6. Civil and Criminal Liability
Except as provided in permit conditions on "Bypassing" (Part II, A-5)
and "Power Failures" (Part II, A-7), nothing in this permit shall be
construed to relieve the permittee from civi] or criminal penalties
for noncompliance, whether or not such noncompliance is due to
factors beyond his control, such as accidents, equipment breakdowns,
or labor disputes.
7. Oil and Hazardous Substance Liability
Nothing in this permit shall be construed to preclude the institution
of any legal action or relieve the permittee from any responsibilities,
liabilities, or penalties to which the permittee is or may be subject
under section 311 of the Act.
8. State Laws
Nothing in this permit shall be construed to preclude the institution
of any legal action or relieve the permittee from any rcsponsibilities,
liabilities, or penalties established pursuant to any applicable State
law or regulation under authority preserved by section 510 of the Act.
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pai'.j- )i
J'flgc 16 of 17
Permit No. JA-0022039
9• 1'ropcr ty Ri;;hL.s
1!io issuance of this permit does not convey nny property rights
in either real or persona] property, or any exclusive privileges,
nor docs it authorize any injury to private property or any
invasion of personal rights, nor any infringement of Federal,
State or local laws or regulations.
10. Severability
The provisions of this permit are severable, and if any provision
of this permit, or the application of any provision of this permit
to any circumstance, is held invalid, the application of such
provision to other circumstances, and the remainder of this permit,
shall not be affected thereby.
11. Prohibition of Additional Service Connections
Should there be a violation of any conditions of this permit, the
Environmental Protection Agency has the authority under Section
402(h) of the Federal Water Pollution Control Act Amendments of
1972 to proceed in a court of competent jurisdiction to restrict or
prohibit further service connections to the treatment system covered
by this permit by any sources not utilizing the system prior to the
finding that such a violation occurred. It is intended that this
provision be implemented by the Agency (or by the State of Iowa)
as appropriate.
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P'ifce 17 o£ 17
rcrmlt No. iA_0022039
PART III
OTHER REQUIREMENTS
1. Outfall description(s):
Outfall Serial Number Description
001 Outfall from trickling filter treatment
plant.
2. The permittee shall employ, contract with, or otherwise maintain
an operation and maintenance staff adequately trained and knowledgeable
in the operation of any treatment or control facilities or systems
installed or used by the permittee to achieve compliance with the terms
and conditions of this permit, in accordance with Part 2 of Division
III of Chapter 455B, Code of Iowa, 1973, or any rules promulgated pursuant
thereto.
3. Flows are to be determined with a calibration device providing a
maximum deviation of + 15 percent from true discharge rates throughout
the range of discharge levels. It is recommended that devices and
techniques be selected from the "U.S. Water Measurement Manual, 2nd
Edition, 1967" which is available from the Government PrinLing Office
at $5.80, Stock Number 2403-00086. Selection of flow monitoring methods
not contained in this reference will require submission of adequate
proof to document accurate calibration.
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APPENDIX B
Priority Pollutants Listing
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RECOMMENDED LIST OF PRIORITY
POLLUTANTS
Compound Name
1. *acenaphthene
2. *acrolein
3. *acrylonitrile
4. *benzene
5. *benzidine
6. *carbon tetrachloride (tetrachloromethane)
*Ch1orinated benezenes (other than dichlorobenzenes)
7. chlorobenezene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
*Chlorinated ethanes (including 1,2-dichloroethane,
1,1,1-trichloroethane and hexachloroethane)
10. 1,2-dichloroethane
11. 1,1,1-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14 1,1,2-trichloroethane
15. 1,1,2,2-tetrachloroethane
16 chloroethane
*Chloroa1 k.yl ethers (chloromethyl, chloroethyl and mixed ethers)
17. bis(chloromethyl) ether
*Specific compounds and chemical classes as l".;"-"1
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2
18. bis(2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
*Chlorinated naphtalene
20. 2-chloronaphthalene
*Chlorinated phenols (other than those listed elsewhere;
includes trichlorophenols and chlorinated cresols)
21. 2,4,6-trichlorophenol.
22. parachlorometa cresol
23. *chloroform (trichloromethane)
24. *2-chlorophenol
*Dichlorobenzenes
25 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
*Dichlorobenzidine
28. 3,3'-dichlorobenzidine
*Dichloroethylenes (1,1-dichloroethylene and 1,2-dichloroethylene)
29 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. *2,4-dichlorophenol
*Dichloropropane and dichloropropene
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. *2,4-dimethylphenol
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3
*Dinitrotoluene
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. *1,2-diphenyl hydrazine
38. *ethylbenzene
39. *fluoranthene
*Haloethers (other than those listed elsewhere)
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl) ether
43. bis(2-chloroethoxy) methane
*Halomethanes (other than those listed elsewhere)
44. methylene chloride (dichloromethane)
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. trichlorofl uoromethane
50. dichlorodifluoromethane
51. chlorodibromomethane
52. *hexachlorobutadiene
53. *hexachlorocyclopentadiene
54. *isophorone
55. *naphthalene
56. *nitrobenzene
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4
*Nitrophenols (including 2,4-dinitrophenol and dinitrocresol)
57. 2-nitrophenol
58. 4-nitrophenol
59. *2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
*Ni trosamines
61. N-nitrosodimethylamine
62. N-nitrosodiphenyl amine
63. N-nitrosodi-n-propylamine
64. *pentachlorophenol
65. *phenol
*Phtha1ate esters
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
*Pol,ynuclear aromatic hydracrarbons
72. benzo(a)anthracene (1,2-benzanthracene)
73. benzo (a) pyrene (3,4-benzopyrene)
74. 3,4-benzofluoranthene (benzo(b)fluoranthene)
75. benzo(k)fluoranthane (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
78. anthracene
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5
79. benzo(ghi)perylene (1,12-benzoperylene)
80. fluroene
81. phenathrene
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)
83. indeno (1,2,3-cd)pyrene (2,3-o-phenylenepyrene)
84. pyrene
85. *tetrachloroethylene
86. *toluene
87. *trich1oroethylene
88. *vinyl chloride
Pesticides and Metabolites
89. *aldrin
90. *dieldrin
91. *chlordane (technical mixture & metabolites)
*DDT and Metabolites
92. 4,4'-DDT
93. 4,41-DDE (p.p'-DDX)
94. 4,4'-DDD (p.p'-TDE)
*endosu!fan and metabolites
95. a-endosulfan-Alpha
96. b-endosulfan-Beta
97. endosulfan sulfate
*endrin and metabolites
98. endrin
99. endrin aldehyde
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6
*heptachlor and metabolites
100. heptachlor
101. heptachlor epoxide
*hexachlorocyclohexane (all isomers)
102. a-BHC-Alpha
103. b-BHC-Beta
104. r-BHC (1indane)-Gamma
105. g-BHC-Delta
*polychlorinated biphenyls (PCB's)
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 (Arochlor 1254)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1232)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. *Toxaphene
114. *Antimony (Total)
115. *Arsenic (Total)
116. *Asbestos (Fibrous)
117. *Beryl1iurn (Total)
118. *Cadmium (Total)
119. *Chromium (Total)
120. *Copper (Total)
121. *Cyanide (Total)
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7
123. *Mercury (Total)
124. *Nickel (Total)
125. *Selenium (Total)
126. *Silver (Total)
127. *Thal1ium (Total)
128. *Zinc (Total)
129. **2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
*Specific compounds and chemical classes as listed in the consent decree
**This comDOund was specifically listed in the consent decree. Because
of the extreme toxicity (TCDD). We are recommending that laboratories
not acquire analytical standard for this compound.
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APPENDIX C
Flow Monitoring Techniques
Salsbury Laboratories - Charles City, Iowa - June 1978
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FLOW MONITORING TECHNIQUE - SALSBURY LABORATORIES
CHARLES CITY, IOWA
JUNE 1978
Flow monitoring at Salsbury Laboratories was accomplished with the
tracer dilution technique, using lithium as the tracer. The concept
employed is that mass is conserved (i.e., mass of tracer in equal mass
of tracer out). Fundamental to the use of this technique are the
following conditions:
1. A conservative tracer.
2. A constant tracer injection rate and an accurate measurement
of the rate.
3. An accurate measurement of the tracer concentration, background
tracer levels, and diluted tracer in the flow stream to be
measured.
4. Complete mixing in the flow stream to be measured.
It was determined that all these respective criteria could be met
by:
1. Using lithium (1i) in the form of lithium chloride as a
tracer. Preliminary studies included spiking the waste-
water with known amounts of lithium and analyzing for %
recovery. Overall recovery was 101%.
2. Metering the injected tracer solution with low flow rate,
high precision pumps. During the survey, injection rate
was checked approximately three times/day with a granulated
cylinder and stop watch.
-------
3. Measuring Li concentration with a Perkin-Elmer Model 403
Atomic Absorption Spectrophotometer. This instrument was
calibrated before each use with lithium standards of known
concentration. Concentrate samples were analyzed at least
once/day during the survey. Background samples were col-
lected and analyzed each time a flow measurement was per-
formed.
4. Injecting the lithium chloride concentrate solution into the
overflow standpipe at the southeast corner of the equilization
pond and monitoring the diluted Li tracer at the lift station
wet well. Preliminary studies conducted on site indicated the
tracer reached the discharge monitoring site in less than one
minute and subsequently reached a steady state condition.
During the survey, five minutes of tracer dosing was allowed
to provide a factor of safety.
Flow was calculated with the following equation:
n = Q Cq F
Q~ C"Cb
where Q is unknown flow (mgd)
q is injection rate (1/min)
Cq is lithium concentration of injection solution (mg/1)
C is lithium concentration downstream of injection (mg/1)
C^ is background concentration of lithium (mg/1)
F is factor to convert 1/min to mgd
(380 45 x 10"6 min " 9a^
x iu day-Titer )
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APPENDIX D
Methods, Analytical Procedures and Quality Control
-------
BIOLOGY
-------
BIOLOGY
MUTAGEN ASSAY METHODS
Sample Extraction
A 4:1 (80% benzene, 20% isopropanol) mixture of solvents was placed
in a clean, 1-gallon amber solvent bottle and continuously stirred during
the extraction procedure to assure adequate mixing.
For basic extractions, one-liter portions of sample were adjusted
above pH 12 with NaOH. Each one liter aliquot was extracted three times
(5 minutes each) with 35 ml of fresh solvent. The solvent fraction was
then separated, mixed with anhydrous sodium sulfate to remove any emulsion
and filtered into a one-liter round bottom flask. The aqueous fractions
were retained for acidic extraction. These were adjusted below pH 2 and
the above procedure repeated.
The combined solvent fractions (approximately 420 ml) were evapor-
ated to dryness at 50°C in a rotoevaporator. The residue was resuspended
into 25 ml sterile dimethylsulfoxide (DMSO), labeled and stored at 4°C
until assayed by the Ames Procedure.
Bacterial Mutagenicity Assay
The Standard Ames Bacterial Assay was performed using the plate
incorporation assay as described by Ames, et al^.1 Sample extracts were
screened with Salmonella typhimurium tester strains TA 98, TA 100, TA
1535 and TA 1537, first individually and then in the presence of rat
liver homogenates (S-9 mix). A dose-response relationship between concen-
tration of sample extract and number of revertant colonies was determined
on all samples demonstrating an elevated reversion rate during the screen.
-------
Quality Control
A one-liter volume of sterile distilled water was added to a clean,
1-gallon amber glass bottle and treated as a sample. This served as a
blank on the sample bottles, distilled water, extracting solvents, emul-
sion removal, and the concentration process. A DMSO blank was tested to
ensure that this material did not interfere with test results.
The tester strains, TA 1535, TA 1537, TA 98 and TA 100 were exposed
to diagnostic mutagens to confirm their natural reversion characteristics.
The strains were tested for ampicillin resistance, crystal violet sensitivity,
ultra-violet light sensitivity, and histidine requirement. Spontaneous
reversion rates were tested with each sample analyzed.
Rat liver homogenate was tested with 2-aminofluorene against strains
TA 98 and TA 100 to confirm the metabolic activation process.
Sterility checks were performed on solvents, extracts, liver
preparation, and all culture media.
PERIPHYTON ASSAY METHODS
Attached algal growths were sampled using artificial substrates, 1
x 3-in glass microscope slides. The substrate assemblies consisted of
floating wooden racks that exposed the slides horizontally under 2 to 4
centimeters of water. After an 8-day exposure in the stream, a portion
of the slides were placed in acetone, refrigerated, and held in the dark
for subsequent chlorophyll anlyses. The other slides were preserved in
formalin for subsequent determination of periphyton density and identifi-
cation of prevalent algal types.
-------
In the laboratory, the slides preserved in acetone were scraped
and rinsed into the acetone solution. Periphytic chlorophyll a was
determined fluorometrically, by comparison to acetone-extracted stan-
dards read on a spectrophotometer.
Slides preserved in formalin were scraped to remove attached
growths and rinsed into the formalin solution. Aliquots of the
formalin solution containing detached growths were examined micro-
scropically to determine density and types of periphyton.
The ash-free weight of the material covering the slides was de-
termined as a measure of biomass. Aliquots from the formalin-pre-
served samples were washed with several volumes of distilled water
and centrifuged. The concentrated samples were dried to a constant
weight at 105°C in tared porcelain crucibles. The samples were ashed
at 500°C for 1 hour, cooled, rewetted with distilled water, brought
to constant weight at 105°C, and weighed. Values for biomass (ash-free
weight) and chlorophyll a were used in calculating the ratio known
as the autotrophic index.
-------
BIOMONITORING METHODS
Toxicity tests consisted of 96-hour bioassays performed according
to EPA standardized methods (EPA-600/4-78-012). A continuous flow propor-
tional diluter was used which provided a series of six effluent concentra-
tions and a 100% dilution water control. Test chambers were of all glass
construction and of 8 liter capacity. Flow rates were regulated to provide
a minimum of nine volumetric exchanges of test solution for each chamber
for each 24-hour period. Each test chamber contained ten fish and each
concentration was done in duplicate.
The test fish used were young of the year fathead minnows obtained
from a commercial fish dealer in Minneapolis, Minnesota. All fish were
acclimated for a minimum of 48 hours in Cedar River water prior to testing.
Dilution water was obtained from the Cedar River at the suspension
bridge in Charles City (Station 10). The dilution water was stored in
1100 liter (300 gal) epoxy-coated wooden reservoirs and was replenished
twice daily.
Test water from the La Bounty dump site was obtained from a shallow
well (Station 06) drilled and cased by Region VII personnel. Approximately
130 liters (35 gal) of water was pumped from the well and delivered imme-
diately to the bioassay laboratory every six hours. Prior to each collec-
tion the pumping system was flushed with a minimum of 38 liters (10 gal)
of groundwater to assure freshness of the sample. Effluent from Salsbury
Laboratories was collected by hourly flow proportional compositing at
Station 01. The composite was held in a locked 190 liter (50 gal) plastic
barrel and delivered to the bioassay laboratory at six hour intervals.
Test water for the Charles City WWTP bioassays was obtained by direct
and continuous pumping from the primary clarifier overflow (Station 30)
and the final effluent discharge (Station 04).
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All test chambers were monitored daily for pH, temperature, and
dissolved oxygen concentration (Tables 1 to 4). In addition, the high,
middle and low concentrations were analyzed for total alkalinity. Water
temperature in the test chambers was maintained at 21.5°C±1°C by use of
a constant temperature recirculating water bath.
Mortalities in each test chamber were recorded at 24-hour inter-
vals. The 96-hour LC50 values and 95% fiducial limits were calculated
by Statistical Analysis System probit procedure.
FISH SURVIVAL AND PALATABILITY METHODS
In situ fish exposures were done using epoxy-coated wooden cages
(approximately 90 cm long, 30 cm high and 60 cm wide), ventilated on
four sides with wire mesh screening to permit continual and rapid flushing.
The cages are sufficiently buoyant to allow access through a hinged door
at the surface interface. Each cage was monitored daily for pH, water
temperature and dissolved oxygen concentration. Six test fish were exposed
in each cage and mortalities recorded at 24-hour intervals.
All test fish surviving the entire exposure period were retained
for flavor evaluation. The fish were removed from the exposure cages
live, returned to the mobile laboratory and immediately cleaned and frozen.
Flavor evaluation was performed by the Oregon State University Depart-
ment of Food Science and Technology, Corvallis, Oregon. The frozen samples
were received in Corvallis on July 21, 1978, and stored at -10°F until
4:00 p.m. on July 26, when they were placed at 40°F. The next morning,
July 27, the fish in each sample were separated, washed, then each frozen
sample was tightly enclosed in aluminum foil, placed on a broiler type
pan and cooked in a large commercial style gas oven at 400°F until the
flesh flaked from the bones, approximately 40 minutes.
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The cooked fish in each sample were boned, lightly mixed to insure
uniform serving samples, then placed in the top of double boilers over
hot water to keep warm for serving.
Two tests were conducted using the same procedure and the same
twelve judges. On test A, the judge received a tray containing five
coded sample cups and one cup lableled "Ref" which contained the control
sample. The five cups coded with three digit random numbers contained a
duplicate control sample and samples 40, 41, 42, and 43. The test B
tray contained three coded samples, which were samples 45, 46, and 47.
The judges were asked to score all coded samples on the intensity
of off-flavor from 7, no off-flavor to 1, extremely off-flavor, and then
score the hedonic flavor from 7, very desirable to 1, very undesirable.
The judges were experienced in this type of flavor difference testing.
Because of the limited quantity of samples, it was possible to secure
only 12 judgments on each test.
INDIGENOUS FISH POPULATION METHODS
Fish collecting for indigenous population estimates was done using
15 meter (50 foot) double wing trap nets. To the degree possible, site
selection was made to reflect similar environmental conditions and water
depth. All traps were set and retained in place during the same 24-hour
period.
Captured fish were removed from the traps on site, identified,
measured for total length and returned live to the Cedar River. Repre-
sentative fish of species which could not be positively identified on
site were preserved in an alcohol formalin solution and returned to the
NEIC laboratory in Denver for conformation.
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Table 1
PHYSICAL-CHEMICAL CHARACTERISTICS
SALSBURY LABORATORIES PROCESS WASTEWATERS
June, 1978
Effluent Concentration (%)
Control
Parameter (Cedar River Water)
4.0
7.2
12.8
22.4
30.0
40.0
24-
hour
DO mg/1
6.0
6.0
5.5
5.5
5.0
5.0
5.0
pH
8.4
8.3
8.2
8.1
8.0
8.0
8.0
temp °C
20.6
20.7
20.8
20.8
20.8
20.7
20.8
Total Alkalinity
105
111
121
48-
hour
DO mg/1
7.3
6.5
6.3
6.8
5.5
5.8
5.5
PH
8.5
8.3
8.2
8.1
8.0
7.9
7.9
temp °C
20.7
20.6
20.6
20.6
20.6
20.6
20.8
Total Alkalinity
162
163
177
72-
hour
DO mg/1
8.0
7.0
6.3
5.3
5.0
5.0
5.0
PH
8.1
8.0
7.9
7.8
7.8
7.7
7.7
temp °C
21.5
21.3
21.4
21.4
21.4
21.4
21.5
Total Alkalinity
173
203
232
96-
hour
DO mg/1
7.0
6.3
5.8
5.3
5.3
pH
7.6
7.7
7.6
7.6
7.5
temp °C
21.2
21.3
21.3
21.2
21.2
Total Alkalinity 173
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Table 2
PHYSICAL-CHEMICAL CHARACTERISTICS
LA BOUNTY DUMP SITE GROUNDWATER
June, 1978
Effluent Concentration (%)
Control
Parameter (Cedar River Water)
1.1
2.0
3.5
6.2
8.2
11.0
24-
hour
DO mg/1
6.8
6.3
5.5
5.5
5.0
5.0
5.5
pH
8.5
8.4
8.3
8.3
8.3
8.2
8.2
temp °C
21.0
21.0
21.0
21.0
21.0
21.0
21.0
Total Alkalinity
105
165
206
48-
hour
DO mg/1
8.0
6.0
6.0
5.8
5.0
5.0
5.3
pH
8.7
8.3
8.3
8.3
8.3
8.2
8.2
temp °C
21.0
21.0
21.1
21.2
21.0
21.1
21.2
Total Alkalinity
162
217
261
72-
hour
DO mg/1
8.0
5.8
6.0
5.5
5.0
5.0
5.0
pH
8.1
7.9
7.9
7.9
7.8
7.8
7.8
temp °C
21.4
21.4
21.4
21.4
21.4
21.4
21.4
Total Alkalinity
173
233
275
96-
hour
DO mg/1
7.0
6.3
5.0
5.3
pH
7.6
7.5
7.5
7.5
temp °C
21.1
21.0
21.0
21.0
Total Alkalinity 173
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Table 3
PHYSICAL-CHEMICAL CHARACTERISTICS
CHARLES CITY WWTP PRIMARY OVERFLOW
June, 1978
Effluent Concentration (%)
Control
Parameter (Cedar River Water)
6.0
10.8
19.2
33.6
45.0
60.0
DO mg/1
6.0
24-
6.0
hour
6.0
6.5
6.0
6.8
4.0
PH
• 7.6
7.5
7.8
7.5
7.6
7.6
7.3
temp °C
22.1
22.1
22.0
21.7
21.8
21.3
21.2
Total Alkalinity
191
195
200
DO mg/1
6.3
48-
6.8
hour
7.0
6.8
6.0
6.5
5.5
PH
7.8
7.8
7.8
7.9
7.6
7.5
temp °C
21.7
21.6
21.6
21.5
21.4
21.0
21.0
Total Alkalinity
198
198
DO mg/1
6.8
72-
6.3
hour
5.0
6.3
5.8
5.8
PH
7.7
7.7
7.7
7.6
7.5
7.6
temp °C
22.0
21.9
21.7
21.7
21.5
21.3
Total Alkalinity
198
201
DO mg/1
6.0
96-
6.3
hour
5.0
6.0
6.3
5.8
PH
7.9
7.8
7.6
7.8
7.5
7.5
temp °C
22.1
22.1
21.9
21.8
21.7
21.4
Total Alkalinity
208
205
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Table 4
PHYSICAL-CHEMICAL CHARACTERISTICS
CHARLES CITY WWTP EFFLUENT
June, 1978
Effluent Concentration (%)
Control
Parameter (Cedar River Water)
10
18
32
56
75
100
DO mg/1
7.0
24-
5.8
hour
6.5
7.0
6.0
6.8
5.5
pH
¦7.7
7.7
7.8
7.7
7.7
7.5
7.4
temp °C
22.0
22.0
21.7
21.7
21.5
21.2
21.1
Total Alkalinity
191
178
185
DO mg/1
7.0
48-
6.0
hour
6.8
7.0
6.8
7.0
4.5
pH
7.6
7.5
7.7
7.5
7.7
7.6
7.3
temp °C
21.4
21.7
21.3
21.5
21.3
21.0
20.8
Total Alkalinity
198
206
210
DO mg/1
7.0
72-
5.8
hour
6.8
7.0
6.0
6.8
pH
7.5
7.5
7.8
7.6
7.4
7.5
temp °C
21.7
21.7
21.5
21.6
21.5
21.2
Total Alkalinity
198
204
DO mg/1
7.0
96-
6.3
hour
6.8
7.0
6.5
6.5
pH
7.7
7.5
7.9
7.7
7.5
7.6
temp °C
22.1
22.2
21.9
22.0
21.8
21.3
Total Alkalinity
208
204
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CHEMISTRY
-------
CHEMISTRY ANALYTICAL METHODOLOGY AND QUALITY CONTROL
The analytical procedures used by the Chemistry Branch are described
in the following sections which are organized by working groups Inorganics,
Organics, and Trace Metals. The quality control procedures and data used
to verify the quality of the analytical data are also discussed.
INORGANICS
The samples from this study were analyzed for the following inorganic
parameters - BOD, COD, TSS, TOC, NH3, phenolics. Methods approved by the
EPA for the NPDES program (40 CFR 136, Federal Register, December 1, 1976)
were used to analyze all samples. The references to the methods for each
parameter are listed in Table I below.
Parameter Technique
BOD Multiple bottle dilution
COD Dichromate reflux-titration
TSS Glass fiber filter filtration
TOC Combustion-Infrared
NH3 Automated phenolate
Phenol ics 4-AAP colorimetric
Detection Limit,
mg/1 Reference
2 Std. Methods, pg. 543
5 " pg. 550
1 " pg. 94
1 " pg. 532
0.05 " pg. 616
0.001 " pg. 574
Std. Methods = "Standard Methods for the Examination of Water and Waste-
water", 14th edition (1975).
Written methods prepared from "Standard Methods" for BOD and TSS are included
as Attachments I & II. Additional precautions taken during the analysis of
the samples are discussed below by parameter.
BOD
The dissolved oxygen meter was calibrated by the azide modification of
the Winkler method ("Standard Methods", 14th edition, 1975, pg. 443) to assure
accurate D.O. measurements. The D.O. depletions were normal for all dilutions
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-2-
of a1! samples except those from the LaBounty Dumpsite. The BOD results from
those samples indicated the samples were toxic as the more dilute bottles had
higher depletions. The values reported were calculated from the greatest valid
depletion and are probably quite conservative.
Quality control consisted of duplicate analysis of five samples and multi-
ple analysis of reference samples in addition to those procedures described
in the method. The quality control results are excellent. The 4.4% precision
and 0-10% low bias in reference sample results are well within the acceptable
limits listed in "Standard Methods".
TSS
The attached method and quality control procedures were closely followed.
The 3.0% precision and 97 - 103% agreement of experimental and true values on
the reference samples are well within acceptable limits.
Phenolics
The methods used for the phenolic samples were the direct photometric
and chloroform extraction procedures referenced in "Standard Methods14th
ed., pages 574, with the following additions:
Samples from the five sites had varying amounts of ONA* which, if present
would have interfered with the spectrophotometric determinations. 500 ml
aliquots of samples 07104-01 to 07104-06 and 07102-01 were pre-extracted at
pH 12 with 2-25 ml portions of methylene chloride to remove excess ONA.
Background corrections were performed on all samples except the field
blanks. For the direct determinations 100 ml aliquots of the distillate or
aliquots brought up to 100 ml were used. Two such aliquots for each sample
were analyzed. One aliquot had all reagents including 4AAP** added; the
other aliquot used for background correction had an equal volume of distilled
water instead of the 4AAP added. The background absorbance was then subtracted
from the total absorbance obtained from the aliquot to which 4AAP was added.
For the chloroform extraction determinations, the 500 ml distillate
typically obtained from the sample was split into two equal portions. One
portion was treated with all reagents and extracted into 25 ml chloroform;
the other portion, used as a background was treated with all reagents except
4AAP and extracted into 25 ml chloroform. The absorbance obtained for the
chloroform extract from the background portion was then subtracted from the
total absorbance obtained for the chloroform extract from the other portion
before computing the final phenolic sample concentrations. Samples 07102-01,
all 07104 and the three field blanks were analyzed by the chloroform ex-
traction procedure.
In order to enhance the sensitivity of the direct method, 5 cm path-
length cells were used instead of the normal 1 cm path cells. Additionally,
the concentrations of the standards were lowered by a factor of 10.
*o-Nitroaniline
-------
Table II. Summary of Inorganics Quality Control Data
Reference Samples
Parameter Precision 1 % n Spike Recovery^ % n Experimental True, n
mg/1
mg/1
BOD
4.4
5
—
148
203
139
146
221
147
1
5
2
TSS
3.0
4
38
938
262
899
39
957
252
884
1
1
1
1
Phenolics
9.0
2
87 - 99%
2
0.19
0.192
1
COD
2.3
6
94 - 103%
5
230
231
2
TOC
0.9
4
96 - 100%
3
90
90
1
nh3
1.2
6
89 - 101%
5
1.59
1.80
0.18
1.59
1.72
0.15
5
1
1
^Precision was determined by duplicate analysis of samples. The values reported
are the % difference of the duplicate measurements.
^Spike recoveries are reported as % spike recovered compared to the amount added
to the sample.
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-3-
Three field blanks were analyzed. All had concentrations below the
detection limit of 0.001 mg/1. Two field duplicates were analyzed and the
results agreed within 9%. The mean spike recovery of 93% and the close
agreement of values on the reference samples are well within acceptable
1imits.
COO
The approximate chloride concentration of each sample was checked and
mercuric sulfate added to eliminate any interference. Precision and spike
recovery data and results on the reference samples are well within acceptable
1imits,
TOC
All samples with non-homogeneous particulate matter were homogenized
before analysis. -In addition, each sample was acidified and purged with
nitrogen to remove the inorganic carbon. Several samples were analyzed for
inorganic carbon to be sure that all of it was removed by the sparging pro-
cedure. Precision and spike recovery data and results on the reference
samples are well within acceptable limits.
NH3
Precision and spike recovery data and results on the reference samples
are well within acceptable limits.
ORGAN ICS
Several techniques for the analysis of organic compounds were utilized
for the Salsbury survey. Identification of individual organic compounds was
made by combined gas chromatography/mass spectrometry (GC/MS) while both packed
column gas chromatography (GC) and capillary column gas chromatography (CPGC)
were used for quantitation and confirmation of identity. The samples were
analyzed for neutral extractables, volatiles, and selected samples were analyzed
for priority pollutants. Approved EPA methodology was used where applicable.
NEUTRAL EXTRACTABLES ANALYSIS
GC/MS Identification: Methylene chloride extracts of the water samples
concentrated to small voTumes and exchanged with acetone were analyzed by
GC/MS. The initial identification was made using a computer assisted evaluation
program. (1) A library of standard spectra of the commonly occurring compounds
found in the extracts was created and a routine computer search was made of
each sample after GS/MS analysis. Each identification was verified by a manual
search using reference spectra analyzed under the same instrumental conditions
used for the samples. In those instances where other than the commonly occur-
ring compounds appeared, a more complete search was made utilizing the complete
computer library and a follow-up manual search. (2) (3) (4)
Packed Column Gas Chromatography: All the sample extracts were analyzed
by packed column gas chromatography using a computer controlled automatic in-
jector. Initial screening and quantitive analysis were carried out on this
-------
-4-
gas chromatograph. The compounds were identified and quantitated by an external
standard computer method. (5)
Capillary Column Gas Chromatography: The lower limit of detection for
o-Nitroaniline using the packed column chromatography was much higher than
expected, because of numerous interfering peaks that made it difficult to
identify and quantitate low level peaks. Several positive identifications
by mass spectrometry at low levels were not confirmed. It was necessary, to
utilize glass capillary gas chromatography which readily separated these com-
pounds and gave a confirming identification. Quantitation was made using peak
height measurement.
References
1. "INCOS Data System - MSDS Operator's Manual, Revision 3". Finnigan Instru-
ments, March 1978.
2. "Eight Peak Index of Mass Spectra", Mass Spectrometry Data Centre, Alder-
maston, Reading, NY. Second Edition 1974.
3. "Registry of Mass Spectral Data", Stenhogen, Abrahamson and McLafferty,
John Wiley & Sons, New York 1974.
4. "Atlas of Mass Spectra Data" edited by: Stenhagen, Abrahamson and McLafferty,
John H. Wiley & Sons, New York 1969.
5. "Hewlett-Packard, 3352 Data System User's Manual".
Qua!ity Control: Quality control procedures consisted of analysis of
selected duplicate samples, analysis of solvent and procedure blanks to identify
interferences, and gas chromatographic analysis of standards on a daily basis
to confirm the integrity of the GC system. For mass spectrometry, a daily
calibration was used to tune the mass spectrometer, then another standard (1)
was analyzed by combined GC/MS and this spectrum used to verify the proper
tuning of the mass spectrometer and the integrity of the complete system.
The quality control procedures are completely documented in the attached
methodologies. (See attachments III, IV, V, & VI).
VOLATILES ANALYSIS
GC/MS Identification: An aliquot (5 ml) of a water sample was purged
with inert gas. The lower molecular weight purgable organic compounds were
stripped from the sample and trapped on a porous polymer. These compounds
were then desorbed from the column by reversing the gas flow and rapidly
heating the trap. The volatile organics released were collected on an
analytical GC column at room temperature. After collection, the GC column
oven was heated at a uniform rate and the eluted compounds analyzed by the
mass spectrometer. The common volatile organic solvents are all identified
using this technique and it also includes the identification of the volatile
priority pollutants. This procedure is the method recommended for the priority
pollutants. (1) The identification again was made using a computer assisted
evaluation program as for the neutral extractables. (2) A library of stand-
ard spectra was created by analyzing all the commonly occurring organics in
the Salsbury samples, and adding these to the library. The samples were
routinely searched for these compounds for each sample analyzed by GC/MS.
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-5-
Quantitative results were obtained using an internal standard computer tech-
nique. (2)
References
1. "Samples and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants", U. S. EPA, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, March 1977, revised April 1977.
2. "INCOS Data System - MSDS Operator's Manual - Revision 3", Finnigan
Instruments, March 1978.
Quality Control: Quality control procedures consisted of daily routine
calibration of the GC/MS, analysis of an organics free water blank, and a
standard mix at a concentration near midpoint of the standard calibration
curve. The calibration curve was previously established by analyzing each
standard over a typical working range of 20 to 200 ppb concentration, with
response factors calculated relative to an internal standard. Field blanks
were analyzed with each set of samples. Replicate analyses were run on at
least two samples for every set of twenty samples or less. Again, the complete
quality control data and procedures are documented in the attached methodolo-
gies. (See attachments VII & VIII).
PRIORITY POLLUTANTS ANALYSIS
GC/MS Identification: Selected samples were analyzed for priority
pollutants by GC/MS using the recommended EPA procedure. (1) The volatiles
were measured using the same technique described previously for the volatiles
analysis, because both techniques are the same. The extractable organics
were analyzed for both acids, and neutrals, and bases combined as recommended.
References
1. "Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants", U. S. EPA, EMSL, Cincinnati, Ohio, March 1977,
revised April 1977.
METALS
The samples from this study were analyzed for the following metals:
As, Ba, Cd, Cr, Cu, Hg, Pb, Se, and Zn. Methods approved by the EPA for the
NPDES program (40 CFR 136, Federal Register, December 1, 1976) were used in
the analysis of all samples. The references to the methods for each metal
are listed in Table III.
The methods listed in Table III for each element were closely followed.
There were no significant deviations from the approved methods. As an added
precaution, all analyses, with the exception of Ba and Hg, were performed using
background correction procedures in order to preclude extraneous signals from
the sample matrix.
-------
Table III
Metal Technique
Detection Limit,
mg/1
Reference^
As
Flameless Atomic Absorption
0.01
A
Ba
Flame Atomic Absorption
0.50
B, p. 97
Cd
Flame Atomic Absorption
0.04
B, p. 101
Cr
Flame Atomic Absorption
0.10
B, p. 105
Cu
Flame Atomic Absorption
0.09
B, p. 108
Hg
Atomic Absorption, Manual Cold Vapor
0.0003
B, p. 118
Pb
Flame Atomic Absorption
0.10
B, p. 112
Se
Flameless Atomic Absorption
0.01
A
Zn
Flame Atomic Absorption
0.01
B, p. 155
Atomic Absorption Newsletter, 14 111, (1975)
B =
Methods for Chemical Analysis of Water and Wastes, Environmental
Agency, (1974)
Protection
-------
-6-
Arsenic
The method listed in Table III was closely followed. Arsenic was found in
higher concentrations in the study samples than any other element. In one set
of samples from the LaBounty Site Leachate, the arsenic concentrations ranged
from 550 to 680 mg/liter.
Sample replicates and spikes were analyzed for arsenic. All replicates
were within acceptable limits (- 10%). The recoveries for the sample spikes
ranged from 97 to 110% with an average recovery of 105%. An EPA reference
standard (#3 lot 575) was also analyzed. The experimental value was 0.158
mg/1, while the true value was 0.154 mg/1 arsenic.
Barium
The method listed in Table III was closely followed. Barium was found in
detectable amounts in samples from the LaBounty Site Leachate only. The barium
concentrations at this site ranged from 0.5 to 0.9 mg/liter.
Sample replicates for barium were all in good agreement with the original
analyses. The samples were spiked at a level which was not detectable. No AQC
data was available for barium because barium is not contained in the reference
standards.
Cadmium
The method listed in Table III was closely followed. Cadmium was not found
in any of the study samples.
Sample replicates for cadmium were all in good agreement with the original
analyses. Sample spikes ranged from 96 to 112% with a mean recovery of 104%.
The EPA reference standard #3 lot 575 was analyzed. The experimental value was
0.07 mg/liter, while the true value was 0.073 mg/liter cadmium.
Chromium
The method listed in Table III was closely followed. Chromium was not
found in any of the study samples.
Sample replicates for chromium were all in good agreement with the original
analyses. Sample spikes ranged from 88 to 120% with a mean recovery of 107%.
The EPA reference standard #3 lot 575 was analyzed. The experimental value was
0.20 mg/liter, while the real value was 0.209 mg/liter chromium.
Copper
The method listed in Table III was closely followed. Copper was found in
detectable amounts in the Salsbury Process Wastewater, the LaBounty Site
Leachate, and the LaBounty Site Direct Discharge. The copper concentrations
for these sites ranged from 0.09 to 0.10 mg/liter.
-------
-7-
Sample replicates for copper were all in good agreement with the original
analyses. Sample spikes ranged from 94 to 116% with a mean recovery of 103%.
Jhe EPA reference STD #3 lot 575 was analyzed. The experimental value was
0.10 mg/liter, while the real value was 0.102 mg/liter copper.
Lead
The method listed in Table III was closely followed. Lead was not found
in any of the study samples.
Sample replicates for lead were all in good agreement with the original
analyses. Sample spikes ranged from 86 to 100% with a mean recovery of 98%.
The EPA reference standard #3 lot 575 was analyzed. The experimental value was
0.35 mg/liter, while the true value was 0.352 mg/liter lead.
Mercury
The method listed in Table III was closely followed. Mercury was found at
all study sample sites. The mercury concentrations for the study samples ranged
from 0.0003 mg/liter to 0.0170 mg/liter.
Sample replicates for mercury were all in good agreement with the original
analyses. Sample spikes ranged from 107 to 200% with a mean recovery of 131%.
This represents a positive bias in the mercury results. However, at these low
concentration levels, this deviation magnitude is typical. The EPA reference
standards #1, 2, and 3 lot 575 were analyzed. The experimental values were
0.7, 4.2 and 9.6 ug/liter, while the true values were 0.8, 4.5, and 9.4 ug/liter
mercury respectively.
Zinc
The method listed in Table III was closely followed. Zinc was found in
all study samples except those taken at the LaBounty Site Direct Discharge,
Salsbury Cooling Tower Discharge, Cedar River U.S.G.S. Gage, Cedar River -
Above W.W.T.P. Discharge, Cedar River Spring, and Cedar River Seep. The zinc
concentrations for the study samples ranged from 0.01 mg/liter to 0.34 mg/liter.
Sample replicates for zinc were all in good agreement with the original
analyses. Sample spikes ranged from 97 to 110% with a mean recovery of 104%.
The EPA reference standard #3 lot 575 was analyzed. The experimental value
was 0.19 mg/liter, while the true value was 0.174 mg/liter zinc.
-------
Attachment I
BIOCHEMICAL OXYGEN DEMAND - DO PROBE PROCEDURE
(5 Days, 20°C) STORET NO. 00310
Scope and Application
1.1 The biochemical oxygen demand test is a laboratory bioassay procedure
used to estimate the quantity of oxyqen that is required to stabilize
the biodegradable matter in a wastewater.
1.2 The test was originally designed for and works most reliably ori raw
and treated domestic wastes. The test can be applied to industrial
wastes with careful attention to interferences and correct choice of
biological seed.
Summary of Method
2.1 An appropriate number of dilutions of each sample are prepared usinq
dilution water with added nutrients so that at least one dilution has
a depletion of at least 2 mg/1 and a residual DO of at least 1 ma/1
after incubation for 5 days in the dark at 20°C.
2.2 Dissolved oxygen is measured by a DO probe based on the polaroqraphic
prmcip.e. The probe is calibrated with air saturated water at known
temperature and atmospheric pressure.
San.ple Handling and Preservation
3.1 Samples should be stored in ice or in a refriqerator at 4°C and analyzed
as soon as possible but no later than 24 hours after collection.
Apparatus
4.1 Glass or tin-lined still to produce distilled water.
4.2 Five nallon qlass bottles wrapped with nylon tape to store dilution
water.
4.3 Incubation bottles, approximately 390 ml, with standard ground qlass
tops and plastic caps to maintain water seals. The exact volume of
each bottle is measured using water at 20°C with class A volumetric
glassware and any that are not 300 +_ 5 ml are discarded.
4.4 An incubator with a continuous temperature recorder controlled at 20°
+ 1 C. A calibrated mercury thermometer is placed in the incubator
water-c°ntaining flask and the temperature is checked daily.
A ^solved oxygen meter, automatically temperature compensated, if
possible, with a self-stirring probe.
4.6 A Tekniar SDT Tissuemizer with variable speed control to homoqenize
samples.
4.7 Barometer
-------
Reagents
5.1 Distilled water, free of orqanic contaminants as indicated by the
Permanganate Test as follows: Determine the consumption of potassium
permanganate by adding 0.20 ml of KMnCty solution (0.316 g/1) to 500 ml
of the distilled water and 1 ml of conc. H^SO^ in a stoppered glass
bottle. The water has passed the test if the permanqanate color does
not disappear in less than 10 minutes upon standing at room temperature.
Ideally, the color should be retained for 30 minutes.
5.2 Phosphate buffer solution: Dissolve 8.5 g potassium di-liydrogen phos-
phate, KHqPO^, 21.75 q dipotassium hydrogen phosphate, K^HPO/j, 33.4 g
disodium hydrogen phosphate heptahydrate, ^HPOW^O arid 1.79 g
ammonium chloride NH^Cl in about 500 ml distilled water and dilute to
one liter. The pH of this buffer should be 7.2. Store in the refriger-
ator and discard (including any of the following reagents) if there is
any sign of biological growth in the hottle.
5.3 Magnesium sulfate solution: Dissolve 22.5 g MgSO^I-^O in distilled
water and dilute to one liter.
5.4 Calcium chloride solution: Dissolve 27.5 g anhydrous CaCl2 in distilled
water and dilute to one liter.
5.5 Ferric chloride solution: Dissolve 0.25 g FeCl3-6H20 in distilled water
and dilute to one liter.
5.6 1 N H2SO4 and 1 N NaOH solutions.
5.7 Sodium sulfite solution, 0.028 N: Dissolve 1.77 g anhydrous NapSO-i in
one lite- distilled water. Prepare daily.
5.8 Reagent grade potassium iodide.
5.9 Starch indicator solution: Add a cold water suspension of 59 g soluble
starch to 800 ml of boiling v:ater, with stirring and boil for a few
minutes. Cool, dilute to approximately 1 liter and let settle over-
night. Use supernate and preserve with 5 ml of chloroform.
5.10 Glucose-qlutamic acid solutions: A) Dissolve 150 mg of each in dis-
tilled water and dilute to 1 liter. B) Dissolve 100 mg of each in
distille-d water and dilute to 1 liter. Split up each solution into 25 ml
bottles or tube, autoclave at 121°C for 1/2 hour, and store at 4°C or
prepare fresh daily.
5.11 Biological seed.
Glassware and Dilution Water Preparation
6.1 All dilution water and reagent storage bottles, BOO incubation bottles,
and other glassware must be free of orqanic contaminants and toxic
metals. Clean all qlassware with hot soapy water, rinse with 3 N HC1,
rinse three times with hot tap water and twice with distilled water.
Any qlassware with a film should not be uspd.
6.2 The distilled water should be cooled to 20^C, saturated with oxygen by
bubbling air through the water and then stored at 20°C until use. Oust
prior to using the dilution water, add 1 ml each of the magnesium
sulfate, calcium chloride, ferric chloride, and phosphate buffer solution
solutions for each liter of water. The biolomcal seed should be added
(5 ml seed/1 of dilution water) to the dilution water just before use.
-------
- 3 -
7. Selection of Seed
7.1 All chlorinated domestic wastes and most industrial wastes require
seeding because of low microbial populations. The standard seed
material is primary treated sewage that has been stored at 20°C for
24 hours. However, it is important that, if possible, the seed to
be used has been exposed to the waste that is being measured. There-
fore, an effluent from a treatment process or a receiving water col-
lected below the outfall will sometimes be used as seed material.
-8. Interferences and Pretreatment of Samples
871 Blend samples containinq non-homogeneous particulate matter with the
Tekmar SDT Tissuemizer. Thirty seconds is usually adequate.
8.2 Neutralize samples with a pH outside of the ranqe 5-10 using the 1 N
acid or base. Most samples do not require neutralization because the
buffering capacity of the dilution water and dilution of the samples.
8.3 Residual chlorine kills the seed organisms. All samoles except those
known not to contain residual chlorine should be checked as follows:
Add 5 ml of 1 N H2SO4, 2 g KI crystals and 1 ml of starch solution
to 100 ml of sample. Add the 0.028 N sodium sulfite solution in
0.1 ml increments until the purple color disappears. Each O.l ml
increment corresponds to 1 mg/1 CI2- Add a proportional volume of
0.028 N sodium sulfite to an aliquot of sample for testing. If there
is any uncertainty, add an extra increment of sulfite. An excess of
sulfite solution of 1 ml/1 sample causes a BOD of less than 0.5 ma/1,
which is insignificant.
8.4 Many organic compounds and trace metals are toxic to the seed organisms.
Sometimes this interference can be eliminated by sample dilution.
Higher BOD values from the more dilute aliquots is evidence of sample
toxicity. These results should be carefully evaluated before beinq
reported.
8.5 Samples containing more than 9 mg/1 DO at 20°C may be encountered during
winter months or in localities where alqae are growinn actively. To
prevent loss of oxygen during incubation of these samples, reduce the
DO to saturation by bringing the sample to about 20°C in a partly filled
bottle and agitating it by vigorous shaking.
9. Calibration of Dissolved Oxygen Meter
9.1 Carefully fill 3 BOD bottles by use of a siphon with dilution water
(containing nutrients but not seed) that has been saturated with air
at 20°C. Using the table in the DO meter manual, find the DO concen-
tration at the ambient atmospheric pressure and 20°C. Set the tem-
perature dial on the meter if necessary to 20°C and adjust the cali-
bration knob until the meter reads the value determined from the table.
Save the other two bottles for checking the meter during the analysis.
9.2 Driftina of the meter response or a very slow response to DO changes
is usually caused by a coated or torn electrode membrane.
10. Sample Analysis Procedure
10.1 Since most samples require more than 7 mg/1 of O2 for stabilization,
dilutions are required before incubation. Prepare a sufficient number
of dilutions so that at least one aliquot depletes at least 2 mg/1 and
has a residual DO of at least 1 mq/1 after incubation. Usually three
and sometimes four dilutions are required. Dilutions up to 1% are
made directly in the BOD bottles. A guide to sample size selection
follows:
-------
- 4
Measurable? POD Range Sample Size, ml Factor % Pi In lion
4 - 12
8 - 24
12 - 36
20 - 60
40 - 120
60 - 180
120 - 360
200 - 600
150
75
50
30
15
10
5
3
2
4
6
10
20
30
60
100
50
25
16.67
10
r
y
3.33
1.67
10.2
10.3
10.4
10.5
10.6
For dilutions less than 1%, the sample is first diluted 1/10 or
1/100 with dilution water and then the dilutions are comoleted in
the BOD bottles. The samples should be homoqenized and shaken just
before aliquots are taken. A qraduate cylinder is used to measure
volumes of 15 ml or larger. Large bore pi pets are used for smaller
volumes. One bottle per'dilution is prepared. Exercise care in
filling the bottles with dilution water so as not to have the water
into the neck of the bottle more than 1/8".
Prepare two bottles with seeded dilution water. Depletion of these
samples should be about 0.6 mg/1 if domestic sewage is used for seed.
Blank values over 1.0 mg/1 indicates contaminated dilution water or
incubation bottles.
Prepare one bottle with 5 ml of glucose-qlutamic acid standard A and
one bottle with 10 ml of standard B and fill with seeded dilution
water. The results for standards A and B should be about 200 and
160 mq/1, respectively.
Measure the initial DO of all samples, being careful not to displace
any of the dilution water. At the same time the DO is measured, the
probe mixes the samples. Wash the probe with distilled water between
each sample. After determinina the DO it may be necessary to add a
small amount of dilution water to prevent trapDinq bubbles in the
bottle when stopperinq. Place a water seal in the neck of the bottle
and place a cap over the neck to maintain the water seal.
It is helpful to measure the DO of the samples after two days in order
to judge the adequacy of the dilutions selected. Pour off the water
seal before measurinq the DO. Calibrate the DO meter according to the
directions given in Section 9. Measure the DO of the most concentrated
dilution of each sample. If there is less than 2 mq/1 residual HO,
increase the dilution factors on subsequent days and measure the DO in
the next most dilute sample. If the DO on the second sample is less
than 4 mq/1, re-aerate with an air stone attached to an air pump beinq
careful not to displace any of the water. Record the initial residual
and re-aerated DO values. Discard any sample with a residual DO below
1 mg/1. If there is less than a 2 mq/1 depletion, increase the strenqth
of the dilutions on subsequent days.
The final DO measurements are made within 4 hours of 5 days of when
the samples were set up. Calibrate the HO meter by the method qiven
in id'Co.'vjn 9. Any dilutions resulting in residual DO1 s that are
1 mg/1 or greater, and depletions that are 2 mg/1 or greater are valid.
Calculate the BOD values by the following formula:
-------
- 5 -
BOD5 = F[(DrDf)-f(B)]
where Dj = initial DO of sample, mg/1
Df = final DO of sample, mg/1
B = the mean depletion of the two seeded dilution water blanks,
mg/1
f = decimal fraction of dilution water in sample bottle
f = whole number dilution factor of sample
For example, 30 ml of sample was used, the initial DO was 8.2 mg/1
and the final DO was 1.7 mg/1. The initial DO of both of the seeded
blanks was 8.1 mg/1 and the final DO was 7.3 mg/1
B0D5 = 10[(8.2-1.7)-0.9(8.1-7.3)]
= 10[6.5-0.9(0.8)3
= 10[6.5-0.7]
= 10[5.8]
= 58 mg/1
10.7 Report the average value of all of the valid dilutions to the nearest
whole number with at most two significant figures. If the 00 deple-
tions increase with increasing dilution, toxicity is indicated and
the results should be carefully evaluated before being reported.
10.8 The results of the ASB glucose-nlutamic acid standards should be be-
tween 160-240 and 130.-190 mg/1, respectively. High results indicate
a very efficient seed or contaminated samples. Low results indicate
a poor seed or blank values that were too hiqh.
10.9 The mean of the seeded dilution water blank depletions should be be-
low 1 mq/1, ideally 0.6 mg/1. High values indicate contaminated
nutrients and minerals, dilution water or qlassware. Correct any
problems before proceedinq.
10.10 Report the BOD .values from different dilutions as duplicates on the
AHC sheets.
10.11 Attach the incubator temperature recorder chart to the BOD Data/
Calculation Sheet (attached).
Prepared by M. Carter 6/9/78
-------
BOD Data/Cnlculation.-Sheet, Rev. 6/9/78
Analyst Study Date/Time In
Date/Time Out
ScT"! le No.
•-: •< 1 o pH
-"ile vol. ml
I n i' i a 1 DO', mq/1
1
2-ri* y DO, mq/1
Re-. crate DO, ing/1
' ^ al DO, mq/1
'ire: 2 0? dep. , mq/1
Blank Corr., mq/1
Net Op depl., mq/1
Fac tor
1301^, mg/1
Mean liODq, mg/1
Sample No.
Sam;le pH
Sam; le vol , nil
Inilial DO, mq/1
l-dc. / DO , mq/1
'to-;*orate DO, mq/1
Tinr.) DO, mg/1
-> Op depl. ,mq/l
Blan!' Corr. , mq/1
tiet 0p depl. , mq/1
Fee Lor
BODr;, mq/1
Mean CODc;, mg/1
DO Probe Calibration
temp horr.
press.
DO, mg/1
initial
2-day
5-day
-------
Attachment II
TOTAL SUSPENDED SOLIDS
STORET NO. 00530
Scope and Application
1.1 The method is applicable to drinking, surface and saline waters,
and to domestic and industrial wastes.
1.2 The detection limit of the method is 1 mg/1.
Summary of Method
2.1 A homogenized sample is filtered through a pre-washed glass fiber
filter. The residue retained on the filter is washed and then dried
to constant weight at 105°C and weighed to the nearest 0.1 milliqram.
The TSS is calculated from the amount of residue per unit volume of
sample.
2.2 The filtrate from this method may be used to determine the total
dissolved solids.
Sample Handlinq and Preservation
3.1 Samples should be stored at 4°C and analyzed as soon as possible,
but no later than 7 days after collection.
Apparatus
4.1 Whatman GF/C glass fiber filter discs, 43 mn.
4.2 Millipore membrane filtering apparatus with reservoir and a coarse
fritted disc as a filter support.
4.3 Aluminum drying pans, 50 mm and metal tray.
4.4 Tekmar SDT Tissuemizer.
4.5 Drying oven, 103°-105°C.
4.6 Desiccator, with Drierite indicating desiccant.
4.7 Analytical balance, 160 g capacity or larger, sensitive to 0.1 mg
and one weight equivalent to the optical ranqe of the balance.
4.8 Graduate cylinder and wide bore pi pets.
Balance Calibration
5.1 Using a balance with an optical ranqe of 1.0 q, place a 1.0 q (15%)
weight on the balance pan, set the weight control knob to 1.0 g,
release the balance and set the zero point with the optical zero
knob. With the balance released, slowly turn the weight control
knob back to zero. The optical scale should come to rest exactly
at 1.0 g. If the reading is more or less than 1.0 q, arrest the
balance, remove the top housinq cover and adjust the sensitivity
weight. Repeat the calibration check.
Procedure
6.1 Preparation of qlass fiber filter disc: Place the glass fiber fil-
ter on the membrane filter apparatus with wrinkled surface up.
While vacuum is applied, wash the disc with 100 ml of distilled
water. Remove all traces of water by continuing to apoly vacuum
after water has passed through. Remove filter from membrane filter
apparatus, place in aluminum pan, and dry in an oven at 1Q3-1Q5°C
for one hour. Remove to desiccator and store until needed. Weigh
immediately before use. After weighing, handle the filter with
forceps only.
-------
- 2 -
6.2 Homogenize all non-uniform samples with blender and shake the
bottles before withdrawinq an aliquot to assure taking a represen-
tative sample.
6.3 Choose a maximum sample volume that will filter in 5 minutes or less.
Measure volumes smaller than 15 ml with wide bore pi pets and larger
volumes with graduate cylinders. Discard any sample which does not
filter in 5 minutes and filter a smaller sample volume.
6.4 Wash the graduated cylinder or pipet and with the suction on, wash
the filter funnel wall, filter and residue with two twenty-five ml
portions of distilled water allowing complete drainaqe between
washings. Remove all traces of water by continuing to apply vacuum
after water has passed through.
6.5 Carefully remove the filter from the filter supDort. Place in an
aluminum pan and dry at least one hour at 103-105°C. Cool and weiqh
immediately or place in a desiccator for later weiohinq. Re-dry and
re-weigh 10% or at least one filter per set of samples. If the in-
cremental weight loss is less than 0.5 mg, calculate the results
based on the original weights. If the weight loss exceeds 0.5 mq,
re-dry and re-weigh all of the filters and re-check 10% of the filters.
6.6 Analyze two blanks per set of samples by filtering 100 ml of distilled
water through two prepared filters. The amount of additional weight
loss after the filters have been prepared is nearly independent of
the volume of water filtered. Therefore, add the mean blank weight
loss to the residue weight for each sample.
6.7 Analyze 10% or at least one sample per set in duplicate.
6.8 Analyze a standard sample with each sample set.
6.9 Calculate the results as follows:
TSS = (Wfi - WT) + B
Wq = Gross weight of filter and residue, mg
Wy = Tare weight of filter, mg
B = The mean of the two blank results, mg
Where B = B-| + B2
2
B1 = bt - bg
Bt = Tare weiqht of filter, mg
Bf; = Gross weight of filtering
V$ = Volume of sample filtered, 1
-------
TSS DATA/CALCULATION SHEET, REV. 6/9/78
Analyst Study Date/Time Filters in Oven
Date/Time Out
Sample No.
Sample Vol., 1
Re-check Wt. mg
Gross Wt., mq
Tare Wt., mg
Residue Wt., mc[
Blank Corr., mcL
Corr. Res. Wt., mg
CT1
E
*
CO
IS)
1—
-
Sample No.
Sample Vol., 1
Re-check Wt., mg
Gross Wt., mcj
:are Wt., mg
Residue Wt., mg
31ank Corr., mg
Corr. Res. Wt. , mg
TSS, mg/1
Sample No.
Sample Vol., 1
Re-check Wt., mg
Gross Wt. , mg
Tare Wt,, mg
"?sidue Wt., mg
Si ank Corr., mq
Corr. Res. Wt., mq
[TSS, mg/1
Balance Calibration
Reading on 100 mg weight, mg
Tare
Gross
Re-check
-------
Attachment III
Neutral Extraction Technique for Organics Analysis August 1978
1.0 Scope and Application
1.1 This procedure is applicable for analysis of
water and wastewater samples for a broad
spectrum of organic pollutants.
2.0 Summary of Method
2.1 Water and wastewater samples are extracted with
CH2C12 (dichloromethane) at a neutral dH. The
extract is dried and concentrated with the
addition of acetone to exchange solvents. The
resultant extract concentrate is subjected to GC and
GC/MS analysis to identify and quantitate the organic
pollutants present.
3.0 Sample Handling and Preservation
3.1 Prior to extraction, samples are refrigerated
and extracted as soon as possible, generally
within 48 hours. Samples may be held 5 days or
more if necessary.
4.0 Definitions and Comments
5.0 Interferences
5.1 Solvents, glassware and reagents could be sources
of contamination. Therefore, at least one "Reagent
Blank" must be prepared contacting the solvent with
all potential sources of contamination. This blank
should then be processed through the same analytical
scheme as the associated samples.
5.2 Typical interferences from reagents are:
4-methyl-4-hydroxy-2-pentanone (diacetone alcohol)
from acetone, phthalate esters from ^SO^,
cyclohexene from dichloromethane.
-------
6.0 Apparatus
6.1 Separatory tunnels: 21 and 41 glass with glass
or teflon stoppers and stopcocks. No stopcock
grease used.
6.2 Drying column: All glass 3 cm x 50 cm with
attached 250 ml reservoir.
6.3 Concentrator: 250 or 500 ml Kuderna-Danish
evaporative concentrator equipped with a 5 or
10 ml receiver ampule and a 3 ball Snyder column.
7.0 Reagents
7.1 Extraction solvent: Pesticide analysis gradeCH2CI2
(dichloromethane) (Burdick and Jackson or
equivalent)
7.2 Exchange solvent: Pesticide analysis grade acetone
(Burdick and Jackson or equivalent)
7.3 Drying agent: Analytical reagent grade granular
anhydrous Na^SO. (sodium sulfate). Washed with
CH2CI2 prior to use.
7.4 Glass wool that has been extracted with CH^C^
prior to use.
7.5 6N NaOH for pH adjustment.
7.6 6N HC1 for pH adjustment.
7.7 pH paper for pH measurement.
8.0 Procedure
8.1 If low concentrations of pollutants are expected,
measure 3 1 of sample for extraction. Otherwise, one 1
is sufficient.
8.2 Measure and record the initial pH. Adjust the pH
to 6-8 if necessary and record the adjusted pH.
8.3 Extract the sample with 3 successive extractions
of 100, 50 and 50ml of C^c^ per liter of sample.
If emulsions form, use a wire or stirring rod to break
it, pass the emulsion through glass wool or
centrifuge if necessary. Combine the extracts and
measure the volume recovered. 85 percent constitutes
an acceptable recovery.
-------
8.4 PI ace' a glass wool plug in a drying column and
add ca 10 cm of ^SO^. Wash the with
at least 50 ml of C^C^. Pour the combined
extract through the column. Follow with 100ml
of acetone. Collect the CHpCU and acetone and
transfer to a KD assembly.
8.5 Concentrate on a hot water bath at 80-90°C to
2-5 ml. Wash down the KD with acetone and trans-
fer the extract to a graduated 12-15ml centrifuge
tube. Dilute to 5.0ml with acetone. If necessary,
concentrate to 5.0 ml under a gentle stream of
purified air. Transfer to a 12ml vial and cap with
a teflon lined cap. (Note: The final extract volume
should depend on the sample. Extracts containing
high concentrations of pollutants may not require
concentrations to 5ml while cleaner samples may
require a final volume of 1ml.)
9.0 Quality Control
9.1 A representative group of the organic pollutants of
interest should be spiked into water and carried
through the extraction procedure, recoveries
calculated and compared to literature values
(if available).
10.0 Calculations
10.1 Solvent Recovery:
% recovery = Volume recovered (ml)*100/volume added (ml)
10.2 Pollutant Recovery:
% Recovery = (Concentration measured - initial concentration)*100
Concentration added
11.0 Precision and Accuracy
11.1 Precision and accuracy vary with the pollutants
being measured. Recoveries range from 40 to 100
percent and precision values range from 1 to 70
percent relative standard deviation (% RSD).
Typical values are however 90 - 5% RSD.
12.0 References
(1) "An EPA GC/MS Procedural Manual-Review Copy,"
Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio.
-------
Attachment IV
Computer Assisted Evaluation of Charles City
Neutral Extractable Organics GC/MS Data 7/78
1.0 Scope and Application
1.1 This procedure is applicable to GC/MS data collected under con-
stant conditions for qualitative data analysis.
2.0 Sunroary of Method
2.1 GC/MS data files are processed by comparing the spectrum of a
known or suspected pollutant from a library to each spectrum
within a retention time (RT) window. If a spectrum matches
the library spectrum sufficiently, an entry is made in a table
showing at what spectrum the match occurs and how good the
match is. After completion of the search, each spectrum that
was identified as a probable pollutant is printed. Manual
comparison of the sample spectra to spectra obtained frcm pure
compounds on the same instrument confirm or deny the presence
of the pollutant.
3.0 Sample Handling and Preservation
4.0 Definitions and Comments
4.1 In sane cases, compounds may be identified by external refer-
ence spectra only (1,2,3). These "unconfirmed" compound data
may however be useful since the computer matching still traces
the presence of each compound through each sample analyzed.
Therefore, even the "unconfirmed" pollutant can serve as a
tracer for the waste stream under investigation.
-------
- 2 -
4.2 Quantitation of pollutants identified is effected by locating
the corresponding GC peaks on GC/FID (flame ionization detec-
tor) chrcmatograms. The areas of the peaks are measured and
compared to the areas' of standards containing known amounts
of pure components. The concentrations are then determined
by siirple calculation. (4)
5.0 Interferences
5.1 Since absolute RT's are used for setting the search windows,
the windows must be wide enough to account for slight varia-
tions in instrument and operation conditions, This could al-
low misidentification of a peak by the computer. Manually
checking each spectrum produced, however,essentially eliminates
this problem.
6.0 Apparatus
6.1 Finnigan BCOS data system running at least Revision 3.1 soft-
ware. To initially set up and run this procedure, the user must
understand and be proficient in the use of MSDS (5).
7.0 Reagents
8.0 Procedures
8.1 Method Setup and Initial Calibration
8.1.1 Using predetermined conditions analyze standard solu-
tions of suspected or known pollutants.
8.1.2 Create a MSDS library containing the spectra of the com-
pounds of interest. Include the absolute retention times
determined from the standards runs. Appendix A is a
typical library list.
-------
- 3 -
8.1.3 Copy the procedures onto the systsu disk from another
disk or type in the procedures shown in Appendix B.
8.2 Procedure Operation
8.2.1 Create a name list containing the name(s) of the data
file(s) to be processed.
8.2.2 Call the procedure with the procedure name fo3 lowed by
the namelist and "NO":
SALSEE namelist, NO
"NO" causes the procedure to search the "SE" (Salsbury
Ex tract ables) library only (Appendix A). A "yes" an-
swer causes a search of the "NB" (National Bureau of
Standards) library for any peaks found but not identi-
fied in the "SE" library.
8.2.3 The procedure will generate a list of the acquisition
parameters/ a chromatogram, an identification table
(Appendix C) and the spectra of any identified peaks.
After each file is processed, the terminal will beep
once. When all the files in the namelist are processed,
the terminal will beep 3 times.
9.0 Quality Control
9.1 Each analysis day, a spectrum is obtained from the standard
reference compound decaf luoro triphenyl phosphine (6) a lid
evaluated for an accurate and reproducable spectrum.
-------
- 4 -
9.2 Each identification is verified by manually comparing the
sample spectra to the reference spectra in the "SE" library.
Inaccurate computer results are re-evaluated and the correct
data reported.
10.0 Calculations
11.0 Precision and Accuracy
11.1 The auto processing method's accuracy is limited only by
the quality of the data being processed.
12.0 References
(1) "Eight Peak Index of Mass Spectra," Mass Spectrometry Data
Centre, Aldenmaston,Reading, UK. Second Edition 1974.
(2) "Registry of Mass Spectral Data" Sterihagen, Abrahams son and
McLafferty, John Wiley & Sons, New York 1974.
(3) "Atlas of Mass Spectra Data" edited by: Stenhagen, Abrahams-
son and McLafferty, John H. Wiley & Sons, New York, 1969.
(4) "Salsbury Organics Methodology and QC" EPA, National Enforce-
ment Investigations Center, July 1978.
(5) "INCOS Data System - MSDS Operators Manual - Revision 3", Fin-
nigan Instruments, March 1978.
(6) Eichelberger, Harris and Budde, Anal. Chem. 47(7), 995 (1975)'
-------
APPENDIX A
hAPI HUM: NAME
UT FOPMl'LA
REL.RET.TIMS'CAS*
RET TIME BASE AREA U.P.»1 U.P.*2
MASS AMT. REF.PEAK RESP.FILE RESP.FACTOR
SE 1:
103 C5
SE 2:
93 C5.
ACETYL ACETONE
¦H8.02
0.000
ANILINE
H3.H
0.000
0.603 0.03
3:06
5:41
0.0S0 0.00
43
B
0.
93 260352.
0.000
6.03d
e.Bee
0.003
0.000
e.eea
SE 3:
94 C6.
SE 4:
123 C6
SE S:
12? CS.
SE 6:
139 C6
SE 7:
157 CS
SE 8:
135 CS.
PHENOL
.H6.0
0.000
NITROBENZENE
H5.C2.N
0.009
B.060 0.00
0.000 B.00
5:41
8:16
94 192768.
O-CHLOROANILINE
.H6.N.CL 10:23
e.oaa 0.000 0.00
O-NITROPHENOL
,H5.C3.N 9:18
0.000 B.BB0 0.B0
P-CHLORONITROEENZENE
.H4.02.N.CL 11:53
0.OQ0 0.000 0.00
ACETANILIDE
H9.0.N
6.000
14:57
0.086 0.00
SE 11:
133 C8
SE 12:
6 C6.
SE 13:
6 C6
SE 14:
6 C7
SE 15:
0 C7
2-0CTAN0L
•HI3.0 6:31
0.800 0.E00 0.C3
EEftZOFURAN (NOT CONFIRMED)
¦H4.G.N2 7:09
6.0C0
0.000 0.00
0
77 241409.
0
127 280576.
0
139
0
0
34432.
Ill 212480.
0
93 9S916.
SE 9: O-NITROANILINE
138 C6.h5.02.N2 15:18 138
0.000 0.680 0.00 0
SE 10: P-MITROANILINE
136 CS.H5.02.H2 19:22 138
6.000 0.600 0.00 0
64030.
17056.
45
90 46144.
0
BENZENE,1.2-DICHLORO-3-NITRO (NOT CONFIRMED)
.H3.02.N.CL2 13:57 145 2704.
0.003 0.003 0.03 0
EENZENE.I-CHL0R0-2-rETHYL-3-NI730- (MOT CONFIRMED)
.HS.02.N.CL 14:40 125 32032.
0.060 0.080 0.00 0
EE!IZ0NITRILE.2-CHL0R0-6-NITR0- (NOT COU=IRr£D)
•H2.C2.N2.CL 16:32 136 2323.
0.OC0 0.G00 0.03 B
SE 16- PIC'iLGROSENZ AMIDE ISCMER (NOT CONFIRMED)
189 C7.H5.0.H.CL2 2O:0G 1?3
e.cao 0.eaa 0.03 c
2936.
6.830
0.680
B.63J
B.C09
6.008
C.003
0.003
a.esa
0.000
0.630
0.033
0.033
0.000
c.oao
6.000
6.603
0.003
0.630
0.e63
6.630
B.6C0
o.ecs
6.693
6.CC9
e.oea
e.oae
0.030
e.eeo
0.033
o.eeo
6.039
0.003
0.633
e.ooa
e.000
0.03B
0.630
0.600
6.063
0.633
8.033
0.003
SE 17: D1CHL0R0BENZAMIDE ISOrEf? (NOT CO'lFIRfED)
-------
APFENDIX A cont.
189 C7.H5.C.H CL2
0.000
22:32
0.060 0.00
173
0
2168.
SE 18: BENZflMIDE.4-CHL0R0-3-NITRO- ChOT CONFJPt^D)
200 C8.H6.03.N.CL
8.000
24:03
0.600 0.03
184
0
33929.
SE 19: L'NKNOUN PEAK A
0 26:09
0 000 0.000 0.00
105 111363.
0
SE 20: 2-FHENYL BENZAMIDAZOLE (NOT CONFIRMED)
0
31:34
3.000
0.000 0.00
SE 21: BENZENE. 1.2.4-TRICHL0t?0-
180 C6.H3.CL3 10:36
B.Geo 0.000 0.00
194
0
180
0
SE 22: DINITR0CHLCR06EHZENE ISOMER CN3T CONFIRMED)
202 C6.H3.04.N2.CL 17:31 202
0.000 0.000 0.00 0
19828.
0.
11360.
SE 23: 3-KEPTfiNONE
114 C7.H14 0
0.003
3:51
0.000 0.00
57 13424.
0
SE 24: 2-ETHYLHEXANAl
128 C8.H16.0 5:13
O.C00 0.030 0.80
SE 25: 2-ETHYL-l-HEXAHOL
130 CS.HIE.O 7:03
a.eeB b.obo 0.00
57
8168.
265723.
0.008
o.fces
0.eea
0.000
0.003
o.eco
0.000
0.623
0.030
0.033
3.000
0.E33
0.003
0.0P0
0.000
0.220
0.033
0.0?0
0.000
8.099
C.000
0.000
0.009
8.303
0.000
0.000
0.090
-------
APPENDIX B
iRACE OF PRGCERIKE SALSBfc
* t PROCEDURE FOR EVALUATION OF SALSBURY SURVEY (JUNE 1978)3
[NEUTRALS EXTRACTA9LE MS DATA. THE PROCEDURE FIRST 3
[PRINTS THE PARAMETERS ABOUT THE ACQUISITION. THEN J
[PLOTS A CHROMATOGRAM (FROM MAP) U1TH PEAKS LABELED BY 3
[BtEMANN-BILLER. NEXT THE FILE IS REVERSE SEAPCKED FROM]
[SPECTRA IN LIBRARY SE (SALSBURY EXPECTABLE SJ.A TABLE J
[OF THE RESULTS IS PRINTED FOLLOUED BY EACH OF THE J
[SPECTRA THE COMPUTER DETERMINED TO BE PRESENT. IF THE 3
[USER RESPONDED 'NO' AT THE PROCEDURE START. THIS 3
[ ROUTINE UILL CONTINUE FOR AS MANY FILES AS UERE IN 3
[THE NAMEL1ST. IF THE USER RESPONDED "YtS". THE SYSTE1 3
[UILL CONTINUE AND DO A NB LIBRARY SEARCH ON EACH PEAK 3
[IT FOUND IN THE MAP. THE EXCEPTION IS. HOUEVER. THAT 3
[ANY PEAKS IDENTIFIED EARLIER FROM LIBRARY SE UILL NOT 3
[BE RE-SEARCHED. 3
[CALLED BY: SALSBE NAMELIST.YES(NO) 3
[URITTEN JUNE 29,1978 BY O.J.LOGSDON II 3
[USEPA/NEIC 303-234-4661 3
SETN $1
SETL S2
SALS91
FILE(K SALSB1.SL/N;K SALSB2.SL/N;E)
BEEP;BEEP;BEEP
ERASE
[PROCEDURT SALSBE IS COMPLETES
*
*
*
*
m
*
*
K
*
*
*
*-
*
*
*
*
*
*
*
*
*
*
*
*
#
SETN SI
SETL S2
SALSB1
* GETN
* ;SET1 *0
* JSALSB2
* jEEEP
* ;LOOP
*
GETN
SET1
SALSB2
* PfiRAU ;H;E)
* ;SETS SALS92;EDSL(-;U:E)
* ;SET5 SALS31;EDSL(-;U;E)
* ;MAP(l;F1;U1O0;V758900;33.260;N>2.5.10;HI,900,320;E)
* ; SET'S SE
* ;SET4 «0
* ;FILE(K PRIN.99/N;E)
* ;SALSB3
* ;PRIN(eSE)
* ;FILE(C PR!N.99.M:/N;E>
* ;FEED
* ;SET10 *0
* ;SETS SALSB2;EDSL(-110:11: E):SETS *0
* ;SALSB4
* ;IF 126 SALSB2.SPLSB2
* ;SET4 NB
* ;SETS SALSBljSETS *3
* ;SALSB5
w ;FEED
*
Pfi'tA (1 ;H;E)
SETS SALSB2
EDSL (-;L);E)
SETS SALS3I
EDSL (-;U;E)
TOP (I;F1;U180:V7560D0:33,200:N>2,5.10;H1,S00.330;E) .
SET4 SE
SET£
FILE (K PRIN.99/N.E)
SALSB3
* SET4 14,,~!;SETI4 *0
-------
APPENDIX B cont.
* ;IF #1 124 SRLSB3.I4 SALSB3
* jSERR'VCI;S;&; K33.30O;V?50003;H1.59.700;D-25.25;E)
* ;PR1N/KX(>4.12;!14.5;!15.8;!16.6;C;E)
* ;SETS SRLSB2;EDSL
* ;LOCP
*
GETS
LIBR (I;'jF;X1.5;H;HSl;EJ
LOOP
FEED
BEEP
LOOP
FILE
-------
Attachment V
Summary:
The ten below listed compounds, which are anticipated to be detected fre-
quently in the Salsbury survey, were analyzed for percent recovery and
linear quantitative response:
Of these, all, except acetyl acetone and aniline, showed good recovery
characteristics at the'500 ppb level and with the exception o* acetanilide
and the nitroanilines, all were detectable at the 10 ppb level. Addition-
ally, all compounds, except o-nitrophenol, showed a linear relationship
between computed peak area and concentration throughout the examined range
of 10 to 500 ng/ul (equivalent to approximately 50 to 2500 ppb in a 5 ml
concentrated extract of one liter sample or 3.3 to 167 ppb from a 1 ml
concentrated extract of a 3 liter sample).
Acetyl Acetone
Aniline
Nitrobenzene
o-Chloroaniline
o-Nitrophenol
p-Chloroni trobenzene
Acetanilide
o-Nitroaniline
p-Nitroaniline
Caffeine
-------
Instrumental Analysis Methodology:
All samples were analyzed on a Hewlett-Packard (HP) 5700a qas chromatograph
(GC/FID) equipped with an automatic sample injector system and a HP3352
data system.
The automatic injector delivers 1.25 ul (Microlitres) of samole to the
injection port yielding retention time data with a standard deviation of
about +0,015 minutes and response data of + 3% relative standard deviation.
Injection sequence, intervals, and sample names are described on a computer
routine.^
Compounds of interest were identified and quantified by an external stan-
dard computer method. The method works by looking for peaks within a
specified retention time window. If a peak is found within the window,
the computed area is multiplied by a factor to yield an amount in nano-
grams per microlitre (ng/ul) units, then the peak is given the compound
name assigned to that window.
The factor was obtained from stored data from an initialization run of the
component samples at the 100 ng/ul level. The computer divided 100 ng/ul'
by the stored area to obtain a factor for each compound. This was done
once, prior to running samples for data, and the factors were then left
unchanged thereafter. A Cg-Clg hydrocarbon performance standard run,
made daily throughout the analysis, was used to adjust for slight changes
in instrument sensitivity.
^Hewlett-Packard 3352 Data System Users Manual
-------
Copy of method used to identify and quantify confounds of interest.
READY
~LI,M,PPQNT
1. CHAN, PP.0C, RPRT, RDVC
1 , £.S i D , M T I
2. SAMP, UNTS, TITLE
, NG/UL , PRI POL'S FID QUANT METH
3. £'PXS, RTM, PP.G
83, 52 • 00, YES,
4. MIN AR, MV/M, DLY, DVT, DIL-FTR%
10eS, .030, 0.03, 0.00, 130.00
5. REF-RTV, £R?7, I D-LVL, ?.F-UKK
.15, 7, 1003, 1.0G0
6. » KVN PKS
10
e
TIME
AMT
FACTOR
NAME
1
1.67
1 •0020E
2
= 1 . 4790E-
4
ACTL A
2
4.15
1 •0300E
2
=2.5145E-
4
#ANILN
3
6.82
1 •3000E
2
= 3 • 5 1 26 E-
4
/?NI ENZ
4
8 . 17
1 .3030E
2
=4.1684E-
4
#cla:ja
5
8 . 39
1 . 30CT0E
2
=9•5437E-
4
NI PH EM
6
1 1 .22
1 . 0033E
2
=4.3762E-
4
#CLW3Z
7
16.42
1 » 0302E
2
= 6. 3 43 1 E-
4
ACETAN
8
16 . 56
1•0320E
2
=4.1853E-
4
0-NIAU
9
22.62
1 . 0 2 2 0 E
2
=5.3633E-
4
P-NI A:J
10
28.43
1 .SPSSE
2
=7.5152E-
4
#CAFE.\*
DOME
-------
Co, -y of computer routine used in conjunction with the automatic sample in-
j" tion system.
READY
*L I .> AL S> 4
1. 1ST 3TL, *3TLS, RCAL, INJ/7C
2 j 2/ 9,t 108
2. VSHS, ?M?S, 5T0°, #INJ
5, 5, \j 1
3. CTM,V3TL, ISO
73.3, NO, NO,
4. SiETHD
p?o:it
5. NAMES
BTL 2: II 120
STL 3: 1100
DOME
Extraction Accuracy and Effeciency:
The accuracy and effeciency of the overall neutral extraction was eval-
uated by analyzing one liter aliquots of tap water spiked at 10 and 500 ppb
levels of the compounds listed below:
% Recoveries
NAME
500 pph
10 ppb
Acetyl Acetone
46 + 2%
883a
Aniline
47 + 67%
45
Nitrobenzene
92 + 4%
66
o-Chloroani1ine
91 + 3%
59
o-Nitrophenol
148a+ 26%
170a
p-Chloronitrobenzene
97 + 11%
65k
Acetani1ide
77 + 15%
NDb
o-Nitroaniline
95 + 3%
ND
p-Nitroaniline
106c+ 4%
ND
Caffeine
69 + 2%
HOC
apeaks coincident with an interference
knot detected
cwithin experimental error
Spike samples were extracted with 100, 50, and 50 ml portions of methylene
chloride. To this was added 100 ml of acetone (exchange solvent), and the
product was then concentrated to 5 ml in a Kurderna-Danish evaporative condensor.
-------
Recoveries listed at the 500 ppb level represent the average of three
extractions, while the 10 ppb spike recovery data is the result of a sinqle
extraction. Data appears comparable to that published in An EPA GC/MS
Procedural Manual by EPA's Cincinnati Environmental Monitoring and Support
Laboratory.
Linearity:
The area under a component peak is proportional to the amount injected.
Whether or not this relationship in a linear one, i.e. whether or not
there is a constant factor which can describe the ratio of concentration
to peak area for a component, over a broad concentration range, is a
question worthy of addressinq. If the relationship is linear, then a known
component peak, of any size, may be quantitated against that component's
standard concentration peak, regardless of relative size. However, if
the relationship in non-linear, then the unknown and known concentration
peaks will have to be made similar in size, through dilution, for an
accurate quantification to be made.
As eliminating the need to adjust condensation, and make multiple GC
analytical runs would save much time, it would be hiqhly desirable to
know the range throughout which the concentration: area relationship is
linear for each specified component. In an effort to determine this, each
of the below listed compounds was analyzed at 10, 50, 100, 250, and 500
ng/ul levels and the results plotted on a graph of area vs. calculated
concentration.
-------
Linear range
COMPOUND
*L0W END (nq/ul)
*HIGH END (ng/ul)
Acetyl Acetone
Aniline
10
10
10
10
250
10
10
10
10
10
500
500
500
500
500
500
500
500
500
500
Nitrobenzene
o-Chloroaniline
o-Ni trophenol**
p-Chloroni trobenzene
Acetanilide
o-Nitroaniline
p-Nitroaniline
Caffeine
*While 10 and 500 ng/ul are the lowest and highest values listed, these
are not necessarily the end points of the linear ranqe. These values
merely encompass the range analyzed.
**o-Nitrophenol plots as a wide parabola with an appearance of linearity
'in the upper end of the area vs. injected concentration plot.
Detection Limits;
A 10 ug/1 (10 ppb) concentration of sample components in 1 liter water
concentrates down to 2 ng/ul at 100% recovery in 5 ml acetone. Despite
percent recoveries as low as 45%, all compounds were detected at this leve
except Acetanilide, o-Nitroaniline, and p-Nitroaniline. That these were
not detected was somewhat surprising as these showed otherwise good re-
coveries and chromatographic characteristics. Noise peaks were well belov
interest peak size (0.1 to 0.01 times as large). Therefore, with these
recovery and chromatographic characteristics in mind, detection limits
can be placed between 5 and 10 ppb for a 1 liter extraction on the HP
GC/FID alone.
-------
Attachment VI
Organic Identification by Glass
Capillary Gas Chromatography
1. Scope and Application
1.1 This method is applicable to surface waters and industrial ef-
fluents. It is used for low ppb concentration levels of organic
canpourcls that do not separate completely using packed column
gas chromatography.
1.2 The limit of detection for this method is 1 ug/1 (ppb).
1.3 The concentration range is from 1 to 50 ug/1 (ppb).
2. Summary of Method
2.1 Concentrated extracts of 1 to 3 liter water samples in acetone
or iso-octane are injected into a glass capillary column using
flame ionization detector. Coincidence of retention time in
minutes with those of standard compounds establishes identity,
and quantitative results are made using peak height measurements.
3. Apparatus
3.1 Varian Model 3700 Capillary Gas Chranatograph with flame ioni-
zation detector (1).
3.1.1 Grob type injector for splitless injection
3.1.2 Capillary column glass
3.1.2-a Carbowax 20M 25 - 30 meters x 0.25 mm ID for
polar compounds
3.1.2-b 07-101. 20 - 30 meters x 0.25 mm ID for general
use.
4. Procedure
4.1 Inject 1 ul of sample into the gas chromatograph with the splitter
-------
turned off. Keep the splitter off for exactly 1 minute after
injection then turn on. (Splitter flow 100 ml/min)
4.2 The initial column temperature is equilibrated at 60°C and held
for 1 minute after injection, then a temperature program is
initiated at 4°C/min. to from 200-230°C depending on column in
use.
Identification
5.1 The compound of interest is identified by comparing the reten-
tion time of the peak with that of a standard. Confirmation is
effected by comparison with data from GC/MS identification when
possible.
Calculation
6.1 Prepare a standard curve plotting peak heights of 20, 15 and 10
nanogram standards. Calculate concentration in ng/ul by com-
paring peak heights of samples with standard curve.
6.2 Quantitation
6.2.1 Calculate sample concentration in ug/1 (ppb) in the water
sample as follows:
ug/1 = A x B x 100
C D
where:
A = ng/ul read frcm standard curve
B = concentrated extract volume in ml
C = original water sample in liters
D = the % solution of the concentrated extract
References
(1) "Series 3700 Gas Chrcmatograph Operating and Maintenance Manual"
Pub. No. 85-001139-00, Varian Instrument Division.
-------
Attachment VII
VOLATILE ORGANIC COMPOUNDS BY GC/MS - NEIC 7/78
1.0 Scope and Application
1.1 Water and wastewater samples may be analyzed for purgeable
organic compounds, typically methylene chloride through ethyl
benzene by GC/MS. Both qualitative and quantitative data are
generated. This procedure includes data evaluation as defined
for screening of industrial wastes for "priority pollutants"
as well as data for complete organics characterization of any
purgeable components.
2.0 Summary of Method
2.1 Aliquots of aqueous samples are purged with an inert gas. Low
molecular weight and slightly soluble components are stripped
from the solution and trapped on a porous polymer adsorbent
trap. Organic components are then desorbed from the trap by
rapid heating onto an analytical gas chromatographic (QC) col-
umn. As separated components elute from the GC column, they are
detected by a quadrupole mass spectcmeter. Quantitation of
compounds identified frcm their spectra is effected either by
external or internal standard techniques.
3.0 Sairple Handling and Preservation
3.1 Samples may be collected as duplicate grab samples. Duplicates
are useful for reanalysis of the sample if needed. If data
are to be correlated to other 24 hours composite samples, col-
lect multiple grab samples at regular intervals. They may be
composited at the lab prior to analysis.
3.2 Preserve the samples by maintaining at or below 4°C during
-------
- 2 -
shipment and storage. Samples containing residual chlorine
require the addition of O.lg Na2S203 per 100 ml of sample to
reduce the remaining chlorine.
4.0 Definitions and Comments
5.0 Interferences
5.1 Samples containing residual chlorine can produce halogenated
organics in excess of what was present at the time of collec-
tion. Therefore the addition of a reducing agent is necessary
if residual chlorine is suspect.
5.2 No head space is allowed in a sample. Samples containing head
space may loose volatile species and produce erroneous results.
5.3 Samples exposed to vapors of volatile organic compounds may
absorb those vapors and produce erroneous data. Blanks mast be
handled and transported concurrently with samples to identify
potential contamination.
6.0 Apparatus
6.1 Sample Bottles: 1 oz. glass bottles equipped with teflon-lined
silicone septa and screw caps (Pierce #13074 and #12722 or
equivalent). Before sampling, wash used bottles with soap
(Alconox or equivalent) and tap water, rinse with tap water.
New bottles require only washing with tap water. Bake bottles
at 200°C and septa at 80°C for 30 minutes. Allow to cool in a
desiccator with charcoal adsorbant to maintain an organics free
atmosphere. Then cap the bottles and hold for sampling.
6.2 Sample handling syringes: Samples are transferred using 5.0 ml.
gas-tight syringes equipped with gas-tight valves and 6"- needles.
(Tekmar or equivalent)
-------
- 3 -
6.3 Liquid sample concentrator: Tekmar LSC-1 or equivalent with
the following modifactions:
6.3".l Replace existing trap with a thin wall (0.020" stain-
less steel (SS) trap packed with 15 cm 60/80 mesh Ten ax
GC (Applied Sciences). Wrap the trap with fiberglass
insulated heating wire (Briskheat, 7 ohm per foot Nichrcme
wire for direct contact with metal or equivalent). Yfcap
the platinum resistance element between the SS tubing
arsd the heating wire. Attach the heater wire and resis-
tance element to the appropriate terminals.
6.3.2 Add a trap made of 12" of 3/8" copper tubing packed with
activated charcoal (190°C for 4 hours) immediately ahead
of the purging chamber.
6.3.3 Add a GC flow controller such that flow'going to the
GC column is regulated. The GC column then becomes com-
pletely independent of the existing GC flow systems.
6.4 GC column: Separations are effected using an 8' by 1/8" SS
column packed with 0.2% Carbowax 1500 on 60/80 Mesh Carbopack C
(available frcm Supelco).
6.5 Gas chranatograph: A Varian 1400 or equivalent equipped with
a linear temperature progranmer.
6.6 Detector: Finnigan 1015 mass spectrometer with Systems Indus-
tries System 150 data system, or equivalent instrument capable
of collecting continuous repetitive nass spectra (CRMS) over
a range of 33 to 260 arru in 5 seconds or less. The data system
must be capable of generating multiple extracted ion current
profiles (EIPC).
-------
- 4 -
6.7 Glassware: All glassware is washed as described in section
6.1 and baked at 105°C (up to 200°C) for at least 30 minutes.
6.8 Analytical Balance: Capable of measuring O.OOOlg for standards
preparation.
7.0 Reagents
7.1 Organic Free water: Pass tap water through a 2 x 40 cm column
of charcoal activated by heating to 190°C for four tours.
7.2.a Concentrated Standards (Liquid components): Stock solutions
are prepared at ca. 1 mg/ml in pesticide analysis grade meth-
anol. Due to the high volatility of sane carrpounds, exact
concentrations are calculated from the volume of pure compound
used and its density. To 10.0 ml of methanol in a 14 ml vial
with a teflon lined screw cap, add 10.0 ul of pure compound,
seal, mix and store in a freezer at -20°C. This stock standard
nay be stable for two months dependent upon the volatility of
the component. Calculate the concentration from the volume
of pure compound and its density as follows:
nq/ul = 10.0 x 10"-W x (density) g x 1 ng x 10~^ ml
10.0 ml ml 10-yg 1 ul
7.2.b Concentrated Standards (Gaseous coirponents): Stock solutions
of gaseous components may be prepared similarly to liquid cotv-
ponents with the following change. Prepare a vial containing
10.0 ml of methanol, weigh the capped bottle and record this
tare weight. Carefully bubble the pure gaseous component into
the methanol. When enough gas has been absorbed into the meth-
anol (estimated), reseal the vial and reweigh. The increase
in weight represents the amount of pure component added. Calculate
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- 5 -
the concentration as follows:
ng/ul = (net weight) mg x 1 ng x 10~~3 ml
10~6 mg U1
7.3 Working concentrate: Ranove the stock standard from the freezer
and allow to equilibrate to ambient temperature. With a 250
microliter syringe, prepare a mixed Standard with each component
at 20 ng/ul in methanol. Seal the solution in 2 ml crimp seal
vials with teflon lined septa. These working standards may be
stable up to one month depending on the volatility of the com-
ponents.
7.4 Analytical standards for GC/MS: Using a microliter syringe,
add 1 to 50 ul of the working concentrate to a 5.0 ml aliquot
of organic-free water. Analyze inmediately. Each ul of working
concentrate when added to 5.0 ml of water is equivalent to 4 ug/1
(ppb).
7.5 Internal standards: In the same manner as 7.2 and 7.3, prepare
a single working concentrate of branochlormethane (C^BrCl)
and 1,4 dichlorobutane (C^gC^) at 100 ng/ul each.
8.0 Procedure
8.1 Instrument Preparation
8.1.1 Install the gas chromatographic (GC) column by directly
passing through the injection port. Attach the column
using teflon ferrules only to allow subsequent disman-r
teling the system. Connect the other end of the tubing
to the trap exit of the Tekmar LSC-1. Attach a source
of ultra-pure helium to the inlet of the Tekmar. Adjust
the column flowrate to 30ml/min. Carefully check the
system for leaks.
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- 6 -
8.1.2 Periodically, replace the charcoal in the internal filter
of the LSC-1.
8.1.3 Set up the GC for 60°C initial and 170°C final temperatures,
an 8°C/min. program rate, and hold at the final tenper-
ature.
8.2 Mass spectrometer calibration
8.2.1 Adjust and calibrate the mass spectrometer according to
the manufacturer's specifications.
8.2.2 Analyze an organics-free-water blank to verify a clean
system.
8.2.3 Analyze a standard mix at a concentration near the mid-
point of the calibration curve. Check the response of
factors calculated for the multipoint calibration curve.
Check the response of each compound and verify if it is
within the range of response factors calculated for the
multi point calibration curve. If not, determine the
cause of the problem, make the necessary corrections
and reanalyze the standard.
8.3 Sample Analysis
8.3.1 Equilibrate sample bottles to ambient temperature and
pour and aliquot directly into a 5.0 ml syringe. Imme-
diately insert the plunger, invert the syringe, expel
any and adjust the volume to 5.0 ml. Ccnposite
samples may be prepared by adjusting the volume to the
desired anount for the individual aliquot and adding
this to a second syringe." Continue preparing the individual
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- 7 -
aliquots until the composite is prepared. Dose the
sample with 10 ul (1 ug each standard) of the internal
standard solution to yield a concentration of 200 ug/1.
8.3.2 Rsrove a glass purge device from the oven and cool in
the charcoal filled desicator. Attach to the Tekmar
and introduce the sample.
8.3.3 Purge the sample for 12 minutes at 40 ml/min. onto the
Tenax trap. At the same time, cool the GC oven to ambi-
ent tanperature by leaving the oven door open.
8.3.4 Set the trap desorb temperature to 180°C, switch to the
. desorb node and start a timer. After 3h minutes, begin
collection of CRMS using the following conditions:
Mass range: 20-27; 33-260
Integration time: 17 ms.
Or scan time up: 4 seconds
And scan time down: 0.1 seconds
After four minutes, switch back to purge mode, close
and set the temperature to 60°C.
8.3.5 After eight minutes, begin the GC temperature program.
8.3.6 While the sample is running, remove the purge device
and join the purge inlet and outlet line with a short
piece of 1/4" tubing. Turn on the trap bake and adjust
the tenperature to 200°C. Bake out the trap for at least
5 minutes. Wash the purge device with methanol and
place in an oven as described in section 6.1.
8.3.7 Collect data until the last components have eluted frcm
the GC column. Typically, 30 minutes.
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- 8 -
8.4 Data Evaluation
8.4.1 After each analysis, plot the reconstructed ion chromato-
gram (RIC) and extracted ion current profiles (EICP) for
each internal standard added. Integrate the areas of the
selected peaks and compare to the limits calculated in
section 9.6. If the base peak areas are outside the
acceptable ranges, evaluate the problem and reanalyze
the sample. If the data are acceptable, process the
data as required for organics characterization or pri-
ority pollutants as described below.
8.4.2 Organics Characterization. Select a spectrum and sub-
tract the background for each peak of interest. Generate
a plot of the spectrum for analysis. In addition, per-
form a search of the current NBS spectra library and
print out the results, (ref. 2)
8.4.3 Priority Pollutant Evaluation. Using the protocol pro-
cedures (ref. 3), generate and evaluate each compound's
EICP for the selected ions. Compounds that are present
may be quantitated as described in the protocol and sum-
marized in section 8.4.4.
8.4.4 Quantitation. Compounds identified are quantitated by
the internal standard techniques. An ion of the compound
is selected and integrated over the GC peak. The area
of an internal standard (typically 1,4-dichlorobutane,
m/e 55) ion is also determined. The concentration of
the component is then determined based on the amount of
internal standard (200 ppb here) and the r< lative response
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- 9 -
factor determined in section 8.4.5 by the following
equation:
CP = Ac x Cs
As Rf
Where: Cc = concentration of component (ppb)
Ac = area of component ion
As = area of internal standard ion
Cs = concentration of internal standard (ppb)
Rf = relative response facton (unitless)
8.4.5 Determination of Response factors: Prior to the analysis
of samples, response factors for the compounds of interest
relative to the internal standard must be determined and
verified over a concentration range. Analyze 200 ppb
(typical for VQA's) for each compound. Mixed standards
are acceptable. Measure the areas of the ions of interest
of the internal standard and the components in the stand-
ards. Calculate the response factors as follows:
Rf = Ac x Cs
As Cc
Where: Rf = relative response factor
As = area of internal standard ion
Ac = area of component ion
Cs = concentration of internal standard (ppb)
Cc = concentration of component.1 (ppb)
9.0 Quality Control
9.1 Standard Curve - Prior to the determination of any sample com-
ponents by CC/MS using internal standards, linearity for each
standard component must be established over a typical working
range of 20 to 200 ppb. This requires analysis of at least
four concentration levels: 0, 20, 100 and 200 ppb. Cal-
culate the response factors relative to one internal standard
-------
- 10 -
and determine the mean and percent relative standard deviation
(%RSD). Acceptable data are indicated by a %RSD of less than
20. Values outside this range indicate problans with response
linearity and the linear range must be carefully evaluated.
Table I shows typical data for 22 of the priority pollutants.
Daily, one standard mix at the midpoint of the linear range
must be analyzed and the response factors should fall within
the range indicated above. The %RSD range should be updated
as more data are generated to reflect changes in the method1 s
performance.
9.2 Precision - To determine the percision of the method a regular
program of analyses of replicate aliquots of environmental sam-
ples must be carried out. The precision criteria should be
developed frcm 15 sets of replicate results accumulated over a
period of time during the routine analysis program. At least
two replicate aliquots of a well mixed sample must be analyzed
with each set of 20 samples or less analyzed at a given time.
These replicate data must be obtained for each parameter of
interest.
Initially, samples selected for replicate analyses should
be those that are most representative of the interference poten-
tial of the sample type. As the program progresses, samples
representing the entire range of concentrations and interference
potential should be designed into the replicate analysis program.
After 15 replicate results have been obtained, calculate
the range (R^) of these results as follows:
-------
- 11 -
Ri ~ xil ~ xi2
where is the difference between the results of the pair
(X-q and X^2) fran sample i-1 through n. The concentration of
each sample is represented by the mean:
=
2
where X is the average of the results of the replicate pair.
A preliminary estimate of the critical difference (Rc) between
replicate analysis for any specific concentration level (C)
can be calculated as:
n n_
R = 3.27 (CZR^AZXi)
i=l i=l
Fran these data develop a table of such values for various
C values that span the concentration range of interest.
These preliminary critical difference values may be used
to judge the acceptability of the succeeding replicate results.
To do this, calculate the mean (X) and difference (R) between
the replicate results. Referring to the table of critical range
values developed above, find the C nearest to X and use its R
to evaluate the acceptability of R. If the R is greater than
Rc, the system precision is out of control and the source of
this unusual variability should be identified and resolved be-
fore continuing with routine analysis and periodically (after
25 to 30 additional pairs of replicate results cure obtained)
revise, update, and improve the table of critical range values.
9.3 Recovery - Determine the recovery of the method for the analysis
-------
- 12 -
of environmental samples by adding a spike (T-^/ true value)
sufficient to approximately double the background concentration
level (X^) of the sample selected earlier for replicate anal-
ysis (Section Al). If the original concentration is higher
than the midpoint of the standard curve (range of the method),
then the concentration of the spike should be approximately
one-half the original concentration. If the concentration of
the original sample was not detectable, the concentration of
the spike should be five to fifteen times the lower limit of
detection. The volume of standard added in aqueous solution
should not dilute the sample by more than ten percent. The
volume of standard added in an organic solvent solution should
be kept small (100 ul/1 or less), so that the solubility of
the standard in the water will not be affected.
Analyze the sample, calculate the observed value (0^),
and then calculate the recovery for the spike as follows:
P = 100(0i - Xi)/Ti
where is the percent recovery. If the sample was diluted
due to the addition of the spike, adjust accordingly.
After determining for at least 15 spike results, cal-
culate the mean percent recovery (P) and standard deviation
(Sp) of the recovery as follows:
n o n 2
P = (E P. - (E Pi) 7n
i-11 i=2
n n 2
S = 1 I P? - (I Pi) /n
p ST i-l i=2
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- 13 -
where n = the number of percent recovery values available.
If the percent recovery of the spike is not within the
interval of P ± 3 Sp, the syston accuracy is out of control
and the source of this systenatic error should be identified
and resolved before continuing with routine analysis.
At least one spiked sample must be analyzed along with
each set of 20 samples or less that is analyzed at a given time.
This spiked data must be obtained for each parameter of interest.
Record the recovery data of all spiked analyses and periodically
(every 25 to 30 data points) revise, update, and improve the
accuracy criteria.
9.4 System Blank - An organics free water blank must be analyzed
daily showing no contamination of the analytical system. If
EICP methods are being used to located pollutants," the blank
must also be subjected to the same analysis procedure. Data
collected frcm blanks may also be used to determine detection
limits based upon the responses of any components present. Cal-
culate detection limits for each component as twice the noise
measured. Typical detection limits are 1 to 2 ppb.
9.5 Field Blanks - A field blank must be analyzed with each set
of samples from a given source. This is particularly important
since volatile organics samples can potentially be contaminated
due to exposure of organic solvents. The blanks must be ana-
lyzed in the same manner as the sample. Field blanks for pur-
geables are sent frcm the laboratory to the sampling site and
re curried as a check on possible contamination of the sample by
permeation of volatiles through the septum seal.
-------
- 14 -
When interferences occur, the analytical results nust be
discarded unless sufficient data from these blanks is available
to permit correction of the results.
9.6 Internal Standards - Measure the areas of the quantitation ions
selected for the internal standards. Record the measured values
in the GC logbook. Since instrument variations are usually
small with an operating day, let the internal standard response
from the calibration standard be X and reference any variation
to X. Check each subsequent measurement and if it is outside
the range of X ± 15%, consider the analysis out of control.
Resolve the problem and reanalyze the sample. As more data
are collected, update the limits periodically.
10.0 Calculations
10.1 If the concentration of standard solutions and internal
standards in aqueous solutions are reported in ppb (parts per
billion), no further calculations are necessary. Dilutions,
when necessary, may be calculated assuming a 10% solution is
one part sample diluted to 10 parts with organic free water
by:
true conc. = measured conc. x 100
%sol.
11.0 Precision "and Accuracy - This section summarizes the quality con-
trol for precision, accuracy, recoveries and detection limits.
These data show that for the 16 pollutants evaluated:
a. The within-day precision is ca. ± 10% (compound dependent).
b. The day-to-day precision is ca. ± 26% (based on the second
internal standard response).
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- 15 -
c. The mean average recovery below 50 ppb is 110%.
d. All 16 compounds are detectable at 1 ppb.
11.1 Precision - Insufficient data have been collected to determine
ranges described in section 9.2. However, the data from 2
Replicate Analyses are reported here:
Name
Avg.
Diff.
Avg.
Diff,
benzene
1
2
5.6
0
carbon tetrachloride
ND
—
ND
—
chlorobenzene
ND
—
1.85
0.1
1,2-dichloroethane
ND
—
1.45
0.1
1,1,1-triehloroethane
ND
—
4.65
0.7
1,1,2-trichloroethane
2.4
0.2
333
14
1,1,2,2-tetrachloroethane
ND
—
ND
—
chloroform
ND
—
20
2
1,2-trans-dichloroethene
ND
—
ND
—
1,2-dichloropropane
ND
—
ND
—
ethyl benzene
ND
—
ND
—
methylene chloride
a
—
13.8
1.5
bromoform
ND
—
ND
—
brcmo dichloropropane
ND
—
ND
—
toluene
ND
—
8.75
0.1
trichloroethene
ND
_
1.45
0.1
a Replicate Analysis contaminated with methylene chloride
These data show the method to be reproducable to ca. 10%
(compound dependent) for analysis performed on the same day.
Another measure of precision is the analysis of sanples collected
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- 16 -
in duplicate at the sampling site. One such sample was ana-
lyzed and the results shown below:
Name
Avq.
Diff
benzene
1.4
0
carbontetrachloride
ND
—
chlorobenzene
3.75
0.3
1,2-dichloroethane
7.6
4.4
1,1,1-trichloroethane
ND
—
1,1,2-trichloroethane
981
29
1,1,2,2-tetrachloroethane
ND
—
chloroform
1.35
2.7
1,2-trans-dichloroethene
ND
—
1,2-dichloropropane
ND
—
ethylbenzene
ND
—
methylenechloride
3.87
6.06
broroform
ND
—
bronochloronethane
ND
—
toluene -
1.25
2.5
trichloroethene
1.65
0.5
11.2 Accuracy - The accuracy of the method may be estimated frcm
the recovery data in section 11.3. Another measure of the
overall method accuracy may be obtained from evaluation of
the measured concentrations for the second internal standard
(brcmochloromethane). Since this standard is added to every
sample at a constant concentration, it provides a measure of
the accuracy of the results in each sample. Overall, for 90
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- 17 -
determinations, the measured concentration was 199/ ± 51 ppb
(199 ± 26%) for brorrochloromethane at 200 ppb added concen-
tration.
11.3 Recovery - The accuracy of the method may be estimated based
on the recoveries obtained from spiking real samples with
known amounts of pollutants. For 5 samples spiked below 50
ppb, the average recoveries and standard deviations are shown
below:
Name %Recovery
benzene
136
+
37
carbontetrachlaride
110
+
20
chlorobenzene
124
+
32
1,2-dichloroethane
102
+
15
1,1,1-trichloroethane
115
+
19
1,1,2-trichloroethane
93
+
28
1,1,2,2-tetrachloroethane
112
+
26
chloroform
113
+
24
1,2-trans-dichloroethene
110
+
26
1,2-dichloropropane
104
+
9.5
ethylbenzene
103
+
14
methylene chloride
96
+
33
bramoform
91
+
22
branodichloranethane
113
+
24
toluene
142
+
31
trichloroethene
106
+
19
One sample spiked at 200 ppb yielded the following recoveries:
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- 18 -
Name %Recovery
benzene3 29
carbontetrachloride 76
chlorobenzene 107
1,2-dichloroethanea 7 5
1.1.1-trichloroethane 78
1.1.2-trichloroethane3 4 2
1,1,2,2-tetrachloroethane 96
chloroform3 11
1,2-trans-dichloroethene 79
1,2-dichloropropane 10
ethyl benzene 144
methylene chloride 24
branoform 80
bromcd ichloromethane 91
toluene 83
trichloroethene 86
Compounds noted "a" were present in the sample at high con-
centrations and the addition of 200 ppb exceeded the linear
response range.
11.4 Detection Limit - When using automatic data processing pro-
cedures, the detection limit is difficult to define. Since
the first step in data processing is identification of the
spectrum, the detection limit has been defined here as: The
minimum amount producing an identifiable mass spectrum. Once
the compound is identified, the amount present is measured.
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- 19 -
A reagent water blank was spiked at 1 ppb, analyzed and the
data autanatically processed. The results are listed belcw:
Name %Recovery
benzene 139
carbontetrachloride 97
chlorobenzene 148
1,2-dichloroethane 129
1.1.1-tr ichloroethane 133
1.1.2-trichloroethane 120
1,1,2,2-tetrachloroethane 106
tr ichloroethane 119
1,2-trans-dichloroethene 132
1,2-dichloropropane 94
ethyl benzene 105
methylenechlor ide 17 6
brcmoform 75
brarvodichlorcmethane 171
toluene 114
tr ichloroethane 111
These data show detection of all the compounds spiked at 1 ppb.
During the reduction of sample data, many canpounds can be .
identified at concentrations as low as 0.2 ppb. In these
cases, the concentrations are reported as "MS" indicating a
mass spectral identification but the concentration is below
the verified limit of 1 ppb. Canpounds not detected are
reported as "ND".
Methylene chloride generally shows large variability in
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- 20 -
quantitative results near the detection limit. This is due
to 2 factors, first is its volatility and second is the poten-
tial contamination of samples from the laboratory air. There-
fore the detection limit is defined as 3 times the standard
deviation of blank determinations (16 ppb). The mean back-
ground (2.9 ppb) is subtracted from each value followed by
application of the detection limit.
Toluene elutes coincident with the internal standard
1,4-dichlorobutane. The carbon isotope peak at m/e 91 there-
fore yields a constant toluene background (2.8 ± 1.2 ppb).
The detection limit is then defined as 3 standard deviations
of the background (3.6 ppb). Due to the consistancy of the
background, 2.8 is subtracted frcm each value measured before
applying the 3»6 ppb detection limit.
12.0 References
(1) Mono frcm James Eichelberger and William Budde to EPA GC/MS
users titled "Perfluorobromobenzene Reference Compound for
use with Typical Purge and Trap Columns that do not Transmit
DFTPP Readily," March 10, 1978.
(2) National Bureau of Standards, EPA-NIH-MSDC Mass Spectral
Library.
(3) "Samples and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants," U.S. EPA, Environmental
Monitoring and Support Laboratory - Cincinnati, Ohio, March,
1977 revised April, 1977.
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- 21 -
(4) "The Determination of Volatile Organic Compounds at the ug/1
Level in Water by Gas Chromatography." Thomas A. Bellar and
James J. Lichtenberg, Jour. Am. Water. Works Assoc., 66^ (12),
739, (1974).
-------
Compound
c
Mean Rf
% RSD
T1ICHL0RDFLU0R0METHANE
0.180
35
1,1-DICHL0R0ETHYLENE
1.20
24
BR0r10CHL0R0r1ETHANE 3
0.783
14
1,1-DICHLOROETHANE
1.03
15
TRANS-1,2-DICHL0R0ETHYLENE
0.762
16
CHLOROFORM
0.957
16
1,2-DICHL0R0ETHANE
0.734
15
1,1,1-TRICHL0R0ETHANE
0.544
21
CARBON TETRACHLORIDE
0.593
1B
BROMODICHLOROMETHANE
0.992
3.5
1,2-DICHL0R0PR0PANE
0.735
13
TRANS-1,3-DICHLOROPROPENE
0.314
15
TRICHLOROETHYLENE
0.559
15
DIBROMOCHLOROMETHANE
0.464
36
CIS-1,3-DICHLOROPROPENE
0.240
10
1,1,2-TRICHL0R0ETHANE
0.429
6.3
BENZENE
1.40
13
BROMOFORM
0.200
11
TETRACHLOROETHYLENE
0.441
11
1,4-DlCHL0R0BUTANEa'b
1.0
NA
1,1,2,2-TETRACHLOROETHANE
0.725
5.7
TOLUENE
1.38
16
CHLOROBENZENE
0.866
7.5
a Internal standards always at 200 ppb.
^Used as relative response of 1.0.
CMean of 4 determinations at 20, 50, 100, and 200 ppb.
-------
Attachment VIII
Computer Assisted Evaluation of Volatile
Organics GC/MS Data 7/78
1.0 Scope and Application
1.1 This procedure is applicable to any GC/MS data utilizing in-
ternal reference standards for both quantitative and qualita-
tive data analysis.
2.0 Summary of Method
2.1 GC/taS data files are processed by initial location of a rela-
tive retention time (RRT) internal standard (IS) within a fixed
retention time (RT) window. After successful location of the
RRT IS, a spectrum of each compound of interest is selected
from a library and compared against each sample spectrum within
a relative retention time window (RKTW). If the compound is
located, the area of a preselected ion is measured and stored.
A complete spectrum of any compound identified is then printed
for verification of the identification. After all library
entries have been processed, the quantities are calculated
based upon the integrated response of an ion for each compound
and of the IS. ; The procedure 'is calibrated daily from the anal-
ysis of a standard mix.
3.0 Sample Handling and Preservation
4.0 Definitions and Ccrnnrents
4.1 Interned standard: An internal standard (IS) is a compound
added to each sample prior to analysis. The same amount is
always added to all standards and samples to allow reference
to the IS retention time and response.
-------
- 2 -
570 Interferences
5.1 When processing volatile organics data, toluene elutes coin-
cident with the IS, 1,4-dichlorobutane. A background of ca
3 ± 2 ppb of toluene is subsequently observed due to the
carbon isotope peak at 91.
5.2 Internal standards must be selected to avoid conflicts between
the IS and compounds at interest if at all possible.
6.0 Apparatus
6.1 Finnigan INCOS data systen running at least Revision 3.1 soft-
ware. To initially setup and run this procedure, the user
must understand and be proficient in the use of MSDS. (1)
7.0 Reagents
8.0 Procedure
8.1 Method Setup and Initial Calibration
8.1.1 Create a library containing spectra of the compounds of
interest. These may be suspected pollutants or compounds
found during reconnissance survey sample analysis.
8.1.2 Analyze data frcm standards run by GC/MS with the con-
ditions to be used for sample analysis by manually lo-
cating the compounds and creating a quantitation list.
Edit the quantitation list and add the library references.
8.1.3 Quantitate the manual calibration data and set the li-
brary response factors, retention tunes and relative
retention times using conmands in "QUAN."
-------
- 3 -
8.2 Procedure Operation
8.2.1 Create a name list containing the name(s) of the data
file(s) to be processed.
8.2.2 Call the procedure with the procedure name followed by
the library name (XY) and the namelist name:
PPEVAL XY, namelist
PPEVAL was described in general section 2. See Appen-
dix A for a listing of the current version.
8.2.3 The procedure will generate hard copy spectra and chroma-
tograms as well as the quantitation and identification
reports (Appendix B) for each file entered in the name
list. After each file, the terminal will beep once.
When al 1 the files are processed, the terminal will beep
3 times.
8.3 Routine Calibration
8.3.1 Recalibrate -the method as often as required, typically -
each runday for volatiles.
8.3.2 TO calibrate automatically, evaluate a standard mix ana-
lysis. Manually check the finished data for accuracy
of the peak assignments and for duplicate o r missing
assignments. Correct any problems if possible.
8.3.3 Using the "QUAN" commands, update the library's response
factors and (relative) retention times if needed. Gen-
erate a hard copy list of the new parameters with the
library list editor.
-------
- 4 -
9.0 Quality Control
9.1 The accuracy of the procedure's qualitative identifications
is audited in every case by ccmparisim of the spectra generated
from the sample to reference spectra generated from'standards
analysis. Any misidentifications will be found at this time.
9.2 Quantitative accuracy is more dependant on the GC/taS operator
than the procedure. Checks however include evaluation of stand-
ards, spiked and duplicate samples and blanks. See reference
2 for a discussion of. some GC/toS quantitation errors.
10.0 ."Calculations
.10.1 The complex calculations used by the computer to examine and
natch spectra are described in detail in reference 1 for the
interested reader.
10.2 Quantitation by the internal standard method may be described
by two equations:
Resp. Fact = Area * Ref. Amnt./(Ref. Area * Amnt.)
and
Amnt. = Area * Ref. Amnt/(Ref. Area * Resp. Fact)
Where Amnt. and area refer to the respective quantity and
response of the compound of interest and ref. amnt. and
fef. area refer to the respective quantity and response of
the internal standard.
11.0 Precision and Accuracy
11.1 As noted in Section 9, the auto processing method's precision
and accuracy^ is limited only by the quality of the data being
processed.
-------
References
(1) "INCOS Data Systan - MSDS Operator's Manual - Revision 3",
Finnigan Instruments, March 1978.
(2) Quantitative Mass Spectrometry, Brian J. Millard. Hegdon & Son
Ltd., Philedejphia, PA U.S.A., 1978.
-------
ICE OF PROCEDURE PPEVAL
* ERASE
* ;>>***«:*** PRIORITY POLLUTANT EVALUATION PROCEDURE ********
* ;t T>! IS PPOCEDUPE MAY BE USED TO EVALUATE GC/MS DATA
* jrro^ PRIORITY POLLUTANT (EPA SECTION 307(A)) COMPOUNDS
* jC TnE PPOCEDURE UTILIZES INTERNAL STANDARDS AND RELATIVE
* ;CPESPONSE FACTORS FOR QUANTITATION. THE CCDS OPTION
* ;CSEARCH IS USED TO LOCATE AND IDENTIFY PEAKS. THE EPA
W :CIDENTIFItATION CPITEPIA, E.G.. THREE IONS PER COMPOUND
* .C.IS USED TO LOCATE THE COMPOUND OF INTEREST. MORE IONS
- ;CHOUEVER MAY BE USED AS THE FIT OF THE SEARCH ROUTINE UILL
* :CYIELD MP'E SPECIFICITY FOR THE COMPOUND. THE FULL
* .CSPECTRUM IS OUTPUT IN ORDER TO PROVIDE CONFIRMATION OF
* ;CTH; PRESENCE Or THE COMPOUNDS.
tr (*#«*~»*********«
« .CTO USE PPEVAL. BUILD A LIBRARY CONTAINING THE SPECTRA OF
» ,CTHE COMPOUNDS OF INTEREST. INCLUDE THE QUANTITATIVE DATA
* .CTHAT IS NECESSARY AS DESCRIBED IN THE MSDS MANUALS.
* .CCPEATE A NAMEL1ST U1TH THE NAMES OF THE FILES TO BE
* ;CF-?OCESS£D. EXECUTE THE PROCEDURE AS FOLLOUS:
w ;C PPEVAL LIBRAPYNAME, NAMEL1ST E.G. PPEVAL VO.SAMPLE
* ;C REVISED 01JUN7B O.J.LOGSDON II EPA-NEIC 303-234-4661
* ;ScTS PPSCAN.SETN £2;SET4 £1;PPEV1;BEEP;BEEP;BEEP
*
ERASE
SETS P°SCAN
SETN 73
SET4 •-"!
PHEV1
w ERASE
* ;CPART OF PROCEDURE PPEVAL 3
* ;CGET THE NEXT NAMEL1ST ENTRY AND CONTINUE PPOCESSING 3
* ;tAT PPEV2 3
* ;GETN;PPEV2:LOOP
»
ERASE
GETN
PPEV2
* EPASE
appendix
;CPART OF PPEVAL. THIS PROCEDURE SETS THE LIBRARY ENTRY
jCPOINTtR TO THE FIRST ENTRY. UH1CH MUST ALUfiYS BE THE INTERNAL
;[STANDARD. LOCIS IS THEN CALLED AND THE INTERNAL FOUND
;CTHE SPECTRUM NUMBER OF THE INTERNAL STANDARD IS,
:CSTORED IN HQ FOR FUTURE REFERENCE. THE LIBRARY POINTER
jCIS THEN RESET TO THE BEGINNING. THE QUANTITATION LIST SET TO
;CTHE FILE NAME AND EMPTIED OUT. DETECT IS CALLED TO LOCATE EACH
;CCOMPOUND (IF PRESENT). OUAN IS THEN CALLED TO CALCULATE
:Cn-1 RESULTS AND THE PROCEDURE RETURNS TO PPEV1 TO GET THE
;CMXT FILE TO FROCESS.
:SET1 oijCH^OCl.H 1,900.300:E):SET4 oi;LOCIS;SET 10 IK;SET4*B
;SETO SI;EDQLC-;U;E);EDSL(-;U;E);DETECT;QUAN(I,H;E);PPRPT
*
*
*
*
*
*
*
*
*
*
*
*
ERASE
SET1 el
CHRO CI;H1.903.300;E)
SET4 ol
LOCIS
* ERASE
* sCPBRT Or PPEVAL. 3
* ;CROUTINE TO FIND AN INTERNAL STANDARD IN A SAMPLE 3
* ;CUSE A REVERSE SEARCH TO LOCATE THE INTERNAL STANDARDS
* .'SET14 #3
* ;SEAR/V<1;S;V250D0O0;N2.10.750;&;D-60,60;E>
* ;L0CIS1
*
ERASE
SETI4
SEAR UjS;V2500300;N2.10,750;&;D-60.60;E)/V
L0CIS1
* IF L0CIS1 .114
-------
;[PART OF PPEVAL 3
:tNO INTERNAL STANDARD FOUND3
,P.!!N«MS)
,-:nj VOAPR2
IF LOCISl. 114
PRIM CDlS)
RETU V0APR2
SETIO Tt4
SET4
SETQ SI
EDOL C-;U;E)
EDSU t-;U;E)
DETECT
CPART OF PPEVftL
C THIS ROUTINE LOCATES COMPOUNDS IN THE
CSarfuE Fll E BY COMPARING THE SPECTRA IN THE LIBRARY
CUtTH Tn? SAMPLE. PELATIVE RETENTION TIMES ARE USED
CAND ¦J->C0ENCED TO THE INTERNAL STANDARD FOUND EARLIER.
CTrie L'^mPV POINTER IS BUMPED AND TESTED TO
CSEE If- THE LAST LIOPAHY ENTRY HAS BEEN PROCESSED.
C THEN THE CURRENT SCAN NUM3ER IS SET TO THE INTERNAL
C STANDARD LOCATIOtl OY RECALLING THE CONTENTS OF 110.
CSTORE THE SCAN NUMBER OF
C THE BEST MATCH IN VARIABLE 14 AND ALLOU INTEGRATION
CAT THAT SPECTRUM NUrT3ER ONLY
[ IF. THE.COMPOUND, IS NOT,FOUND,,PLACE,A NOT^FOUND..,,,.,
[ENTRY INTO THE QUANTITATION LlST FOR LATER REFERENCE
SET4 14, , • 1
IF I24»1.I4
SET14 *3
SETI T13
SEAP/VC 1;£;"; V25Ct?3O0:Nl, 10.10;D-10.10;E)
EDSL(14;114;!15;I1S;U;E>
DETECI
LOOP
*
*
if
Ml
*c
*
*
*
SETA !4..»1
IF «1 (24. 14
SET14
SETI 110
SEAR (I;S;X;V2500030;N1,10,10;D-18,10;E)/V
EDSL (14;!14;I IS;116;U;E)
DETECI
* [PART OF PPEVALJ
* ;CIF THE FIT IS LESS THAN OR EOUAL TO ?50 3
* ;CLTJITE A NOT DETECTED, NAMTD ENTRY INTO THE]
* ;tQUANTITATION LIST FOR FUTURE REFERENCE 3
* ;DZTEC2
* ;EDQL(-;H;*;A;E)
*
DETEC2
* [PART OF PPEVAL
* ;CACCESS ANY SCANS IDENTIFIED IH DETECT,
* ;CAND INTEGRATE THEIR A3EAS. RECORD THE
* ;CDATA IN THE 0UANL1ST ASSIGNED EARLIER.
* ;CALSO CHECK AND PASS ONLY PEAKS UITH
* :CA FIT OF ?50 GR GREATER
* ;IF DETEC2 !1S.DETEC2 #750
* ;SETl 114
* ;CHRO5,3;G-4,4;D-20.20;E)
* ;SPEC5.3; G-4,4;D-20,20;E)
SPEC (I;';D;E)
RETU DETECI
EDQL C-;N:®;fl:E)
-------
LOOP
cunii ci.h.e)
PPRPT
* FILE (K PRIN.99/N;E>
* ;SETS
* ;PPPPT1
* ;PRIN (0PP)
* ;F II E(C PRIN.93/N, M:; E)
* .FTSD
*
FILE
-------
QUANTITATION REPORT FILE: SM200H
APPENDIX B
data; SM2aoH.ni ~
0•03:00
SAMPLE: STAHDfiRD MIX 200 PPB U/I.S. JULY 6, 1978
CONDS.:
FORMULA: INSTRUMENT: SVSIND UEIGHT: 0.000
SUBMITTED BY: ANALYST: ACCT. NO.:
fir.OUHT=AREA * REF.AMNT/CREF.AREA* RESP.FACT)
NO NAME
1 BUTANE,1,4-DICHLORO- (INTERNAL STANDARD)
2 METHANE,BROMOCHLORO- (INTERNAL STANDARD)
3 BENZENE
4 METHANE,TETRACHLORO-
5 BENZENE,CHLORO-
6 ETHANE,1,2-DICHLORO-
7 ETHANE,1,1,1-TRICHLORO-
8 ETHANE,1,1,2-TRICKL0R0-
9 ETHANE,1,1,2,2-TETRACHLORO-
10 METHANE,TRICHLORO-
11 ETHENE,1,2-DICHLORO-,(E)-
12 PROPANE,1,2-DICHLORO-
13 BENZENE,ETHYL-
14 METHANE,DICHLORO-
15 METHAIIE.TR IBROMO-
16 METHANE.BROMODICHLORO-
17 BENZENE,METHYL-
13 ETHENE,TRICHLCRO-
NO
M/E
SCAN
TIME
REF
RRT
METH
AREA
AMOUNT
"TOT
1
55
225
3:45
1
1.000
A
BB
1051290.
200.000
PPB
5.56
2
49
48
0:43
1
0.213
A
BB
574710.
200.000
PPB
5.56
3
78
150
2:30
1
0.667
A
BB
1423380.
200.000
PPB
5.56
4
117
113
1:53
1
0.502
A
BB
928944.
200.000
PPB
5.56
5
112
247
4:07
1
1.098
A
BB
1396180.
260.000
PPB
5.56
5
62
92
1:32
1
0.439
A
EB
893740.
200.000
PPB
5.56
7
97
103
1:43
1
0.430
A
BB
801574.
260.030
PPB
5.56
B
83
163
2:43
1
0.724
A
BB
493308.
200.000
PPB
5.56
9
83
221
3:41
1
0.982
A
BB
711106.
200.000
PPB
5.56
10
B3
83
1:23
1
0.3S9
A
BB
1174380.
200.003
PPB
5.56
11
96
63
1:03
1
0.200
A
BB
602939.
200.003
PPB
5.56
12
63
141
2:21
1
0.627
A
BB
684727.
200.G00
PPB
5.56
13
91
283
4:43
1
1.253
A
BB
1740730.
200.000
PPB
5.56
14
84
14
0:14
1
0.662
A
BB
597488.
200.099
PPB
5.56
15
173
125
3:15
1
0.G67
A
DB
772180.
200.603
PPB
5.56
16
e3
128
2:03
1
0.569
A
BB
11SS050.
200.033
PPB
5.56
17
91
225
3:45
1
1.000
A
eB
1513140.
200.003
PPD
5.56
18
25
151
2:31
1
0.671
A
BB
7G6330.
200.000
PPB
5.56
-------
[DIMTIFICATION REPORT
FILE: D:Sn203H.MI
rtU
SCAN
.PURITY
FIT
1
225
424
902
2
48
543
996
3
150
,252
999
4
113
657
999
5
247
358
998
6
92
474
994
?
103
510
993
G
163
409
997
,9
221
425
1000
10
B3
588
998
11
63
598
991
12
14!
262
994
13
203
526
996
14
M
602
997
15
195
513
997
16
128
538
993
17
2?4
412
993
18
151
354
999
-------
APPENDIX E
June 1978 Self Monitoring Data
Charles City, Iowa, WWTP and
Salsbury Laboratories, Charles
City, Iowa
-------
CPB 69724 3/75
OPERATION PERMIT SYSTEM
INDUSTRIAL/COMMERCIAL CONTRIBUTOR MONITORING REPORT
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Identity of Industrial/Commercial Contributor
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Title
-------
STATE OF IOWA
DEPARTMENT OF
WAFER QUALITY
environmental quality
management division
OPERATION PERMIT SYSTEM
MONTHLY MONITORING REPORT
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SUSPENDED SOLIDS MG/L LBS/0AYI5) [ 74024]
AMMONIA NITROGEN MG/L L BS/DAYUI [ 70424 ]
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signature or e»ECuiivi officer or agent
TITLE
FORM WOMD-VI TRICKLING FILTER
-------
APPENDIX F
Performance Audits
Salsbury Laboratories, Charles City, Iowa
and
Charles City, Iowa WWTP
-------
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
Thomas Dahl date August 1, T978
om R. C. Ross
jbject Performance Audit at Salsbury Laboratories, Charles City,
Iowa, June 20th, 1978
Contacts: Larry Frahm, Analytical Supervisor
Dorothy Hoy, Analyst (ill during time of evaluation)
Rita Bond, Analyst temporarily assigned to Dorothy Hoy's
duties
Purpose
The subject lab was inspected to determine whether or not
data was being produced by EPA prescribed/recommended procedures.
Scope
The lab performance audit included an examination of B0Dr, metals,
ammonia, total non-filterable residue, settleable matter, coldr, pH,
TQC, COD, and phenolic procedures, and an evaluation of laboratory
equipment, personnel and quality control procedures. Performance
samples were left at the time of inspection for subsequent analyses.
General
The laboratory space and equipment were fairly new and of
excellent quality. A DI system is present which is monitored by
a conductivity meter; distilled water is produced in an all-glass still.
Mr. Frahm seemed quite knowledgeable in all areas of testing
being conducted at the lab. Detailed written procedures were made
available at the time of inspection which are available in the
records from this survey. Dorothy Hoy was absent because of illness
at the time of inspection. This unfortunately made it impossible
to assess the normal laboratory handling of samples. Rather, the
details of this report were obtained from inferences drawn from
observation of equipment and procedures, the discussions with
Mr. Frahm, and finally the results of the performance samples.
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An audit of BOD data for April 20, 1978 showed that it
was consistent with what was reported on State and Federal forms.
These and other records appeared to be complete and proper.
TOC
A Beckman Model 915 total Organic Carbon analyzer was used
for the determinations. The procedure followed Standard Methods,
14th ed. p. 532. Replicate injections into the 915 were performed;
4% of agreement between replicate injections was stated as the
criteria for acceptance.
COD
The procedure used is referenced on page 550, Standard
Methods, 14th ed. (high level). Equipment for this procedure
was observed to be of adequate quality and in good repair.
BOOj
The procedure used is referenced in Standard Methods,
14th ed. p. 543. Three different dilutions are made for each
sample diluting the sample directly in the bottle and using the
same bottle for the initial and final DO measurements. The
probe method is used for DO measurements; the probe is calibrated
each day used by the air calibration technique specified by the
manufacturer. Acclimated seed was used for seeding of samples.
Examination of BOD data revealed poor agreement between different
dilutions of the same sample. Further investigation revealed that
samples aliquots for testing purposes were being taken from the
settled supernatant of the original samples. This procedure
would tend to produce low results as well.
A reference chemical standard such as glucose-glutamic acid
was not being routinely employed to detect errors or abnormalities
in the day to day analytical testing. Dilution water was being
aerated by using laboratory, house compressed air. Since no
external filter was present on the house air system, such a pro-
cedure may introduce trace amounts of hydrocarbons into the dilution
water. It was recommended that this procedure be modified.
No other deficiencies or potential problems were sited.
Total Non-Filterable Residue (TSS)
The only deficiency sited with this method was the omission
of the pre-washing steps specified by the prescribed method. The
analytical balance was adequate and it was serviced each month;
however, day to day calibration checks were not being made and
documented. The oven thermometer was a standard mercury-glass
type, but it had not been calibrated against a higher order
standard or against ice/boiling water to certify its accuracy.
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Settleable Matter
No deficiencies were noted in regard to equipment or
analytical procedure.
Ammonia, as N (NH^-N)
Ammonia samples after approximately May 15th have been
analyzed by the selective ion electrode method referenced in
EPA Methods for Chemical Analysis of Water and Wastes, 1974. No
problems with the procedure or equipment were detected.
Total Arsenic
The silver diethyldithiocarbamate method referenced on p. 283,
Standard Methods, 14th ed. preceeded by an ashing treatment to reduce
organic arsenic to inorganic arsenic is used to determine total arsenic.
The ashing procedure was apparently developed at Salsbury Labs and
tested using standard additions of arsenic trioxide and several organic
arsenic compounds. This pre-treatment step does, however, vary from
the normal preliminary treatment for metal samples to be analyzed
by colorimetric procedures referenced on pp. 166-170, Standard
Methods, 14th edition and there is some concern over potential loss
of organic arsenic.
Since the ashing portion of the procedure does vary from accepted
procedures, an application for use of an alternate procedure must be
submitted to the Regional Administrator/or standardized procedures
such as those referenced in the preceding paragraph must be used.
Mercury
This is analyzed by the cold vapor atomic absorption technique
using a Coleman MAS 50 analyzer. Equipment and procedure appeared
to be completely adequate. The procedure follows EPA Methods
for Chemical Analysis of Water and Wastes, 1974.
Total Heavy Metals
This parameter is reported as the sum of the individual analyses
on a particular sample for the following total metals: Barium,
cadmium, chromium, copper, zinc, lead, selemium and mercury.
Barium is analyzed by atomic absorption spectrophotometry (AAS)
using nitrous oxide. Cadmium and lead are first extracted into
methyl isobutyl ketone before AAS determination. Selemium is
analyzed by the hydride-AAS technique. Other metals are determined
directly by AAS following the addition of 1 ml of HNO, per 100 ml
of sample.
Other aspects of the procedures and equipment appear adequate.
Standard addition techniques were said to be used at times when problems
were suspected with the accuracy of results.
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Phenolics
The chloroform extraction method referenced on p. 577, Standard
Methods, 14th ed. is used in conjunction with HACH* reagents to
analyze samples. The spectrophotometry determination is done on
a Beckman Model B spectrophotometer. No equipment or procedural
problems were indicated. Background interferences were said to be
adequately removed by distillation/extraction; Mr. Frahm stated that
this has been experimentally verified.
£H
Reference buffers were available. Equipment and procedure
appeared satisfactory.
Performance Samples
Results of performance samples are as follows:
Parameter
Reported Value
True Value
Rating**
pH Sample 1
7.60
7.9
Marginal
Non-filterable Residue-
•BC 910 mg/1
884 mg/1
Acceptable
Phenol
0.072 mg/1
0.13 mg/1
Unacceptable
COD Sample 1
138 mg/1
114 mg/1
Marginal
COD Sample 2
430 mg/1
419 mg/1
Acceptable
T0C Sample 1
45 mg/1
44.8 mg/1
Acceptable
T0C Sample 2
190 mg/1
165 mg/1
Acceptable
BOD* Sample 1
19 mg/1
28.7 mg/1
Acceptable
BOD* Sample 2
212 mg/1
264 mg/1
Acceptable
Arsenic Sample 1
0.037 mg/1
0.040 mg/1
Acceptable
Arsenic Sample 2
0.272 mg/1
0.300 mg/1
Acceptable
Chromium Sample 1
0.091 mg/1
0.060 mg/1
Marginal
Chromium Sample 2
0.26 mg/1
0.250 mg/1
Acceptable
Copper Sample 1
0.055 mg/1
0.040 mg/1
Acceptable
Copper Sample 2
0.38 mg/1
0.350 mg/1
Acceptable
Zinc Sample 1
0.090 mg/1
0.060 mg/1
Acceptable
Zinc Sample 2
0.40 mg/1
0.400 mg/1
Acceptable
Selenium Sample 1
1.8 mg/1
0.020 mg/1
Unacceptable
Selenium Sample 2
5.41 mg/1
0.050 mg/1
Unacceptable
Mercury Sample 1
0.0014mg/l
0.003 mg/1
Acceptable
Mercury Sample 2
0.0036mg/l
0.008 mg/1
Acceptable
Cadmium Sample 1
0.009 mg/1
0.010 mg/1
Acceptable
Cadmium Sample 2
0.056 mg/1
0.070 mg/1
Acceptable
Lead Sample 1
0.035 mg/1
0.080 mg/1
Marginal
Lead Sample 2
0.27 mg/1
0.400 mg/1
Acceptable
*Hach Chemical Company, Ames, Iowa
**The acceptance criteria for pH was taken from statistical data for EPA
Laboratory Performance Evaluation WP 002; no such data exists for the
above TSS sample but results were acceptable because the reported value
was very close to the true value; limits for the phenolic sample were
set by the manufacturer, Environmental Research Associates, at + .02 mg/1 -,
the remainder of the above parameters were judged on the basis of EPA
Performance Evaluation Samples WP 003.
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Required Changes
The June 20th performance audit at Salsbury Laboratories
indicated a good degree of compliance with agency analytical
requirements. However, the following changes must be implemented
into existing operating procedures:
1. Periodic use of a referenced chemical material such as glucose-glutamic
acid for BODg analyses to demonstrate the quality of dilution water, the
effectiveness of the seed and the technique of the analyst.
2. BODj. samples must be kept at or very slightly below 4°C between
the time they are collected until immediately before they are
analyzed; at which time they should be rapidly brought up to 20°C.
3. For TSS pre-washing of the filters is mandatory.
4. All samples should be thoroughly mixed before aliquots are
withdrawn for analysis. This was not evidenced in the case of
BOD testing at the time of inspection.
5. Barium, chromium, cadmium, copper, lead, and zinc procedures should
contain a digestion step such as that referenced in Standard Methods,
14th ed., p. 148 titled "Extractable Metals Analysis." Since a small
amount of suspended matter is present in the samples, omission of this
step may lead to slightly low results in both samples directly introduced
into the flame and samples extracted into MIBK.
6. Approval must be obtained from the Regional Administrator as speci-
fied in Federal Register, Vol. 41, No. 232 for the use of ashing in
the determination of total arsenic as an alternate test procedure,
or prescribed digestion procedures must be used, such as those referenced
on pp. 166-170 of Standard Methods, 14th ed.
Recommendations
1. Calibration and record of calibration each day the analytical
balance when used;
2. use of an NBS grade thermometer (thermometer calibrated against an
NBS thermometer) or use of a thermometer calibrated in some acceptable
manner such as a freezing boiling point determination of water;
3. Use of an oil free aquarium pump to aerate dilution water;
4. establishment of a quality control program to include:
a. routine analysis and documentation of analysis of reference
chemical materials for those parameters where applicable;
b. 10% duplication of testing to establish precision of
analyses—documentation of such;
c. addition of known amounts of chemical constituents
to samples on a periodic basis to establish recovery levels;
d. participation in a sample split program with another
reputable lab on a yearly basis.
m • M P
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ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
TO Thomas 0. Dahl, Salbury Labs/Charles City, date 7/20/78
Iowa Project Coordinator, Field Operations Branch
THRU : Chief, Chemistry Branch
from R. C. Ross
subject Performance Audit at Charles City, Iowa Wastewater Treatment
Plant Laboratory, June 19-20, 1978
Attendees: Virgil Reis, Superintendent
Don Nicholson, Assistant Superintendent
Purpose
The subject lab was inspected to ascertain whether or not
data was being produced by EPA prescribed/recommended methods.
Scope
The lab performance audit included an examination of B0D5,
total non-filterable residue, settleable matter, color, and
pH procedures, and an evaluation of laboratory equipment, personnel
and quality control procedures.
General
The laboratory area was small but adequate for the testing
being performed. Provided the air conditioning/heating system
is operating properly, the area is suitably protected from dust
and temperature excursions. The equipment appeared to be relatively
new and in good repair. A tin lined still was available for pro-
ducing distilled water.
Personnel appeared knowledgeable in the testing being con-
ducted, but appeared to rely heavily on outside sources of infor-
mation when problems arose in the laboratory.
A date of May 12, 1978 was selected at random to audit data
reported. The bench sheets and calculations were in agreement
with what was reported to the State of Iowa on that day. These
and other records appeared to be complete and proper.
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BOD^
The method of analysis closely followed Standard Methods,
14th ed., p. 543, using a D.O. probe. The probe was calibrated
every other week against the Winkler method using PAO as the
titrant.
BOD dilution water was made up from distilled water pre-
pared from the lab's tin-lined still. This distilled water
was last checked for mineral and metals content approximately
two years ago. Before use, the distilled water was said to sit
for one to two weeks in the lab with a cotton cloth over the mouth
of the container used. Dilution water was said to be prepared once
each week. At the time of inspection, a thin film of algae was
observed on the bottom of the dilution water jug.
Bottles are cleaned as necessary with Clorox to stop bacterial
growth. The incubator consisted of a constant temperature water
bath in which the samples were immersed. At the time of inspection,
using one of the laboratories thermometers, the temperature of the
bath was observed to be 22°C. No official calibration of any of
the laboratories thermometers was on record.
The calculations appeared to be correct for non-seeded BOD's.
However, a blank of 2.0 mg/1 or less was ignored; Mr. Nicholson
stated that values of 1.0 to 2.0 mg/1 were common. At the time of
inspection, algal growth on the bottom of the dilution water bottle
was observed and was the probable cause for these high blanks.
As quality control procedures, the influent was analyzed in
duplicate each time the testing was performed; the effluent was
analyzed at three different dilutions each time. Two dilution
water blanks (un-seeded) were analyzed each time as well. No reference
standard, e.g. glucose glutamic acid was in routine use. An EPA
type check sample was analyzed once about a year ago, but the
results could not be recalled.
Total Non-filterable Residue (TSS)
Schleicher & Schuell 47 mm glass fiber filters were used in
conjunction with a Millipore type holder. The filter is approxi-
mately 0.75 mm thick. No required pre-washing of the filters was
being performed at the time of inspection. The analytical balance
used was about one year old, in good contion and of sufficient
sensitivity. It had not, however, been calibrated since its
installation. Constant weight checks were not being performed on the
filters themselves.
The desiccant in use was non-indicating CaCl2- The method
requires that indicating desiccant be used.
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Other than these deficiencies the rest of the procedure followed
closely what is prescribed in Standard Methods, 14th ed., p. 94.
No quality control procedures were in use.
Settleable Matter
No problems were observed with analytical procedures for
this parameter.
The procedure and equipment used were satisfactory. The pH
electrode was stored in an open beaker of buffer, however. Even
though the buffer solution was changed weekly, such a procedure is
ill-advised since evaporation of the buffer solution does (and
contamination may) result from such a practice.
Color
A platinum-cobalt standard color wheel was used in a Hach
comparitor (Wheel #2092). The pathlength used is approximately
1.5 cm. The procedure used appeared to be adequate.
Performance Samples
EPA check samples for BOD,- and TSS* were left for analyses
at the time of inspection. Results were as follows:
Parameter
B0Dr
BODr
TSS
True Value,
mg/T
264
28.7
957
Reported Value,
mU
166
19
870
% Deviation
-37
-34
-9
Rating
Acceptable
Acceptable
The acceptance limits used
EPA Performance Evaluation 003,
for judging the TSS sample. It
true value and therefore should
acceptable.
for BOD are taken from results of
1976. No criteria is available
is, however, reasonably close to the
be considered slightly low but
Required Changes
The June 19th, 1978 performance audit at the Charles City, Iowa
Wastewater Treatment Plant indicated lab personnel were con-
sciencious and in general using EPA prescribed procedures.
However, the following modifications must be instituted in order
to comply with all EPA requirements:
*Total non-filterable residue
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1. BOD samples must be kept at or very slightly below
4°C between the time they are collected until
immediately before they are analyzed; at which time
the sample should be brought quickly up to 20°C.
2. Dilution water for the BOD test must be prepared fresh
just prior to the test; at least the phosphate buffer
must be omitted until just prior to actual testing.
3. Samples where the dilution water control depletes by
more than 0.2 mg/1 should be voided for BOD testing.
4. The BOD probe must be calibrated each day it is used.
5. Periodic use of a reference material such as glucose-glutamic
acid is necessary for BOD testing to demonstrate the
quality of the dilution water and the technique of the
analyst. The discrepancy evidenced by the performance
sample results for this audit must be resolved.
6. For TSS an indicating desiccant must be used.
7. For TSS pre-washing of the filter is mandatory.
8. For TSS a Reeves Angle 934 A or H or equivalent must be
used rather than^the thick glass fiber filter currently used.
9. The reference buffer solution used for pH testing must
be protected from evaporation and the laboratory environ-
ment in some manner (it cannot be left out and expect
reliable calibration over a period of one week).
10. The BOD incubation system must be maintained at 20°- 1°C.
Recommendations
The following, although not strictly required, would be
desirable implementations:
1. Calibration and record of calibration each day the
analytical balance is used.
2. Checks on the labs distilled water for minerals and heavy metals
every three months. Conductivity measurements would suffice.
3. Periodic cleaning of the dilution water bottle with 10% HC1
or equivalent followed by sufficient rinsing to prevent
contamination.
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4. Use of NBS grade thermometer (thermometer calibrated
against NBS thermometer) or use of thermometer
calibrated in some acceptable manner such as freezing-boiling
point determination.
5. Establishment of a quality control program to include:
a. Routine analyses of BOD reference material;
b. 10% duplication of other testing with records
to show this;
c. Yearly split sample program with State or other
reputable lab.
cc: M. Carter
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