ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-78-002
Compliance Monitoring
and
Waste water Characterization
Fike Chemicals, Inc.
Coastal Tank Lines, Inc.
and
Cooperative Sewage Treatment, Inc.
N i I r o. West Virginia
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER. COLORADO
AND
REGION III. PHILADELPHIA. PENNSYLVANIA
FEBRUARY 1978
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APPENDICES
A Chairrof-Custody Procedures
B Field Study Methods
C Analytical Methods - Inorganics, Trace
Metals and General Organics
D Analytical Methods - Nitrosamine
E Analytical Methods - Volatile Halogenic
Organics
F Bioassay Methods
G Materials Hauled in Coastal Tank Trailers
H Mutagen Methods
I Laboratory Bench Scale Treatability
Study - Methodology
J Activated Carbon Treatability Study -
Analytical Procedures
K Laboratory Bench Scale Treatability
Study - Fish Bioassay
L Raw Chemical Data for Bioassay Studies and
Cyanide Concentrations in Coastal Tank
Truck Discharges to the Evaporation Pond
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APPENDIX A
CHAIN-OF-CUSTODY PROCEDURES
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GENERAL
ENVIRONr.1ENTAL PROTECTION AGENCY
NATIONAL ENFORCHiENT INVESTIGATIONS CENTER
CHAIN OF CUSTODY PROCEDURES
June 1,1975
The evidence gathering portion of a survey should be characterized by the minimum
number of samples required to give a fair representation of the effluent or water body
from which taken. To the extent possible, the quantity of samples and sample loca-
tions will be determined prior to the survey. . .
Chain of Custody procedures must be followed to maintain the documentation necessary
to trace sample possession from the time taken until the evidence is introduced into
court. A sample is in your "custody" if:
l.
2.
It is in your actual physical possession, or
It is in your view, after being in your physical possession, or
3.
It was in your physical possession and then you locked it up in a manner so
that no one could tamper with it. .
All survey par~icipants will receive a copy of the survey study plan and will be
knowledgeable of its contents prior to the survey. A pre-survey briefing will be held
to re-appraise all participants of the survey objectives, sample locations and Chain
of Custody procedures. After all Ch'lin of Cust~.dy sar.1ples are collected, a de-briefing
will be held in the field to determine adherence to Chain of Custody procedures and
whether additional evidence type samples are required.
SAMPLE COLLECTION
1.
To the maximum extent achievable, as few people as possible should handle
the sample.
Stream and effluent samples shall be obtained, using standard field sampling
techniques.
2.
3.
Sample.tags (Exhibit I) shall be securely attached to the sample container
at the time the complete sample is collected and shall contain, at a minimum,
the following information: station number, station location, data taken,
time taken, type of sample, sequence nu~ber (first sample of the day -
sequence No.1, second sample - sequence No.2, etc.), analyses required and
sampler~. The tags must be legibly filled out in ballpoint (waterproof ink).
4.
Blank samples shall also be taken with preservatives which will be analyzed
by the laboratory to exclude the possibility of container or preservative
contamination.' . .
5.
A pre-printed, bound Field Data Record logbook shall be maintained to re-
cord field measurements and other pertinent information necessary to refresh
the sampler's memory in the event he later takes the stand to testify re-
garding his actions during the evidence gathering activity. A separate
set of field notebooks shall be maintained for each survey and stored in a
safe place where they could be protected and accounted for at all times.
Standard formats (Exhibits II and III) have been established to minimize
field entries and include the date, time, survey, type of samples taken,
volulile of each sample, type of analysis, sample numbers, preservatives,
sample location and field measurements such as temperature, conductivity,
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DO, pH, flow and any other pertinent information or observations. The
entries shall be signed by the field sampler. The preparation and conser-
vation of the field logbooks during the survey will be the responsibility
of the survey coordinator. Once the survey is complete, field logs will be
retained by the survey coordinator, or his designated representative, as a
part of the permanent record.
6.
The field sampler is responsible for the care and custody of the samples
collected until properly dispatched to the receiving laboratory or turned
over to an assigned custodian. He must assure that each container is in his
physical possession or in his view at all times, or locked in such a place
and manner that no one can tamper with it.
7.
Colored slides or photographs . should be taken which would visually show the
outfall sample location and any water pollution to substantiate any con-
clusions of the investigation. Written documentation on the back of the
photo should include the signature of the photographer, time, date and site
location. Photographs of this nature, which may be used as evidence, shall
be handled recognizing Chain of Custody procedures to prevent alteration.
TRANSFER OF CUSTODY AND SHIPNENT
1.
Samples will be accompanied by a Chain of Custody Record which includes the
name of the survey, samplers' signatures, station number, station location,
date, time, type of sample, sequence number, number of cont;.iners and analy-
. ses required (Fig. IV). When turning over the possession of samples, the
transferor and transferee will sign, date and time the shEet. This record
sheet allows transfer of custody of a group or samples in the field, to the
mobile laboratory or when samples are dispatched to the NEIC - Denver labora-
tory. When transferring a portion of the samples identified on the sheet to
the field mobile laboratory, the individual samples must be noted in the
column with the signature of the person relinquishing the samples. The field
laboratory person receiving the samples will acknowledge receipt by signing
in the appropriate column. .
The field custodian or field sampler, if a custodian has not been assigned,
will have the responsibility of properly packaging and dispatching samples
to the proper laboratory for analysis. The "Dispatch" portion of the "Chain
of Custody Record shall be properly filled out, dated, and signed. .
2.
3.
Samples will be properly packed in shipment containers such as ice chests, to
avoid breakage. The shipping containers will be padlocked for shipment to
the receiving laboratory.
All packages will be accompanied by the Chain of Custody Record showing icen-
tification of the contents. The original will accompany the shipment, and a
copy will be retained by the survey coordinator.
4.
5.
If sent by mail, register the package with return receipt requested. If sent
by corrmon carrier, a Government Bill of Lading should be obtained. Receipts
from post offices, and bills of lading will be retained as part of the perma-
nent Chain of Custody documentation.
If samples are delivered to the laboratory when appropriate personnel are not
there to receive them, the samples must be locked in a designated area within
the laboratory in a manner so that no one can tamper with them. The same per-
son must then return to the laboratory and unlock the samples and deliver
custody to the appropriate custodian.
6.
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LABORATORY CUSTODY PROCEDURES
1.
The laboratory shall designate a "sample custodian." An alternate will be
designated in his absence. In addition, the laboratory shall set aside a
"sample storage security area." This should be a clean, dry, isolated room
which .can be securely locked from the outside.
All samples should be handled by the minimum possible number of persons.
All incoming samples shall be received only by the custodian, who will in-
dicate receipt by signing the Chain of Custody Sheet accompanying the samples
and retaining the sheet as permanent records. Couriers picking up samples at
the airport, post office, etc. shall sign jointly with the laboratory custodian.
Immediately upon receipt, the custodian will place the sample in the sample
room, which will be locked at all times except when samples are removed or
replaced by the custodian. To the maximum extent possible, only the custo-
dian should be permitted in the sample room.
The custodian shall ensure that heat-sensitive or light-sensitive samples,
or other sample materials having unusual physical characteristics, or re-
quiring special handling, are properly stored and maintained.
Only the custodian will distribute samples to personnel who are to perform
tests.
,he analyst will record in his laboratory notebook or analytical worksheet"
identifying information ~escribing the sample, the procedures performed
and the results of the testing. The notes shall be dated and indicate who
performed the testS. The notes shall be retained as a permanent record in
the laboratory and should note any abnormaHies "'Ihich occurred during the
testing procedure. In the event that the person "'Iho performed the tests is
not available as a witness at time of trial, the government may be able to
introduce the notes in evidence under the Federal Business Records Act.
Standard methods of laboratory analyses shall be used as described in the
"Guidelines Establishing Test Procedures for Analysis of pollutants,"
38 F.R. 28758, October 16, 1973. If laboratory personnel deviate from
standard procedures, they should be prepared to justify their decision dur-
ing cross-examination. .
Laboratory personnel are responsible for the care and custody of the sample'
once it is handed over to them and should be prepared to testify that the
sample was in their possession and view or secured in the laboratory at all
times from the moment it was received from the custodian until the tests
were run.
Once the sample testing is completed, the unused portion of the sample to-
gether ...Iith all identifying tags and laboratory records, should be returned
to the custodian. The returned tagged sample will be retained in the sample
room until it is required for trial. Strip charts and other documentation
of work will also be turned over to the custodian.
Samples, tags and laboratory records of tests may be destroyed only upon the
order of the laboratory director, who will first confer with the Chief,
Enforcement Specialist Office, to make certain that the information is no
longer required or the samples have deteriorated.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
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g
~
o
...
o
..
........
'.
o
EXHIBIT I
EPA, NATIONAL ENFORCEMENT INVESTIGATIONS CnITER
Stalion No. I Dato I Time Sequence No.
Station .loci3!ion
BOD
Solids
COD
Metals
Oil anCJ Grease
D.O. " .
Bad.
Other.
Remarks I PrC5ervalive:
Nutrients
Samplers:
-.--.-..
Front
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDI:;RAL CENTER
DENVER, COLORADO 80225
ro GT~~,p
. ,; an ~
~~)
Back
-.-
Grab
Compo
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APPENDIX B
FI~LD STUDY METHODS
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APPENDIX B
FIELD STUDY METHODS
FLOW DETERMINATIONS AND MONITORING LOCATIONS
CST Effluent (Outfall 001)
The sampling location for the CST effluent was at the Parshall
flume prior to discharge to the sewer line which terminates at the
Kanawha River. CST measures flow from the final sedimentation pond with
a broad-crested weir installed in the throat of the 9-in Parshall flume
(the flume functions as a,weir box). The head is measured with a bub-
bling device located upstream of the weir plate. The head is recorded
on a Foxboro 24-hr circular chart. A table for a standard rectangular
weir is used to convert the head readings into flow. Because the table
is not applicable to the head over a broad-crested weir, a standard
rectangular weir was installed by NEIC personnel and the head recorded
with a Stevens Model 64 recorder. The standard rectangular weir was
installed according to the criteria required by the WATER MEASUREMENT
* .
MANUAL. Since the weir length measured 21.6 cm (8 1/2 in), a table was
constructed according to the formula Q =3.33 (L-0.2H) H3/2 [Table B-1),
and the flow determined from the Steven's chart readings, and the hourly
instantaneous readings.
Fike Influent to CST
The Fike influent to CST was collected from the manhole adjacent to
Coastal's maintenance shop. Wastewaters from Coastal combine with Fike
wastewaters at this location, however, the Fike flow could be sampled
before mixing occurred, but flows could not be measured.
* United States Dept. of Int., Bureau of RecZamation, Second
Edition, Denver, CoZorado, 196?
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Coastal Influent to CST
Only the Coastal contribution to CST from the trailer washing
operation was sampled. Samples were collected as the wastewater dropped
into the manhole adjacent to the CST influent sump. Instantaneous flows
were measured with a bucket and stopwatch each time a sample was collected.
Old Evaporation Pond
This evaporation pond was constructed approximately 8 years ago.
The useful life remaining is less than one year, therefore, Coastal
began discharging the pre-rinse wastewater into the newly constructed
pond. Fike continued to discharge into the old pond. Samples were
collected twice from the pond during the survey; liquid samples were
taken from the top 30 cm (1 ft) level at each corner and composited into
one sample. Sediment samples were collected once during the survey from
each corner and also composited into one sample. A dredge was used to
collect the sediment sample. The flow from Fike was determined by
rating the sump pump. The sump pump delivered an average flow of 65.2
liters/min (17.2 gpm). A time-elapse meter was attached to the pump to
record the hours of operation.
New Evaporation Pond
The new evaporation pond was constructed south of the old pond.
Settled solids from the CST final sedimentation pond were being pumped
into two Coastal trailers and then emptied into the new pond prior to
the survey. During the survey, only the Coastal pre-rinse wastewater
was being discharged into the new pond. Because the surface area of the
pond bottom was not covered with wastes, a sample of the soil which had
not come into contact with the wastes was collected to determine if it
had been contaminated.
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APPENDIX C
ANALYTICAL METHODOLOGY FOR VOLATILE HALOGENATED ORGANICS
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Coastal Tank Trailer Discharge to New Evaporation Pond
Samples were collected from the tank trailer as it discharged to
the pond. 'These individual samples were composited into a single sample
for each discharge. Only one discharge was not sampled; NEIC personnel
were not notified that the tank trailer was dumping the evening of
October 3.
" '
Groundwater
Three wells have been drilled by Fike Chemicals to monitor the
percolation from the evaporation ponds. These wells were sampled twice
during the survey. Well No.1, located in the Fike processing area
(nort!l of the ponds), was sampled using Fike's permanently installed
pump. The pump was allowed to run for several minutes before ,the
samples were collected.
Wells Nos. 2 and 3 are located west of the old evaporation pond.
Well No.2 is located between the old and new evaporation ponds and the
Well No.3 about 91 m (300 ft) west of the old pond. Because pumps were
not installed in these two wells, a bailer was used to collect the
*
samples.
Huntington, West Virginia Water Treatment Plant
Raw water and treated water were grab sampled once during the
survey. Samples were collected in the plant's laboratory from spigots.
The raw water had been prechlorinated and the finished water had been
post-chlorinated.
* A portable pump ~as placed in Well No. 33 h~ever it immediately
clogged ~ith sand. The pump ~as cleaned and replaced in the ~ell3
ho~ever it clogged again. The bailer ~as then used to collect samples.
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SAMPLE COLLECTION PROCEDURE
Twenty-four hour Composite Samples
Beginning at 7 a.m. on October 3, individual grab samples were
collected hourly from the CST effluent, and Fike1s and Coastal IS in-
fluent to CST. The CST effluent samples were composited continuously on
a flowpweightedbasis; the Fike and Coastal influent samples were com-
posited continuously on an equal-volume basis. All samples, except.
those collected for bioassay, were stored at 4°C. For those samples
requiring preservatives other than storage at 4°C, the preservatives
were added to the composite container prior to sampling.
Grab Samples
Grab samples for oil/grease were collected three times/day from the
CST effluent and the Fike and Copstal influent to CST; volatile organics
were grabbed once/day from these three locations.
All other monitoring locations were grab sampled for all parameters
analyzed. The Coastal tank truck pre-rinse wastewater was sampled
periodically during the period of discharge to the new evaporation pond
and composited into a 1 gallon amber glass bottle~ A sample for vola-
tile organics was collected from each discharge.
Field measurements of pH and temperature were taken each time a
grab or aliquot for the composite samples were collected.
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30
l1J
(f)
Z
0
0.. 20
(f)
w
cr:
10
40
30
w
(j)
t5 20
Cl..
(.')
W
c:r
-10
o .
o
10
20
30
40
CS 2 (mg/l)
40
o
o
. 5 0
C H C/3 (u g/ J)
1000
1500
Figure 1. Typical linearity of response from standard solutions of
volatile organic compounds. .
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f--
.
I
3
. - ..", . ... .
... ".-. ..
.". .".- ..- ..
".. ... .. ..-.
.' 0..
Figure 2. Typical chromatogram showing CH2C12' CHC13' CC14'" and C2C14"
at peaks 1, 2, 3, and 4, respectively.
Table 1. Duplicate Analysis Results
0"
Concentrations in mgjl (ppm) "3
CS? CH?C12 CHC12: CC14 C?HC1~ f29-4
2400-10-6-1430 6.4 <1.3 <0.042 0.005 0.12 0.26
2400-10-6-1430 dup.a 5.9 <1.3 <0.042 0.006 0.087 0.23
2420-10-6-1400 3.9 <1.3 <0.042 0.001 0.033 0.008
2420-10-6-1400 dup.a 3.4 <1.3 " <0.042 0.003 <0.025 0.006
2400-10-3-1435. 4.6 <1.3 <0.042 0.015 0.25 0.007
2400-10-3-1435 dup. 5.8 <1.3 <0.042 0.017 0.27 b
a
Analysis from duplicate bottles collected in the field.
b
Not measured.
...' _.-- "-""--'-'-"--"-..~
. -. _.. .._.. -_..
--."-.------. _.
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APPENDIX D
ANALYTICAL METHODOLOGIES
INORGANIC PARAMETERS, METAL PARAMETERS,
GENERAL ORGANICS, AND NITROSAMINES
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Analytical Methodology for Volatile Halogenated.prganics
. .
. .
Mieure and Richard and Junk simultaneously reported similar methods
for the extraction and analysis of organo~alides in environmental sam-
ples (1,2). Anothe~ similar extraction method has been reported by
Henderson et.al. (3). Each of these methods allows rapid, simple, and
accurate determination of halogenated species in water utilizing organic
solvent extraction and an electron capture detector (ECD) gas chroma-
tograph (GC). These methods are significant to'industrial waste analysis
due to their selectivity of halogenated species with minimal interfer-
ences by volatile hydrocarbons, alcohols, and other industrial solvents
and chemicals. .
Pro<:edure
.
Extraction. Industrial effluent extractions are performed in
1 dram screw cap vials. About 1.5 grams of NaCl are added with a mea-
suring spatula followed by 5.0 ml of pesticide quality hexqne. 5.0 ml
of sample are added, the vial sealed and shaken for 30 seconds. The
layers are allowed to separate and 1 ml of the hexane transferred to
GC auto sampl~r vials and sealed.
Drinking water samples are similarly extracted; however, the water:
solvent ratio is increased to 8:1 to add a concentration factor of 8 for
increased sensitivity.
Reagents. Rexane may require further purification to remove traces
of CH2C12' CHC13' and C2HC13' Passing the solvent through a volume of
activlty-l basic alumina (Woelm, ICN Pharmaceuticals, Cleveland OH) as
described by Richard and Junk should prove effective (2).
Sodium chloride should be checked for interferrences by analyzing a
reagent blank. Contaminated NaCl should be replaced or cleaned by
heating in an oven at 2000C. . .
Standards are prepared from 100 mg/10 m1 concentrates in methanol.
Microliter aliquots (10 ug/ml) are diluted in deionized di~tilled water
for analysis. Concentrates may be stored up to five days in a freezer
without significant deterioriation.
Gas Chromatography. Separation of components is effected with an
8 ft. x 1/8 in. stainless steel column packed v/ith 60/80 mesh Tenax GC.
Typical conditions are: Injector temperature 200°C, detector temperature
2500C, carrier gas 10% methane in argon at 35 ml/min and column temperature
programmed from 120-200oC at 4°C/min. Typical analysis are performed
on a Hewlett-Packard 5713 gas chromatograph equipped with a 15 mCi Ni63 ECD.
Discussion
Richard and Junk have shown consistent recoveries for the extraction
of halomethanes over concentration ranges of 0.1 to 200 ug/l (2). Rather
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than measure extraction efficien~ies, Figure 1 illustrates the linearity of
response for synthetic samples over large concentration ranges. This ver-
ifies the consistent extraction of the pollutants from aqueous solutions
and also provides support for the large linear response ranges needed for
the analysis of industrial waste waters. ~
Response factors vary si gnifi cantly with di fferent halogenated speci es.
CC14 is easily detected to less than 1 ug/l while CH2C1Z is difficult to
detect at 1 mg/l. These varying sensitivities are attnbutable to ECD
response characteristics as well as the extraction efficiency of the method.
For typical industrial effluents, this .poses no significant problem. With
finished or open waters, ho\~ever, the method should be limited to compounds
of similar response factors like trihalomethanes as described by Richard
and Junk (2). .. . . . .
The selectivity of the ECD for response to only halogenated species
plus the gas chromatographic retention times provide accurate identification
of the species of interest. A typical chromatogram is shown in Figure 2.
,
Qual i.ty Control
. Relative retention times are reproducible to less than 0.6% based on
data from analysis of CHC13 standards on various days during the survey.
Day-to-day variations in response to a 500 ug/l CHC13 standard were less
than 11% based on nine analyses of a CHC13 standard throughout the survey.
Duplicate analysis on samples were performed and the data shown in Table I.
Small variations can be attributed to differences in sample extraction and
GC injections.
S ununa ry
This quick, simple, and reliable method for analysis of volatile
halogenated species may be.used for grossly polluted industrial wastes or
as well for finished and open waters. The method is limited, however,
when species not easily extracted like CH2C12 or species with poor ECD r~-
sponse like CS2 are encountered. .
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-'-'-----'---.-'--- ....- ----.---------..... "'-'.-.___n_____u
ANALYTICAL METHODOLOGIES
Inorganic Parameters
Analytical Methods: Samples for compliance monitoring and other composite
and grab samples were analyzed for permit parameters. The methods used
were the approved test procedures as defined under section 304(g) of the
Federal Water Pollution Control Act. The methods used for each parameter
are summarized below: .
. Pa rameter
M. B.2[\. S.
S04':
Total Solids
T.S,..S. .
Cr+o
cr
B.O.D.
C.O.D.
CN-
NHrN
N03+NOZ-N
Phenollcs
" ."
~1ethod
Methylene Blue
Turbidimetric
Residue, Total
. Residue, Total Non-Filterable
Diphenylcarbazide
~1ercuri c Nitrate
Cylinder Full Bottle Winkler
High Level Dichromate Reflux
Total, Reflux Distillation
Automated, Phenate
Automated Cadmium Reduction
4-AAP with Distillation and
Extraction
Freon Extractables, Separatory
Funnel Extraction
. .
Grease and Oil
Sample Preservation: Samples were preserved during collection as prescribed
by each method, iced and shipped via air freight to the laboratory for.
analysis. In all cases except the first day were the samples analyzed
during the prescribed holding times. On the first day, CN and phenolics
were analyzed within 28 hours but not the prescribed 24 hour holding time.
Comparison of the data, however, shows results comparable to the other
day's samples. .
Discussion: The samples collected during this survey showed lar~e quantities
of orqanic compounds which may interfere with the analysis of some inorganic
parameters. Extraordinary steps were taken to analyze samples 2400 (10/8)
and 2410 (10/4 and 10/7) for phenolics. The 4-AAP method is subject to
interferences from non-phenolic organic comQounds and turbidity. Three
samples showed slight turbidity even after distillinq twice. The distil-
lates were made basic then extracted with chloroform to clean up inter-
fering organics and the analysis for phenolics repeated. The results
before and after extraction are shown below:
Sample #
2400
2410
2410
Date
10/8
10/4
10/7
Before
mg!l
Extraction
22
26
11
Phenol
After Extraction
3.4
17.
7.3
. ...... ~..
-~--.- '-'- ----.-.. -~_..~. -'..- -- "'._.r_~ '._-..,.Jo.-.~._. "".",--",,",,-~_t.~(.... --";".'..---'......,'-
---
-------
The data after extraction are consistent with the results of samples from
other days and help confirm the validity of the extracted sample results.
Spikes of Cr+6 standard solution added to samples being analyzed for Cr+6
disappeared and were not recovered. The disappearance undoubtedly was
caused by reduction due to the gross organic matter present. Considering
this, it is not surprising that no hexavalent chromium was found.
Analyses for BOD were also complicated by toxic species for samples 2400-
1008, 2410-1004, and 2410-1005. The more dilute sample aliquots had,
larger DO depletions indicating toxicity of the samples to this test. No
dilution for these ,samples had a valid depletion and therefore no analy-
tical results have been reported,. ,~1any, of the other samples had low
BOD/COD ratios indicating toxicity and/or the'presence of a substantial
number of organic compounds that are difficult to digest. Therefore, BOD
is not the best measure of gross organic matter in these samples. J TOC o~
COD would be more appropriate. ' ' . " "
Quality Control: During the analysis of samples for the inorganic para-
meters, certain quality control practices have been followed. They include
analysis of reagent blanks, standard additions (spikes), and duplicates.
These internal quality control data are used to verify correct operation
of the method and are used on a go/no go basis, i.e., if quality control
data are unacceptable, correct the problem and rerun the samples. In
some cases, this is impossible. For example, the unacceptable DOdeple-
tions on'sOTlle BOD samples as already mentioned. Otherwise, the method
performance met internal quality control limits.
A more rigorous test of the entire sampling and analysis scheme is the
collection of duplicate samples in the field followed by laboratory
analysis of the separate samples. Also reagent blanks prepared in the
field and analyzed will show any contamination of the samples from con-
tainers or preservatives. A number of reagent blanks and duplicates
were collected during the survey and analyzed. The data are shown in
Tables I and II. The results show good comparison between most duplicates.
Too few samples are available for a statistical evaluation, however.
..,,::" - ...._------...-..__.>;--
--".- - ..- -. "'_""-~"~~'-'---""'_"''''''.~--;----~-_'''-'-''''''''''''''--~_..J'''- .... --
.........--
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REFERENCES
(1) Mieure, J.P., "A Rapid and Sensitive Method for Determining Volatile
Organoha1ides in Water," JAW~JA, 69(1), 60(1977).
(2) Richard, J.J. and Junk, G.A., illiquid Extraction for the Rapid Deter-
minination of Halomethanes in \~ater," JAWWA 69(1), 62(1977). .
(3) Henderson, J.E., Peyton, G.R., and Glaze, W.H., Chapter 7, Identifi-
cation and Analysis of Organic Pollutants in Water, (L.H. Keith, editor),
Ann Arbor Science, Ann Arbor, Michigan, (1976) p. 105.
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APPENDIX E
SUPPLEMENTAL ORGANICS ANALYSIS RESULTS
-------
General Orqanics
Introduction: Briefly, water samples were extracted to yield two fractions,
acids like phenolics and neutrals and bases like aromatics and amines, re-
spectively. The extracts were then analyzed by gas chromatography-flame
ionization detector (GC-FID) or gas chromatoqraphy-mass spectrometry (5C-MS).
Compounds were subsequently identified and quantified usinq manual and/or
computer assisted analysis techniques.
Sample Collection and Preservation: Organic~ samples were collected in
1 liter or 1 gallon glass containers with Teflon lined caps. The sample
size, i.e. 1 liter or 1 gallon, was chosen based on analysis of presurvey
grab samples and estimated concentrations. Containers were either new
bottles or empty pesticide analysis grade solvent jU9S. Composite and grab
samples were packed in ice and extracted as soon as possible after receipt
at the laboratory. All water samples were extracted within two days of
collection.
Extraction and Concentration: A 1 or 3 liter aliquot of sample was mea-
sured and transferred to either a 2 or 4 liter separatory funnel. The pH
of the aqueous solution was adjusted to >12 with 6 N NaOH and extra~ted
with two portions (150 and 100 ml) of pesticide analysis grade methylene
chloride. Emulsions were treated by cent}'ifugation or in simpler cases,
by physically breaking the emulsion with a wire or stirrinq rod. The ex-
tracts were combined and dried over ca 20 q of anhydrous Na2S04 that had
been prewashed with 50 ~l methylene chloride. The Na2S04 was then rinsed
with 100-150 ml pesticide analysis grade acetone and the acetone combined'
with the methylene chloride extracts. The resultant solution was transferred
to a Kuderna-Danish evaporative concentrator and concentrated to 10 ml in a
water bath at 850C. ' The extract was then transferred to a 3 dram glass vial
and capped with a Teflon lined screw cap. The aqueous layer was then aci-
dified with 6 N HCl to pH <2 and extracted and concentrated as described
above to obtain the acids fraction.
Sediment and sludge samples were air dried for 24 hours. An aliquot was
used for dry weiaht determination (drying at 1050C for 24 hours). A second
aliquot (ca 25 g) was removed and placed in a stainless steel blender and
made basic (pH>12) with 6 N NaOH. Na2S04 was added to produce a dry mixtur~
which was extracted with 100 ml of methylene chloride for two minutes in a
high speed blender. The solvent decanted and the extraction'repeated.
The extracts combined, filtered, dried over ca 5a q Na2S04 and concentrated
to 10 ml in a Kuderna-Danish evaporative concentrator.
The sludge was then acidified with 6 N HCl to pH<2and additional NaZS04
added to take up water if necessary. The extraction and concentration pro-
cedure was then repeated as described above.
GC-FID and Quantitative Analysis: The organic extracts were analyzed by
GC-FID to determine optimum concentration or dilution factors for r,C-~S
analysis and to obtain response information for quantitation of the
, .
. . -",.''':'-. . ...~ ."--.C._'.:, ~~-"~'.... - -...-
- -.;- --_.'~. ~~ ~..:.:_.""-~- ~-- "::-- .~ ,'" .=-."-- .
-------
compounds present; GC-FID analyiis was carried out on a Varian Mbdel 1400
gas chromatograph equipped with a single flame detector and a linear tem-
perature programmer. The column was 10 ft by 2 mm 10 glass packed with
6% OV-101 on 60/80 mesh Gas Chrom-Q. The carrier qas was helium at 20 ml/min.
Typical temperature 'conditions were: injector 2250C, detector 250oC, column
oven programmed 80-220oC at 6oC/min and held at 2200C until all components
had eluted.
Concentrati ons of components i dentifi ed by GC-t~S were measured by compari son
of peak heights of dilute solutions of the pure component in acetone or
hexane. Extracts with components either too dilute or too concentrated,
i.e. off scale response, were concentrated or diluted to yield p~ak heights
near those of standards. On numerous occasions, pure compounds were not avail-
able. Then, concentration estimates have been made based upon the response
of a similar compound at a similar retention time. Retention times of pure
compounds were also compar~d to the sample extract as added confirmation of
the r,C-MS assignment.
GC-MS and Qualitative Analysis: Compounds were separated and identified by
GC-MS analysis. Typically, 1 ul of the concentrated extracts was injected
into the GC and mass spectra were measured continuously after elution of the
solvent peak. The GC conditions were identical to those described in the
GC-FIO section. Iilstrumentation was: Varian 1400 GC, Finnigan 1015 e1ectrof'!
impact quadrupole mass spectrometer and Systems Industries System 150 Data
System. Mass spectrow.eter conditions were as follows:
Ionization Potential:
Scan Range:
Integration Time:
Samples per iTi/e:
70 vo lts
20-250 m/e
8-10 ms
1
The resultant mass spectra were evaluated by comparison to libraries of
reference spectra or by manual interpretation based on known fragmentation
patterns. Since all the components in the samples were not available for
confirmation of their mass spectra by on-site standards, two classes of
identifications must be defined. First are compounds found in the samples
that have mass spectra irlentical to spectra of the pure compound measured
at this laboratory and that have retention times the same as the pure
standard. These compounds are confirmed, meaninq their identification is
unambiguous. Second are compounds that have been identified from spectra
in published references but are not available on-site for direct ~omparison
of spectra. These compounds are reported as not confirmed. Included in
this class are compounds that manual interpretation produced structures
similar to other compounds identified by other means and that fit excellently
with known fraqmentation characteristics. Reference libraries used were:
Eight Peak Index of Mass Spectra, Mass Spectrometry Data Centre,
A1dermaston, UK. Second Edition, 1974.
Reqistry of Mass Spectral Data, John Wiley ~ Sons, New York, 1974.
Mass Spectral Search System, EPA/MSDC/NIH computerized spectra
matching system, Revision 3.7.
- ,_. -~~-_.
. '. -....-..-.-- -" -'--------'-------.--.---:- --'-----------"""'-----...--.------.....~~-_..._c.-....
-',.,,--~._..... ....--..,...-.- -''''-'''''''-'''.-' -" '''''''.-''-.---''ri''''-.- .
..- '-. -_.. ...-. -.' .. -- -
"- '-''''-'''-'''''---",,'''_'n'' "''''~-'-'''''''-'--._'''''''''--' ._.. --- ,""""-'--. ""--.- -'-r-- --,...-.. . ...-.
-------
Quality Control: Duplicate samples were collected during the field survey
and analyzed independently in the laboratory. Due to the large number of
components in the samples, comparison data are reported here on only con-
firmed compounrls. The data are shown in Tables V.a., b., and c. The
variations seen here include sampling differences as well as variations
in extraction efficiencies, concentration, and GC-FID analysis.
Reagent blanks were analyzed for both acids and base-neutrals fractions.
The resu1ts showed no significant contamination of the samples by the re~
agents used for sample preparation and extraction. Toluene, diacetone
alcohol and a few other very early eluting compounds were found but
typically, data collection was started after elution of these compounds
and no erroneous results were obta'i ned. .
-._. '.- .'_.-
. . -'-" _''''':'_~--''''~-'''''-' ..- ----"-.--- ----.-------..-..------..--
. -. ..--.-
. - ,- ~... -. ... .. .
. .- . - ."
. '<....,- .-.....- ....~ "....".
-...._,--,.- ".
. . -. ,.- ---..- "-"
-------
TABLE V.a.
Results of Duplicate General Organics Analysis.
Station 2410, Date 10/7.
Concentrations in mq/l.
Only confirmed compounds listed.
Compound Name Sample Duplicate
2-n-butoxyethanol 2.9 2.8
1,3,4-trimethylbenzene 13. ll.
n-nonane " 4.3 2.4
n-decane 11. 6.3
-
n-undecane 16. 19.
n-dodecane 25. 26.
n-tridecane 54. 34.
n-tetradecane 56. 37.
n-pentadecane 52. 36.
n-hexadecane 53. 34.
n-heptadecane 50. 34.
pristane (C19 alkane) 23. 17.
n-octadecane 52. 25.
phytane (C20 alkane) 13. 6.3
n-nonadecane 59. 20.
n-eicosane 13. 9.9
n-heneicosane 8.5 6.7
n-docosane 6.2 3.6
'-'--- .....'.-r."_,'
..-".".-.. -- .""'_';""";;;"'4._",,_,_~___"""'1""-' ..-.- ;~&..._-'.-...'---.-
~ -.-......
-------
GC-FID analysis was monitored by injecting 1 ul of a mixed standard
ing 50 ng/ul each of C9 throuqh C19 linear alkyl hydrocarbons. The
and retention times (RT) were then recorded and compared for nonane
tridecane (C13), and octane (C18). The results are shown below:
CgC13
RT ResDonse"-RT Response
contain-
responses
( C9) , .
C18
ResDonse
RT
n 12 12 12 12 9
t1ean 4.98 9.8 13.9 8.3 24.0
Std. Dev. 0.103 0.93 . 0.131 0.56 0.116
~~ RS 0 2.1 9.5 0.90 6.8 0.50
9
6.6
0.55
3.3
These data show that durinq the survey, r,C-FID quantitative results vary
+8.2% at 1 standard deviation (STD. DE V.). The retention times vary an
average of +1.1%. Since confirmed identifications are based on GC-MS
identificatTons and only supplemented by GC-FID, this variation presents
no problem.
GC-MS performance was monitored by measuring the mass spectrum of decafluoro
triphenyl phosphi~e (OFTPP) prior to analyzing samples. The performance
criteria and backqround are in the literature (1). This procedure monitors
the ability of the quadrupole mass spectrometer to generate spectra compar-
able to those trom other instruments and also monitors day to day instrument
performance. The acceptable criteria and data obtained duri~q this survey
are Sho'dn:
m/e .A.cceptable Range ~,1eas ured Ranqea
-
51 30- 60~~ 32-52%
68 <2~~ of m/e 69 <2~~
70 <2% of m/e 69 <2%
127 40-60~~ 39-49~~
197 <1% <1%
198 100% 1 OO~~
275 10- 30% 15 - 19%
365 10l 1.3-1.9%
10
441
-------
These data show acceptable results for most cases. Occasionally, one value
may have been slightly out of range whil~ other criteria were acceptabje and
no instrument retuning was warranted. When significant deviations were ob-
served, however, the instrument was retuned and the DFTPP standard reanalyzed
until acceptable results were obtained.
Nitrosamine Analysis
Sample Collection and Preservation: One liter grab or composite samples
were collected in amber glass bottles with Teflon lined screw caps. The
samples were preserved by storage in ice and analyzed as soon as possible
upon recei pt at the 1 aboratory (extracted withi n 48 hours typi cally).
Extraction and Analysis: One liter of sample was transferred to a 2 liter
separatory funnel and extracted with two 50 ml portions of pesticide
analysis grade methylene chloride. The extracts were combined~ dried with
anhydrous Na2S04 and then concentrated to 1 or 2 ml in a Kuderna-Danish
evaporative concentrator at 58-600C. One-half to one ml of isooctane was
added as a keeper. .
The concentrates were analyzed by gas chromatography-thermal energy analysis
(GC-TEA)(2). GC-TEA res~onses were compared to the responses of a standard
mix of 14 nitrosamines. Identifications were made by comparison of reten-
tion times of the sample components to the standards. Quantitative da~a
were obtained by peak heiaht measurement.
Quality Control: A reagent blank was prepared and analyzed and detection
limits determined from two times the standard deviation of the noise. The
detection limits were:
Nitrosamine Detection Limit ug/l
dimethyl- 0.1
methyl ethyl- 0.1
diethyl- 0.1
me thy 1 propyl- 0.1
ethyl propyl.. 0.1
di propyl- 0.1
ethyl butyl- 0.1
(2) Anal. Chern. 47(7), 1188 (1975).
-------
-continued-
Nitrosamine
,Detection Limit ug/l
propyl butyl-
0.2
0.2
methyl amyl-
dibutyl-
0.2
0.2
nitro so piperidine
nitrosopyrrolidine
" '
0.2
0.2
nitrosomorpholine
diamyl-
0.3
Three sets of duplicate samples were collected and analyzed. The results
were in good aqreement considerinq the concentrations were near the detec-
tion limits. The duplicate analysis results were:
S';;ati on No. Dat.e Time D~.1N DAN
2400 10/6 0630 0.2 <0.3
2400 dup 10/6 0630 0.1 <1).3
2410 10/5 0630 0.1 <0.3
2410 dup 10/5 0630 0.1 <0.3
2420 10/5 0600 0.1 0.9
2420 dup 10/5 0600 I). 1 0.6
The other nitrosamines were below the detection 1 imits.
Recovery data at this laboratory show that extraction efficiencies with
this technique are excellent with the exception of lighter species, di-
methyl nitrosamine. Typical recoveries are:
Nitrosamine Recovery
dimethyl 32%
diethyl 87%
dibutyl 96~;'
These data compare well to recovefj data published in the literature (3).
(3) ESH, 11(6), 577 (1977).
- . _.-. """".'-'''-~' 6-
.- ~-"'. ~., ........".-' --A ..---.--... ~ _..-.-~--~~-
.~.:...-.;-:-..:..-;:" -._'~ '....'r-.;..~', :"''''' "''- . -
'-~'-.,-;---:'':: .',",-,-......- ....._-.,.s::......~.. '-._~ .-_.. -
. - .. ." .. .--
-------
TABLE 1. Analytical Results from Field Duplicates for Inorqanic Parameters
Concentration (mg/l)
Parameter Station Date Sample Duplicate
Phenolics 2400 10/6 -.5.4 5.5
2410 10/6 5.0 5.0
2420 10/6 3.9 3.9
COD 2400 10/5 6260 6210
2410 10/6 4560 4550
2420. 10/4 1760 1730
CN- 2400 10/6 0.10 0.07
2410 10/7 0.07 f).05
2420 10/4 0.54 0.55
NH3-N 2400 10/5 530 500
2410 10/5 8.2 7.7
2420 10/5 13.2 13.6
N03+N02-N 2401) 10/5 1.0 .1.0
2410 10/5 4.4 .4.4
2420 10/5 12.4 12.4
Grease and Oi1 2400 10/4 390 550
2410 10/4 130 150
2420 10/4 56 51
r'.1B AS 2400 10/5 5.0 5.0
2410 10/6 66 68
2420 10/4 6.0 6.S
S04 2400 10/5 420 430
2410 10/6 180 190
2420 10/4 780 850
TS 2400 10/5 4601) 4600
2410 10/15 340D 3200
2420 10/4 3400 3LtOO
TSS 2400 10/5 520 500
2410 10/6 180 201)
2420 10/4 58 .59
Cr+6 2400 10/5 <0.2 <0.2
2410 10/6 <0.2 <0.2
2420 10/4 <0.2 <0.2
BOD 2400 10/5 780 820
2410 10/6 860 500
2420 10/4 570 , '570 ..
:. ""'~"__'_'"''''':'''''~''' '. -'.._...._--.....~~._~- oJ"'''-~---''''';'------~';'''-...............-_~~......-.--.............-..._--
'-''''-...-
-.. ". ----- .
. ". .~_.- -- "--
-------
TABLE I. -continued-
Pa rameter
Station
Date
Cl-
2400
2410
2420
10/5
10/6
10/4
--------- -
-_._~--""'----..,....-_._.~.......,..-~.....!.._,=,-""."",-,,,,,=-~,,,"~~..;..--,,,-. .
Concentration (mg/l)
Sample Duplicate
710
98
910
. 740
94
920
~-~.~~~.."~-.,.,,. -- ....
..-----.- - ..-..---.
-------
TABLE I I. Analytical Results from Field Reagent Blanks for Inor~anic Parameters
Parameter Date Concentration ( mq /1)
Phenol i cs 10/4 0.2
10/6 <0.1
10/7 <0.1
COD 10/5 <70
10/6 <70
CN 10/8 <0.01
NH3-N " . 10/6 <0.05
10/7 <0.05
N03+N02-N 10/6 <0.05
10/7 <0.05
Grease and Oil 10/6 <1
10/7
-------
Meta 1 Pa rameters
Analytical Methods: Samples for aluminum, silver, bari~m, cadmium, iron,
and lead were prepared using method 4.1.3, page 82 of ~1ethods for Chemical
Analysis of Water and Wastes, EPA, 1974, and analyzed by flame atomic
atsorption. Arsenic was determined by flame less AA on the undigested sam-
ple using the method of standard additions.
Sample Preservation: Samples were preserved as described in the EPA Methods
Manual and all analyses were performed within the prescribed holding times.
Quality Control: Similar to the inorganic parameters, analyses of blanks,
duplicates and spikes were performed to monitor the methods. If results
were outside acceptable limits, the samples affected were reanalyzed.
Field reagent blanks and duplicates were collected. and their results shown
in Tables III and IV.
. h.. ..'.." ~--
. --"""'--"-
~- - -.-. .-",- .'f_"""'-'.~-'~,,,,,_---,.,_.----~,-~ "---....--.......----------,"-." ....-;r--~...----
. -'--. _.- .. ~".-..,...,.. -'-'-- ., -
. -. - - -'4~" .. ..-'...---.... ...-. '. ,.-~ ".-- "'---......---.-....... ---_. .-...--. .-- --...-.,..
.u --- ---.-.
-------
TABLE II!. Analytical Results from Field Duplicates for ~eta1s Parameters
Concentration (mg/1)
Parameter Station Date Sample Duplicate
As 2400 10/5 0.29 0.30
2410 10/6 <0.Q2 0.02
2420 10/4 0.44 0.44
Ag 2~Oa 10/5 <0.01 <0.01
2410 10/6 <0.01 <0.01
2420 10/4 <1).01 <0.01
. . ,~
A1 2400 10/5 1.9 1.8
2410 10/6 6.9 6.9
2420 10/4 1.2 1.3
Sa 2400 10/5 0.20 0.20
2410 10/6 <0.20 0.30
242J 10/4 0.20 <0.20
Cd 2400 10/5 0.02 0.02
. 2410 10/6 0.13 0.11
2420 10/4 <0.01 0.03
Fe 2400 10/5 27 23
241') 10/6 14 18
2420 10/4 8.3 8.9
Pb 2~O,) 10/5 1.6 1.3
2410 10/6 0.5 0.6
2~.20 10/4 0.9 0.6
. . ~._-~---~._.-.".. - .. '~_. ._.
"' -,--,--"-,----.,,,,:,------:..---.---. -'.-::.--_.-..---.:-~....;/.:..-.. "';ofo_""~_' . :..-. .-:- ..
'. -. ~.. -. '-' . ...'~ .~-.._....... --" . ~.... - "-."-., --. . - '"'
~ '- -~.---. - -., - ..-.' '-- .~. -
.._-.- ..-. '-".'.- .'- "-"'--~-'- ..-.... "'--"---~._--....- -
-------
TABLE IV. Analytical Results from Reagent Blanks for ~1eti3.1s Parameters
-
Parameter Date Concentration (mq/1)
As 10/5 <0.02
10/6 <0.02
Ag 10/5 <0.01
10/5 <0.01
Al 10/5 <0.1
" 1-0/6 . 0.1
Ba 10/5 <0.28
10/6 <0.20
Cd 10/5 <0.01
10/6 <0.01
Fe (total) 10/5 0.24
10/6 0.21
Pb' 10/5 <0.1
10/6 <0. 1
. '.- -- .--.
-...;:..................or......;..
._---.- .-.
. ",,-: -'.' ,'..---- . ~'.':'':'-:''_-~'.'-.------...
--.... ....,'.. '''''''''''''''''..~' '-'" -'.- .- - .
-------
TABLE V. b.
Results of Duplicate General Organics Analysis.
Station 2420, Date 10/7.
Concentrations in mg/l.
Only confirmed compounds listed.
Compound Name
Sample
Duplicate
4-methyl-3-pentene-2-one(mesityloxide)a 9.9
67.
17.
Cyclohexylamine .29.
Aniline 3.3
Isophorone 1.9
Phenol 1.0
2.8
1.9
0.8
a
Large difference due to very early elution time of mesityl oxide.
- -
. ~-' -.'" ,-, .- ..... ..,.,.-.'''''.'''.. ._--."~--'_."-----""'->---""--,--" -----
... --..--
-------
TABLE V. c.
Results of Duplicate ~eneral Organics Analysis.
Station 2400, Da~e lQ/7.
Concentrations in m~/l.
Only confirmed compounds listed.
Compound Name Sample Duplicate
.
Cyclohexylamine 1.9 4.1
Analine 7.8 8.7
1,2,4 trimethylbenzene 0.67 0.80
Phenol 2.4 4.5
Tri-n-butylphosphate 6.0 7.3
-pO.. ..'" - ... . n.,...._n' ..- -.": ...- ,.-..L.,',' .",,,,"'--.'-"
. '-.o;--,--,.._.._~....-..._-.....--,.-- ~~~.
-------
APPENDIX F
BIOASSAY METHODS
-------
BIOASSAY METHODS
All bioassays were performed according to standardized methods
(1,2,3) for time durations ranging from 24 to 96 hours. Continuous-
flow-bioassays were performed using a proportional diluter which pro-
vided a series of six effluent concentrations plus a 100% dilution water
control. Test chambers were of all glass construction, and water flow
rates regulated to provide a minimum of nine volumetric turnovers for
each test chamber for each 24-hour period. Stati~ tests were performed
in 8-l1ter glass aquariums.
Dilution water was obtained from the Kanawha River at a point
approximately 2 river miles (3.2 km) upstream fro~ the mouth of the Elk
River. Dilution water for continuous-flow bioassays was stored in 1,100
liter (300 gallon) epoxy-coated reservoirs and was replenished every 24
hours. CST effluent water for all bioassays was obtained from 24-hour,
flow-weighted composites.
Each test chamber (static and flow through) was monitored daily for
pH, temperature, and dissolved oxygen. In addition, the high and low
concentrations of the flow-through system were tested for total alkalinity
[Table F-l]. Temperature variation of the test waters was restricted to
+ 1°C for the duration of each test. Gentle aeration of test water was
necessary to maintain a dissolved oxygen concentration greater than 50%
saturation.
Mortalities in each test chamber were recorded at 24-hour intervals.
LC50 values were calculated by applying straight line graphical inter-
polation and Litchfield-Wilcoxon (1949) Methods.4
-------
Table F-1
PHYSICAL CHARACTERISTICS OF DILUTED EFFLUENT
CST~ INC. (OUTFALL 001)
October 1977
Effluent Concentration (%)
Control
Kanawha
Parameter River 0.18 0.32 0.56 1.0 1.35 1.8
24-hr
00 - mg/l 6.5 6.5 6.0 6.0 5.0 4.0 4.0
pH 6.2 6.2 6.3 6.3 6.4 6.4 6.5
Temp. °C 19 19 19 19 19 19 19
T. A1 ka1 ine mg/1 55
48-hr
00 - mg/l 8.0 8.0 8.0 8.0 8.0 8.0 6.0
pH 6.4 6.4 6.5 6.6 6.6 6.7 6.7
Temp. °C 18 18 18 18 18 18 18
T. Alkalinity mg/l 56
72-hr
00 - mg/l 8.5 8.0 8.0 8.0 6.0 5.0 4.5
pH 6.4 6.4 6.5 6.6 6.6 6.7 6.8
Temp. °C 18 18 18 18 18 18 18
T. Alkalinity - mg/1 55
96-hr
00 - mg/l 8.0 8.0 8.0 8.0
pH 6.8 6.8 6.7 6.8
Temp. 0C 18 18 18 18
T. Alkalinity - mg/l 55 55
-------
APPENDIX G
MATERIALS HAULED IN COASTAL TANK TRAILERS
PRIOR TO CLEANING COASTAL TANK LINE5, INC.
SEPTEMBER 30 - OCTOBER 7, 1977
-------
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
. BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
Barrett Benson, Coordinator
Fike Chemical Survey
TO
DATE:
November 22, 1977
fROM:
O. J. Logsdon, Chemistry Coordinator
Fike Chemical Survey .
Chief, Chemistry Branc~~~
Fike Chemical Survey - Supplemental
Organics Analysis Results
THRU:
SUBJECT:
Attached are the analytical results for the remaining sediment, well,
evaporation pond~and tank truck washing samples from the $ubject survey.
The sediment samples contained numerous aromatic hydrocarbons and a
number of isocyanates and isothiocyanates which were also present
in water samples 2400 and 2420. The largest component, 2-phenyl
benzimidazole at 7300 mg/kg, could not be confirmed due to the
unavailability of a standard. .
Samples from the wells and the evaporation pond collected 10-4 and
10-5 were similar to those collected 10-7. Of the compounds listed,
four were found in the wells and the evaporation pond. Of these,
only p-isopropyl phenol and 1,4 oxythiane could be confirmed. .
The tank truck washings from Coastal Tank Lines (2411) were very
difficult to analyze. Many samples contained heavy, sticky, resinous
materials that were insoluble in water and methylene chloride. One
sample, 2411-10-6-1100, showed such gross amounts of very heavy and
late eluting compounds by GC-FID that GC-MS analysis was impractical
and not performed. A large number of the compounds present were
related to the components found in undiluted creosote. Others like
ethyl hexanoic acid and phenol are pure chemicals handled in bulk
by Coastal. Still others like 2-ethyl-l-hexanol, t-butyl ketone
and styrene may be components of chemical mixes hauled by Coastal for
uses such as plasticizers, resin solvents and plastic materials.
o J :ft;/(Ji>,
O. i
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-------
REFERENCES
1.
Office of Research and Development, July 1973. Biological Pield
and Laboratory Methods. Cincinnati: EPA, EPA-670/4-73-00l.
2.
National Environmental Research Center, April 1965. Methods for
Acute Toxicity Tests ~ith Fish~ Macroinvertebrates~ and Amphibians.
Corvallis, Oregon: EPA, EPA-660/3-75-009.
3.
4.
Water Control Criteria 1972.
EPA-R3-73-003, March 1973.
Litchfield, J.T. Jr. and F. Wilcoxon, 1949. A Simplified Method
of Evaluating Dose-Effect Experiments. J. Pharm. Exp. Ther.
96:99-113.
-------
APPENDIX H
r~UT AGEN METHODS
-------
APPENDIX H
I.
SAMPLE COLLECTION ~
" '
Samples for mutagen testing were taken from the 55-gallon poly-
ethylene carboy used for the collection of the bioassay composite sam-
ples. After the 24-hr flow-proportioned composite sample had been
collected, a1iquots were drawn off into 1 gallon amber glass containers
and stored at 4°C until analysis.
II.
SAMPLE EXTRACTION
One liter a1iquots were extracted three times with 35 mg of iso-
propanol-benzene (20% to 80%), yielding 105 m1 of extract. A total of
three liters was extracted to yield a combined volume of 315 m1.
Emulsions were removed by treatment with sodium sulfate, which was sub-
sequently removed by filtration. The extract was then evaporated to
dryness in a rotoevaporater at 60°C. The residues were suspended in 20
m1 sterile dimethylsulfoxide (DMSO) and stored at 4°C. This concentrate
was retained for bacterial mutagenicity testing.
I I I.
BACTERIAL MUTAGENICITY ASSAY
The test was performed as described in the Ames methods paper.l
IV.
QUALITY CONTROL
A three-liter volume of sterile distilled water was added to a
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 the material did not interfere with test results.
. .
The tester strains, TA1535, TA1537, TA98 and TA100, were exposed to
diagnostic mutagens to confirm their natural reversion characteristics.
The strains were then tested'~o~ th~ factors described in the methods
paper, 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 strain against
TA98 and TA100 to confirm the metabolic activation process.
Sterility checks were performed on solvents, extracts, liver pre-
paration, and all culture media.
-------
APPENDIX I
LABORATORY BENCH SCALE TREATABILITY STUDY
METHODOLOGY
-------
REFERENCES
1.
Ames, B. N., McCann, J., and Yamasaki, E., Methods for Detecting
Carcinogens and Mutagens with the SaLmonella/Mammalian - Microsome
Mutagenicity Test~ Mutati9n.Research~ 31 (1975) 347-364.
2.
Commoner, B., Chemical Carcinogens in the Environment~ Presentation
at the First Chemical Congress of the North American Continent,
Mexico City, Mexico, Dec. 1975.
3.
Commoner, B., Development pf Methodology~ Based on Bacterial
Mutagenesis and Hyperfine Labelling~ For The Rapid Detection and
Identification of Synthetic Organic Carcinogens in Environmental
Samples~ Research Proposal Submitted to National Science Foundation,
Feb., 1976.
-------
FIGURES
1
2
Locat i on Map. . . . . . . . . . . . . . . . . . . . . . .
CST Evaporation Ponds & Solid Waste
Di sposa 1 Area. . . . . . . . . . . . . . . . . . . . .
Coastal Trailer Cleaning Procedure &
Waste Disposal Routing to CST. . . . . . . . . . . . .
CST Biological Treatment for Fike Chemical
and Coastal Tank Lines. . . . . . . . . . . . . . . . .
CST Sewer Schematic & Monitoring Locations. . . . . . .
Dose Effect, CST, Effluent. . . . . . . . . . . . . . . .
CST Effluent Extract 10-7-77 Dose
Response Curve. . . . . . . . . . . . . . . . . . . . .
CST Effluent Extract 10-8-77 Dose
Response Curve. . . . . . . . . . . . . . . . . . . . .
3
4
5
6
7
8
TABLES
1
2
3
NPDES Permit Limitations - CST. . . . . . . . . . . . . .
Products and Raw Materials - Fike . . . . . . . . . . . .
List of Chemicals on the EPA
Priority Pollutant List - Fike . . . . . . . . . . . . .
4
5
Summary of Field Measurements. . . . . . . . . . . . .. 44
Summary of Analytical Data for NPDES
Permit Compliance. . . . . . . . . . . . . . . . . . .
Summary of Heavy Metal Analyses. . . . . . . . . . . . .
Summary of Oil and Grease Analyses. . . . . . . . . . . .
Processes Operating During Monitoring Survey. . . . . . .
Summary of Discharge Monitoring Reports. . . . . . . . .
96-hour Flow-Through Bioassay Survival Data. . . . . . .
24-hour Flow-Through Bioassay Survival Data. . . . . . .
Bioassay Survival Data. . . . . . . . . . . . . . . . .
Summary of Analytical Data for Influents to CSC . . . . .
Summary of Heavy Metal Analyses for Influents to CST. . .
Organic Chemical Data - Equal-Volume Composite Samples. .
Volatile Organic Chemical Data. . . . . . . . . . . . . .
Organic Chemical Data - Flow-Weighted Composite Samples
Nitrosamine Analyses. . . . . . . . . . . . . . . . . . .
Organic Chemicals Identified in Sediments. . . . . . . .
Organic Chemical Data, Grab Samples. . . . . . . . . . .
Summary of Heavy Metal Analyses. . . . . . . . . . . . .
Organic Chemicals Identified in Prerinse Tank
Trailer Discharge to New Evaporation Pond. . . . . . . . 82
Toxicity of Organic Compounds. . . . . . . . . . . . . . 84
Mutagenic Activity of CST Effluent Extracts
on Salmonella Tester Strain. . . . . . . . . . . . . . 105
Pollutant Reduction as a Function of
Carbon Concentration. . . . . . . . . . . . . . . . . . 110
Laboratory Bench Scale Treatability Study
Characteristics of Final Treated Wastewater. . . . . . 112
Cost Estimate of Recommended Treatment. . . . . . . . . . 115
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
3
32
33
35
36
54
106
107
6
20
28
45
46
47
48
50
55
57
58
59
60
61
70
71
72
75
76
80
-------
III
VII
VIII
CONTENTS
I
INTRODUCTION. . . . . . . . . . .
.. .. .. .. .. .. .. ..
II
SUMMARY AND CONCLUSIONS.. . . . . . . . . . . . .. 7
NPDES PERMIT COMPLIANCE. . . . . . . . . . . . .. 7
ORGANIC CHEMICAL IDENTIFICATION. . . . . ... . .. 9
TOXICITY. . . . . . . . . . . . . . . . . . . .. 11
MUTAGENIC ACTIVITY. . . . . . . . . . . . . . . . 11
SOLID WASTE DISPOSAL. . . . . . . . . . . . . " 13
AIR POLLUTION CONTROL. . . . . . . . . . . . . .. 13
WASTEWATER TREATABILITY STUDIES. . . . . . . .. 14
IV
RECOMMENDATIONS. . . . . . . . . . . . . . . . .. 15
CST, INC. EFFLUENT. . . . . . . . . . . . . . " 15
EVAPORATION PONDS. . . . . . . . . . . . . . .. 15
SOLID WASTE DISPOSAL. . . . . . . . . . . . . .. 16
PROCESS OPERATIONS AND POLLUTION
ABATEMENT PRACTICES. . . . . . . . . . . . .. 19
FIKE CHEMICALS, INC. . . . . . . . . . . . . . .. 19
COASTAL TANK LINES, INC. . . . . . . . . . . . .. 31
CST, I NC. ............ . . . . . . .. 34
V
MONITORING PROCEDWRES. .
.. .. .. ..
.. .. .. .. .. ..
. . . 41
VI
NPDES PERMIT COMPLIANCE. . . . . . . . . . . . . 43
DISCHARGE MONITORING REPORTS. . . . . . . . . . . 49
FLOW. . . . . . . . . . . . . . . . . . . . . . 52
BIOASSAY RESULTS. . . . . . . . . . . . . . . .. 53
EFFLUENT VIOLATIONS. . . . . . . . . . . . . .. 63
ORGANIC CHEMICAL IDENTIFICATION. . . . . . . .. 69
CST INC. EFFLUENT. . . . . . . . . . . . . . . .. 69
EVAPORATION PONDS AND MONITORING WELLS. . . . .. 74
COASTAL TANK LINES PRE-RINSE DISCHARGES TO
NEW EVAPORATION POND. . . . . . . . . . . . 81
TOXICITY EVALUATION
.. .. .. ..
. . . . . 83
.. .. .. .. .. ..
IX
MUTAGEN TESTING. . . . . . . . . . . . . . . . . 103
DISCUSSION. . . . . . . . . . . . . . . . . . . . 108
WASTEWATER TREATABILITY STUDY. . . . . . . . . . 109
ACTIVATED CARBON ADSORPTION. . . . . . . . . . . 109
HEAVY METAL PRECIPITATION. . . . . . . . . . . . III
TREATABILITY RESULTS. . . . . . . . . . . . . . . 113
RECOMMENDED TREATMENT AND COSTS. . . . . . . . . 114
TREATMENT APPLICATION. . . . . . . . . . . . . . 116
REFERENCES. . . . . . . . . . . . . . . . . . . . 117
X
-------
1.
I NTRODUCTI ON
On June 28, 1977, the Environmental Protection Agency (EPA),
Region III requested that the National Enforcement Investigations
Center (NEIC) conduct a thorough study of the Fike Chemical site in
Nitro West Virginia [Figure 1]. The site includes Fike Chemicals, (CST)
Inc., Coastal Tank Lines, Inc., and Cooperative Sewage Treatment,
Inc. The primary objective of the study was to identify and quantify
all toxic chemicals discharged to the Kanawha River from the site.
The survey data were also to be used to determine compliance with the
National Pollutant Discharge Elimination System (NPDES) permit limi-
tations for CST, Inc., and to revise or establish new permit limits.
and conditions for the latter.
Fike Chemicals, Inc. (Fike), is a small-volume chemical manu-
facturing firm in Nitro, West Virginia. Fike specializes in the
development of new chemicals, small-volume specialty chemicals, by-
product recovery and custom manufacturing. Approximately 50 differ-
ent chemicals are produced, with 18 considered major products. All
50 of these chemicals are produced in batch operations based on sales
demand; thus, the wastes from the plant are highly variable. Since
many of the chemicals are manufactured only as required, production
varies from a few hundred to about one million kilograms (2 x 106 lb)
per year.
Coastal Tank Lines, Inc. (Coastal), headquartered in Akron, Ohio,
operates a truck terminal adjacent to Fike Chemicals, Inc. The Company
hauls finished chemical products and raw materials interstate; no
wastewater o'r waste materials are hauled. Empty tank trailers are
returned to the terminal, washed inside and outside and repaired
-------
ENVIRONMENTAL PROTECTION AGENCY
Office of Enforcement
EPA 330/2-78-002
COMPLIANCE MONITORING
and
WASTEWATER CHARACTERIZATION
of
FIKE CHEMICALS, INC.
COASTAL TANK LINES, INC.
and
COOPERATIVE SEWAGE TREATMENT, INC.
Nitro, West Virginia
February 1978
National Enforcement Investigations Center - Denver
and
Region III - Philadelphia
-------
TABLE L-1
SUMMARY OF ANALYTICAL DATA FOR DILUTED BIOASSAY WASTEWATER
CST, INC. EFFLUENT PLUS DILUTION WATER
October, 1977
*
Date Concentrations (mg/ 1 )
( Oc t) CN NH -N ND2+N03-N As Ag A1 Ba Cd Fe Pb
3
5 0.11 4.3 1.6 0.06 NDt 0.9 ND ND 3.1 0.1
6 0.06 14.0 1.3 0.04 ND 0.7 ND ND 3.0 0.2
7 0.21 3.2 1.0 ND NO 0.5 NO NO 2.3 0.2
8 0.14 0.88 1.2 NO NO 0.8 NO NO 3.4 0.2
9 0.27 1.2 2.5 ND ND 1.4 ND ND 4.5 ND
10 0.22 0.25 2.0 NO ND 0.6 ND NO 2.2 0.4
* Volatile Organics were not detected. See text Table l6 for
t detection limits.
ND = Not Detected
Compound Detection Limit (mg /1)
As 0.02
Ag 0.01
Ba 0.02
Cd 0.01
Pb 0.01
-------
TABLE L-2
CYANIDE CONCENTRATIONS
COASTAL TANK TRUCK DISCHARGES TO EVAPORATION POND
October 3-7, 1977 . .
Date Time Period pH Cyanide
(Oct) of Discharge S.U. mg/1
3 0915-0930 12.3 <0.01
5 0055-0110 12.5 <0.01
5 1455-1510 11.3 0.02
6 11 00- 111 5 11.4 0.01
7 0545-0600 12.3 0.02
-------
APPENDIX L
RAW CHEMICAL DATA FOR BIOASSAY STUDIES AND
CYANIDE CONCENTRATIONS IN COASTAL TANK TRUCK
DISCHARGES TO THE EVAPORATION POND
-------
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGA nONS CENTER
BUilDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
TO
: A1~t Masse
DATE: February 15, 1978
FROM:
B. A. Binkley
SUBJECT:
Treatability Studies on CST Wastewater,
The follCMing data are the results of toxicity tests conducted at NEIC
of three samples of treate:1 CST effluent.
. 'Sample I (19 December 1977)
This screening test was conducted using CST effluent treated only by
activate:1 carbon filtration. Five fathead rnirmCMS were exposed to the un-
dilute:1 treated effluent and a control consisting of Kanawha River water.
This treatment was ineffective. Test fish were severely stressed ,,,ithin boX>
hours of exposure and none, Slirvive:lthe 24-hour-exposure. The control fish
showed no ~igns of stress and all survived the 24-hour test. This treated
wastewater as received still contained finely divided residual charcoal p3.r-
ticles. To detennine if the carbon could p::>ssibl y be acting as a carrier
for toxic substances the Wastewater was pressure filtered to clear and. a
secorrl 24-hour bioassay was conducte:1. Again none of the test organisns
survived a 24-hour exp::>sure, indicating residual carbon was not a signif-
icant fq.ctor relating to toxicity. ' ,
. 'Sample 'II (13 january 1978)' ,
, , ' ~IIIE~EJJ '
This effluent sample was carbon"treated with scdium sulfide to renove
,heavy metals, pH adjusted to 4 and aerate:] to remove cyanide. Prior to tox-
icity testing the waste:ticlter was readjusted to pH 8. Screening tests were'
done on a 100% concentration of the treated waste. None of the test or-
ganisms survived a 24-hour exp::>sure. The effluent "1O.s'then diluted to a
, 50% concentration and a second screening test conducted. All of the test
organisms survived a 24-hour exp::>sure, although obvious s-igns of stress were
evident. This test was allOwed to continue for a full 96-hour exp::>sure per-
icxl, resulting in survival of 60% of the test fish.
Sample III, (27 January 1978)
This sample of effluent was treated identical to sample two with one'
exception. Prior to canmencing the toxicity test the treated wastewater
was heavily aerated for 72 hours. A 96-hour static bioassay was done'
-------
- 2 -
utilizing five concentrations of effluent (100%, 56%, 32%, 18%, 10%) and a
Kanawha River water control. All concentrations except the 100% wastewater
were done in duplicate using 5 fathead minnows Per chamber. Insufficient
treated wastewater precluded duplication of the 100% concentration. Results
of the bioassay indicate the third treabTIent method was very effective in
reducing the toxicity of the CST effluent. Twenty percent of the test fish
survived a 96-hour exposure to a 100% concentration of treated effluent.
No mortalities associated with .the toxicity of the wastewater occurred at any
of the lower concentrations. Because mortality was restricted to only the
100% concentration an Le50 value for this treated wastewater cannot be cal-
culated. However, by use of graphical interpolation the 96-hour I.C50 was
estimated to be a concentration of treated effluent of approximately.80%.
To determine that the reduced toxicity of the CST effluent ,vas due to
the applied treatment and not aging of the wastewater, two additional tests
were perfonned. A screening test was done exposing 5 fish to undiluted ra,;v
CST efflu,ent. All of the test fish were .imrobilized within five minutes of
exposure'~ A 96-hour static bioassay was conducted utilizing five raw efflu-
ent concentrations (10%, 5.6%, 3.2%, 1.8%, 0.56%) and a dllution water con-
troL 'l11e raw csr effluent rercained highly toxic to fish. The ~6-hour IC50
\'TaS calculated to be a 2.1% effluent concentration. 'l11e results of these
two tests indicate detoxification of the CST effluent resulted fran applied
treatment and not exces~ive aging of the sample.
It should be noted that with the exception of aeration, samples II and
III received identical treatment. However, sample III was significantly
less toxic when testro. 'l11is :implies that the additional aeration may have
had a significant effect on the treatment.
-»= ANJ Jri) /#.);f.lt,jt.> 3£ )-'\11"''''' +0 ...f e:l.pOHn'<.c..
-------
APPENDIX K
LABORATORY BENCH SCALE TREATABILITY STUDY
. FISH BIOASSAY
-------
Gas Chromatographic Conditions
Instrument
Hewlett Packard, Model 7626
Column
Flame Ionization, dual detector H2-25 ml/min
Air 350 ml/min
2 mm 10 x 101 stainless steel, 6% OV-10l on 60/80 GCQ
Detector
Carri er
Helium, 30 ml/minute
Temperatures:
Oven
Temperature programmed
Start 800C, Final 2200C, Hold at 220°C for 20 min
60C/min rate
Injector
250°C
225°C
Detector
-------
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
TO
: Chi ef
Chemistry Branch
DATE:
December 7, 1977
FROM:
J. J. Slovinski
SUBJECT: Treatability Study - Final Effluent from CST, Nitro, West Virginia
Summary of Study
A study was undertaken to determine if the final effluent from the activated
sludge plant treating wastes from Fike Chemical and Coastal Tank Lines could
be further treated to remove complex organics that remain in the effluent.
I
It was believed that adsorption on activated carbon will remove most of the
organic materials, particularly the high molecular weight complex organics.
Inorganic cyanide which is present in the activated sludge plant effluent
:. was also analyzea to determine if carbon treatment would remove cyanide
moieties.
The results of this study indicate that substantial removal of most of the
complex organics listed on the table was accomplished by treating the waste
with a concentration of carbon> 7000 mg/l. Cyanide and TOC removal was not
as efficient as the complex organics, however. TOC was monitored to deter-
mine the removal efficiency of organic carbonaceous material.
Analytical Procedures
A four-liter aliquot of the final effluent from the activated sludge plant
that treats wastes from Fike Chemical and Coastal Tank Lines (Sample
Station 2420, October 8, 1977) was used for this treatability study. The
sample was filtered through a #1 Wattman filter paper. Total suspended.
solids were measured on the sample both before and after filtration. The pH
of the filtrate was approximately 7.5~ 375 ml of the filtered effluent
sample was placed in each of six 500 ml glass stoppered erlenmeyer flasks.
Varying amounts of powdered carbon were added to the flasks (Table 1) and
the mixture was agitated on a wrist action shaker for two hours. All sam-
ples were allowed to settle for one hour and then filtered through a 0.45
. micron millipore filter which had been previously washed with distilled
water. .
A 125 ml aliquot of each mixture was used for TOC and cyanide analyses and
the remaining 250 mls was extracted for complex organics.
-------
- 2 -
The pH of the mi11ipore filtered samples for complex organic analysis was
adjusted to 11 with 6N NaOH. Each sample WaS then extracted with 100 ml
of methylene chloride followed by two additional 75 ml methylene chloride
extractions. All three extracts were combined and concentrated to a
volume of 10 m1 using Kuderna-Danish evaporators. "~
The same water samples were then acidified to pH 2 wJLth-6~2S04 and ex-
tracted and concentrated in the same manner as the'~neutra,l...a'nd basi c
fraction described above. The two extracts were t~Tyzed with a gas
chromatograph equipped with a Flame Ionization Detector (FID-GC). The
six organic compounds listed in the table were identified by coincidence
of retention time and/or by the use of a gas chromatograph mass spectrometer
system (GC/MS). .
c
Quantitation was accomplished by comparing response factors (using peak
height) of standards or cQmpounds similar to those identified in the extracts.
"
Since the samples were filtered prior to extraction, organics adsorbed on
particulate matter was not detected. In addition, no emulsions were encountered
during the extraction steps. No acetone was used in the extraction process
and thus no acetone reaction products were encountered in the analysis.
For these reasons, the results obtained for the untreated effluent sample
will not be exactly comparable to the previously reported data. However,
these results do reflect the waste removal characteristics of the varying
amounts of carbon since all samples were analyzed in the same manner.
Inorganic parameters were analyzed according to prescribed methods as out-
lined in the 14th edition of Standard ~ethods and EPA Methods of Chemical
'Analysis.
---~~..~'/ //)J!i
,_.... ." ~. 1
-'" /,". /' :.... \
.,;({j", .' i ,fi
-------
APPENDIX J
ACTIVATED CARBON TREATABILITY STUDY
ANALYTICAL PROCEDURES
-------
10.
I/Jo/7~
J/fl ~ i JJ-(
Treatment Procedures-CST Effluent Samples of 10/8/77
The samples are stored in the first floor walk-in refrigerator and are
clearly marked as CST Effluent for treatability. Each bottle should
hold about 1 gallon so seven bottles can be treated using the following
procedure:
1.
Add 7000 mg/2 of F-300 powdered activated carbon supplied by the
Ca1gon Corporatio~ (26.4~'g~/ga1~on).
2.
Agitate vigorously for two hours so that there is. intimate contact
between the carbon and the wastewater.
3.
Let settle for 1 hour and filter to remove carbon.
4
Add twice the barium sulfide necessary to precipitate the iron
(19 mg/2), lead (0.8 mg/2) and silver (0.018 mg/~) present in the
sample. (426 mg. BaS/gallon) .
5.
Agitate slowly for 2 hours, let settle for 1 hour and then filter
to remove the precipitated heavy metals.
6.
Reduce the pH to 4.0 with sulfuric acid and blow with air for four
hours to remove the cyanide.
7.
Raise the pH to 7.0 and blow with air for t\'JO days.
8.
Take sample and analyze for cyanide, sulfide, arsenic, heavy metals,
TOC and conductivity.
9.
Conduct bioassay study on treated effluent using Kanawha River
water as dilution water.
Keep wastewater refrigerated v/hen it is not being worked on.
-------
5
before resuming service. Approximately 70 truck tractors and 107
.
tank trailers are served by the Coastal terminal.
Cooperative Sewage Treatment, Inc. (CST) was formed as a joint
venture by Fike and Coastal to treat the industrial wastewaters.
Process wastewaters are discharged either to one of two evaporation
ponds or to a biological treatment system (biosystem). The Coastal
tank trailer pre-rinse wastewater, and the Fike process wastewaters
considered highly toxic or of low volume, are discharged to the ponds
south of the Fike processing area. All other process and sanitary
wastewaters from both facilities are discharged to the CST biosystem
on the southwest corner of the Coastal property. Wastewaters dis-
charged from the biological system flow to the Kanawha River and are
limited by NPDES Permit No. WV 0001651 [Table 1J.
Monitoring was conducted October 3-7, 1977, at the following
locations:
1.
2.
3.
4.
5.
6.
CST effluent (NPDES Outfall 001)
Coastal's washing facilities discharge to the CST biosystem
Coasta1's tank trailer discharges to the evaporation pond
Fike's process wastewater discharge to the CST biosystem
The older evaporation pond contents and sediment
Three monitoring wells adjacent to the evaporation ponds
Treatability studies were conducted on the CST effluent at the
NEIC Denver-laboratory to determine the treatment necessary to enable
the permittee to comply with the NPDES permit limitations and to reduce
the toxicity of the discharge to aquatic life.
This report summarizes the results of the NEIC survey and treat-
ability studies.
-------
Effl uent
Characteristic
Flow m3/day (mgd)
COD
BOD5
Total Suspended Solids
Oil and Grease
Phenols
Ammonia
Chloride
Arsenic
. .
Surfactants
Fecal' Col Horm
Nitrates
Sulfates
Total Solids
Aluminum
Iron, Total
Heavy Metals
pH
Other
TabZe 1
.,
NPDES PERMIT LIMITATIONS
CST~ INCORPORATED
OUTFALL 001
Discharge Limitations
Daily Average, Daily Maximum
kg/day lb/day kg/day lb/day
N/A
522
95.3
18.9
3.8
0.22
10.9
1 ,362
0.05
N/A
N/A
5.0
72.5
835
7.3
3.6
N/A
1 , 1 50
210
41. 7
8.3
0.48
24
3,000
O. 1
N/A
N/A
11
160
1,840
16
8
N/A
2,088
191
37.9
5.7
0.50
16.3
2,043
0.09
N/A
200/100 ml
46.8
318
4,177
:10.9
7.3
N/A
4,600
420
83.4
12.5
1.1
36
4,500
0.2
1 . 0 mg / 1
400/100 ml
103
700
9,200
24
16
(J)
Monitoring Requirements
Measurement Sample
Frequency Type
l/week
l/month
l/week
l/week
l/week
l/week
l/week
l/week
l/week
l/week
5/week
l/week
l/week
l/week
l/week
l/week
Measured
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24-hr comp
24.-hr comp
As, Ba, Cd, Pb, and Ag shall not be discharged in amounts that will violate
West Virginia Water Quality Criteria. These parameters to be monitored 1/3
months, 24-hr compo .
pH shall not be less than 6.0 or greater than B.5 standard units and shall be
monitored l/week, grab sample.
There shall be no discharge of floating solids or visible foam in other than
trace amounts.
-------
II.
SUMMARY AND CONCLUSIONS
Fike Chemicals, Inc., is a small-volume firm which specializes
in the development of new chemicals, custom chemical processing, and
specialty chemicals. About 50 different chemicals are produced, all
by batch reaction, on an "as-needed" basis. Coastal Tank Lines, Inc.,
operates a truck terminal adjacent to Fike Chemicals, Inc., and hauls
finished chemical products and raw chemical materials. The empty
tank trailers are cleaned and repaired at the terminal. CST, Inc.,
was formed as a joint venture by both companies to treat their in-
dustrial wastes. Process wastewaters are discharged either to the
CST biological treatment systp.m and then to the Kanawha River via
Outfall 001, or to two unlined evaporation ponds.
On October 3 to 7, 1977, the National Enforcement Investigations
Center (NEIC), conducted a monitoring survey to determine compliance
with the NPDES Permit limitations and to identify toxic chemicals
discharged from these facilities. The orga~ic and toxic compounds
detected during this survey were not necessarily representative of
all compounds which could be discharged due to the batch operations
by both companies. In addition, other organic compounds may have
been discharged in concentrations below detectable limits.
NPDES PERMIT COMPLIANCE
Previous flows reported by CST were about 35% greater than the
flows measured by NEIC. The flow device used by CST, a broad-crested
weir, had not been rated and a standard flow table for a sharp-crested
rectangular we~r was being used to determine flows. NEIC installed a
standard rectangular sharp-crested weir to measure the flows during
3
the survey; the flow averaged 151 m (39,900 gal)/day.
-------
8
A 96-hour flow-through bioassay conducted on the CST effluent
showed the effluent to be acutely toxic. The calculated LC50* was
0.22% effluent. The 96-hour static bioassays showed that Fike and
Coastal discharges to the CST biological system were also acutely
toxic. The estimated LC50 values for these discharges were 0.56 and
2.2% effluent, respectively.
NPDES limitations were violated for the following parameters:
pH -
Oil/grease -
Phenols -
Ammonia -
Surfactants -
*
The pH exceeded the permissible range of
6.0 to 8.5 on 45 of 115 individual measurements
The daily maximum limitation 5.7 kg (12.5 lb)
was exceeded on all 5 days. The load
averaged 12.4 kg (27.4 lb)/day
The daily maximum limitation [0.5 kg (1.1 lb)]
was exceeded on 4 of the 5 days. The load aver-
aged 0.7 kg (1.5 lb)/day
The daily maximum limitation was exceeded
by 20% on October 5
The daily maximum limitation of 1.0 mg/l
was exceeded each day. The average concen-
tration was 6.2 mg/l
LCSO indicates the concentration (actual or.~nterpolated) at
WhlCh 50% of the test organisms died, or would be expected to die.
-------
9
ORGANIC CHEMICAL IDENTIFICATION
CST Effluent
Thirty-five organic chemicals were
which were confirmed as being present.
on the Priority Pollutant List.* These
identified -- twenty-three of
Eight of these chemicals are
include:
Chemical
Maximum Concentration
mg/l
0.12
O. 18
1.8
3.3
0.018
0.29
0.008
O. 1 I-Ig/l
Anthracene
Phenanthrene
Phenol
Isophorone
Carbon tetrachloride
1,1,2-trichloroethylene
Tetrachloroethylene
Dimethylnitrosamine
Eighty-four organic compounds were identified in the Fike and
Coastal discharges to the CST. Fifty-nine of the compounds were confirmed,
thirteen of which are on the Priority Pollutant list. Forty-seven of
the compounds were found in the Coastal wastewaters, twenty-eight in
the Fike wastewaters, and nineteen compounds detected in both. Of
the thirteen known priority pollutants, six were discharged from both
facilities and seven were detected only in the Coastal discharge.
These thirteen chemicals include:
*
Priority Pollutant list per the Consent Agreement, Natural
Resources Defense Council vs. Russell E. Train, June 1976.
-------
10
Chemical Coastal Fi ke
Anthracene X
Fluorene X
Naphthalene X
Phenanthrene X
Phenol X X
1,2,4-trichlorobenzene X
Isophorone X X
Dimethylnitrosamine X X
Dichloromethane X
Chloroform X
Carbon tetrachloride X X
1,1,2-trichloroethylene X X
Tetrachloroethylene X X
Evaporation Ponds
Two evaporation ponds have been constructed on Fike property.
The newer, built in September 1977, was only being used by Coastal;
Fike continued to discharge to the older pond. There was no waste-
water in the new pond as the material discharged was resinous and had
solidified.
Twenty-one organic compounds were identified in the old pond,
eleven were confirmed. Five are on the Priority Pollutant list and
include phenol, chloroform, tetrachloroethylene, 1,1,2-trichloroethylene,
and dimethylnitrosamine.
Three wells adjacent to the ponds were grab sampled twice. .The
data indicate that the-groundwater is being contaminated. The fol-
lowing organic'compounds were detected in the old pond and the No.2
well (closest to the evaporation ponds):
-------
11
p-isopropyl phenol (confirmed)
phenyl isocyanate
propylbutylthiourea
tetramethyl urea
1,4-thiaoxane (confirmed)
chloroformt (confir~ed)
tetrachloroethylene (c~nfirmed)
1,1,2-trichloroethylene (confirmed)
diamylnitrosamine (ronfirmed)
dimethylnitrosamine (confirmed)
t
Priority pollutant
Moreover, based on the field measurements, rainfall and evaporation
data, and quantities of wastewater discharged to the old pond, it is
evident that the pond contents must percolate to the groundwater.*
Thirteen compounds were detected in the soil &le from the new
pond. This soil had not yet come into contact with the wastewaters.
The data show that the soil is becoming contaminated by unsafe and
careless disposal techniques such as dumping waste materials directly
onto the ground, or leakage from drums. These contaminants saturate
the soil and eventually reach the groundwater.
TOXICITY
One hundred thirty-seven organic chemicals and six heavy metals
were detected in the NEIC survey. It has been determined that seventy-
two of these compounds have identified toxic properties. Additionally,
twenty-six of the one hundred thirty-seven organic compounds are closely
related isomers whose toxic properties would be similar to those identi-
fied. Thus, over 50% of the compounds identified have known toxic
effects. Including heavy metals, fifteen of these compounds have
known carcinogenic or neoplastic effects and five have known teratogenic
or mutagenic properties. Twenty-two compounds have known aquatic
toxicities ranging from lto 1,000 ppm. Nineteen compounds are on
the EPA Priority Pollutant list, eleven are EPA selected as a priority
point source pollutant, and three are EPA pesticide candidates for
*
In a July 14, 1971 letter to the State of West Virginia Water
Resources Division, Mr. Fike stated that the older pond was
built so that the wastes would percolate into the ground. .
-------
1 2
additional onicological testing. The compounds have varying detri-
mental effects on the central nervous system. blood. or glandular
involvement. A total of three hundred seventy-five individual pieces
of toxicity data are available for the seventy-two chemicals listed.
Fifty compounds were actually identified as either being dis-
charged to the Kanawha River or leaching into local groundwater. The
likelihood is quite high that all chemicals identified are discharged
on an intermittent basis.
Seventeen of the thirty-seven organic chemicals discharged from
CST to the Kanawha River have known toxic effects: nine are carcinogens
and five (including three carcinogens) have been previously detected
in the Cincinnati drinking water. The Cincinnati water supply is the
Ohio River. downstream of the Kanawha River.
Twenty of the organics and four of the heavy metals detected in
the groundwater have known toxic effects. Twelve of these are carcino-
gens and one is a teratogen. Six organic compounds. including two
carcinogens. have been detected in Cincinnati drinking water.
None of these compounds are normal metabolites of humans. but
instead all are of industrial origin. Moreover. none are known to be
essential to humans. nor are there any known beneficial effects from
the ingestion of any of the detected compounds in any form. However.
much is known about the adverse effects of the compounds to humans
and to the biota of the receiving waters.
MUTAGENIC ACTIVITY
Results of the Ames Bacterial Assay for mutagenesis conducted at
the NEIC Laboratory demonstrated that the CST effluent discharged on
October 7 and 8 contained potential carcinogens. The volumes causing
-------
13
mutagenesis for the October 7 effluent ranged from 1.20 to 4.20 ml of
effluent. The October 8 effluent displayed mutagenic activity between
0.75 and 2.25 mls. All extracts tested between these ranges for the
October 7 and 8 effluent samples exhibited a mutagenic activity ratio
greater than 2.5, indicating, with greater than 90% probability, that
the substance could induce tumors in laboratory animals. The mutagenic
effects of effluent concentrations greater than 4.20 and 2.25 ml for
October 7 and 8, respectively, could not be measured due to bacterial
toxicity of the samples.
SOLID WASTE DISPOSAL
Used drums, still bottoms, and various reaction byproducts are
disposed pf on-site by Fike. The normal practice is to dig a pit in
the area south of the processes and to place empty drums and drums
which contain wastes into the pit. The pit is not backcovered daily;
once the pit is full, it is backcovered. Before backfilling, many
drums containing wastes rust and the wastes flow onto the ground.
Other drums and discarded material are just left in the open with no
effort to dispose of the material in an environmentally safe manner.
AIR POLLUTION CONTROL
Control of air emissions is minimal. Only 2 of the 4 scrubbers
are operational and these only remove chlorine and hydrochloric acid.
Many nauseating odors were detecteq by NEIC personnel throughout the
plant, but were not identified.
-------
14
WASTEWATER TREATABILITY STUDIES
Bench scale studies were conducted in the laboratory on the CST
effluent collected on October 7 to determine the treatment required
to bring the discharge into compliance with the NPDES permit limita-
tions and to reduce its toxicity to aquatic life. For the average
flow of 151 m3 (40,000 gal)/day on October 3 to 7, the phenol concen-
tration in the CST effluent would have to be 1.4 mg/l to comply with
the daily average limitation of 0.22 kg (0.48 lb)/day. The laboratory
data showed that the addition of 2,000 mg/l of powdered activated
carbon reduced the phenol concentration from 3.7 to 1.4 mg/l.
In full-scale application at the CST facility, the powdered
activated carbon could be added to the aeration basin's influent
flpw. This treatment, plus raising the pH to 10 to precipitate heavy
metals, would reduce the aquatic toxicity of the effluent from an
LC50 of 2.1% to one of 80% and bring the effluent into compliance
after the pH had been readjusted to the range of 6.0 to 8.5.
The capital cost for the carbon addition equipment would be
approximately $4,600 and the chemical costs about $250/day.
-------
III.
RECOMMENDATIONS
CST, INC. EFFLUENT
Due to the batch operations at Fike and Coastal, and due to the
toxicity of the wastewaters demonstrated during the NEIC survey,
biological treatment alone should not be relied upon to achieve
compliance with the NPDES permit limitations. Treatment systems
which are not susceptible to toxicity or process upsets are required
to ensure that reliable and consistent treatment is achieved. NEIC
laboratory studies showed that powdered activated carbon addition and
pH adjustment incorporated into the current CST biological treatment
system could bring the effluent into compliance. CST must investi-
gate and ~valuate this treatment method or other treatment alterna-
tives, incorporate the modifications or alternatives into the CST
treatment system and achieve compliance with the NPDES permit limitations.
Once a treatment system is approved and operating, the effluent
. should be monitored at least once/week for toxicity using a fish
bioassay.
In the interim period,
housekeeping procedures and
should be isolated from the
Fike and Coastal should improve in-plant
reduce water usage. Toxic chemicals
discharges to the CST.
EVAPORATION PONDS
To protect the groundwater from further contamination, all
diseharges to the two evaporation ponds should cease. New evap-
oration ponds of adequate size to provide sufficient volume for
-------
16
rainfall and all discharges must be constructed with two impermeable
liners. A buffer zone must exist between the liners and a collection
system installed in the zone to determine if the first liner is
preventing percolation. The collection system should be monitored
weekly. In addition, the groundwater should be monitored weekly.
the liners are not effective barriers due to chemical reactions or
If
improper installation (and can't be repaired), then the wastewaters
must be transported to an approved hazardous waste disposal site.
Tb prevent further contamination of the groundwater, wastewater,
solids, and contaminated soil presently in the two evaporation ponds
must be removed and transported to an approved hazardous waste dis-
posal site.
As an alternative to constructing new exaporation ponds, the
wastewater could be transported to an approved hazardous waste dis-"
posal site.
SOLID WASTE DISPOSAL
The current method of on-site disposal of process solid wastes
and discarded containers should be discontinued. The groundwater has'
become contaminated from this disposal method. If on-site disposal
is continued, a secure landfill area (with liners.and monitoring
requirements as described for the evaporation ponds) must be con-
structed. Pressure-producing material in containers, reactive ma-
terial, explosive material, etc., must not be placed in the landfill
but transported to an approved hazardous waste disposal site. All
waste material placed in the landfill should be recorded as to quantity,
type, and location of burial.
-------
Direct or indirect discharge of chemicals to the ground must
cease to prevent further soil contamination and possible river
pollution from stormwater runoff.
17
-------
IV.
PROCESS OPERATIONS AND POLLUTION ABATEMENT PRACTICES
FIKE CHEMICALS, INC.
During the presurvey reconnaissance August 22-25, 1977, Mr.
Elmer A. Fike, President of Fike Chemicals, Inc., discussed each
process with NEIC personnel. Mr. Fike considers the processes to be
proprietary and process descriptions are therefore not included in
this report.
The fifty products manuf2ctured at the site, the associated raw
materials, and the waste disposal methods are listed 'in Table 2.
Thirteen of the chemicals produced or used at Fike are on the
Priority Pollutant list* [Table 3].
All processes at Fike are small (maximum 2,270 kg (5,000 lb)/day)
batch type operations and the reaction time can be as long as one
week/batch. This type of operation results in intermittent dis-
charges to the wastewater treatment system or evaporation ponds.
Fike has three different sewer systems within the plant. Waste-
waters not treatable in the CST biosystem are disch~rged to an evapora-
tion pond via the contaminated sewer and the wastes considered treat-
able are discharged to the CST sewer. Spent cooling water is returned
via the cooling water sewer to the cooling tower, installed in 1976.
Most of the recycle flow consists of noncontact water; however, the
water from several barometric condensers is also collected in the
recycle system, thereby contaminating the water. According to Mr.
Fike, the water is presently contaminated with phenolics from the
ortho-benzyl phenol process. Cooling water from the tower is bled-off
for several hours twice/month to the CST sewer.
-------
Tob le 2
PRODUCT::; AND IWi MATEHIALS
FIKE CIlEMIC!lDS,WC.
Raw materials
and byproducts
N
o
Product
Location of .
product waste and
reaction materials -
disposal
Reaction
Batch Time
(hr)
Priority M~j(r
Po 11 u ta n t Prod:.ct
Lis t t
n-acety1 ethanolamine
No
Acetic acid
Monoethano1amine
Heptane
Hater
CSTtt
Air + CST
CST
Underground + CST
Ground + CST
Evap 1 agoon ttt
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
.Evap 1 agoon
Evap lagoon
Evap lagoon
Evap lagoon
Underground
Allyl cyanide
Sodium cyanide
Allyl chloride
Monosodium phosphate
Copper sulfate
Hater
Allyl alcohol
HCN
NaCL
St ill Res i dues
Aminoethy1 Sulfuric Acid
Monoethano1 amine
t.1ethano1
Sulfuric acid
Perchloroethy1ene
Water
Air
Underground
Underground
Air + Underground
Air + ground
o-Benz1 Phenol (OBP).
CST + Evap lagoon
Air + CST + Evap lagoon
Air + CST
Air + Evap lagoon
Underground
Underground
Underground
Phenol
Dibenzy1ether
Heptane
p-to1uene sulfonic acid
p-benty1 phenol
di-benzy1 phenol
Bis Ethyl Xanthogen (Bexide)
(EXD)
.CST
CST + Air
CST
Air
Air
Air
CST
Air + CST
Carbon bisulfide
NaOH
Chlorine
Ethano 1
I-later
NaCL
COS
+ CST
+ CST
+ CST
Butyl carboethoxyethy1 sulfide
(BCES)
Butyl Mercaptan
Ethyl acrylate
Sodium methylate
~1ethano 1
, tI)),l;.;)'it!j-'l'oTl~tant List per' the Consent !lgr'eement,
, UCjCnRC qounczl vs Hussell E. Tpain, June 1976.
Tt Coopcratzve Sewaqe Treatment Plant.
'1"1-1. f;on!)())lat",:ve La(loo'l.
Air
No 1iouor or
solid 'waste
Air
Natur'al Resour'ce
48
36
60
24
No
No
No
No
No
Yes
Yes
No
No
Yes
No
No
Yes
No
No
Yes
No
No
No
Yes
No
No
No
Yes
No
No
No
No
No
Yes
No
No
No
No
No
No
No
No
Yes
No
No
No
No
No
Yes
-------
Tab~e 2 (Contin/led)
PROt}UCTS AND JIM" MA TERTALS
FIKE CHEMICALS, INC.
Product Raw materials Location of Reaction Priority Major
and by products product waste and Batch Time Poll utant Product
reaction materials - (hr) Lis t
disposal
Bi s isopropyl xanthogen CST 12 No Yes
(PXD) Carbon bisulfide Air No
NaOH CST No
Chlorine Air + CST No
Isopropanol CST 1'10
H 0 CST 1':0
N&Cl CST No
COS Air No
Xylene Underground No
Rocure 7 CST 48 No No
Polyethylene tetrasulfide Dichloroethyl ether CST Yes
Sodium sulfhydrate CST No
Sulfur CST No
Toluene CST + Air Yes
NaCl CST No
Sodium Amide 8 No No
Anhydrous ammonia Air No
Sodium (Brick) No
Ferri c Nitrate No
Aqueous Ammonia No
H2 No
Sodium butyl a-phenyl phenol CST + Underground 48 No Yes
(RvIA-50) Butanol CST No
NaOH In product + CST No
Ethanol CST + Underground No
a-phenyl phenol CST + Underground Yes
Sulfuric acid CST No
Sulfa Floc Underground No
Sodium sulfate Underground No
S02 Air No
Sodium fluoroacetate Evap lagoon 24 No No
Ethyl fluoroacetate Evap lagoon No
Caustic Evap lagoon No
Hethanol Evap lagoon + Buried No
Ethanol Evap lagoon + Buried No
Sodium methylate No Yes N
25:1: solution Methanol Only leakage & spills to CST No --'
Sodium Hetal No
HZ Air No
-------
N
N
Table 2 (Continued)
PRODUC.TS AND RAW MATERIALS
FJKB CHEMICALS, INC.
Product Raw materials Location of Reaction Priority Major
and byproducts product waste and Batch Time Pollutant Product
reaction materials - (hI') List
disposal
Latex Sensitizer #3 Eyap lagoon 12 No No
paraforma1dehyde Eyap lagoon No
NaOH Eyap lagoon No
Ethyl chloride Eyap lagoon Yes
Ammonia Air No
H 0 Eyap lagoon No
N&C1 Eyap lagoon No
N methy1ne piperidinium cyc10- Undergr~und 12 No No
pentameth1ene dithiocarbamate paraforma1dehyde Underground No
(R-2 crystals) piperdine Underground No
Carbon bisulfide Underground No
methanol Underground No
H20 Underground No
Methoxytriglyco1 acetate Underground 24 No No
methoxy triglyco1 Undergy'ound No
Acetic anhydride L:"dergl'ound No
p-to1uene sulfonic acid Underground No
Acetic acid Undergl'ound No
Potassium phenyl glycinate Eyap lagoon No No
(KPG) KOH Eyap lagoon 24 No
Chloroacetic acid Eyap lagoon No
NaOH Eyap lagoon No
Aniline oil Eyap lagoon No
11a tel' Eyap lagoon No
HCl Eyap lagoon No
NaCl Eyap lagoon No
1 ,3-propanedithio1 Eyap lagoon 24 No No
Tri methylene ch10robromide Eyap lagoon .No
Sodium sulfhydrate Eyap 1 agoon No
H S Air. No
N&Cl Eyap lagoon No
Sodium bromide Eyap lagoon No
Po1ysulfides Underground No
Propylene thiourea CST 36 No Yes
Carbon bi sulfide CST + Eyap lagoon No
HZS Air No
H20 CST + Eyap lagoon No
-------
TabZe 2 (Continued)
--
PRODUCTS AND RAW /.IATERIALS
FIKE CHEMICALS, INC.
Product
Ravi ma teri a 1 s
and byproducts
Location of
product waste and
reaction materials -
disposal
Oimethylaminoethoxydiphenylmethane
(Bristamine Base)
Oimethyloxadiazene thione
(R-240)
1,3-dimethyl thiourea
Oiphenyl thiourea
(A- 1 )
Oithiooxamide
(OTO)
o Benzyl Phenol
Beta dimethyl amino ethyl chloride
HCl
NaOft
. Toluene
Water
NaCl
Oimethylamine ethanol
Residue
Evap lagoon + CST
Evap lagoon + CST
Evap lagoon + CST
Evap lagoon + CST
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Buried
+ CST
+ CST
+ CST
+ CST
1,3-dimethylthiourea
Paraformaldehyde
Heptane
H20
CST
CST
Air + CST
Air + CST + Underground
CST
Monomethylamine
Carbon bisulfide
Water
H2S
Air
Air
Air
Air
Air
Carbon bisulfide
Aniline
~Ja ter
H2S
CST
CST + Air
CST + Air
CST + Air
CST + Air
Chlorine
Ethano 1
H S
AI~moni a
Sodium cyanide
\1a ter
NaCl
Ammonium chloride
Evap lagoon
Evap. lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Evap lagoon
Reaction Priority ~1aj or
Batch Time Pollutant Product
(hr) List
12 No Yes
No
No
No
No
Yes
No
No
No
No
12 No No
No
No
No
No
48 No No
No None.produced
No this year
No
No
24 No No
No
.No
No
No
12 No No
No
No
No
No
Yes
No
No
No
N
W
-------
N
Table 2 (Continued) ~
PRODUCTS AND RAw MAfERIALS
FIKE CHt~ICALS, INC.
Product Raw materials Location of Reaction Pri ority Major
and byproducts product waste and Batch Time Poll utant Product
reaction materials - (hr) List
disposal
Ethanedi thi on Evap lagoon + Air 24 No No
Ethylene chloride Evap lagoon + Air Yes
H S Air No
S6dium sulfhydrate Evap lagoon No
Carbon Nuchar Evap lagoon No
NaCl Evap lagoon No
Dimercapto ethyl sulfide Underground No
Residue (ethylene poly sulfide) Underground No
Hater Evap lagoon No
KMn04 Evap lagoon No
Air No No
Propylene diamine Air No
Platinum Alumina Catalyst Air No
H20 Air No
H2 Air No
Air + Evap lagoon No Yes
Ethylene diamine Air + Evap lagoon No
Carbon bisulfide Air + Evap lagoon No
H S Air No
S6lfur Trash No
Evap lagoon No Yes
Ethyl chloroacetate Evap lagoon + Underground 20 No
Potassium fluoride Evap'lagoon No
H 0 Evap lagoon No
P6tassium chloride Evap lagoon No
Air + Underground Poison No
Ethyl fluoroacetate Air + Underground No No
Ammonia Air No
Methanol Air + Underground No
No No
Coarse !)lutaric Anhydride Grinding only. Spi 11 s
go to CST.
Bexide Spi 11 s go to CST No No
Xylene All blended No
Stexox and put into
Sulfonic Acid containers
Butylamine
2 ethyl 4 methyl imidazole
(EMI-24)
Ethylene thiourea
Ethyl fluoroacetate
(EE3)
Fluoroacetarnide
This is a rat poison
Glutaric Anhydride
Herbisan-5 Blend of
EXD for agriculture
-------
Table:: (Coll!;-inOl,:JJ
PRODUCTS AND RAW MATtR1AiS
FIXE CIIEMICALS, It/C.
Product Raw materials Location of Reaction Priority Major
and byproducts product waste and Batch Time Poll utant Product
reaction materials - (hr) List
disposal
I
N N dibutylammonium N N
dimethylcyclohexyl Di-n-butylamine No
dithiocarbomate (RZ-100) Carbon disulfide Air No 1 iquid or solid No No
Dimethyl cyclohexylamine waste No
Di butyl thiourea Air 24 No Yes
n-butylamine Air No
Carbon bisulfide Air No liquid or solid No
H2S Air waste No
Diethyl thiourea Air 24 No Yes
Ethylamine Air No
Carbon bisulfide Air No
Hater Air No liquid or solid No
H2S Air waste No
Di ethyl oxadiazene thione CST 12 No No
(R-235) 1,3 Diethyl thiourea CST No
Paraformaldehyde Air + CST No
Heptane Air + CST + Underground No
Su lfuri c aci d CST No
Diisopropyl carbodiamide Evap lagoon 12 No No
Diisopropyl thiourea Evap 1 agoon No
Water Evap 1 agoon No
Deformer Evap lagoon No
Emulsifier EVJp 1 agoon ,No
Litharge (PBG) Evap lagoon Yes
Lead sulfide Evap lagoon Yes
Diisopropyl thiourea Air 24 No No
I sopropyl ami ne Air + Evap lagoon No None produced
Carbon bisulfide Air + Evap lagoon No this year
l'later Air + Evap lagoon No
H2S Air
Di-o-tolyl thiourea Air + Evap lagoon + CST 36 No No
(<< « dimethyl thiocarbanalide) o-toluidine Air + Evap lagoon + CST No
Carbon bisulfide Air + Evap lagoon + CST No
Hater Air + Evap lagoon + CST No N
H2S Air CJ1
-------
Tab~e 2 (Continued)
PRODUCTS AND RAW MATERIALS
FIKF: CIIF:I.fTCA['S, INr..
N
0'\
Ra\~ materials
and byproducts
Major
Product.
Product
Location of .
product waste and
reaction materials -
disposal
Reactipn Priority
Batch Time Pollutant
(hr) List
Benzyl mercaptan Underground + Air + Evap lagoon 24 No
Benzyl chloride Evap lagoon No
Sodium sulfhydrate Evap lagoon No
Hater Evap lagoon No
Dibenzyl sulfi de Underground No
NaCl Evap lagoon No
KMn04 Evap lagoon No
Butyl phenyl phenol sodium sulfonate CST 48 No
(RIoJA-50) Butanol CST No
(RWA-375) NaOH Underground 1:10
Ethanol Air No
Oleum (H2S0 ) CST No
o-phenyl ph~nol CST No
Sulfuric acid CST No
$0 Air No
S06ium sulfate Underground No
Salka floc Underground No
Chloromalcic Anhydride Underground + CST 240 No
(Ct~A) Maleic anhydride Underground + CST No
Chlorine Air + CST No
Ferric chloride Underground No
HCl CST No
Water CST No
Chloromaleic anhydride
tHBK MIBK Blend only no reaction No
CMA or waste No
Cutain II Mixture of No
propyl ene thiourea & thiourea Propylane thiourea Dry blending - any waste No
Thiourea would go on ground No
Cyclohexylamine Air + CST 72 No
(CHA) CHA-crude (purchased) Air + CST No
Aniline Air + CST No
Cyclohexanol Air + CST No
Diphenylamine Ai.r + CST No
Water CST . No
Oiammnnium Ethylene bis- 24 No
dithiocarbamate Ethylene diamine Air No
Carbon bisulfide Air No
Ammonia Air No
Hater . Product No
H2S Air No
No
Yes
No
. No
Yes
Yes
No
-------
'i'abZe:: (Continucd)
PlIO/JlICTS IiND 1IMI/.I/iTl-.'HII1&S
PI.:E ClfE~JICI1/'S, INL'.
Product
Ra\~ materi a 1 s
and byproducts
Location of
product waste .and
reaction materials -
di sposa 1 .
Sodium nickel cyanide
Evap lagoon
Evap lagoon
Evap 1 agoon
Evap lagoon
Evap lagoon
Nickel chloride
Sodium cyanide
H °
N~Cl
Thioacetamide, technical
toxic
Acetonitrile
H S
I~opropanol
Dimethyl cyc:~hexylamine
Underground
Underground
Air
Underground + Air
Underground
Trimethyl thiourea
Monomethylamine
Dimethylamine
Carbon bisulfide
Zeolex
Phosphoric acid
H20
H2S
Air
Evap lagoon + Air
Air
Zinc dibutyldithioca~bamate
(Butyl Ziram) .
Carbon bisulfide
Methanol
Zinc oxide
dibutyl amine
H20
Underground
Underground
Underground
Underground
Underground
Underground
Zinc dimethyldithiocarbamate
(r~ethyl Zi ram)
Carbon bisulfide
DMA
Zinc oxide
H20
CST
Air
CST
CST
CST
Vin Vat B-1
Sodium nickel cyanide
Sodium formaldehyde sulfoxolate
Solids blending only
Reaction Priority Major
Batch Ttme Pollutant Product
(hr) Li st
8 Yes No
No
Yes
No
No
24 No No
No
No
No
No
No Yes
No
No
No
No
No
No
No
12 No No
No
No
No
No
. No
12 No No
No
No
No
No
No Yes
N
'-I
-------
28
Table 3
LIST OF CHEMICALS ON THE EPA
PRIORITY POLLUTANT LISr
FIKE CHEMICALS3 INC.
Chemical
Allyl cyani de
Sodium cyanide
Copper sulfate
HCN
Phenol
Perchloroethylene
Litharge (PbO)
Lead Sulfide
Toluene
Ethylene chloride
Fluoroacetamide
(not on list but is a poison)
Ethylchloride
Dichloroethylether
Sodium nickel cyanide
a Priority Pollutant List per the
Consent Agreement3 Natural Resource
Defense Council vs Russell E. Train3
June 1976.
-------
29
The sewer system was built between 1915 and 1920. The origin
and destinations of most of the sewers are unknown. Complete segre-
gation of the three wastewater streams is improbable due to the
conditions of the sewers, possible cross connections, and processing
techniques. There are almost no fixed connections from a reaction
vessel to either the contaminated or CST sewers. Hoses are manually
connected from the reactors to the sewers for disposal of the waste-
water. However, when a reaction is completed, the wastewaters are
frequen~)y dumped on the ground beneath the reactors and flow to the
closest sewer. Some wastewaters are placed in steel drums for burial
or storage above ground. Most of these drum~ are left where they are
filled and allowed to rust until leaks develop. The leaks either
flow to a sewer or percolate into the ground.
During the August reconnaissance, several wastewater streams
that were reported as discharged to the contaminated sewer were
actually being discharged to the CST sewer. Many rusting steel drums
containing waste chemicals were observed throughout the processing
area. The entire processing area appears to be soaked with unknown
chemicals which may be leached into the sewers and groundwater.
Also, there are areas on the plant site that contain rain water and
unknown amounts of chemical wastewaters. It is evident that efforts
are not being made to keep
housekeeping practices and
existent.
the materials segregated. It appears that
environmental controls are almost non-
The condition of the equipment is extremely poor; most equipment
is corroded and employee safety in these areas is questionable.
During the August inspection, some sodium metal lying on the ground
in the landfill area exploded within minutes after NEIC personnel
left the area.
-------
30
Control of air emissions is minimal. Only two of the four
scrubbers are operational. The Ethyl Xanthic Disulfide process has a
batch caustic jet scrubber to remove chlorine. The scrubbing liquid
is pumped from an open tank through a jet to create the vacuum which
pulls the gas stream from the reactor. The gas stream enters the jet
and contacts the scrubbing solution as it recycles to the open tank.
Only chlorine is removed, the other contaminants are emitted.
The Chloromaleic Anhydride process uses a 3.7 m diameter x 3 m
I
deep (12 ft x 10 ft) column to scrub HC1. The gas stream enters the
bottom of the column and water is added at the top.
discharged to the CST. Chlorine is not absorbed and
the atmosphere.
The liquid is
is emitted to
In the production of benzyl mercaptan, potassium permanganate
(KMN04) is used to control odors and is added to the water-steam jet
used to create the vacuum in the process to control odors. The
KMN04-water solution is used on a once-through basis and is dis-
charged'to the old evaporation pond.
Many nauseating odors were detected throught the plant during
-the August reconnaissance and again during the October monitoring
survey. The most proba~le sources of air emissions would be the
uncontrolled reaction vessels and associated equipment. These odors
were also detected adjacent to the CST biosystem, from the manholes
on the CST sewer, and near the old evaporation pond, indicating that
fugitive emissions are also a significant problem at the site.
Paper, trash, etc., are hauled away by private contractor to a
sanitary landfill. On-site disposal is used for drums, still bottoms,
and various reaction byproducts. The normal practice is to dig a pit
in the area south of the processes and place the drums containing
these wastes into the pit. Once the pit is filled, a bulldozer is
-------
31
used to crush the drums and the pit is backfilled with about 1.8 m
(6 ft) of earth. Daily covering with earth is not practiced. Before
backfilling, many of the drums rust through and the wastes flow onto
the ground. The pit [Figure 2J used during the survey had an approxi-
mate volume of 1,500 m3 (53,500 ft3). During the August reconnais-
sance, this pit was about 10% full; by the October survey the material
in the pit had increased approximately fourfold. The expected life
of the pit cannot be estimated due to the varying amount of material
added.
Mr. Fike is aware that these methods of disposal are not acceptable
or environmentally safe. He is hopeful that he will be able to in-
cinerate burnable solid wastes along with most of the liquid chemical
wastes discharged to the evaporation pond. An incinerator has been
built for this purpose, however, to date he cannot secure an operating
permit from the local regulatory agency because of the non-degradation
of ambient air regulation.
COASTAL TANK LINES, INC.
Empty tank trailers are cleaned and maintained at the Nitro
facility. About,25 trucks and trailers are washed each day, 6 days
per week. The empty trailers normally contain only 19 to 38 liters
(5 to 10 gallons) of the material hauled when these are returned to
the terminal.
The interior of the trailers first receives a pre-rinse using
water that had been used for a final rinse [Figure 3J. After the
pre-rinse, a cleaning solution is added to the interior of the trail-
ers; this solution is recycled to the cleaning solution make-up tank.
The trailers then receive a final wash and this water is recycled and
used for the pre-rinse. When the cleaning solution is spent, it is
pumped to a tank trailer dedicated for this use. Occasionally, the
-------
~* --'-
25'
75'
SOLID WASTE
DISPOSAL PIT
95'
W
N
40'
FIKE CHEMICALS, INC. PROCESSING AREA
WELL NO.1
o
/'
97'
,I,
ISO'
. !. 42' -I
42'
OLD EVAPORATION
PO N D---""\
_130'
65 '
SUMP
40'
2Y2" 9
/'
COASTAL TANK LINES INC.
TRAILER DISCHARGE AREA
290'
OWELL NO.2
95'
NEW EVAPORATION POND
200'
COASTAL TANK LINES, INC. TERMINAL
(NO T TO SCALE)
WELL NO.3
o
Figure 2. Schematic of C51 Evaporation Po'nds and Solid Waste Disposal Area
-------
STEP 1 PRE RINSE
Flow
33
Flow
Flow
I ALl
Flow
B
" c I G
E
Flow'
STEP 2 RECYCLE OF CLEANING SOLUTIONS
Flow
Q
A B C
3
0
-
IL
STEP 3 FINAL RINSE
Overflow to CST Sewer
Q'-----I A
I
G I
I 3 .
o
I u=
I Spent Solutions
I - - -a-; R eq -;-d-:- - -
I
--To CST Ggoon-
NOTES:
A.
B.
C.
D.
PRE RINSE WATER STORAGE TANK
CLEANING SOLUTION STORAGE TANK
RINSE WATER STORAGE TANK
PRESSURE PUMP
8
Flow
Flow
Flow
B
Flow
C
E
Flow
E. RETURN PUMP
F. TANK TRAILER
G. PORTABLE HOLDING TAN.K
Figure 3. Coastal Tank Lines, Inc. Trailer Cleaning Proceedure
and Waste Disposal Routing to C.5.T.
-------
34
cleaning solutions will overflow the make-up tank and discharge to
the CST biosystem.
Coastal has two ways of disposing of the wastes from washing of .
the trucks. First, the pre-rinse water is pumped into a 19 m3 (5,000
gal) tank trailer (discussed above), and dumped into the evaporative
pond along with the spent cleaning ~olution. Secondly~ after the
final washwater is transferred to the pre-rinse tank, any excess is
disch~rged to the CST sewer (the excess final washwater does not
enter the pre-rinse tank). The tank trailer is emptied into the
evaporation pond about 3 times in a 48-hour period.
Coastal does not have any air pollution
only sources of stationary emissions are th:
tanks for cleaning solutions. These make-up
which exhaust to the atmosphere.
control devices; the
vapors from the make-up
tanks are in buildings
CST, INC.
Prior to discharge to the Kanawha River, wastewaters from Fike
and Coastal are sent to CST. The treatment facility capital expenses
were equally split by each Company while operating expenses are
assessed on the flow contributed by each Company. Because influent
flows to CST are not measured, the flows used for accounting purposes
are based on the potable water meter readings.
responsibility for operating the CST facility.
Fike has the
The CST biosystem [Figure 4J is located on the northwest corner
of the Coastal property. Sanitary and process wastewaters from Fike
are discharged-to the plant sewers which are intercepted by the 76 cm
(30 in) diameter CST sewer. The CST sewer runs southwesterly from
Fike across Coastal property and discharges into the sump at the CST
facility [Figure 5J. Sanitary wastewaters, boiler bleed-off water,
-------
100,000 GAL
CINDER BLOCK TANK
TO CATCH OIL ~
(TO BE OPERATIONAL OCT 77)
15' cp x 21' D CLARIFIER
\ - \-- - ~ - - - - - - - --I
Shed, .I ,
t!J / "1 PADDL\ WHEEL AERATOR'
~"
:~~
-s.
a
C S T T r a ; I e r ,0 ffi c e
I 'I
FINAL POND
100,000 GAL
-e- .
a
- - -- - -
10" f
cPo
INNER RACE 42,500 GAL
OUTER RACE 105,000 GAL
-
8" ~
TO KANAWHA RIVER
~
VISCOSE ROAD
Figure 4. CST Biological Treatment for Fike Chemicals, Inc. and Coastal Tank Lines, Inc.
w
U1
-------
o
\
\ ---------- \
\
\ MA INTENANC E SHOP \
~ 9 \
\ ' --
,.:: - -
W
0'1
-----_.rt._---- -0
FROM FIK-E Ii,
// I ~ FIKE INFLUENT
/ I MONITORING LOCATION
/ I
/ I
/ \
// \
/ COASTAL \
lomCE i
I
\- - - - - II!:
\ UJ ~
-I 0
\ \ 0 0
I \ !X) I!:
0...0 - - -0
- - - - - - ~ S.2" .: .:. ~E ~ ..:::: '-~ - - - - - - - - - - - - - - - -~
COASTAL INFLUENT J
MONITORING LOCATION ~~
"
,,"'CST SUMP
"
,,"
,,"
?
/
'\\\/
.' /
fb/
/
/
/
/
...CJ
,'"
",'"
'"
,'"
./
/1-.
",'" r0-
O"
I
(j)
« -
~ MAIN CLEANING
I!: >
0 « BAY
-ID
Ir
UJ
f-
X
UJ -
Figure 5. CST Sewer Schematic and Monitoring Locations
(Not to Scale)
-------
37
zeolite softener (for boiler water make-up), regeneration water, and
other wastewater from Coastal are discharged to the CST sewer at the
manhole adjacent to the Coastal maintenance building. Washwaters
from truck and trailer cleaning and chemical solutions which overflow
the make-up tanks are discharged to the CST sump via a 20 cm (8 in)
diameter sewer.
Wastewaters from the CST sump are pumped to the 379 m3 (100,000
gal) equalization pond. The wastewater then flows by gravity through
a cinder block rectangular basin and then into the inner race of the
biosystem. The cinder block basin was built as an oil collection
device; however, the device does not work. The wastewater from the
inner race is introduced into the outer race upstream of the paddle
wheel aerator. The wastewater then flows to a 379 m3 final settling
pond before discharge to the Kanawha River [Figure 4].
The sludge recycle method for returning the biomass from the
final settling pond to the biosystem is ineffective. A floating
suction .pump rated at 380 liters (100 ga1)/min located in the final
pond returns the settled solids to the outer race. However, the pump
is moved manually only several times per day and little biomass is
returned.
A consultant
system. The data
to December 1976,
retained by Fike analyzed the biological treatment
for the mixed liquor in the outer race for October
are summarized below:
Parameter No. of Avg. Max. Mi n.
Samples ppm
Suspended solids 25 210 1,072 32
Dissolved oxygen 5 8.0 9.8 6.0
pH 30 7.4 10.0 2.0
-------
38
Based on this limited data and other observations, the consultant
concluded that the residence time in the final pond was too long to
effectively recycle the sludge back to the outer race. It was also
concluded that the wastes may contain certain compounds which inhibited
the biological treatment.
Since data were not provided for volatile suspended solids, and
because influent suspended are not known for the October-December
period, it cannot be determined if a biomass was present in the mixed
liquor to degrade the wastes. The mixed liquor was not examined by
the consultant to determine the species of microorganlsms present.
The mixed liquor was not examined by NEIC during the October survey.
It was stated by the CST operator during the August inspection that
the effluent is seeded with settled sewage to determine the BOD and
that a 10% reduction of the influent BOD was achieved. This minor
reduction, however, was probably due to sedimentation in the fir~l
pond rather than to biological degradation.
In an effort to improve treatment and develop a viable activated
sludge system, a 4.5 m diameter x6.4 m deep (15 ft x 21 ft) conical
clarifer was being installed during the October survey (the unit was
not operational during the monitoring period). Settled sludge will
be returned to the outer race and the overflow will be sent to the
Kanawha River, bypassing the final pond. The final pond will be
connected to the equalization pond to increase detention time.
It is doubtful that the new clarifier and modifications will
upgrade the treatment to satisfactory levels. Because of the numerous
chemicals in the waste stream and the intermittent flows, biological
treatment alone may never achieve NPDES effluent limitations. There
are many constituents present which can be biologically degraded,
such as alcohols, but other constituents may prove toxic to the
biomass. If ~hese toxic or inhibiting chemicals can be eliminated,
or their effect negated, biological treatment might be effective.
-------
39
There are two evaporation ponds in use, both located south of
the Fike processing area [Figure 2]. The older and largest pond was
constructed about 8 years ago while the new pond was constructed
between August and October, 1977. The ponds overlie sandy material
characteristic of the area. Neither pond is lined. In a letter
dated July 14, 1971 to the State of West Virginia Department of
Natural Resources, Mr. Fike stated that approximately one acre of
land was excavated at the south end of the plant and wastes were
being dumped into this sump. The wastes percolate into the ground
and the water goes back into the sewer system. The wastes absorbed
in the soil were to be removed at a later date. This sump was excavated
to isolate sewage contaminants going to the biosystem. Mr. Fike.did
not tell NEIC personnel that a sewer system existed beneath the sump
(evaporation pond) to catch the percolating water.
Process wastewaters considered too toxic by Fike to be discharged
to the CST biosystem are discharged to 5 trunk sewers which flow into
a 20 cm (8-in) diameter contaminated sewer which runs southerly down
the center of the plant. The toxic wastewaters discharge into a 3.8
m3 (1,000 gal) sump adjacent to the cooling tower. The wastewaters
are then pumped through a 6.4 cm (2.5 in) diameter plastic pipe to
the northwest corner of the old evaporation pond. The sump pump is
activated by a float control; the flow is irregular and, according to
Fike personnel, averages about 7.6 m3 (2,000 gal)/day. To assist
evaporation, a spray system has been installed along the east dike
which continuously pumps the wastewater from the lagoon through the
spray nozzles. The liquid level in the old evaporation pond is
within 30 cm (1 ft) of the top of the berm; the wastewaters occasion-
ally overflow the berm and there are several leaks in the spraying
system. These wastewaters flow onto the ground surrounding the pond.
-------
40
The newest pond was being used by Coastal during the October
survey. The trailer contents are discharged through a hose on the
north side of the pond. In addition. prior to the October survey,
settled solids from the CST final settling pond were being pumped
into 2 tank trailers. About 68 m3 (18,000 ga1)/day of solids were
being discharged to the new pond. At the request of NEIC personnel,
solids pumping was discontinued during the survey.
Three wells have been drilled to monitor possible percolation
from the ponds. Groundwater movement is to the west toward the river
according to the State Department of Water Resources. The No.1 well
is located in the Fike processing area. about 114 m (375 ft) north of
the old evaporation pond. and is approximately 18 m (60 ft) deep.
The Nos. 2 and 3 wells are located about 4.5 m (15 ft) and 91 m (300
ft) west of the old pond. respectively; both are about 9 m (30 ft)
deep. The No. 2 we~l is located between the old and new evaporation
ponds. Only the No.1 well has a permanently installed pump for
monitoring purposes; a bailer is used for the other two wells.
-------
v.
MONITORING PROCEDURES.
During the period October 3 through 7, 1977, samples were
collected from the CST effluent (NPDES Outfall 001), Fike1s and
Coastal's influent to CST, the old evaporative lagoon, Coastal tank
truck discharge (prerinse) to the new evaporation pond, and the
groundwater surrounding the evaporative lagoons [Figure 1].
Chain-of-custody procedures [Appendix A] were followed for the
collection of the samples* and for laboratory analyses.
Flow measurement procedures, sampling locations, and sample
collection methods are discussed in detail in Appendix B. The CST
effluent flow was measured with a standard ~ectangular weir installed
by NEIC personnel in the throat section of the 9-inch Parshall flume.
The flow was continuously recorded. The flow from Coastal IS wash
shed** was measured instantaneously each time a sample was collected.
The Fike discharge to the old evaporative pond was measured by rating
the sump pump and recording the hours of operation with an elapsed
time meter. No other flows were measured.
*
At 10:30 a.m. October 3, the sample case was found unlocked. There
did not appear to be tampering with the lock or the samples. One
sample case arrived in Denver with a broken lock hasp on October 8.
This sample case was placed on the plane with the hasp intact.
Samples collected for bioassay were not kept under custody during
collection because of the volume of water required for the tests
[up to 208 liters (55 gallons)]. However, the ,sample containers
were kept next to the monitoring location and were checked at least
hourly for tampering. There was no evidence of tampering.
Dilution water for the flow-through bioassay was stored in wooden
tanks outside of the mobile laboratory at the S. Charleston Waste- .
water Treatment Plant. There was no evidence of tampering.
Coastal's contribution to the CST sewer, which 'contains Fike's flow
to the CST, was not monitored because it was not possible.
**
-------
42
The CST effluent was manually sampled hourly* and continually
composited on a flow-weighted basis for all parameters except
oil/grease and volatile organics.** Interim NPDES limitations
required that oil/grease be monitored on a grab basis, however the
final limitations (in force during the survey) require that
oil/grease be monitored on a composite sample basis. The Fike and
Coastal influents to CST were also sampled hourly* and continually
composited on an equal-volume basis for all parameters except
oil/grease and volatile organics. Three.oil/grease samples and one
volatile organic sample were collected daily from each of the three
locations. A11 other monitoring locations were sampled on a grab
basis. All samples were analyzed by the procedures in Appendices C,
D, and E.
'}:
-
Static and flow-through bioassays were conducted on the CST
effluent and on Fike's and Coastal's influents to CST. The effluent
wastewater was continually compositedon a flow-weighted basis daily,
while the influents were continuously composited on an equal-volume-basis.
During collection, the wastewaters for the bioassay were not preserved
or iced. Dllution water was obtained from the Kanawha River at a
~.
point approximately 3.2 km (2 miles) upstream of the mouth of the Elk
River. A discussion of the bioassay procedures is contained in
Appendix F.
All samples were collected over the period 7 a.m. to 7 a.m.
which corresponded to Fike's production day. The first set of com-
posite samples was collected beginning 7 a.m. October 3 and the final
composite sample was completed at 6 a.m. October 8.
* On October 6, samples were not collected at 0800, 0900,. 1000 and
1100 due to heavy rains which flooded the influent and effluent
monitoring locations. .
** Volatile organics are not a permit parameter.
-------
VI.
NPDES PERMIT COMPLIANCE
Compliance monitoring of CST Outfall 001 was conducted on
October 3 through 7 by NEIC personnel for all final NPDES permit
parameters [Table 1] except fecal coliform bacteria densities.*
Although the permit requires that oil/grease samples be collected on
a 24-hour basis, NEIC personnel collected three grab samples per day
to determine compliance with the limitations (the interim limitations
specified grab samples for oil/grease analyses).
Part III of the permit requires that the 96-hour median toler-
ance limit applicable to the indigenous species, using standard
static bioassay procedures and a 24-hour composite sample, be deter-
mined on the effluent from Outfall 001, on a quarterly basis. Static
and flow through bioassays were conducted by NEIC personnel.
Due to the batch operations at Fike and tank trailer scheduling
at Coastal, the data from the NEIC survey are not necessarily character-
istic of the wastewaters discharged throughout the year, as individual
constituents may be absent or present in different concentrations.
The results of the monitoring of Outfall 001 and the influent waste-
water streams to CST are summarized in Tables 4 through 7. Contents
of the Coastal tank trailers prior to cleaning and the processes
operating at Fike during the survey are listed in Appendix G and
Table 8, respectively. Only nine of the eighteen major products were
being manufactured by Fike during the survey. The three processes
*
The permit requires that fecal coliform bacteria be sampled on a
24 hour composite sample basis. It is impossible to composite
fecal coliform due to growth after samples are collected. Grab
samples should be used for fecal coliform bacteria.
-------
CST, INC. EFFLUENT
Tab le 4
SUMMARY OF F IEW MEASUREMENTS
(001), COASTAL TANK LINES WASH FACILITIES INFLUENT TO CST,
AND PIKE CHEMICALS INFLUENT TO ~ST
Octobe~ 3-7, 1977
+::>
+::>
F10wa pH Temperature °C
CST CST
Effluent Coas ta 1 CST Effluent Coastal Fike Effluent Coastal Fike
m3/ m3/ No. No.
gpd gpd avg min max samples samples avg min max avg min max avg min max avg min max avg min max
day day pH 8.5
b
129 34,160 13.4 3,550 6.6 5.7 8.5
1/24
124 32,710 13.6 3,580 7.7 6.0 9.zb 0/24
150 39,670 15.4 4,080 8.4 4.gb 12.oh 1/24
208 54,950 15.3 3,7909.1 7.6 11.3b 0/19
144 38,120 12.7 3,360 8.5 7.6 10.7b 0/24
151 39,920 13.9 3,670 8.1 6.4 10.f 2/115
OCT. :3
0/24 9.8 4.5 12.2 6.9 4.0 8.5 14 11. 5 17.5 23.5 20 28 19.7 12 38
OCT. 4
4/24 10.9 6.5. 13 8.1 6.3 11.7 14.5 11 .21 22.6 19 33 19.5 16 21
OCT. 5
11/24 9.4 2.6 13.5 9.1 3.6 12.6 15.1 12 20 23.4 16.5 32 21.4 17 29
15/19
OCT. 6
11 . I 8. 8 > 14c 1 0 .6 7.3 > 14c
15.4 13
20
23
19 27
19.6 16
23
12/24
10.2
OCT. 7
45 12.1
9.3 5.6 11.5
14.2 11. 5 20
25.6 21 33
20.6 18
24
5-DAY AVERAGE
42/115
10.4 5.4
13
8.8 5.4 11.7
14.6 11.8 19.7
23.6 19.1 30.6 20.2 15.8 27
a Pike Chemical flow to CST could not be meas~ed.
b Exceed NPDES Pe~mit Limitation fo~ pH ~ange of 6.0-8.5
c Reading 011 pH mete~ exceeded 14.0.
-------
Tah le 5
SU,',J/ARY OF ANALYTICAL DATAa FOR NPDES PERt/IT COMPLIANCE
CST, mc. - OUTFALL 001
OetobeJ' .~-7, 1977
Da te
OCt.
COD BOD TSS Total Solids Phenols Ammonia, Chloride.
mg/l kg/day 1b/day mg/1 kg/day 1b/day mg/1 kg/day 1b/day mg/1 k9/day 1b/day mg/1 kg/day 1b/day mg/1 kg/day 1b/day mg/1 kg/day 1b/day
3 1,730 220 490 570 70 160 58. 7.5 16 3,400 430 960 6.ge b 1.9~ 10 1.2 2.8 910 110 250
0.8/;
4 2,800 340 760 530 65 140 110 13.6 30 3,900 480 1,060 5.9 0.71 1.6/; 13 1. 6, 3.6 1,200 140 320
5 2,800 420 920 780 115 250 96 14.4 31 3,600 540 1,190 3.9 0") 1.2b 130 19')' 43 1,200 180 390
,J/;
6 3,300 260 1,500 840 175 380 150 31. 1 68 4,100 850 1,880 3.9 0.8 1.7 70 14 32 1,300 270 590
7 4,000 570 1,270 1,000 140 310 140 20.2 44 5,000 720 1 ,,590 3.7 0.5 1.1 78 11 24 1,200 170 380
5-dgy 2,980 450 990 760 115' 250 110 17.3 38 4,000 600 1,330 4.7 0.7b 1.5b 63 9 21 1,170 170 390
avg
Date
Oct.
Arsenic Nitrates Sulfates
mg/l kg/day 1 b/day mg/l kg/day 1 b/day mg/l kg/day 1 b/day mg/l
Cyanided
kg/day 1b/day
Surfactants
mg/l
3 0.44 0.05 0.12 4.4 0.5 1.2 780 100 220 0.54 0.07 0.15 6.0;)
4 0.68 0.08 0.18 12.4 1.5 3.3 760 94 200 0.90 0.11 0.25 5.3~
5 0.32 0.04 0.10 2.4 0.3 0.8 810 120 260 0.29 0.04 0.10 5.7 J)
6 0.40 0.08 0.18 3.8 0.7 1.7 880 180 400 0.23 0.05 0.11 5.9:-
7 0.37 0.05 0.11 7.2 1.0 2.2 980 140 310 1.1 0.16 0.35 8.3b
5-dgy 0.06 0.14 5.7 0.8 1.8 840 120 280 0.57 0.08 0.19 6.2b
avg 0.43
a See Table 6 for Heavy Metal Data and Table 7 for Oil and Grease Data.
b E:r:ceeds NPDES Per'mit Daily Maximum Limitations.
e Flol,J-1,)cighted aveJ'a(7es.
d Cyanide tiot Dimi ted b!.i NPDES Pel'mit. Same footnote as Table 26 [OJ' CN.
e Phenol saMple on October :1 analyzed 2 1/2 hoUl's beyond recommended hoZding
time of ;14 hours.
~
U1
-------
+>-
O"t
Table 6
SUMMARY OF HEA VY METAL ANALYSES
CST, INC.
OUTFALL 001
Oatobe!' 3-7, 1,977
Date Aluminum Barium Cadmium Hexavalent Chromium Iron, Total Lead Silver
(Oct.) mg/l kg/day lb/day mg/l kg/day lb/day mg/l kg/day lb/day mg/l kg/day lb/day mg/l kg/day lb/day mg/l kg/day lb/day mg/l kg/day lb/day
3 1.2 0.16 0.34 0.20 0.026 0.057 <0.01 <0.001 <0.003 <0.02 <0.003 <0.006 8.3 1.1 2.4 0.9 0.12 0.26 <0.01 <0.0013 <0.0029
4 0.8 0.10 0.22 0.20 0.025 0.055 <0.01 <0.001 <0.003 <0.02 <0.002 <0.005 6.1 0.8 1.7 0:4 0.05 0.11 <0.01 <0.0012 <0.0027
5 1.1 0.17 0.36 0.40 0.060 0.132 0.02 0.003 0.007 <0.02 <0.003 <0.007 6.3 0.9 2.1 0.4 0.06 0.13 <0.01 <0.0015 <0.0033
6 1.6 0.33 0.73 <0.20<0.042 <0.092 0.02 0.004 0.009 <0.02 <0.004 <0.009 15 3.1 6.9 0.6 0.13 0.28 0.018 0.0037 0.0083
7 1.6 0.23 0.51 <0.20<0.029 <0.064 0.02 0.003 0.006 <0.02 <0.003 <0.006 19 2.7 6.0 0.8 0.12 0.25 0.018 0.0026 0.0057
5-day
Avg.a 1.3 0.20 0.43 <0.24<0.04 <0.08 <0.02 <0.003 <0.006 <0.02 <0.003 <0.007 11 1.7 3.8 0.6 0.09 0.21 <0.014<0.0021 <0.0046
a Flow-weighted averages
-------
TabLe 7
SUMMARY OF OIL AND GREASE ANALYSES
CST~ INC. EFFLUENT (001) ~ COAS'l'AL TANK LINES IIASH FACILITIES INFLUENT
TO CST~ AND FIKE CflEi'HCALS INFLUENT TO CST
Octobel' J - 7~ 1977
CST Effl uent Coastal Fiki
Instantaneous Flow O/G Instantaneous Flow O/G O/G
Date Timea m3/day gpd mg/l kg/day 1b/day m3/day gpd mgj1 kg/day 1bjday mg/1
3 1400 230 61,000 25 5.8 12.7 102 27,000 240 25 54 22
1800 83 22,000 46 3.8 8.4 19 4,980 1,600 30 66 44
4 0110 178 47,000 74 13.2 29.0 20 5,230 150 3 7 25
24-hr Avg.c 46 7.6d 16.7d 410 19 42 30
4 1300 106 28,000 56 5.9 13.1 9 2 ,350 130 1 3 390
1900 152 40,100 58 8.8 19.4 88 23,140 430 38 83 1 , 1 00
2200 152 40, 1 00 78 11.8 26.1 204 54,000 190 39 86 30
24-hr Avg;C 65 8.9d 19.5d 26'0 26 57 590
5 0800 204 54,000 54 11.0 24.3 78 20,560 74 6 13 440
1400 178 47,000 55 9.8 21. 6 33 8,760 150 5 11 39
2300 152 40,100 81 12.3 27.1 . 30 7,900 44 1 3 450
24-hr Avg.c 62 11d 24.3d 87 4 9 310
6 1200 556 147,000 84 46.7. 103 77 20,250 21 2 4 160
1700 128 33,700 50 6.4 14. 1 11 2,920 2;::0 2 5 300
2200 83 22,000 99 8.2 18.2 32 8,530 140 5 10 58
24-hr Avg.c 80 20. 1 d 45.1d 68 3 6 170
7 0900 204 54,000 120 24.5 54.1 16 4,320 780 13 28 23
1400 46 12 ,100 87 4.0 8.8 13 3,360 1 ,400 18 39 38
8 0400 128 33,700 110 14.0 30.9 11 2,950 380 4 9 180
24-hr Avg.c 112 14.2d 31.3d 860 11 25 . 80
5-day Avg.c 72 12.4d 27.4d 250 13 28 240
a Tillie of collection fOl> Coastal and Fike influents to CST weY'e appY'o.rc-imately 15 and 30 minutes~ +::>
l'ccpcetivcl!J~ aftc!" c:ollcct-ion of the CS~L' efflucnt DC'lJple. ---.J
b FlO1JS eOllld not be IIIcacl/Y'cd foY' Pike Chemica l c ~ Inc.
c Flow weigl-rted avel'Clue for- CST and CoastCll; Pike cOIwentY'at'ion ClY'ithme.tie aveY'age.
J E:cceeda NPDES PeY'mit Dany Maximwn Limi.tat'ions.
-------
48
Table 8
PROCESSES OPERATING DURING MONITORING SURVEY
FIKE CHEMICALS~ INC.
September - October 1977
Sept. 26 thru October
Process Oct. 2 3 4 5 6 7
Diethyl Thiourea X X X
Propyl xanthic Disulfide X
Diorthotolylthiourea X X
Ethylene Thiourea X X X X X
Dibutyl Thiourea X X X
R-235 X
Trimethylthiourea X
Sodium f.1ethylate X X X X X X
Ethyl Fluoroacetate X X X X
Sodium Amide X
BCES X X X X X
Bis Ethyl Xanthogen X X X X X
Bis Isopropyl Xanthogen X
Allyl Cyani de X X X X X
. Ethyl Fluoroacetamide X X
2 Ethyl 4 Methyl Imidazole X
1,3 Propanedithiol X
Butyl Ziram X
-------
49
using phenol (o-benzyl phenol, Bristamine Base, and sodium butyl-o-
phenyl phenol) were not operating. In an August 29, 1977 letter to
Region III, Mr. Fike stated that these processes would not be oper-
ated until modifications were made to the process equipment. These
processes are the major contributors of phenol wastes to the CST
treatment system.
DISCHARGE MONITORING REPORTS
Effluent data from the Discharge Monitoring Reports (DMR1s) for
January through June 1977 are summarized in Table 9. For the first
three months of 1977, the flow data were ten times greater than the
flows reported for April through June. However, the load data for
the effluent parameters were of the same magnitude, indicating that a
decimal point error had been made in reporting.
The DMRls show that in the 6-month period the effluent violated
the daily average permit limitations as follows:
COD 3 months Surfactants
BOD 5 months Fecal Coliforms
TSS 5 months Nitrates
O/G 0 months Sulfates
Phenols 6 months Total Solids
Ammonia 0 months Aluminum
Chloride 0 months Iron, Total
Arsenic 2 months pH
6 months
1 month
o months
4 months
3 months
o months
o months
6 months
The concentrations reported for January through June are com-
parable to concentrations found October 3 through 7 for all parameters
except oil/grease, phenols, ammonia, and chlorides. The oil/grease
concentrations discharged during the survey were more than seventy
times greater than the concentrations reported in the DMRls while the
latter three parameter concentrations were much lower than those on
the DMRls. This could be due to the types of chemicals processed in
the first six months of 1977, or analytical errors.
-------
50 Tab le9
SUMMARY OF DISCHARGE MONITORING REPORTS
CST~ INC.
January - June 1977
Monthly AverageSa
Parameter January February ~la rc h Apri 1 ~lay June
3 1 ,970 2,120 2,050 210 240 150
Flm'J - IT) /day
mgd 0.520 . 0.560 0.543 0.056 0.063 0.040
COD - mg/l 2,815 941.8 117 2,727.9 1,768.5 572.8
kg/day 540 "195 . 25 - 745 155 180
1b/day 1 , 185 427 .6 . 55 1,642 344.9 403.8
BOD - mg/1 257.9 572.8 2,292.9 1,502.5 988.5 952
kg/day 50 190 530 255 130 . 270
1b/day 108 414.7 1,173.6 566.8 293 593
TSS - mg/1 208 118.8 54 241 261. 5 282
kg/day 50 30 13 2 , 560 50 75
1b/day 117.6 71 29 321 108 167.9
TS - mg/1 3 ,Of.? 2,706 2 , 997 4,631. 5 5,353 2,840
kg/day 630 520 "760 1,500 1,015 1 ,050 .
lb/day 1,387.5 1 ,142 1,676.9 3,307 2,239 2,32CJ~7
O/G - mg/1 1 0.4 0.5 0.3 0.7 0.6
kg/day 0.20 0.1 0.1 0.05 0.1 0.3
1b/day 0.5 0.3 0.3 O. 1 0.3 0.6
Phenols - mg/l 442.5 2,917.5 536 1.9 11.8 3.6
kg/day 55 450 335 1.0 4.5 1.2
lb/day 126.9 992.7 742.9 .. 2.3 9.9 2.6
Ammonia - mg/l 3 0.8 4 3.6 5.7 . 2
kg/day 0.86 0.1 0.9 0.82 0.9 5.4
lb/day 1.9 0.3 2 1.8 2 1-1 .8
Chloride - mg!1 118 198 957 343 474.8 488
kg/day 16.6 37.5 . 275 80 80 110
lb/day 36.6 82.7 609.9 177.7 178.9 244
Arsenic - mg/l 0.06 0.05 <0.02 0.2 0.7 0.1
kg/day 0.02 0.01 <0.005 0.04 0.2 1.0
lb/day 0.04 0.02 <0.01 0.08 0.4 2.0
Surfactants - mg/l 4 23 96 28.5 32.6 27
Fecal Coliform,ml/l00 ml 17.6 29.8 24.8 58 673 121.9
Nitra tes - mg/l 1.5 3 4.3 3.7 3.6 3
kg/day 1.7 0.7 0.7 0.7 0.5 1.3
lb/day 3.8 1.6 1.6 1.5 1 2.8
Sulfates - mg/l 204 4?.5 28,052 1,043.9 1 ,940.6 645
kg/day 25 10 7,200 340 320 230
1b/day 58.7 22 . 1 5 ,900 757 704 511"
Aluminum - mg/l 1 0.7 14.8 2 3.7 2.0
kg/day 0.2 0.1 4.5 1.0 0.86 0.7
lb/day 0.5 0.3 9.9 2. 1 1.9 1.6
-------
51
Table 9 (Continued)
SUMMARY OF DISCHARGE MONITORING REPORTS
CST~ INC.
January - June 1977
Monthly Averagesa
Parameter "January February ~1a rc h Apri 1 May June
Iron Total - mg/l 2.7 1.6 4.6 3 6 3.5
kg/day 0.5 0.3 1.2 0.5 1.4 1.6
lb/day l.0b 0.7 2.7 1.0 3.0 2.4
Barium - mg/l NR NR <0. 1 NR 0.4 NR
kg/day NR NR <0.03 NR 0.09 NR
lb/day NR NR <0.07 NR 0.2 NR
Cadmium - mg/l NR NR 0.12 NR 0.001 NR
kg/day NR NR 0.04 NR 0.0002 NR
1 b/day NR NR 0.08 NR 0.0004 NR
Chromium - mg/l NR NR <0.01 NR 0.06 NR
kg/day NR NR <0.003 NR 0.01 NR
lb/day NR NR <0.007 NR 0.03 NR
Lead - mg/l NR NR 0.45 NR 0.6 NR
kg/day NR NR O. 1 NR 0.1 NR
lb/day NR NR 0.3 NR 0.3 NR
Silver - mg/l NR NR 0.05 NR 0.01 NR
kg/day NR NR 0.01 NR 0.002 NR
1 b/day NR NR 0.03 NR 0.004 NR
ph S.U. 6.9 7.5 6.3 7.4 6.5 8.0
Range 3.8-10.4 4.0-10.0 4.0-8.8 4.5-8.5 2.5-8.6 5.7-8.6
Bioassay, % LC50 NR NR 1. 15 NR NR 0.9
3
a = kg/day and m /day not reported by CST; values computed by NEIC.
b = not reported~ permit requires monitoring once/three months.
-------
52
FLOW
Over the five-day monitoring period, the effluent flow ranged
3 3
from 124 to 208 m (32,700 to 54,950 gal)/day and averaged 151 m
(39,900 gal)/day. The high flow on October 6 was due to heavy rains
which began in the early morning hours and ceased by noon. During
3
dry weather, the flow averaged 137 m (36,160 gal)/day. Flow rates
may have been higher if the three major phenol processes had been
operating. However, it is not possible to estimate the amount of
wastewater contributed by these processes.
If an error was made in the reporting of the flow for January
through March 1977 in the DMR's, the average daily flow for the first
six months of 1977 would be 200 m3 (54,000 gal), or about 35% more
than the flow for October 3 through 7. The CST measured flow with an
unrated, broad-crested rectangular weir and a standard weir table;
NEIC personnel installed a standard rectangular weir plate and the
proper conversion table was used to compute flows. Incorrect flows
would be obtained by the CST weir and a standard weir table. There-
fore, the previously reported flows must be considered nonrepresenta-
tive. The NEIC weir plate was left installed in the flume after the
survey and the conversion table [Appendix B] provided for flow calcu-
lation. If CST personnel calibrated their height-sensing device
correctly after the survey was completed, future flows reported in
the DMR's should be representative of actual conditions.
Since the influent flows to CST from Fike and Coastal could not
be accurately measured, the precise quality and quantity contributed
by each cannot be determined. However, approximate flows can be
estimated from the data. Instantaneous flows of Coastal's washing
facility discharge were measured hourly. The total daily flows
averaged 13.9 m3 (3,670 gal)/day and varied about +10%. However, the
-------
53
hourly instantaneous flows varied by more than 200%, therefore the
instantaneous flow data is only a rough approximation of the washing
facil ity IS di scharge. .
Based on this limited data, the flow to CST from the Fike and
Coastal processes (exclusive of the washing facility) averaged about
137 m3 (36,250 gal)/day. Daily pot~ble water meter records show that
Coastal used an average of about 70 m3 (18,500 gal)/day. During this
period, 7 tank trailers were discharged to the evaporation pond and
another was ready for discharge when the survey ended; each trailer
contained about 19 m3 (5,000 gal). Discounting water used in the
boilers, about 40 m3 (10,500 gal)/day of wastewater from Coastal com-
bined with 97 m3 (25,750 gal)/day from Fike in the CST sewer; thus
Coastal contributed about 25% of the CST sewer flow. Including the
Coastal washing facility discharge, Coastal contributed about 35% of
the total CST influent flow and Fike about 65%.
BIOASSAY RESULTS
A series of flow-through and static bioassays were conducted on
Outfall 001 and on the Fike and Coastal influents to CST to determine
whether the waste streams were acutely toxic to fish. Juvenile fat-
head minnows (Pimephales promelas Rafinesque) averaging 3 to 4 cm. in
total length were used as the test organisms.
A 96-hour flow-through bioassay was conducted on the CST effluent
instead of a 96-hour static bioassay; the former bioassay is more
accurate and can be run at a higher degree of confidence. The 96-hour
flow-through bioassay showed that the effluent was acutely toxic to
,",
the fish. The LC50 for this effluent was calculated to be 0.22%
concentration of effluent (95% confidence limits: 0.16 - 0.30%)
[Figure 6, Table 10J. The DMR data for March and June, 1977 has
96-hour ~tatic LC50 concentrations of 1.15% and 0.9%, respectively,
again demonstrating acute toxicity of the effluent.
-------
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ern
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o 99.99
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--'
% Mortality
50 .
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o
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::::I '
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-------
55
TabZe 10
96-HOUR FLOW-THROUGH BIOASSAY SURVIVAL DATA
CST3 INC. EFFLUENT
October 1977
% Survival
Effluent Concentration
Time Period Control O. 18 0.32 0.56 1.0 1. 35 1.8
24-houra 100 100 100 95 25 25 0
48-hour 100 70 70 40 0 0 0
72-hour 100 70 55 20 0 0 0
96-hour 100 55 35 10 0 0 0
a 24-hour LC50 = 0.82%.
-------
56
Because the two inf1uents to CST originate from batch opera-
tions, it is highly probable that the toxicity of CST effluent can
vary considerably. To estimate the range of toxic variability that
might occur during the 96-hour testing period, three consecutive
24-hour flow-through bioassays were conducted. The estimated LC50
values for these three tests were 1.7%,0.68% [Table 11], and 0.82%
[Table 10] effluent, respectively, indicating no extreme variability.
The high BOD of the CST effluent (range 530 to 1,000 mg/1)
required aerating test waters to maintain dissolved oxygen levels
adequate for fish survival. To determine if aeration significantly
affected the toxicity of the effluent, duplicate 48-hour static
bioassays were conducted, one test chamber aerated and the other not. .
The 48-hour LC50 values for the aerated and unaerated t~sts were 0.7%
and 0.6% respectively, indicating short term, mild aeration did not
significantly affect the relative toxicity of the effluent [Table 12C].
The 96-hour static bioassays showed the Fike and Coastal dis-
charges to the CST to be acutely toxic. The estimated 96-hour LC50
values for these discharges were 0.56% and 2.2% effluent, respec-
tively [Table 12A and B]. These data indicate that the Fike dis-
charge is approximately 4 times more toxic than the Coastal discharge.
Since Fike contributed approximately 65% of the total wastewater flow
to the CST (during this survey), Fike was the major contrfbutor of
toxic substances to the CST facility.
Although desirable, it was not possible to designate any single
chemical species or group as the principal toxicant. Each of the
waste streams contained a variety of inorganic compounds [Tables 13
and 14], from 29 to 51 identifiable complex organic compounds [Table 15],
in addition to large numbers of unidentified trace organics. Many of
these compounds are known toxicants to fish. Furthermore, there may
be synergistic and antagonistic chemical reactions occurring that can
either enhance or reduce the toxicity of the individual chemical compounds.
-------
57
Tab Le 11
24-HOUR FLorI-THROUGH BIOASSAY SURVIVAL DATil
CST~ INC. EFFLUENT
October 1977
Control
% Survival LC 50 = 1.7%
EFFLUENT CONCENTRATION (%)
1.8 3.2 5.6 7.5
10
Date
1.0
Oct. 5
100
100
45
o
o
o
o
Date
Contro 1
% Survival LC 50 = 0.68%
EFFLUENT CONCENTRATION (%)
0.32 0.56 1.0 1.8 2.4 3.2
Oct. 6
100
95
75
o
o
o
o
-------
58
Table 12
BIOASSAY SURVIVAL DATA
CST, INC., FIKE CHEMICALS, INC., AND COASTAL TANK LINES, INC.
October> 1977
A. FIKE CHEMICALS (96-HR STATIC TEST)
Effluent Concentration LC50 = 0.56%
%
Survival Control 0.10 O. 18 0.32 0.56 1.0 1.8
24-hr 100 100 100 100 100 0 0
48-hr 100 100 100 100 50 0 0
72-hr 100 100 90 100 50 0 0
96-hr 100 100 90 100 50 0 0
B. COASTAL TANK LINES (96-HOUR STATIC TEST)
Effluent Concentration LC50 = 2.2%
%
Survival Control 0.32 0.56 1.0 1.8 3.2 5.6
24-hr 100 100 100 100 100 0 0
43-hr 100 100 100 100 90 0 0
72-hr 100 100 100 100 90 0 0
96-hr 100 100 100 100 80 0 0
C. CST (48-HR STATIC TEST)
Effluent Concentration LC50a
%
Survival Control 0.032 0.056 0.10 0.18 0.32 0.56 1.0 1.8
24-hr
Aa 100 100 100 100 100 100 100 100 40
B 100 100 100 100 100 100 100 100 40
48-hr
A 100 100 100 100 100 100 80 0 0
B 100 100 100 100 100 80 60 0 0
Samples A and B are duplicate samples. Only sample Aa is aerated test water.
a Sample A - LC50 = 0.7%; Sample B - LC50 = 0.6%
-------
Tab le 13
SUMMARY OF ANALYTICAL DATA FOR INFLUENTS TO CST, . INC. - EQUAL-VOLUME COMPOSITE SAMPLESa
COASTAL TANK WASH FACILITIES INFLUENT AND PIKE CHEMICALS INFLUENT
Oatobe~ 3-7, 1977
COD
Cb
BOD TSS TS Phenols Ammonia Chloride Arsenic Nitrates Sulfates Cyanide Surfactants
C F C F C F C F C F C F C F C F C r- C F C F
d 11 6.3 f OCT. 3
1 1,300 510 200 5,400 4,300 lTl2 65 600 0.07 0.48 6.0 1.0 200 .90 <0.01 0.09 6.0 1.0
Fa
3,300 4,000
4,550 4,600
1,200
3,400 3,900 5.0 5.4
OCT. 4
7-:4500 65
OCT. 5
3-:s-66 98
710
0.02 0.29 4.4 1.0
110 ~20 0.08 0.33 4.4 1.0
3,700 6,210
T
. 780
370 520
3,500 4,600 8.4 5.1
860
180 360
1-,200 <0.02 0.37 4.4 2.8
180 ~80 0.04 0.07 4.4 2.8
3,500 24,000
T
3,900 5,700 6.4 3.4
OCT. 6
5~0 110
OCT. 7
8-:4360 95
3,400 <0.02 0.30 5.0 4.0
23 760 0.05 0.07 5.0 4.0
4,400 2,200
1,000 1,400
310 740. 4,400 9,200 7.3 4.5
690
410 590
580
0.02 0.30 8.0 4.4
360 530 0.18 0.84 8.0 4.4
3,890
8,200
850
1,170
350 480
4,100 5,500 8.8 4.9
5-DAY AVG. e
5.3 200 86
1,300 <0.03 0.35 5.6 2.6
175.550 <0.07 0.28 5.6 2.6
a All units in mgll
b C = Coastal
a P = Pike
d T =.Toxia, ~eliable BOD data aould ~ot be dete~mined
e A~ithmetia average
f Phenol sample on .Oatobe1' 3 analyzed 2 112 hours beyond ~eaommended holding time of 24 hours.
U1
1.0
-------
0'\
a
Table 14
SUMMARY OF HEAVY METAL ANALYSES FOR INFLUENTS TO CST~ INC. a
COASTAL TANK WASH FACILITIES INFLUENT AND FIKE CHEMICALS INFLUENT
October 3-7~ 1977
Hexava1~nt Iron,
Date Aluminum Barium Cadmium Chromium Total Lead Silver
Oct. Cb FC C F C F C F C F C F C F
3 10.3 2.8 0.60 0.20 0.09 0.02 <0.02 <0.02 32 28 1.8 1.3 <0.01 <0.018
4 6.4 1.9 0.40 0.20 0.17 0.02 <0.02 <0.02 23 27 1.1 1.6 <0.035 <0.01
5 6.9 1.8 <0.20 0.40 0.13 0.02 <0.02 <0.02 14 28 0.5 1.6 <0.01 <0.01
6 6.3 3.5 0.40 0.50 0.12 0.05 <0.02 <0.02 20 64 0.9 4.8 <0.01 <0.01
7 5.8 3.4 0.30 0.20 0.03 <0.01 <0.02 <0.02 17 30 0.8 7.1 0.018 <0.01
5-daYd 7.1 2.7 <0.40 0.30 0.11 <0.02 <0.02 <0.02 21 35 1.0 3.3 <0.02 <0.01
avg.
a Equal-volume composite samples
b C = Coastal
c F = Fike
d Arithmetic average
- all units in mg/Z
-------
TabZe 15
ORGANIC CHEMICAL DATA - EQUAD- VOUIME COMPOSITE SAMPLES
COASTAL TANK LINES (WASH FACILITIES) AND PIKE CllE:MICALS DISCHARGES TO CST
October' 3-7 J 1977
Concentration (mg/l)
Compound Oct. 3 Oct. 4 Oct. 5 Oct. 6 Oct. 7
Coastal Fike Coastal Fike Coa s ta 1 Fike Coas ta 1 Fike Coas ta 1 Fike
Acenaphthenea 0.61 0.33
Allyl b,lltyl disulfide 0.55 8.0 2.9. 7.8
Aniline b 3.8 5.5 7.8 3,400
Anthracenea (T) c 3.2 1.6 1.8
8enzothiazolea 1.5
a-Benzyl phenol 0.13
p-Benzyl phenol 0.13
Bipheny1a 2.1 2.4 0.60 2.3
2-n-Butoxyethano1a 25 27 180 2.9 12
Butyl isothiocyanate 1.1 2.0
Carbazo1ea 3.0 1.8
Ch1orohexy1aminea 1.0 84 1.9 1,200
Creosotel1 130 35 21
D-Creso 1a 0.21 0.69
Cyc1ohexanol 0.43 0.13 1,100 '
Cyc1ohexylisothiocyanate 1.5 6.2 11.0
2,4-Diaminotgluene 1.7
D ibenzofuran 2.0 0.54 0.27
JJ i benzothi ophenEf 0.47
N,N'-Diethylthioureaa 200 22 52 69 540
Dimethyl naphthalene jsomer 0.86
2,5-Dimethyl pyrazinea 4.0 45 8.2 14
Dipheny1ethera 2.0 2.6 0.68
Ethyl-N-butylthionocarbamate 3.9 3.6
2-Ethylhexanojc acida' 42
p-Ethylphenola 0.62
Ethyl to)uene isomerG 0.59
F1uorenea (T) 0.77 0.33
Hexyl phenol isomer 0.54
2-Indolene thione 0.30 0.55 0.29 0.70
p-Isopropyl phenol~ 2.1 0.60 0.42
a-Isopropyl phenola 7.7 6.4
Methyl biphenyl isomer 5.4
N-Methylcyclohexylamine 420
N,N-Dimethylcyclohexy1amine 78
2-f1ethyl-5-ethyl pyrazene 0.99
6-f1ethy 1- l-hepta no1 1.8
Methylnaphthalene isomera 1.7 0.28
Methylnaphthalene isomera 0.71 0.18
4-f1ethyl-3- penten-2-one (mes i tyl ox i deja 3.3 530
Methyl Dheny1 acetyl ene 0.90 0"1
--'
-------
Table 15 (Cpntinued)
ORGANIC CHEMICAL DA7'A - EQUA&-VOLUME COMPOSI7'E SAMP&ES
COASTA& TAN!: LINES ([-lASH FAC.UJ'I'IES) ;1:'Ji) FIKE CHEMICA&S DISCHARGES 7'0 CST
, Gatoh]]' ,3-7, 1,Q7'1
CT\
N
Compound
Concent~ation (mg/l)
Oct. 4 Oct. 5 Oct. 6 Oct. 7
Coastal Fike Coa~Fike Coastal Fike Coastal Fike
1.1 0.75
3.1 1.5 1.7
5.1 3.0 3.8 2.4 2.1
0.05
0.86 55
0.48
15
0.23 0.55
0.36
0.08 0.83
2.2 1.9 7.5 2.9
0 0 0
0.09 6.0
0.61 0.54 13 1.9
0.20 13 0.67
8.0 10 1.2 1.7
17
4.3
11 .0
16.0
25.0
54 0.09
56 0.22
52
53 0.50
50 0.71
23
52 0.50
13
59
13
8.5
6.2
,2.9
500
NaphthaleneCl (T)
Phenanthrenea(T)
Pheno(l (T)
2-Phenoxyethanol
Phenyl isothiocyanate
2-Phenylphenol
Propyl-N-butylthionocarbamate
Propyl butyl thiourea isomer
Propyl-N-ethylthionocarbamate isomer
Propyl-N-ilthylthionocarbamate isomer'
Quinoline
2,2,4,4-Tetramethyl-3-pentanone-t-butyl ketone
N,N,N' ,N'-Tetramethy1thiourea(!
1 4- Thiaoxanea '
o~Toluidine''<
Tri-n-butylphosphatea
1,2,4-Trichlorobenzenea (T)
l,2,4-Trimethylbenzenea
3,5,5-Trimethyl-2-cyclohexenone (isophorone)a(T)
N,N,N'-Trimethyl-N'-ethylthiourea
n-Nonanea
n-Decanea
n-Undecanea
n-Dodecanea
n- Tri decane':1
n-Tetradecanea
n-Pentadecanea
:z
n-Hexadecane
n-Heptadecanea
PristaneCl (CJ9 alkane)
(J
n-Oc tadl1cane
Phytanel,(C20 alkane)
n-Nonadecanea
n-Eicosanea
n-Beneicosanea
n-Docosanea
n-Tricosanea
Heavy Refined Oile
Oc t. j
Coastal Fike
7.8
9fJ
12
3.8
0.42
3.1
0.80
0.61
0.51
1.6
0.75
1.9
4.9
0.12
Quantity bw,ed on .l'esp0>1ce of st:w/dm'cl oj'
a Jde>1t-i.j'1:cat-i.on confirmed by Gas Chromatograph/Mass SpAatY'ometY'Y and GC Y'etention t,ime.
PIU'C eom!)()wld.
/, (7') indic~ltes compound on Pl'ioY'ity Pollutants List pel' C01isent Agl'eement, NatuY'al. ReDouY'ees Defense Council VD Russell E'. :i'l'ain,
.Julle 197/:.
c i'hcIWI1t1lJ'ime alld anthracene could not be r'esolved. Amount is total faT' both compo/md,:.
d CI"'Oosol;e ,w quant1:trxted 1'epT'esents mix'tuN! of a nwnbm' of the eompowzdu pY'euent.
c 1'.,,,,.,/ ,,<,{',jpr.'rl n/7. """."6';> t 1:11 ()etoz.,(!r 6 t:alimZ'c,. Amow1t enti.l,1atAd em at 'least the sum of h!Jd!'oca!'bmw )'(?;!or.ted.
......,',' .., -,.....u - '-
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63
EFFLUENT VIOLATIONS
Pollutants are limited by the NPDES Permit on a daily average
and daily maximum basis. The daily average is determined by the
summation of all the measured daily discharges divided by the number
of days during the calendar month when measurements are made. To
determine compliance with this limitation, samples would have to be
collected daily for the calendar month and the daily average calcu-
lated. Since samples were collected for 5 days only, compliance with
the daily average cannot be determined, however a trend can be observed
to ascertain whether the effluent is capable of meeting the limitations.
The daily maximum applies to any calendar day and compliance was
determined from the survey results.
The daily maximum permit limitations were violated for pH, oil
and grease (D/G), phenols, ammonia, and surfactants.
~
The effluent pH was below 6.0 on 3 of 115 measurements and
exceeded 8.5 on 42 of the 115 measurements [Table 4J. When a pH
violation was observed, NEIC personnel checked the calibration of the
portable pH meter and found the meter reading correctly.
CST has a pH probe in the 55-gallon drum used to collect effluent
samples. Several checks of the probe with the NEIC prepared standard
pH buffers of 4.0 and 9.0 showed that the probe would not stay in
calibration. The CST pH recording chart rarely indicated pH values
above 8.5 when NEIC readings exceeded this limit. The instrument
appears to be unreliable and should be completely reconditioned or
replaced, and checked frequently until reliable data can be.con-
sistently obtained.
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64
The influents from Coastal and Fike both exceeded the 6.0 to 8.5
range. Coastal's pH averaged 10.4 and Fike's 8.8. The method of pH
adjustment with acid or caustic in the inner race of the biosystem
does not work properly. This may be due in part to faulty sensing
devices. With wide variations in pH in the influent streams, the pH
should be adjusted to the desired range before entering the inner
race as high and low pH streams will inactivate the biomass. The pH
sensing and adjustment should be done as the flow leaves the equali-
zation pond. Final effluent pH adjustment should be available if an
upset occurs.
Oil/Grease
The permit limits the oil and grease load to a daily average of
3.8 kg (8.3 lb) and to a daily maximum of 5.7 kg (12.5 lb). During
October 3 through 7, the oil and grease load averaged 12.4 kg (27.4
lb)/day [Table 7J, or 3.3 times the daily average limitation and
twice the daily maximum limitation. The daily average concentration
discharged was 72 mg/l. On a weekly basis, Coastal and Fike con-
tributed about the same oil and grease concentrations (250 and 240
mg/l, respectively), although daily concentrations varied greatly.
About 70% of the incoming oil and grease was removed,* however, at
the flow rate of approximately 151 m3 (40,000 gal)/day, the oil and
grease concentration should be about 25 mg/l or less tobein com-
pliance. This would have required an overall reduction of 90%.
The effluent did not have an oily sheen. Conversely, both
influents were highly colored and visible oils and greases were
*
The actual treatment efficiency was not determined for any
constiuent as the detention time in the system was equal to or
greater than 5 days. The efficiencies discussed are theore-
tically based on an assumption of equivalent loads for the
detention time.
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65
observed. The parameter lIoil and greasell is a misnomer since the
analysis consists of freon extraction at a neutral pH. From the
appearance of the effluent, it can reasonably be assumed that most,
if not all, of the freon extractable materials in the effluent were
organic compounds rather than oils and greases. The treatment system
did not adequately remove the freon extractable materials. There are
numerous toxic compounds discharged to the CST (Section VIII) which
would either hinder or prevent biological degradation of these organic
compounds.
Due to the amounts and varieties of organic compounds discharged,
this permit parameter should be changed from oil and grease to freon
extractable material.
BOD
The daily maximum 5-day biochemical oxygen demand (BOD) is
limited to 95.3 kg (210 lb)/day. This daily average was exceeded on
three of the five days, and the average BOD for five monitoring days
exceeded the daily average limitation by 20% [Table 5]. This trend
indicates that the daily average BOD limitation may not be met. The
DMR data confirms this as the daily average BOD limitation was exceeded
for five months from January to June 1977 [Table 9].
The average BOD concentration in the effluent was 760 mg/l;
Fike1s and Coasta)'s influent BOD concentrations averaged 1,170 mg/l
and 850 mg/l, respectively [Table 13]. Using the maximum concen-
tration, the treatment efficiency was only 36%. This degree of
reduction is characteristic of primary treatment due to sedimenta-
;
tion. T~e average total suspended solids (TSS) reduction was 23%*
! .
and most of the BOD may have been removed in the solids.
*
Inf+uent TSS = 480 mg/l (Table 13); Effluent TSS = 110 mg/l (Table 5).
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66
Two of Coastal's influent samples (October 3 ana 4) and one of
Fike's influent samples (October 7) were toxic to the organisms and
the BOD could not be determined. The more dilute sample aliquots had
larger dissolved oxygen (DO) depletions indicating toxicity of the
samples to the BOD test. No dilution for these samples had a valid
DO depletion; many of the other samples had a low BOO/COD* ratio
indicating toxicity and/or the presence of a substantial number of
organic compounds that are difficult to degrade. Therefore, the
total organic carbon (TOC) or COD tests are better indicators of the
gross organic material present.
Phenols
It was reported during the August NEIC reconnaissance that the
CST sewer was receiving phenolic wastes, possibly from the ortho-benzyl
phenol process. The January-June 1977 DMR's [Table 9] indicate very
high concentrations of phenol (440 to 2,900 mg/l) for the first three
months and then a marked decline to a range of 1.9 to 11.8 mg/l.
Whether th{s was due to correcting possible sources of phenol contam-
ination or to inactivity of the batch processes using phenol is not
known. During October 3 through 7, the phenol concentrations ranged
from 3.7 to 6.9 mg/l, characteristic of the concentrations for April
through June.
For the period September 26 through October 7, 1977, processes
which use phenol were not operating, yet the effluent load was greater
than 3 times the daily average limitation. The daily maximum limitation
was violated on four of the five days. The influent concentrations
of phenoJjcs from Fike and Coastal averaged 4.9 and 8.8 mg/l, respec-
tively. Although the Coastal influent phenolic concentration was
*
. C,~emical Oxygen Demand.
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67
higher than Fike's, based on the estimated influent flows, Fike
contributes about 80% of the influent phenolic load. The estimated
influent load is about 0.6 kg (1.3 lb)/day while the effluent load
was 0.7 kg (1.5 lb)/day. There was no appreciable reduction of
phenolics in the CST biosystem.
Ammonia
The daily maximum limitation for ammonia [16.3 kg (36 lb)] was
exceeded on one day, October 5, by about 20%. Fike contributes
almost all of the ammonia to the CST.
Sulfates
The daily averlge limitation [7.25 kg (160 lb)] was exceeded on
each day. Over the monitoring period, the average daily discharg~
exceeded this limitation by 175%; the January-June 1977 DMR data
[Table 9] show that the daily average limitation for sulfates was
exceeded for four months. The daily maximum limitation was not
exceeded on any day. Fike contributes most of the sulfate to the CST
system.
Surfactants
Surfactants are limited to a daily maximum of 1.0 mg/l. This
limit was exceeded on all 5 days. The average concentration dis-
charged was 6.2 mg/l. Although the concentration of surfactants was
high in the Coastal washing facilities discharge, Fike contributed
more because of higher influent flows. Correspondence between Fike
and EPA, plus the DMR data, reveal that surfactants have been a
problem for a considerable period.
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68
Arsenic
Arsenic is limited by the NPDES permit [Table 1] and also by the
West Virginia Water Quality Standards. The Water Quality Standards
limit the concentration of arsenic to 0.01 mg/l in the Kanawha River.
The average concentration discharged was 0.43 mg/l. The daily maxi-
mum limitation was never exceeded, however, the effluent load was
greater than the daily average limitation on all 5 days. Fike con-
tributes almost all of the arsenic to the CST.
Heavy Metals
Heavy metals are limited to the following concentrations in the
Kanawha River by the West Virginia Water Quality Standards:
Barium
Cadmium
0.50 mg/l
0.01 mg/l
0.05 mg/l
0.05 mg/l
0.05 mg/l
Hexavalent chromium
Lead
Silver
Only lead was found in the CST effluent in concentrations greater
than those allowed in the river water.
Cyanide
Cyanide is not limited by the NPDES permit, however, the West
Virginia Water Quality Standards limit this constituent to 0.025 mg/l
in the river. The effluent concentration of cyanide averaged 0.57
mg/l.
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VII.
ORGANIC CHEMICAL IDENTIFICATION
Over 135 different organic compounds were identified. Many
could not be confirmed by analysis due to the nonavailability of pure
compounds. The chemicals for which pure compounds were available and
which were confirmed by Gas Chromatography/Mass Spectrometry (GC/MS),
and therefore known to be present have been footnoted in the data
tables. Other compounds were identified by reference to mass spectra
in published libraries or by interpretation of the spectra based on
known ion fragmentation patterns. The quantitative results for the
confirmed compounds were based on the response of dilutions of the
pure compound. Other quantitative data were based on estimates made
from the response of similar compounds with similar GC retention
times. For most cases, these estimates will be within +50% of the
real values measured by gas chromatography.
Volatile organic compounds were analyzed by a selective solvent
extraction technique used to measure halogenated species as well as
carbon disulfide which is a major raw material for Fike Chemicals.
Nitrosamines were analyzed by combined gas chromatography/thermal
energy analysis. A description and evaluation of the methods and
quality control data are contained in Appendices C, D, and E.
CST INC. EFFLUENT
Thirty-five organic chemicals including two nitrosamines were
identifieq in the CST effluent [Tables 16, 17 and 18]. Twenty-three
of the ~ompounds were confirmed as being present, eight of which are
on the Priority Pollutant list. Only twelve of the compounds were
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Table 16
VOLATILE ORGANIC' CHEMICAL DATAa -....J
a
CST EFFLUENT; COASTAL TANK LINES (WASH FACILITIES) AND FIKE CHEMICALS DISCHARGE TO CST
October 3-7, 1977
Instantaneous (mg/l)b
., Flow Compound
Location Date Time m3/day gpd CS2 CH2C12 CHC13 CC14 C2HC13 C2C14
Fike Chemicals 3 1435 NMc N~1 4.6 NDd ND 0.015 0.25 0.007
Discharge to CST 4 2035 NM Nr'1 6.0 ND ND 0.007 0.054 0.024
5 1720 NM Nr~ 2. 1 ND ND 0.001 0.030 0.011
6 1430 NM NM 6.4 ND ND 0.005 0.12 0.27
7 1830 NM NM 6.3 ND ND 0.003 0.056 0.23
Coastal Tank Lines 3 1425 102 27,000 ND ND 0.13 0.18 0.35 0.008
Discharge to CST 4 2010 82 21,600 ND ND 0.17 0.72 ND 0.013
5 1710 9 2,400 ND ND 0.23 0.36 ND 0.026
6 1415 18 4,910 ND ND O. 16 0 0.22 ND 0..050
7 1015 8 2,060 ND 2.1 0.42 0.39 O. -25 0.16
CST Effl uent 3 1400 230 61,000 6.8 ND ND 0.018 0.29 0.003
Outfa 11 001 4 2000 106 28,000 8.2 ND ND 0.004 ND ND
5 1700 151 40,000 4.9 ND ND ND ND ND
6 1400 322 85,000 3.9 ND ND 0.001 0.033 0.008
7 1500 30 7,900 5.6 ND ND ND 0.039 0.011
a One grab sample per day.
b All compounds except CS2 are on "Priority Pollutant List" per Consent Agreement,
Defense Council vs Russell E. Train, June 1976.
c NM = Not measured. .
d ND = Not detected at limits used for analysis:
Compounds confirmed by analysis'
on a halogen specific detector
and gas chromatographic retention
times
Natural Resources
Compound
CS2 = Carbon disulfide
CH2Cl2 = Dichloromethane
CHCl3 = Chloroform
CCl = Carbon tetrachloride
C2H8l3 = 1,1,2-Trichloroethylene
C2Cl4 = Tetrachloroethylene
Detection Limit
0.12
1.3
0.042
0.001
0.025
0.001.
(mg/1 )
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Tab Ze 17
ORGANIC CHEMICAL DATA - FLOFi-WEIGHTED COMPOSITE SAMPLES
CST INC., EFFLUENT (OUTFALL 001)
October' 3-7, 1977
Compound Oct. 3 Oct. 4 Oct. 5 Oct. 6 Oct. 7
mg/l kg/day 1b/day mg/l kg/day 1 b/day mg/1 kg/day 1b/day mg/1 kg/day 1b/day mg/1 kg/day 1b/day
Allyl butyl disulfide 0.15 0.02 0.04 0.67 0.08 0.18 1.4 0.29 0.64
Ani1inea b 2.2 0.28 0.63 1.1 0.14 0.30 0.67 0.10 0.22 3.3 0.69 ,1. 5 2.9 0.42 0.92
Anthracenea (T) 0.12 0.02 0.04
o-Benzy1ghenol 0.35 0.05 0.12
Biphenyl 0.041 0.006 0.01
Butylethanethioate 2.2 0.27 0.60
N-Buty1isothiocyanate 0.22 0.03 0.06 0.43 0.06 0.14
p-Creso1a O. ~ 7 0.02 0.05
Cyclohexylaminea 2.6 0.34 0.74 1.0 0.12 0.27 1.9 0.29 0.63 29 6.0 ,13 13 1.9 4.1
Cyclohexy1isothiocyanate 0.73 0.09 0.21 1.2 0.15 0.33 2.1 0.32 0.70 1.3 0.27 0.60 0.46 0.07 0.15
N,N-Diethyl-N'-methy1thiourea 2.2 0.28 0.63 1.2 0.15 0.33 1.3 0.27 0.60
N.N'-Diethy1thioureaa 20 2.6 ' 5.7; 51 5.3, 13.9 27 4.1 8.9 24 5 11 11 1.6 3.5
2.5-Dimethyl pyrazinea 6.8 ,0.9 1.9 6.4 0.8 1.75 6.7 1.0 2.2 5.7 1.2 2.6 4.5 0.6 1.4
Ethy1-N-buty1thionocarbamate 1.1 0.14 0.30 0.93 0.14 0.31
F1uoronaphtha1ene isomer 0.47 0.07 0.16 1.0 0.21 0.5 1.4 0.2 0.45
p-Isopropylpheno1a 0.63 0.08 0.18 2.3 0.28 0.63
o-Isopropylphenola 0.12 0.02 0.03 0.31 0.04 0.08 0.24 0.04 0.08
2-Methyl-5-ethy1 pyrazine 0.24 0.03 0.07 0.21 0.03 0.07 2.3 0.48 1.05
4-Methyl-3-penten-2-one(mesity1 oxide)a 9.9 2.1 4.5 4.3 0.6 1.4
2-Methylthiobenzothiazo1e <0.50 <0.06 <0.14
Phenanthrenea (T) 0.18 0.02 0.05 0.13 0.02 0.04
Phenol a (T) 1.8 0.23 0.51 1.4 0.17 0.38 0.83 0.12 0.27 1.0 0.21 0.46 1.6 0.23 0.51
Propyl-N-buty1thionocarbamate 1.4 0.18 0.4 0.55 0.07 0.15 0.59 0.09 0.20
Propyl butyl thiourea isomer 2.0 0.26 0.57 0.50 0.10 0.23 2.2 0.32 . 0.70
N.N,N',N'-Tetramethy1thioureaa 1.2 0.65 1.4" 1.2 0.15 0.33 0.63 0.09 0.21 0.40 0.06 0.13
1,4- Thiaoxanea 0.18 0.02 0.05 0.77 0.10 0.21 0.17 0.003 0.01
3,3,5-Trimethyl-2-cyclohexenonef
(Isophorone)a (T) C 0.83 0.10 0.23 3.3 0.50 1.1 1.9 0.40 0.87 0'.17 0.02 0.05
Tri-N-buty1ghosphatea 0.45 0.06 0.12
o-To1uidine 3.2 0.41 0.91 2.0 0.25 0.55 1.2 0.18 0.40 0.26 0.05 0.12 6.5 0.94 2.1
a Identification confirmed by Gas Chromatograph/Mass Spectrometry and GC ~etention time; quantity based on response of standard of pure compound.
b (T} indicates compound on Pridl'ity PdlZutant ,List per"Consent Agreem(Jn/;~, 'NatziraZ Resources Defense CowiciZ vs Russell E. Tl'ain~ June 1976.
'-J
--'
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72
Table 18
NITROSAMINE ANALYSES
NITRO, WEST VIRGINIA
October 1977
Date Samp 12 Concentration ~g/la
Location (Oct.) Time Type Dimethylnitrosamine (T)c Diamylnitrosamine
Fike discharge to CST 5 C 0.1 NO d
6 C 0.2 NO
Coastal discharge to CST 5 C 0.1 NO
6 C O. 1 NO
CST effluent (outfall 001) 5 C O. 1 0.9
6 C 0.1 0.6
9~d Evaporation Pond 4 1645 G 0.4 9.5
.~~ 7 16:30 G 0.6 16
Well No.1 4 1440 G NO 0.3
7 1450 G NO 0.5
Well NO.2 5 1200 G 0.2 1.5
7 1405 G O. 1 2.2
We 11 No.3 5 1145 G NO ND
,', 7 1350 G NO NO
a Detection limit for DMN = 0.1 ~g/l
for DAN = O. 3 ~g/l
b' C indicates 24-hr composite sample; G indicates grab sample.
c Dimethylnitrosamine on "Priority Pollutant List" per Consent Agreement,
Natural Resources Defense Council vs. Russell E. Traih, June 1976.
d ND = Not Detected.
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73
discharged in concentrations of less than 1 mg/1; two known toxic
chemicals, phenol and isophorone,* exceeded 1 mg/1 in the effluent.
The maximum concentrations of phenol and isophorone were 1.8 and 3.3
mg/1, respectively. Although loads and concentrations were low, the
effluent was acutely toxic to fish, the LC50 concentration being
0.22%. Moreover, the effluent also caused mutagenicity in test
organisms (Section IX). This is the first known instance where an
effluent has been demonstrated to have this effect.
Eighty-four organic compounds, excluding the heavy refined oils,
were identified in the Fike and Coastal wastewaters discharged to the
CST [Tables 15, 16, and 18]. Fifty-nine of the compounds were con-
firmed as being present, thirteen of which are on the Priority Pollu-
tant list. Forty-seven of the compounds were detected in the Coastal
wastewater stream, twenty-eight in the Fike wastewaters, and nine
compounds detected in both. Of the thirteen known priority ~ollutant
compounds, six were discharged from both facilities and seven were
detected only in the Coastal wastewater. Many of the chemical com-
pounds may have been formed in the sewer lines, the Fike reactors, or
in the CST treatment system, as these compounds are not hauled by
Coastal or used in the reactions at Fike. Six compounds detected in
the CST effluent -- buty1ethanethioate, cyc1ohexy1amine, diamy1nitrosa-
mine, N,N-diethy1-N-methy1thiourea, 2,5-dimethy1pyrazine, and 2-methy1-
thiobenzothiazo1e -- were not detected in either of the discharges to
the CST. Compounds detected in the inf1uents, but not the effluent,
were either diluted to concentrations below the analytical detection
limits, or had not passed through the system. It is highly improbable
that the compounds had been biologically degraded due to the toxic
effects of the wastewaters.
*
3, 5, 5-trimethyl-2-cyclohexenone
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74
The solid material which had settled in the CST sewer upstream
of the manhole where Coastal discharges to the CST sewer was grab
sampled. Twelve compounds were detected, seven of which were con-
firmed as being present [Table 19]. Only one toxic chemical, ethyl
benzene, was identified. There may be similar sediments in the CST
sewer which contain toxic and organic compounds which could contin-
ually or periodically leach into the wastewater passing overhead,
thus adversely affecting biological treatment.
On October 5, grab samples of the raw intake water and treated
water were collected from the Huntington, West Virginia potable water
treatment facilities. Compounds detected in the CST discharge during
the survey were not detected in.these samples.
The organic compounds detected during this survey were not
necessarily representative ~f all the compounds that could be dis-
charged by the CST to the Kanawha River due to batch operations by
both contributors. In addition, other organic compounds may have
been discharged which were not detected.
EVAPORATION PONDS AND MONITORING WELLS
Prior to the survey, both Fike and Coastal discharged wastewater
to the older evaporation pond. A new pond was constructed in Sep- -
tember and Coastal then discharged only to the new pond. Grab samples
were collected of the sediment in the old pond, of the earth used to
construct the new pond before wastewater came into contact with the
soil, and of the wastewater in the older pond.
Twenty-one organic compounds were identified in the wastewater
in the older pond [Tables 18 and 20], eleven of these compounds were
confirmed as being present. Five are on the Priority Pollutant list.
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75
Table 19
ORGANIC CHEMICALS IDENTIFIED IN SEDIMENT~
CST~ INC. AND FIKE CHEMICALS~ INC.
October 1977
Compound
Old Evap. New Evap.
Pond Pond
mg/kg
230
33
~1Sd
49
98
380
6.8
Fike
CST
Sewerb
Anil i nec
o-Benzyl phenol
p-Benzyl phenol
BiphenylC
Cyclohexylisothiocyanate
Dicyclohexyl disulfide
Ethyl benzeneC(T)e
2-Ethylhexylacrylate
m-Ethyl toluenec:?
p-Ethyl toluenec
o-Ethyl toluenec
n-Heptadecanec
n-Hexadecanec
2-Indolene thione
Methylene diphenol isomer
l-Naphtholc
n-Nonadecanec
n-Octadecanec
2-Phenylbenzimidazole
Phenyletherc
Phenyl isocyanate
Phenyl isothiocyanate
Phenyl phenoxyphenol isomers
Pristana (C19 Alkane)c
Styrene
1,1,3,3-Tetraethoxypropane
Tri-n-butyl phosphateC
m&p-xylenesC
730
87
380
48
640
39
33
20
11
21
18
7,300
24
485
720
44
26
43
28
380
210
810
3,200
370
160
a Grab samples.
b Sediment sample collected from settled material in the CST sewer manhole
north of Fike Chemicals~ Inc. main office.
c Identification confirmed by GC/MS and GC retention time. Quantity
based on response of standard of pure compound.
d MS = identified by mass spectrometry~ but below GC-FID detection limit.
e (T) indicates compound on "Priority Pollutant List;' per Consent Agreement~
Natural Resources Defense Council vs Russell E. Train~ June 1976.
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.......
Table 20 ~
ORGANIC CHEMICAL DATA, GRAB SAMPLES
OLD EVAPORATION POND AND MONITORING WELLS
Octobe2' 1977
o.
Compound Oct 7
2-Ami nO,i-methyl propanol 1.8
Analine 37 85
Benzothiazoled 0.013
Bis(2-chloroethy1)etherd (T)e 2.2 4.1
Bis(2-ch~oropropyl)ether 0.34 0.64
p-Cresol d 0.30 1.5
Cyclohex~lamine 0.97 2.0
n-Decane d 3.5
2,6-Di-t-butyl-p-cr~sol 0.005
Di-n-butylphthalade (T) 0.008
O-Dichlorobenzen3 (T) 0.003
p-Diethylbenzene 0.006
N,N~Diethylthiourea 0.13 1.7
2,5-Dimethyl-3,4-dithiahexane 0.22
1 ,2.!oDimethyl-l ,2,3,4
-tetrahyaroquinoline 0.003
n-Dodecane 1.2
Ethyl-N-ethylth~onocarbamate 0.11 0.20
m-Ethyl toluened 0.005
p-Ethyl toluened 0.005
o-Ethyl toluene 0.70 0.003
Fluoronapthalene isomer 0.70 4.6
Heptano 1 0.024
2-Indolene thione d 0.12 0.62
o-Isopropyl phenold 0.080 0.58
p-Isopropyl phenol 0.30 2.4 0.020 0.18
4-Methyl decane 0.86
2-Methyl-5-ethy1 pyridine 0.003
Methyl isopropyl benzene d f 0.011
Methyl naphthalene isome& f 0.002
Methyl napt9alene isomer' 0.005
Naphtha13ne (T) . 0.006
n-Nona~e 0.26
Phenol (T) 4.2 76
Phenyl isocyanate 0.30 1.7 0.10 MSg
Phenyl isothiocyanate 5.3 19
Propyl butyl thiourea 0.30 6.5 0.009 3.4 5.9
Pr?pyl-Njethylthionocarbamate 0.060 .0.087
lsomer
Pr?pyl-Njethylthionocarbamate 0.080 0.13
lsomer
-------
Table 20 (Continued)
ORGANIC CHEMICAL DATA GRAB SAMPLES
OLD EVAPORATION POND AND MONITORING WELLS
OciJober> 1977
Concentrations
Evaporation Pond Hell No. la Hell No. f
Compound Oct 4 Oct 7 Oct 4 Oct 7 Oct 5 Oct 7
1,2,4,5-Tetramethyl benzened. 0.010
2,2,4,6-Tetramethyl-l,3-dioxage 0.43
ii, N, N I , tl I - Tetramethylthi ourea 0.51 1.6
Tetramethyl ugea 14 21 0.19
1,4-Thiaoxage 1.5 8.2 0.002 0.026 0.23 0.12
o-Toluidine 10 31
Tri-n-butylphosphated 0.21
n-Tridecane 0.24
1,2,4-Trimethylbenzened 0.45 0.015
1,2,3-Trim~thylbenzene 0.012
n-Undecane .l 4.6
VOLATILE ORGANICS
Carbon disulfided d 0.65 1.3 rwh NO NO NO NO NO
Carbon tetaachloride (T) NO NO ND tlD NO NO NO NO
Chloroform (T) NO 0.069 NO NO 0.35 NO NO NO
Oichloromethaned(T)d NO NO NO NO NO NO NO NO
Tetrachloroethylene (TA NO 1.6 NO NO 0.009 0.008 NO NO
1,1,2-Trichloroethylene (T) 0.27 0.094 . NO NO 0.17 0.30 " NO NO
a Monitor>ing well No.1 about 114m (375 ft) l1Or>th of old eVapor>ation pond.
b Monitoring well No.2 about 4.5m (15 ft) west of old evapol>ation pond.
c Monitol>ing well No.3 about 91m (300 ft) west of old eVapor>ation pond."
d Identification confirmed by Gas Chr>omatogr>aphIMass Spectr>ometr>y anc GC r>etention time. Quantity based on r>esponse of
standar>ds of pure compound. Volatile or>ganics confir>med by analysis 01; .l halogen specific detector and gas chr>omatogr>aphic
retention times.
e (T) indicates compound on "Pr'ior>ity Pollutant List" per> Consent Agr>eement, NatUT'al Resources Defense Council vs Russell E. Train,
June 1976.
f Isomers detected at tlJO differ>ent GC r>etention times.
g MS = i.dentified by mass spec tome try, but below GC-FID detection limit.
h Volatile 01'ganic Chemicals detection limits (mgll) were as follou1S: Car>bon disulfide = 0.12; Carbon tetrachlor>ide = 0.001;
Chloroform = 0.042; Dichloromethane = 1.3; Tetrachloroethylene = 0.01; 1,1,2-Trichlor>oethylene = 0.025. ND indicates that
the compounds were not detected at these concentrations.
"
"
-------
78
The concentrations were low for four of the five compounds: the
phenol concentration was 76 mg/1. Six compounds were detected in the
pond sediment sample, but only styrene was confirmed as being present
[Table 20J. None of the compounds are on the Priority Pollutant
list.
From field measurements, the approximate surface area of the old
pond is 1,400 m2 (15,100 ft2) and the depth ~verages about 0.46 m
(1.5 ft); the calculated volume of the pond is 640 m3 (22,660 ft3).
The flow rate from Fike's sump averages about 65 liters (17.2 ga1)/min,
but is not continuous. Over the 5-day monitoring period, about 95 m3
(25,160 gal) of wastewater had been pumped into the older pond. At
this rate, it would take about 35 processing days to fill the pond to
the level observed during the survey. About 0.30 m (1 ft) of freeboard
existed before the pond would overflow, giving an added capacity of
430 m3 (15,100 ft3). This extr~ capacity would last about 23 proces-
sing days if there was no percolation or evaporation. The evaporation
rate in the area is 84 cm (33 in)/year and the rainfall is 114 cm
(45 in)/year.* Based on the evaporation rate, about 1,175 m3
(310;000 ga1)/year of wastewater would be lost from the pond. This
amount of evaporation would be equalled in approximately 60 processing
days, excluding rainfall and the Coastal discharges to the pond.
Therefore, it is evident that the wastewater in the?ld pond percolates
into the groundwater. Based on five days of processing per week, the
average rainfall and evaporation rates, and a f10wrate from the sump
of 95 m3 per five operating days, and assuming that the freeboard in
the pond remains at 0.30 m, the net water and wastewater reaching the
pond would be 5,360 m3 (1.4 x 106 ga1)/year. Under steady-state
conditions, 5,360 m3 (1.4 x 106 ga1)/year of the pond wastewater
could be lost to the groundwater. As discussed in Section IV, the
pond was designed to allow the wastes to percolate.
* Water Atlas of the United States.
-------
79
The capacity of the new pond, from field measurements, is about
1,230 m3 (43,450 ft3). Neglecting rainfall and evaporation, at the
present flow rate from the sump and the Coastal contribution of
113 m3 (30,000 gal) per five-day period, the new pond will be completely
full in approximately thirty working days, if the pond does not leak
to the groundwater.
The three wells adjacent to
data [Tables 18 and 20] indicate
inated. ,The No.2 well, closest
compounds present than the other
were detected in the pond and the
the ponds were also monitored. The
that the groundwater is being contam-
to the older pond, had more organic
two wells. The following compounds
No.2 well:
p-isopropyl phenol
phenyl isocyanate
propyl butyl thiourea
tetramethyl urea
dimethylnitrosamine
(confirmed)
(confirmed)
l,4-thiaoxane (confirmed
chloroform (confirmed)
tetrachloroethylene (confirmed)
l,l,2-trichloroethylene (confirmed)
diamylnitrosamine (confirmed)
Dimethylnitrosamine (DMN), chloroform, tetrachloroethylene, and
l,l,2-trichloroethylene are on the Priority Pollutant list. Other
compounds detected in the pond and two other wells include propyl
thiourea, l,4-thiaoxane, and diamylnitrosamine. Aluminum, arsenic,
barium, cadmium, iron, and lead were found in well No.2 and the pond
[Table 21]. These data indicate that the evaporation pond percolates
through the soil to the groundwater.
Other organic chemicals were also detected in the wells, but
were not found in the pond. This indicates contamination from sources
other than the pond. Since Fike disposes of waste material directly
on the ground, it is highly probable that the compounds eventually
reach the groundwater. It was also observed during the survey that
excessive leaks were present in the piping serving the recently
installed spray evaporation system for the old pond. The wastewater
from these leaks flowed onto the ground outside of the pond diking.
-------
80
Table 21
. SUMMARY OF HEAVY METAL ANALYSE~ .
EVAPORATION POND AND MONITORING WELLS
October 1977
Parameter
Concentration (mg/l)
Evaporation Pond Well No.1 Well No. 21 Well No.3
Oct. 4 Oct. 7 Oct.4 Oct.7 Oct.5 Oct.70ct.5 -Oct.7
Aluminum 2.3 2.4 0.2 0.2 7.6 5.6 6.1 0.9
Arsenic (T)b 0.32 0.32 NOc NO 0.04 NO 0.02 NO
Barium 0.30 0.30 0.40 0.30 NO 0.30 0.60 0.40
Cadmi um (T) 0.23 0.24 NO NO 0.05 0.05 0.03 NO
Chromium, hexavalent (T) NO NO NO NO NO NO NO NO
Iron 50 55 120 42 4~ 46 23 22
Lead (T) 6.0 10.5 0.2 0.2 0.7 0.9 0.8 0.1
Silver (T) NO 0.045 NO NO NO NO NO NO
a Grab samples.
b (T) indicates on "Priority Pollutant List" per Consent Agreement.,
Resources Defense Council vs. Russell E. Train., June 1976. -
c ND indicates Not Detected.
Natural
-------
81
Thirteen compounds were detected in the soil sample from the new
pond. This data show that the soil in the vicinity is becoming con-
taminated by operations at Fike or Coastal, or both. The contamin-
ation is probably due to the careless and unsafe disposal techniques.
COASTAL TANK LINES PRE-RINSE DISCHARGES TO NEW EVAPORATION POND
The samples collected from the tank truck discharges to the new
pond were difficult to analyze. The sample collected on October 6
showed such gross amounts of very heavy and late-eluting compounds by
GC-FID that GC/MS analysis was impractical and not performed. Other
samples contained heavy, sticky resinous materials which were insoluble
in water and methylene chloride. Many of the compounds present were
related to the components found in undiluted creosote. Other compounds
appeared to be components of the chemical mixes for use as plastici-
zers, resin solvents and plastic materials.
Thirty-two organic compounds were detected in the discharges
from the tank trucks, nine of which are on the Priority Pollutant
list [Table 22]. Twenty-six of the compounds were confirmed as being
present. Due to the resinous nature of the material, it solidified
in the pond after a short period of time. Depending upon solubility,
some of this material may be benefical in that an impervious barrier
can be formed in the pond preventing percolation. However, the
possibility of this material completely sealing the pond is low.
-------
82
Table 22
ORGANIC CHEMICALS IDENTIFIED IN PRERINSE
TANK TRAILER DISCHARGE TO NEW EVAPORATION PONDa
COASTAL TANK LINESJ INC.
October 1977
Compound Concentrationb (mgfl)
Oct. 3 Oct. 5 Oct. 5 Oct. 7
@ 0055 hrs @ 1455 hrs
Anthracenec (T)d 200 4.0 51 0.41
Benzothiazolec 15
BiphenylC 32 4.1 . 33 3.9
Bi phenyl enec 5.2
2-n-Butox~ethanolc 9.4
Carbazole 77 1.5 0.50
Creosotee 3,500 25 190 5
p-Cresolc 12
Crotonic acid 22
Diamino toluene isomer 0.63
Di benzofuranc 44 0.48
Di-isopropylphenol isome~ 0.60
Di-isopropylphenol isomerf 0.20
Diphenyl etherc 11 48 0.099
2-ethylhexanoic acidc 350
2-ethyl-l-hexanolc 0.76
Fluorenec (T). 56 0.71
o-Isopropylphenolc 77
p-Isopropylphenolc 2.4 6.9
l-MethYlnaphthalenp'c~f 32
2-Methylnapthal~neq,< 62 0.58
Methylphen~lacetylene 26
Na ptha 1 ene (T) 270 2.7 15 0.J3
Phenathrenec (T) 230 3.0 37 0.30
Phenolc (T) 15 4.2
Resinous materialg 1,400
StyreneC 0.28
Tert-butylketone 380 7.4 170 1.0
VOLATILE ORGANICSa
Carbon disulfidec ND ND ND ND
Carbon tetrachloridec (T) 0.20 ND 0.001 0.006
Chloroformc (T) ND ND ND ND
Dichloromethaoec (T& 190 10 190 ND
Tetrachloroethylene (T& ND ND 0.003 ND
1,1,2-Trichloroethylene (T) 0.26 ND ND ND
a Grab sampZes coZZected periodicaZZy during tank traiZer discharge and. composited
on equaZ voZume basis into one sampZe. VoZatiZe organic sampZes coZZected once
during discharge.
b Contents of traiZer discharged Oc~ober 6 contained onZy very heavYJ Zate eZuting
compounds u.'hich cOllZd not be anaZyzed by CG/MS. Tank t2'ci>~' ;'::"-,,?,::,:rS'ed on
Oct. 4 not sampZed. .
c Identification confirmed by Gas Chromatograph/Mass Spectrometry and GC retention
time. Qucntity based on response of standard of pure compound. VoZatiZe or-
ganics confirmed by anaZysis on a haZogen specific detector and gas chromato-
graphic retention times.
d Indicates compound on "P2'iority PoUutant List" .per Consent AgreementJ NaturaZ
Resources Defense CounciZ vs. RusseZZ E. TrainJ June 1976.
e Creosote as quantitatzd from'sampZe represents mixture of a number of the com-
pounds present. Concentrations summed to give estimate of probabZe creosote
concentration.
f Isomers detected at two different G.C. retention times.
g Concentration in soZution in extract at Zeast amount; much materiaZ was insoZubZe.
. Concentration estimated from responses of seZected G.C. peaks. '
h ND = Not Detected.
-------
VII 1.
TOXICITY EVALUATION
The purpose of this section is to interpret the significance of
the organic compounds found in the NEIC survey, with particular
emphasis on adverse environmental and health effects. Because of the
large number of compounds involved (121), much of this information
has been condensed into tabular format [Table 23].
It has been commonly accepted that organic compounds occur in
sewage effluents, rivers and, more recently, drinking water. In the
past, most data relating to these occurrences were from gross measure-
ments, such as carbon-chloroform extracts and non-volatile total
organic carbon. Today, the use of ultra-sensitive analytical tools
such as the computer-assisted gas chromatography-mass spectrometer
scan has led to detection of many organic molecules present in small
amounts in such waters.
Although Tables 15 through 20 list one hundred thirty-seven
separate compounds, recent EPA estimates indicate that these identi-
fied compounds constitute about 10% by weight of the total organic
compounds present in such waters. A much fuller discussion of these
methods is found in the recently published book IIIdentification and
Analysis of Organic Pollutants in Water. "I
The compounds listed in Table 23 are not unique to the waters
sampled. Exposure to the compounds by various segments of the United
States population exists via some foods, ambient air, occupational
environment, and household products including over-the-counter medi-
cations, cleaning solutions, and cosmetics. Exposure to such chemicals
-------
'l'obZe <:J
TOXICITY OF ORGANIC CO/.fPOllNi'S
nKE: CHEMICALS INC., COAD'I'M, 1',1NK LTilES, fiND CST, JNC.
Compound Name
Molecular
Formula
Chemical
Abstracts
Service No.
Aquatic Toxicitya Route of
Entry - Species
Effec ts
Oth~r 'Toxicity Dati;
Type of, Dose
Dose
Duration
(p
Exposure .j:::o
L imi tsC
Acrylic acid, CllH2002 103 - 11-7 TLm96:l,000-
2-Ethylhexyl ester 100 ppm
(2-Ethylhexyl acrylate)
Aluminum chloride A1C13 7446-70-0
(1 :3)
Ammonia NH3 7664-41-7 TLm96:l0-l ppm
Aniline
C6H7N
Arithracene
C14HlO
Arsenic
As
62-53-3
120- 12-7 ,d
7440-38-2'd
TLm96:l00-10 ppm
Oral-rat
Intraperitoneal-mouse
Skin-rabbit
Oral-rat
Oral-mouse
Inhalation-human
Inhalation-human
Inhalation-rat
Inhalation-mouse"
Inhalation-cat
Inhalation-rabbit
Oral-human
Unreported-human
Ora 1 - ra t
Inhalation-rat
Skin-rat
Intraperitoneal-rat
Inhalation-mouse
Subcutaneous-mouse
Unreported-mouse
Skin-dog
Oral-cat
Inhalation-cat
Ski n-ca t
Intraperitoneal-rabbit
Subcutaneous-rabbit
Skin-rabbit
Intravenous-rabbit
Skin-guinea pig
Skin-guin~a pig
Ora 1- ra t
Subcutaneous-rat
LD50:6,500 mg/kg
LD50:1,506 mg/kg
LD50: 16 gm/kg
LD50:3,700 mg/kg
LD50:3,805 mg/kg
LCLo:10,000 ppm
TCLo:20 ppm
LCI.o: 2 ,000 ppm
LC50:4,837 ppm
LC50:1O,066 ppm
LCLo:10,066 ppm
LDLo:350 mg/kg
LDLo:357 mg/kg
LD50:440 mg/kg
LCLo:250 porn
LD50:1,400 mg/kg
LD50:420 mg/kg
LC~O: rn ppm
LDLo:480 mg/kg
LD50:572 mg/kg
LDLo:l,540 mg/kg
LDLo:l ,750 mg/kg
LrLo:180 ppm
LDLo:l,540 mg/kg
LDLo:200 mg/kg
LDLo:l,OOO mg/kg
LD50:820 mg/kg
LD50:64 mg/kg
LDLo:l,750 mg/kg
LD50:1,290 mg/kg
TDLo:18 gm/kg
TDLo:3,300 mg/kg
Intramuscular-rat LDLo:25 mg/kg
Subcutaneous-rat LDLo:300 m9/kg
Intraperitoneal-guinea,pig LDLo:lO mg/kg
Subcutaneous-guinea pig LDLo:300 mg/kg
3H
4H
lH
lH
lH
OSHA std(air)
TWA 50 ppm
tlI OSH recm s td
(air) Cl 50 nom
Irritant
OSHA std(air)
THA 5 pprn(skin)
4H
7H
8H
78 WI Carcinogenic
33 WI Neoplastic
OS HA s td ( air) 3
TWA 500 IJg/rn
NIOSH recm std 3
(air) Cl 2 IJIJ/m
-------
Compound Name
'l'ulAe ;;,5 (('olltim(~d)
'--0- ------
'/'(!.'I[CITl OF Uf!i;...IV re C(}!-:!'/lUNVS
FIA"E CIl/,,\IICIil.:; INC., C(I.'1:;'1'..1/, 1';I,'/;{ /.n.'!,s, /ifl/} C:;'f', JiW.
f.iolecular
Formula
Chemical
Abstracts
Service No.
Aquatic Toxicity(l
Effects
Exposurc
Limit~L'
Route of S .
Entry - peclcs
Ora l-Iluman
Barium Chloride
Benzene, Ethyl-
BaC12
C8HlO
Benzene, Isocyanato- C7HSNO
(Phcny 1 i socyana te)
Benzene, 1, 2, 4-
Trichloro-
l3enzene, 1, 2, 3-
Trilile thyl-
l3enzene, 1, 2, 4-
Trilllethyl-
C6H3C13
C9H12
C91112
10361-37 -2
100-41 -4d, e TLm96: 100- 10 ppm
103-71-9
120-82-ld TLm96: 10-1 ppm
526-73-8
95-63-6
Benzothiazole C7f1SNS 95-16-9
Biphenyl C12f110 92-52-4 e
Oral-rat
SubcUtaneous-rat
Intravenous-rat
Intraperitoneal-mouse
Subcutaneous-mouse
Intravenous-mouse
Ora I-dog
Subcutaneous-dog
Intravenous-dog
Subcutaneous-cat
Intravenous-cat
Ora l-rabbi t .
Subcutaneous-rabbit
Intravenous-rabbit
Subcutaneous-guinea pig
Inhalation-human
Oral-rat
Inhalation-rat
Ski n-rabbit
Inhalation-guinea pig
Oral-rat
Oral-rat
Oral-mouse
Intrc~eritoneal-mouse
Ora 1- ra t
Oral-rat
Intraperitoneal-rat
Intraperitoneal-guinea~
piC]
Intraperitoneal-mouse
In tl'avenouS-lIlouse
Inhalation-human
Oroll-I'at
S"I>CI1 ta ncous -mouse
O,'a l-rablyi t
o theT T ox i city Da tal'
Type of. Dose
Dose
TDLo:80 mg/kg
LDLo:335 mg/kg
LDSO: 178 mg/kg
LOLo: 20 mg/kg
LDSO:54 mg/kg
LDLo: 10 mg/kg
LOSO: 12 mg/kg-
LOLo:90 mg/kg
LOLo:15 mg/kg
LOLo:26 mg/kg
LDLo:38 mg/kg
LOLo:50 mg/kg
LOLo: 170 mg/kg
LDLo:55 mg/kg
LOLo:17 mg/kg
LOLo:55 mg/kg
TCLo:100 ppm
LDSO:3,500 mg/kg
LCLo:4,OOO ppm
LOSO;5,OOO mg/kg
LCL:IO,OOO ppm
L050:940 mg/kg
L050:756 mg/kg
LD50: 766 Ilig/kg
LDLo:SOO mg/kg
LDLo:5,000 mg/kg
LOLo:5,000 mg/kg
LOLo:2,OOO mg/kg
LOLo:l ,788 lng/kg
LDLo:100 lng/kg
L050:95 lng/kg
TDLo:4,400 ~g/m3
LOSO:3,280 lng/kg
TlJLo:46 m<]/k9
LD50:2,400 mg/kg
O-uration
Gastroin-
testinal
tract
8H
Irritant
411
Irri tant
Neoplastic
------
OSHA std(a ir)
HIA sog IJg
(Ba)/m
OSHA std(air)
TWA 100 pplll
(skin)
*
DTL VS
TLV (air) 25 [1:
*
OTL VS
TLV (air) 25 J'
OSHA std(air~
THA O. 2 ppill
-------
Table ::.~ (ContinzwrlJ
'('OXICI7'Y OF OIt'GMIJC COMI'OUNIJS
FIKE CHEMICALS INC., COASTAL TANK LINES, AND CST, If/C.
ex>
0'\
Compound Name
~1olecular
Formula
Chemical
Abstracts
Service No.
Aquatic Toxicitya
Route of - Species
Entry
Other Toxi city Da tab
Type of. Dose
Dose
Duration
Effects
Exposure
Limits(.'
2-Biphenylol
(2-Phenylphenol)
Cadmium
Carbazole
Carbon disulfide
C12H100
Cd
C12H9N
CS2
Carbon tetrachloride CC14
90-43-71
7440-43-9d
86-74-8
75-15-0g
TLm96:l,000-
100 ppm
56-23-gd,e,g TLm96:l00-l0 ppm
Oral-rat
Inhalation-man
Intramuscular-rat
Intramuscular-rat
Intramuscular-hamster
Ora 1 - ra t .
Intraperitbneal-mouse
Oral-human
Inhalation-human
Inhalation-human
In~raperitoneal-rat
Subcutaneous-rabbit
Oral-human
Inhalation-human
Inhalation-human
Oral-rat
Inhalation-rat
Inhalation-rat
Intraperitoneal-rat
Subcutaneous-rat
Oral-mouse
Inhalation-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Intravenous-dog
Inhalation-cat
Subcutaneous-cat
Oral-ratibit
Inhalation-rabbit
Subcutaneous-rabbit
Inhalation-guineapig
Oral-hamster
LD50:2,700 mg/kg
TCLo:88 \Jg/m3
LDLo:15mg/kg
TDLo:mg/kg .
LDLo:25 mg/kg
LDLo:500 mg/kg
LD50:200 mg/kg
LDLo:14mg/kg
LCLo:4,000 p~m
TCLo:50 mg/m
LDLo:400 mg/kg
LDLo:300 mg/kg
LDLo:60 mg/kg
TCLo:20 ppm
LCLo:l,OOO ppm
LD50:1 ,770 mg/kg
LCLo:4,000 ppm
TCLo:300ppm
LD50: 1 ,500 mg'/ kg
TDLo: 133 gm/ kg.
TDLo:4,800 mg/kg
LC50:9,526 ppm
LD50:4,620 mg/kg
LDLo:3,200 mg/kg
LDLo:l,OOO mg/kg
LDLo:125 mg/kg
LCLo: 38,11 0 ppm
LDLo:4,785 mg/kg
LD50:6,380 mg/kg
LCLo:550 ppm
LDLo:3,OOO mg/kg
LCLo:20,000 ppm
TDLo:3,680 mg/kg
B.6Y
3or~
7Y
Systemic
Carcinoqenic
Cen tra 1
nervous system
OSHA std(air) 3
TWA 200 \Jg/m ;
Cl 600
OSHA std(air)
HJA 20 ppm;
Cl 30; Pk 100/30M
OSHA std(air)
Central TWA 10 ppm;
nervous system Cl 25; Pk 200/5M/4.
NIOSH recm std
(air) HJA 2 ppm
. 4H
( 6-150)
preg)
25 WI
8801
8H
2H
2H
30\H
T era togen i c
Neoplastic
Carcinogenic
Carcinogenic
-------
Table 2.3 rr:o"t{ll/ledJ
TUX Ie.! 'l'r rw (.'[" ;AN Ie CO/.lPOI III os
~'I;:!': ClJr::t.J[C,1IJ.r;~ lNC., CO.:1.f;'i'lll. 1:'1N/\ Lif/f:S., ANn (V:;'r, TIYC.
Compound Name
r101ccu1ar
Formula
Chemical
Abstracts
Service No.
Aquatic Toxicity?
Routc uf
En tl'Y - Spec i es
Other Toxicity Oatah
Type of. Dose
Dose'
Duration
Effects
E~posuse
L 11111 ts
Chloroform
CHC13
Chromium
Cr
p-Creso1
C7H80
p-Creso 1, 2. (i-
Oi,tert-Buty1- C fI 40
(2.6-0i-t-butY1-p-cre~617
67-66-3(1, P., fl TLm96:100-~0 ppm
7440-47-3d,h
106-44-5
128-37-0 g
Oral-human
Inh,11 iI t ion-human
Oral-,-at
liral-rat
Inhal,ltion-rat
inha lation-rat
Ora l-liiouse
Ora l-lilOuse
Inhalation-mous~
Intra~critonea1-mouse
Subc 1/ La neous -mouse
Ora I-dog
Inhalation-dog
Intravenous-dog
Inha 1.1 tion-rabbi t
Subcutaneous-rabbit
Inhalation-guinea pig
Inhalation-human
Intravenops-rat
Implant-rat
In traperi tonea 1-mouse
O,'a l-ra t
Skin-rat
O"a I-mol/se
Subcutaneous-mouse
Unr'cporterf -mous e
Subcutaneous-cat
Oral-rabbi t
;kin-rabbit
Subcutancous-rabbit
Intravenous-rabbit
Intraperitoneal-guineapig
Subcutaneous-frog
Oral-rat
Oral-rat
Ora 1-mouse
Intraperitoneal-mouse
Oral-cat
Ora 1-rabbi t
LOLa: 140 mg/kg
TCLo: 1 0 ~1"11
L050:eOO mg/kg
TOLo:/O '.1m/kg
LCLo:8,OOO ppm
TCLo: 100 ppm
LOLa: 2.400 mg/kg
TOLo: 18 '.1m/kg
LC50:28 pprn
L050:1,671 mg/kg
L050:70'1 mg/kg
, LOLo:l,OOO mg/kg
LC50: 100 ppm
LOLo:75mg/kg
LC50:59 ppm
LOLo:800 mg/kg
LCLo:20,OOO ppm
TOLo: 4,500 IJg/m3
TOLo: 2 mg/ kg'
TOLo: lillo/kg
L050:102 mg/kg .
L050:207 mg/kg
L050:750 mg/kg
LD50:344 rng/kg
LOLa: 150 mg/kg
L050: 160 mg/ kg
LOLo:80 mg/kg
LOLb:F?i1 ma/kCj
L050:301 mil/kg
LOLo:300 mg/kg
LOLo: 180 mg/kg
LOLa: 100 mg/ kg
LOLo: 150 mg/kg
L050:3,510 mg/kg
TOLo:5,500 mg/kg
, L050: 1.040 mg/kg
LOLa: 250 mg/kg.
LOLo:g40 mg/kg
LOLo: 2.100 mg/kg
1Y
78f1l
4f1
7H
(6-150
(preg)
Sys terni c
Neoplastic
T era togen i c
preo)
12001
Carcinogenic
2H
5Y
Pulmonary
System
NI?oplastic
Neoplastic
Neoplastic
6WI
61-11
6WI
,Teratogenic'
OSIIA s td (a i i-) :
TVlA 50 pprn
NIOSfi recm s td
(air) TWA 50 ppm
OSHA std(ajr)
TV/A 1 mg/m .
OSHA std(air)
TI~A 5 ppm (skin)
00
'-J
-------
Table ;JJ (Co>ztimwdJ ex>
ex>
TOXII.'T7'Y OF (JHGNIIC CmfPOU,vfJS
FIKE CII~"i1.n/I/,S IN':', (.'(J;I.':'l'I1[' TI1NK LINt-'S, I1N/J CS7'. INC.
Chemical Other Toxicity Data], Exposure
Molecular Abs trac ts Aquatic Toxicity~ Route of Species Type of, Dose Dura t i on Effects Limits'"
Formula Service No. Entry - Dose
C4H602 3724-65-0 Oral-rat LD50:1.000 mg/kg
Intraperitoneal-rat LDSO: 100 mg/kg
Skin-guinea pi~ LDSO:600 mg/kg
Intraperitoneal-guinea pigLD50:60 mg/kg
C6H120 108-93-0 TLm96: 100-10 ppm inhalation-human TCLo:75 ppm Irritant OSHA std(air)
Oral-rat LDSO:2.060 mg/kg TWA 50 ppm
Subcutaneous-mouse LD50:2,480 mg/kg
:ntravenous-mouse LD50:272 mQ/kg
Intra mu'~ular-mouse LOS0:1,nnn mq/kg
Oral-dog LDLo:l,300 "19/K9
Subcutaneous-cat LDLo:800 mg/kg
Oral-rabbit LDLo:2,200 mg/kg
Skin-rabbit LOLo:12 gm/kg
Intraperitoneal-rabbit LOLo: 1,420 mg/kg
C9H140 78-59-ld,e Oral-rat LDSO:2,330 mg/kg OSHA std(air)
Inhalation-rat LOLo:l,840 ppm 4H TWA 25 ppm
Ski n-rabbi t LD50:1,500 mg/kg
Compound Name
Crotonic Acid
Cyclohexanol
2-cyclohexen-l-
one,3,5,5-
trimethyl-
(3,S,5-Trimethyl-
2-cyclohexenone
or i sophrone)
Cyclohexylamine
C6 H13 N
108-91-8
LD50:710 mg/kg *
TLmg6: 1, 000- Oral-rat DTLWS
100 ppm Inhalation-rat LCLo:8,OOO ppm 4H TLV (ai r) 10
Intraperitoneal-rat LD50:200 mg/kg ppm (skin)
Intraperitoneal-mouse LDSO:300 mg/kg
Subcutaneous-mouse LD50:1 ,150 mg/kg
Skin-rabbit LDSO:320 mg/kg
Parenteral-rabbit LOLo:500 mg/kg
Ora I-human TOLo:86 mg/kg Central
Nervous system
Ora 1- ra t LOSO:4.750 mg/kg
I nha 1 a t i on-ra t LCLo: 5,000 ppm 45M
Intraperitoneal-guinea pigLDLo:2,162 mg/kg
Oral-ra t LD50:26 mg/kg USOS-carcinogen
Oral-rat TDLo:248 mg/kg , 31WI Carcinogenic
I nha 1 a t i on-ra t LCSO:78 ppm 4H
Inhalation-rat TCLo:37 mg/kg Carcinogenic
Intraperitoneal-rat LDSO:36 mg/kg
Intraperitoneal-rat TDLo:30 mg/kg Neoplastic
Subcu taneous - ra t LDSO:4S mg/kg
Intravenous-rat LDLo:40 mg/kg
Intr~~uscular-rat TDLo: 18 mg/kg tJeop 1 as ti c
Parentera l-ra t TOLo:? mg/kg (15-210 "reg) rJeoplastic
Intravenous-rat TDLo:18 mg/kg Neoplastic
Ora I-mouse TDLo: 370 mg/ kg , S6HC Carcinogenic
Inhalation-mouse LCSO:S7 ppm 3 4H
Inhalation-mouse TCLo:200 ~g/m 26 WC Carcinogenic
p-Cymene ClOH14 99-87-6
(r1ethyl isopropyl
benzene isomer)
Oimethylamine, C2H6N20 d'
62-75-9
N-Nitroso-
-------
Table ;;3 (Conti'luedJ
TOXICITY OF OHGANIC CO,'.7'CUNDS
FH.E CIIEMICAIA> INC., COASTA& TANK ,GINE'S, AND C,';T, IIiC.
Compound Name
Exposuse
limi ts
1,101 ecul ar
Formula
Chemical
Abstracts
Service No.
Aquatic Toxicityn
Route of
Entry - Species
Other Toxicity Oatab
Type of. Dose
Dose'
Dura t ion
£ffec ts
Dimethylamine,
N-Nitroso-
Oipentylamine,
N-rJj troso-
(Diamylnitrosamine)
Ethanol, 2-Butoxy-
(2-n-ButoxyEthanol)
(Continued)
ClOH22N20
C6H1402
Ethanol, 2-phenoxy- C8H1002
l3256.06-9a
111-76-zI
122-99-6
TU1 96: 1,000-
, 100 ppm
Intraperitoneal-mouse LOLo:9 mq/k9
Intraperitoneal-mouse TOLo:7 m9/kg
Subcutaneous-mouse TOLo:4.375 pg/kg
Unreported-mouse TOLo:13 mg/kg (preg)
Unreported-mouse LOLo:20 mg/kg
Ora l-dog LOLo:20 mg/kg
Inhalation-dog LCLo: 16 ppm 411
Ora l-rabbit TDLo:202 IIIg/kg 23WC
Unreported-rabbit LDLo:10 IIIg/kg
Unreported-guinea ~i9 LOLo:25 mg/kg
Ora l-hams ter ,TOLo:21 mg/kg
Subcutaneous-hamster L050:28 109/kg
Subcutaneous-hamster TOLo: 50 109/kg 6WI
Oral-rat L050:1,750 109/kg
Ora 1- ra t TOLo:48 gill/kg 5lHC
Subcuta"~ous-ra t 1050:3,000 mg/kg
Subcutaneous-rat. TOLo:12 gm/kg 24HC
Inhalation-human TDLo: 195 ppm 8H
Ora 1- ra t LD50:1,480 mg/k9
Inhalation-rat LCLo:500 ppm -4H
Intraperitoneal-rat L050:550 mg/kg
Intravenous-rat LD50:340 m9/kg
Oral-mouse LD50:1,230 mg/~9
Inhalation-mouse LC50:700 mg/k9
Intraperitoneal-mouse L050:536 mg/kg
In t,'aver.uus-mouse LD50: 1 .130 mg/kg
Oral-rabbi t LD50:320 mg/kg
Intravenous-rabbit LD50:280 mg/kg
Or~l-guinea pig LD50:1.200 mg/kg
Skin-guinea pig LD50:230 mg/kg
Oral-rat L050:1.260 mg/kg
Skin-rabbit LD50:5.000 mg/kg
Neoplastic
Carcinogenic
Teratogenic
Carcinogenic
Carcinogenic
Carcinogenic
Carcinogenic
fleoplastic
Irritant
OSHA std(air)
TWA 50 ppm (skin)
00
'.0
-------
'!'rlbZe ::., ((.'cllltillllCdJ
TOXICITY DF (!.'?G/IIVTC COMPOUNDS
FIXE CHEMICALS INC._,- COAS1'IIL TANK LINt::;, AND CST, INC.
1.0
a
Compound /lame
Molecular
Formula
Exposu~e
Limitsc
Chemical
Abstracts
Service No.
Aquatic Toxicitya Route of
Entry - Species
Other 'Toxicity Oatai>
Type of. Dose
Dose
Duration
Effects
Ether, Bis C4H8C120 111-44-4d,e,g
(Z-ch1oroethyl)
Ether, Diphenyl C1ZH100 101-84-8e
Ethylene, Tetra- C2C14 127-18-4d,g
chloro-
Ethylene, Trichloro C2HC13
Ferric chloride
FeC13
79-0l-6,4:e,g
7705-08-0
TLm96: Ora l-ra t
1,000-100 ppm Inhalation-rat
Ora l-mouse
Skin-rabbit
Skin-guinea pig'
Ora 1-ra t
TLmg6:
100-10 ppm
I nha 1a t ion-human
I nha 1a ti on-man
Inhalation-man
Inhalation-rat
Inhalation-rat
Intraperitoneal-mouse
Ora 1-dog
Intravenous-dog
Oral-cat
Oral-rabbit'
Subcutaneous-rabbit
TLmg6:
1,000-100 ppm
Ora l-huma n
I nha 1 ation-human
Inhalation-man
Oral-rat
Inhalation-rat
Ora I-mouse
Inhalation-mouse
Intravenous-mouse
Ora 1-dog
Intraperitoneal-dog
, Intravenous-dog
Inhalation-rabbit
Subcutaneous-rabbit
Ora 1-ra t
Ora I-mouse
Intraperitoneal-mouse
LD50:75 mg/kg
LCLo:l,OOO ppm
TDLo:33 gm/kg
LD50:720 mg/kg
LD50:300 mg/kg
LD50:3,370 mg/kg
TCLo:230 ppm
TCLo:280 ppm
TCLo:600 ppm
LCLo:4,OOO ppm
LCLo:4,OOO pprn
LD50:5,671 mg/kg
LDLo:4,000 mg/kg
LDLo:85 mg/kg ,
LDLo:4,OOO mg/kg'
LDLo:5,000 mg/kg
LDLo:2,ZOO mg/kg
LDLo:857 mg/kg
TCLo: 160 ppm
TCLo:110 ppm
LD50:4,920 mg/kg
LCLo:8,DOO ppm
TDLo:135 gm/kg
LCLo:3,OOO ppm
LD50:34 mg/kg
LDLo:5,860 mg/kg
LD50:l,9DO mg/kg
LDLo:150 mg/kg
LCLo: 11 ,ODD ppm
LDLo:l,80D mg/kg
LD50:900 mg/kg
LD50:440 mg/kg
LD50:68 mg/kg
2H
lor1
83M
8H
4H
27WI .
2H
4511
79 WIC
OSHA std(air)
C1 15 ppm(skin)
Carcinogenic
4H
4H
Systemic
Eye
Cen tra 1
Nervous
Sys tem
Centril I
Nervous
System
I rri tallt
OSHA std(air)
TWA 1 ppm
OSHA std(air)
TWA 100 ppm;
C1 200; pk
300/5M/3H
NIOSH recm std
(air)
OSHA std(air)
- TWA 100 ppm; C1 200;
Pk 300/5M/2H
NIOSH recm std (air)
TWA 100 ppm; -
150/1 Of1
Carcinogenic'
..
DTL VS
TLV (air) 1 mg/m3
as (Fe)
-------
T(JX'! C:.l ~!ry OF (1f~'(;.' ;jl! C ,.'O:':/!Jc)UiJiJ.(;
Fl;:'-: ('/!l.:'.:l"C/1!/; Ii/C..J C(J.'1!.;'~L':1T, ": i:'f.!: I:l:':'!-.:.~:, ..iil'/J (.',','7', L'N',
- -, - ----- ----_.---------". --- -.--.,.- ---- Datal> . ------..----.---.
Chelllical .Other Tox.i£!J:X Exposure
Compound 1Iallle '.101 ecular Abs trac ts Aquatic ToxicityU Route of - Spccies Type of. Dose Duration Effects L ill1i tsC
Fonllllla Service No. Entry Dose
lIeptyl alcohol C711160 111-70-6 Ora l-I"a t LD50:3,250 ug/kg
Ora 1-rnouse LD50:1,500 mg/kg
Oral-rabbi t LD50:750 rng/kg
lIexallcic Acid, , C8H1602 149-57-5 Oral-rat LD50:3,000 mg/kg
2-ethyl- Skin-rabbit LD50:1,260 mg/kg
l-llexanol, 2- C8111 :\0 104-76-7 Oral-rat LD50:3,200 mg/kg
e thy 1- Ora l-mouse LDLo:3,200 mg/kg
Skin-rabbit LD50:Z,380 mg/kg
Iron(2+) Fe 7439-89-6 Intraneritoneal-mouse LD50:26 mg/kq
I ron( 11) FeC1Z 7758-94-3
Chloride (1 :2) Intraperitoneal-mouse LD50:59 Il1g/kg
'\
Isothiocyanic Acid, C7H5NS 103-72-0 Oral-mouse LD50:400 mg/kg
phenyl ester Intraperitoneal-mouse LD50: 1 00 m9/kg
(Phenyl isothiocyanate
Lead Pb 7439-92-1d OSHA-std(air) 3
HJA 200 I,g/m
NIOSH recm std
(a i r) HIA
150 "g (Pb) m3
Lead Chloride PbC12 7758-95-4 Oral-guinea pi" LDLo:2,000 mg/kg OSHA~std(air) 3
Intravenous-hamster TDLo:50 mg/kg (8D preg) Teratogenic TWA 200 ug(Pb)/m
tlI OSH reclII s td
(air) THA
150 pg (Pb)/m3
t1a 1 ona 1 dehyde, CllH2404 122-31-6 Oral-rat LD50:1,610 mg/kg
Bis'(rHethyl /Iceta 1) Intraperitoned1-mouse LDLo:200 109/kg
(1,1 ,3,3-Tetraethoxy-
propane)
Methane~ Dichloro- CH2C12 75-09-2d,e TLm96: Inhalation-human TCLo:500 ppm lYI Central OSHA s td (a ii')
1,000-100 ppm Nervous HIA 500 pprn; C
Systern 1,000; Pk 2,000/
5r'I/2H
Inhalation-human TCLo:500 ppm 8H Blood NIOSH recm std
Oral-rat LD50:2,136 mg/kg
Intraperitoneal-mouse LD50:1,500 mg/kg (air) HJA 75 pplll:
Subcutaneous-mouse LD50:6,460 mg/kg Pk 500
Oral-dog LDLo:3,000 mg/kg 1.0
Intraperitoneal-dog LDLo:950 Ilig/kg ......
Sllbcu ta ncvuS -dog LlJLo:2,700 mg/kg
Intravenous-dog LDLo:200 Il1g/kg
Ora l-rabb i t LDLo:l,900 mg/kg
SnbC11 t.lnr,oIIS -".lbbi t LlJLo:Z,700 Il1g/kg
Ildlnlill i"II-'lIlin";, pin 1 CI I): f,. nno 111'111 211
-------
1.0
N
TaMe 23 (ConUmwdJ
TOXICL1T Of OIlGN/IC COMPOUNDS
FIKE ClIEMICALS INC., COASTAL TANK LINES, AND CST, INC.
Compound Name
Chemical
Abs tracts
Service No.
Effects
l-101ecu1ar
Fonnu1a
Naphthalene
91-20-l,e
C10Ha
Naphthalene, Cl]H1O 1321-94-4
methy1-
l-Naphtho1 C1OHaO 90-15-3
3-Penten-2-one, C6H100 141-79-7
4-methy1-
(Hesity1 oxide)
Phenanthrene
C14H10
as-OJ-ad
Aquatic ToxicityG Route of - Sp cies
Entry e
Other Toxicity Oatab
Type of
Dose: Dose
Exposure
limitS'
Duration
TLm96:10-1 ppm Oral-child LOLa: 100 mg/kg OSHA s td (a i r)
Oral-rat L050:1,780 mg/kg TWA 10 ppm
Subcu taneolJs -ra t TOLo:3,500 mg/kg 9801 Neoplastic
Intraperitoneal-mouse LOLa: 150 mg/ kg
Oral-rat L050:4,360 mn./kg
Ora 1- ra t L050:2,590 mg/kg
Skin-rabbit L050:880 mg/kg
TLm96: Ora 1- ra t L050:1,120 mg/kg OSHA std(air)
100- 10 ppm I nha 1 a t i on-ra t LCLo:1,OOO ppm 4H TWA 25 ppm
Intraperitoneal-rat LOLo:1,OOO m9/kg
Intraperitoneal-mouse L050:354 mg/kg
Oral-rabbit L'050:1,OOO mg/kg
Skin-rabbit L050:5,990 mg/kg
Ora 1-mouse L050:700 019/kg
Skin-mouse TOLo:?l mg/kg Neoplastic
Ora l-human TOLo: 14 mg/kg' Gastrointes- OSHA std(air)
tina1 trac t TWA 5 ppm( sk i n)
Ora 1-human LOLo: 140 mg/kg
Ora 1-ra t L050:414 mg/kg
Skin-rat L050:669 mg/kg
Intraperitoneal-rat L050:250 mg/kg
Subcutaneous-rat LOLo:650 mg/kg
Ora 1-mouse L050:300 mg/kg
Skin-mouse TOLo:4,OOO mg/kg 20WI Carcinogenic
Subcutaneous-mouse L050:344 mg/kg
Subcuta neous -ca t LOLo:80 mg/kg
I ntr. '/enous-ca t LOLo:50 mg/kg
Ora 1-rabbit LOLo:420 mg/kg
Skin-rabbit LOLo:2,OOO mg/kg
Intraperitoneal-rabbit LDLo:620 mg/kg
Subcu taneous-ra bb it LOLo:620 mg/kg
Intravenous-rabbit LOLo: 180 mg/kg
Intraperitonea1-guineapig LOLo:300 mg/kg
Subcutaneous-guineapig LOLo:450 mg/kg
Parentera 1-frog LOLo:290 mg/k9
Phenol
C6H60
1 08-95-2d, e,f'!frLm96:
100-10 ppm
-------
'I'abl" ~,) (r:(mthZllfJd)
'i'OXIC17'Y 01-' Wi'r.1I1! I C CO,'.j!'OUNDS
FIKF: C/IEMICIIJ,S INC., COIISTIIL TIINK LTNE:S, IIND CST, JNC.
Chemical Aquatic Toxicitya Other Toxicity Data IJ Exposure
Compound Name Molecular Abstracts Route of - Species Type of. Dose Duration Effects L imi tsf!
Forlllula Service No. Entry Dose
Phenol, p- C9H120 99-S9-S Intraperitoneal-mouse LDLo:250 mg/kg
i sopropy1-
(4-lsopropy1 Phenol)
Phenol, 4,1]' - C13H1202 620-92-S Oral-rat LD 50:4,950 mg/kg
r1ethy1 enbi s-
(Methylene dipheno1
isomer)
Phosphoric acid, C12H2704P 126-73-S Oral-rat LD50:3,000 mg/kg OSHA s td (a i r)
Tri butyl es ter Intraperitoneal-mouse LDLo:63 mg/kg TWA 5 ppm
(Tri -n-butyl phosphate)
Phthalic acid, C16H2204 d TDLo: 140 mg/ kg Cen tra 1 OSHA std(air~
84-74-2 TLm96: Oral-human
dibutyl ester 1,000-100 ppm Nervous TWA 5 mg/m
(Di-n-buty1 phthalate) System
Intraperitoneal-rat LD50:3,050 mg/kg
Intraperitoneal-rat TDLo:S74 mg/kg (5-15 D preg) Teratogenic
2-Pico1ine, CSH 11 N 104-90-5 TLm96: Oral-rat LD50:1,540 mg/kg
5-ethy1- 1,000-100 ppm Skin-rabbit LD50:1,000 mg/kg
l-Propanol, C4HllNO 124-6S-5 C.-a 1-rabbi t LDLo:l,OOO mg/kg
2-ami no-2-
r~ethy1-
Pyrazine, 2,5- C611SN2 123-32-0 Intraperitoneal-mouse LD50:1,350 mg/kg
Dimethyl-
Quinoline C9H7N 91-22-5 Oral-rat LD50:460 mg/kg
Intraperitoneal-mouse LDLo:64 mg/kg
Sk in-rabbit LD50:540 mg/kg
Silver Ag 7440-22-4d Inhalation-human TCLo: i mg/m3 Skin OSHA std,(<1ir)3
Imp 1 ant-ra t TDLo:2,400 mg/kg Neoplastic TWA 10 pg/11l
Styrene CSHS 100-42-5e,g , OSHA std(air)
TLm96:100-10 ppm Inhalation-human LCLo:10,000 ppm 30r~
Inh<11ation-human TCL:o:600 ppm Irritant nvA ] 00 ppm;
Inh<11ation-human TCLo:376 ppm Cen tra 1 C1 200;
Nervous Pk 600/5NI3H
3 . System
I nha 1 <1 t i on-l'lOman TCLo:20 mg/m G1andu1Jr
Ora 1-rat lD50 :5,000 1IIr./kg
[nha1<1tion-rat lClo: 5 .ono prH~ u:>
(h-a l-lIlouse LD50:316 II1{J/kg w
Inh<1l<1tion-mouse lClo: 1 0,000 ~pm
Inh<11ation-guinca pig lClo:12 911l/m 1411
-------
Table 23 (Continued)
TOXTCITY OF ORGANIC COMPOUNDS
PIX"" ClIEro/ICAL,'] INC., COAS'i'/IL TANK LINES, AND CST, INC. 1.0
~
Chemical Other Toxicity Datab . Exposure
Compound Name Molecular Abstracts Aquatic ToxicityQ Route of - Species Type of. Dose Duration Effects L imitsC!
Formula Service No. Entry Dose ..
Toluene-2,4- C7H10N2 95-80-7g Oral-rat LDLo:5DO mg/kg
Diamine Oral- -at TDLo: 11 gm/kg 36HC Carcinogenic
(2,4-Diaminotoluene) Unreported-ra t LDLo:50 mg/kg
Subcutaneous-dog LDLo:200 mg/kg
Unreported-dog LDLo:350 mg/kg
Unreported-rabbit LDLo:400 mg/kg
Unreported-guinea pig LDLo:200 mg/kg
Toluene-2,5- C7H10N2 95-70-5 Oral-mammal LDLo:3,600 mg/kg
Diamine
(Diamino toluene isomer)
Toluene, o-Ethyl- C9H12 611-14-3 Oral-rat LDLo:5,000 mg/kg
Toluene, p-Ethyl- CgH12 622-96-8 Oral-rat LDLo:5,000 mg/kg
o-Toluidine C7HgN 95-53-4 Oral-rat LD50:900 mg/kg OSHA .std(air)
Oral-rat TDLo:8,200 mg/kg 24 ~JI Neoplastic TWA 5 ppm(skir
Oral-mouse TDLo:870 gm/kg 78 HC Neoplastic
Intraperitoneal-mouse LD50:150 mg/kg
Ora l-cat LDLo:300 mg/kg
Sk in-rabbit LD50:3,250 mg/kg
Oral-frog LDLo:5 mg/kg
Urea, N,N'- C5Hl thS 105-55-# Intraperitoneal-mouse LDLo:500 mg/kg
Di ethylth i 0-
Urea, 1,1,3,3- C5H12N20 632-22-4 Ora l-mouse L050:2,920 mg/kg
Tetramethyl- Intravenous-mouse LD50:2,230 mg/kg
Xylene C8H10 1330-20-7 TL~196: 1 00-1 Oppm Inhalation-human TCLO:200 ppm I rrita nt OSHA (air)
Oral-rat LD50:4,300 mg/kg TlIA 100 ppm
Intraperitoneal-mouse LDLo:2,OOO mg/kg NIOSH recm std
( air) HIA 1 00
ppm
m-Xylene C8H10 108-38-3 Oral-rat LD50:5,OOO mg/kg NIOSH recm std
Inhalation-rat LCLo:8,OOO rrm IIH ( air) TWA 1 00
Intrareritoneal-rat LDLo:2,OOO mg/kg ppm
Subcutaneous-rat LDLo:5,OOO mg/kg
p-Xylene C8HlO 106-42-3 TLM96:100-10 ppm Oral-rat LD50:5,OOO mg/kg NIOSH recm std
Intraperitoneal-rat LDLo:2,OOO mg/kg . (a i r) TWA 1 00
Subcutaneous-rat LOLo:5,OOO mg/kg ppm
Inhalation-mouse LCLo:3,460 ppm
-------
Tal.Le
23 (Coni;O n:.l(!J)
TGXfCI'1'l' ;")F OJi'GIIN.l C ('O:',:F('~:.r:DS
rIKE CHEMICALS INC.. (Y)I1STt!I~ T/1NK U::r::;. 11'/[J CST, mc.
;1 !i!,' ::'/','!I.f/ 1 'j'J()i;:;
(per /legistry of Tox'~c E:ffee/;s of Chc::lical Substances - NIOSlJ)
a
Aquatic To:cici ty:
96-ho/.ll' G tI1t1'..., 01' COIl UIIIIIJ//G j'lOL' tJ tm/d'lrd Pl'o toeol. ill /.'Ill't:; pel' mi II ion (p['nI)
'l'Lm!J6 :
b
Other 1~xicity Data
LD,sO - lethal dose ,so:' k.~ll
LCLo - lOLlest publish.,': lethal ee';ecntl'atio>J
LC50 - lethal concent)',/,tiol! 5(};~ /dlL
LDLo - lOLlest publish-9rl let/wl dDDC
TDLo - lOuJest published to:dc dose
TCLo - lOLlest published toxic cOilcentJ'at1:on
TD - toxic dose
M - minute; H - haul'; /) - day; II - Lleck; Y - year
I - inteJ'mittent
C - continuous
c
EX[Josw'e Limits:
Nit' - not repol'tcd
NTOSH - Niltional fm:t'U:>de j'or' Decupo!:ioHf1l Sr.fptll.
-------
96
can cause adverse reactions in people, modified by individual suscepti-
bility in terms of specific adaptation. Adverse reactions, which are
manifested in a wide variety of physical and mental symptoms, are
often chronic in nature and cyclic in occurrence, producing conditions
which are frequently undiagnosed or poorly identified. Interpretation
of the clinical ecological effects of data in Tables 15 through 20 is
difficult and beyond the scgp~ of this report, but may be found in
"Clinical Ecology."2
One of the most critical aspects of this study to emerge is that
the effects of long-term exposure to anyone or exposure to the whole
spectrum of one hundred thirty-seven compounds identified are unknown.
.
It has been determined' that seventy-two of these compounds have
identified toxic properties. Additionally, twenty-six more of the one
hundred thirty-seven compounds are closely related isomers whose
toxic properties would be similar to those identified. Thus, 60% of
the compounds identified have known toxic effects.
Table 23 summarizes the number of reported toxic doses or concen-
trations to various organisms of the chemicals identified and the
effect produced as given in the 1976 edition of the "Registry of
Toxic Effects of Chemical Substances, II published by the U. S. Depart-
ment of Health, Education, and Welfare. Of particular interest is
the fact that thirteen of these compounds have known carcinogenic or
. neoplastic effects and five have known teratogenic or mutagenic
properties. Twenty-two compounds have known aquatic toxicities
, .
ranging from 1 to 1,000 ppm. Nineteen compounds are on the EPA
Priority Pollutant list. Eleven are EPA selected as a priority point
source pollutant. Three are EPA pesticide candidates for additional
onicological testing. Numerous other effects such as on the central
nervous system, blood, or glandular involvement are given. A total
of three hundred seventy-five individual pieces of toxicity data are
reported for the seventy-two chemicals listed. How~ver, important
-------
97
considerations remain unknown regarding these 375 reports. Most of
the toxic dosage and lethal dosage studies were of short duration,
using relatively high concentrations of the substances investigated,
and, importantly, the toxic and lethal effects of each substance were
evaluated on an individual basis. Virtually no reports are available
concerning long-term effects of exposure to most of the substances
identified and data are not available on the combined effects of
exposure to this wide spectrum of toxic substances.
Only thirty-seven of the one hundred thirty-seven chemicals
identified occurred in the CST effluent during this survey.
Additionally, seven organics and six heavy metals were identified in
the monitoring wells. Thus, a total of fifty chemicals were identi-
fied as actually occurring in ground or surface waters. The specific
emphasis of this report, then, is directed toward those fifty chemicals.
However, it is quite logical to presume that most of the one hundred
thirty-seven chemicals identified will, at one time or another, be
discharged to surface water or seep into groundwater or both. Certainly,
the fifty chemicals identified are sufficient to demonstrate the
exceptionally toxic nature of these discharges.
The most general observation of a toxic nature that can be made
with regard to the thirty-seven organic chemicals discharged from CST
[Tables 16, 17 and 18J as well as all the other organics identified
[Tables 15, 19 and 20J, is that none of these compounds represents
normal human metabolites. They are all of industrial origin.
A review of Table 23 shows such a wide variety of toxic effects
that it is likely that many of these compounds are foreign and inhibi-
tory to the metabolism of organisms normally found in biological
treatment systems, to organisms inhabiting receiving waters, and to
organisms drinking such waters. The fact that there are wide variations
in loadings results in slugs of these toxic chemicals, which may
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98
further complicate the abilities of organisms to adjust their
metabolic processes to accommodate them.
Seventeen of the thirty-seven organic chemicals discharged from
the CST to the Kanawha River have known toxic effects. All seventeen
compounds were discharged at levels below their immediate thresholds.
This is to be expectedt particularly since acute effects could be
immediately noticeable both in CST plant operation and in the Kanawha
River.
What is of much greater concern is the unrelenting .hazard of a
continuoust subacute discharge from CSTt particularly since the
receiving waters are a source of downstream drinking water supplies.
The hazards of ingesting minute amounts of chemical pollutants in
drinking water over long periods of time are difficult to evaluate.
Chronic exposure to a low dose often results in irreversible toxicity.
Today, more than 300 specific organic chemicals have been identified
in various drinking waters and a recent EPA report, "Monitoring to
Detect Previously Unrecognized Pollutants in Surface Waters" (EPA
560/6-77-015 and 015A) lists over 200 compounds from surface drinking
water supplies taken near heavily industrialized areas. Most of the
37 organic chemicals discharged from CST do not occur on either of
these lists and so represent new compounds to be added to the growing
list of chemicals found discharged to surface water supplies in the
United States. Howevert 5 of the compounds discharged from the CST
have been reported in Cincinnatit Ohio, drinking water.ltll Those
are carbon disulfide, chloroformt carbon tetrachloride, trichlor-
ethylene and 3t3,5-trimethyl-2-cyclohexenonet also known as Isophorone.
Isophorone occurred in the Cincinnati drinking water at about 1/4tOOOth
the level discharged from CST.
From the standpoint of adverse health effects, the most serious
concern is that 9 of the 13 carcinogens identified in this survey are
discharged from the CST to the Kanawha River. These were anthracene,
.~
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99
biphenyl, chloroform, carbon tetrachloride,
diamylnitrosamine, phenanthrene, phenol and
these, chloroform and carbon tetrachloride,
Cincinnati drinking water.l,ll
dimethylnitrosamine,
o-toluidene. Two of
were reported in the
For the residents of communities afflicted with waterborne car-
cinogens, the low-level expqs~res Qecome a day-in and day-out, una-
bating series of cellular insults, and there is much evidence that
cancer risk increases with length of exposure. A statistical relation-
ship between cancer mortality and drinking water contaminated by or-
ganic chemicals for populations consuming water from the Mississippi
and Ohio Rivers has been demonstrated.3,4,5,6,7,S So far, it has not
been possiQle to determine any level of exposure to chemical carcino-
gens that does not present some risk of cancer no matter how small
the concentration over a long period of time. For example, a miniscule
risk factor of 0.001% of 7,000,000 people in a metropolitan area
means that for 70 people, there is a 100% risk of cancer. In brief,
there are no proven tnreshold values below which the compounds are
not carcinogenic.9'lo,ll,l2,l3'l4
This being the case, it is only wise and prudent to seek to
minimize the discharge of any carcinogen to drinking water supplies,
and, if at all possible, eliminate it entirely so that no one is at
ri sk.
All of the above comments certainly apply to the groundwater
contamination occurring from the evaporation pond as determined from
the monitoring wells samples, which were analyzed for both organics
[Table 20J and heavy metals [Table 21J. Twenty of the organics
detected have known toxic effects [Table 23J; ten have known carcino-
genic effects; and one is a teratogen. Six of the organic compounds
detected in the monitoring wells, carbon disulfide, carbon tetra-
chloride, chloroform, dichloromethane, tetrachloroethylene, and
-------
100
trichloroethylene, have also been detected in Cincinnati drinking
water. I 'II Seven of these organic chemicals, bis (2-chloroethyl)
ether, bis (2-chloropropyl) ether, n-decane, o-dichlorobenzene,
napthalene, n-nonane, and tetrachloroethylene have been reported in
the New Orleans drinking water supply. I Ten other chemicals --
p-diethylbenzene, n-dodecane, m-ethyl toluene, p-ethyl toluene,
o-ethyl toluene, methyl nap~t~alen~, tetramethyl benzene, tridecane,
triethyl benzene, and n-undecane -- have been reported in various
drinking waters in the United States.I'IO'II'12'15
Four of the six heavy metals (arsenic, barium, cadmium, and
lead) detected in the evaporation pond and the groundwater [Table 20J,
are of particular concern. The method of chemical analysis used.does
not permit determination of metal salts or organic complexes. However,
total chloride was determined and these metals could reasonably be
expected to form chlorides under the condition sampled. For this
reason, chlorides of these heavy metals were selected for the toxicity
data listed in Table 23 even though other salts are known to be more
toxic.
The toxicity of arsenic depends greatly on the chemical form,
the rate, and the duration of exposure. It is not known to be essential
to humans, nor are there any known beneficial effects from its ingestion
in any form. Certain arsenic compounds are absorbed by the gastroin-
testinal tract, the lungs, and the skin, and become distributed
through body tissues and fluids. Considerable portions are retained
at low intake levels with slow excretion. Arsenic can accumulate in
bones, muscles, skin, and human hair. Inorganic arsenic is an enzyme
inhibitor (SH enzymes). Arsenic poisoning may have latent effects as
well as exhibiting progressive increasing toxicity; the symptoms of .
which are fatigue, loss of energy, impairment of gastrointestinal
function, neurological disturbance, kidney and liver dysfunction, and
skin trouble.16'17'18 The maximum contaminant level (MCL) in drink-
ing water permitted for arsenic is 0.05 mg/l. The highest level
detected in the groundwater was 0.04 mg/l [Table 21J.
-------
101
Barium is not essential to human health.
Soluble barium salts
are very toxic. Ingestion of soluble barium compounds may affect the
gastrointestinal tract, the central nervous system, the muscles,
including the heart, and the blood vesse1s.16'17'18 The MCL in
drinking water for barium is 1 mg/1. The maximum level detected in
this survey was 0.60 mg/1,
Cadmium is not known to be essential or beneficial to human
health. Critical concentrations vary from one individual to another.
Both zinc and calcium, which are essential elements, may protect
against cadmium toxicity. Persons deficient in these elements may
constitute a high-risk group in terms of cadmium toxicity. Cadmium
poisoning causes intense pain because of a loss of bone minerals and
consequent softening of the bone. Studies in humans as well as
animals indicate that, after ingestion, cadmium also is absorbed into
body tissues and then stored mostly in the kidneys and liver and is
excreted at an extremely slow rate.16.17.18 Cadmium has demonstrated
carcinogenic effects [Table 23]. The MCL for drinking water is 0.01
mg/l. The highest amount detected in this survey was 0.05 mg/l, five
times the maximum contaminant level permitted.
Lead has no known beneficial or nutritional effects.
Lead tends
to accumulate in human and animal tissues. The major toxic effects
of lead include anemia. neurological dysfunction. and liver and
kidney impairment. Biochemically, lead seems to interfere with
certain enzyme activities, such as those that help in the production
of red blood cells. Although seldom seen in the adult population,
irreversible brain damage is a frequent result of lead poisoning in
chi1dren.16'17'18 Lead has demonstrated carcinogenic effects
[Table 23]. The MCL for lead in drinking water is 0.05 mg/l. The
highest amount detected in this survey was 0.9 mg/1, eighteen times
the maximum contaminant level permitted.
-------
IX.
MUTAGEN TESTING
Analyses for mutagenic activity were performed on two 24-hr
)
flow-proportional composite samples collected October 7 and 8, 1977
from the CST effluent. The purpose of the tests was to determine the
potential carcinogenicity of the wastes.
The Standard Ames Bacterial Assay* for mutagenicity showed
positive results with standard Salmonella tester strain TA 1535,
indicating the presence of potential carcinogens in the CST waste-
water. The Ames test for mutagenicity consists of specially de-
veloped strains of Salmonella typhimurium that have a nutritional
defect which requires that the amino acid, histidine, be supplied for
growth. If these bacteria are subjected to a carcinogenic substance,
they will mutate and regain the natural ability to synthesize this
amino acid. Thus, mutant colonies can be detected on media which
does not contain histidine.
Concentrated aliquots of CST effluent were screened for muta-
genic activity using four tester strains, TA 98, TA 100, TA 1535 and
TA 1537. All of the tester strains failed to show evidence of induced
mutation. However, many carcinogenic compounds must first be converted
metabolically into an active substance before cancer is induced. The
Ames test employs microsomal rat liver preparations as a source of
activating enzymes.
*
Ames, B. N., McCann, J., and Yamasaki, E., IIMethods for
Detecting,Carcinogens and Mutagens with the Salmonella/
Mammalian-Microsome Mutagenicity Test,1I Mutation Research, 31
(1975) 347-364.
-------
104
When the CST sample extracts were treated with the rat liver
preparation, Salmonella tester strain TA 1535 showed obvious muta-
genic activity. Table 24 shows the equivalent volumes of effluent
and the resultant mutagenic effect on tester strain TA 1535 for
samples collected on October 7 and 8, 1977. Both samples exhibited
similar results. In the case of Sample 1, volumes causing muta-
genesis ranged from 1.20 to 4.20 ml. Sample 2 displayed mutagenic
activity between 0.75 and 2.25 ml of effluent. All extracts tested
between these two ranges for the two samples exhibited a mutagenic
activity ratio* greater than 2.5. The mutagenic activity ratio is a
measure of the tester strain mutation rate compared to control rates.
A ratio of 2.5 or higher indicates, with greater than 90% probability,
that the substance could induce tumors if administered to laboratory
animals.2,3 The mutagenic effects of effluent volumes greater than
4.20 and 2.25 ml for Samples 1 and 2, respectively, could not be
measured due to bacterial toxicity of the samples.
Further testing showed a typical dose/response relationship
[Figures 7 and 8] between the tester strain and each sample, illustrat-
ing an increasing number of revertant colonies with increasing concen-
trations of extract. Within the range of 1.2 to 4.2 ml, CST extracts
of Sample 1 induced revertant colonies ranging from 65 to 189. The
optimum concentrations causing maximum reversions occurred at 1.80 ml
of effluent. Volumes of extract greater than 1.8 ml resulted in
bacterial toxicity and a consequent decrease in the reversion rate.
Sample 2 displayed a similar pattern; the optimum concentration of
extract producing maximum reversion rates occurred at 2.25 ml.
Complete bacterial toxicity resulted at concentrations of 4.50 and
2.70 ml for Samples 1 and 2, respectively.
*
E-C
The mutagenic activity ratio is defined as -c- where E is the
of mutant colonies per plate with the samele added, C is the
corresponding value for the control, and C is the average con-
trol value for 100 or more tests.
-------
105
Table 24
MUTAGENIC ACTIVITY OF CST INC. ~ EFFLUENT EXTRACTS
ON SALMONELLA TESTER STRAIN TA 1535a
October 7 and 8~ 1977
Equiv. V'olume No. relevant colonies.
Sample Date Sample PEr plate Mutagenic Aativity
No. (1977) m1 Control Experimenta1C Ratio
1 Oct. 7 0.02 20 15 <1.0
0.15 " 20 21 <1.0
0.45 20 61 2.0
0.75 20 65 2.1
1.20 20 90 3.3
1.35 20 110 4.3
1.80 20 189 7.6
2.10 20 164 6.9
2.40 20 132 5.3
2.70 20 139 5.7
3.00 20 101 3.9
3.20 20 101 3.9
3.60 20 101 3.9
4.20 20 109 4.2
4.50 20 0 toxice
7.50 20 0 toxic
11.30 20 0 toxic
15.00 20 0 toxic
Oct. 8 0.15 20 16 <1.0
0.38 20 22 <1.0
0.75 20 88 3.2
1. 12 20 97 3.7
1.50 20 95 3.6
1.88 20 96 3.6
2.25 20 122 4.9
2.70 20 0 toxic
3.00 20 0 toxic
a Mutagenic effect on strain TA 1535 in the presence of J:'at liver
activating enzymes.
b Average of six plates.
c Average of two plates. E C
d Mutagenic Activity Ratio = -:- ~ UJhere:
c
E is the no. of colonies/experimental plate
~ is the no. of colonies/control plate
~ is the historic control value averaged
over 100 tests
e Toxic to test strain.
-------
.......
a
0"1
200
CD
-
a
A.
-...
'"
CD
II:
0 150
0
v
-
iii
a
-
..
CD 0
:I>
CD 100 CI
a:::
- 0
o
..
CD
.a
E
D
Z 50
o
()
o
I 1 ~O
o
~
5.0
6~0
3.0
4.0
2.0
ml of Extract (Sample 1)
Figure 7. CST Effluent Extract JO-7-77 Dose Response Curve
-------
200
CD
-
a
D.
........
'"
CD
c 150
0
0
v
-
c
a
-
..
CD
> 100-"
CD . .
ar:: 8
-
0
..
CD
..a
E
~ 50-
::z
o
o
1.0
2.0
3'.0
4'.0
5'.0.
6.0 ;
ml of Extract (Sample 2)
,
\
\
\
\
Figure 8. CST Effluent Extract 10-8-77 Dose Response Curve
a
"
-------
108
DISCUSSION
The Standard Ames test determines bacterial mutagenicity; an
activity which correlates closely (with greater than 90% probability)
with inducement of cancer in laboratory animals by organic compounds.
Results of the Ames Bacterial Assay for mutagenesis clearly show that
CST effluent samples contain potential carcinogens. Concentrated
extracts collected from the CST effluent satisfy both requirements
for determining if mutagenic and/or potential carcinogenic substances
are present. These are: 1) the material must demonstrate a muta~
genic activity ratio of 2.5 or greater, and 2) the material must show
a typical dose response relationship, i.e., the substance causes
increasing numbers of mutations with increasing doses of material
over optimum volumes (usually the curve will decline at the point of
toxicity).
-------
x.
WASTEWATER TREATABILITY STUDY
The data from the NEIC survey [Tables 5, 6, 16, 17, 18] show
that the materials contribu}iD9 to, the toxicity of the CST effluent
include complex organic materials and heavy metals. Treatment
processes required to remove these components would include carbon
adsorption of the complex organic materials and precipitation of the
heavy metals at an elevated pH. The cyanide [Table 5] exists as a
complex (probably with iron) which is not toxic to fish in the con-
centrations detected. These methods were evaluated in the NEIC
laboratory [Appendices I and J] on a 24-hour composite sample col-
lected from the CST effluent on October 7* to determine if the treated
wastewater would comply with the NPDES permit limitations and if the
aquatic toxicity could be reduced or eliminated.
ACTIVATED CARBON ADSORPTION
A carbon isotherm study was conducted to determine the effective-
ness of activated carbon in reducing the complex organic materials.
The results [Table 25] show that the complex materials can be removed
by adsorption on activated carbon. The data also show that the
carbon will remove only about 30% of the total organic materials, as
represented by the total organic carbon (TOC). Since activated
carbon is particularly effective in removing high molecular welght
materials, but not as effective for low molecular weight materials,
*
Aliquots of the 24-hour composite sample collected for the
bioassay were placed in I-gallon amber glass bottles with
teflon-lined lids, stored at 4°C, and transported to the NEIC
laboratory at the conclusion of the survey. The samples were
not preserved during the 24-hour collection period.
-------
-'
-'
a
TabZe 25
POLLUTANT REDUCTION AS A FUNCTION OF CARBON CONCENTRATION
CST~ INC. EFFLUENT
October 7~ 1977
Pa rameter
o
Dosage of Powdered Activated Carbon
200
1 ,000
(mg/l)
7,000
20,000
Cyclohexylamine
2,5 Dimethylpyrazine
Aniline
Phenol
Propyl butyl Thiourea
N,N' Diethyl Thiourea
Total Organic Carbon (TOC)
38
23
7.2
4.0
7.6
29
960
Total Suspended Solids (TSS)
Before
Filtration
125
41
23
7.0
4.0
4.4
29
940
31
19
5.6
2.6
2.2
19
890
8 3.5
<0.2 <0.2
<0.2 <0.2
0.1 <0.05
<0.3 <0.3
<0.5 <0.5
680 570
After
Filtration
20
-------
111
it is assumed that the CST effluent contains high concentrations of
lower molecular weight organic compounds.
In the laboratory study, the carbon acted as an adsorbent only
and it was not possible to estimate the effect of the biological
activity expected in the CST after powdered carbon was added.
However, it is believed that the powdered activated carbon will
remove the toxic organics and allow the development of an active
biomass in the CST aeration basin which wiJl metabolize the lower
molecular weight, non-toxic organic materials.
HEAVY METAL PRECIPITATION
In the development of the laboratory bench-scale treatabil ity
studies, metals and cyanide were to be removed by increasing the pH
to 10 and chlorinating for cyanide destruction. It was not known at
that time that the cyanide was present as an iron complex. Chlorin-
ation for cyanide removal was eliminated from the study when the
results of the adsorption study demonstrated that only 30% of the
organic materials were removed. Chlorination could have resulted in
the formation of chlorinated hydrocarbons with the remaining organic
materials.
The laboratory study was revised; heavy metal precipitation was
attempted by the addition of the sulfide ion and removal of the
cyanide ion by air stripping at pH 4 [Appendix IJ. The final, treated
wastewater was analyzed [Table 26J and a static bioassay conducted to
determine toxicity [Appendix KJ.
-------
112
..........
Tab Ze 26
LABORATORY BENCH SCALE TREATABILITY STUDY
CHARACTERISTICS OF FINAL TREATED WASTEWATER
(CARBON ADSORPTION~ HEAVY METAL PRECIPITATION~ AND AIR STRIPPING)
CST~ INC.
.october ?~ 1977
Parameter
Concentration
Untreated* Treated
mg/1
Arsenic
Cyanide
Sulfi de
0.37 0.92
1.1 -**
NA*** <0.01
NA 220
NA 7,220 ).Imho
TOC
Conductivity
* See TabZe 5
** Laboratory resuZts indicate that cyanides increased with time~
probably as a result of the decomposition of other compounds.
Cyanide was not appreciabZy affected by treatment provided and
was not toxic in the concentrations encountered~ indicating that
the cyanide ion was compZexed~ probabZy within.
*** NA - Not Analyzed .
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113
TREATABILITY RESULTS
The aresenic concentration in the treated effluent (0.92 mg/l)
was greater than the arsenic concentration in the raw effluent
(0.37 mg/l) [Table 5]. This anomaly cannot be explained. It has
been demonstrated, however, that the arsenic concentration of a
wastewater can be reduced to less than 0.1 mg/l by adjustment of the
pH to 10 and removal of the precipitate formed.
The BOD was not measured during the laboratory study. However,
if the activated carbon allows the development of an active biomass
in the aeration basin, there will be a considerable reduction of the
BOD in the final effluent. As the BOD is reduced, it is probable
that the surfactants will also be reduced by biological degradation.
The adsorption and biodegradation mechanisms will both reduce the
surfactant level, but the degree of reduction cannot be estimated.
Sulfate and ammonia reductions were not determined.
The de-
velopment of a biomass in the aeration basin may oxidize some of the
ammonia to the nitrate ion but this is not predictable. Because
there is a nitrate limitation for the effluent, it does not appear
that compliance with both the nitrate and ammonia limitations can be
achieved without a nitrogen removal process or an in-plant process
modification to reduce the nitrogen input to the CST.
The processes evaluated in the laboratory will not affect the
sulfate content in the wastewaters. A method of complying with the
sulfate limitation is to modify in-plant processes to reduce the
sulfates discharged to the CST.
The carbon isotherm drawn from the data [Table 25] indicate that
a powdered carbon addition rate of 2,000 mg/l will reduce the phenol
3 .
level to 1.4 mg/l which, at a flow rate of 151 m (40,000 gal)/day,
-------
~
114
will comply with the daily average limitation of 0.22 kg (0.48 lb)/day.
The actual amount of carbon required may be considerably less than
2,000 mg/l because of the combined adsorption-biodegradation m~chanisms
occurring in the aeration basin.
The static 96-hour bioassay conducted on the final treated
effluent [Appendix K - SamPle ,III],indicated that the LC50 of the
treated effluent was increased from 2% (raw effluent) to 80%.
RECOMMENDED TREATMENT AND COSTS
The treatment processes recommended for evaluation at the CST
include the addition of 2,000 mg/l of activated carbon to the aeration
basin. Following settling, the pH of the effluent should be raised
to 10 with the addition of caustic, and then well mixed. Laboratory
studies showed that the caustic demand to reach a pH of 10 would be
4 lb/1,000 gal. Heavy metals should be allowed to 5ettle in a part
of the basin currently being used for final sedimentation. A down-
stream part of the final sedimentation basin should be segregated and
acid added to the wastewater as it flows from the settling basin to
adjust the final effluent pH to the permitted range of 6.0 to 8.5.
If necessary, this part of the basin may be mixed by the introduction
of air.
In calculating the capital and chemical costs [Table 27] for the
treatment sequence, it was assumed that the existing CST operating
staff would be able to operate and maintain the additional equipment. .
Information was not available on the amount of acid required to
adjust the pH to the 6.0 to 8.5 range, therefore this was not included
in the cost. It is believed that the size of the facility does not
justify the installation of automatic control equipment, therefore
this was not included in the cost estimate.
-------
115
Table 27
COST ESTIMATE OF RECOMMENDED TREATMENT
CST, INC.
*
CAPITAL COST
Carbon Make-up Tank:
FRP Tank, 6 ft dia. x 5 ft high
1/4-inch shell with 3-inch top
fl ange
$ 833
Mixer for Carbon Tank:
1 Horsepower Lightnin' Model
NDCA-Clampmount
945
Carbon Slurry Feed Pump:
Chemcon Simplex Model A 52-50
(316 SS)
959
Mixer for R~pid Mix Tank:
Li ghtni n I Mi xer
(after caustic addition)
392
Caustic and Acid Addition Pumps:
Chemcon Duplex Pump
Model A 52-50
To ta 1
1 ,500
$4,629
Activated Carbon:
**
CHEMICAL COST
2,000 mg/l dose, 40,000 gpd @ $0.35/1b
To ta 1
$233
13
$246
Caustic:
160 1b/day @ $0.0825/1b
* The description of commercial equipment does not imply endorsement
by the EPA.
** The carbon addition rate ~as calculated as that being necessary to
reduce the phenol concentration to 1.4 mg/l. The chemical cost
does not include the cost of the acid required to return the pH to
the 6.0 to 8.5 range specified in the NPDES permit because quantita-
tive information ~as not available. .
-------
116
Because the cost of the activated carbon is a major portion of
the overall cost and because the -amount of carbon required cannot be.
accurately determined without pilot or full scale testing at the
site, a precise cost estimate cannot be developed. However, the
estimated cost (capital cost of $4,629 and daily chemical cost of
$246) is conservative and the actual daily operating cost should be
less than presented.
TREATMENT APPLICATION
One method of applying powdered activated carbon to the CST
treatment system would be to add a powdered carbon slurry to the
influent to the CST aeration basin (outer race). This process has
been extensively developed by the E. I. DuPont DeNemours Company and
others, and has been patented by DuPont as the PACT (powdered acti-
vated carbon treatment) process. The powdered carbon adsorbs and
concentrates the higher ~olecular weight materials, settles with the
activated sludge, and, with the sludge, is either recirculated or
wasted. The concentration of sludge and carbon will increase in the
aeration basin to an equilibrium level which can be controlled by the
sludge-carbon waste rate.
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117
REFERENCES
1.
Lawrence H. Keith, 1976. Identification and Analysis of Organic
Pollutants in Water, Ann Arbor Science, Box 1425, Ann Arbor,
Michigan, 48106, 553 p.
2.
Clinical Ecology, 1976. Lawrence C. Dickey, Ed.; Charles C.
Thomas, Pub1, Springfield, Illinois, 807 p.
Environmental Defense Fun'd, Inc. v. Russell E. Train, Adminis-
trator, EPA, No. 75-2224, U.S. Court of Appeals for the Distr.
of Columbia, Sept. 1976.
3.
4.
Environmental Defense Fund, Comments by the Environmental
Defense Fund on the EPA's Proposed Interim Drinking Water
Standards, Apr. - May 1975.
5.
"Nitrosamines: Scientists on the Trail of Prime Suspect in
Urban Cancer. II . Science 191: 268, Jan. 23, 1976.
6.
"P. L. 92-500: Changes Down Stream,1I Environ. Sci. and Tech.,
11(5):441, May 1977.
7.
Neely, W.Brock, "Defining a Harmful Quantity,1I Envir. Sci. and
Tech., 11(7):666-668, July 1977.
8.
Harris, Robert H., et a1, IICarcinogenic Hazards of Organic
Chemicals in Drinking Water,1I Proc. of Cold Spring Harbor Conf. ,
Origin of Human Cancer, Sept. 1976, in pub.
9.
Angino, Ernest, et a1., "Drinking Water Quality and Chronic Dis-
ease,1I Envir. Sci. and Tech., 11(7):660-665, July 1977.
10.
Donaldson, William T., "Trace Organics in Drinking Water,"
Environ. Sci. and Tech., 11(4):348-351, Apr. 1977.
11.
U.S. EPA, IIPre1iminary Assessment of Suspected Carcinogens in
Dril)king Water," Report to Congress, Dec. 1975.
12.
Haber, George, "Organic Chemicals in Drinking Water,1I The'
Sciences, Sept.fOct. 1976, pp. 23-26.
13.
Leenheer, Jerry A., et a1., IIInvestigation of the Reactivity and
Fate of Certain Organic Components of an Industrial Waste after
Deep-Well Injection,1I Envir. Sci. and Tech., 10(5):445-451, May
1976.
14.
Ko~fer, F.C., et a1., Human Exposure to Water Pollutants,
pr~sented at the Division of Environmental Chemistry Meeting,
Amer. Chern. Soc., Apr. 1975.
-------
118
15.
IIMonitoring to Detect Previously Unrecognized Pollutants in .
Surface Watersll EPA report EPA-560/6-77-015.
16.
Drinking Water and Health, Summary Report, Nat. Res. Coun., Nat.
Sci., Nat. Acad. Engfneeri ng, ,Comm. on Safe Dri nki ng Water 1977.
17.
U.S. EPA, Statement of Basis and Purpose for the Proposed
National Interim Primary Drinking Water Standards, Mar. 14,
1975.
18.
U.S. EPA, Quality Criteri'a for Water, 1977.
...-
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EXHIBIT III
Samplers:
FiElD DATA RECORD
-
Gage HI.
TEMPERATURE CONDUCTIVITY pH D.O. or Flow
STATION . NUMBER DATE TIME °C J.L mhos/em S.U. mo/I Fl. or CFS
~
.
-
-
"'
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EXHIBIT II
'OR
SURVEY, PHASE
, DATE
YPE OF SAMPLE
ANALYSES
REQUIRED
. V')
~ 0 ~ ~ w tJ
::; V1
W lU 0 ' <1:
~ Z V1 V1 >- . 0 0 lJ.J Z
~ = ill <1:
=:J 0 LJ... ,.... ~
0 > ~ ::; ::; l::> l::>
....J I- -' >- ::J V')
0 z V1 0 lJ.J I- ;::: I- 0 0 lJ.J u:
>- 0 u >- 0 0 UJ
> 0 z V1 Z 4. U U I- 0 ....J C;
U Z ::J "" 0 z V1 Q 0
....J lJ.J ....J lJ.J ....J 0 lJ.J ....J -, <1: -' lJ.J
e>:: <1: ;= z z
STATION <1: w 0 <1: 0- <1: Z o. ~ j CD ;::: c:J U
I- I- 0 U t- V1 ~ . ~ t- u.: >- U V1 c.: -
o >- 0 0 O ::J ....J :I: 0 lJ.J ::J ~ UJ U I
NUMBER STATION DESCRIPTION PRESEk'lATIVE <1: u w O :E I u
I- I- Z CD U I- I- V1 0 C. ..... t- u.. t- oJ 0- t- a..
I--- ,-
.
E/.\Aj:; KS
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EXHIBIT'IV
ENVIRONf.A.ENT AL PROTECTION AGENCY
Office Of Enforcement
NATIONAL ENFORCEN.ENT INVESTIGATIONS CENTER
Building 53, Box 25227, D~n"er Federal Center
Denver. Colorado 80225,
CHAIN OF CUSTODY RECORD
SURVEY SAM P L E RS: {Signature}
SAMPLE TYPE - .-----.
, STATION STATION LOCATION DATE TIME Water SEQ. NO. OF ANAL YSIS
NUMBER Air NO. CONTAINERS REQUIRED
Camp, Grab.
I '.
I -
I
I I .
I I
I
I I I
I
Relinquished by: (Signolure) Received by: (Signature) Dote/Time
I
Relinquished by: (Signot~re) Received by: (Signature) Dote/Time
L
Relinquished by: (Signature) Received by: (Signo/u.e) Dote/Time
I
Relinquished by: (Signature) Received by Mobile Loboratory for field Dotc/TimL
analysis: (5ignutu..) I
Dispatched by: {Signature} Datc/Time Received for Laboratory by: Date/Tim,
I I
Method of Shipment:
Distribution:
0,;<). - Accompany Shipment
: --t~1 -- -.., . - i ~uord;noto'
ficid Files
-------
Figure 1. Location Map
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