NEIC
COMPLIANCE EVALUATION
AND
WASTEWATER CHARACTERIZATION
UNION CARBIDE COMPANY
National Enforcement Investigations Center, Denver
U.S. Environmental Protection Agency
Office of Enforcement
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Environmental Protection Agency
Office of Enforcement
EPA-330/2-79-013
COMPLIANCE EVALUATION
AND
WASTEWATER CHARACTERIZATION
UNION CARBIDE COMPANY
SOUTH CHARLESTON, WEST VIRGINIA
James L. Hatheway
March 1979
National Enforcement Investigations Center - Denver
and
Region III - Philadelphia
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CONTENTS
I INTRODUCTION.'. . . . . . . . .
. . . .
. . . . . . .
. . . .
1
3
3
3
II SUMMARY AND CONCLUSIONS. . . . . . . . . . . . . . . . . . .
SUMMARY OF INVESTIGATIONS. . . . . . . . . . . . . . . . .
CONCLUSIONS. . . . . . . . . . . . . . . . . . . . . . . .
III INSPECTION METHODS AND RESULTS. . . . . . . . . . . . . . .. 7
POLLUTION SOURCES TO DISPOSAL METHODS. . . . . . . . . .. 7
SELF-MONITORING EVALUATION. . . . . . . . . . . . . . . .. 8
NEIC SAMPLE ANALYSES. . . . . . . . . . . . . . . . . . . . 10
IV SURVEY METHODS AND RESULTS. . . . . . . . . . . . . . . . . . 11
FLOW MEASUREMENT. . . . . . . . . . . . . . . . . . . . . . 12
SAMPLING. . . . . . . . . . . . . . . . . . . . . . . . . . 14
TOXICITY EVALUATION. . . . . . . . . . . . . . . . . . . . 19
APPENDICES
A - Union Carbide South Charleston (Inspection)
B - Lithium Flow Verification Procedures and Sampling
. Techni ques
C - Chain-of-Custody Procedures
D - Analytical Methods and Quality Control
E - Technical Information - Data Base Description
TABLES
1
2
3
4
Cooling Water Flows. . . . . . . . . . . . . . . . . . . . . 13
Summary of Field Measurements and Analytical Data. . . . . . 15
Volatile Organics Data. . . . . . . . . . . . . . . . . . . . 16
Toxicity of Organic Compounds. . . . . . . . . . . . . . . . 21
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1.
INTRODUCTION
The Union Carbide Corporation, Chemical and Plastics Division,
South Charleston, West Virginia, operates one of the largest petro-
chemical plants in the world. Union Carbide South Charleston (UCSC)
produces about 400 different specialty-type chemicals and mixtures.
Most of these products are intermediates used in other processes or
sold for use in finished products. The production facilities and
mixing and drumming area occupy an area of approximately 93 hectares
(230 acres) on Blaine Island and the south bank of the Kanawha River
[Appendix A, Figure 2, p. A-12].
The Kanawha Valley contains numerous industrial plants engaged
in the production of organic and/or inorganic chemicals. The passage
of the Toxic Substance Control and Resources Conservation and Recovery
Acts in 1976 focused attention on the need to control the discharges
of toxic substances. Large volumes of such wastes are produced and
disposed in the Kanawha Valley with a resultant potential for release
to the environment.
The Environmental Protection Agency, Region III, requested that
the National Enforcement Investigations Center (NEIC) inspect the
Union Carbide facility to: a) determine the sources and types of toxic
pollutants discharged, b) evaluate pollution abatement practices, and
c) determine if NPDES* permit requirements are being met. NEIC con-
ducted a detailed plant inspection and a subsequent field survey.
* NPDES: National pollutant Discharge Elimination System, Public
Law 92-500, Sec. 402 of the Federal Water Pollution control Act
as amended in 1972, and subsequently Sec. 402 of the Clean Water
Act as amended in 1977.
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The inspection results are summarized in this report, and presented
in full context in Appendix A.
The objectives of the April 1978 plant inspection were to:
1.
2.
3.
4.
inspect process operations [Appendix A]
evaluate pollution sources and abatement practices
evaluate self-monitoring procedures
analyze a process wastewater sample for toxic pollutants
and organic compounds
The objectives of the August 7 to 12, 1978 survey were to:
1.
2.
measure flow from each of the cooling water discharges
determine if NPDES permit limitations were being met from
three selected cooling water discharges
collect samples from these three cooling water discharges
and the water intake for organic characterization.
3.
In addition to determining the sources and types of toxic pollu-
tants, NEIC evaluated the potential health effects of all organic
compounds identified in wastewater and water intake samples.
2
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II.
SUMMARY AND CONCLUSIONS
SUMMARY OF INVESTIGATIONS
NEIC conducted an inspection of the UCSC facility in April 1978.
During this inspection, each process operation was discussed in detail
with Company personnel [Appendix A]. Evaluations were made of air,
water and solid waste pollution sources and associated abatement prac-
tices. Self-monitoring procedures including sample collection, flow
monitoring, sample analysis, bioassay procedures, and discharge moni-
toring reports (DMRs) were also evaluated. The inspection team collec-
ted a sample from the process wastewater for organic analyses in the
NEIC Denver laboratory.
From August 7 to 12, 1978, NEIC personnel conducted a survey at
the UCSC facility. Cooling water flows were measured using lithium
chloride dilution procedures. Twenty-four hour composite samples of
cooling water discharges and intake water were collected to determine
compliance with NPDES effluent limitations, and to identify organic
compounds. Each organic compound was searched in the Registry of
Toxic Effects and Chemical Substances and the Toxline data bases to
obtain toxic information.
CONCLUSIONS
Inspection
Air pollution control devices used at this facility appear to be
adequate. Control devices include scrubbers, electrostatic precipitators,
nitrogen blanketing and conservation vents on tanks, and collection
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4
and burning of all combustible wastes. The air emission inventory
provided by Company personnel show that pentane, acetone, isopropanol,
methylacetate, methanol, diethylamine, butylchloride, propylene oxide
and ethanol constitute the majority of the hydrocarbons emitted from
this facility.
Solid wastes disposal in the Fillmont Landfill, Goff Mountain
Chemical Landfill, and Holz pond appears to be adequate. According
to Union Carbide officials, only non-chemical (lumber, paper, scrap
polymer, etc.) solid wastes are sent to the Fillmont landfill. Hazar-
dous chemical wastes are trucked to the Goff Mountain Chemical Landfill
for disposal. Non-hazardous chemical wastes are pumped to Holz pond.
Sampling techniques were inadequate. The automatic sample con-
tainers are not routinely cleaned and some contained algae growth,
flaking paint and solid accumulations. Samples are not refrigerated
during collection. In addition, the water containers are sometimes
full in less than 8 hours precluding the collection of a representative
24-hour sample.
In general, bioassay procedures were adequate. Discrepancies
observed include: a) not starting tests within 8 hours as recommended
by Standard Methods, b) using city dechlorinated tap water for dilution
water instead of Kanawha River Water, c) not running tests in duplicate,
d) aerating samples throughout the 96-hour test period. It is advisable,
though not required, that the laboratory use a constant temperature
water bath to maintain test temperature rather than depending on ambient
air temperature.
Discharge monitoring reports, October through December 1977,
show that the daily average and/or maximum TOC limitations were exceeded
on five outfalls. Based on the sampling technique procedure discrepancies
discussed above, these DMR data are questionable, probably low.
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5
The process wastewater discharged to the South Charleston Sewage
Treatment Company contains numerous organic chemicals and priority
pollutants. A grab sample collected in April showed a total of 39
organic chemicals, including 14 priority pollutants:* benzene, chloro-
benzene, 1,2-dichloroethane, chloroform, 1,2-dichlorobenzene, 1,1-di-
chloroethane, ethyl benzene, methylene chloride, bis (2-ethylhexyl)
phthalate, 2,4-dinitrophenol, isophorone, di-N-butyl phthalate, tetra-
chloroethlene and toluene.
Survey
Total flow discharged by UCSC to the Kanawha River, based on one
measurement from each outfall was about 457,000 m3/day. As required
by the NPDES permit, Company personnel had previously measured the
flows using the same techniques and found flows of approximately
402,000 m3/day.
Effluent data collected during the August survey show that UCSC
exceeded permit limitations. Results show daily maximum net TOC con-
centrations on Outfall 025 ranged from 8 to 20 mg/l with 2 of 3 days
exceeding the NPDES permit limitation (12 mg/l). The average net TOe
concentration of 15 mg/l was almost 4 times greater than the permit
limitation (4 mg/l). Projecting from these data, the daily average
limitation would not be expected to be met. Maximum TKN loads were
11 kg/day, approximately 3% of the total plant limitation.
Outfalls 023 and 035 samples had net TOe concentrations of 2 mg/l
or less which is within permit limitations. Maximum TKN loads were 8
and 11 kg/day respectively, less than 3% of the permit total plant
limitation (460 kg/day).
* See explanation in Section III of priority pollutants.
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6
During the NEIC survey, twelve organic compounds: butyl carbitol,
pristane, benzene, bromodichloromethane, chlorobenzene chloroform,
chlorodibromomethane, 1,2-dichloroethane, l,l-dichloroethane, 1,2-di-
chloropropane, ethylbenzene, and methylene chloride were identified
and confirmed in the Outfall 023, 025, 035 and water intake samples
at low concentrations ranging from 1 to 82 ~g/l. All except butyl
carbitol and pristane are priority pollutants. Of these, benzene is
a known carcinogen to man and chloroform is carcinogenic to animals.
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III.
INSPECTION METHODS AND RESULTS
During the April 4 to 6, 1978, inspection [Appendix AJ, NEIC
personnel obtained information on process operation and associated
pollution sources and self-monitoring procedures. Production rates
and process schematics are not included because UCSC considers that
information confidential.
POLLUTION SOURCES AND DISPOSAL METHODS
The Kanawha River is the source of process, cooling and boiler
feed waters. All process and domestic wastewaters are discharged to
the South Charleston Sewage Treatment Company (SCSTC) through an open
redwood flume. UCSC had installed monitoring stations on their process
sewer to measure flow and total carbon [Appendix A, Figure 2J. The
pH, temperature and organics are measured at selected stations.
Once-through non-contact cooling water is discharged into the
Kanawha River through 22 outfalls.* Two cooling water discharges
(Outfalls 023 and 025) are equipped with organic spill detectors cali-
brated at 50 ppm isopropanol. If the organic concentration of the
wastewater should exceed this value, an alarm is sounded. At that
time a sample is collected and analyzed in the company laboratory to
determine the compounds discharged.
Air pollution emissions are controlled by scrubbers,
precipitators, nitrogen blanketing and conservation vents
and collection and burning of all combustible waste gases.
electrostatic
on tanks,
Union Carbide
* During the study cooling water was discharged from only 19 of these
outfalls.
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8
has installed 11 ambient air monitoring stations in and around the
plant to detect leaks and/or equipment malfunctions. The air emission
inventory provided by company personnel shows that pentane, acetone,
isopropanol, methyl acetate, methanol, diethyl amine, butyl chloride,
propylene oxide and ethanol consistute the majority of the hydrocarbons
emitted from this facility [Appendix A].
Solid wastes are disposed of in Goff Mountain Chemical landfill,
Fillmont landfill, and Holz pond.* Hazardous chemical wastes and
toxic substances are hauled to the Goff Mountain landfill. Landfill
leachate, which is collected in an under-drainpipe system, is treated
in the Union Carbide Institute (UCI) wastewater treatment facility.
Non-hazardous chemical wastes, UCI and SCSTC waste-activated sludge
and UCSC powerplant fly ash are pumped to Holz pond, an anaerobic
lagoon. Overflow from this pond is treated at SCSTC. UCSC non-chemi-
cal solid wastes (lumber, paper, scrap polymer, etc.) are disposed of
in the Fillmont landfill.
SELF-MONITORING EVALUATION
The evaluation of self-monitoring procedures consisted of inter-
views with UCSC sampling, analytical and bioassay personnel, and evalua-
tions of sampling, monitoring and analytical equipment [Appendix A].
The findings of this evaluation are discussed below:
Company personnel analyzed standard reference TOC samples provided
by NEIC [Appendix A]. TOC reference samples results were 3 to 12%
lower than true value, which are acceptable. All chemical analyses
are performed according to EPA-approved methods.
* Goff Mountain landfill is operated by Union Carbide Institute personnel.
Fillmont landfill and Holz pond are operated by UCSC personnel.
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'I
9
Company personnel conduct bioassay testing quarterly as required
by the NPDES permit. Discrepancies noted in their bioassay procedures
include a) not starting tests within 8 hours as recommended by Standard
Methods, b) using dechlorinated city water as dilution water instead
of Kanawha River water, c) not running tests in duplicate, and d)
aerating samples throughout the 96-hour test period. It is advisable,
though not required, that the laboratory use a constant temperature
water bath to maintain test temperature rather than depend on ambient
air temperature.
The NPDES permit requires 24-hour flow composite samples. Company
personnel have installed automatic samplers designed by their own
personnel. Samples are collected starting at approximately 5:00 a.m.
daily. Observations made during the initial inspection (April 4 to 6)
and the NEIC survey (August 9 to 12) showed that within 7 to 8 hours
some of the sample containers were full and others were over 2/3 full
indicating an improper sampling rate. The samples collected are not
24-hour composites as required by the NPDES permit nor are they repre-
sentative.
Other discrepancies noted include the lack of proper sample refri-
geration during collection and sampling buckets which contained algae
growth, flaking paint and an accumulation of solids. Company officials
indicated that they do not have a routine maintenance program for the
samplers.
The Discharge Monitoring Reports (DMR) [Appendix A, Tables 3
through 9] show that during the last quarter of 1977 the daily average
and/or daily maximum TOC concentration (4 and 8 mg/l respectively)
were exceeded on five outfalls.* Based on the discrepancies
*
Composite samples from Outfalls 009,014, 015, 016, 017, 024, 028,
031, 036, 039, 040, 042, 075 and 076 are composited into one sample
and the limitation is based on the total discharge from all 16 out-
falls. TOC violations are reported for these samples as well as
samples from Outfalls 025, 032, 035 and 074.
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10
discussed above, DMR data are considered to be questionable, i.e.,
probably low.
NEIC SAMPLE ANALYSIS
During the April reconnaissance survey, NEIC personnel collected
a grab sample from the UCSC industrial/domestic effluent to SCSTC.
This sample was analyzed for toxic pollutants and other organic com-
pounds. A total of 39 organic chemicals, including 14 priority pollu-
tants,* were identified. The priority pollutants were benzene, chloro-
benzene, 1,2-dichloroethane, chloroform, 1,2-dichlorobenzene, 1,1-di-
chloroethylene, ethylbenzene, methylene chloride, 2,4-dinitrophenol,
bis-(2-ethylhexyl) phthalate, isophorone, toluene, di-N-butyl phthalate,
and tetrachloroethylene.
* Priority Pollutants are derived from the June 7, 1976 Natural
Resources Defense Council (NRDC) vs. Russell Train (USEPA)
Settlement Agreement.
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IV.
SURVEY METHODS AND RESULTS
During August 1978 NEIC personnel measured the cooling water
discharge flow, determined compliance with NPDES permit [No. WV0000078]
effluent limitations from three selected cooling water oufalls and
characterized the wastewater discharged from these three outfalls and
the water intake. Permit compliance was based on the following effluent
limitations which have been in effect since May 1, 1977:
Parameter
Limitation
Daily Average Daily Maximum
TOC mg/l (net)
Temp °C (oF)
pH range
4
NA
12
43.3 (110)
6-9
The permit also established net load limitations for the following
parameters based on the total plant discharge:
Parameter
Limitation in kg/day (lb/day)
Daily Average Daily Maximum
Chlorides
Phenolics
Dissolved Solids
Kjeldahl Nitrogen
Organic Nitrogen
5,774 (12,718)
NA
NA
233 (492)
198 (436)
8,820 (19,427)
NA
NA
460 (1,014)
396 (872)
Instantaneous flow is to be measured on each outfall once/year
by the dye tracer technique. These measurements are then used to
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12
determine flows for the next 12 months based on intake meter readings.
In addition, the company is required to monitor Outfalls 023 and 025
twice/year for vinyl chloride monomers. Toxicity is to be monitored
by bioassays conducted quarterly.
FLOW MEASUREMENT
The NPDES permit requires that flow be measured once/year on
each outfall by the dye tracer technique. These measurements are
then used for the next 12 months to determine flows from each outfall
based on intake meter readings. During the period August 7 to 11, NEIC
personnel measured the flow once from each cooling water discharge
using lithium chloride as a tracer* [Appendix BJ.
NEIC results show that the discharge flow was approximately
456,700 m3/day [Table 1J. Company data collected one year prior to
the NEIC data indicate the flow was about 10% less.
A comparison between intake meter readings and NEIC lithium flow
results cannot be made as some intake flow meters were not operating
during the study. Company personnel, however, estimated the total
cooling water being discharged based on rated pump capacities and
consumptive uses as follows:
9 pumps at 9500 gpm - 123 mgd
less water treated - 3.2 mgd
less water supplied to technical center - 1.7 mgd
total cooling water - 118.2 mgd or 447,000 m3/day
* Company personnel also use lithium chloride to measure flows from
these outfalls.
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Table 1
COOLING WATER FLOWSa
UNION CARBIDE SOUTH CHARLESTON
Outfall NEIC Company
No. m3/day mgd m3/day mgd
009 3,670 0.97 727 0.192
014 25,000 6.6 30,848 8.15
015 2,120 0.56 318 0.084
016 2,230 0.59 2,225 0.588
017 17,800 4.7 18,054 4.77
023 41,600 11 40,500 10.70
024 24,200 6.4 11,620 3.07
025 106,000 28 81,378 21. 50
027 7,570 2.0 2,271 0.600
028 No Discharge
031 32,600 8.6 16,805 4.44
032 19,700 5.2 18,054 4.77
035 53,000 14 22,029 5.82
036 4,160 1.1 3,085 0.815
039 9,080 2.4 10,484 2.77
040 26,500 7.0 33,914 8.96
042 29,900 7.9 38,985 10.30
072 No Discharge
074 23,500 6.2 46,555 12.30
075 110 0.029 636 0.168
076 28,000 7.4 23,202 6.13
TOTAL 456,700 120.65 401,700 106.13
a Flows were measured using lithium chloride. Company data are
approximately one year prior to NEIC measurements.
13
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SAMPLING
Three cooling water discharges (Outfalls 023, 025 and 035) and
the water intake were sampled August 9 to 12, 1978. The three cooling
water discharges were selected by NEIC personnel based on volume dis-
charged and past self-monitoring data which showed that discharges
from Outfalls 025 and 035 were in violation of NPDES TOC limitations.
Aliquots were manually collected every two hours and continually com-
posited on an equal volume basis for total organic carbon, phenolic
compounds (i.e., phenols), NH3, TKN and organics analyses. Grab samples
were randomly collected three times per day for volatile organic analysis*
(VOA). Temperature and pH were measured each time a sample was collected.
Details on sampling and flow measurement procedures, Chain-of-Custody
procedures, and analytical and quality control procedures are contained
in Appendices B, C and D respectively.
Sampling results are summarized in Tables 2 and 3 and discussed
by individual outfalls.
Outfall 023
The maximum net TOC concentrations in the cooling water discharged
through Outfall 023 was 2 mg/l, 17% of the NPDES permit limitation
(i.e., daily maximum of 12 mg/l). These data are somewhat lower than
those reported in UCSC's self-monitoring data [Appendix A, Table 4],
which show monthly maximum values ranging from 3 to 7 mg/l. The net
TKN and NH3 loads for the survey were each 8 kg (17 lb)/day.
Outfall 023 neutral
this discharge contained
estimated at less than 2
extractable organics results showed that
a few organic compounds with concentrations
ppb. Of these compounds only pristane could
* GC/MS analysis was requested only on an equal volume composite of
those grab samples collected August 11, 1978.
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Table 2
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL DATA
UNION CARBIDE SOUTH CHARLESTON
August 9-11, 1978
TOC Phenol Chlorides NH,,-N TKN
Station Flow pH Temperature mg/1 I-Ig/1a mg/l kg/day 1b/day mg/1 kg/day lb/day mg/1 kg/day lb/day
Description Date m3/day mgd range Range DC Gross Net Gross Gross Net Net Gross Net Net Gross Net Net
Water 8/09 6.9-7.4 23-25 8 <15 6 <0.2 0.5
Intake 8/10 7.2-7.6 23-26 7 <10 6 <0.2 0.6
8/11 7.2-7.9 24-25 8 <10 5 <0.2 0.5
Outfall 023 8/09 41,600 11 6.7-7.7 28-31 8 <2 <10 6 0.2 8 18 0.7 8 18
8/10 41,600 11 7.1-7.6 28-31 7 <2 <10 5 <0.2 0.5
8/11 41,600 11 7.1-7.7 27-30 10 2 <10 7 83 180 <0.2 0.7 8 18
Outfall 025 8/09 106,000 28 7.0-10.3 27-30 16 8 <15 29 2400 5400 <0.2 0.6 11 23
8/10 106,000 28 6.6-7.4 27-30 25 18 <10 21 1600 3500
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Table 3
VOLATILE ORGANICS DATA a
UNION CARBIDE SOUTH CHARLESTON COOLING WATER DISCHARGES
Outfall Outfall Outfall Water
Station Descri tion -+ 023 025 035 Intake
Compound Concentration (I-Ig 1)
Acrolein NOb NO NO NO
Benzene 1 ND 1 ND
Bromodichloromethane 2 2 6 ND
Bromoform NO ND ND NO
Carbon tetrachloride ND ND NO NO
Chlorobenzene ND 2 NO NO
2-Chloroethylvinyl ether ND NO ND NO
Chloroform 8 7 25 2
Chlorodibromomethane ND 1 2 NO
1,2-0ichloroethane 3 2 NO 5
l,l-Oichloroethene NO 8 NO NO
trans-l,2-0ichloroethene ND ND ND NO
l,2-Dichloropropane ND 2 ND ND
Ethyl benzene ND ND NO 4
Methylene chloride NO ND 82 14
l,l,2,2-Tetrachloroethane ND ND ND ND
Tetrachloroethene ND ND ND ND
Toluene ND NO ND ND
1,1,I-Trichloroethane NO NO NO NO
1,1,2-Trichloroethane NO NO NO NO
Trichloroethene NO NO NO NO
Vinyl Chloride ND NO ND NO
a Equal volume composite of three grab samples collected August 11,
1978.
b ND - none detected. Detection limit 1 I-Ig/1 for all components except
acrolein, which has a detection limit of 50 I-Ig/l.
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17
be identified.
The concentration of pristane, however, was less than
the detection limit (1 ~g/l).
VOA data [Table 3] show the cooling water contained 4 organic
compounds (benzene, bromodichloromethane, chloroform and 1,2-dichloro-
ethane) at low concentrations ranging from 1 to 8 ~g/l. The intake
water contained 1,2-dichloroethane at a higher concentration (5 ~g/l)
than the discharge (3 ~g/l). These volatile compounds are priority
pollutants.*
Outfall 025
The daily maximum TOC limitation on Outfall 025 was exceeded.
The net TOC concentrations ranged from 8 to 20 mg/l [Table 1] with
two out of the three days exceeding the NPDES limitation (i.e.,
12 mg/l) by 50 and 67% DMR data for the last quarter of 1977 show
that this outfall exceeded the maximum limitation by 2.3 times in
November.
The average net TOC concentration for the three-day survey was
15 mg/l, almost 4 times greater than allowed by the NPDES permit (i.e.,
daily average of 4 mg/l). The NPDES permit defines the daily average
limitation as the arithmetic average of all the daily determinations
made during a calendar month. Because samples were only ~ollected
for 3 days, compliance with the average cannot be determined. Survey
results, however, indicate that the daily average TOC limitation would
not be met. DMR data show that the monthly average concentration for
December was 5 mg/l, or 25% greater than the permit limitation (4 mg/l).
Numerous organic compounds were observed in Outfall 025 samples.
Concentrations, however, were estimated to be below 5 ppb except for
* Listed in Consent Agreement, Natural Resources Defense Council vs.
Russell E. Trains, June 1976.
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18
two compounds which were estimated at less than 10 ppb. Some of the
compounds were halogenated oxygenated aliphatics but could not be
specifically identified. Two compounds, butyl carbitol and pristane,
were identified but, due either to interferences or difficulties in
correlation to the flame ionization chromatogram, could not be quanti-
fied.
The volatile organic analyses showed that this discharge contained
bromodichloromethane, chlorobenzene, chloroform, chlorodibromomethane,
1,2-dichloroethane, 1,1-dichloroethene and 1,2-dichloropropane at low
concentrations ranging from 1 to 8 ~g/l [Table 3J. All of these com-
pounds are priority pollutants.
Outfall 035
During the survey, the gross TOC, NH3 and TKN concentrations at
this outfall ranged from 7 to 9 mg/l, <0.2* mg/l and 0.4 to 0.7 mg/l,
respectively. These concentrations are similar to those found in
the intake water (7 to 8 mg/l TOC, <0.2* mg/l NH3 and 0.5 to 0.6 mg/l
TKN). DMR data for October, November, and December 1977 show maximum
TOC concentrations of 21, 10 and 39 mg/l, respectively [Appendix A].
The NPDES limitation (12 mg/l) was exceeded during October and December.
Samples collected from this outfall contained several neutral
extractable organics compounds with concentrations less than 2 ppb.
None of these compounds, however, could be identified by GC/MS. Vola-
tile organic samples contained benzene, bromodichloromethane, chloroform,
chlorodibromomethane and methyl chloride at concentrations of 1, 6,
25,2 and 82 ~g/l, respectively. These compounds are also on the
priority pollutant list.
* All values were the same.
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Water Intake
As previously noted, the water intake contained small concentrations
of TOC (7 to 8 mg/l), chlorides (5 to 6 mg/l), NH3 «0.2 mg/l) and
TKN (0.5 to 0.6 mg/l). Self-monitoring data for the last quarter of
1977 are similar to those obtained during the survey.
At least eight isomers of bis (C6) phthalic acid esters were
identified but could not be verified in the intake water composite
samples. Concentrations were estimated as less than 10 ppb for all
isomers. Pristane was also identified in the intake samples but, due
to interfering compounds and/or difficulty in correlation to the flame
ionization chromatogram, could not be quantified. Volatile organic
analysis showed that the intake water contained small amounts of chloro-
form, 1,2-dichloroethane, ethylbenzene, and methylene chloride (2, 5,
4 and 14 ~g/l, respectively), all of which are priority pollutants.
TOXICITY EVALUATION
The twelve organic compounds identified in the cooling water and
water intake samples were searched in the Registry of Toxic Effects
of Chemical Substances (RTECS)* and in the Toxline** database to obtain
health effects data [Appendix E].
The RTECS search yielded information on 10 to 12 compounds [Table 4].
The Toxline search yielded 205 references to human health effects
from the 10 compounds, providing support to the toxic data from RTECS.
* This Registry is compiled annually by the National Institute for
Occupational Safety and Health.
** Toxline is a computerized bibliographic retrieval system for
toxicology.
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No information on toxic and health effects of dichlorobromo-
methane and chlorodibromomethane was available in either RTECS or
Toxline. However, it should be noted that bromodichloromethane was
included in the National Cancer Institute's Carcinogenesis Bioassay
program as of February 1978.
As previously noted, the concentrations of these compounds ranged
from 1 to 82 ~g/l [Table 3]. Seven of the 12 compounds identified
have demonstrated human effects associated with them [Table 4]. The
hazards of ingesting minute quantities of these organic pollutants in
drinking water over long periods of time are difficult to evaluate.
From the standpoint of adverse health effects, three of the compounds
are known carcinogens. Benzene is carcinogenic to man and chloroform
to animals.
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APPENDIX A
UNION CARBIDE SOUTH CHARLESTON
(INSPECTION)
April 1978
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CONTENTS
I INTRODUCTION. . . . . . . . . . .
. . . . ,. . . . . . . .
. . A-5
II PROCESS OPERATIONS AND POLLUTION SOURCES. . . . . . . . . . . A-7
POLYVINYL ACETATEt SOLUTION RESINS AND AYAC RESINS
PRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . A-13
2-ETHYL HEXANOIC ACID PRODUCTION. . . . . . . . . . . . . . A-13
2-DIMETHYL AMINO ETHANOL AND OTHER ALKANOL AMINES
PRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . A-14
PROPYLENE AND DIPROPYLENE GLYCOL PRODUCTION. . . . . . . . A-14
ACETIC ANHYDRIDE PRODUCTION. . . . . . . . . . . . . . . . A-15
DIACETONE ALCOHOL PRODUCTION. . . . . . . . . . . . . . . . A-15
VINYL ACETATE-VINYL CHLORIDE COPOLYMERS AND FINISHED
RESINS PRODUCTION. . . . . . . . . . . . . . . . . .
NIAX POLYDS PRODUCTION. . . . . . . . . . . . . . . . .
HEXANE GLYCOLS PRODUCTION. . . . . . . . . . . . . . .
ORGANIC ACID AND HYDROGENATED CROTON OIL ALCOHOL
PRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . A-20
UCON AND UCAR PRODUCTION. . . . . . . . . . . . . . . . . . A-2I
BUTRALDOL AND METHYL PENTENAL PRODUCTION. . . . . . . . . . A-2I
VINYL METHYL ETHER PRODUCTION. . . . . . . . . . . . . . . A-22
VACUUM AND ATMOSPHERIC ESTER PRODUCTION. . . . . . . . . . A-22
PLASTICIZER PRODUCTION. . . . . . . . . . . . . . . . . . . A-24
ESTER DIOL 204 AND DIENE 234 PRODUCTION. . . . . . . . . . A-24
DIISOBUTYL CARBINOL AND 2-ETHYL HEXANE DIOL PRODUCTION. . . A-24
POLYGLYCOL-DIAMINE PRODUCTION. . . . . . . . . . . . . . . A-25
NIAX CATALYST PRODUCTION. . . . . . . . . . . . . . . . . . A-25
ETHYL SILICATES PRODUCTION. . . . . . . . . . . . . . . . . A-26
GLYCOL ETHERS PRODUCTION. . . . . . . . . . . . . . . . . . A-27
BUTYL CHLORIDE PRODUCTION. . . . . . . . . . . . . . . . . A-27
DRUMMING AND MIXING AREA. . . . . . . . . . . . . . . . . . A-27
ENERGY PRODUCTION. . . . . . . . . . . . . . . . . . . . . A-30
. . A-17
. . A-I7
. . A-20
III POLLUTION ABATEMENT AND WASTE DISPOSAL PRACTICES. . . . . . . A-33
IV EVALUATION OF SELF-MONITORING PRACTICES. . . . . . . . . . . A-37
BIOASSAY PROCEDURES. . . . . . . . . . . . . . . . . . . . A-37
ANALYTICAL PROCEDURES. . . . . . . . . . . . . . . . . . . A-38
SAMPLING PRACTICES. . . . . . . . . . . . . . . . . . . . . A-38
SELF-MONITORING DATA. . . . . . . . . . . . . . . . . . . . A-39
-------
A-II
TABLES
I
2
3
4
5
6
7
8
9
NPDES Permit Limitations. . . . . . . . . . . . . . . . . . . A-IO
Wastewater Monitoring Stations. . . . . . . . . . . . . . . . A-II
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-40
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-4I
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-42
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-43
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-44
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-45
Summary of Discharge Monitoring Reports. . . . . . . . . . . A-46
FIGURES
I
2
3
4
5
6
7
8
So. Charleston Plant, Major Prod. Units. . . . . . . . . . . . A-8
Plot Plan. . . . . . . . . . . . . . . . . . . . . . . . . . . A-12
Diacetone Alcohol Schematic. . . . . . . . . . . . . . . . . . A-16
No. I Solvent Vinyl Resins Schematic. . . . . . . . . . . . . A-18
Solvent Vinyl Resins Unit No.2 Schematic. . . . . . . . . . . A-19
Vinyl Methyl Ether Processing System Schematic. . . . . . . . A-23
Glycol Ethers Process Schematic. . . . . . . . . . . . . . . . A-28
Butyl Chloride System Schematic. . . . . . . . . . . . . . . . A-29
ATTACHMENTS
A - Company Organic Chemical Monitoring
B - Organic Chemicals Screening Analyses
C - Bioassay Procedures Evaluation
D - Chemical Laboratory Procedures Evaluation
-------
A-5
1.
INTRODUCTION
Union Carbide Corporation, Chemicals and Plastics Division (NPDES
Permit No. WV0000078), operates a chemical manufacturing facility at
South Charleston, West Virginia producing approximately 400 different
chemicals and mixtures. The plant operates 24 hr/day, year around
and employs 1,700 people.
The Environmental Protection Agency, Region III, requested that
the National Enforcement Investigations Center (NEIC) inspect the
Union Carbide facility to: a) determine the sources and types of
toxic pollutants* discharged, b) evaluate pollution abatement prac-
tices, and c) determine if NPDES permit requirements were being met.
On April 4, 5 and 6, 1978, Dr. Wayne C. Smith, Mr. James L. Hatheway,
Mr. Bruce A. Binkley and Mr. D. David Vietti of NEIC visited the plant
to inspect process operations, probable pollution sources, waste disposal
practices and pollution abatement practices and to evaluate self-monitoring
procedures which included sampling, flow measurement, analytical and
bioassay procedures used. The Company, represented by Mr. J.L. Worstell,
provided information and assistance.
* Toxic Pollutant List published January 31, 1978 in Federal Register
Vol. 43, No. 21.
-------
A-7
II.
PROCESS OPERATIONS AND POLLUTION SOURCES
Union Carbide produces approximately 400 different chemicals and
mixtures that include about fifty major products. These 50 products
and about 700 other chemicals are used to formulate the balance of '
the products. Production rates and most process schematics are consid-
ered confidential. Figure 1 shows the major production units, products
and raw materials for this plant.
Kanawha River water, about 340,000 m3/day (90 mgd), is used for
non-contact cooling and process water. The non-contact cooling water
is discharged, untreated, to the river through 22 NPDES-permitted
outfalls. The Company has no NPDES limits for the process wastewater.
The two major coo'-ing water outfalls (023 and 025) are continuously
monitored for specific organics. If the organics concentration exceeds
50 ppm (calibrated as isopropanol), a grab sample of this cooling
water is collected and analyzed to determine what process area is
causing the problem. NPDES limitations [Table 1] for these discharges
were effective May 1, 1977. Approximately 18,000 m3/day (5 mgd) process
wastewater, domestic waste and floor washings, are collected and dis-
charged to the South Charleston Sewage Treatment Company (SCSTC) for
treatment. Union Carbide has an extensive total carbon monitoring
system (21 analyzers) on the process sewers [Table 2 and Figure 2].
These total carbon analyzers are used to detect process upsets and
for treatment billing costs to the individual processes.
Solid waste is disposed in one of two landfills or in an on-site
lagoon. Non-chemical (lumber, paper, scrap polymer, etc.) solid wastes
are disposed in the Company owned and operated Fillmont landfill (State
approved). Chemical solid waste is sent to the Goff Mountain landfill
-------
lice tic IInhydr i de
!
Glycol
Esters
Ketene
p,.
Upper
Island
Chemicals
Complex
Alcohols
t>-
'~T
~
~
Middle
Island
Chemicals
Complex
Vacuum
Esters
Atmospheric
Esters
-
IIldehydes
t>
-
/I.: r-' tone
-~
Upper
Island
Chemicals
Camp I ex
IJ
Diacetone Alcohol
Oiethyl 11alcat('{to-
Di isobut.'{1 Keto~
Piperi1zinc &
Forma I clchyd;.
Acr y \ on i t r i Ie,
C~ustic Diethylene
~ Glycol & other r
Chemicals
I ,ol>u tyra I deh~. Complex Ucar Filmer 351
lJimet.hylilmino
Ethoxyethilnol
~ Specialty
Niilx Catillyst A-99
Trim~thylami~ Chemicals
Complex
~
HydroC)en
+
Specialty
Chemicals
Complex
Other R,lW
Ha tel' i ;:J!~
!!cxylene Glycol
Diethyl Succinate
CI-
c'lrb i no I
;:\0-
Diisobutyl
"ethy I
Piper;)zinc
Polv
/liiJX Catalyst
A-I, A-397.
F.S/I, E tc.
Middle
Island
Chemicals
Complex
Organic
Acids
~
Middle
Island
Chemicals
Complex
Pla"ticizr-'C5
.-
Glycols
~
Form;:llc:1ehyde
v
):>
I
;:;0
Est e r D i 0 I 201,-
DIene 2)/'
Middle
IsI"nd
ChemiCills
Comp 1 ex
Chemicals
Complex
Isobutyraldehyde
>
TetrilbenzaldehYd('~
Upper
Islilnd
Chemicals
Complex
~
'Jinyl 'Ethyl Ethc,=-
Speci,lI ty
Chemicals
"Cellosolye"
Siliciltes
JI>-
/lcetaldehY~
E~
Si licone Tetrachloride
"Cellosolye"
, .....
Ethilno
~
Eth I Silici:!t~
Complex
, Fi gure 1.
Major Production Units, Products and Raw Materials
South Charleston Plant
en
-------
Villyl
Water
Butano
Ii,: l ha '1',.1
gut,)nol
-~-
Hydroyen
Chlori(~
- -1.Lil.~-L.Lu.i..J..:J~'-f---------- --------.
So I uti on '1' I I
Lthyl Ether .ct 1;:111'.1.1.
Vinyl Resins --f""
-
Allyl,Jlcohol
II>-
Butanol
-~
Propy1eno:,oxide
..~
Chemicals
Complex
Ucars
.,..
Propvlene Oxide
I snprop.1nn 1
Cilust;c Soda
J
Flexible
Polyols
Polyols
Butyl Chloridc-
.-
De p t.
Propylene
Glycol: ,..
G I ycer.! n
Ethylene
Oxide,
r:--
fliax Trio1s
lIi"x Dials
Polyols
Dept.
Blocked & Cilpped
Polyo!s
Major
Fi gure 1. (Cont.)
Production Units, Products and
South Charleston Plant
Raw t1aterials
DLlanroyl
Peroxide
Vinyl Chloride
Misc. Feedstock
i-
t
I!
I.
~
\
Vinyl
~ Dispersion
~ Resins
~ (085)
r I n I " he
Rcsin'L
.,
if
i'
"
!;
fi
;i
;::
.~
,I
I
':
~
Diethylene
Glycol
Sulfuric Acid~ Mainland
~ilU5t1C ~ Chemicals
Soda
Do-
Styren~
Acryloni tri I.
VilZ~
"
f) iOX'-1I1<
~,
'i
~ Complex
~~
,:
~
Palvols
Dept.
,.
,.
!":
~;
)::0 I
I :~
I.D
'.'
'.
Resin Blends
..., .
E.v.l.R
.... ..... ~r-
-------
A-10
Tabl e 1
NPDES PERMIT LIMITATIONS
UNION CARBIDE
SOUTH CHARLESTON, WEST VIRGINIA
Pa rameter
Net Discharge
Limitations
Daily Daily
Avq. Max.
kg/day (lb/day)
r'loni tori ng
Requirements
fleasurement Sample
Frequency Type
Flow m3/day (mgd)
TOC
Temperature
Vinyl Chloride Monomer
pH (range)
Other
a
5/~leek
l/week
2/year
6.0-9.D l/week
.
There shall be no discharge of floating solids
in other than trace amounts.
4 mg/l
N/A
NA
12 mg/l
43.3 (110)
N/A
24 hr. com.b
Instantaneous
24 hr. com.
Grab
or visible foam
a Outfalls 009, 014, 015, 016, 017, 023, 024, 025, 027, 028, 031,035, 036, 039, 040, 042, 072
074, 075, 076. Flow measurements shall be made once a year by the dye tracer test method on each
of the twenty-two outfalls. These measurements will then be used to determine the relative flows
of the twenty-two outfalls for the next twelve months. Each month, the flow for any of the indi-
vidual outfalls shall be determined from (a) the plant cooling water intake for that month (which
is metered) and (b) relative outfall flowrates as determined from the last dye tracer test measure-
ments.
From May 1 , 1977, until the expiration date, TOC analyses shall be made using 24-hour composite
sc~~ples for 4 days of the week, and a 72-hour composite sample for the remaining 3 days of the
week.
Beginning on the effective date of the permit and continuing through December 31, 1977, the Envi-
ronmental Protection Agency and the permittee will jointly investigate the qualitative and quanti-
tative presence of organic chemicals in the outfalls using analytical techniques and instruments
appropriate to the probable constitutents and their expected concentration ranges in the discharges.
Beginning on January 1, 1978, the permittee shall initiate monitoring and reporting for such specific
organic chemicals at such frequency as jointly determined to be appropriate in the prior testing
period. .
Quarterly the permittee shall determine the 96-hour median tolerance limit applicable to the
fathead minnow (Pimephales promelas) using the latest EPA approved static bioassay procedures
and 24-hour composite samples from the outfalls as indicated below. The results of the bioassay
tests shall be reported quarterly to the Environmental Protection Agency, Region III, and to
the State of West Virginia, Department of Natural Resources, Division of Water Resources.
Separate tests shall be conducted for 24-hour composite samples from outfalls 023, 025, 035, 072
and 074, and a single test shall be conducted on a flow-weighted aggregate prepared from 24-hour
composite samples from autfalls 009, 014, 015, 016, 017, 024, 027, 028, 031, 036, 039, 040, 042,
075, and 076.
b Composite
-------
A-ll
Tab 1 e 2
WASTEWATER MONITORING STATIONS
UNION CARBIDE CORPORATION
SOUTH CHARLESTON PLANT
South Charleston, West Virginia
Station No.
Area
Monitored
Parameters
Monitored
7
8
9
mcc
EPD
EPD (t.1ain Flume)
EPD U1ain Flume)
Flow,
Flow,
. Flow,
Flow,
Flow,
pH
Flow,
pH
Flow,
Flow,
Flow,
pH
Flow, TCa,b
pH b
Flow, TCb
Flow, TCb
Flow, TC b
Flow, TCa,
Specific Organics
Analyzer (SOA), pH,
TemperatHre
Flow, TCb
Flow, TC
Flow, TCb
TCa,b
TCa,b
TCb
TCa,b
TCa,b
TCa,b
TCa,b
TCb
TCa,b
1
2
3
4
5
6
UICC
urcc
Distribution
UICC
EPD (Main Flume)
MICC
10
11
12
13
14
Polyols
Chemi ca 1 t.1i xing
Solvent Vinyl Resins
EPD (t~a in Fl ume)
15
16
17
Distribution
Specialty Chemicals
LPH
Specialty Chemicals
t.10deri nza t ion
Specialty Chemicals
Po 1 yo"'s
Mainland Chemicals
Flow,
Flow,
Flow,
pH
Flow
Flow
Flow, TCa,b
pH, Biomonitor,
Temperature
TCa ~ b
TCa,b
TCa,b
18
19
20
21
22
23
EPD (Holz Return)
Tech Center
SCWTW
a Continuous Total Carbon Analysis
b Daily Composite Total Carbon Analysis
-------
A-12
fORAGE -J
LVAGE AREA'N ,
Ethanol
Denaturing
M ONITORING STATIONS
5
(o
10
II
AREA MONITORED
UPPCR XS»-^MD
CHEMICAL CO^flLf
U X C C
DISTRIBUTION
U XC C
MiOIXE
COMPLEX
K1XCC
E PD
'v^/^iN^
FLuncJ
POLYOLS
CHO-OIML
ARCA
rs
H
15
RFSIKS
Jfc_
17
18
IS
zo
Zl
.22
Z3
(DISTRIBUTION
"SPEO^tTLY
LPH
SPECIALTY CHS-MAl
SPCCIfltTY
POLYOLS (NfW)
MAINLAND
CHCKUCAUS
EPDUBft
CR CENTER
SCWTW
SOUTH CHARLESTON
WASTE TREATMENT
WORKS
Figure 2. Plot Plan - South Charleston Plant
Union Carbide Corporation
-------
Cfy
x,Et Hanoi
iDenatur i n
-v*_JL *"\ i~~t^
'^T-SS:t"^' •"•^''^f-''
,-,... ..^r*—^lU!
SLAND CHEMICAL. fefeL>:
SOLVENT
SPECIALTY
• I sland
, Powerhouss
ISLAND
*CHEMICAL
-:-f;;r—i:^;
-------
\
*
NORTH CHARLESTON
A N A W H A
MAINLAND
-------
A-13
which is owned by Union Carbide and operated by the Institute facility.
Flyash, secondary solids from the SCWWTF and the Institute wastewater
treatment facility sludge are lagooned in Holz Pond.
POLYVINYL ACETATE, SOLUTION RESINS AND AYAC RESINS PRODUCTION
Polyvinyl acetate, solution resins and Ayac (chewing gum) resins
are produced by a process considered confidential. Process equipment
includes a reactor product drying system, packaging system and a sol-
vent recovery system. The solvent recovery system is a common system
located in the solvent-vinyl-resins area.
Wastewater from the solvent recovery
process sewer and all non-contact cooling
river through Outfall 023.
system is discharged to the
water is discharged to the
Some scrap polyvinyl acetate is disposed, once every six months
in the Fillmont Landfill. There are no other solid waste or air emissions
sources from this process.
and have conservation vents.
Solvent storage tanks are nitrogen blanketed
2-ETHYL HEXANOIC ACID PRODUCTION
The product 2-ethyl hexanoic acid is formed by reacting 2-ethyl
hexaldehyde with oxygen. The crude acid is refined in vacuum distilla-
tion columns. This product is produced on a semi-continuous basis 7
times per year for about 20 days per run. The process schematic is
considered confidential.
At the time of the inspection, two vacuum jets were used on the
distillation columns and the wastewater from the jets was discharged
to the process sewer. Company officials stated that the two jets
-------
A-14
would be replaced by surface condensers by June 1978. At that time,
the unit would use only non-contact cooling water that would discharge
through Outfall 027.
Air emissions are the inerts from the vacuum jets; however these
emissions will be eliminated in June.
2-DIMETHYL AMINO ETHANOL AND OTHER ALKANOL AMINES PRODUCTION
The products 2-dimethyl amino ethanol and other alkanol amines
are formed by reacting oxygen with dimethylamine in a reactor and
refining unit. This process schematic is considered confidential.
Wastewater sources include the reactor wash water and the reactor
scrubber water. These wastewaters contain about 90 kg (200 lb)/day
of TOC and are discharged to the process sewer. Company officials
stated that the reactor water scrubber will be replaced with an acetic
acid scrubber by September 1978. The scrubbing media will be burned
in the powerhouse, thus eliminating 68 kg (150 lb)/day of TOC from
this process. Non-contact cooling water, 28 m3/min (7,500 gpm), is
discharged through Outfall 074.
The air emissions from the reactor scrubber, containing amines,
are discharged to the atmosphere.
PROPYLENE AND DIPROPYLENE GLYCOL PRODUCTION
Propylene and dipropylene glycol are produced continuously in a
reactor and refining system by reacting propylene oxide and water.
Wastewater, 142 m3 (37,600 ga1)/day, from the reactor, containing
86 kg (190 lb)/day of TOC is discharged along with vacuum jet water
to the process sewer.
-------
A-15
The only air emission source is the vacuum jet off-gas.
from the refining system is burned at the powerhouse.
Residue
ACETIC ANHYDRIDE PRODUCTION
Acetic anhydride and the ketene by-product are produced by thermal
cracking acetic acid in the presence of a triethylphosphate catalyst.
Equipment includes thermal cracking furnaces and a refining system.
Wastewaters from the cracking furnace clean-out and area cleanup
are discharged to the process sewer. Non-contact cooling water is
discharged through Outfalls 035 and 036. Residue from the refining
unit are burned at the Island powerhouse. There are no air emission
or solid waste sources.
DIACETONE ALCOHOL PRODUCTION
Diacetone alcohol is produced by a catalytic reaction of acetone
with acetone [Figure 3].
Vacuum jet water and area wash-up are discharged to the process
sewer. Non-contact cooling water is discharged through Outfalls 040
and 042.
The only air emissions are from storage and mixing tanks [Figure 3].
These emissions are controlled by conservation vents. Distillation
column residue is burned at the Island powerhouse and the metal catalyst
recovered and returned to the vendor.
-------
Ie 2e Glycol 3e
12% OM
Re tu rn :>
I
Line ~
'"
Acetone
from
North 1230/31
Charleston #4 Still OM Converters 1212
Feed
#4 Still
#2 OAA
Vaporizer
#2 Vaporizer
Feed
4e
Refined 0l1li
LPII Feed
......
.
.
.
.
.
.
.
.
.
.
.
.
.
:'
..................................... ........ w. .-.-.-............
LPII 0l1li
D
............
#2 Still
1200
#3 Still
Figure 3.
Diacetone I\lcohol Schematic
. .
-------
A-17
VINYL ACETATE-VINYL CHLORIDE COPOLYMERS AND FINISHED RESINS PRODUCTION
Approximately 10 to 15 different vinyl acetate-vinyl chloride
copolymers, terpo1ymers and finished resins are made in these pro-
cesses [Figures 4 and 5]. Raw materials for these processes are methanol,
methyl acetate, acetone and vinyl chloride.
Wastewaters discharged to the process sewer from the No.1 and
No.2 solvent vinyl resin units [Figures 4 and 5] include the vinyl
chloride vent scrubber media, slurry tank filter wash and still con-
tents during an upset. During a No.1 unit still upset, vinyl chlor-
ide at 400 ppm/1b product could be discharged to the process sewer;
however Company officials stated that most of the vinyl chloride would
go to the atmosphere. Non-contact cooling water is discharged through
Outfa1ls 023 and 025.
Air emission sources include the vinyl chloride vent scrubber,
slurry tanks, centrifuge, resin collector and storage areas, cyclones,
stills, storage tanks and baghouses. The air emissions inventory*
indicates that as much as 135 kg (300 1b)/hr acetone, 3.6 kg (8 1b)/hr
vinyl acetate, 3.6 kg (8 1b)/hr acetaldehyde, 13.5 kg (30 1b)/hr isopro-
pona1 3.7 kg (7 1b)/hr vinyl chloride, 132 kg (290 1b)/hr methyl acetate
and 75 kg (165 lb)/hr methanol are emitted during normal operations.
Solid scrap product is hauled to the Fi1lmont landfill.
NIAX POLYOLS PRODUCTION
The Niax polyo1s units (2) are used to produce Niax po1yo1s,
Niax dio1s (flexible), Niax triols, blocked and capped po1yols, polymer
* Data source is a UCSC-developed air emissions inventory.
emissions discussion is based on this inventory.
All air
-------
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~::~:':'~';'IL- ;::::':.:::..::':~./~ .... ["'v"n".,, ,.."::] . : . LI~'~~ '\ 0,D-r-'~'i"~:"i-~. .
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_I/~\"~:::', .:..:~,~' J ~-'''~=''~~~l . ..:~-~ : 11--'-' .. !l;'----t=:--~-r:-i,>r rl:",~~:'-1 L
o c'"'' ,\ :':: : .- " /'.,-L~d,. \£j " ' '
(.J.....~.....) ,J , .. . ....~. .
[ '-,....-~ )'" 'r'" \'."'''.''1 ~. .
. ---:L .: ,:~;:::.;- ;'- '- '., ..,-.0. '..'. '. ' .:. . '. . FLO\.J .".
, :' A.c?... ',',' ,', : ' (i) -J 0:lJ>:: ' ,,' , '. ",'IL'l.::" . \: ="<>\!-"'- ::.4 ,... ~!~~R~~:~~rr'I'
, ,~.,.... " '-:=- "" ',"'.',' " '.=r;,~=I[J ~ , " ---:~ "
,", .
Figure 5.
Solvent Vinyl Resins Unit #2 Schematic
>
I
--'
1.0
-------
A-20
polyols and resin blends.
Polyols contain styrene and acrylonitrile.
Wastewaters from the vacuum jets and area clean-up are discharged
to the process sewer. Non-contact cooling water and tank farm runoff
are discharged thro~gh Outfalls 014, 015 and 023.
Air emissions from the reactors and the jet system are discharged
uncontrolled. All storage ,tanks emissions are controlled by conservation
vents. The air emissions inventory indicates that 90 kg (200 lb)/hr
of propylene oxide and 1.4 kg (3 lb)/hr acrylonitrile are emitted
from these sources.
Semi-liquid residue waste is put into containers and hauled to
the powerhouse for burning.
HEXANE GLYCOLS PRODUCTION
Hexane glycols are produced in batches on an infrequent basis by
hydrogenation of diacetone alcohol. Company officials stated that
one more batch of hexane glycol would be produced in late 1978. The
only wastewater source, the vacuum jet water, is discharged to the
process sewer.
All water and residue from the distillation unit is burned in
the powerhouse.
this process.
There are no air emission or solid waste sources in
ORGANIC ACID AND HYDROGENATED CROTON OIL ALCOHOL PRODUCTION
Organic acids (C4, Cs and Cg) are produced by the oxidation of
organic aldehydes (C4, Cs and Cg) and purified by vacuum distilla-
tion. Company officials stated that organic acid production would
-------
A-21
stop by mid 1979. Hydrogenated croton oil alcohol is received from
the Institute plant and refined in the vacuum distillation unit.
Wastewaters from the vacuum jets and distillation column and
storage tanks clean-up are discharged to the process sewer. Non-con-
tact cooling water is discharged through Outfall 028.
The only air emission sources are the vacuum jet inerts.
distillation residues are burned in the powerhouse.
All
UCON AND UCAR PRODUCTION
Ucon and Ucar, Tergitol precursor and Ucon HB 50
are made using ethylene and propylene oxide, butanol,
and isopropanol.
series polymers
diethylene glycol
The ion exchange unit beds used in the process are flushed and
regenerated once per week with sulfuric acid and sodium hydroxide.
This is the only wastewater from the system and it is discharged to
the process sewer. Non-contact cooling water is discharged through
Outfall 075.
This system operates under pressure; therefore the only possible
air emission sources are from pressure relief valves on the equipment.
Ion-exchange bed filter paper is disposed in the Union Carbide
Goff Mountain Chemical Landfill. No other solid waste is generated.
BUTRALDOL AND METHYL PENTENAL PRODUCTION
Butraldol and methyl pentenal are produced
propionaldehyde, isobutryaldehyde and caustic.
an oxidizer and vacuum distillation unit.
from butryaldehyde,
Equipment includes
-------
A-22
Water from the vacuum jets and area cleaning is discharged to
the process sewer. Non-contact cooling water is discharged through
Outfall 032.
Emissions from. the oxidizer vent and the distillation residues
are burned at the powerhouse.
VINYL METHYL ETHER PRODUCTION
Vinyl methyl ether is produced [Figure 6] by reacting acetalde-
hyde and methanol. Vacuum for the vacuum distillation is created by
a barometric condenser.
The barometric condenser, other process and clean-up waters are
discharged to the process sewer. Non-contact cooling water is discharged
through Outfall 039.
All air emission sources are controlled by pressure relief valves.
Distillation residue is burned in the powerhouse.
VACUUM AND ATMOSPHERIC ESTER PRODUCTION
Vacuum (high molecular weight) and atmospheric (low molecular
weight) esters are produced by esterification and distillation of
glycol esters, alcohols and acetic anhydride.
Vacuum jets and esterification reaction waters are discharged to
the process sewer. Non-contact cooling water is discharged through
Outfall 031.
The only air emission source is the inerts discharged from the
vacuum jets. Distillation residues are burned in the Island power-
house.
-------
,: " " ~~ '. ,0 L.
" , , .,'( ,I "r, " ,
. ,I f~ '1,/ ,1<>'"(,, " : ~ , . , ,
" .' I ',' , ,1)1<. '1_- ~l""-
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! i I - - -' '}----..u. "" II-~'I ;
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~ i. ;t/~ 1"" I. ~I . j "" (.t., ,.- ,II 'l' .'.-
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! i N L I-"~J ~.' -,- -. LFI .
:: rllO~ //e: . r.. .h<." Q ...
: : , -l,,,,H . ./. .' r)L'Ii;'~ V':~.r-.;... 'I, \'0\
;; M.o- I '.~ "."j,Uj, 0-oll...s
: : --" "... p. . ,. k,.- "".':"-
;; ~.. $0/ ,,' >.r~., "':,- Gjl 1 ] .
: ' [f~..:"rT l ;0;'-: ...1::~1~~..t,,,,JL~.'[" '.'[~." .t~'~~i~E~
'. "" ~J 1- ~IJ-
~ ! . .' . . '. . -'- ..,..,..,,! ~'. "'" .
< . . .
o :
, ,
, ,
, ,
, ,
, '.
" .
~. i
tI .
, "
o :
~ ! ,
' u ,
,f~1 '
, L_~I",,=>
::.c \ 'oj ( ..-
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Figure 6.
atic
' '. S stem Schem
,-' Proccsslng y
1 Ether,
Vinyl ~1cthy
>
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-------
A-24
PLASTICIZER PRODUCTION
A variety of plasticizers are made from organic acids in a con-
fidential process that includes vacuum distillation. The vacuum jet
water, the only process wastewater source, is discharged to the pro-
cess sewer and the cooling water is discharged through Outfall 023.
Air emissions are the inerts from the vacuum jets. Distillation
residues are collected and hauled to the powerhouse for burning.
ESTER DIOL 204 AND DIENE 234 PRODUCTION
Ester Diol 204 and Diene 234 are produced by reacting formalde-
hyde, isobutyraldehyde and tetrabenzaldehyde followed by vacuum distil-
lation for refining.
The process wastewater from the vacuum jets is discharged to the
process sewer and the non-contact cooling water is discharged through
Outfall 028.
The vacuum jet inerts are the only emissions from the units.
Distillation residues are burned at the Island powerhouse.
DIISOBUTYL CARBINOL AND 2-ETHYLHEXANE DIOL PRODUCTION
Diisobutyl carbinol and 2-ethyl hexane diol are produced by hydro-
genation of diisobutyl ketone and butyraldehyde followed by refining
in a batch vacuum distillation unit.
The vacuum jet water and
charged to the process sewer.
through Outfall 017. The air
and the storage tanks.
process equipment wash waters are dis-
Non-contact cooling water is discharged
emission sources are the vacuum jets
-------
A-25
The vacuum jets discharge directly to the atmosphere and the
storage tank emissions are controlled by nitrogen blanketing. Dis-
tillation column bottoms, water and residue, are burned in the power-
house.
POLYGLYCOL-DIAMINE PRODUCTION
Po1yg1yco1s and diamines are produced by reacting
mines, diethylene glycol, hydrogen and acrylonitrile.
is followed by vacuum distillation and hydrogenation.
various dia-
The reaction
Wastewater sources include vacuum jets, equipment clean-up and a
caustic scrubber. This wastewater is discharged to the process sewer
and cooling water is discharged through Outfall 017.
Air emission sources include the vacuum jets and the amine handling
and storage system. The vacuum jet gases are discharged uncontrolled
to the atmosphere. The amines which are very volatile, are controlled
by two systems emissions. The first system collects and sends the
amines to the powerhouse for burning. In the event a malfunction of
the first system occurs, the amines are collected, scrubbed with caustic
and emitted to the atmosphere. In addition, the distillation bottoms,
water and residue, is burned in the powerhouse.
NIAX CATALYST PRODUCTION
The basic catalyst (A-99), an organic catalyst, is manufactured
by reacting amino ethyl ethanol amine, Ch10rex (dichloroethyl ether)
and trimethyamine. After the reaction, the precursor is dehydrated
and refined (batch, vacuum distillation). In addtion, Niax catalysts
A-1, A-397, ESN and others are made by blending A-99 with water and
other materials.
-------
A-26
The wastewater sources include an acetic acid scrubber, vacuum
jets, process clean-up and the dehydration unit. These wastewaters
are discharged to the process sewer. The dehydration water, about 19
m3 (5,000 gal)/month, contains approximately 1% organics and is dis-
charged intermittently (once per month) to the process sewer. Non-contact
cooling water is discharged through Outfalls 023 and 025.
Air emission sources are the vacuum jets, storage tanks and process
vents. The vacuum jets discharge to the atmosphere and the vapors
from the process and storage tank vents are collected and burned at
the powerhouse. In the event that the-process and tank vent collection
system cannot discharge to the powerhouse, these gases are scrubbed
in the acetic acid scrubber and then discharged to the atmosphere.
The storage tanks are pressure vessels and emissions are controlled
by pressure relief valves.
ETHYL SILICATES PRODUCTION
Ethyl silicates are produced by reacting silicon tetrachloride
with ethanol and then filtered to remove solids. Hydrochloric acid
(HC1) vapor is released during the reaction and removed in a water
scrubber.
Wastewaters from the HCl scrubber and equipment clean-up are
discharged to the process sewer. Cooling water is discharged through
Outfall 025.
The only air emission source is the HCl scrubber. After scrubbing
to remove HCl these gases are discharged to the atmosphere.
Solid wastes from the filter, one dumpster per month, are dis-
posed in the Fillmont Landfill.
-------
A-27
GLYCOL ETHERS PRODUCTION
Glycol ethers are produced by reacting alcohol with ethylene or
propylene oxide [Figure 7].
Wastewaters from r,efining neutralization, and distillation are
discharged to the process sewer. Non-contact cooling water is dis-
charged through Outfall 074.
Air emission sources are from the refining unit and storage units.
The refining unit vents are uncontrolled and the storage tank emis-
sions are controlled by nitrogen blanketing of the tanks. Distilla-
tion column residues are burned at the powerhouse.
BUTYL CHLORIDE PRODUCTION
Butyl chloride is manufactured by reacting butanol with hydrogen
chloride [Figure 8].
Wastewater sources are from the reactor and the distillation
system. The reactor water is collected and burned in the powerhouse.
Approximately 1,500 liter (400 gal)/day of water is discharged from
the production unit to the process sewer along with the scrubber water.
Cooling water is discharged through Outfall 014.
Air emissions from the reactor, still and storage tanks are collec-
ted, water scrubbed and are then discharged to the atmosphere.
DRUMMING AND MIXING AREA
A variety of products are handled, mixed, blended, placed in
drums, etc. in this area.
-------
Reaction
le
2e
»
I
N
co
t t
Refini.n9 Tanks Tanks
fleutraliza- Distilla- Tanks
tion tion
Tanks
Figure 7.
Glycol Ethers Process Schematic
-------
1
3
2e
e e
I
Reactor Still Storage
System Sys telll Tank
Figure 8.
Butyl Chloride System Schematic
:;x::.
I
N
I.D
-------
A-3D
Area clean-up (spills, etc.) water is discharged to the process
sewer.
The major air emission sources are building ventilation and storage
tanks. Emissions due to local ventilation are discharged directly to
the atmosphere. The storage tank emissions are controlled by nitrogen
blanketing or conservation vents.
ENERGY PRODUCTION
The two powerhouses, one on the mainland and one on the island,
burn coal, natural gas, natural gas concentrates and distillation
residues. Company officials estimate the residue burned to be 5% of
the total heat requirement. The mainland powerhouse consists of two
68,100 kg (150,000 lb) steam/hr boilers that discharge through one
stack. The island powerhouse consists of two boilers rated at 68,100
kg (150,000 lb) steam/hr, two at 45,500 kg (100,000 lb) steam/hr and
one at 131,600 kg (290,000 lb) steam/hr that discharge through 3 stacks.
Particulate emissions from each boiler are controlled by an electro-
static precipitator (ESP). A Honeywell transmissometer is used to
monitor each boiler outlet. There are no monitors on the stacks, but
the Company plans to install a Lear Siegler transmissometer on each
stack. Visual monitoring via a camera is conducted by the operators.
Sulfur dioxide (S02) emissions are controlled by burning low sulfur
coal. Particulate source tests were conducted at the time of installa-
tion; however, none have been conducted since that time; also no 502
source tests have been conducted. Visible emissions from these stacks
were in compliance with the State regulation (i.e. <10% opacity) at
the time of the NEIC inspection.
Wastewater sources include the storm water from the diked area
around the powerhouses and water treatment waste.
The storm water is
-------
checked for total carbon and if the total carbon is less than a given
value, (not specified), the water is discharged to the river. If the
total carbon is high, the water is trucked to the South Charleston
Sewage Treatment Company for treatment.
Boiler and process waters are coagulated, settled, filtered and
zeolite softened. The zeolite is washed with caustic and regenerated
with H2S04' This regeneration waste and the settled solids are dis-
charged to the river through Outfall 009.
Flyash from the boilers is pumped to Holz pond. Bottom ash is
collected and used as fill cover at the Fillmont landfill.
A-31
-------
A-33
III.
POLLUTION ABATEMENT AND WASTE DISPOSAL PRACTICES
There is no wastewater treatment at this plant.
The NPDES permit issued to Union Carbide Corporation - South
Charleston Plant authorizes the discharge of non-contact cooling water
to the Kanawha River through 22 outfalls. All process and domestic
wastewaters are collected and flumed to the South Charleston Sewage
Treatment Company (SCSTC).
The Company has installed 22 monitoring stations* on their pro-
cess sewers [Table 2J, which monitor flow and total carbon. Selected
stations measure pH, temperature, and specific organics. These monitoring
stations are used to identify the processing area responsible for
spills and/or poor housekeeping practices.
The two largest cooling water discharges (Outfalls 023 and 025)
are each equipped with organic spill detectors, calibrated at 50 ppm
isopropanol. When the discharge exceeds this value, an alarm is set
and the spill detection unit collects a sample. The sample is imme-
diately taken to the Company laboratory and analyzed with a gas chroma-
tograph to determine what compound(s) was (were) discharged.
All outfalls are equipped with Union Carbide designed automatic
samplers which collect time composites. The Company stated that the
flow through these cooling water outfalls remains constant, therefore
the composite samples are flow proportional.
*
In addition, the Company also installed a station on the
industrial influent to the SCSTC. This station is equipped
with a total carbon analyzer, pH and temperature recorders,
and a biomonitor.
-------
A-34
The Company monitors on a daily basis for 43 specific organic
chemicals in the process wastewater and cooling water [Attachment A].
During the inspection, NEIC personnel collected a grab sample from
the process waste stream discharged to the SCSTC to screen for toxic
pollutants and other organics. The analyses identified a total of 39
organic chemicals in this sample [Attachment B]. Fourteen of these
were on the Toxic Pollutant List and ten had concentrations of greater
than 10 ~g/l. These are: benzene (130 ~g/l). chlorobenzene (12 ~g/l),
1,2-dichloroethane (48 ~g/l), chloroform (22 ~g/l), 1,2-dichlorobenzene
(19 ~g/l), ethylbenzene (470 ~g/l), methylene chloride (30 ~g/l),
isophorone (57 ~g/l), 2,4-dinitrophenol (11 ~g/l) and toluene (200
~g/l). No nitrosamines were detected.
The air pollution controls at this facility are extensive and
include scrubbers, electrostatic precipitators, nitrogen blanketing
and conservation vents on tanks, and collection and burning of all
burnable wastes. Union Carbide has installed 11 ambient-air monitor-
ing stations in the plant and the surrounding area. The air emissions
inventory lists the emissions of hydrocarbons and NO for each source
x
in the plant. This inventory indicates that only 9 hydrocarbons are
emitted at greater than 9 kg (20 lb)/hr. These are pentane (21 kg/hr),
acetone, (158 kg/hr), isopropanol (72 kg/hr), methylacetate (132 kg/hr),
methanol (80 kg/hr), diethylamine (16 kg/hr) butylchloride (27 kg/hr),
propylene oxide (53 kg/hr) and ethanol (32 kg/hr).
Solid wastes are placed in the Fillmont Landfill. Goff Mountain
Chemical Landfill, and Holz pond. Non-chemical (lumber, paper, scrap
polymer, etc.) solid wastes are disposed in the Fillmont Landfill
operated by Union Carbide. The waste is put into the landfill and
covered daily with bottom ash from the boilers. Chemical wastes are
trucked to the Goff Mountain Chemical Landfill* for disposal. The
Goff Mountain landfill is owned by Union Carbide and operated by Insti-
tute plant personnel. Both landfills are State approved.
* See Union Carbide Institute report for discussion of this landfill.
-------
A-35
Holz Pond~ an anerobic lagoon owned and operated by the Company~
has a capacity of 760~000 m3 (200xl06 gal). The Company plans to
expand the pond to provide capacity until the year 2000. Details of
construction for the pond were not provided. This pond receives
9~OOO kg (20~OOO lb)/day of sludge from the South Charleston waste
treatment facility~ l3~600 kg (30~OOO lb)/day of sludge from the Union
Carbide Institute wastewater treatment facility~ 45~400 kg (lOO~OOO
lb)/day of flyash from the South Charleston plant and 11~800kg
(26~000 lb)/day of lime.
The supernatant from Holz Pond is collected and
SCSTC for treatment. At the time of the inspection~
evidence of leaking or leaching from Holz pond.
returned to the
there was no
-------
A-37
IV.
EVALUATION OF SELF-MONITORING PRACTICES
BIOASSAY PROCEDURES
The bioassay evaluation [Attachment C], conducted on April 11,
1978, showed that the Company bioassay facilities are maintained at
the Union Carbide Technical Center in South Charleston. The facility
is environmentally controlled and properly equipped for bioassay testing.
The bioassays and the associated chemical tests are performed according
to Standard Methods except as noted below:
1.
The effluent sample collected for bioassay testing is a
24-hour equal-volume composite rather than a 24-hour flow-
proportional composite as required by the NPDES permit.
2.
The bioassay tests do not always commence within eight
hours after sample collection as recommended by Standard
Methods.
3.
Dechlorinated city tap water is used as dilution water
rather than Kanawha River water as required by the NPDES
permit.
4.
The bioassay tests are not done in duplicate as recom-
mended by Standard Methods.
5.
All bioassays are aerated throughout the 96-hour test
period. Aeration should be discontinued except in cases
where BOD or COD are sufficiently high that adequate dis-
solved oxygen concentrations cannot be maintained.
-------
A-38
6.
The laboratory depends on controlled ambient
ture to maintain a constant test temperature.
but not required, that a constant temperature
used to maintain test temperatures.
air tempera-
It is advisable
water bath be
ANALYTICAL PROCEDURES
The Company performs all the analyses required by the NPDES per-
mit. The analysis are performed according to EPA-approved methods.
Analytical. quality control procedures consisting of routine and blind
duplicates as well as spikes and reference samples are routinely per-
formed and the test results are well documented.
Company laboratory personnel analyzed standard reference TOC
samples provided by NEIC. The results were in close agreement with
the true values [Attachment DJ.
SAMPLING PRACTICES
Some of the automatic sampling units contained algal growth,
flaking paint and an accumulation of solids which could contaminate
the samples. Officials indicated that the Company does not have a
preventative maintenance program to clean and repaint these samplers.
Because of the poor maintenance practices the samples collected with
these units may not be representative.
The samples are reportedly 24-hour composites, as required by
the NPDES permit, with the first aliquot collected at approximately.
5:00 a.m. each day. Observations showed that at 1:30 p.m. several of
the sample containers were already full and others were more than 2/3
filled. The samples, therefore, are not 24-hour composites as speci-
fied in the permit. Furthermore, the samples are not refrigerated
-------
A-39
during collection, which is contrary to the requirement of maintaining
the sample at 4°C. Adequate container capacity or a reduction in the
sample aliquot size plus adequate temperature controls are necessary.
SELF-MONITORING DATA
Discharge Monitoring Reports (DMR's) from October through December
1977, for the cooling water discharges are contained in Tables 3 through
9. The DMR's show, that during this last quarter of 1977, the Company
exceeded both daily average and daily maximum TOC limitations on the
total discharge from 16 small discharges [Table 3]. In addition,
daily maximum TOC violations were reported for Outfalls 025, 032, 035
and 074.
-------
;r:..
I
~
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Tab 1 e 3
SUMMARY OF DISCHARGE MONITORING REPORTS*
SOUTH CHARLESTON UNION CARBIDE
OUTFALLS 009, 014, 015, 016, 017, 024,
027, 028, 031, 036, 039, 040, 042, 048, 075, 076
Parameter Permit Limitations October November December
Daily Ave. Daily Max. Ave. Max. Ave. Max. Ave. Max.
Flow - m3/day (103) N/A N/A 110.9 123.0 116.2
MGD N/A N/A 29.3 32.5 30.7
Tota) Organic Carbon
mg/1 4 12 2 8 4 71 5 67
Temperature (OC) N/A 43.3 23.3 22.8 11. 1
pH range 6.0-9.0 7.1-7.3 7.2-7.7 7.4-8.6
* m3/day and °C are not reported by the plant; values are computed by NEIC.
-------
Table 4 .
SUMMARY OF DISCHARGE MONITORING REPORTS*
SOUTH CHARLESTON UNION CARBIDE - OUTFALL 23
Parameter Permit Limitations October November December
Daily Ave. Daily Max. Ave. Max. . Ave. Max. Ave. Max.
Flow - m3/day (103) N/A N/A 67.0 74.2 70.0
MGD N/A N/A 17.7 19.6 18.5
Total Organic Carbon
mg/l 4 12 1 7 0.6 5 0.3 3
Temperature (OC) N/A 43.3 20 21.1 11.7
Vinyl Chloride
Monomer N/A N/A 0
pH range 6-9 7.2-7.4 7.4-7.6 7.3-8.0
3 0C are not reported by the plant; values are computed by NEIC.
* m /day and
:x::-
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)::>
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Table 5
SUMMARY OF DISCHARGE MONITORING REPORTS*
SOUTH CHARLESTON UNION CARBIDE - OUTFALL 25
Parameter Permit Limitations October November December
Daily Ave. Daily Max. Ave. Max. Ave. Max. Ave. Max.
Flow - m3/day (103) N/A N/A 58.7 64.7 61.3
~1GD N/A N/A 15.5 17.1 16.2
Total Organic Carbon
mg/l 4 12 3 12 4 28 5 10
Temperature (OC) N/A 43.3 23.3 25.6 16.7
Vinyl Chloride
Monomer N/A N/A 0 0
pH range 6.0-9.0 7.2-10.2 7.3-7.9 7:1-7.7
* m3/day and °C are not reported by the plant; values are computed by NEIC.
-------
Table 6
SUMMARY OF DISCHARGE MONITORING REPORTS*
SOUTH CHARLESTON UNION CARBIDE - OUTFALL 32
Parameter Permit Limitations October November December
Daily Ave. Daily Max. Ave. Max. Ave. Max. Ave. Max.
3 3 N/A N/A 15.1 16.7 15.9
Flow - m /day (10 )
MGD N/A N/A 4.0 4.4 4.2
Total Organic Carbon
mg/l 4 12 0.7 3 3 15 0.4 3
Temperature (OC) N/A 43.3 24.4 27.2 22
pH range 6.0-9.0 8.5-9.0 8.1-9.0 7.3-9.5
* m3/day and °C are not reported by the plant; values are computed by NEIC.
::x:-
I
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-------
:x>
I
+=-
+=-
Tab 1 e 7
SUMMARY OF DISCHARGE MONITORING REPORTS*
SOUTH CHARLESTON UNION CARBIDE - OUTFALL 35
Parameter
Permit Limitations October November December
Daily Ave. Daily Max. Ave. Max. Ave. Max. Ave. Max.
N/A N/A 14.8 16.3 15.5
N/A N/A 3.9 4.3 4.1
4 12 21 2 10 2 39
N/A 43.3 22.8 22.2 9.4
6.0-9.0 7.4-7.9 .6.6-7.6 7.3-8.0
Flow - m3/day (103)
MGD
Total Organic Carbon
mg/l
Temperature (OC)
pH range
* m3/day and °C are not reported by the plant; values are computed by NEIC.
-------
Table 8
SUMMARY OF DISCHARGE MONITORING REPORTS*
SOUTH CHARLESTON UNION CARBIDE - OUTFALL 74
Parameter Permit Limitations October November December
Daily Ave. Daily Max. Ave. Max. Ave. Max. Ave. Max.
3 3 N/A N/A 23.5 26.1 24.6
Flow - m /day (10 )
MGD N/A N/A 6.2 6.9 6.5
Total Organic Carbon
mg/l 4 12 0.6 5 0.8 4 2 13
Temperature (OC) N/A 43.3 25 24.4 10
pH range 6.0-9.0 7.1-8.8 7.4-8.9 7.5-7.7
3 0C are not reported by the plant; values are computed by NEIC.
* m /day and
>
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-------
>
I
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Table 9
SUMMARY OF DISCHARGE MONITORING REPORTS
SOUTH CHARLESTON UNION CARBIDE - TOTAL ALL OUT FALLS
Parameter Permit Limitations October November December
Daily Ave . Daily Max. Ave. Max. Ave. Max. Ave. Max.
Flow - m3/day (104) N/A N/A 30 32.1 30.3
MGD N/A N/A 76.6 84.8 80..1
Chlorides - mg/l ':4/A N/A 5.5 21 .99 2.06 4.0 2.1 4.0
1 b/day 12,718 19,427 421 1,684 1,456 2,828 1 ,411 2,672
kg/day 5,774 8,820 191 765 659 1,284 639 1,213
Phenolics - mg/l N/A N/A 0.004 0.008
1b/day N/A N/A 2.5 5.1
kg/day N/A N/A 1.1 2.3
Dissolved Solids
mg/l N/A N/A 6 23 7.7 13 15 37
1b/day N/A N/A 475 1 ,762 5,479 9,191 9,886 24,716
kg/day N/A N/A 215 800 2,481 4,178 4,477 11,221
Kje1dahl Nitrogen
mg/l N/A N/A 0.21 0.60 0.07 0.14 0.09 0.19
1b/day 492 1,014 16 46 49 99 63 127
kg/day 223 461 7.2 21 22 45 29 58
Organic Nitrogen
mg/l N/A N/A 0.09 0.25 0 0 0.01 0.05
1 b/day 436 872 7 19 0 0 7 33
kg/day 198 . 396 3.2 8.6 0 0 3 15
3
* kg/day and m /day not reported by plant, values computed by NEIC.
-------
A-~.7
ATTACH~1ENT A
COMPANY ORGANIC CHEMICAL MONITORING
-------
i Y£~~
\" ~,,~r;T''r;:;..
. ,iJ~~~1i!.
~"C'I~
~~~,.'
-.~~~
UNION CAR B I DE CO H PO RAT \0 ~J
CHE0.'ICALS AND PL,\Sl iC,~
p ~}. e ()" c C.ti 4. So, Il: 1 i. ~:' . .-. .. t I '. .
. ~ \',
i CMAFtLf'.::.TON PLANT
,\ ',I ~ L1 S t II.
:')77
Dr. T. E. Fielding
Enviror~-:1ental Protection AgCIli.'Y
Region- III
\-,est Virginia S.action, i::nf:JY'.:cr.:(':l':. :"-., ',',
6th c.nd "':alnut Streets
Philadelphia, Pei1,.sylv.11~ia
. ,',','1
l'jl(l."!
I~.':: t . :
~. I~ \! ~:: i t
i:-" f] 0 COO 7 8
~:": Dr. Ir.
L. "'lorstell
E. Fieldinq,
H,' r . :
TJet...tcr, J.
..~ '..I :12 ::: J ,
1977
De a r Dr.
Fieldin':; :
A re\'i\O:w of t:Ll: ill;: ~!;;;::ti(';; ,;t',;t to you s"~ ":,\i,.:ti('1~ r"'sults hu'~'e alway.;
~!-~:;..-:~ .yirt.uall:: :10 Gth'~'.l2ne '.
-------
. '
::(!!':1ic.:il *
cAaldehyde
,.::;P[one
'CI~ lonitrill:!/HVA/:'EK, .:~( 1(~L.l,:,"~," :.
.'...1 nol
~ 1 rtcetatc .
.'~~vl Ac=1'I.)t~
',:..111 C.:lrbitol
,'.1 '1 Curbi~ol Ac~t:'1i.'!
,ut)'l Ccllcsolve A,.>~'t.Jtl.,;! J~,:~~)'.':
'~I=a Idol
".:::, i tal
: 3 =:,i to 1 ,\ce t.a te
'~I' ~ 0501 '.Ie, Aceta te
'i etcne Alcohol
~i~ obut1'l Cellosolve
)it; sobu ty 1 Ke t.one/ 2 - E t :'1' 1 nl.' :-:a ll.~'_':' ';', 1
:t nol
:t: 1 Butanol
:-Ethyl Hexanol
: jthY 1 p.cxy 1 ChI o=i (~8
,1 hyl ?entaldehyd2/!'~ct~yl Vi.lyl :\'."l.': ~lt..
:~h1' 1(: ne Glycol
_I" pt.J.:-.ol
; xJ.;101
:,~ yl Cel:'Qso1ve
~51~butYl C~rbitcl
~2 ~utyl Cello501v~
-5 propanol
:esi ty 1 Oxide
:e8~anol
'~.hc:.:y Ace to:ie
,:ethyl A.."7ty1 Alcc:;ol
';1:1'.'1 Ca=!:;i tol
:.' :;11 Ce11c501v2 ;".>.:~'3t.(. 'j'r~)t'.), ,.'~!)
,~.;. t~'"j 1 T ....OD' U t"j' 1\".'1 ~ C :-.-'" ':',~ -;;. '1' '3'" \; ,",' ~ ,. .,' ',' :
"-.. .. ~ ....... - ..'Ii;;;, ,. .1.,:- "". -
il'''~;'''I' Fe"'''ena.l/'''''''h','l qljo,,'l i','1' n' ,-
- --_...- .,"- -'-01.] LJa"': "......,1..
~.~ l? ~cdiQne
::'':'ii3colcne
::'1- " .... 0 1 'Q / n - Hex.:l " c 1 ' , ;; i <.: ," \ '.' , . ,,', '. ' .1 !' ~, I : 1 ' ' :
...- Z"" - ..::J .,.. .. ,* I"'" _. -- :. \,.. 1 ..
..' ,?.!'.:scl D:-1
~- pasol M/n-auta~ol
?':-o?ic~henQne
:->I?y lene G' ycol
: 1'1 E~h1'l Ether
i !: ~ ~ . ,
"I Q co P e C 1, ~ . C C.. r>'~ ; ,. .., I 'r' 1 ' , -" '
.- - ....... ~.._.II~"-...4_... ~..... : ~\"'.,
o\.'u i~(:rl~ifi~~:'lGr~ is t.: l"L't,
, ,
I ~ " J
:1>5
, ....
-I
I
': f,:~..i ~ \,..::-
.. . , . .
5p~C't:'-O:7iet.~~! :...~
:OJ t:F~,
"', ,
. I',
. !
A-49
t.. ": ~. p P ~1
10
456
l32
289
:04
4.1
115
42
67
2
6
14
77
67
2i3
2
401)
4
200
2
153
4
18
75
10
4
...:.10::>
954
", '; l1' .
67
365
46
46
40
46
87
87
137
.,
,
2
--
2
..,
-
40
:00
8
, .
'. ' ~ ~! I .: :, ! r' '~;- ~ ~_.;; 0.: \ 1 r~ (~ t. ~ (!
: ~; I' ' , : ~ ~ ~ ~;.... . ~ ~.. c .; r :-~ !-J ;"'i .
I ,,,\o!, I"..
. . . -. S t : ~ '..1 C r-. t i ~
".' '\' ,
, .' --
," "'...
-------
H CHARLESTON P'~T
------- --
urHON CARBIDE CORPOP',,\TICN
CHEMiCALS AND rL;\SIIC:~
PO. 1:10)( 8()04. ',20TH C" '11' r ',1 " ..,
Protection
Agency
E:wi rO:-....'1le nta 1
P.egion III
Per~its Application S~ctio~
6th and Walr.~t Streets
Philadelphia, Pennsylvania
Attn:
Dear Dr.
19106
Dr. T.
E. Fielding
1\U'.Jt~3t 0 I
i. ') -; 7
Subjc\..'r '.
Fielding:
~H'DES pf~rr.1 it
\'i'-,,' 0 0 0 f) iJ7 8
As r e qui red by Par t 11 I, :.; ,). 3. p " (.j(~ 2 4 0 feu r
~'IPD:SS Permit, attachec is an .:J.nc;.lytii.'.11 c:-t:n-ac:erization of
t~ec801ing water discharges from :~c South Charleston Plant.
,T ~"/"'" 1
~ _..., r'-
Att~ch~ent
cc:
Vr::.r'l tr:'Jl'f ~'ours
--; ..1 ...J:./ / J(
i .' . I /., f" . '"I .\ -f' Lv
I ,I"~ ... ,-,....:
J. L. ~oJo r s t e 11
F: : . ''; 1. r ,OJ ~ ;i~ ~ t.;. 1
(:~)ord i.!"1d tor
?r:;~.~c t~'J:1
VJest. Vir;i~i,~ DC:tJ~rtrr.(-':::' '-'~- ~.~..1t'_~~::l ::O":::cP.1~ces
Division of W~t2r R~50U~CCS
1201 Greenbrier Straet
Charleston, ""est Virci.:11::
At:.tn: Mr. R.. M. Sovic'
2-~r. J.
D. :-!oo re - :..:c c
::;')11
.. . ..J... ..
-------
SPE2IFiC
C:~C;l\~ ne /1~ - ?rci:>:~101/~":: lhy lb'.: t ';'~.1 :.':. ':-y.:':- 0 -
:thyl Vinyl ~cetatc J -
'~I?a~Ol ~ -
~:= 'o:;:::-:enone ') -
. -:: ~)' l e :: e G 21' co 1 0 -
:,j - ] J 5
....~ -
,
"
;:; -
o -
') -
() -
) -
" -
v
o -
o -
() -
I) -
o -
o -
o -
a -
'J -
I,
~~e s~eci~ic chc~:=al ~~al~.scs
:~I ~bc':e i C8n t i .: ica ti:);1 is by
,.H"<'; J0;1,-'
1)'.:' (::~3
. .-
~.:rr:::ld~o~r.!~~n1~ ard...1
r!: the c::rc:7"latc.!;raph.
~C::.':'.:.i,:-,;~ tL:.'l~S
:'~ tee tee.
23
~ ..,
7
14'
17
, "'
..~
,; :;
lS
.
..
1
2
7
3
20
24
2
1
...
I
1
6
1
-'
,
J..
1
1
3
2
1
1
1
1
13
11
1
1
3
1
1
2
1
1
oJ
G
38
6
3
1
.:.
0)
"! "'t "'"
- ~ .J
') .
-...
')
L.
1 'J
1
~ "
~ "':'
1
c
l'~ I)
~"':'J'C:= 0: t~~-es ,j-2te.::'C-::d frc:ii ~:1'\:" :l~c"of ~~'.l-' r_-':..),...': ~ ~.:~..; '.,,'.It"2~ OU-::311S
. ~ 1::;0 ~Z:.1' tii7~I:; ?f~=:.o,:l. :"uL'. :.: i 1 ~ :'l' I ':::'," t; ~"'.i"r': ,-:)r.!?(")'_:;""~'J co\,;,ld =~
~:..-,.-- :"",; .,',,- "') ('\."" -~,-"-"-" ."1''''''' "',....~... i-, :,-.,."" ",."., .
---_C_-'-' Q...:r -,,'-'vO ~_...c.:- -"..:1....:, ,l."" .' ----'"
-------
A-52
S?:::C!FIC
c\ ~G .:'.>i 1 C .l::: S~.~ ! (.~ :"', :..3 ':":,~ ?: ': ~?
-.---.------.- .--- ---
FRO:-l COC~,1 ::C '..:X:"~~;;:
: : :- =- ."'. =- i J S
----. -- -
.-----..-
p.:;:r~ical *
1"'" .:~7 .
~?:.!k
2tone
::'.It.::.n~l;tJ=c~a.~c~ :,1
-:.y1 ;\cetate
::y1 CJ.==:tol
=yl C~rbi~ol Acetate
C:lSO
''0--:- Q :? 0
0.020
o . r,; 7 0 .
O ;,,, ":<
.. 41 \J "
~......: Ce::':os.::;l"/e
,. " ,.., ..,
u......;..
. .:::, u t 'j' l C .;. ::- :: =- to 1
~ ::-?:-o?ai1:)1
.sityl Cxi6eiMet~yl
: -:.1;cxy .;ce :.or.e
... -~, ,t 1
.-."0.: I..
.=-. -: C :. ::~ t c
0.001
O.()07
0.003
0.040
C.020
0.009
0.003
0.020
0.080
0.007
0.001
0.001
0.006
0.001
O.0S0
0.020
0.001
0.020
:.yl Cellos~lve Acetate/Diet~yl CJr~~~0~
::-~itQ1
::-:>.:.tol ;"cetate
2.1osclve
::lcetone Alcohol
~thyl Ethanolamine/Dimethyl Ethan0iJ.mi~c
isobutyl Carbinol
~sobutyl ~e~one/2-Ethylhexaljehydc
~=o?ylene Glycol
'~yl Ee:-:anol
.yce 1
'~ex3.nol
:::y1 Ce1lcsolve
;":h1' 1
CtJr~it.ol
0.003
O.a20
"-~'1i I 1-., --r1 ;: - -. /~._"'''--''- 01 '7""...'n~"";;"~r...........1" ,~...., "':10
:_..1- SO_Ll_j- .,e\...o..e h r_,,-,::.::n "''''''''':'! .....-:. ...'1,...;,-,,-
:~~;l Vi~yl ~c~tu~e
-:: :-S?c=.r.ol
O.C01
-:-:'?'.1'lene
Glycol
0.004
0.0~0
:.~?lo?ne~C:-le
rct\::~":i;-):)
t i :~:(")5
C:l r0r:-o,::i ~.:)gr21p::J~ a~.d
()il t~c= C~r0!7~a tog::aph.
"::e spec~::.c cheDi'':3.1 ;;nalysc..:s
:~~ above id~nti:ication is by
arc \1,:::0
L. 'i '~ ,;:.s
.:-.2 C'1:lc~nt.::-a tio~; (ifl ~p;::) ~) t ;jl:io
~ cooling water from the ~lant.
_0 ~~.
.>: ," .\ :.
.'1 v.:::: I.-l . ~". \ l i
~~'./...~!" -
t:;c t:~ta1
f :. O\v
-------
\\TASTE\'l.~TER i-10NITORI~G STl\TIONS
Area
Monitored
Station #
(1 )
(2 )
JL\'l
1/78
1
2
3
4
5
UICC
UICC
Distribution
UICC
EPD (Main Flume)
6
HICC
7
8
9
HICC'
EPD
EPD (Main Flume)
10
EPD (Main Flume)
11
12
13
14
Po1yo1s
Chemical Mixing
Solvent Vinyl Resins
EPD (!-lain Flume)
15
16
Distribution
Specialty Chemicals
LPH
Specialty Chemicals
t-1oc.erni za tion
Specialty Chemicals
Polyols .
Mainland Chemicals
17
18
.19
20
21
22
23
EPD (Holz Return)
Tech Center
SC\\TT'iv
Continuous Total Carbon Analysis
Daily Composite Total Carbon Analysis
~U01M ~~K~~~~LU~
-
;;"~c'l.L'
A-53
Parameters
~1oni tored
Flow, TC (1,2)
Flold, TC (1,2)
Flo...', TC (2)
Flow, TC (1,2)
Flow', TC (1,2),
pH
F 10''', TC (1,2)
pH
Flow, TC (1,2)
F 1 0'.-', TC ( 2)
Flow, TC (1,2)
pH
Flow, TC (1,2)
pH
Flow, TC ( 2)
F 10,'1, TC (2)
F10'tl, TC ( 2)
Flow, TC (1,2)
Specific Organics
.~nalyzer ( S OA), pH,
Te:TIpe=ature
Flow, TC ( 2)
Flo'"" TC (2) -
F 10"",
TC ( 2 )
Flo\-;, TC
Flow, TC
Flo'"" TC
pH
Flo',.,
( 3 )
F10'..,r, TC (1,2),
pH, Biomonitor,
Ter.:pera ture
(H2 )
(1& 2)
(1&2)
--
-------
.. ~j'" L.I J.""" ~ i..41"" \",.... .1.,.'. J' ~ ...
BASED ON 31 i4HlHJirC(:>l~;rpnsi1'tsAMPLES
SPECffiC-oRGANIC
MAX ppm
~
AVE ppm
270 17
-.
26 2
-
41 4
--
- 50 -- 4
132 9
--.
18 2
__250. 3l.
--"-.-
18 2 -
No. of Times Detected
-
-
-
- -
- - - --
~~-.:..~getal~~ ~lyQ.~-
2. A( etone
---- ----' .-- ---- ---- -------------.------
-1. A( !y!on- ~!i1~L t~~!h tJan. ~.lAc~ _'lte.,~ _9J~ra _deh~. ~~Ar .~"
-~~Y.l 5.0 2!'9.RYl pg_b'e~1._- --
5. A1!~ISO~:9P~r~~.olv~.. !t~ -.
6. Al!~Q:)ropyl ;olve. ;~3 ._-
_l_. Bt t.C!~2.L~~~---_. -
8. Bt tyl Acetate 'Area'
-'-'-' -n- ----- .-
-..9_~~ !¥.l Ci rbital -----
10. E Jtyl C arbita . Acet Jte II f. rea II
11. B-Ityl C ~lasa-:;.,e-;;~ ~ea-'-;-
---f--~.- ~-- .-
12. E Ityl C~llsal1e ACE late
..::._-
---D...o.-.C a rbitc fL Acet 1 t e-
14. C ellas( lve
-------
15. C ellas( lve A( etate
--- --_-c_---
-1~~~ hlore~ - II Are~ II -- ---
J. 7.!-_[,Jacet( ne Al( .oh.oL 'Area'
.18. Dlmet~l :!~ce 9te
)9. ~Ieth\.lene Cavcal
l~-thanq
21!-~ .t\Y!~ tanal. "Af~ ~
~~~t}Y!b~ ~alde 1Y..4L [!rea.1I
23. EthylhE~{an.ol"Area I
-- -------
24. Ethyl B Ityl K tane 'Area
25. E:.hvl P QQYJ9~Jolei 1
.1__G-!-~ !yc.ol. Pii,g::_~ .Q~ .-- - 1---'
27. f eptan >1 IIAr< a II
28. f exan.o "Are"
29. 1- e~l ( e11a51 lve IIl\rea"
-"--- --
30. I obuty Carl- t.o1
----- ----
31. lf~'?_E!".op_...n.ol-
32. I. apr.op r1 Ace -ate" \rea II
33. )'" cthan )1
34 0 tv ethyL ~'El!..{ 'ce~t. ~._--- --- -.---.- --.-. --- -- ---- '--
"35. l\,' ethyl ~ella. aive
36. 1\. .. . -~ p.l!o; Q hTP. r"!r>t.:\ I II:-> "A rl' '", "
-_.
..
11
26
2
..
2
ll.
22
6
1
3
1
9
7
5 1
'3
23
4
lQ
5
4 --
4
3
14
.11
_.
.-
..
--
-
-
-----'
--
..
-
1.t.4 If 1~~~~
70 17
23 I -i --
:~=-i=-- ~--
10 I 4 -
45 6
.---.-
61 2
31 2- f--
67 2
17.6-
-- _4.1
1.77
50
-- -.If>-. -
J-
7
11
971
151
-. -~
._.JL- - ---- L~?__.
'.
5
'3
5~.IJ-9573
,.t}-f7)1 t--'/I )./('~.Jr 7'
C.ont. Page I of 2 Pages
------,------ ----. . ~
. ---._-
--------
-------..- -.-.-- .-----.-
11
.---.--- ----- --.
35
16
6
1.
-~-- --..------ ..---
-------
IlfuSF.jIiN ~H.C~O~i~AWS -
..
_J
..
..
w--____9~r~U;_lC_QB~mPS ------- -----
~Z~_Jetb.Y __~r!!Y! ~!col~L-. - ~
-~~:- A~~~ i'La-ifi~nel----- -------:-
------- '--.--"-'--' .
40. ropanJ} "Ar~a"
- .-- "-- .---
-1t!-lrQPJ.Q hg!lQ.._Q.--
_1~_!- J.9~Yl.- ..D~ Gl 'col I Pueg" --
43. tyren
---
--
No. of times Detp-cted
i
I
I
I
- --
- -- -_.-
2 4 11
2 .-5. (j ----2-
, -1,~1 1
--
3 34 1
1 11" *
- --- -- -- --
...- ..--
---
-
--
.-
-- --.
.---
I
-
--
\--
I -
-
.,
I
,-
I -
.
I --
I
I
I I
~"T\
AV~-
--
-
-.--
-
-I
~l
I
-:
---
--
-----.--
---
--
---
--
-.----
_.-
--
---
--
--
--
--
--.--.
-
--
--
--
--
-
-_.~-_..-
---.
--
--
.--
--
--
* L 98 t1sn
pp
51'l-9513
PAGE 2 of 2
:x=-
I
U1
U1
-------
L '.~" It. J. J. 4. L.J , """j...1 '"-' LJ. ,\ ...,) It, , ., IJ .i. .... .~ I l
llASED ON 31 2:fHoUi{COlvfPC'5si'l'ESAMPLES
..,.
I
t.h
0'1
SPE~TITTt)RGA~IC
--
--
----
2
--.---.
--
"-
.-----
17
139
17
_.4-
17
16
-
~L.."._~"-
94 1~
--'
---
7
21-
2
--
_L_-
1qO
----
38
1.3
------
1~-
-"
---
---'
21 '-----r
---
47- -~
---2 --- 1.
-"
--
.-.-
--
-,~
---
2 16 1.
3 53 3
15 30 ---I
9 :
"--
:31 376 100
2 53 2
_31 166 42
~L 2
2 14 4
Cont. Page 1 of 2 Pages
-"
--
-----
G.e ..
"
-------
"'E_'~8iiiSji;.-geaM.
srECIFl~p.GANlGS
No of times Detected
M~Y11
lWr. R~m..
. -- ..- -.,-.:... . . -..-.....- --- ,.. ~- .. ~ . u .--
.-. _. ---.. - -
27 !.- .1Q!hY.1!r:!!Y.! l\lcohbl ~ 11}\ ~9
38. ).1 etho.N Ac€ Lone 1 16 *
J-g :-. ,1esIt") COxI e 1 67 I 2
--..- --,--- ------ -
40. ropanpl "Ar'u" 10 1{~2 9
_..- ---- -.--- --
41. I rop!Q{ h~no!. g -. ~- -
_.1f.~_. IQRY! .ne Gl \fcol~ Nea" . 2 31 1
43. tyren I> --
--
----- --- --
- ... .
--- -- - -
-- - ..
'
-. -. .
---- --
--- ..
;
I
- l --. -- -- -
-- .-.
.--- .-
~- .--
._-
-. -
.- -- -
~ --.
.-- - -..
- -- .-.
.- ----
-
-
..
* I Les ~--sw i1 1 1 .--- -. -
pm I
~
511~-9573
PAGE 2 of 2
I
Ul
-...J
. -.-- - --- - --- -..-..---
------.
. .-. -. - - -----_._- ----...-------- - ~
-------
BASED o'N'" '3'0 ,,, .. ..,. 24Hd'UR~6HtX~bsI'i"E;;'gAM PLES
,
U'1
;::0
SPECIFIC-ORGANIC
---
.-
---
.~- --- .- - -
J.~~~,=- etaldE b~ --
2. A( etone
---- -------- -- .. .----. ------- ---- ._--
3. A( !Y!~!!- ~g~- Ivfeth 1 Vln '1 Ace ~!~L.~ _Q!era Q~.b~ e liAr ~a"
_'!~1~Y.J~~ ~~11050 ve "~rea"
---- -..-------.---.--------------
12. Butyl C011sol e ACj tate
- -----"- ------ -
-1_~~a rh!t~ _J\c..et t~
14. ( elios( Ive
-f5. ( eUos~.lve A< etate
16. ( h~o-~~-; -~;Are( 'I
6: __I.1a~~g ~;-~!~ ahol 'Area'
18. Dlmeth I Ace ate
.----------_. --._---- --
-1~~. ~fE:~~~ ~~r}~-~ ~=CQ~ -- ~-- == ------ -.
~1JJJY1J~t_tgnQt "Ar.~.9. I -- -- -- .
~f~ thY!h~ ?fQht~--ly_q~-' ALe.Q.~ --- -- - -
23. -I thyllu:xanol "Area I
_..:...-=---- ---- '--- ----
24. I thyl n Ity1 K'.tone 'Area
---- ------- -------.- --=-:-=---- ------ "--
.1~ :bYLP. ~1QY..!9 ::Jolel L_--- ..
~.2_!-( !y£Q!- 2.l~g.Qf.iJ~ --------- '"--' ---- -- -- .
27. 1- eptanbllfArl.a"
20 . 1- exa no. If Are 1 "
-.-- -------- ._--- -----.-
29. 1- exyl Cellos JIve "~ea If
--- ------ -----.---' .---'---'------ - .--
lQ~ 9..bu!X - C~rl:: tol
31. I ~ Qprop no1
32. I oprop~l Ac~ :ate If~rea-;; .---
33. Iv ethanp1
340 N eth~.fu.!!~ 'cetate
35. ~I ethyl t:ello~ olve
3Ji fllleth~1 b~llil~ nh,p - .-t:P. ::Arr:~'
51JI-9513
.-.-
._h_-
'---'
--
--.--"
-
-
----
. -- --.- -..-----
--
No. of Times Detected
MAX ppm
AVE ppm
--h:67 I i-~1-
==:l~61 2~-
1..7 --1 -
._--
30
29
--.2
-
--
.
-
12 39 8
25 14 ~!r
1 281
- ---2 __it1
:5 3~9 17 -
1 10 *
1 27 *
---I-
9 - 244 19f-
-- f-----
--.3 8 *
---.-
14 I J-.9.L_- __22- -
--
.0___-
-
10
~!L
1
9
12
J
91 12
..- --- ----.--... --.
592 38
-- --
87 3
1'21 --Pf -
.'..---
101 9
---
12 --- ---.! -
--
---
..
.--.--
--
----
,
---
-.
"--"-- -----
--------
*
1
.L
]2
15
64
tQL
52).
2454
66L
-
6
13
---
-
30-
12
.~
-------
III""""
- .E_i~wbw~iii-s-fiiilM8ii
s ~EGIITc..J:W rilltIIG S
No. of times Detected
~I\X p~
AVE :n~=
--- - .;.--_.__\..~ .L - -- ' -- -- --
~_Z~- v1 eth" --~!!!Y1. !l1co} QL- -J 1 114 I 4
-- ---_J.- _.- --- --
30. :letho C" Ace. one 1 10 *
-3 9 ~-. Xc s it'. T-o-if ]e--
--.-.- ---- --- -- 9 -
40. ropan )1 liAr a" 11 72
-..- ----. *
--11~r !:Q2!Q.l h~nor.: r:- 1 3
.-_. ---- --- ---- -
~~ ropyl .ne GJ 'col ' ~e~~~ '} 402 2J_- I--
-
43. .!yre~- --- c--
---'--- ---- --- ---
--- - -- f--
-- -- -- - - I---
-
-
- -- -- -- -- -- --- - -
-- -- --- - -- --
--- - -- -
I
--- -- -- ..-- -
;
I
- l- --- --- ---- --- -
--- - -.-. --- -- ---
--- .-.-- ..-- ._--- ---- --- ---. -- ---- ---- -
~ -- -
-..- -
-- - --
.. -
-- -- - -- --- -- -
--- _0.0- -
- -- -- ---- - -- -
- --- -- - -- --
-- u
-- -- ---
--
--- - - -- - -- - --
-- ~
I'J: --
Le. 8 th In 1 ppm I
p
5111-9573
PAGE 2 of 2
I
U1
\.0
- -- -~-----
-------
MAX ppm AVE ppm__-
-- __f-.r--~~
m-II ~g-
4. ok
-- ---
93 ,==1. 22=
_1~ .,~.-
45 3
--- --
31 -..-----1--
149 14
-16-5 -..6
'" '-...'. '1. 1 ... 1.1 . Lt. \ 1 \..J J...J. "'.... .\ \ I I J I.. ''''' ;. #. I I
BASED ON -3.L 24"Honl~~cuiVr?(5sT'.fE-'gAMPLES
--SPECrnc--oRGA1.Jl C
- .
. No. of Times Detected
-_._------
----=-~=f=-~- -1=
- ..31-
31
.1!Lera .Q~by~e II Ar. :{1~ --
.-
----
--
2
--
.-
---
24
__-.2.L
5
2
13
4
--.
--
--
--- ---
.---
.-.
--
51
13
---
150
18
--
8
6
--
--
-.---
195-.--
21
-
--
_..
:..- -,...---
-.--
--
187
..-
-- J..8.9-
44
------
38
_30-
18
67
134
30
1192
254
4/.6
----
/10
-rCfIT-
42
--.
9
- 15
6
-.-- 5
---
--
--
__L
. 6
14
_._~
3
31
2
.--
29
4
- 5-:--
9
.-
_.
.--
Cont. Page 1 of 2 Pages
- -. . - -- - -.
):>0
I .
0"1
o
_.-- ---
9
--
--'-
6
--
2
-'--"-
2cf--
-.--.-
9
---"-
20
- ------.
3
------
2
--...-". --
2
--_._-- --
1.
--..-.-
3
-.14
1.
-265 -
9-
-62-
I;~
-2-
---s -
-------
J. \."'1' J. t,1J... 4 IJ1\'1\JJ....j \..t'".I.J.'..I~'''''''''
IiiIEDIii-i8- i]iF>~t5wr18ltMP-
...-' I j
arECI EIG-ORGlillICS
No. of times Detected
i
MAL~~~ -
..- . J. - , -- ..- - - - ~ 2~-r----- -.---
~j;~ ~'I~!i;YIi;;'y!i>,lCO]E I 1 *
-~ ~~-- .~~-~~~-~ 'l(-~~~ ~~~~~-- 9 343 17 1---
J. J csh xi c
----.--.------------- ~--- 5
40. .~ fOpal'! pI liAr ~a" 10 t.9 -
-.--- -
_1!!-) rQQ!.QI hg!!or ~ 4 32 2
-- -1----- -
.-1~ :rQ2Y! - ~ne GJ tt£:oL'- Area~~ 13 637 37 -
43. ~: tyrel'!. .._- -
-- --- --
- - --
--.-
--
-- -
1 -- -- I--
j~- -
-- --
.--. --- ---- - .--. . -_.---' --
I--
;
-
I
- t= --- --- f-
.-
-- - f-
- - - I--
-1--- .- --- -
~
--- '----
-- -
---
-
- -- -
--
-, _.
-A.. I egs -han pptt
511~-95-n
PA\-;F, ? of ?
):I
I
0"1
--'
-------
"'-- SPECI:"'!C-ORGJrnIC No. .of Times Detected MAX Epm AVE p~
~'.-~t~t~ff~!i~~-== .------'-~=---~=------"- =3~ I
--1------ ",,,-----'--'-----"'---'''- .-.--' ~3-_'.05.~____- -_-l~0~'7~1- .~~~-
3. ~';.~9~!!"H~.L ~:::_~!h .1 Vln 'L~ce A~ aler9 .gehy.- ~ "AI. ,.(;l~_.. -- .-- .. I I
4. AI1Y..!~2 I~gy! ?Qtvc,lH -' 1. 5 L *
~~~!L.!.sa ~?py~~lve ~-~ -'-' 4 24 I- 2
~: ~!~::,~~_:lv~!t3 -----==~==-=--- --'3Q - _159_-~_!J1 =
8. DI ty1 A etate 'Area' -~~~ 17 if=
9~;ltyiC ~bitol -'. .--- 1 20 .!_- .*." --
10. [-IJty1 - rbito Acet te " rea"
--,- -_..- -- _.-
J.!.~'lt~~5;; ~~lo~.9-ve " r._~~ --. 7 112 7
12. r Jty1 - .,1.!sol !.!£...Ac tate 4 54. _L-
~3._a-..C arhlt, _Ace.t 111L-.~ -- -- .
14. C eUos lve
15. (eUos Ive A etate
--" ---- _._-- ----
J~~~ !!!Q~ .~~Are( ~~ .--
l.?~-L1ace~- !.le At oha1 ~8:rea~.
..!.L!ji!11eth .!. Ace f,!tL.'
J~-.-.-I)A1et1}11ene ~1 col
20. 11~hano
flo jJi;yl!J 1anQl''-IAI~g ~ =- = --- - -
?_~.!-rkhY!b. !{a.!ge ly-diL. Area '~ -- ._-- - .--l{~
23 . r ~l!Y..!.!!.. a n01 II Area I 19
~_~~thy1 D~ty1 K tone 'Area - .---- ~-
J.~. EJJy1 P QI2Yl9.~'I91Ql_- ---- .-- .. 9_.
_26. (lycol_.lQQ~.at~ -- - ---- -
27. I eptan 11 IIA.r~a II . 5
2'8:-1: exano - II Ar~ 1"------:--. ~- 6-
-~: i~~y ~g;~lt~~ II reall_===.~. .-- ~. --' If_- -
31. -.!~ oprop~ n~~ - 9-
l.~~ ~ oproe 1 Ace .ate II ea II -- 9
330 l~ ethan.1 - --- - , 5.-
34. fI.eth 1 In' 1 cetat
-- -. "---
~ 5. fl. athy 1 ello. 01 ve
3.~.;:eth~el
51!~-957 j
. '...." """".' . . .' ~ ...., ...~ t '" '," . a. .""" . " ( J
BASED ON 30 24hUU1CCtJMFO'sItE'.'SAMPLES
14
57
--
----
-'
--
8
I
--
30
--- --
--------
----
~
I
(jT
N
8
---_.-
4
'-.---- --
1
26 *
-.--------
.2.2.2- _.29-.-
--
, 2)9-
81
._~
615
---
12
21-
-2.8
57
fiL
70
8L
-
--.
5
3
Cont. Page 1 of 2 Pages
202
16
..:Ar£ It
28
_.._-- -
18
*
----
32
---- ._-
-'-1 -
----2'- -
.-.--
_.J,2.-
1
.-- -
154
11
..J..8- -
15
1
-
-------
. ......" J. J.u... t J..I\tVU i',I) 'J l'.t',LH:'I\. J..:J I I
,"SEJ88'I ~CiliiliiiiCoiiiIf5BTfIii8\M'"
~ SE.EC'dflC...ORGlUllCS
~i:' i~~1~~~~~~~~ifi
-19:-- Jle'sYf\ l-O-il-le-----
---- --_._-~, -----_._---
~,~. L?p~~b.L~~, ~.~
--1.l.!-I [QPJ-2r b~!:!on ~-_.
-1f..!-...-c~.LQ.P-'y! ~'le Glycol I Area"
43. i tyren
-_.-
--- r
I
----{
-
-
-
No. of times Detected
-
---
1.
9
-
M ~x...P~'!1
lJL-
57
-
-
-----.-
-
14
9-
5
...-----.
-
1.
'-
--
-
..-
'-----.
-
--~--
_...
511~-9573
* LESS t ian 1 ppm
--
---
-
-
..
PAGE? of ?
63/.
295
693
--..1.2
A,!F. ,-~i1JI.!=
* >--
6
-
38__-
21
.---"-
27
-----.-
.
.----
_1_- -
--'---
-
-
f--
-
-----.
~---
-
-
-
)::>
I
0'\
W
-------
.... ....,.. A .J...f.J .. I~~"&.'~.;~. ..~. ..l"..-..... ...,; f I
B.!\SED ON 31 i4if~Tn~T;-(:fMPl)SiliB-gAMPLES
SPEcrrrC-Of
MAX PEm AVE ppm
~ Lm ~j ltr
- -
2
-.11
29
27
2l~
5
1
5
129
71--\
lis r
19
105
--
2
- 19
51
104
-
5
- l.
3
22
129
47
52
._--
152
--
5
10
:)
"I.
279
154
18
5
--
--
J
5
-1h
2
30
-...--
26
23
'-.-
1
1
3
114
21
--
119
33
224--
-213
--"359
7
17
44-
--
--
Cont. Page 1 of 2 Pages
----- -
27
9
9
------ -
20
---r2
11
-_.-
1
'---
-I.:
--
4
--
-'--
22
--
1
-bl-
-5"5
-87--
---oj -~
*
-------
~~IV1\_)~~1"3ir~1-H_l~.
-------
A-57
ATTACHMENT B
ORGANIC CHEMICALS SCREENING ANALYSIS
-------
'A-5R
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCE/v\ENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FE:DERAL CENTER
DENVER, COlORADO 80225
TO
D)~. \'Jayne Smi th
Process Control Branch
DATE: June 2, 1973
fROM:
O. J. Logsdon
SUBJECT:
Organics Analysis Results:
WWTC Recon Samples
Union Carbide Institute Plant and South Charleston
Summary:
I'later samples from Union Carbide Institute Plant andSo;Jth Charleston HHTC
were received under chain-of-custody procedures and analyzed for organics
characterization and selected priot'ity pollutants. These reconnaissance
samples contuined numerous chemicals, some of which were priority pollutants.
Recommendations:
Analysis of the reconnaissance samples showed many organic solvent components,
cellosolves, etc. If a full survey is conducted, analysis by direct aqueous
injection techniques will be required to acquire accurate quantitative data
for these compounds. Only small amounts of phenol and 2,4-dinitrophenol -
and some low molecular weight acids were detected in the acidic fractions.
Therefore, with only a minor compromise in data quality, samples from the
survey should be analyzed for neutrals extractables instead of the time
consuming acids and base/neutrals procedure. for these two locations un~ess
priority pollutants are specifically requested.
Union Carbide Institute Plant
*
Table I shows the results of organics characterization analysis of sample
number 003-30-A-4-l1-78-0900. Seven chemicals were confirmed by comparison.
of their mass spectra to in-house reference spectra. Ten additional com-
pounds ~Iere identified but not confirmed. Priority pollutant analysis de-
tected 12 compounds, 7 of which exceeded 10 ug/l. The da~ are attached.
This sample ~'/as also analyzed for extractable nitrosamines. Attached is
Mr. Nott~n"h~m's memo descr~b~ng the analysis. None of the following nitro-
sa8ines were detected: dimethyl, diethy', methyl ethyl, methyl' propyl,
ethyl propyl, dipropyl, ethyl butyl, propyl butyl, methyl amyl, dibutyl,
and diamyl nitrosamine:;, nitrosopiperidine, nitrosopyrolidine, and nitroso-
morpholine.
The sample
togra phy.
discussion
*
was also subjected to analysis by high performance liquid chroma- .
The herbicide Carbaryl was detected at 260 ug/l. Mr. Nottingham's
of the analysis is ~ttach~d.
not included' in this report; av~ilable apon request from NEIC.
Ta b 1 e I
-------
A-69
- 2 -
South Charleston H\HC
Tables II and III show the results of the organics characterization analysis
of samples: 003-40-A-4-12-78-lll5, 003-4l-A-4-l2-78-1030, 003-43-A-4-12-78-1100,
and 003-45-A-4-12-78-l050. Thirteen chemicals were identified and confi~ned
by GC/i.:) analysis. Thirty other chemicals \'/ere identified but not confirmed.
Numerous other components were not identified; however, many mass spectra
had the characteristics of alkyl ethers and alcohols. Available self-
monitoring data (SCSTW influent and effluent July - December, 1977) show
r;i:;71erous oxygenated solvents e.g. cellosolves, acetates, and alcohols, a
fe~ of which have been identified in these samples.
Priority pol1utJrot analysis was limited to acid and base/neutrals extractables
and volatile organics. Numerous compounds were detected and are reported in
the attached tables. In addition, sample 003-45-A-4-l2-78-l080 was analyzed
for nitrosamines. None of the following nitrosamines were detected: dimethyl,
diethyl, methyl ethyl, methyl propyl, ethyl propyl, dipropyl, ethyl butyl,
propyl butyl, methyl amyl, dibutyl, and diamyl nitrosamines, nitrosopiperidine,
nitrosopyrolidine, and nitrosomorpholine.
r\~,vl~ ~'- r-
O. JohrrJLogsdon
Attachments
cc:
Hatheway
Young
rq ass e
-------
A-70
Table II
SOUTH CHARLESTON WWTC
GRAB SAMPLES COLLECTED 4/12/78. COMPOUNDS CONFIRMED.
CONCENTRATION IN ~g/l
Name 003-40-A 003-41-A 003-43-A 003-45-A
acrylonitrile a 55
benzothiazole c
bis-(2-chloroisopropyl) ether 2.7
n-butanol a
2-n-butoxy-ethanol 3,700
dichloromethane (methylene chloride) 55 c 180
2-ethyl-1-butanol 1,500
2- ethyl hexanoic acid 9,900
2-propanone (acetone) a a
trichloromethane (chloroform) 43
vinyl benzeneb(styrene) 4,000
ethyl benzene 470
a could not quantitate - does not purge quantitatively during volatile
organics analysis.
b quantity based on priority pollutant analysis.
c unable to quantitate.
-------
A-7l
Table III
SOUTH CHARLESTON WWTC
GRAB SAMPLES COLLECTED 4/12/78. COMPOUNDS IDENTIFIED BUT NOT CONFIRMED.
Name 003-40-A 003-41-A 003-43-A 003-45-A
acetyl-(beta)-methylcholine X
benzoic acid X X
butanoic acid X X
2-butanone (methyethyl ketone) X
n-butyl chloride X X
2-butoxyethoxy ethanol isomer X X X
2-butyl-l-octanol X
carbon disulfide X X
diethylether X X X
diisopropylether X X X
l,l-dimethoxyethane X
N,N-dimethyl butylamine X
4-ethyl-2-octene X
heptanoic acid X X
isopropanol X
2-(hexyloxy)-ethanol X
methylcyclopentane isomer X
2-methyl-l,3-dioxolane X
2-methyl-2-pentanol
2-methyl propanenitrile X X X
methoxyacetone X
l[l-methyl-2-(2-propenyloxy)]ethoxy- X X
2-propanol
octadecanoic acid (steric acid) X
1,11-oxybis-(2-ethoxy)ethane X X
3-pentanone X
phenylacetic acid X
2-n-propoxyethyl acetate X X
1,trans-2,cis-4-trimethyl cyclopentane X
2,2,4-trimethyl pentane (isooctane) X
trioctyl phosphate X X
-------
- - .'. . .
" - - " .. .,
'" -. '- ...~-
-.------------------------
A-72
C lj ,. r. L ~ ~ 1 0 ;.j ~ \J T C
~ A R L L ~. T -:. r.! h' V
,OR::1 1;Q
T~TION LOCATIO~: INF
~R02~TCRY SAMPLE NO:
~T~ ~ TIMF OF S~MFLE
}M?OSIT~ TIME: CO PR
TO BASI;..
:JJ3-LO
COLLFCTION: 12APR78
1115 HF.S
( 0 ~: r Q U :.! G N A 11 E
UG/L
CONC.
NO
NA
Nil
130.
NA
NO
12.
NO
NO
48.
"'D
i~O
NO
N8
NO
NA .'
NA
NO
NO
NO
NO
ND
22.
ND
19.
NO
,..;0
~A
3.1
"9"iD
J 1.. t C ~ ,'i A P H THE ~~ E
J2, ACROLEIN
J34 ACRYLONllRILE
J l... [3 F ~! ZEN E )(
:; 'S. S :- j.; Z I DIN E
J~. CAFBON TETRACHLORIDE (TETRACHLOROMfTHANE>*.
)7. C~LJR08ENZE~E*
38. 'J2J4-TRICHlCR08ENZENE
j 9 't H f X.~ C H LOR 0 S E h Z r: N E
10. 1,2-DICHLOROfTHANE*
'; 1. 'j J 1 , 1 - T Ii; I CPo L GR 0 E T H A ;, E ,.
j 20M E X ~ C-! LOR 0 E T H AN E
!3. 1,1-JICHLORG~THAN~M
: .~ 0 1 J 1 J 2 - T FIC:-: L C R 0 L T H A ;'i c ~
~ :.- ~
1,1J2J2-1ETFACHLGROETHANE*
76. CULJROETHANE-
i7. ~IS(CHLGROM[THYL) EiHffi~
j~. ~IS{~-CHLORJ~THYL) ETHFR
i9. 2-CHLO?O[THYL VINYL ETHER (MIXED)*
~J. 2-CHLORO~APH1HALENE
~1. 'l,4)6-TRICHLG~OPHENOL
~2. rARAC~LOROME1A CR~SOL
?~o CHL020FGRM (1RICHLOROHFTHANE>*
?4'" 2-CiiLJ~GPYENGL
~5" 1 ,2-DICHLORG8fr~Zt.NE
260 1,3-JICHLORGbFNZENE
~7o 1,l-DICHLORu5E~2ENE
280 ::; J ? I - ~ I CH LOR l;8 r: ri Z I 0 I ri E
?9o 1J'-CICHLORa~T~YLENE*
~ CJ" 1 J~ - T ~ ':. ~; S -:: led L ~Hi Q E 1" rl '( L E i\ f "
v v t. A:J A L Y ~ :: s ( U ~J P R!? S E R V ED / PRE S E K V ED)
IF.AfE .
i; J T t. :.; A L '( Z E!) FOP-
i';:J T :J t: T E ( TED
~ I r.. G T A S L E 1 0 A f, A L .t Z ~ 0 u r- T GIN 1 E R FER ENe E
-------
r~'-: :::-:--=- ~ ., - - - - - - - - -
C l! ~. /, L r. S ~ :) r; \.. ,,' T C
'IL" <: T,'," " './
.1 C...., . U I" ....
;j [1 ::C
.. T j '2 >.: L U L A T I 0: ~: I 1\ F
.It\ ,.. T 0;\ Y S l' ;.': P LEN Q :
. ~ T 1 ;.: ~ 0 F S j, ~: F U
: ;i PUS! T f T I : I L: C 0 H:\
T 8 5 A S PI
OCi3-4J
CULLfCTICt.;:
12Ar:!\78
I -"' v,., - lJ ,. [ \; I '1 -
I.. L.i, ,r U I. I''',' 1::
: I ~ J /, - 0 I C:1 LOR J r Y ~ ~. 0 L
~2. 1J2-r.ICnLOr:CPRC?t.:~~"
-; 1_, i J"?', - DIe :-1 LOR 0 r R 0 r Y L E ('J I:: *
t!. , 4 - ~ I ~1 :: 'I H Y L ? H ~ I ~ 0 L
2:'. 2JL-GP'IT~OTOL!JE.!.E
:: I' i. J 6 - 0 Ii!! T ROT 0 L!J Ui::
~ 'J~-DIPHENYLHYDRAZINE
3~. ETHYL3E~LE~~*
319 FL 110 R A ~I T rlEt~ E
: 4-CHLOROFHENYL PHE~YL fTHFR
~, 4-8ROt10PP.E~YL PHE~:YL ETHE~
~~. 3IS op" 0 :-: Cd'. ~
:: 5, I', A P H T H ;\, L t. ~~ E
:, I ~:! T R 0 SF. t.: ZEN c
~. 2-~ITRorHENCL
:; s . l. -:n T ~ C F :-! F. "i C L
5 11 2 J L. - J I NIT ~ G r H E ~~ 0 L
s~ h,6-D!~r1RO-G-CRESDL
v~t ~NALf~ES
-------
A-74
C :H. ;.: L r: S T 01\
UiiC
~1~' Q L t;: 3 .. 0 r; '~v
TOR:::' i;O
i t.. T i J ~.; L C r: AI! G t,: ! t\ F T 0 8,t, S I j'J
~30RATO~Y SA~PL~ NJ: 003-48
~ T r ,~ T 1 r.; (: 0 F S t, :: P L [ C 0 L LEe T I 0 ~J : 1 2 A P R 78
j ~ P G S TT t= T 1:'1 E: 0 C ~i ~
1115 HitS
C (; ;-.i F 0 :J ;, C r,:;~ ;.: f
)1" ~~-iJ!TROSOJlr.:t.THYLA~nNr
:: 2.. r: - !J I T ~ Q SOD! F H E ~J Y L A:~ I ~ ~
S1. ~-NITROSCDI-~-PRCPYLA~INE
)/0 PEt!TACHLCROFHEriOL
:1 5, F \..I ow L ( 4 A" P )
~6. F,ISC2-;:THYLHCXYL) PHTHALATE
:; 7. (; U T Y L :3 t N Z Y L F H 1 HAL ... .. E
)8. C!-N-BUTYL fHTHALATE
~9. uI-N-O~TYl PHTHALATE
70. CIr::HTYL PTHTHALATJ:
71. )If'lI:THYL PTI-i1HALt.TE
''2. SO:ZOCA)AinHi',\CENE (1,2 BENLATHr{ACENE)
'3. 6~~ZO(A)FYRENE (3,4-aEr:Z8PYR~NE)
7L.. 3,L-EENZOFL'JG~.~,THEr~E
>5. ~r~ZC(K)FLUOkA~1HANE (1,,12-3~NZGFLUJRA~THENE)
?".. CH!nS~NE
? 7 ~ ;. (" ~ i4 A ? H THY L [. I'; ~
7 8. .u.: T ~ R ;. C ENE
79. S E tJ Z 0 C G J H , ! ) r. F. R Y LEN E C 1 , 1 2 -6 E N Z 0 t> E R Y LEN E )
~o. F L IJ 0 R ENE
~1 ~ PHqi.A.NTHRE~:::.
32. CIBENZO (A,H)AN1HRACENE
33. I ~~ D:: NO (1 J 2 13 - CD) P Y R c~;::
)4. PYD_a~E
3 5-. i f j' R I. C H L C ROc T H '( L E. ~ E ~
36.. TO!..UE:':::*
37. TP!CHLQR0ETHYLENE*
38" V I NY L C H L 0 i{ ICE (C H L 0 r{ 0 E T ~iY U:~, E ) ;(
~9. ."'L~RIN
Jr.).. D1:L:)~IN
V;jl ,q;~L'i'SES
(U\PH~SE~VFD/?REScRV~O)
1i:;1,C'i
t.: u T At-J A L Y ZED F 0 :\
:~ 0 T D E l' Eel F 0
-I :~'JT ABLr 10 ;,r,;.LYIE
DUE 10 1NIE~FERF.NCE
iJG/L
CONC.
NIJ
t;O
l'f 0
ND
NA
3.4
!liD
1 .1
NO
NO
tJ D
NO
NIJ
NO
tJO
NO
N~
NO
Nt,
ND
ND
NA
- t~ A
NO
3.4
200.
NO
tU,
NA
NA
~
-------
r. H /\1. L E= S T C ~~ \d.' T C
""'1:: S T.O t: \.i 'J
;). .1 \0
A T I ~,:'-' L U C " T lOt.': ! r.J F
S.j.10~Y St.r,PL[ ~!O:
~ ~ TI~E OF SA~PLE
;~, D~ In: TI~[: 00 /-iH
TO bASIN
OC~-40
C 0 L L E r. T lOt.;: 1 2 A F R 7 3
1115 ~ES
I C 0 p~ P 0 J i j !J
Nt, 11 E
U(, /L
CONC
11 C!-1 L C !:: " ;.: l (T c C i-! , 1-; I x T U F: t & '1 E 1 A:3 (j LIT [: S )
2. 4,l~I-:Jc)1
'314 J41 -DOE
1. ~,41-DDu (F,P1-TDE)
J 5. A - ::: i.JD 0 S J L FAN - ALP H A
'f. d -=NiJOSuLFA/';-8ET,i,
'71 c::r'!f)QSULF I,t~ SULF t. TE
.;.;. r. NO F. I I'~
. 9 o. U! D R HJ .t. L DE H Y D f
);)1 rii:PT ACHLOR
~'j foE?T AC~LCR (~OX I D!=
}~. ,t,-3HC-ALrHA
I ?-I [. -3;; C - 8 E1 A
-; !, f.; - 3 :-1 C - ( L 1 i'~ [) h t~ E ) - G t.. ~ 1'i A
!:.. G-SHC-!)[LTA
; .S, P C 3 -1 "2 4 (;. (A R L C L u R 1 24 2 )
;7 ir:~-1254 (AROCLOh 1254)
}:3 ? C G -1 2 21 (A R C C L G 1-' 'j 221 )
;9. PCS-'i232 OROCLOi\ 1232)
11 H: g -1 2 4 8 (A R J C LOR 1 24 8 )
1 FC8-1260 (Ai\JCLOI\ 1260)
'?" PCP,-1D16 (ARuCLO" 1016)
:1 10XAPHE~E .
.~ A~TI~ONY .(TOTAL)
,5. ARSENIC (TO~AL)
'AI tS!?ESTOS (FIBROuS)
.7 ~E~YLLIU~ (ICTAL)
13. C" D ~~ I J :.: (T 0 T ,.. L )
9 r ( H () 0 :., I I Jt-i (T 0 1 "L )
~ JI C J P P c: R (T 0 TAU
VCA ANALYS~S (UNP~~S~RV~D/PRiSERVED)
II".~CE
~OT J..t-.'/J.L '(LED FOR
t:OT l:,::TECTED.
-IljJT f.:3LE 10 Aj~AL Y2~ DUE iO I,\jTERFEREiJCE
~i A
NA
Nt.
NA
Nt-
t~ A
NA
NA
NA
NA
NA
NA
~A
t.; A
~A
tj A
NJ.
~; A
NA
nA
NA
NA
NA
tJ A
NA
NA
lU.
t-;A
NA
i, A
~
A-is.
-------
. 'A-76
(' 1.1/. F L:- S 1 0 tJ ~d; T C
~A!n;.:STU~ 'riV
iQ~ri ~o
;'.1 T I .J t.; L u CAT! 0 i'~: I t.; F
, 3 a i\":. TOR Y S":~ P L E tJ 0 :
I~ ~ TI~F OF SA~PLE
;:-'. r 0 SIT E T I ~1 [: Q 0 H R
TO 2,ASIN
003-40
C aLL F C T I J r~: 1 2 A F R 7 8
1115 HF.S
\.:O:.~P0U:!D rUd.a:
IJG/L
CONe.
2'. CYJ,~n~E cT01Al)
2?e L~;.D (TOTAL)
23.. ;jF~CURY (TOTAL>
?~~ N!C~LE (TOTAL)
2 ::" :) r L E r~ I 'J~: (T 0 TAL)
~S. SILVFR (TOTAL)
27s l~ALLIUX (T01AL)
2~.. ZINC (TGTAl)
29. 2J3,7,8-TETRACHLOROOIBENZO-P-DI0XIN
(Teoo>
~~~ F~iENCL (3Y GC;f~O O~ GC/MS)
V;j.A At-,ALYSES
(UNPRES[RVFD/?R~SfRVED)
T;~11;CE
, ~uT ANALYZED FOR
) ;\ lJ T D E T ~ C 1 E :J
:-1 i~~T A5L~ 10 H~AL YLE DUE TO INTERFERENC;:
11 A
NA
NA
NA
NA
NA
NA
NA
NA
NO
-------
A-77
ATTACH~1ENT C
BIOASSAY PROCEDURES EVALUATION
-------
'A-78
ENVIRONMENT Al PROTECTION AGENCY
OFFICE OF ENFORCElv\ENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COlORADO 80225
TO
\'Jayne Smi th
DATE:
t.iay "I 6, 1 9~" 0
FROM
Bruce Binkley
SUBJECT:
Laboratory Evaluation Inspection of Industries in the Kanawha Valley,
Charleston, West Virginia
On April 11,1978, NEIC conducted a laboratory evaluation
inspection of the Union Carbide Corp. plant at Charleston, West
Virginia. The purpose of this inspection was to determine whether
laboratory facilities and test procedures were adequate to satisfy
the se1f-monitcrirg bioassay req~irements of NPOES Permit Number
\1V0000078.
The bioassay facilities are maintained at the Union Carbide
Corporations South Charleston Technical Center. In general, this
laboratory is adequately equipped and staffed to perform static bio-
assay tests. The testing area is environmentally controlled for
temperature and photoperiod; however, it appeared to be somewhat limited
in adequate working space. Bioassay, physical and chemical tests are
performed according to recognized standard methods. Procedural incon-
sistancies and recommendations for improvement of this testing facility
are as foll O\'IS:
1 )
Expansion of existing floor space could be utilized to
~cr2 2f~ici2~t ~lar~~~ng ~I ~~~.
.-. ,...-." ~ .,~.-
jw: ~...: . o...i:::
2) Effluent samples for bioassay consist of 24-hour equal
volume composites. This is inconsistent with the permit limitation
which specifies a 24-hour flow proportioned composite for bioassay
testing. The current sampling method should be modified ~reflect
NPDES Permit specifications.
3) It was reported that bioassay tests do not always commence
within eight hours of the sample collection. These tests must be
init;~t2d w~~~in eight hours nf the comDl~tion of comoosite sampling.
-------
-~--- ~ - --~- .
-2-
4) Dechlorinated city tap water is used for holding test
organisms and as the dilution water for bioassay testing. This
water supply is acceptable for long-term holding of test fish;
however, dilution water for bioassay testing should consist of
Kanawha River water. Test fish should be acclimated to Kanawha
River water at least four days prior to bioassay testing.
5) Bioassay tests are not done in duplicate.
that all bioassay tests be done in duplicate.
It is recommended
6) Physical and chemical parameters (dissolved oxygen concen-
tration, pH, and temperature) are monitored daily. Because ammonia
buildup can be a problem in static bioassay testing, measurements
for total ammoni a-N shoul d be i ncl uded. f'1easurements for total
ammonia-N should be made at the high and low test concentrations at
the beginning and end of the test period. Calculations for un-ionized
ammonia concentrations should then be made.
7) This laboratory currently conducts bioassays on a l2-hour
light photoperiod. This photoperiod should be increased to a l6-hour
light and 8-hour dark interval.
8) All bioassays are aerated throughout the 96-hour test period.
Aeration should be discontinued except in cases where B.O.O. and/or
C.O.D. are sufficiently high that adequate dissolved oxygen concen-
trations cannot be maintained. Any use of aerated test water must
be documented on the bioassay bench sheets.
9) Washing procedures for bioassay test chambers should include
a solvent rinse. Acetone is an acceptable solvent for this purpose.
10) Thi s 1 abora "COr,Y depenas un ccntrOi I eo a:nbl em: air -ce:npeta-
ture to maintain a constant test temperature in bioassay test solutions.
It is advisable that test chambers be placed in a constant temperature
water bath for more precise temperature control.
'8;r-
cc:
J. Ha the\'Jay
R. Harp
Biology Branch Files
A-79
-------
'A-RO
.,
.~~
EIOASSAY LAnOPv\TORY EV,\LUATION
D.Jte
2i/Jr..,)C1r.i~(L 0Y2'
!-~:l Q:J,L!~ (?j'lnt~ l~i I
/ / /117121 / /q;;(~-
, ;'
InvcstiGo.tor ,0~{{/c ,/1/. &~"L L/
Compan\' Rc~';~sentative Iv!(' 1 (J",,/,ro.;{ ,4)-, t {)"'"', k4->?Y' .
9~,- /-U'~7 --5;, ac: ' /LrS (]v/. H!'J~;~J
.i/A E ~ r:;,.- 0, 4 j '. :.'~. cd '//i/:: ,,-.ILI-/',; .- ,,/<.
L~boratorv or Indu~try
lij~~.;- j/~JjJ,:JJ~-~'---
Loc~tion
,/,"
\ i' t ~\' ~: ',." 1."1 U
-7 I
I
=i
.. '-
,Dilution ,.Jat cr
Source a - ~-l j.r/~:"~ 1,/ r.)y LQ i:,;=-k,:- ( ~t!.J.'(;I''LJ'? / J2/(.,~~/)
-- I . i 1/ . ," I I ; )11 ',"~ . II ' /
. . --:,1-;.:; '" ,. ,:' -.:'" I, ,; \. .4-:.,
,. ',- ", J ~ ... ';'.. .,.1 . ., .,
,
Che~ical Analyses Performed /I~"~;'f'-
-.-----..-
(? " / J
~,.; /') h-- ;vj!, / r,c ;''' f ic ,'-.1
/
Pretreatment
---" --.
-------
A-fll
.
"
-,
Effluent \~a tcr
Spurce 2).';";" (7-:1.' 1,,). !2f j',)i/(.,,---,' /,,-,:-::, r 2;-, /" :;.2:
( ~/Yl c;lLj C/":" /,//. /'/7 f'ji.j (27 (?r> >:%:/ ;
Retent~on t'iT7le o~.a'~ J ' . " .
1:' z~- ,/I/:/. r7 t.J
<:~: . ; ;;9 ) >:L.~--:-_., ',< ~
, '/ / 0,/ '"
Sampling technique ~? "-I j."(I1-I~
..,:.?; 'r ,"I <; -h, ~r 111-; 'I' ~:
. ;
Holding tirae and conditions
Pv/',:-)-; ;:;: - ~.,: ',1 ~;
Pretreatment -/:-''';'' i C
/ /'j'
pc;:;,/. i.'- I: "I"
,
(.;.,; L.',i.07-,~" f-; - ,.<;;~ t, '1 ~ j
rj' "
,
, 1
Ii. (';, '~,7
I. _,7 ,,;/:.... /"""/ )1,', .,'
~",\'I'1:-',.~i':' - /,.~' -- ~ -'
/' ,
(f./,-,.'c-,i-.. d 11,/
Chemical Analyses Performed 17;/ .J.:) 4..l,,~j i1-=:,,,ro~... n.~,,(".,,-f.r.,,1.o/'I'1U
,-f~'I' - 0 / , . I ' (
".. .'.t ;') =>,' ,I : --, I f. ~,.;
.
I
Test Or~anisms
- -
Species
-=l: )/6t) ().. ~,f' ,~, I..
I
Life stage
I / I I'
1.',,';'/7'i.~ .?,L ~'w--Iut-
--
..
0'
-
--,
j-LJd~~~v
I
Holding facilities, <::::;"I/f'lif~.:<.~..(.,J, ~,.,..s';'~oll'lll,~/,? 'J...:c.;:,.L
\-i":'I",\\~i('i!""I::I,lr .l..,~r/'I II-'".+",,;~ I . - ,/
AccliI:1.:1tion Procedure -1-,..J...,,,.... '11 ",:,;"4,I/..U
Source
Yt"217',5
r:=, ~ b
Treat-""....pnt '-/-/"";..;£J,C,/.. ,,'> ".' 1 /7/'/.'" J../- «';~",--, '.- b"']" . !;-i~ I,..J-
........ - -----....:-.~~._- ~ ..~,;.!.!..-; .,_..~,.... 1". ,'. -".1~....J. . _"4~-1." !!I~
. //:; j'fO-'t L.-;- i"')) ,'r-!;, !.j . /:!:~'-1';<' JLJ. - / -,-
. I I )
Experimental Desi~n
Test Chambers
Construction Hatcrial (] ~1 < 5:
Dimens ions (?,!: I dr j~""tf{ /3: / ;JC::2!
/;; J, J~i'>
...
d+:J ~.,,-»
I I
---
Volume
\
i; f ,.; i J
'":-r- ~~-'t'.... I.. ~ .'. j..J-:
/ i I
ri /i..J' ~
I
I
I
Volumeteric exchange rate
/1-'/ f1
,
Test concentr3tions
,-. t ; ./
I /":' ')
£)' -A-~,-+ (':-'.1"-""',.,: ~;"~-r-If,-"~"
/
(~ '..., .-."' ~-'C J \..... /.;:...
I
Nuru~cr of organis~s per
'--=~ :,..,:..-:- h.. .. . ~
/-
. I / / ,- ('; --., I i
conccntr.:1::1on -."'" '-'" 1'",,) l t~~Y\_~!" ~(:;>"';'T-li.'17'
//J II I I . i
/[.et C'i;:A-~ -'IV a~tJ.,J11t:.../.-1-~ .
, '-
-------
-A-82
I..
L03cling rate ).{'/ i<. / /'::"'c is) Cd. /.20 .~
. / ;I / /
/~7-0M~>//5 Ika.--__-
1r!! - - ". ( ,
Duration and frequency of test
Definition of adverse effect
Frcquency of observations
<7. I
:./. ., L., ,
,
/, ~
J
.;..,,-.
Ii... )Ir-~)'
Methods used for all chemical analyses
E,Pi-i
..~J 0;'.(><' ( \-J .. -- ~ IT cJr; 1;' J LLJJ. ~ )5__.
//
I
I
I
-P,.....;
I.A i1",~
~1";:':~" .;.1.
.'': (:-~J?;. "",-.(
/
.~ ::JJ
- .:s; ).,,:, /d
..:l
, I
-------
A-83
ATTACHMENT D
CHEMICAL LABORATORY PROCEDURES EVALUATION
-------
I
10M:
leJECT:
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, CClO~A.r::'O 30225
Dr. Wayne C. Smith
Process Control Branch
DATE: June 1 ~ 1978
Technical Coordinator for
Inorganics and Air Analysis
Compliance Monitoring Inspections for Union Carbide - Institute~ West
Virginia; South Charleston WWTP - South Charleston~ West Virginia; and
Union Carbide - South Charleston~ West Virginia
Attached are my evaluations of the two above-mentioned Union Carbide
facilities as well as the South Charleston Wastewater Treatment Facility
along with completed "Self-Monitoring Program" sheets.
If there are any questions concerning the inspections~ please contact me.
.~~~ V~ .
D. David Vietti
J1.ttachments
cc:
Meiggs
Carter
Slovinski
r~a sse
A-85
-------
A-R6
UNION C,;RGIDE
South Charleston, West Virginia
April 12,1978
Inspection Attendees
Affiliation
Connie McCorkle
G i 1 be rt t':e 11 n
David Vietti
Department Head, Environmental Protection
Department, Union Carbide
Department Head, Analytical Section, Union
Carbide.
Chemist, Union Carbide
Chemist, Union Carbide
Chemist, EPA-NEIC
Jack \-!orstell
r1. E. G riff i t h
Introduction
The laboratory was inspected for its skill to produce and report reliable
NPDES self-monitoring data. The evaluation consisted of a review of the
testing methods in use, laboratory techniques, instrument maintenance and
calibration, sample preservation and holding times, data handling ann re-
duction, as well as bookkeeping and quality control practices and documen-
tation being follGwed.
. The department heads and analysts ~ll had a number of years of experience -
vlith Union Carbide in many different areas of analytical and instrumental
chemistry. They were interviewed concerning chemical procedures.
A standard reference sample for TOC was left with the company and they were
asked to return the results by the ~nd of the month.
Based on the observations and findings during the evaluation, the data and
information obtained, the inspection form presented on the following pages
was completed and conclusions, summary, and recommendations vlere prepared.
Conclusions and Summary
Proper preservation procedures for composite samples were not being adhered
to. ComDos i te sampl es \'Iere not iced duri n<:1 the compos i ti n~pe\"i od.
Excellent method development and implementation has been established for
the analysis of the vinyl chloride monomer.
The method that is referenced is "Organics by Purge and Trap-Gas Chromatography"
contained in the protocol for Priority Pollutant screening distributed by
EPA-E~SL in Cincinnati.
An excellent analytical quality control program consisting of routin~ and
blind duplicates as well as blind and routine spikes a~d reference samples
-------
-2-
A-8?
is being utilized for all permit parameters. The technical staff has been
and is workinq jointly with the Union Carbide staff on methods development
and implemen~ation in regard to the paranietetS in their NPDES permit.
Results of the reference sample was excellent.
Recommenda t ion's
l.
2.
The sar.1ples should be iced 'Ilhile compositing.
Their excellent quality assurance program, quarterly round robins, etc.
should continue.
3.
Their methods developments for NPDES monitoring in conjunction with the
Union C~rbide Te(hn;c31 Center with regard to GC/MS work en toxic or-
ganics should be augmented.
-------
Union Carbide - South Charleston
A-88 SELF-MONITORING PROGRAM
On the follov:ing items, code 1 = yes, 2 = no, 3 = undetermined,
4 = not applicable.
RECORDS AMD REPORTS .-
/~ 1. Properly maintained records of date, exact place and time of
sampling.
/T7 2. Properly maintained records of the dates samples were analyzed.
/T7 3. Properly maintained records of who performed the analyses.
/Ty 4. Properly maintained records of the analytical techniques and
methods used.
/!/' 5. Properly maintained records of the results of analyses.
one
/17 5. Records maintained for a minimum of^^^ee years including all
original strip chart recordings (continuous monitoring instru-
mentation calibration, maintenance records).
r~/ 1. Plant operating records kept including operating logs of each
•treatment unit.
/T7 8. Results of sample analyses correctly calculated and recorded.
/ V 9. Self-monitoring frequency and oarametsrs conform to permit
requirements.
/I7 10. Laboratory records consistent with D'-'R data.
/__/ 11. Records maintained of major contributina industries usinq
publicly ov.'ned treatment works.
r~l 12. Records maintained of major contributing industries' compliance/
non-compliance status. . "
/ '/ 12. Quality assurance records kept including spiked samples, laboratory
equipment calibration, etc.
Other Comments on Records and Reports:
2-6. An excellent data and recordkeeping system in use. All the original
documents and benchsheets are kept and stored in a central file for one
year and then sent to the company's headquarters central file for storage.
Each analyst has their own record notebook and they are reviewed period-
ically by the supervisory chemists.
13. A "first class company internal auditing system in existence and in use.
-------
__ A-89
/_/ 7. When answer to Mo. 6 is yes, results are beinn reported in
permittee's Discharge Mcnitorina Form (EPA Mo. 3320-1).
/~27 8. When necessary during compositinq, samples are properly iced.
/j[j 9. Proper preservation techniques used.
/~7 10. Flow proportioned samples obtained where required by permit.
^
/T7 11. Sample holding times prior to analyses in confer ma nee with 40
CFR 136.3 regulations.
Other Comments on Semolina Technicues:
8-9. During compositing, the samples are not beinq iced.
LABORATORY PROCEDURES
/I/ 1. EPA approved analytical testing orocedures used (40 CFR 136.3).
/T7 2. If alternate analytical procedures are used, proper approval
has been obtained.
/T7 3. Parameters other then those required by the permit are analyzed.
/~27 4. Commercial laboratory utilised.
Name
Address
/ 4-- 5. Commercial laboratory State certified.
/I/ 6. Satisfactory calibration and maintenance of instruments and
equi piT.ent.
/17 7. Quality control procedures used.
/T 8. Duplicate s^mc-l^s ars ^;:^;vz2d. ""'
-------
A-gO
117 9.
and reference
Spiked sa~ples are used.
50
% of tir;;e.
I~ '0
U' I.
Labor J to rj
records
properiy maintained.
/-1' 11
'-- .
Labore tOl'Y er;;p 1 oyees qua 1 i fi ed.
Ger.er.::l
Comments on Laboratory Procedures:
5. The state of West Virqinia does not have a state certification
program.
7 q ",hi:,> lab01'''''O''y qu::-"~"'I -"s"r-l1-a n'rOG"-m con<:;:::,"-<:: OT~ qlj~ll'ty
-.". - \~;... I a 11.,J Q...,; ~ u \........ i--' _olall ...J1_l....J a
control analysis of routine and blind duplicate sa~ples as well as
known and unknown spiked and reference samples. Also, round robin
samples supplied by the Union Carbide Technical Center coordinator
are analyzed quarteriy. The program is administered internally
within the Union Carbide South Charleston Plant and the results look
excellent.
Results of NEIC Quality Control Check Samoles Analyzed
by L2bot~atory
Parameter
Union Carbide,
~outh Charleston
mg/l
Time
man
~
TOC
1) 39.5
2) 1 60 . 0
1) 44.8
2) 165.0
-------
APPENDIX B
LITHIUM FLOW VERIFICATION PROCEDURES
AND SAMPLING TECHNIQUES
-------
B-1
Lithium Flow Verification Procedures
Flow verification was accomplished with the tracer dilution
technique, using lithium as the tracer.
The concept employed
is that mass is conserved (i .e., mass of tracer in equals mass
of tracer out).
Fundamental to the use of this technique are
the following conditions:
A conservative tracer.
l.
2.
A constant tracer injection rate and an accurate
measurement of the rate.
3.
An accurate measurement of the tracer concentrate,
background tracer levels, and diluted tracer in the
flow stream to be measured.
4.
Complete mixing in the flow stream to be measured.
It was determined that all these respective criteria
could be met by:
1.
Using lithium (Li) in the form of lithium chloride
as a tracer.
Previous studies have shown that spiking
various types of wastewater with known amounts of
lithium results in an overall average recovery of 100%.
Metering the injected tracer solution with low flow
2.
rate, high precision pumps.
During verification,
injection rate was checked at least blice with a
graduated cylinder and stop watch.
-------
R-4
3.
Measuring Li concentration with a Perkin-Elmer Model
403 Atomic Absorption Spectrophotometer.
This instru-
ment was calibrated before each use with lithium
standards of known concentration.
Concentrate samples
were analyzed each time a batch was mixed.
Background
samples were collected and analyzed each time a flow
measurement was performed.
4.
Injecting the lithium chloride concentrate solution
into the suction side of the effluent pump and moni-
toring the diluted Li tracer on the discharge side.
Flow was calculated with the following equation:
Q = q Cq F
. C-Cb
where Q is unknown flow (mgd)
q is injection rate (l/min)
Cq is lithium concentration of injection solution (mg/l)
C is lithium concentration downstream of injection (mg/l)
Cb is background concentration of lithium (mg/l)
F is factor to convert l/min to mgd
(380.45 x 10-6 min - gal)
day-liter
-------
Sampling Techniques
Composite samples were collected by hand at regular
intervals throughout a 24-hour period and aliquoted pro-
portional to the volume of the discharge into iced sample
containers.
For those samples whose nature could change
during the (ol~ection period chemical preservatives were
added to the sample container prior to the start of the
collection period.
se .
Each of the sample aliquots were chemically
preserved upon collection.
At the end of the sampling period,
the chemically unpreserved portion of the sample was trans-
ferred into appropriately preserved containers, identified
and transported to either NEIC mobile laboratories located at
the South Charleston Sewage Treatment Company plant or the NEIC
laboratory Denver, Colorado.
Grab samples we~~ handled as discussed above with the
exception that the sample consisted of a single aliquot rather
than multiple samplings.
B-5
-._-------
-------
APPENDIX C
CHAIN-OF-CUSTODY-PROCEDURES
-------
C-3
CHAIN-OF-CUSTODY PROCEDURES
(March 29, 1978)
Due tp the evidentiary nature of samples collected during en-
forcement investigations, the possession of samples must be traceable
from the time the samples are collected until they are introduced as
evidence in legal proceedings. To maintain and document sample posses-
sion, Chain-of-Custody procedures are followed.
SAMPLE CUSTODY
A sample is under custody if:
1. It is in your actual possession, or
2. 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 to prevent tampering, or
4. It is in a designated secure area.
FIELD CUSTODY PROCEDURES
1. In collecting samples for evidence, collect only that number
which provides a fair representation of the media being
sampled. To the extent possible, the quantity and types of
samples and sample locations are determined prior to the
actual field work. As few people as possible should handle
samples.
-------
C-4
2.
The field sampler is personally responsible for the care
and custody of the samples collected until they are trans-
ferred or properly dispatched.
3.
Sample tags (see attached) shall be completed for each sample,
using waterproof ink unless prohibited by weather conditions.
4.
During the course and at the end of the field work, the
Project Coordinator determines whether these procedures
have been followed, and if additional samples are required.
TRANSFER OF CUSTODY AND SHIPMENT
1.
Samples are accompanied by a Chain-of-Custody Record (see
attached). When transferring the possession of samples,
the individuals relinquishing and receiving will sign, date,
and note the time on the Record. This Record documents
transfer of custody of samples from the sampler to another
person, to a mobile laboratory, or to the NEIC laboratory
in Denver.
2.
Samples will be properly packaged for shipment and dispatched
to the appropriate NEIC laboratory* for analysis, with a
separate Record prepared for each laboratory (e.g., Mobile
Chemistry Lab, Mobile Biology Lab(s), Denver Chemistry Lab,
Denver, Biology Lab). Shipping containers will be padlocked
for shipment to the Denver laboratory. The "Courier to
Airportll space on the Chain-of-Custody Record shall be dated
and signed.
* See Appendix B of NEIC policies and Procedures Manual for Safety
Precautions When Accepting Samples From Outside Sources.
-------
C-5
3.
Whenever samples are split with a facility or government
agency, a separate Chain-of-Custody.Record is prepared for
those samples and marked to indicate with whom the samples
are being split.
4.
All packages will be accompanied by the Chain-of-Custody
Record showing identification of the contents. The original
Record will accompany the shipment, and a copy will be re-
tained by the Project Coordinator.
5.
If sent by mail, the package will be registered with return
receipt requested. If sent by common carrier, a Government
Bill of Lading should be used. Receipts from post offices
and bills of lading will be retained as part of the permanent
documentation.
LABORATORY CUSTODY PROCEDURES
1.
A sample custodian or a designated alternate will receive
samples for the laboratory and verify that the information
on the sample tags matches that on the Chain-of-Custody
Record included with the shipment. The custodian signs the
custody record in the appropriate space; a laboratory staff
member performs this function in the field. Couriers picking
up samples at the airport, post office, etc., shall sign in
the appropriate space.
2.
The custodian distributes samples to the appropriate analysts.
The names of individuals who receive samples are recorded
in internal Branch records. Laboratory personnel are responsible
for the care and custody of samples from the time they receive
them until they return them to the custodian. Samples received
after normal working hours may be analyzed immediately or
stored as appropriate.
-------
C-6
3.
Once field-sample testing and necessary quality assurance
checks have been completed, the unused portion of the sample
may be disposed of. All identifying tags, data sheets and
laboratory records shall be retained as part of the permanent
documentation. Samples forwarded to the Denver laboratory
for analysis will be retained after analyses are completed.
These samples may be disposed of only upon the orders of
the Chief, Enforcement Specialist Office and Assistant Director
for Technical Programs, and only after all tags have been
removed for the permanent file.
-------
C-7
SAMPLE TAG
--.- --.-
Proj. Code Station No. Sequence No. Mo.lOay/Yr. Time
Station Location Camp. Grnb
o ENVIRONMENTAL PROTECTION AGENCY
r- ..
l;'- ~ ~
OFFICE OF ENFORCEMENT U1
-~-' :.. NATIONAL ENFORCEMENT INVESTIGATIONS CENTER a
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER ~
DENVER, COLORADO 80225
Samplers: (Signature)
- -- -. ----.
---
obverse
--- -..---
----.- .
,;~.~@;
\~D..
"':,.....~. :
Sample Type/Preservative(s)
1. General Inorganics/lce
2. Metals;,HNOJ
3. Nutrients/H"SO. & Ice
4. Oil & Greasel H"SO. & Ice
5. Phenolics/HJPO. & CuSO. & Ice
6. Cyanide;,NaOH & Ice
7. Organic Characterization/Ice
8. Voiatile Organics/Ice
9. General Organics/Ice
10. Tracer/None
11. Solids - Inorganics/lce or Freeze
12. Solids - Organics/Ice or Freeze
13. BioI. - Inorgznicsjlce or Freeze
14. BioI. - Organics... Ice or Freeze
15. Source Filter/None
16. F-robe Wash; None
17. In:pinger Catch/None
18. Ambient Filter/None
19. Solid Adsorbant/lce or Freeze
20. Ambient Impinger/Amb. or Ice
21. Benthos/ Ethanol or Formal
22. Bacteriology/ Ice .
23. Plankton/Formal; HgCI2; Lugol's
24. Ch!orophylljlce or Freeze
25. Pathogenic Bacteria/Ice
26.
Remarks:
reverse
tlGPO 777.941
-------
n
I
():)
. ____0'-___'_-- -.----.-.
'NATIONAL ENFORCEMENT INVESTIGATIONS CENTEI
Building 53. Box 25227, Denver Federal Center
Denver. Colorado 80225
ENVIRONMENTAL PROTECTION AGENCY
Ofllce 01 Enlorcement
CHAIN OF CUSTODY RECORD
Proj. No. Prolect Name SAMPLE TYPE
~ .
0 1i .. II .!i I;'t
SAMPLERS: (Sigos/urs} .~ ~ .~ 'c ;.~.~ n c .. C g- ~ UI
a:
01 . ~.." ~fII;.-t ~.,.a'Ci Q) a: w
IS ~ ~"'.. ~"'''c "."~E if - uJ Z
c .un ad _.5~~~~U~ - -}~ 1Du.-
i~~ai~lli ~~5a~~ii~I~!~~! ::;0"
::J ....
. .. .- ." C c - tJ t '0 :\? I I ~ ! ,c .- '0 ... S ! ~ ... ,g z z
-.. "" lQ~u,..._-~ Q..t.I._.o~uco
ST". NO. SEO. NO. DATE TIME STATION LOCATION ti~5~f. ~ ~~~.. eEE~E .~E~ 0 Remarks
u zo oo>~~ ~mm ~_~~~mm~u~ 0
~NM.~~~~~~~~p~~~~~~~~~~~~~~~
.,' ~,' W~. t~
TOTAL NO. OF CONTAINERS
%' ~ft~~* ."
. Relinquished by: (Sigos/ure} D3leflme Received by: (Signsturs} Relinquished by: ISlgnsturs} Dotel'me Received by: (Sign.tuft}
.
Relinquished by: (Slgns/ure} 08terlme Received by: (Signe/urs} Relinquished by: (Slgnsture} Date/Time Received by Courier
I (Signstu/e}
Relinquished by Courier . Oalerme Rece.lved by Mobile Lab Relinquished by Mobile Lab Oaterlme Received by Courier
IS/9ns/ure} I Signs/ure} ISigno/uro} ISign./ure}
Method 01 Shipment: Shipped by: ISlgn.,u/e} Courier Irom Alrporl Received lor Laboratory by: oaleiTime
ISigos/ure} ISigna/ura}.'
.,-. '.
." ..' :, ':: '. ,.;' ~~: .
ouoo
". . ~ '.
" "
. ..
. .
Distribution: Original Accompanies Shipment: Copy 10 Coordinator Flcid Flies
-------
APPENDIX D
ANALYTICAL METHODS
AND
QUALITY CONTROL
-------
D-3
CHEMISTRY ANALYTICAL METHODOLOGY AND QUALITY CONTROL
The analytical procedures used by the Chemistry Branch are de-
scribed in the following sections which are organized by working
groups, Inorganics and Organics. The quality control procedures
and data used to verify the quality of the analytical data are also
discussed.
INORGANICS
The samples from this study were analyzed for the following in-
organic parameters: TOC, NH3, total Kjeldahl nitrogen, chloride and
phenolics. Methods approved by the EPA for the NPDES program (40
CFR 136, Federal Register, December 1, 1976) were used to analyze
all samples. The references to the methods for each parameter are
listed in Table 1 below.
Table 1
Detection Limit,
Parameter Technique mg/l Reference
TOC Combustion-Infrared 1 a pg 532
Std. Methods
NH3 Automated phenolate 0.05 Std. Methods pg 616
Phenolics 4-AAP colorimetric 0.001 Std. Methogs pg 574
TKN Kjeldahl digestion, EPA Manual pg 175
Automated phenolate 0.2 Std. Methods pg 616
Chloride Mercuric nitrate 1 Std. Methods pg 304
a Std. Methods = "Standard Methods for the Examination of Water and
Wastewater", 14th edition (1975).
b EPA Manual = "Methods for Chemical Analysis of Water and Wastes", 1974.
Additional precautions taken during the analysis of the samples are dis-
cussed below by parameter.
TOC
Samples were acidified and homogenized before analysis to drive off
the inorganic carbon and reduce the particle size. Samples were alter-
nately homogenized and analyzed until two successive results agreed within
2 mg/l. One reference sample was analyzed with an accuracy of 101%.
Three samples were spiked with a mean recovery of 107%.
-------
0-4
Chloride
Low and high level mercuric nitrate reagents were used for samples
below and above 25 mg/l. Eight samples were spiked with a mean recovery
of 100%. A reference sample was analyzed on five days with an accuracy
of 100%. Fifteen samples were analyzed in duplicate with a mean FSD of 1%.
Ammonia
The auto-analyzer method was adapted to 0-30 mg/l full scale by
adding a dulution loop onto the front end of the manifold. Two ref-
erence samples were analyzed six times each with accuracies of 98 and
104%. Seven samples were analyzed in duplicate with five samples'
below the detection limit. The RSO of the two pairs of data is 1.6%.
Phenolics
All absorbance were measured against a chloroform blank. Three
samples were spiked with a mean recovery of 98%. One reference sample
was analyzed with 92% recovery.
TKN
The method was set up for 20 mg/l TKN-N full scale. Samples
over 20 mg/l were diluted and re-digested before analysis. A refer-
ence sample was analyzed five times with 92% accuracy.
ORGANICS
Several techniques for the analysis of organic compounds were
utilized for the waste source evaluation. Identification of indi-
vidual organic compounds was made by combined gas chromatography/mass
spectrometry (GC/MS) while capillary column gas chromatography (CPGC)
was used for quantitation and confirmation of identity. The samples
were analyzed for neutral extractables and volatiles. A grab sample
collected in April was analyzed for priority pollutants.
NEUTRAL EXTRACTABLE ANALYSIS
GC/MS Identification: Methylene chloride extracts of water, and
acetone extracts of the sediment samples were concentrated to small
volumes and exchanged with isooctane and analyzed by CG/MS. The ini-
tial identification was made using a manual search utilizing reference
spectra analyzed under the same instrumental conditions used for the
samples.
-------
0-5
A library of standard spectra of the commonly occurring compounds
was made using a computer assisted evaluation program (1). In those
instances where other than the commonly occurring compounds appeared,
a more complete search was made utilizing the complete computer libra-
ry and a followup m~nual search (2) (3) (4) (5).
Capillary Column Gas Chromatography: All the sample extracts were
analyzed by capillary column gas chromatography. Initial screening and
quantitation were carried out on this gas chromatograph. Compounds were
identified by coincidence of retention times with standards and quanti-
tation was made using peak height measurement.
Packed Column Gas Chromatography: All the extracts were analyzed
by packed column gas chromatography using a computer-controlled auto-
matic injector. Initial screening was carried out on this gas chro-
matograph.
References
1.
"INCOS Data System - MSDS Operator's Manual, Revision 3".
Finnigan Instruments, March 1978.
2.
"Eight Peak Index of Mass Spectrall, Mass Spectrometry Data
Centre, Aldermaston, Reading, UK. Second Edition 1974.
3.
"Registry of Mass Spectral Data", Stenhagen, Abrahamson and
McLafferty, John Wiley & Sons, New York 1974.
4.
"Atlas of Mass Spectra Data" edited by: Stenhagen, Abraham-
son and McLafferty, John H. Wiley & Sons, New York 1969.
5.
Computer Ass i sted Eva 1 uat i on of Organi c Pri ority Po 11 utant
GC/MS Data - NEIC, September 1978.
Quality Control: Quality control procedures consisted of analysis
of selected duplicate samples, analysis of solvent and procedure blanks
to identify interferences, and gas chromatographic analysis of standards
on a daily basis to confirm the integrity of the GC system. For mass
spectrometry, a daily calibration was used to tune the mass spectrometer,
and assure the integrity of the complete system. The quality control pro-
cedures are documented in the attached methodologies. Attachments 5, 6,
7,8,9, 10.
-------
0-6
VOLATILE ANALYSIS
GC/MS Identification: An aliquot (5 m1) of a water sample was
purged with inert gas. The lower molecular weight purgab1e organic
compounds were stripped from the sample and trapped on a porous polymer.
These compounds were then desorbed from the column by reversing the gas
flow and rapidly heating the trap. The volatile organics released were
collected on an analytical GC column at room temperature. After collec-
tion, the GC column oven was heated at a uniform rate and the eluted
compounds analyzed by the mass spectrometer. The common volatile organic
solvents are all identified using this technique and it also includes the
identification of the volatile priority pollutants. This procedure is
the method recommended for the priority pollutants (1). The identifica-
tion again was made using a computer-assisted evaluation program as for
the neutral extractab1es (2). A library of standard spectra was created
by analyzing all the commonly occurring organics in the UCSC samples,
and adding these to the library. The samples were routinely searched
for these compounds for each sample analyzed by GC/MS.
Quantitative results were obtained using an internal standard
computer technique (2) (3).
REFERENCES
1.
IISamples and Analysis Procedures for Screening of Industrial
Effluents for Priority Po11utantsll, U.S. EPA, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio, March
1977, revised April 1977.
2.
IIINCOS Data System - MSDS Operator1s Manual - Revision 311,
Finnigan Instruments, March 1978.
3.
Computer Assisted Evaluation of Organic Priority Pollutant
GC/MS Data - NEIC, September 1978.
Quality Control: Quality control procedures consisted of daily
routine calibration of the GC/MS, analysis of an organics free-water
blank, and a standard mix at a concentration near midpoint of the
standard calibration curve. The calibration curve was previously
established by analyzing each standard over a typical working range
of 20 to 200 ppb concentration, with response factors calculated rel-
ative to an internal standard. Field blanks were analyzed with each
set of samples. Replicate analyses were run on at least two samples
for every set of twenty samples or less.
-------
0-7
QUALITY CONTROL
Blanks
One contaminant, methylene chloride, appeared consistently in
the blank results. Blanks for the fifteen days of analysis gave a
methylene chloride value of 3 ! 2 ~g/l.
Summary of blank results (~g/l
Compound
Times Detn
15 samples
Range of Values
Average
Methylene chloride
Toluene
l,l,l-Trichloroethane
12
2
1
2-13
2-5
3
3 + 2
nl1
nil
Duplicates
Nine samples, six of them composites, were analyzed in duplicate.
Ten compounds of interest were determined in these analyses. The re-
sults are summarized as follows:
Compound
Times Detn
(9 samples)
Deviation
Benzene
Bromodichloromethane
Carbon tetrachloride
Chloroform
1,2-Dichloroethane
Ethylbenzene
Methylene chloride
Tetrachloroethene
Toluene
l,l,l-Trichloroethane
2
1
1
6
1
1
6
1
2
1
+ 8%
:;: 100%
:;: 50%
:;: 27%
:;: 20%
:;: 80%
:;: 45%
:;: 25%
:;: 48%
:;: 17%
Recoveries
Four samples were spiked with standard mix to give each component
at a concentration of 200 ~g/l. Recoveries are listed below.
-------
0-8
Compound
Percent Recovery
Benzene
Bromodichloromethane
Bromoform
Carbon tetrachloride
Chlorobenzene
2-Chloroethylvinyl ether
Chloroform
Ch1orodibromomethane
1 t2-0ichloroethane
ltl-Oichloroethene
trans-l,2-0ich1oroethene
l,2-0ich1oropropane
Ethylbenzene
Methylene chloride
l,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
l,l,l-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Vinyl chloride
Average
60
108
127
80
86
125
88
113
114
81
77
84
72
93
140
83
87
78
121
85
97
95
EPA Quality Control Sample
An internal quality control sample, prepared by the EPA Environ-
mental Monitoring and Support Laboratory Quality Assurance Branch, Cin-
cinnatit was analyzed in triplicate. This QC samplet containing vola-
tile organics, was No. 1276 WS.
Analytical
Compound Results "True" Values Error
Bromochloromethane (IS) 180 .: 20 I-Ig/l 200 10%
Bromodich1oromethane 13 + 2 12 8
Bromoform 13 :+: 1 14 8
Carbon tetrachloride 9 :+: 1 13 31
Chloroform 60 :+: 7 68 12
Chlorodibromomethane 12 :+: 1 17 29
lt2-0ichloroethane 23 :+: 2 27 15
Tetrachloroethene 8 :+: 1 9 11
ltltl-Trichloroethane 9 :; 1 11 18
Trich1oroethene 17 :+: 2 19 11
-------
D~9
ATTACHMENT I
Neutral Extraction Technique for Organics Analysis
September 1978
1.0 Scope and Application
This procedure is applicable for Bnalysis of water and
wastewater samples for a broad spectrum of organic
pollutants.
2.0 Summary of Method
1.1
2.1 Water and wastewater samples are extracted ~/ith CH2C12
(dichloroMethane) at a neutral pH. The extract is cried
and concentrated with the addition of acetone and iso-
octane to exchange solvents. The resultant extract
concentrate is subjected to GC and GC/MS analysis to
identify and quantitate the organic pollutants present.
3.0 Sample Handling and Preservation
3.1
Prior to extraction, samples are refrigerated and
extracted as soon as possible, generally within 48
hours. Samples may be held 5 days or more if necessary.
4.0 Definitions and Comments
5.0
Interferences
5.1
Solvents, glassware and reagents could be sources of
contamination. Therefore, at least one IIReagent Blankll
must be prepared contacting the solvent with all
potential sources of contamination. This blank should
then be processed through the same analytical scheme
as the associated samples.
5.2 Typical interferences from reagents are:
4-methyl-4-hydroxy-2-pentanone (diacetone alcohol)
from acetone, phthalate esters from Na2S04'
cyclohexene from dicholormethane.
6.0 Apparatus
6.1
Separatory funnels: 21 and 41 glass with glass or
teflon stoppers and stopcocks. No stopcock grease used.
Drying column: All glass 3 cm x 50 cm with attached
250 ml reservoir.
6.2
-------
D-io
6.3
7.0 Reagents
7.1
7.2
7.3
Concentrator: 250 or 500 ml Kuderna-Danish evaporative
concentrator equipped with a 5 or 10 ml receiver ampule
and a 3 ball Snyder column.
Extraction solvent: Pesticide analysis grade CH2C12
(dichloromethane) (Burdick and Jackson or equivaTenE)
Exchange solvents
7.2.1
Exchange solvent: Pesticide analysis grade
acetone (Burdick and Jackson or equivalent)
Exchange solvent: Iso-octane suitable for
pesticide analysis (Burdick and Jackson
or equivalent)
Drying agent: Analytical reagent grade granular
anhydrous Na2S04 (sodium sulfate). Washed with
CH2C12 prior to use.
7.2.2
7.4 Glass wool that has been extracted with CH2C12
prior to use.
7.5
7.6
6N NaOH for pH adjustment.
6N HCl for pH adjustment.
7.7
pH paper for pH measurement.
8.0 Procedure
8.1
If low concentrations of pollutants are expected, measure
3 1 of sample for extraction. Otherwise, one 1 is sufficient.
8.2 Measure and record the initial pH. Adjust the pH to 6-8 if
necessary, and record the adjusted pH.
8.3
Extract the sample with 3 successive extractions of 100, 50
and 50 ml of CH2C12 for 1 liter samples and 200, 100, 100 ml
of CH2C12 for 3 liter samples.
If emulsions form, use a wire or stirring rod to break it,
pass the emulsion through glass wool or centrifuge if
necessary. Combine the extracts and measure the volume
recovered. 85 percent constitutes an acceptable recovery.
-------
8.4
0-11
Place a glass wool plug in a drying column and add ca 10 cm
of Na2S04. Wash the Na2S04 with at least 50 ml of CH2C12.
Pour the combined extract through the column. Follow with
100 ml of acetone. Collect the CH2 and acetone and transfer
to a KO assembly. Ad~1ml of iso-octane for 1 liter extracts
and 5 ml iso-octane for 3 liter extracts.
8.5 Concentrate on a hot water bath at 80-90oC until the extract
stops boiling. Quantitatively transfer the receiving tube
contents to a graduated centrifuge tube. Adjust the volume
to 2 or 5ml by either adding more iso-octane or evaporating
the excess iso-octane under a gentle stream of carbon filtered
air. Transfer to a 12 ml vial and cap with a teflon lined
cap. (Note: The final extract volume should depend on the
sample. Extracts containing high concentrations of pollutants
may not require concentrations to 5 ml while cleaner samples
may require a final volume of 2 ml).
9.0 Quality Control
A representative group of the organic pollutants of interest
should be spiked into water and carried througn the extraction
procedure, recoveries calculated and compared to literature
values (if available).
10.0 Calculations
10.1
10.2
9.1
Solvent Recovery:
% recovery = Volume recovered (ml)*lOO/volume added (ml)
Pollutant Recovery:
% recovery - (Concentration measured - initial concentration)*lOO
Concentration added
11.0 Precision and Accuracy
11. 1
Precision and accuracy vary with the pollutants being measured.
Recoveries range from 48 - 119 percent and precision values
range from 1 to 9 percent relative standard deviation (% RSO).
Typical values are ~5 % RSO.
12.0 References
(1) "An EPA GC/MS Procedural Manual-Review Copy", Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio.
-------
0-12
ATTACHMENT II
Summary of Recovery Data
for Neutrals Extractable Organics
in Kanawha River Project
Backaround
J
A number of organic compounds were identified in the Kanawha River
Project reconnaissance samples.
Some of these compounds were available
and synthetic sample recoveries were measured to help validate the extrac-
tion methods used.
Even though few of the compounds used in this evalu-
ation were found in subsequent survey samples, the diversity of the com-
pounds used illustrate the method's capability to recover a broad spectrum
of pollutants.
Experimental
A standard mix was prepared containing 50 ng/ul of each compound
in acetone.
One and 3 1 tap water samples were spiked with the standard
mix resulting in concentrations of 2500 and 10 ug/l respectively.
The
samples were then extracted with CH2C12 and concentrated with the addition
of iso-octane as an exchange solvent in Kuderna-Danish evaporative concen-
trators.
The final volumes were 5 and 1 ml for the 1 and 3 1 samples
respectively.
The extracts were then analyzed by gas chromatography with
a flame ionization detector using a 6 ft x 2 mm glass column packed with
60/80 mesh GC-Q coated with 6% OV101.
The response of each component was
measured by area integration using a computerized data reduction system.
Results & Discussion
The nine compounds and their recoveries are listed in Table 1.
The
1 1 samples at high concentrations show good recoveries.
The large vari-
ation of butyl carbitol acetate may be attributable to a data system
error.
Results for 3 1 samples at 10 ug/l show large variations and a
-------
Table 1.
Recoveries for selected organics from tap water for neutral pH extractions.
methyl cellosolve acetate
79 :!: 9
3 1 extraction 10 ug/l
% Recoveryb
16 :!: 0.3
Name
1 1 extraction - 2500 ug/l
% Recoverya
styrene
99 :!: 1
167 :!: 25
anisole
119 :!: 4
328 :!: 20
phenol
48 :!: 3
o
o-cresol
98 :!: 4
105 :!: 0.1
88c -
N,N-dimethyl aniline
108 :!: 5
butyl carbitol acetate-
86 :!: 69
27c
83c
benzothiazole
103 :!: 4
2,G-dinitrotoluene
119 :!: 53
217 :!: 2
a = Values represent results of 3 replicate sample analyses
b = Values represent results of 2 replicate sample analyses.
c = No recovery in one sample, value is result where recovery \'/as observed.
o
I
-'
w
-------
D-14
- 3 -
number of cases of no recoveries.
The limiting factor for detection ;s
most likely the use of packed column gas chromatograrhy and could account
for a large part of the variation.
Recoveries at low levels, however, can
be expected to be more variable due to the larger samples and extreme
concentration factors required.
Conclusion
Extraction recoveries can be expected to be quite good at high com-
ponent concentrations.
At low levels, 10 ug/l, the variation will be
larger and with packed column gas chromatography, may be unacceptable.*
*Note: GlassCapillary column gas chromatography (GC) was used for quanti-
tation of survey samples lowering the effective GC detection limit by a
factor of ca 10.
-------
and acrylonitrile were prepared in a separate standard mix. 0-15
For gaseous standards - only vinyl chloride in this pro-
cedure - a primary standard solution was prepared by bubbling
the gas into a tared volumetric flask of suitable solvent
(methanol in this instance). The mass increment was measured
and the concentration calculated. As with the liquid standards,
a calculated volume was then diluted for the standard mix.
For internal standards, 100 mg each of bromochloromethane
and 1,4-dichlorobutane were made up to 20 ml in methanol. For
each day of analysis, 20 ul of this solution was diluted to
1.0 ml in water, and 10 ul of this preparation was added to
each 5 ml sample aliquot, to give 200 ug/l of each component.
Analysis Procedure
The helium purge gas flow on a liquid sample concentrator
(LSC) was adjusted to 40 ml/min. and the LSC valve set to the
purge position. The VOA sample was removed from cold storage
and brought up to ambient temperature. The bottle was carefully
opened and the sample water poured into a 5-ml syringe to over-
flowing. The syringe plunger was replaced and the sample volume
adjusted to 5.0 ml, and the syringe valve was closed. A 10 ul
aliquot of the internal standard (IS) mixture was introduced
into the sample by opening the valve and injecting the IS into
the syringe. An S-inch needle was attached to the syringe valve,
and the sample was injected into the purging chamber of the
LSC. The timer of the LSC was set to purge the sample for 12
minutes, with the silica gel-Tenax trap at ambient temperature
( 2 0 - 2 50 C ) . .
.
At this time, the oven of the gas chromatograph was brought
to near ambient temperature by opening the oven door with the
heater off.
. After the l2-minute purge time the sample from the trap wis
injected into the GC by turning the valve to the desorb position
and starting a timer for the analysis cycle (time zero). The
GC-MS data collection was started at one minute; at four minutes
the desorb was ended by turning the valve back to the purge.
position, and simultaneously the GC oven was closed and the oven
temperature was set at 600C. The temperature program conditions:
isothermal at 600 until S minutes; program at SOC/mm to 1700;
hold at 1700 to the end of the program at.29 minutes.
After the sample purge, and while data was being collected,
the trap was baked out at 2100C for ten minutes, then allowed to
cool to ambient temperature. Also, the sample tube was removed
from the assembly, washed in methanol and baked out, and replaced
on the LSC by a clean tube.
-------
0-16 .
August, 1978
ATTACHMENT III
METHODS: VOLATILE ORGANICS ANALYSES
Purge and Trap - Gas Chromatography-Mass Spectrometry
This method is basically dra\'/n from "Sampling and Analysis
Procedures for Screening of Industrial Effluents for Priority
Pollutants", U.S.E.P.A. Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio,45268, March, 1977, revised
April, 1977, and "Volatile Organic Compounds by GC/MS",
U.S.E.P.A., NEIC, Denver, Colorado, 80225, July, 1978.
Scope
The Volatile Organics Analyses (VOA) method ,is designed to
determine "priority pollutants" associated with the Consent
Decree that are amenable to the purge and trap method. It is
a gas chromatographic-mass spectrometric (GC-MS) method intended
for the qualitative and quantitative determinations of these
compounds.
The purge and trap method is complementary to the liquid-
liquid extraction method. There is an area of overlap between
the two methods, and some compounds may be analyzed by either
method. The efficiency of recovery depends on the vapor pressure
and water solubility of each compound. The overlap region in .
general consists of compounds which boil between 1300 and 1500C
(1 atmosphere pressure), with a water solubility of approximately
two percent. The method of choice for these overlap region com-
pounds is selected according to overall method efficiency and
dependability:
Special Apparatus
Tekmar Liquid Sample Concentrator, Model LSC-l; Tekmar
Company, P.O. Box 37202, Cincinnati, Ohio, 45222.
Special sorbent trap for LSC: stainless steel tube 1/8-
inch 0.0. by ll-cm.; packing from inlet, 1 cm glass wool, 5 cm.
type 15 silica gel, 8 cm Tenax, 60/80 mesh; 3 cm. glass wool.
GC Column: a 6-ft. by 1/8-inch 00 column packed with
0.2% Carbowax 1500 on 60/80 mesh Carbopack C; manufactured by
Supelco, Supelco Park, Bellefonte, ~ennsylvania, 16823.
Standards
For liquid standards, a primary standard solution for each
compound was prepared from 10 ul of the compound in 10 ml of
methanol. Concentrations were calculated from the desnity of
each compound, and a standard mix was prepared by diluting a
calculated volume of each solution (ca 150 ul) together to a
total volume of 10 ml in methanol. Due to instability, acrolein
-------
0-17
steps are taken by the operator to stabilize the operation.
To determine the precision of the method, replicate aliquots
of environmental samples are analyzed, with at least one set of
replicate analyses made for each group of 20 samples or less
analyzed. Over the course of a survey, replicate analyses are
made on samples which represent the entire range of concentrations
and interferences found in that survey.
To determine the recovery of the method, at least one en-
vironmental sample for each group of 20 samples or less is re-
analyzed after the addition of a spike mixture. The spike con-
centration should approximately double the background concentra-
tion. If the background is negligible, the spike concentration
sould be five to fifteen times the lower detection limit.
The qualitative and quantitative determinations of the
volatile priority pollutants are based upon the characteristic
masses and their relative and absolute intensities, from which
an extracted ion current profile is obtained for each compound.
Details of these determinations are presented in IIComputer-
Assisted Evaluation of Volatile Organics GC/MS Datal', NEIC,
July, 1978.
-------
0-18
Mass Spectrometer Parameters
The mass spectrometer used was a Finnigan 1015 S/L inter-
faced to a Systems Industries System 150 data system. The
operational parameters include: electron energy, 70 ev; mass
range, 20-27 and 33-260 amu; integration time/amu, 17 milli-
seconds; samples/amu, 1.
GC Column Preparation
The column was connected at the inlet, the helium flow
was adjusted, and the column was baked out overnight. This
column must be handled with care, due to the fragile character
of the Carbopack.
MS Calibration
The mass spectrometer was calibrated daily with perfluoro-
tributylamine (FC 43), according to the Finnigan instrument
manual. A further calibration check was made with the first
run each day of analysis of a blank with internal standards
added. ' The mass spectrum of bromochloromethane must meet
these specifications:
m/e
Relative Intensity
49
130
128
51
100
65-98
50-75
25-35
guality Assurance
The analysis of blanks is most important in the purge and
trap technique, since the purging device and the trap can be
contaminated by residues from very concentrated samples and by
vapors in the laboratory. Blanks are of low-organic water,
prepared by passing distilled water through an activated carbon
column. If positive interferences are observed, the blank is
repeated; if interferences persist, appropriate measures are
taken to eliminate them before analyses are made.
The precision of the method is determined by running blanks
dosed with the internal standards, bromochlbromethane and 1,4-
dichlorobutane. These compounds represen~ early and late eluters
over the range of the Consent Decree compounds and are not on
the list.
Each sample is dosed with the internal standards and
analyzed by the set procedure. The operator monitors the sensi-
tivity of the system to the internal standards as compared with
blank runs; if 'the deviation is too great, a sample run is re-
peated. If excess deviation of sensitivity persists, appropriate
-------
0-19
ATTACH~1ENT IV
Computer Assisted Evaluation of
Organic Priority Pollutant GS/MS Data
NEIC - September 1978
1.0 Introduction
This procedure is applicable to GC/MS data collected under constant
analytical conditions for the organic priority pollutant defined
in "Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants". (1)
2.0 Summary of Method
1.1
2.1
GC/MS data files are processed by location of an internal standard
that is used for response and retention time reference. Components
of interest are then located by reverse searching from library
spectra. If a compound is located and the match is sufficient, it
is quantitated and its spectrum optionally printed. The concen-
trations are then calculated from each component found using a
relative response quantitation technique. Printed reports of both
quantitative and qualitative results are available.
3.0 Definitions and Comments
3.1
Unlike the 3 ion and retention time compound identification tech-
nique described for priority pollutant analysis in reference 1,
this procedure allows the user to audit each identification where
the spectra are printed. Thus, each identification is unambiquous
and marginal data may be eliminated.
4.0 Interferences
4.1
In some cases, a spectrum may match the library reference
sufficiently to be passed. During quantitation, however, the ion
of interest may be too weak to locate and no entry will be made in
the quantitation list. In such a case, no entry at all (e.g. no
"not found" entry) will appear in the quantitation report. The name
and match results will, however, appear in the qualitative data
report.
Occasionally, multiple peaks will be detected during quantitation
due to background interferences and multiple entries will be made
in the quantitation list. Generally, the entry having the same
label as the correct spectrum is used for quantitation and the
others are disregarded. In some instances, however, the correct
selection is not obvious and manual evaluation of the quantitation
results must be done.
4.2
-------
1)-20
5.0 Apparatus
5.1
Finnigan INCOS data system software, Revision 3.1 or later. To
initially setup this procedure, the user must understand and be
proficient in the use of MSDS. (2)
6.0 Procedure
6.1
Procedure Setup
Load the procedures listed in Appendix I into the system
disc or create the procedures from the trace of PPEVAL in
Appendix II.
Library Setup
6.1.1
6.2
6.2.1
6.2.2
6.2.3
Build user libraries for each analytical class of priority
pollutants (VOAs, base-neutrals and phenols). Appendicies
III, IV and V are library lists of example libraries. The
first entry must always be the internal standard and each
entry must include the quantitation parameters and relative
retention times.
Execute PPEVAL, edit the quantitation list for accuracy and
update the library parameters using commands in "QUAN".
Using the "LIBR" program, generate hard copies of library.
spectra for reference. Using the library list editor, .
"EDLL", generate summaries of the entries and quantitation
parameters as in Appendicies III, IV and V. .
6.3
Routine Use
6.3.1
6.3.2
6.3.3
Analyze samples, standards and quality control samples using
the same instrument conditions used to set up the libraries.
Using the namelist editor, create a namelist containing the
names of the data files to be processed.
Execute the procedure as follows:
PPEVAL library, namelist, yes (no)
~Jhere :
library is the appropriate user library name.
namelist is the list containing the files to be
processed.
yes (no) selects print out of the spectra at a peak that
was identified by the procedure.
6.3.4 Appendix VI is an example of PPEVAL output for a sample con-
ta; n i ng one i nterna 1 standa rd and one component. The "yes II
option ',';;;S selected.
-------
0-21
7.0 Quality Control
7.1
7.2
8.0
8.1
9.0
Each identification can be manually audited if the "yes" option
was selected. Inaccurate qualitative results may then be checked
and manually corrected.
Quantitation data accuracy is monitored by use of standard quality
control techniques such as daily standardization, replicate analysis
and spikes. (~) Daily calibration of the method can be accorrrnodated
by analyzing the standard data first, updating the relative response
factors, obtaining hard copy of the new factors (library list editor)
and then analyzing sample data.
Precision and Accuracy
The overall precision and accuracy is limited to the quality of the
raw data being processed.
References
(1)
"Sampling and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants", US EPA, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio, March 1977, Revised
April 1977.
(2)
"INCaS Data system - HSDS Operators Manual - Revision 3", Finnigan
Instruments, March 1978.
(3)
"Quality Assurance Program for the Analyses of Chemical Constituents
in Environmental Samples", US EPA, Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio, March 1978.
-------
0-22
II.
III.
Appendices
1.
List of procedures, file names, and functions for PPEVAL
Trace of PPEVAL
VOAs library list
IV.
V.
Base neutrals library list
Phenols library list
VI.
Example PPEVAL output
--. - --,-
-------
IREQUIRED PROCEDURES AND METHODS FOR OPERATION OFPPEVAL
0-23
I~;~;~~::~~;::
FUNCTION
**,!OIOIC*:1OfC
PPEVAL
'PPEVA
IN ITIAL IZATlON
.
H
X
H
o
:z
~
c:I.I
~
PPEV8
DATA FILE PROCESSING LOOP
DATA FILE PROCESSING
PPEVC
LOCATING THE INTERNAL STANDARD
PPEVD
INTERNAL STANDARD ERROR HANDLER
PPEVE
CO~OOUND LOCATER
PPEVF
NOT DETECTED ERROR HANDLER
PPEVG
IDENTIFICATION CHECK
PPEVH
SPECTRA PRINTING
PR IHP 1
IDENTIFICATION REPORT HEADER
'PRINP2
INTERNAL STANDARD ERROR MESSAGE
-------
0-24
APPENDIX IIA.
.. a... ... --.... ~. ~ .
. . .--.--..-" '---" ..
TR~CE OF PROCEDURE PPEV~L
:'fC EF.:~S::
* ;[******** PRIORITY POLLUTANT EVALU~TION PROCEDURE ~J
* ;[THIS PROCEDURE MAY BE USED TO EV~LU~TE GC/MS D~TA ]
* ;[FOR PRIORITY POLLUTAHT CEPA SECT lOti 367CA» co!",pomlDs ]
* ;[THE PROCEDURE UTILIZES INTERHAL STANDARDS AHD RELATIVE ]
* ;[RE5PCNSE FACTORS FOR OUANTITATIOH. THE MSDS OPTION]
* ;CSEARCH IS USED TO LOCATE AND IDEHTIFY PE~KS. THE EPA ]
* ;CIDEHTIFICATION CRITERI~. E.G.. THREE IONS PER COMPOUND]
* ;[.IS USED TO LOCATE THE COMPOUND OF INTEREST. MORi I~NS ]
* ;[HOWEVER !"'~Y BE USED AS THE FIT OF THE SEARCH ROUTINE WILL]
* ;[YIELD MORE SPECIFICITY FOR THE COMPOUND. THE FULL ]
* ;[SPECTRUM IS OUT?UT IN ORDER TO PROVIDE CONFIRMATION OF ]
* ;[THE PRESENCE OF THE COMPOUNDS. ]
* ;C*******""""*,*,,,-~-~"''''''''''''''''~'''-]
* ;[TO USE PPEV~L. BUILD A LIBR~RY CONTAINING THE SPECTR~ 0;: ]
* ;.[THE COMPOUNDS OF INTEREST. INCLUDE THE OU~NTIT~TIVE DATA]
* ;[TH~T IS NECESSARY AS DESCRIBED IN THE MSDS MANU~LS. ]
. ;[CREATE A NA~LI5T WITH THE HA~S OF I~E FILES TO BE ]
* ;CPROCESSED. EXECUTE THE PROCEDURE AS FOLLOWS: 1
. ;[ PPEVAL LIBRARYHAME. NAMELIST .YESCNO) ]
* ;[WHERE YESCNO) SELECTS PRINTED SPECTRA OF ~CCEPTABLE ]
* ;[MATCHES. E.G. PPEVAL va. SAMPLE
*;[ WRITTEH 16AUG7B O.J.LOGSDON II EPA-NEIC 363-234-4661 ]
*;[ REVISED DSSEP7B O.J.LOGSDON II EPA-NEIC 363-234-4661 J
* ;SETS PPSCAN;EDLL YESC-;5:W:E):EDLL NOC-:W:E)
* ;SETH 52:SET4 51:PPEVA;FEED:BEEP:BEEP:9EEP
*
ERASE
SETS PPSCAH
EDlL YES C-;5;W;E)
EDLL NO C-;W:E)
SETH 52
SET4 51
PPEVA
* ERASE
* ;[PART OF PROCEDURE PPEVAL
. :CGET THE NEXT NAMELIST ENTRY AND COHTINUE PROCESSING
* ;[AT PPEVS
* ;GETH;PPEVB;LOOP
..
ERASE
GETN
PPEVS
* ERASE
. ;[PART OF PPEV~L. THIS PROCEDURE SETS THE LIBRARY ENTRY ]
* ;[POINTER TO THE FIRST ENTRY. WHICH MUST ALWAYS BE lriE INTERNAL]
* ;[STANDARD. PPEVC IS THEN CALLED AND THE INTERNAL FOUND ]
'" ;[THE SPECTRUM NU~ER OF THE INTERNAL STANDARD IS J
* ;(STORED IN lie FOR FUTU~E REFERENCE. THE LIBRARY POINTER]
'" :(15 THEN RESET TO THE BEGINNING. THE OUANTITATION LIST SET TO ]
'" ;(THE FILE N~ME AND EMPTIED OUT. PPEVE IS CALLED TO LOCATE EACH]
* ;(COMPOUND CIF PRESENT). OUAN IS THEN CALLED TO CALCULATE ]
* ;(THE RESULTS AND THE PROCEDURE RETURNS TO PPEVA TO GET THE ]
* ;(NEXT FILE TO PROCESS. J
* ;FILECK PRIN.99/N:E)
* ;EDLL PPLISTC-;W:E)
* ;SETI .1;P~RACI;H;E);CHROCI;HI.Ie5a.35e;E):SET4 .1:PPEVC:SETle 1 14;SET4 .e
* ;SETO SI:EDOLC-:W:E);EDSLC-:W:E);SETL $3;PPEy~;OU~NCI;H;E)
* ;EDLL PPLISTCB!I;E) .
II< ;?"IHCgPD
* ;FILECC PRIN.99/N.M::E)
* :FEED
* ;BEEP
*
ERASE'
FILE CK PRIH.99/H;E)
EDLL PPLIST C-;W;E)
SET! -I
PARA CI:H;E)
J
J
]
]
-------
0-25
APPENDIX IIB.
. -. ------.. "''''''.'.'-'.--------'''' .--.
CHRO (I;Hl.le5e.35e:E)
SET4 01
PPEVC
'" ERRSE
'" :CPRRT OF PPEVRL )
'" :CROUTINE TO FIND RN INTERNRL STR~DRRD IN R SR~LE )
* :CUSE R REVERSE SERRCH TO LOCRTE THE INTERNAL STANDRRD)
'" ;SET!4 ~
'" ;SERR/vCI:$;V25eeeea:N2.1B.6BB;&:D-6B.6B;E)
* ;PPEYD
'"
ERRSE
SET!4
SERR
PPEVD
'" IF PPEYD . 114
'" ;CPART OF PPEVRL )
'" ; C NO IHTERNAL STANDARD FOUND]
'" ;PRItHl~P2)
'" ; RETU PPEVB
'"
IF PPEYD.II4
PRIN (@P2)
RETU PPEVa
114
(I;S:V2SBBeeB;H2.1B.6eB;&;D-6B.6B:E)/V
SET! a
SET4
SETO 51
EDOL (-;W;E)
EDSL (-;W;E)
SETL 53.
PPEVE
'" ;CPRRT OF PPEVRL )
* :CTHIS ROUTINE LOCRTES COMPOUNDS IN TME ]
'" ;CSRMPLE FILE BY COMPRRING THE SPECTRA IN THE LIBRRRY ]
'" :[WITH THE SR~PLE. RELRTIVE RETENTION TI~S RRE USED]
'" :[RND REFERENCED TO THE INTERNRL STRNDRRD FOUND ERRLIER.]
'" ;(THE LIBRARY POINTER IS BU~2ED RND TES~D TO J
'" ;[SEE IF THE LAST LIBRARY ENTRY HRS BEEN PROCESSED. J
'" ;CTHEN THE CURRENT SCRN HU:13ER IS SET TO ThE INTERNAL J
'" ;[ STANDARD LOCRTION BY RECRLLIHG THE CON~HTS OF liB. J
'" ;(STORE THE SCRN NUMBER OF ]
'" ;[THE BEST ~~TCH IN VARIRBLE 14 AND ALLOW IH~GRATION ]
'" ;(AT THAT SPECTRUM HUr.3ER O~IL Y ]
'" ;( IF THE CO~.?OUHD IS HOT FOUND. PLRCE A HOT FOUND J
* ;[ENTRY INTO THE OUANTITRTION LIST FOR LA~R REFEREHCE J
'" ;SET4 14...1
* ;IF 124-1.14
* ;SET!4 .,g
* ;SET! liB
'" :EDLL PPLISTC$:W;E)
'" ;SEAR/VCI;$:~;V25eeeee;Hl.le.le;D-2e.2e:E)
'" ;PRIN/KX( 14.2: 114.6:! 15.6: 116.7;C:E)
* ; PPEVF
'" ;LOOP
'"
SET4 14...1
IF .1124.14
SET! 4
SET! liB
EDLL PPLIST ($;W:E)
~~~=: (!:-=:.~:\'2=~~ee~:~'~. !9.1e:D-2~.2~:~)/'J
PRIN 04.2; 114.6: 115.6; 116.7;C;E)/KX
PPEVF
'" CPART OF PPEVALJ
'" ;(IF THE FIT IS LESS THAN OR EOUAL TO 756 )
!It ;(WRITE A NOT DETEC"ITD. NA~D ENTRY INTO THE]
'" ; (QUANT! TATIOH LIST FOR FUTURE REFERENCE J
* ;PPEVG
'" ;EDOLC-;N;.;A:E)
*
-------
0-26
APPBwrx IIC.
.. -...-......-....--..-.. ....~_. ...--.......... .....,.-....... . -.. -. .. ... . . - .. .
.. . -...........
PPEVG
'" [P~RT OF PPEVAL
'" :[ACCESS ANY SCANS IDENTIFIED IN DETECT
'" :[AND INTEGRATE THEIR AREAS. RECORD THE
'" ;[DRTA IN THE OUANL!ST RSSIGNED ERRLIER.
'" :CRLSO CHECK AND PRSS ONLY PERKS WITH
'" ;[R FIT OF 756 OR GREATER
'" ;IF PPEVG '!6.PPEVG -766
'" :SET! 114
'" :CHROC I: R; $: .:N 1.3:A)5.3:G-4.4: D-5. S:E)
'" :;:;:~VH
. '" :RETU PPEVF
'"
IF PPEVG.' 16.?PEVG.76e
SET! 114
CHRO CI:R;$;.:NI.3:A)S.3;G-4.4:D-S.5;E)
PPEVH
* IF 126 PPEVH.PPEVH
'" ;SPECC';N:H;E)
*
IF PPEVH!26.PPEVH
SPEC C';N;H:E)
RETU PPEVF
EDOL C-;N;o:R:E)
LOOP
aUAN (\:H;E)
EDLL PPLIST CBll;E)
PR IN C@P1>
FILE CC PRIN.99/H.M:;E)
FESD
BIOS?
LOOP
FEED
BES?
BEEP
BEEP
_.. ...,.... -. .' ....
J
J
J
J
J
J
-------
APPENDIX IID.
-I;~;;~~~-:-~;~-;-;; --- .. ... P?- lOR In' POLLUTANT EVALUATIOH;
C; T; NO I NTERNAL STANDARD WAS FOUND HI SAM."LE ; S 1 ;
;D;F
IT;
,I
. . ''''_____0''''_. -----------...-- --
fINP1.M~ a C2;T;IDENTIFICATION REPORT
~1;C2;T;NO SCAN PUR In' . FIT
C;E
FILE:
I
0-27
-------
UUi'l: N,IIIE j I~ LJ .11.1. LL" .:.:.0 /J 'L. .I,...I,.....I\,. "" ,V\"'I..
r FORtUlA RET TIME BASE AREA U.P..I U.P..Z 0.000 75.00020a.00 VO I VS 1.000
.RET. TlME..-cASo HASS AMT. REF.PEAK RESP.FIlE RESP.FACTOR
VO IBI 33B L Z-TRAHS-D ICHLORO-I-PROPWE
110 C3.H4.CL2 Z.34 75 O. 0.000 o.€eo
II 1.4-DICHlOROBUTANE (INTERNAL STANDARD) 0.000 75.Da0200.DO VO I vs 1.000
'; C4.HB.Cl2 3:30 55 O. 0.000 0.000 ..: I:) eO
1.000 55.0EJ0200.00 VI I C I.oaa ... vo 19: 3B ETH','UIENZENE I ...
... ID6 CB.HIO 0.00 91 O. o.ooa o.eoo N ""
.... ~. ....
2: OROMOCHlOROtETHANE (INTERNAL STANDARD) 0.000 91.00a2DO.DO VO I vs I.oaa
>< ><
J C.HZ.Cl.OR 0:44 130 O. O.Doa 0.000 ... ....
o.ooa 49.00a200.00 VO I vs 1.000 e vo ZD. 44 r1ETIIYlEHECftlOR IDE Q
7-
(.1 B4 C.HZ.Cl2 0104 B4 O. 0.000 o.eoo ""
'" '"
3: 02 ACROllEH ~ 0.000 B4 .IHJI3200. 00 VO I VS 1.000 ~
; C3.H4.0 o.ao 56 O. 0.000 0.000
0.000 56.o00zao.00 vo I vs I.ooa vo ZI: 47 BROMOFORM
25D C.H.BR3 3102 173 O. O.Doa 0.000
4: 03 ACRYlOHITRllE O.DOO 173.D00200.00 vo I VS I. 000
J C3.H3.N 0,00 53 O. 0.000 O.OOD
0.000 53.0e02eD.eo vo I VS I.eao vo 22: 48 BROI1OD ICHlOROtIE THANE
162 C.H.Cl2.0R 1.59 93 O. o.eao 0.000
5: 04 BENZENE O.Deo B3.0a0200.ee vo I vs I.eeo
J C6.H6 2.19 7B O. e.eoo e.ooo
0.000 7B.00020a.00 vo I VS I. eoo vo 23: 49 TRICHlOROFLUOROI1ETHAHE
136 C.CL3.F 0: 19 101 O. 0.000 0.000
6. 06 CARBOHTETRACHlORIDE o.oao 10 I. ee0200. 0e vo I VS I.ooa
z C.Cl4 1:45 117 O. 0.000 0.000
O.DOO 117. oa02eD. 00 vo I vs I.eoo vo. Z4: 51 DIBROMOCHlOROMETHAHE
2eG C.H.CL.BRZ 2132 129 O. o.ooa 0.000
7. 06 CfilOROBEHZEtIE o.eoo IZ9.000200.00 vo I vs I.ODO
2 C6.H5.Cl 3:5D \12 D. 0.000 0.000
O.OOD 112.0DD2DD.eo vo I vs 1.000 vo 25. B5 TETRACHlOROETHENE
164 CZ.Cl4 3:22 166 O. 0.000 O.ODO
B: 10 I. 2-D ICHlOROEnIAII!: O.ODO 129.000200.00 va I vs I. eoo
3 c;!.H4.Cl2 1:26 62 O. 0.000 0.000
0.000 62.000200.00 vo I vs 1.000 vo 26: B6 TOlUEHE
92 C7.HB 3:29 91 O. 0.000 0.000
9: II I. I. I-TRICftlORO"ETHAHE e.oeo 91.DOD2eO.eo VO I VS 1.0130
2 C2.H3.Cl3 1:41 97 o. o.eoo O.ooe
e.Doo 97.0002eO.oe VO I VS I.eoo vo 27. B7 TRICHlOROETHENE
130 C2.H.Cl3 2.20 130 O. 0.000 0.000
10: 13 1.I-OICHlOROETHAtIE 0.000 95.000200.00 VO I vs 1.000
9 C2.Ho1.Cl2 0:52 63 O. o.ooa 0.000
0.000 96.0013200.00 vo I vs 1.000
III 14 1.1.2-TRICHlOROETHAHE
'2 C2.H3.Cl3 2:32 97 O. 0.000 O.ODO
O.OOD 03.000200.00 vo I vs I. aDO
12: 15 1.1.2.2-TETRACHlOROETHAHE
'6 C2.H2.Cl4 3:27 B3 O. O.ODO 0.000
0.000 B3.D00200.00 vo I vs 1.000
13: 23 CHLOROFORM
B C.H.Cl3 112D B3 O. O.OOD 0.000
0.000 B3.000200.00 vo I vs 1.000
14: 29 1.I-DICHlOROETHEHE
6 C2.H2.Cl2 012B 61 O. 0.000 0.000
0.000 96.D00200.00 vo I VS I.OOD
IS. 30 1.2-TRAtlS-D ICtllOROETHEHE
.. C2.H2.Cl2 1.01 96 O. O.ODO 0.000
0.000 96.00D2ao.00 vo I vs I.oeo
16, 32 1.2-D1CHlOROPROPAtiE
1 C3.H6.Cl2 2: II 63 O. O.ODD 0.000
O.ooe 63.006200.00 vo I vs !.ODO
17. 33A 1.3-CIS-DICHlORO-I-PROPEHE
-------
11\..,,: '''11''- ~4U CI2.U9.U.UW ~: Lk.. ,.),~ C. I" . ~,'" '~I 1.1. ""I~.
I8i~A- ~ RET. BASE AREA U.P..' U.P..2 ,"3 1MI0Ba 20.a0 BN I .S 0.153
MT. .PERK_P.FI~.FAC" - - 18IB: 4 S(Z-C SOPRO~ER - - - -
170 C6.IHZ.0.CLZ 0:43 45 a. a.ooa o.aaa
I: DIO-RNTHRRCENE (INTERNAL STANDARD) 0.193 45.00a 50.00 BN I IS a.664
3:44 IBB 44B64. a.DOO 0.000
I. ODD IBB.OOB ZO.OB BN I .5 I.OBO ..; BI1 19: 43 B IS (Z-CHLOROETIIOXY) ME tHRNE ..;
> C5.HI0.OZ.CLZ I :ZB 93 o. a.OOB o.oaa >
.... 17Z ....
Z: 01 RCENRPHmENE >: 0.359 93.0aB 5a.oa BN I :5 a.SB6 ~
: CIZ.Hla Z.39 154 O. a.ooa B.oaa .... '"
0.710 154.0aa ZO.OB BN I :5 0.SB6 '" BN za: 53 HEXACHLOROCYCLOPENTADIENE W
i:i
1>0 Z7a C5.CL6 I.ZB Z37 a. 0.000 o.oao 1>0
3: 05 BENZIDINE ~ 0.000 Z37.aoa zO.ao BN I :5 I.ooa ~
CIZ.HI2.NZ 5:0a IB4 O. 0.000 o.ooa
I. 345 IB4.00B 50.00 8N I :5 0.047 BN ZI, 54 ISOPHORONE
130 C9.Hld.0 lIa9 B2 o. a.Boa a.ooa
4: OB I. Z. 4-TR ICHLOROBEtllENE 0.309 BZ.ooa 50.0a BN I :S a.9B4
C6.H3.CL3 I: IB IBa O. a.ooo 0.000
0.349 74.000 20.0B BN I :S O.IBZ BN 22. 55 UAPHtHALENE
12B CIO.ItB 1.25 12B o. o.ooa O.BOO
5: 09 HEXACHLOR08ENZEtiE 0.379 IZB.BBB za.Ba BN I ,S I. 2B7
C6.CL6 3:2B ZB4 O. B.BOB 0.000
B.B93 284.oaB 2B.00 BII 1 :S 0.Z64 BN 23: 56 III TROBENZENE
123 C6.H5.02.11 . :07 77 O. B.OBa B.aaa
6: IZ HEXACHLOROE mRtlE 0.300 77.Bal3 5a.oa BN I :S a.457
I C2.CL6 a:43 zal a. O.aBO O.OBB
0.192 117.Bela 20.0a eu I ,S 0.39B 8N 24: 62 N-NITROSODIPHEIIYlAHINE (MEAS AS DIPHENYlAMINE)
169 CI2.HII.N 3: IZ 169 a, a.Boa a.OOB
7, IB BIS(2-CHLOROEmYl)ETHER a.857 169.aoa 2a.OB BN I .S a.145
C4.HB.0.CL2 a:37 93 a. a.ooa a.ooo
0.165 93.0aa 50.0a BII I .S 0.205 BN 25. 63 N-NITR050DIPROPYlAHINE
13D C6.HI4.0.IIZ a:ss 70 O. a.Boo o.ooa
B: 20 2-CHLOROtIAPHtHALENE 0.247 13a.aoo 50.0a BN I :S O.OSB
CI0.H7.CL 2,12 16Z a. a.aao a.oaa
0.5B9 162.oea 20.aa BN I ,5 a.612 BN Z6, 66 DJ-(2-ETHYLHEXYL)PHTHALRTE
390 C24.H3B.04 5:44 149 a. a.ooo a.aaa
9: 25 1.2-DICHLOROBENZENE 1.536 149.000 20.oa BN I .S a.B41
: C6. H4. CL2 a:41 146 a. a.aeo a.aaa
a.IB3 146.00a 20.00 BN I :S 0.706 BN 271 67 8Un\.BENZYlPl1mALATE
312 CI9.1120.04 5.27 149 a. o.ooa a.aaB
10: 26 1.3-DICHLOROBENZEHE 1.4Ga 149.aao 2a.oa BN 1 :S a.581
C6.H4.CL2 a:31 146 O. a.ooo o.aoa
0.13B 145.000 20.ea BN I IS 0.519 8N 2B: 6B DI-N-BUn\.PHmALRTE
27B CI6.H22.04 4,06 149 O. a.aoo a.aoa
II, 27 I. 4-D ICHLOR08EIIZEIIE 1.09B 149.000 20.0a ON 1 ,S 1.732
; C6. H4. CL2 0,34 146 O. o.ooa a.ooo
a.152 146.0aa 20.00 BN I :S 0.B95 BN 29. 69 DI-OCTYLPHTHALRTE
390 CZ4.H3B.04 6.5B 149 a. a.ooo o.aaa
12: 35 2.4-DINITROTOLUENE I. B66 149.aoa 2a.oa BN I IS O.SBa
C7 .H6.04.112 2:59 165 o. a.OBB a.aaa
0.B03 165.0~0 50.00 8N I IS 0.191 Bt! 3D, 70 DIETHYlPHTHALATE
222 CI2.1114.04 3:a4 149 a. 0.000 a.aoo
13: 36 2.6-DINITROTOLUEIIE 0.021 149.00B za.aa BN I IS 0.953
C7.H6.04.112 Z:46 165 O. o.ooa a.aoo
0.744 165.000 SO. DB 811 I :S 0.IB4 Bt! 31: 71 DIMETHYLPHTHRLATE
194 Cla.HI0.04 2"14a 163 B. a.OOB a.OBO
14: 37 1.2-DIPHEI1YLHYDRnZINE (MEAS. AS AZOBEN2ENE) 0.714 163.aoo 20.oa BN 1 IS 0.B17
CI2.HI0.1I2 3.a6 77 0. 0.000 B.BOO
0.B34 77.000 50.BO ON I :S I. 066 8H 32, 72 OEII20 (A) AIW1RnCEtiE
22B C18.H12 6:14 229 O. o.ooa O.OOB
15: 39 FlUORAtfmEtlE 1.67a 22B.ooa 20.00 BN I :5 a.lza
C16.H10 4:34 202 8. 8.00a 0.a08
I.Z23 202.aoo 2a.00 BN 1 .S 0.714 BN 33: 76 CHRYSENE
22B CIB.1112 6114 22B a. a.ooo 9.oaa
16: 40 4-CHlOROPHEilYl PHEtlYl ETHER 1.67a 22B.a09 2a.ao ot! 1 IS a.120
CI2.H9.0.CL 2.53 za4 O. B.aoa B.a00
a.799 204.000 Z9.0a BN I :s B.2Ba BN 34. 77 ACEIiAPHTH'ltENE
152 C12.H9 2,33 152 O. B.ooo 8.aOB
17. 41 4-0ROI1JPHEHYl PHEtlYL EmER 0.603 154.00B 2B.aB BN I .5 a.B03
0
I
N
\.0
-------
J~: 10 ,!NIHI,IKUlt
C14.H10 3,44 17B O. 0.000 0.000 WT FORt1lJUI REf T IHE BRSE RREA U.P.., U."..2
I. 600 17B.000 28.00 BPI I ,5 1.433 REL.RET. TltlE/CRSt Hn55 RtIT. REF.PERK RE5P.FILE RE5P.FRCTDR
36, BO FLUORENE
C13.H10 3,00 166 B. B.OOO 0.000 PH II D 10-RNTHRRCENE (INTERNRL STRliDRRD)
0.B04 166.080 20.00 8N I ,5 0.573 U IBB 2,43 18B 44B64. o.oao O.BOO 0
> I. 000 IBB.OOO 5a.oa PH I :5 I.oao
.... t
37: BI PHENANTHRENE >: w>
C14.H10 3,44 17B O. o.aoo O.!)OO .... PH 2, 21 2.4.6-TRICHLDRDPHENOL C>
I.aoo 178.000 20.00 etl I ,5 1.433 p 196 C6.H3.0.CLJ 1:46 196 O. o.ooa 0.000 ><
i;'j ....
o.aoo 196.00aI00.ao PH I ,5 0.461 p
... z
30, 94 PYRENE ~ '"
...
C16.H10 4:34 202 O. 0.000 o.ooa PH 3, 22 4- CHLORO - 3- HE THYlPHEtmL ~
1.223 202.030 20.00 811 I ,5 0.714 142 C7.H7.0.CL 2,06 142 O. 0.000 a.ooo
0.000 142.000100.0B PI! 1 :5 0.524
PH 4: 24 2-CHLOROPHENOL
12B C6.H5.0.CL 0,27 128 O. 0.000 0.000
0.000 129.000 laO. 00 PH I ,5 1.014
PH 5, 31 2.4-DICHLOROPHENOL
162 C6.H4.0.CL2 1,13 162 O. 0.000 O.OOB
B.OOB 162.0BBI00.00 PH I :5 0.714
PH 6: 34 2.4-DIHETHYlPHENOL
122 C8. H HJ.O I,ll 122 O. 0.000 0.000
B.OOO 122.000100.00 PH I :5 0.617
PH 7, 57 2-N ITROPHEHDL
139 C6.H5.03.H 0:37 139 O. 0.000 0.000
0.000 139.000100.0B PH I :5 0.534
PH B: 5B 4-HITRDPHENOL
139 C6.HS.D3.H 5,01 139 B. B.Ooa O.OOB
0.000 65. oeo 100. IHJ PH I 15 B.OOO
PH 9: 59 2. 4-DIN 1 TROPHEtlOL
IB4 C6.H4.0S.H2 2:53 IB4 543744. 0.000 B.OOO
1.000 '04.000"1000. PH I :5 0.219
PH 10: 60 4.6-DINITRO-O-CRESOL
1911 C7.H6.05.N2 2:57 199 791312. 0.000 0.000
1.000 199.000"1000. PH I :5 0.319
PH It, 64 PENTRCHLOROPHENOL
264 C6.H.O.CLS 3: 12 266 O. . 0.000 0.00B
0.000 266.000100.CO PH I ,5 0.242
PH 121 65A PHENOL
94 C6.H6.0 B:52 94 O. 0.000 0.000
0.000 94.000100.\J0 PI! I :5 I. 025
-------
APPE!mIX VIA.
OUA~TITATICH REPORT
. FILE: Sf".A$A
DRTR: SMA$A.Ml
8:e8:ea
SRMPLE: VCR STD MIX R
CO~DS . :
FORMULA:
SU8MITTED 8Y,
W/I.S. SEPT 3. 1978
INSTRUMENT: SYSIND
AHCiL '!'ST:
AMOUNT-AREA * REF.AMHT/(REF.AREA~ RESP.FACT)
NO NAME
I 1.4-DICHLOR08UTANE (INTER~AL STANDARD)
2 8ROMOCHLOROI"'.ETHA~E (INTERNAL STANDARD)
3 132 ACROLIEH
4 83 ACRYLONITRILE
5 134 BEtEEtiE
6 86 CAR80NTETRACHLORIDE
7 137 CHLOROBEHZENE
8 18 1.2-DICHLORCETHANE
9 11 1.1.1-TRICHLOROETHAHE
18 14 1.1.2-TRICHLOROETHAHE
11 15 1.1.2.2-TETRACHLDROETHAHE
12 19 2-CHLOROETHYLVINYLETHER
13 23 CHLOROFORM
14 38 1.2-TRANS-DICHLORCETHENE
15 32 1.2-DICHLOROPROPANE
16 3B ETHYL8ENZENE
17 44 METHYLENE CHLORIDE
IB 47 BROMOFORM
19 48 8RO~QDICHLOROtETHAHE
28 51 D 16ROMOCHLORCMETHAHE
21 B5 TETRACHLOROETHEHE
22 86 TOLUENE
23 B7 TRICHLOROETHENE
24 B8 VINYL CHLORIDE
25 29 1.1-DICHLOROETHENE
WEIGHT:
ACCT. HC.:
0-31
8.eea
NO tVE SCAN TII"'£ REF RRT METH AREA AMOUNT ~TOT
1 55 251 4:11 1 1. ee6 A 86 1191666. 26a.aea PP8 4.55
2 49 75 1: 15 1 6.299 A 88 112<:98a. 2ee.elJa UG/L 4.55
3 NOT FOUND
4 NOT FOUND
5 78 175 2:55 1 13.697 A 68 17341113. 2ea.aaa UG/L 4.55
6 117 139 2: 19 1 13.554 A 88 1242116. 28e.68a UG/L 4.55
7 112 272 4:32 1 1.1384 A 88 19447513. 2aa.eaa UG/L 4.55
8 62 117 1 :57 1 6.466 A BS 11155113. 2ea.aaa UG/L 4.55
9 97 134 2: 14 1 8.534 A 98 1254828. 28e.aea UG/L 4.55
16 83 189 3:139 1 13.753 A 88 6135288. 2eD.eea UG/L 4.55
II 83 247 4:87 1 13.984 A 89 129:0270. 2ea.eee UG/L 4.55
12 1136 2ea 3:2e 1 13.797 A 88 115882. 2aa.aaa UG/L 4.55
13 83 11313 1 :48 1 13.438 A 89 16127513. 21313.131313 UG/L 4.55
14 96. 8B 1 :2B 1 13.351 A 88 774512. 2ea.mJO UG/L 4.55
15 63 167 2:47 1 0.665 A 88 la3866a. 2ea.80e UG/L 4.55
16 91 3136 5:136 1 1.219 A 139 2419718. 2EHJ. eEHJ IJG/L 4.55
17 84 45 0:45 1 EI.179 A 8B 56eS56. 2aO.oaa UG/L 4.55
18 173 221 3:41 1 EJ.B8EJ A 89 lC543sa. 2ae.mm UG/L 4.55
19 83 153 2:33 1 O.61e A 83 161314a. 200.0ee UG/L 4.55
26 129 189 3:139 1 0.753 A 88 1452530. 2ea.eoa UG/L 4.55
. ....' .. ..-- -. .., ...-.---.,...-....'-------'-" -----.-_.- .
NO M/E SCAN
21 129 243
22 91 251
23 95 178
24 NOT FOUND
25 96 63
TIME REF RRT MET!-!
4:03 1 0.968 A S8
4: ! I 1 l.aa9 A 88
2:58 1 8.789 A 88
1:63
6.251 M XX
AREA
le!J9530.
1879528.
998815.
55884.
'::~UHT
21313.0013 UG/L
200.0130 UG/L
200.DEIe UG/L
260.009 UG/L
~TOT
4.55
4.55
4.55
4.5S?
~()/i1vrfi/t71()AI POI2 /filS
Ct-'IJ1{r:W.JiJ N4tVWJLLyItDj)t/)
o{2-
-_. ----
-------
~, .
NRn NUM: tJT FORr:tJLR
VI 1: 126 C~.HB.CL2
VI 2: 128 C.H2.CLB~
VI 3: 56 C3.H4.0
VI 4: 53 C3.H3.H
VI 5: 7B C6.H6
VI 6: 152 C.CL4
VI 7: 112 C6.H5.CL
VI B: 93 C2.H4.CL2
VI 9: 132 C2.H3.C!..3
VI H): 132 C2.H3.CL3
VI 11: 166 C2.H2.CL4
VI 12: 166 C4.H7.0.CL
VI 13: liB C.H.CL3
VI 14: 96 C2.H2.CL2
VI 15: 96 C2.H2.CL2
VI 16: 112 C3 .H6. CL2
VI 17: le6 CB.HI6
VI IB: B4 C.H2.CL2
VI 19: 250 C.H.8R3
VI 2e: 162 C.H.CL2.8~
VI 21: 266 C.H.CL.8R2
VI 22: 164 C2.tL4
VI 23: 92 C7.HB
VI 24: 13" C2.H.CL3
VI 25: 62 C2.H3.CL
IDEHTIFICRTION REPORT
1'10 SCRN PURITY FIT
1 251 4~a 864
2 75 819 978
3 53 41 43
4 45 43 264
5 176 615 94e
6 139 841 977
7 272 776 96e
8 117 673 994
9 134 765 9BI
Ie 189 406 979
II 247 606 964
12 200 643 959
13 leB 825 984
14 63:M. 789 988
15 89 786 977
16 167 726 977
17 367 758 995
18 45 781 976
19 221 798 94"
26 153 837 995
21 183 417 945
22 243 835 961
23 251 56S 955
24 177 525 981
25 6 9 6
FILE: D: SI"'.A$A. MI
Spectra printouts
..._-
NR~
62
93
94
96
66
Ie
11
14
15
19
23
29
3e
32
38
44
47
48
51
65
86
67
88
1.4-DICHLCROEUTAHE (INTERNAL STAHDAR
8ROI"'DCHLORO!"'~THANE (INTE~NAL SiRHDAR
ACROLIEH
ACRYlONITRILE
6ENZENE
CAR80HTETRRCHLORIDE
CHLOR03ENZENE
1.2-DICHLOROETHANE
1,I,I-TRICHLORCETHAHE
1,I,2-TRICHLOROETHRHE
1.1.2.2-TE~ACHLOROEr~AH:
2-CHLOROETHYlVIHYlETHER
CHLCRGi'ORH
l,l-DICHLOROETHENE
I, 2- TRAt~S- D I CHLuROETHEHE
1,2-DICHLOROPROPAHE
ETHYleENZEHE
!"'~THYlEHECHLORIDE
8ROrtDFORn
8Ro~o~rCHLORO~THAHE
DI8RonOCHLCRG!"'ETHAHE
ttt?ACHLORGEr~EHE
TOLUENE
TRICHLOROETHEHE
VIHYl CHLORIDE
deleted
to conserve paper.
-------
ATTACH~1ENT V
Organic Compound Identification by Glass
Capillary Gas Chromatography/Mass Spectrometry
1.
Scope and Application
1.1
This method is applicable to surface waters and industrial
effluents.
1.2 The limit of detection for this method varies from 1 to 10
ug/l (ppb) depending on the type of compound.
1.3 The concentration range is from 1 to 100 ug/l (ppb)~
2.
Summary of Method
2. 1
Concentrated extracts of 1 to 3 liter water samples are injected
into a glass capillary column gas chromatograph directly coupled
to a quadrupole mass spectrometer thru a small diameter heated
stainless steel glass lined tubing. A splitless injection tech-
nique is used. Initial identification is established using a
routine computer search of a library of standard reference spectra.
The identification is confirmed by comparing the mass spectra of
reference standards, analyzed using the same instrumental con-
ditions. The coincidence of the gas chromatography retention
times of standards and sample components provides additional
confirmation of identity.
3.
Interferences
3.1
Concentrated solvent extracts often contribute interferences
and a method blank is always run to differentiate reagent con-
tamination from sample components.
3.2
Common solvent interferences are: diacetone alcohol (4-methyl-
4-hydroxy-2-pentanone) from acetone, phthalates from sodium
sulfate, and cyclohexene from dichloromethane.
4.
Apparatus
4.1
Finnigan Model 9500 gas chromatograph equipped with a glass
capillary column.
4.1.1
4.1.2
Grob type injector for splitless injection.
Capillary glass column, 25 meters x 0.25 mm 10, OV-10l.
0-33
-------
0-34
4.2
4.3
Finnigan Model 3200 electron impact mass spectrometer.
4.2.1
Glass lined stainless steel tubing direct coupling
to gas chromatograph.
Finnigan INCOS data system (1).
5.
Procedure
.--.- -
5.1
Gas Chromatography
5.1.1
5.1.2
Inject 1 ul of sample into the gas chromatograph with
the splitter turned off for 1 minute after injection
then turn on. (Splitter flow 100 ml/min).
The initial column temperature is equilibrated at 600e
and held for 1 minute after injection, then a temperature
program is initiated at 40C/min. to a final temperature
of 2200e and held from 10 to 15 mi nutes. Column flO\..,
is adjusted to give a nominai flow of 1.5 ml/min. at
1 oooe .
5.2
Mass Spectrometry
The following MS instrumental parameters are used:
5.2.1
5.2.2
5.2.3
5.2.4
Electron multiplier voltage
Lens voltage
Collector voltage
Extractor voltage
Ion Energy voltage
Electron Energy voltage
Emission Current
- 1600 vo lts
- 100 vo lts
35 vo lts
6 vo lts
10 volts
70 volts
- 0.5 ma
The follovJing data acquisition parameters are used:
Scan time
Mass Range
Sens iti vity
- 2 sec.
- 33-300
- 1 0 - 7 amp.
The data acquisition is initiated immediately upon
injection of a sample into the gas chromatograph in
a suspended mode with the ionizer turned off. At 4
minutes the ionizer is turned on and at 5 min. the
data acquisition is changed from the suspended mode
to the centroid mode and actual data collection begun.
A normal analysis using the 25 meter capillary OV-10l
column will require data collection for 35 to 40 minutes.
A reconstructed ion chromatogram is generated using the
MSDS program system and specific spectra are then plotted.
A manual computer search of the reference library gives
an identification. The initial identification is then
confirmed by comparison of sample spectra and reference
spectra obtained by analyzing standards under the same
instrumental conditions.
-------
D-35
6.
Qua 1 ity Con tro 1
6.1
Daily calibration of the GC/MS is performed before any sample
analysis using a standard reference compound. (Pufluorotri-
butylamine-FC-43).
6.2 The reference compound is metered into the mass spectrometer
via a variable leak valve at a constant rate. Several scans
are recorded at a scan rate of 3 seconds and a sensitivity of
10-6 amps. The calibration is then made utilizing the MSDS
system calibration routine.
6.3 An ion intensity ratio of 2 to 1 for mass 69 to mass 219 is
desirable for good spectra using the capillary system. The
ion intensity ratio can vary from 3 to 1 to almost 1 to 1 and
still provide legitimate spectra.
References
7.
(1)
"INCOS Data System - f1SDS Operators' Manual - Revision 3",
Finnigan Instruments, March 1978.
-------
0-36
ATTACH~1ENT VI
CCMPlJTER ASSISTED EVALUATION OF
ORGAJ."ITCS CHARACTERIZATION GC/MS DATA
August 1978
1. 0 This procedure is applicable to oc/MSdata collecte:1 under constant
analytical ccnditions for qualitative data analysis.
2.0
Surrmary of Methcd
2.1 GC;MS data files are processed by cOIflFCIing spectra fran the
scullple against spectra of known or suspe:::te::i pollutants con-
tained in a project related library.
If a spectrum rratches
the project library spe::trum sufficiently, an entry is rrade in
a table showing at what specL.---urn nurnb<=>..r the rratch occured and
hotl gocd t.'1e match was.
After canpletion of the search for
each spectrum in the proj ect library, a list of the canpourrls
searched for and the matching results is printed as well as
each .spectrum that was identifie:1 as a probable pollutant.
If
selected by the user, t.'1e proce:1ure will then search the cur-
rent version of the NB (EPA/NIH/MSOC) library attempting to
identify unknO\vn spectra fran peaks selecte:1 by the Biernann-
Billler algorithin in ~~.
3.0 Definitions and Comments
3.1
In some cases, ccrnp:mnds rray be identified by ccrnparison to
external reference spectra only (1,2,3).
These "unconfirmed"
cornpourrl data rray however be useful since the Ccrnp.1ter matching
still traces the presence of selected compounds through each
sample analyzed.
Therefore, even these "unconfirmed" pollu-
tants can serve to trace a Haste stream.
-------
3.2
4.0
0-37
- 2 -
Quantitation of }?:)llutants identifie::1 is effectro by locating
t.~e correspor:ding OC pea.,
-------
D-38
5.1
Apparatus
Finnigan TI-l:OS data system soft:\.;are runnirlg revision 3.1 or
5.0
5.2
- 3 -
later version.
To initially set up this procedure, the user
must understarrl and be proficient in the use of MSDS (4).
Th'COS "NE" mass spectra libra..ry (5).
6.0
Precedure
6.1
Precedure Setup
6.1.1
ItJad the prccedcres listed in apperrlix 1 onto the sys-
tem disc or create the preced'..lres fran the trace of aCEV AL
in Appendix 2.
6.2
Library Setup
Obtain spectra of the ccmpourrls of interest by running
6.2.1
6.2.2
standards under the same analy~ical conditions to be
used for sample analysis.
Using the library editor, create a library containing
the sta."1dard spectra with chemical na'11es and retention
times.
Obtain a reference spectrum of each library
entry for a perrranent record and reference via the li-
brary program:
Gli HS; G2; HSi... etc.
6.3
Routine use
6.3.1 Collect mass spectra of samples to be precessed under
6.3.2
6.3.3
the same conditions as the standards were analyzed.
Using the ne.melist editor, create a namelist containing
the names of the files to be precesserl.
Execute the precedure:
-------
0-39
- 4 -
CJ:::'DJAL library, narr.elist, no (yes)
Where:
library is the user library naTTIe, narnelist is
the file containing the names of the data files
to be prccessro and no or yes select a continued
search through the NB li.br~vy.
If the user wants only to perform all NB search,
the procroure is initiatro as follows:
OCFNAL NB, narnelist
6.3.4
Appendix 3 is a."1 e.,.P
(3) A list of the cC11'1!.=Ourrls beir.g searcheii for and a
surrma.ry of the search results.
(4) A collection of the spectra of peaks identifieii by
the prccerlure
(5) Library matching results for peaks found by MAP but
not identif ieii in the user library.
7.0 Quality Control
7.1
Each identification is manually verifieii by can:;:aring the sam-
pIe spectrum to the reference sPectrum in the user library.
In-
accurate canputer results are re-evaluateii and the correct data
reported .
8.0 Precision and Accuracy
8.1 The auto processing routine I s accuracy for correctly identify-
ing comp:mnds is limited by the quality of the original GC/!-1S
data.
-------
0-40
- 5 -
9.0
References
(1) "Eight Peak Inde.'< of i'1a.ss Spectra, II Mass Spectranetrj Data Cen-
ter, A1de..Y'fl1.3.ston, Reading, UK. Second Edi tio!'l 1974.
(2)
"Registry of !v1a.ss Spectral Data," Stenhage.l'1, Abramsson ar.d
McLafferty, Wiley & Sons, New York, 1974.
(3)
"Atlas of Mass Spectra Data," edited by:
Stenhage!'l, Abrahams-
son and McLafferty, Wiley & sons, New York, 1969.
(4) "ThIDS Data System - !vlSDS Operators !v1a.nua1 - Revision 3, II Fin-
nigan Instruments, March 1978
(5) liNES - NIH/EPA/MSDC Library - Revision 3, II Finnigan Instrurr.ents,
March 31, 1978
-------
D-41
APPENDIX 1.
PROCEDURES 10m :.rETHODS REQUIRED FOR OCEVAL
1. OCEV;~
2. OCEVO
3. OCEV1
4. OCEV2
. 5. OCEV2A
6. OCEV2B
7. OCEV3
8. OCEVS
9. OCEV6
10. OCEV7
11. PRIN01.HE
12. PRIN02.ME
-------
D-42
APPENDIX II. a.
.--., ..-.~. -- . -- '..". r.o'-
-' - .... ,."..' . .
TR~CE OF FP.OCE:!)tC~E O:E\'AL
'" (:;C;C1O;< OCE\lAL **,"'.oc:1=~":=:=:~:":::::;"~ JULY 29. 1978 """""0)
:j( ;tOCEVAL FROVIDES TIE C?E,,170R UlnJ A t":~AtlS OF J
"' ;tLOCATING CON?OU~DS THAT P.~E SUSPECT snSED ON )
"' ; eTHE Ii< RETEtlTION T!i'::S A~;j) SPECT2A. THESE)
'" ;tC00?OljiiDS ARE: SAVED IN H USE:R Ll8:I< ;tSPECT~U) AND RETE~ITIOil T!:';;S. ALSO. ALL r:m~ rlLESJ
* ;[PRO~2SS;:D f'!UST HA'./[: SCA',':; r-IVAILA8L~ FROM 25J
, "' ;(8ELC~1 TIiE EP.RLlEST ELun:.;;:; COr?Ot:::I.rr COR START AT 0)]
'" ; eTO 2S AGGVE Tr::: LATEST ::un:t:G CD~:?mIENT.)
"' ;(TO USER THE Pr.OCEDU~E. ~~E~TE A LI8RP.RY]
"' ;(WlnJ TrlE SPECT:-:'; Ai,!! "E",;:TiON TltES. Cp.E,:rT=: A)
"' ; (tlm~L 1ST CO~!TA ItllliG T:i:: := ILE TO BE PROCESSED.)
* ;( )
>I< ;tTrlal: >OCEVriL XV.li,,!'..oLi3T.r:ocYo:S)
"' ;t )
'" ;Cw.~ER::: xv IS THE USE~ L!~2P.2Y NA~E OR HS ]
'" ;C tH~t~LlST IS Tn::: ::,:f'I!Ll3T CmlTIHNltlG T"E FILES]
'" ; t TO GE P:':;:,CES3ED.
'" ; C NO SELECTS NO m: !.:i2?,:':';' SEARCH C::1 Yo:S SELECTS)
"' ; t AH tl9 s~p,?c~)
* ; ( IF THS LJ3:O" 2:OU::CTC:D T'H::: H!3 L IG~ARY)
"' ;C INITiALLY NO ENTRY IS REQUIRED) ,
* ;CLAST REVISED 9/27/78 OJL8GSDOHII)
* ;SET4 !I
* ;EDLL YES(-;S:W;E).;EDLL HQC-;W;E)
* ;SETH OCTEM?;ED~LC-;SI:$2;W;E)
* :SETII ~EI
* ;OCEVQ
* ;BEEP;8EEP;8EEP
* ;ERASE
"' ; (PROCSDUP.E OCEVAL IS COiPLETE)
"'
SET4 ! I
EDLL YES C-;~;U:E)
EDLL tlO C-;U;E)
SETII OCTEI1P
ED:;L (-; 51 ;~; W; E)
SETII
OL:Sva
'" S:::'711 OCTEt,";SE!:1 ~:9;G:;~j;SET4 ~I
... ;GETII;SETt! $I;S::I:I !11:S:::TlI !IPI:G:::m
* ;GCE'/I
"' ; SElL OCTEt:!"
* ;Ef.'LLC-:W:E)
"' ;F!LECr. PP.III.99/oI;E)
* ; OCE'/2
* ; SETl2 (0
* ;SETS OCEV2;SETS uO
* ;EDSLC-iI2;U;E)
"' ;OCE\l3
"' ;OCEVS
"' ;BEEP
* ;LOOr
*
SETtI OCTEM?
SETtl
GETII
SET~ SI
G!::711
SET:I 51
SETI! J II
SETII (,I! II
GETH
OCEVI
'" PARnCI;H;E)
-------
- .-. ~-_..,
0-43
APPE);DIX II. b.
. -.....- ....,
'.'.- .'
'" ;SETS OCEV2;EDSL(-;~;S)
'" ;SETS OCEV!;EDSL(-;W;E)
'" ;~~P(I;FI;UI80;V2S~~~~;33,3eO;H>2.5,7;HI.2eOO.5ae;E)
'"
PARA Ct;H;E)
SETS OCEV2
EDSL (-;I..!;E)
SETS OCEVI
EDSL (-;W;E)
MAP (t;Fl;Ul~~;V25:~:'~;33.~~O:N>2.5.7;Hl.Z88D.5~~;E)
SEll CCTEr',"
EDLL (-;U;E)
FILE (K FRIH.99/H;E)
OCE'./2
* IF OCEV2 ~25coe.CCE,~ !24
'" ;GCEV2A
'" ;PRIN (@OD
'" ;:DLL (B! I;E)
* ;PRIH (002)
'" ;FILE (C ?RIN.99.M:~I;E)
* ;FEED
* .
IF GCEV2;25000.0CEV2124
OCE'./2n
~ SET4 !4..~I;SET!4 D~
'" ; iF "1 !24 OCE'/2P.. 14 OCEV2A
'" ;OCE'I26
* ;LDO?
'"
SET.. ! 4.. 01,
SETI4
IF DCEV2A#1124.0CE\~A!4
OCEv26 .
* EDLUS;W;E)
* ; SEAR/V( I; $;:!.; \'25S8ee; N I. 2C
* ;SETS OCE'I2;Er~L(114;U;E)
'" ;SETS DCE'/I;EDS:..(-! 14;U;E)
'"
(S;W;E)
(I;Z;:!.;V23JOOO;Hl.200.75e;D-25.25;E)/Y
(!4.G;! 14,5;! 15.9; 116.6;C;E)/1:X
OCEV2
(! 14;W; E)
DCEVI
(-! 14;W;E)
EDLL
SEAR
PRIH
SETS
EDSL
SETS
EDSL
LOOP
PP. !tl WO!)
EDLL (e!I;E)
PR IN (002)
FILE (C PRItI.99.M:/o'I;E)
FEED
SET12
SETS OCEv2
SETS
EDSL (-112;U;E)
OCEV3
'" GETS
~ ;SPEC(I;';T;H30,358;[)
'" ;LOCi'
,.,
GETS
~r-~c (1;':T;H3~.~~~;E)
LOCI'
OCE'/:3
* 5~TL ~
'" ;CCEV6
'" ;SET4 tiS
'" ;SETS OCEVI;SETS ca
~ :G~EV7 '
-------
0°-44
APPENDIX II. c.
'" :FEED
"'
SETL 53
OCEv6
'" IF OCEV6 ~2508e.OC~V6 !24
* :IF OCE'IS !:6.0CE'1S
* :RETU OCEV6
'"
IF OCEV602503D.OCEVG!24
IF OC£V5!26.0CEV5
RETU OCEV6
SET~ NB
SETS OCEVI
SETS
OCEV7
* GETS
'" :LI8~(I:':F:Xl.3:HS:E)
'" LOO?
'" .
GETS
LIS~ (I:':F:Xl.3:~S;E)
LOOP
FEED
BE:::?
LaO?
EE,,?
SEEi'
SE(:P
ERHSE
-------
P?!1'iDI.r-:::: = C;:.1;T;
;::;I;C2;T;
;D;C2;E
. . -- --- .-. . _or -
PR 11,02. r-:Z . C2; T;
;C;E
APPE:iDrx II. d.
O;;'~:~~;~::~ CiiA~AC~RIZqT!ON R:r:G~T
HUM 5F:::Co ?u~ITY FIT
0-45
FILE:
-------
D-46
.." .--.-.
eJ/£);)/EJ'"
NAM HUM:
39
39
39
33
39
33
39
39
33
39
33
33
39
39
33
39
33
39
39
39
39
39
39
33
39
39
39
<1:013:1::0
1 :
2:
3:
4:
5:
6:
7:
8:
9:
Ie:
11:
12:
13:
14:
15:
16:
17:
18:
19:
28:
21 :
22:
23:
24:
25:
26:
27:
HUI1 SPEC~
1 e
2 e
3 13
4 221
5 13
6 13
7 13
8 8
9 13
10 13
11 13
12 13
13 13
14 e
15 696
16 696
17 928
18 e
19 13
213 13
21 4813
22 602
23 0
:.1 0
25 13
25 2G7
27 0
-.. .. ".-.-
WT FORr:tJLA
126 CO.Hl~.O
144 C9.H2tJ.O
146 C6.H4.CL2
138 CS.HI8.0
13'3 C9.HI4.0
162 C8.HIS.03
a
13~ C9.HI0.O
154 CI2.Hle
170 CI2.Hle.O
222 CI2.HI4.04
a
22eJ C!5.H24.C
96 C4.H4.0.1'i2
o
13
a
13
eJ
154 C3.Hla.03
154 Cla.HI8.0
266 CI2.H27.04.P
268 C19.H4e
140 C9.HI6.0
154 C!1.HI4.02
162 C8.HI8.03
222 ClO.H22.05
PURITY
o
o
e
446
13
e
a
e
13
13
13
e
e
e
411
395
6~2
13
13
13
361
572
o
13
o
201
e
APPENDIX III.
-.
ORGi'1NiCS CHAR;:;CiE:::nZ;:;TlOtl REPOr
-------
APPENDIX
E
TECHNICAL INFORMATION
DATA BASE DESCRIPTION
...
-------
E-3
TECHNICAL INFORMATION
DATA BASE DESCRIPTION
RTECS contains toxicity data for approximately 21,000 substances,
but does not presently include all chemicals for which toxic effects
have been found.
Chemical substances in RTECS have been selected
primarily for the toxic effects produced by single doses, some lethal
and some non-lethal.
Substances whose principal toxic effect is from
exposure over a long period of time are not presently included.
Toxic
information on each chemical sub~tance is determined by examining and
evaluating the published medical, biological, engineering, chemical
and trade information and data for each substance selected.
The Toxline data base contains over 650,000 records taken from
. ....
material published in primary journals.
it is part of the MEDLINE
.:
file from the National Library of Medicine and is composed of ten
subfiles:
(1)
Chemical-Biological Activities, 1965-
(taken from Chemical Abstracts, Biochemistry Sections)
(2) Toxicity Bibliography 1968-
(a subset of Index Medicus)
(3) Abstracts on Health Effects of Environmental Pollutants,
1971- (published by the American Society of Hospital
Pharmacists)
(4 )
International Pharmaceutical Abstracts 1970-
(published by the American Society of Hospital Pharmacists)
(5)
Pesticides Abstracts 1967-
(compiled by EPA
(6 )
Environmental Mutagen Information Center 1969-
(Dept. of Energy, Oak Ridge National Lab)
-------
E-4
(7)
Environmental Teratology Information Center 1950-
(Dept. of Energy, Oak Ridge National Lab)
(8) Toxic Materials Information Center
(Dept. of Energy, Oak Ridge National Lab)
(9) Teratol~gy file 1971-1974
(a collection of citations on teratology compiled by the
National Library of Medicine)
(10) The Hayes File on Pesticides
(a collection of more than 10,000 citation~ on the .health
aspects of pesticides compiled by Dr. W. J. Hayes, Jr., EPA)
------- |