ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-79-015
Compliance Evaluation
And
Wastewater Characterization
South Charleston Sewage Treatment Company
South Charleston, West Virginia
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER, COLORADO
REGION
AND
III PHILADELPHIA
MARCH 1979
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Environmental Protection Agency
Office of Enforcement
EPA-330/2-79-015
COMPLIANCE EVALUATION
AND
WASTE.WATER CHARACTERIZATION
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
SOUTH CHARLESTON, WEST VIRGINIA
REGION III LIBRARY
5MVIROWMESTAL PROTECTION AGENCY
James L. Hatheway
March 1979
National Enforcement Investigations Center - Denver
and
Region III - Philadelphia
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CONTENTS
I INTRODUCTION. . . . . . . . . .
. .. .. . .
. .. . .. .. .
.. .. . .
1
II SUMMARY AND CONCLUSIONS. . . . . . . . . . . . . . . . . . . 4
SUMMARY OF INVESTIGATIONS. . . . . . . . . . . . . . . .. 4
CONCLUSIONS. . . . . . . . . . . . . . . . . . . . . . . . 5
III TREATMENT PLANT DESCRIPTION. . .
. . . . .
. .. . . . . .
. . 7
IV SURVEY METHODS. . .
. . .. . .. . .. .
. .. .. .. .
.. .. .. .
. . . . 11
V SURVEY RESULTS. . . . . . . . . . . . . . . . . . . . . . . . 15
PERFORMANCE AUDIT. .................... 15
NPDES EFFLUENT LIMITATION COMPLIANCE. . . . . . . . . . . . 17
WASTEWATER CHARACTERIZATION. . . . . . . . . . . . . . . . 19
BIOLOGICAL STUDIES. . . . . . . . . . . . . . . . . . . . . 34
TOXICITY EVALUATION. . . . . . . . . . . . . . . . . . . . 39
REFERENCES
. .. . . .. . .. ..
. . . . . . .. . .
. .. .. . .
. . . . 50
APPENDICES
A - Chain-of-Custody
B - Lithium Flow Verification Procedures and
Sampling Techniques
C - Analytical Methods and Quality Control
D - Bacteriological Methods
E - Bioassay Methods
F - Mutagen Assay Methods
G - Technical Information - Data Base Description
j
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TABLES
1
2
3
4
5
6
7
8
9
10
11
12
13
14
NPDES Final Permit Limitations. . . . . . . . . . . . . . . . 12
Description of Sampling Stations. . . . . . . . . . . . . . . 14
Summary Field Measurements and Analytical Data. . . . . . . . 18
Summary of Fecal Coliform Densities. . . . . . . . . . . . . 20
Summary of Discharges Monitoring Reports. . . . . . . . . . . 21
Summary Field Measurements and Analytical Data. . . . . . . . 23
Neutral Extractable Organics Sampling Data. . . . . . . . . . 24
Volatile Organics Data. . . . . . . . . . . . . . . . . . . . 25
Direct Aqueous Injection Organic Data. . . . . . . . . . . . 27
Summary Field Measurements and Analytical Data. . . . . . . . 29
Summary Field Measurements and Analytical Data. . . . . . . . 31
96-Hour Flow-Through Survival Data. . . . . . . . . . . . . . 35
Mutagenic Activity of South Charleston Sewage Treatment. . . 37
Toxicity of Organic Compounds. . . . . . . . . . . . . . . . 40
FIGURES
1
2
Schematic of South Charleston Sewage Treatment Company. . .. 2
Mutagen Testing Dose-Response Curve. . . . . . . . . . . . . 38
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1.
INTRODUCTION
The South Charleston Sewage Treatment Company (SCSTC),* South
Charleston, West Virginia, is a joint venture between Union Carbide
and the City of South Charleston. The Company treats approximately
19,000 m3/day (5 mgd) of Union Carbide South Charleston process waste-
waters and 8,000 m3/day (2 mgd) of municipal wastewaters. The indus-
trial and municipal wastewaters are treated separately [Figure 1].
The effluents from domestic and industrial treatment units combine
and discharge to the Kanawha River through Outfall 001.
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 of in the Kanawha Valley, from which toxic substances could
then be released to the environment.
On January 10, 1978, the Environmental Protection Agency (EPA)
Region III requested that the National Enforcement Investigations
Center (NEIC) investigate the SCSTC to identify and quantify toxic
chemicals discharged to the Kanawha River and to determine compliance
with the National Pollutant Discharge Elimination System (NPDES)**
permit limitations. NEIC conducted a detailed plant inspection and
subsequent field survey.
* The treatment facility is referred to by Company personnel as the
South Charleston Waste Treatment Works.
** 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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Emergency
Storage-
Holz
Pond
. Lime
...
). Sludge
...
Industrial Wastewater
Station 39
Bar Screens &
Grit Basin
Clarifiers
pH Adjustment
H2S04 or NaOH
NH3
Recycl e .
Secondary
Treatmetit
Po 1 ymer----1
Sludge
Flash ~1ixing
and Flocculation
Secondary
Clarifiers
Station 41
Station 47
H3P04
2
t1unicipal Hastewater
C12
Bar Screen Grit Basin &
Commi nutors
C12
Vacuum
Filtration
Station 46
To Landfill
Sludge
Secondary
Trea tment
Station 43
Station 45
Outfall 001
Kanawha River
Figure 1.
Schematic of South Charleston Sewage Treatment Company
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3
The objectives of the April 1978 plant inspection were to:
1.
inspect treatment units and evaluate operation practices
2.
evaluate NPDES self-monitoring procedures.
The objectives of the August 1978 survey were to:
1.
2.
measure wastewater flows
determine compliance with NPDES permit effluent limitations
3.
collect wastewater samples for organic characterization.
Organic compounds identified during the wastewater characteriza-
tion were evaluated to determine potential health effects.
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II.
SUMMARY AND CONCLUSIONS
SUMMARY OF INVESTIGATIONS
NEIC personnel inspected the SCSTC facility in April 1978. Plant
operations were discussed in detail with Company personnel. Treatment
units were inspected and operational practices evaluated. Self-moni-
toring procedures including sample collection, flow monitoring, sample
analysis, bioassay procedures, and discharge monitoring reports (DMRs)
were also evaluated.
A monitoring survey was conducted at this facility August 15 to
21, 1978. Seven 24-hour flow-weighted composite samples were collected
to determine compliance with NPDES permit effluent limitations. Com-
posite samples from the industrial influent, industrial effluent,
domestic effluent and final discharge were analyzed for organic com-
pounds. Each organic compound was searched in the Registry of Toxic
Effects and Chemical Substances and the Toxline data bases to obtain
toxic information. Bioassay and mutagenicity tests were also conducted
on the treatment plant effluent.
CONCLUSIONS
Fecal coliform samples are not collected from the final discharge.
These organisms are being monitored in the chlorine contact basin and
domestic effluents. Company data show that while fecal coliform or-
ganisms in the chlorine contact basin effluent are low (0 to 503/100 ml
log mean) the domestic effluent is high (80 to 7,000/100 ml log mean).
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Data from the flow meter installed on Outfall 001 in August 1978
and subsequent DMR data based on these results are not reliable.
Instantaneous measurements using the lithium chloride dilution tech-
nique showed that at the time of the survey the meter was recording
flow 26 to 38% lower than actual. Pollutant loads calculated based
on these flows would also be low.
In general, chemical analyses are performed by SCSTC personnel
according to EPA-approved methods. Fecal coliform analyses were being
performed by the membrane filter procedures. Unless comparability of
an alternate method can be demonstrated, the 5-tube MPN procedure is
recommended for self-monitoring. Vinyl chloride monomer testing has
produced low recoveries on spiked samples. Additional work is required
on test procedures to ensure adequate recovery of spiked samples.
In general bioassay procedures were adequate. Discrepancies
observed include: a) not starting test within 8 hours as recommended
by Standard Methods@, b) using city dechlorinated tap water was used
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, through not required, that the laboratory
use a constant temperature water bath to maintain test temperature
rather than depending on ambient air temperature.
A review of the DMRs showed that the Company violated one or
more of its permit limitation for the period October 1977 through
September 1978. BOD, TSS, COD, NH3, chloride and pH limitations were
exceeded during this period.
Survey data show that the SCSTC is capable of meeting permit
limitations except for fecal coliform. The 7-day average ,concentra-
tions were 20 mg/l BOD, 330 mg/l COD, 24 mg/l TSS, 15 mg/l TKN,
8.4 mg/l NH3, 260 mg/l chloride and 12 ~g/l phenol. These values are
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only 24, 49, 30, 29, 56, 65 and 24% of their respective permit limita-
tions. Fecal coliform densities ranged from 790 to 130,000/100 ml
with a geometric mean of 12,000/100 ml. The permit requires that the
7-day fecal coliform organism geometric mean not exceed 400/100 ml.
Analyses of the WWTF effluent discharge show that the facility
is discharging priority pollutants.* Maximum concentrations of the 6
pollutants identified were 80 ~g/l zinc, 200 ~g/l nickel, 15 ~g/l
chloroform, 41 ~g/l methylene chloride, 4 ~g/l tetrachloroethene and
6 ~g/l 1,1,1-trichloroethane.
Primary domestic sludge and industrial grit containing priority
pollutants are being buried in non-secure landfills (city of South
Charleston and Filmont, respectively). Both the sludge and grit con-
tained As, Cr, Cu, Ni, Pb, Zn and Hg with concentrations ranging from
2.2 to 2,500 ~g/l. The industrial grit also contained isophorone at
120 ~g/g.
The SCSTC effluent is not acutely toxic to fish.
show 95% survival for 96-hours in 100% effluent.
Bioassay results
Mutagenic and potential carcinogenic substances are being dis-
charged from Outfall 001. Each of the 3 samples collected from this
discharge demonstrated a mutagenic activity ratio greater than 2.5
which correlates closely (>90% probability) with inducement of cancer
in laboratory animals.
* For explanation of priority pollutants see Section V.
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III.
TREATMENT PLANT DESCRIPTION
SCSTC is operated and maintained by the City of South Charleston
and is staffed with a superintendent, assistant superintendent, clerk,
four shift supervisors, eight plant operators, 2 vacuum filter opera-
tors, and two maintenance personnel. The laboratory is staffed with
one chemist who oversees the analytical tests conducted by plant opera-
tors.*
The municipal wastewater secondary treatment system, designed
for a population equivalent of 37,500, receives wastes from the city
of South Charleston (population of approximately 23,000). The waste-
water first receives preliminary treatment consisting of prechlorina-
tion, bar screening, grit removal and comminutors. Materials removed
by the bar screen and grit chamber are hauled to the city of South
Charleston (SC) landfill.
The wastewater then enters two 1,050 m3 (277,300 gal) primary
clarifiers operated in parallel. The primary sludge is pumped to a
thickener, concentrated, treated with ferric chloride and lime, vacuum
filtered and buried (approximately 3,200 kg - 7,000 lb/day) at the SC
landfill. Thickener decant water is returned to the clarifiers and
water removed in the vacuum filters is discharged back to the thickener.
Effluent from the primary clarifiers is chlorinated to maintain approxi-
mately 0.5 ppm residual chlorine. The chlorinated wastewater then
enters two Aero Accelators (activated sludge process) operated in
parallels.** These units, 4,280 m3 (1.13 mg) capacity each, provide
* Each operator is responsible for conducting analyses necessary to
run the treatment units, as well as those analyses required by the
NPDES permit.
** During both the inspection and survey, only one unit was being opera-
ted.
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both aeration and secondary clarification. Each unit has a 150 HP
agitator and a compressed air diffuser which maintains a 0.0. concen-
tration of 6 to 7 ppm. Waste-activated sludge is pumped into the
industrial primary clarifier influent. The overflow from the Aero
Accelators combines with the industrial effluent (discussed below)
and is discharged into the Kanawha River through Outfall 001.
Industrial wastewater from UCSC, including supernatant from Holz
Pond and plant domestic wastes, are routed to the SCSTC through an
open redwood flume. Concentrated process wastes and spills are diver-
ted from the flume into a 3,800 m3 emergency storage tank. These
wastes are slowly returned to the treatment plant via the redwood
flume [Figure 1].
The industrial wastewaters pass through two grit basins (each 3
x 6 m - 10 x 19 ft) into two primary clarifiers (each 1,050 m3 -
277,300 gal) operated in parallel. The industrial grit is buried at
the Filmont landfill which is owned and operated by Union Carbide.
As previously noted, the municipal waste-activated sludge combines
with the influent to these primary clarifiers. Sludge removed from
the primary clarifiers is treated with lime and pumped to Holz Pond.
Supernatant from this pond is returned to the treatment facility via
the redwood flume.
The primary clarified wastewater is neutralized with either NaOH
. or H2S04 and ammonia is added* as a nitrogen source. The wastewater
is then discharged into the three 3,800 m3 (1 mg) equalization tanks
operated in parallel.
* One kg of NH3 is added for every 40 kg of BOD removed in the aera-
tion basins.
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Wastewater from the equalization tanks is discharged at a con-
trolled rate into a large aeration basin which has a capacity of
24,400 m3 (6.45 mg). H3P04 is added* to the wastewater as it enters
the basin. The basin is equipped with seventeen - 100 HP surface
aerators and five - 65 HP bottom mixers. Plant officials try to main-
tain D.O. levels of 2 to 3 ppm at the surface and 0.5 ppm at the bottom
of the basin.
Polymer is added to the aeration basin effluent which then flows
to flash mixing and flocculation. The wastewater then enters three
secondary clarifiers, operated in parallel. Each clarifier has a
capacity of 2,420 m3 (640,500 gal). The clarifier effluent combine
with the municipal treated effluent and discharge to the Kanawha River
through Outfall 001. Secondary sludge is combined with primary sludge
and lime and pumped to Holz Pond.
Municipal wastewater influent flow is measured by a 0.46 m (1.5 ft)
Parshall flume. The flow is continuously recorded and totalized.
The flume is located downstream of a small lift station which contri-
butes less than 10% of the domestic flow. As the lift station pumps
do not operate continuously, the flow chart has numerous peaks.
Industrial influent flows are measured with a 0.61 m (2 ft) Par-
shall flume and continuously recorded and totalized. Visual obser-
vations showed that the wastewater is diverging** as it enters the
converging section causing turbulance through the flume. As a result,
the flow recording trace is almost 2.5 cm (1 in) wide. The midpoint
of the trace is used to determine the flow.
* The wastewater is deficient in phosphorus. Plant personnel add
one kg of H3P04 for every 220 kg of BOD removed in the basin.
** The wastewater enters the flow device through a conduit which has
a diameter smaller than the upstream converging section.
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Wastewater entering the industrial aeration basin is measured
with a 0.76 m (2.5 ft) Palmer-Bowles flume. Magnetic flow-meters are
used to measure industrial primary clarifiers underflow and waste-acti-
vated sludge.
During the April inspection, flow rates for the combined discharge
(Outfall 001) were being calculated based on the sum of the industrial
and municipal influents, less the amount of industrial clarifier under-
flow and waste-activated sludge being pumped to Holz Pond. Subsequent
to the initial inspection, a Model 250 March McBirney flow meter was
installed to measure and record the volume of wastewater discharged
through Outfall 001.
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IV.
SURVEY METHODS
Self-monitoring practices, including flow measurement and sampling
techniques, analytical and bioassay procedures and DMR results, were
evaluated April 11 to 12, 1978 at the SCSTC. Sampling was performed
from August 15 to 22, 1978 to determine compliance with NPDES permit
WV 0023117 [Table 1] and characterize wastewater. Samples were collec-
ted from the industrial influent, industrial effluent, municipal effluent,
total plant discharge (Outfall 001) to the Kanawha River, primary
domestic sludge and industrial grit [Figure 1]. Chain-of-Custody
procedures were followed for the collection of the samples* and for
laboratory analyses. Flow verification procedures and sampling tech-
niques are discussed in Appendix B.
The Parshall Flumes installed on the domestic and industrial
influents were checked prior to sampling and found to be installed
according to recommendations of the Water Measurement Manual. The
flow recording devices and totalizers were compared to flume head
measurements and found to be operating properly. The flow measure-
ment devices on the influent to the aeration basin and total discharge
(Outfall 001) were checked using the lithium chloride tracer dilution
technique [Appendix B].
Sample aliquots were manually collected hourly and continually
composited on a flow-weighted basis for all parameters except volatile
* The samples sent to Denver August 20 were received without a lock
on the ice chest. The samples were packaged in either plastic con-
tainers or plastic sacks. There did not appear to be any tampering
with the samples prior to arrival at the NEIC laboratory.
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Table 1
NPDES FINAL PERMIT LIMITATIONS
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
SOUTH CHARLESTON, WEST VIRGINIA
Average Effluent Concentrations 30 Consecutiveb
30 Consecutive 7 Consecutive Day Period
a Day Period Day Period 1 bs/day kg/day
Parameter
(mg/l) (mg/l)
Biochemical Oxygen Demand
(5-day) May-Oct 53 80 5,300 2,400
Nov-Apr 84 126 8,400 3,810
Suspended Solids 53 79 5,300 2,400
Feca 1 Coli forms 200c 400c
pH withi n limits of 6.0-9.0 at
all times
Chemical Oxygen Demand
May-Oct 450 680 45,000 20,400
Nov-Apr 580 870 58,000 26,400
Phenols 0.03 0.05 3.0 1.4
Kjeldahl Nitrogen
May-Oct 35 52 3,500 1,550
Nov-Apr 40 60 4,000 1,820
Ammonia Nitrogen
May-Oct 10 15 1,000 450
Nov-Apr 15 20 1,500 680
Chlorides 200 400 20,000 9,100
Temperature Maximum of 43.3°C (110°F)
a In addition, the Company is required quarterly to determine vinyl
chloride monomer and toxicity. Toxicity is to be monitored by
bioassays.
b The 30 consecutive day average quantity of effluent discharged from
the wastewater treatment facility shall not exceed 15.8 million
gallons per day (mgd) or 59,800 cubic meters per day.
c per 100 ml.
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organicst direct aqueous injection and fecal coliform which were collec-
ted three times each day. All samples were collected over the period
12 midnight to 12 midnight which corresponds to permit requirements.
The parameters monitored and the sample type for each station are
shown in Table 2. All samples were analyzed by the procedures in
Appendices C and D.
Flow-through bioassays were conducted August 15 to 19 on the
plant effluent (Outfall 001). The wastewater was continuously pumped
directly from the outfall to the bioassay laboratory on an equal-volume
basis. Dilution water was obtained from the Kanawha River at a point
approximately 3.2 km (2 miles) upstream of the mouth of the Elk River.
A discussion of the bioassay procedures is contained in Appendix E.
Analyses for mutagenic activity were performed on three 24-hour
flow-proportional composite samples from SCSTC effluent (Station 45).
The Ames Bacterial Assay for Mutagenicity was performed on liquid
sample concentrates using the agar plate incorporation methodt as
described by Amest et al.l The Standard Ames Test determined muta-
genic activity through use of bacteria as indicator organisms; this
information correlates closely ~90% probability) with inducement of
cancer in laboratory animals by organic compounds.2t3t4
Acidic and basic sample extracts were prescreened for mutagenic
activity using four standard Salmonella tester strainst TA 98t TA lOOt
TA 1535 and TA 1537. Samples were first tested individually and then
subjected to metabolic activation by addition of rat-liver homogenate
[Appendix F].
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Table 2
DESCRIPTION OF SAMPLING STATIONS
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY (SCSTC)
Stationa
b
Parameter
Description
Type of Sample
39
41
43
45
46
47
SCSTC Industrial
Influent
24-hour Composite
Chloride; COD; NH3; TKN;
phenol; organics
Volatile organics; direct
aqueous injection
800; TSS; chloride; COD;
NH3; TKN; phenol; organics
Volatile organics; fecal
co 1 iformc
800; TSS; chloride; COD;
NH3; TKN; phenol; organics
Volatile organics; fecal
co 1 iform
800; TSS; chloride; COD;
NH3; TKNa metals; organics;
mutagens
Volatile organics; direct
aqueous injection; fecal
coliform bacteria
Trace metals and organics
Trace metals and organics
Grab
SCSTC Industrial
Effluent
24-hour Composite
a Figure 1 shows station location.
b Temperature and pH were measured periodically at all stations.
c Grab samples collected 3 times each day for this parameter.
d Mutagen samples were collected three times during the survey.
e Primary sludge and industrial grit samples were collected once
during the survey.
Grab
SCSTC Domestic
Effluent
24-hour Composite
Grab
SCSTC Final Effluent
(Outfall 001)
24-hour Composite
Grab
SCSTC Primary Sludgee Grab
SCSTC Industrial
Grit
Grab
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V.
SURVEY RESULTS
PERFORMANCE AUDIT
Evaluations of self-monitoring procedures practiced by SCSTC
were conducted. Plant personnel were interviewed and equipment and
procedures observed. The NEIC evaluation indicated the following
procedures deviated from prescribed/recommended techniques.
Flow Monitoring
SCSTC did not measure the wastewater discharged through Outfall 001
until August 1978. Flow data reported on DMRs prior to August were
determined based on domestic influent and industrial influent. both
measured with Parshall flumes. These flumes are installed properly
and. even with the turbulence previously noted. provide reliable data.
As noted. the feed to the industrial aeration basin from the equaliza-
tion tanks is controlled by the operators. The amount treated is
based on the flow received the previous day. Thus. the daily flow
adjustment lags by at least one day. On a 30-day average. the values
should be reliable.
The Company installed a Marsh McBirney Model 250 meter in August
to measure and continuously record the flow as required by the NPDES
permit.
Bioassay Procedures
The Company bioassay facilities are maintained at the Union Carbide
Technical Center in South Charleston. The facility is environmentally
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16
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 bioassay tests do not always commence within eight hours
after sample collection as recommended by Standard Methods.
2.
Dechlorinated city tap water is used as dilution water rather
than Kanawha River water as required by the NPDES permit.
3.
The bioassay tests are not done in duplicate as recommended
by Standard Methods.
4.
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 dissolved oxygen
concentrations cannot be maintained.
5.
The laboratory depends on controlled ambient air tempera-
ture to maintain a constant test temperature. '.It is advisa-
ble, though not required, that a constant temperature water
bath be used to maintain constant test temperature.
Analytical Procedures
The membrane filter procedure for monitoring bacteria is being
used. The membrane filter technique usually yields low and variable
recovery from chlorinated wastewaters.
Initial testing for the vinyl chloride monomer
has produced low recoveries on the spiked samples.
be placed on improving percentage of recoveries on
vinyl chloride monomer.
in the effluent
Emphasis should
samples spiked with
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Sampling
The company has an in-plant wastewater monitoring program in-
cluding total carbon analyzers. Composite samplers are not refriger-
ated, however, the data are used to aid in-plant operations. Effluent
samples (Outfall 001) are manually collected, composited and refriger-
ated. Plant personnel stated that a new refrigerated automatic flow-
proportional sampler is to be installed on Outfall 001.
Fecal coliform organism samples are collected from the chlorine
contact basin effluent and the Aero Accelator effluent. The NPDES
permit limits fecal coliform organisms in the total plant effluent
(Outfall 001), not at these intermediate points.
NPDES EFFLUENT LIMITATION COMPLIANCE
Results of verifying the Marsh McBirney flow meter (Outfall 001)
with lithium chloride data are tabulated below.
NEIC SCSTC
Lithium Chloride Flow Meter Flow
Date Time m3/day mgd m3/day mgd
18 1725 32,400 8.6 28,800 6.3
19 2043 31,000 8.2 20,100 5.3
20 2041 34,100 9.0 21,900 5.8
21 0841 41,200 10.9 28,800 7.6
Avg. 34,700 9.2 24,900 6.3
These data show that the Marsh McBirney meter was recording value
26 to 38% lower than the actual flow. The sum of the domestic influent
plus industrial aeration basin influent flows, however, were comparable
to Outfall 001 lithium chloride results. Therefore, the daily flow
data reported in Table 3 were calculated based on this summation.
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Table 3
SUMMARY FIELD MEASUREMENTS AND ANALYTICAL DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
. Parameters (August) .. 15 16 17 18 19 20 21 Average
Station 45
DISCHARGE TO KANAWHA RIVER (OUTFALL 001)
Flow
m3/day x 103 35.4 36.0 29.0 35.0 28.5 32.6 33.0 32.8
mgd 9.36 9.51 7.65 9.24 7.54 8.63 8.73 8.67
Temperature °C Range 25-27 26-29 26-:-28 25-28 27-29 27-28 25-26
pH Range 6.1-7.9 7.5-7.8 6.4-7.9 7.5-7.9 7.5-7.8 7.4-8.1 7.7-8.0
BOD
mg/l 18 12 12 34 22 24 21 20
kg/day 640 430 350 1,200 630 780 690 670
lb/day 1,400 950 770 2,600 1,400 1,700 1,500 1,500
COD
mg/l 160 240 370 360 420 390 360 330
kg/day 5,700 8,600 11,000 13,000 12,000 13,000 12,000 11,000
lb/day 12,000 19,000 24,000 28,000 26,000 28,000 26,000 23,000
TSS
mg/l 19 18 23 57 21 18 15 24
kg/day 670 650 670 2,000 600 590 500 810
lb/day 1,500 1,400 1,500 4,400 1,300 1,300 1,100 1,800
TKN
mg/l 18 18 15 15 13 12 11 15
kg/day 640 650 430 520 370 390 360 480
lb/day 1,400 1,400 960 1,200 820 860 800 1,100
NH:\-N
mg/l 9.1 13 8.9 10 5.6 6.8 5.2 8.4
kg/day 320 470 260 350 160 220 170 280
lb/day 710 1,000 570 770 350 490 380 610
Chloride
mg/l 260 330 340 280 200 190 190 260
kg/day 9,200 12,000 9,800 9,800 5,700 6,200 6,300 8,400
lb/day 20,000 26,000 22,000 22,000 13,000 14,000 14,000 19,000
Phenol
IJgl1 12 9 16 10 16 8 13 12
kg/day 0.43 0.32 0.46 0.35 0.46 0.26 0.43 0.39
lb/day 0.94 0.71 1.0 0.77 1.0 0.58 0.95 0.85
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Effluent data collected August 15 to 21 show that all results
except those for fecal coliform bacteria [Table 3 and 4] are less
than permit limits. The seven-day average concentration [Table}]
for BOD (20 mg/l), COD (330 mg/l), TSS (24 mg/l), TKN (15 mg/l), NH3
(8.4 mg/l), chloride (260 mg/l) and phenol (12 ~g/l) were only 25,
49, 30, 29, 56, 65 and 24% of their respective permit limitations.
Fecal coliform bacteria densities in the effluent ranged from 790 to
130,000/100 ml with a geometric mean bacterial density of 12,000/100 ml
[Table 4]. This high fecal coliform bacterial density exceeds the
NPOES permit limitation of ~400/100 ml for each seven day consecutive
period.
DMR data for October 1977 through September 1978 [Table 5] show
that the average BOD, TSS and TKN concentrations during the August 15
to 21, 1978 study were atypically low. For example, reported average
BOD concentrations ranged from 35 to 326 mg/l, approximately 2 to 16
times greater than survey results (20 mg/l). These DMRs also show
that the SCSTC exceeded permit limitations 5, 6, 2, 3, 9 and 1 months
respectively for BOD, TSS, COD, NH3, chloride and pH.
WASTEWATER CHARACTERIZATION
Industrial Influent (Station 39)
Evaluation of the Parshall flume by NEIC personnel showed that
the influent flows were within I10% of actual when the flow recorder
trace was read at the midpoint. During the survey, 16,600 to
20,400 m3/day or process wastewaters were received from UCSC.
The NEIC sampled and analyzed the UCSC process wastewater, indus-
trial influent, for a variety of parameters [Table 2]. The wastewater
contained an average of 2,700 mg/l (52,000 kg/day) COD, 36 mg/l
(690 kg/day) TKN, 5.7 mg/l (110 kg/day) NH3, and 300 mg/l (5,500 kg/day)
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20
Table 4
SUMMARY OF FECAL COLIFORM BACTERIA DENSITIES
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
SOUTH CHARLESTON, WEST VIRGINIA
Fecal Coliform Bacteria
Station No. of MPN/100 ml Geometric
No. Description Samples Maximum Minimum Mean
41 South Charleston, W. Va. Sewage 21 4,900 20 84
Treatment Co. Industrial Effluent
43 South Charleston, W. Va. Sewage 21 350,000 3,300 27,000
Treatment Co. Domestic Effluent
45 South Charleston, W. Va. Sewage 22 130,000 790 12,000
Treatment Co. Fi nal Effl uent
(Outfall 001)
-------
Table 5
SUMMARY OF DISCHARGES MONITORING REPORTSa
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
October 1977 - September 1978
Parameter Oct Nov Dee Jan Feb Mar Apr May Jun Jul Aug Sep
Flow
!ir'/day 21. 0 21.3 25.2 32.7 27.5 29.8 24.3 32.3 27.6 26.1 30.0 29.5
mgd 5.56 5.63 6.67 8.65 7.27 7.86 6.42 8.53 7.30 6.89 7.92 7.8
BOD
mg/l 74 81 217 177 326 76 89 42 50 35 40 46
kg/day 1,591 1,727 5,591 5,794 8,970 2,261 2,162 1,356 1,381 913 1,199 1,358
lb/day 3,508 3,807 12,326 12,777 19,778 4,985 4,768 2,990 3,046 2,012 2,644 2,994
TSS
mg/l 76 76 138 147 254 53 65 28 37 45 48 46
kg/day 1,591 1,591 3,727 4,812 6,989 1,577 1,579 904 1,022 1,173 1,439 1,358
lb/day 3,508 3,508 8,217 10,611 15,410 3,476 3,482 1,993 2,254 2,587 3,172 2,994
COD
mg/l 439 430 785 579 990 513 496 332 314 220 286 256
kg/day 9,273 9,091 20,273 18,955 27,239 15,260 12,051 10,718 8,675 5,737 8,573 7,557
lb/day 20,443 20,042 44,694 41,795 60,061 33,649 26,573 23,633 19,128. 12,649 18,902 16,663
Phenol
IiiQ7T 0.016 0.011 0.019 0.02 0.021 0.02 0.011 0.013 0.015 0.013 0.013 0.016
kg/day 0.30 0.23 0.48 0.65 0.58 0.59 0.27 0.42 0.41 0.34 0.39 0.47
lb/day 0.66 0.51 1. 06 1.44 1. 27 1. 31 0.59 0.92 0.91 0.75 0.86 1. 04
TKN
mg/l 26 21 33 28 37 24 23 27 24 20 20 26
kg/day 564 427 850 917 1,018 714 559 872 663 519 602 768
lb/day 1,243 941 1,874 2,021 2,245 1,574 1,232 1,922 1,462 1,144 1,328 1,692
NH3-~
mg 1 12 8 3 2 6 8 14 17 16 6.2 6.7 10.6
kg/day 255 159 77 65 165 238 340 549 442 162 201 313
lb/day 562 350 170 144 , 364 525 750 1,210 975 356 443 690
Chlorides
mg/l 199 669 597 287 377 433 169 314 182 221 232 539
kg/day 4,895 13,218 15,363 9,395 10,373 12,880 4,106 10,137 5,028 5,752 6,954 15,911
lb/day 10,792 29,140 33,870 20,717 22,872' 28,401 9,054 22,351 11,087 12,684 15,333 35,084
pH Range 7.0-7.6 6.9-7.7 7.0-9.4 7.0-7.6 6.6-8.0 6.8-7.8 7.2-7.9 7.4-8.6 7.4-8.1 7.1-8.2 6.0-9.0 7.5-8.2
Temperature N
max °C 22.2 15.6 11.7 10.6 7.8 13.9 18.9 22 25 28 32 27 ......
a lb/day and m3/day not reported by the plant; values computed by NEIC.
-------
22
chloride and 380 ~g/l (7 kg/day) phenolic compounds [Table 6].
pH fluctuated from 2.3 to 12.0 during the survey.
The
Characterization of the process wastewater resulted in the identi-
fication of 30 organic compounds* [Tables 7, 8, 9]. Concentrations
ranged from <1 to 560,000 ~g/l. Fifteen compounds were found in concen-
trations of 500 ~g/l or greater.
Of the 30 compounds identified, 12 are priority pollutants.**
Except for isophorone, priority pollutant concentrations ranged from
a low of 1 ~g/l to 140 ~g/l. Isophorone was detected in 4 out of 7
composite samples with concentrations ranging from 2,500 to 5,100 ~g/l
(60 to 120 kg/day).
Industrial Effluent (Station 41)
Flow was determined based on the Palmer-Bowles flume and recorder
located on the influent to the aeration basin. The influent to the
basin remains constant for a given period of time. Plan~ operators
change flow rates to the basin once or twice daily to either increase
or decrease wastewater volume in the equalization tanks. Operators
informed NEIC personnel when the flow rate to the aeration basin was
changed so that the flow could be determined with lithium chloride.
Results show that 20,000 to 26,300 m3/day (average 23,100 m3/day) of
industrial wastewater was being treated in the basin.
* One of the compounds, Tri-n-butyl phosphate was identified and
confirmed but could not be quantified due to either interfering
compounds or difficulties in correlation to the flame ionization
chromatogram.
** Priority Pollutants are derived from the June 7, 1976 Natural
Resources Defense Council (NRDC) vs. Russell Train (USEPA)
Settlement Agreement.
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23
Table 6
SUMMARY FIELD MEASUREMENTS AND ANALYTICAL DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Parameters (August) ... 15 16 17 18 19 20 21 Average
Station 39
INDUSTRIAL INFLUENT
Flow
m3/day x 103 16.6 18.8 19.6 20.4 18.7 20.0 19.1 19.0
mgd 4.39 4.98 5.19 5.39 4.94 5.29 5.04 5.03
Temperature °C Range 30-35 29-34 30-33 29-33 30-34 30-33 28-34
pH Range 3.6-11.9 2.3-11.5 7.5-10.84.3-11.4 2.0-12.0 1.5-11.3 6.7-11.6
COD
mg/l 2,000 3,100 2,100 3,100 2,600 2,300 3,700 2,700
kg/day 33,000 58,000 41,000 63,000 49,000 46,000 71,000 52,000
lb/day 73,000 130,000 91,000 140,000 110,000 100,000 160,000 110,000
TKN
mg/l 24 24 32 30 54 32 59 36
kg/day 400 450 630 610 1,000 640 1,100 690
lb/day 880 1,000 1,400 1,300 2,200 1,400 2,500 .1,500
NH::\-N
mg/l 10.0 4. 7 6.7 5.4 4.9 3.9 4.6 5.7
kg/day 170 90 130 110 92 78 88 110
lb/day 370 200 290 240 200 170 190 240
,
Chloride
mg/l 520 430 320 140 260 190 220 300
kg/day 8,600 8,100 6,300 2,900 4,900 3,800 4,200 5,500
lb/day 19,000 18,000 14,000 6,300 11,000 8,400 9,300 12,000
Pheno 1 .
~g/l 240 320 490 420 380 380 400 380
kg/day 4 6 10 9 7 8 8 7
lb/day 9 13 21 19 16 17 17 16
-------
24
39 Industrial Influent
Table 7
NEUTRAL EXTRACTABLE ORGANICS SAMPLING OATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Oate (August) - Concentration in I-Ig/l
Chemical Name 15 16 17 18 19 20 21
Biphenyl N02 NO 430 170 130 180 120
bis-(2-Ethoxyethyl)Ether NO NO NO 370 NO NO MS3
Butyl Carbitol NO 1,800 6,900 15,000 48,000 2,700 14,000
2,6-0i-tert-Butyl-p-Cresol 150 600 90 NO NO NO NO
2-Ethyl-1-Hexanol NO NO 4,100 11,000 NO 16,000 3,500
Isophorone4 5,000 2,900 NO NO NO 5,100 2,500
Phenyl Ether NO NO 710 330 250 360 210
Pristane NO NO NO NO NO NO NO
Tri-n-Butyl Phosphate MS NO NO NO NO NO NO
Biphenyl NO NO NO NO NO NO NO
bis-(2-Ethoxyethyl)Ether NO 15 2 25 150 94 160
Butyl Carbitol NO NO NO NO NO NO NO
2,6-0i-tert-Butyl-p-Cresol NO NO NO NO NO NO NO
2-Ethyl-1-Hexanol NO NO NO NO NO NO NO
Isophorone4 NO NO NO NO NO NO NO
Phenyl Ether NO NO NO NO NO NO NO
Pristane NO 22 8 14 18 16 28
Tri-n-Butyl Phosphate 75 380 110 130 150 NO NO
Biphenyl NO NO NO NO NO NO NO
bis-(2-Ethoxyethyl)Ether NO 7 NO 16 140 160 170
Butyl Carbito 1 NO NO NO NO NO NO NO
2,6-0i-tert-Butyl-p-Cresol NO NO NO NO NO NO NO
2-Ethyl-1-Hexanol NO NO NO NO NO NO NO
Isophorone4 NO NO NO NO NO 4,100 1,000
Phenyl Ether NO NO NO NO NO NO NO
Pristane NO NO NO NO NO NO NO
Tri-n-Butyl Phosphate 41 26 110 34 MS NO NO
Biphenyl NO
bis-(2-Ethoxyethyl)Ether NO
Butyl Carbitol NO
2,6-0i-tert-Butyl-p-Cresol NO
2-Ethyl-1-Hexanol NO
Isophorone4 NO
Phenyl Ether NO
Pristane 5
Tri-n-Butyl-Phosphate NO
Biphenyl 120
bis-(2-Ethoxyethyl)Ether NO
Butyl Carbitol NO
2,6-0i-tert-Butyl-p-Cresol 20
2-Ethyl-1-Hexanol NO
Isophorone4 120
Phenyl Ether 260
Pristane NO
Tri-n-Butyl Phosphate NO
Station
No. Station Oescriptionl
41 Industrial effluent
45 Discharge to Kanawha
River (Outfall 001)
46 Primary sludge
47 Industrial Grit
1.
2.
3.
Samples from station 43, Oomestic effluent were also analyzed for these organic compounds.
None of these compounds were detected.
NO means not detected by computerized mass spectrometric data analysis.
MS means the chemical was identified from its mass spectrum but interferring compounds or
difficulties in correlation to the flame ionization chromatogram prevented quantitation.
Chemical is a priority pollutant (NROC vs Train Consent decree, June 1976).
4.
-------
Table 8
VOLATILE ORGANICS DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Station Oescription Industrial Influent (Station 39) Industrial Effluent (Station 41)
Oate (August 1978) 15a 16 17 18 19 20 21 15 16 17 18 19 20 21
COMPOUND Con c e n t rat ion (I-Ig/l)
Acrolein NOb NO ND NO NO NO ND NO NO ND NO NO ND ND
Benzene 29 29 18 16 24 5 21 40 NO ND NO NO 60 NO
Bromodichloromethane NO 1 1 1 3 NO 2 NO NO ND NO NO NO NO
Bromoform ND NO NO NO NO NO NO NO NO NO NO NO NO NO
Carbon tetrachloride NO NO ND NO NO NO NO NO NO NO NO NO NO NO
Chlorobenzene NO NO ND NO NO NO NO NO NO NO NO NO NO NO
2-Chloroethylvinyl NO NO ND NO NO NO NO NO NO ND ND NO NO NO
ether
Chloroform 46 43 52 24 19 13 34 25 ND 1 2 NO 150 ND
Chlorodibromomethane NO ND ND NO 2 NO ND ND ND ND NO NO NO NO
1,2-Dichloroethane NO 11 ND 14 NO 9 14 ND NO ND 1 NO NO NO
l,l-Oichloroethene NO ND NO NO NO NO ND NO NO ND NO NO NO NO
trans-l,2-0ichloro- NO NO ND ND NO NO ND NO NO ND NO NO NO NO
ethene
1,2-Dichloropropane NO 5 2 NO 4 NO NO NO NO NO NO NO NO NO
Ethylbenzene 7 44 21 27 94 NO NO NO NO NO NO NO NO ND
Methylene chloride 120 9 70 . NO 15 NO NO 150 16 ND NO NO 400 NO
1,1,2,2-Tetrachloro- NO NO ND NO NO NO ND NO NO NO NO NO NO NO
ethane
Tetrachloroethene ND ND NO NO NO NO NO NO ND ND NO NO NO NO
Toluene 81 74 94 98 140 91 ND NO NO 3 NO NO NO NO
l,l,l-Trichloroethane NO NO ND NO NO NO NO NO ND ND NO NO NO NO
1,1,2-Trichloroethane NO 2 NO 1 3 2 1 NO ND NO NO NO NO NO
Trichloroethene NO 1 NO NO NO NO NO NO NO ND NO NO NO NO
Vinyl chloride NO ND NO NO NO NO NO NO NO ND NO NO ND NO
N
a Equal volume composite of three grab samples
-------
Table 8 (Cont'd.)
VOLATILE ORGANICS DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Discharge to Kanawha River
Station Description Domestic Effluent (Station 43) Outfall 001 (Station 45)
Oate (August 1978) 15 16 17 18 19 20 21 15 16 17 18 19 20 21
COMPOUND Con c e n t rat ion (I-'g/l)
Acrolein NO NO NO NO NO NO NO NO NO NO NO NO .NO NO
Benzene NO NO NO NO NO NO NO NO NO NO NO NO NO NO
Bromodichloromethane NO NO NO NO NO NO NO NO NO NO NO NO NO NO
Bromoform NO NO NO NO NO NO NO NO NO NO NO NO NO NO
Carbon tetrachloride NO NO NO NO NO NO NO NO NO NO NO NO NO NO
Chlorobenzene NO NO NO NO NO NO NO NO NO NO NO NO NO NO
2-Chloroethylvinyl- NO ND ND NO NO NO NO NO NO NO NO NO NO NO
ether
Chloroform 4 15 11 8 46 21 15 2 7 4 3 15 NO 9
Chlorodibromomethane NO NO NO NO NO NO NO NO NO NO NO ND NO NO
1,2-0ichloroethane NO NO NO NO NO NO NO NO NO NO NO NO NO NO
l,l-Oichloroethene NO NO NO NO NO NO NO NO NO NO NO ND NO NO
trans-1,2-dichloro-
ethene NO NO NO NO NO NO NO NO NO ND NO NO NO NO
1 ,2-0ichloropropane NO NO NO NO NO NO NO NO NO ND NO ND NO NO
Ethylbenzene NO NO NO NO ND NO NO NO NO ND NO NO NO NO
Methylene chloride 5 30 15 62 58 12 8 11 13 7 22 41 NO 29
1,1,2,2-Tetrachloro- NO NO NO NO NO NO NO ND NO ND NO NO NO NO
ethane ' .
Tetrachloroethene 10 6 2 2 2 4 2 4 3 ND ND 1 NO ND
Toluene NO NO ND . NO NO NO NO ND NO ND NO NO NO NO
1,1,1-Trichloroethane 1 5 NO 1 3 3 ND ND 6 2 ND NO NO ND
1,1,2-Trichloroethane NO NO ND ND NO NO NO ND NO ND NO NO ND NO
Trichloroethene NO NO ND ND 2 NO ,NO NO ND ND ND ND ND ND
Vinyl chloride NO NO NO NO NO NO NO NO NO NO NO ND NO NO N
0"\
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Table 9
DIRECT AQUEOUS INJECTION ORGANIC DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Concentration (mg/l)
Station Oatea acetone methyl ethyl- acryloni- styrene isopro- diethyl isobutro- n-butanol 1-ch 1 oro. ethanol 4-methyl-2- cellosolve
Description (August) ketone tril e panol ketone nitrile butane pentene-2-one acetate
Industrial 15 74 NDd 27 NO 20 <1 3.1 72 1 560 NO ND
Influent 16 280b NO 28 ND 18 <1 ND <1 NO NO NO NO
17 81c NO 66c 2.9 59c NO NO 37c NO NO ND NO
18 8.9 NO 30 1.9 46
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28
Data collected from the industrial effluent show that COD, BOD,
T55, TKN, NH3, chloride and phenol concentrations, averaged 440, 15,
8,19,11, "340 and 0.01 mg/l, respectively, during the survey [Table 10].
COD, TKN and phenol removal efficiencies, based on loading, averaged
81, 38 and 97%, respectively.
NH3 and chloride loads were higher in the effluent than those
observed in the influent. The NH3 increased from 110 to 260 kg/day
and chloride from 5,500 to 7,900 kg/day. As previously noted, NH3 is
added to the aeration basin as a nitrogen source. This addition appar-
ently also increased the amount of NH3 discharged. The chloride
increase is probably due to biological breakdown of organics in the
treatment process.
Bacteriological analysis of the industrial effluent showed fecal
coliform bacteria densities ranging from 20 to 4,900/100 ml (geometric
mean of 84/100 ml) [Table 4].
Organic analyses of the industrial effluent resulted in the identi-
fication of 9 volatile and 3 neutral extractable compounds [Tables 7,
8]. The 9 volatile organic compounds, which were also identified in
the industrial influent, were detected in concentrations ranging from
2 to 400 ~g/l [Table 8]. The neutral extractable compounds - pristane,
bis-(2-ethoxyethyl) ether and tri-n-butyl phosphate - were not detected
in the plant influent. Concentrations of these compounds ranged from
2 to 380 ~g/l [Table 7]. The 9 volatile organic compounds are priority
pollutants.
An examination of the industrial influent and effluent flow data
presents an anomaly. During the survey, the total amount of industrial
wastewater received at 5C5TC was 133,200 m2/day, yet 161,700 m3 was
discharged, 21% greater. This difference, 28,500 m3, could be due to
inaccuracies in flow measurement (t10% on each device), the addition
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29
Table 10
SUMMARY FIELD MEASUREMENTS AND ANALYTICAL DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Parameters (August) -+ 15 16 17 18 19 20 21 Average
Station 41
INDUSTRIAL EFFLUENT
Flow
m3/day x 103 20.4 25.9 20.0 26.3 20.2 24.0 24.9 23.1
mgd 5.40 6.85 5.28 6.94 5.34 6.35 6.58 6.11
Temperature DC Range 26-29 28-32 26-30 27-32 29-34 27-30 25-29
pH Range 7.2-7.9 7.4-8.0 6.4-11.3 7.6-7.9 7.2-8.3 7.3-8.4 6.9-8.1
BOD
mg/l 10 12 14 16 21 17 14 15
kg/day 200 310 280 420 . 420 410 350 340
lb/day 450 690 620 930 940 900 770 760
COD
mg/l 270 310 510 470 560 520 430 440
kg/day 5,500 8,000 10,000 12,000 11,000 12,000 11,000 9,900
lb/day 12,000 18,000 22,000 27,000 25,000 28,000 24,000 22,000
TSS
mg/l 10 10 7 9 9 6 8 8
kg/day 200 260 140 240 180 140 200 190
lb/day 450 570 310 520 400 320 -440 430
TKN
mg/l 24 23 20 21 14 15 14 19
kg/day 490 600 400 550 280 360 350 430
lb/day 1,100 1,300 880 1,200 620 800 770 950
NH3-N
mg/l 15.1 18.0 11. 7 12.7 6.4 8.3 6.8 11
kg/day 310 470 230 330 130 200 170 260
lb/day 680 1,000 520 740 290 440 370 580
Chloride
mg/l 450 450 440 340 250 230 240 340
kg/day 9,200 12,000 8,800 8,900 5,100 5,500 6,000 7,900
lb/day 20,000 .26,000 19,000 20,000 11,000 12,000 13,000 17,000
Phenol
~g/l 12 6 12 9 9 10 9 10
kg/day 0.25 0.16 0.24 0.24 0.18 0.24 0.22 0.22
lb/day 0.54 0.34 0.53 0.53 0.40 0.53 0.49 0.48
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30
of domestic secondary sludge flow to industrial primary
[Figure 1], and less volume of stored wastewater in the
tanks between the start and finish of the survey.
clarifiers
equalization
Domestic Effluent (Station 43)
Effluent flow was based on the influent Parshall flume data.
The flume was checked by NEIC personnel and found to be recording
flows within t10% of actual. During the survey, domestic flows varied
from 8,000 to 15,000 m3/day (9,800 m3/day, average). The highest
flow observed, 15,000 m3/day, occurred as a result of runoff from a
rainstorm. Normal day weather flows reportedly average approximately
8,000 m3/day.
BOD, COD, T55, TKN, NH3, and chloride and phenol concentrations
averaged 35, 74, 44, 6.2, 2.8,81 and 0.004 mg/l, respectively [Table 11].
The T5S concentrations (44 mg/l) are higher than would be expected
from a well-operated secondary domestic WWTF. Visual observations
during the survey showed up to 2.5 cm (1 inch) of floatipg solids on
the Aero Accelator. Plant personnel informed NEIC that the floating
solids resulted because of over-chlorination of the primary effluent;
the excess chlorine killed some of the biota which floated and was
discharged.
Fecal coliform bacteria densities for the survey ranged from
3,300 to 350,000/100 ml with a geometric mean of 27,000/100 ml [Table 4J.
These high coliform bacteria densities show that the domestic effluent
will significantly affect the quality of the combined discharge. As
previously discussed, the domestic wastewater is disinfected after
primary clarificaton, not after secondary treatment.
Organic analysis [Table 8] showed that the domestic effluent
contained chloroform (4 to 46 ~g/l); tetrachloroethene (2 to 10 ~g/l),
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31
Table 11
SUMMARY FIELD MEASUREMENTS AND ANALYTICAL DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
Parameters (August) ~ 15 16 17 18 19 20 21 Average
Station 43
DOMESTIC EFFLUENT
Flow
m3/day x 103 15.0 10.0 9.0 8.7 8.3 8.6 8.1 9.7
mgd 3.96 2.66 2.37 2.30 2.20 2.28 2.15 2.56
Temperature °C Range 24-25 24-28 24-26 24-26 25-27 25-26 24-26
pH Range 6.3-7.2 6.6-7.1 6.5-6.8 6.4-6.7 6.2-6.6 5.5-6.9 6.4-6.9
BOD
mg/1 26 24 36 76 30 28 23 35
kg/day 390 240 320 660 250 240 190 330
lb/day 860 530 710 1,500 550 530 410 730
COD
mg/1 62 53 61 150 55 78 62 74
kg/day 930 ~ 530 550 1,300 460 670 500 710
lb/day 2,000 1,200 1,200 2,900 1,000 1,500 1,100 1,600
TSS
mg/l 38 27 26 84 42 56 38 44
kg/ day 570 270 230 730 350 480 310 420
lb/day 1,300 600 510 1,600 770 1,100 680 940
TKN
mg/l 5.6 5.5 5.5 11,0 5.5 5.4 4.6 6.2
kg/day 84 55 49 96 46 47 37 59
lb/day 190 120 110 210 100 100 83 130
NH3-N
mg/1 3.0 3.0 2.8 3.7 3.3 2.2 1.3 2.8
kg/day 45 30 25 32 27 19 11 27
1b/day 99 67 55 71 61 42 23 60
Chloride
mg/1 61 79 87 83 90 81 88 81
kg/day 910 800 780 720 750 700 720 770
1b/day 2,000 1,800 1,700 1,600 1,700 1,500 1,600 1,700
Phenol
fJg/1 6 3 11 6 0 0 3 4
kg/day 0.09 0.03 0.10 0.05 0 0 0.02 0.04
lb/day 0.20 0.07 0.22 0.12 0 0 0.05 0.09
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32
1,1,1-trichloroethane (1 to 5 ~g/l) and trichloroethene (2 ~g/l).
These volatile compounds are priority pollutants. Although the exact
source of these organic compounds are unknown, they might originate
at the Union Carbide Technical Center, a research facility, which
reportedly discharges wastewater into the domestic sewer.
SCSTC Discharge (Outfall 001) - Station 45
During the study an average of 32,800 m3/day (8.67 mgd) of waste-
water was discharged to the Kanawha River. NEIC sampled and analyzed
this discharge for all NPDES permit parameters, selected metals and
organic compounds [Table 2].
The mixing of domestic and industrial effluent prior to discharge
results in dampening out the high domestic TSS (44 mg/l) and industrial
COD (440), NH3 (11 mg/l) and chloride (340 mg/l) concentrations.
Final effluent concentrations for these parameters averaged 24, 330,
8.4 and 260 mg/l, respectively [Table 3].
Composite samples
concentrations of zinc
The other metals* were
are listed as priority
results show that the discharge contained low
(0.03 to 0.08 mg/l) and nickel (0.09 to 0.2 mg/l).
below detectable limits. Both zinc and nickel
pollutants.
Organic analyses of the discharge to the Kanawha River resulted
in the identification of 7 compounds [Tables 7, 8, 9] with concentrations
ranging from 7 to 4,100 ~g/l. All 7 compounds, 4 identified by volatile
and 3 by neutral extractable analyses, were previously identified in
the industrial and/or domestic wastewaters. The 4 volatile organics
(chloroform, methylene chloride, tetrachloroethene and 1,1,1-trichloro-
ethane) are priority pollutants.
* Samples were analyzed for Ni, Pb, Sn, Zn, As, AI, Cd, Cr and Cu.
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33
Composite samples collected August 15, 18 and 21 were analyzed
for carbaryl. The concentration on the first two samples was below
the detection limit, <3 ~g/l. The sample collected August 21 contained
21 ~g/l carbaryl.
Solids
Samples of the industrial grit and primary domestic sludge filter
cake were analyzed to determine the metal and organic content of the
solids being landfilled. The metal results are listed below.
Metala
Concentration ~g/l
Primary Sludge Industrial Grit
As
Al
Cr (tota 1)
Cu
Ni
Pb
In
Hg
13
4,500
50
140
30
180
440
2.2
6
4,100
180
570
2,500
370
290,-
5.7
a The samples were also analyzed for Cd
and Sn. These two metals were not detec-
ted in either sample.
As, Cr (total), Cu, Ni, Pb, In, and Hg are priority pollutants.
Organics data [Table 7J show that the domestic sludge contained
5 ~g/g of pristane. The industrial grit contained 120 ~g/g biphenyl,
20 ~g/g 2,6-0i-tert-Butyl-p-Cresol, 120 ~g/g isophorone, and 260 ~g/g
phenyl ether. Of these compounds only isophorone is a priority pollutant.
The domestic sludge and industrial grit are buried in the South
Charleston landfill and Filmont landfill respectively. These landfills
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35
Table 12
96-HOUR FLOW-THROUGH SURVIVAL DATA
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
August 1978
% Survival
Effluent Concentration (%)
Time Period Control 10 18 32 56 75 100
(Kanawha River Water)
24-hour 100 100 100 100 100 100 100
48-hour 100 100 100 100 100 100 100
72-hour 100 100 100 100 100 100 100
96-hour 100 100 100 100 100 100 95
-------
34
are not approved for receipt of solid wastes containing priority pollu-
tants.
BIOLOGICAL STUDIES
Biomonitoring
A flow-through bioassay was conducted on Outfall 001 to determine
whether the wastewater was acutely toxic to fish. Juvenile fathead
minnows (Pimephales promelas Refinesque) averaging 4 cm in length
were used as test organisms [Appendix E].
The final effluent discharge from Union Carbide South Charleston
Sewage Treatment Company (Outfall 001) was not acutely toxic to fish.
Ninety-five percent of the test fish survived a 96-hour exposure in
100% effluent [Table 12]. A five percent mortality rate for a 96-hour
bioassay is insignificant and not indicative of toxicity.
Mutagen Testing
Analyses for mutagenic activity were performed on composite samples
for Outfall 001 to determine if mutagens and potential carcinogens
were present in the wastes. Each of three samples collected from the
SCSTC effluent demonstrated the presence of mutagenic material upon
activation with rat liver enzymes. Microsomal rat liver homogenates
serve to convert certain substances into metabolites that are active
mutagens and carcinogens.
Basic extracts from each of the three samples
-------
36
displayed a mutagenic activity ratio* of 2.5 or higher [Table 13] and
a typical dose-response relationship when tested with Salmonella test
strain TA 98 [Figure 2]. The mutagenic activity ratio is a measure
of the tester strain mutation rate compared to control rates. A muta-
genic activity ratio of 2.5 or greater correlates closely (~90% pro-
bability) with inducement of cancer in laboratory animals.2,3,4
Extrapolation of this information to higher organisms (such as
humans) is warranted because mutagens may alter genetic material (deoxy-
ribonucleic acid) in a similar manner in other life forms. If a com-
pound is mutagenic in any organism, it should not be exposed to the
human population. Only one molecule of a mutagen is sufficient to
cause a mutation that is also likely to be carcinogenic. Because
genetic repair systems are not completely effective, safe doses of
mutagens and carcinogens cannot be projected.s'6
Greatest reversion rates were obtained from the basic extract
concentrate from the sample collected on 8/21/78 (mutagenic activity
ratio of 6.4 at 103.3 ml equivalent sample volume). Acidic extracts
from all three samples failed to satisfy requirements for positive
mutagenicity. However, the results of mutagen testing of the basic
extracts demonstrates obvious mutagenic activity; mutagenic and poten-
tial carcinogenic substances were being discharged from the SCSTC at
Outfall 001.
* The mutagenic activity ratio is a measure of the tester strain
mutation rate compared to control rates. A mutagenic activity
ratio of 2.5 or greater correlates closely (>90% probability)
with inducement of cancer in laboratory animals.2,3,4 If the
activity ratio is 2.5 or greater and a typical dose response rela-
tionship can be demonstrated between the tester strain and in-
creasing concentrations of sample, the results are considered
positive (i.e., the substaDce is a mutagen). The mutagenic activity
ratio is defined as (E-C)/c where E is the average number of mutant
colonies per test with the ~ample added; C is the corresponding
value for the control, and c is the historical control value of
40 averaged over 100 or more tests.
-------
Station Number
Description
Samplea
Type
Date-Time
Collected
Table 13
MUTAGENIC ACTIVITY OF UNION CARBIDE INSTITUTE DISCHARGE
ON SALMONELLA TESTER STRAIN TA 9B
SOUTH CHARLESTON SEWAGE TREATMENT COMPANY
August 15-21. 1978
Volume of Sampleb
Concentrate Tested
Extract
pH
(1J1)
Equivalent Volume
of Sample (ml)
No. of Revertant
Colonies Per Plate
Controlc Experimentald
Mutagenic Activity
Ratioe
45 Composite 8/15/78 Base 250 51. 7 40 158 3.0
South Charleston 2306 150 31.0 115 1.9
Sewage Treatment 100 20.7 110 1.8
Company Effluent 58 10.3 53 <1. 0
25 5.2 41 <1. 0
10 2.1 33 <1. 0
5 1.0 46 <1. 0
1 0.2 24 <1.0
45 Composite 8/18/78 Base 500 96.7 40 240 5.0
South Charleston 2312 400 77.3 163 3.1
Sewage Treatment 300 58.0 144 2.6
Company Effluent 200 38.7 143 2.6
100 19.3 100 1.5
50 9.7 70 <1. 0
25 4.8 35 <1. 0
10 1.9 29 <1.0
5 1.0 32 <1. 0
1 0.2 22 <1. 0
45 Composite 8/21/78 Base 500 103.3 40 296 6.4
South Charleston 2312 250 51. 7 262 5.6
Sewage Treatment 100 20.7 157 2.9
Company Effluent 50 10.3 70 <1. 0
25 5.2 36 <1. 0
10 2.1 22 <1. 0
5 1.0 39 <1. 0
.' 1 0.2
a Composite Samples - Compositing was hourly for each 24-hour period; date and
time listed is date and time that period ended.
b Rat-liver homogenate (S-9 mix) added.
c Value based on average of 30 control values.
d Average of 2 plates -
e Mutagenic Activity Ratio = (E-C)/c, where E is the_no. of colonies/experimental
plate, C is the no. of colonies/control plate and c is the historical control w
value of 40 averaged over 100 tests. ......
-------
(/)0::
0'\
I-
z;:::
c;{
I- C
Q: .~
w s...
>~
~ s... 200.
Q)
u.~
o Q)
~
Q: I\j
w,.....
(l)Qj
~ g
:> E
Zr;;;
VI
300
100 -
. 8/'2.1178
. SCSiC
/16
I"CS
. 6
t:.~c, -A
C, WI .......
5 ....... --
~..::::--....... - -a---
;.......
1---/""'"
/ .;
Y
~
/
~
. '
. . ,""to ~
~tO,/
Pu to'/'
vtO
to
-1lY
25
"."=<'~ "~"~~'~"M';"f I,Jr~;, ~,._"." "~'~h""~.u~..~.~",,~. ~~'"r" ""~m" '.~",'~.""'" ~."..~, .~=..w.~"~.t,..,-",,.._-~,,~.~
50 75 100
EQUIVALENT ml of EFFLUENT
w
co
Figure 2. South Charleston Sewage Treatment Company
Mutagen Tasting Dose Response Curve (Basic Extract).
Salmonella Tester Strain TA 98
-------
39
Data for test results that did not exhibit elevated reversion
rates (negative mutagenic activity) are not presented in this report.
TOXICITY EVALUATION
A total of 34 organic compounds and 2 metals were identified in
the SCSTC wastewater samples. These 36 compounds were searched in
the Registry of Toxic Effects of chemical substances (RTECS)* and in
the Toxline** data base to obtain health effects data [Appendix G].
THE RTECS search yielded toxicity information on 32 of the 36
compounds. The Toxline search located 578 references to health effects
(animal or human) from 32 of the 36 confirmed compounds. No information
on toxic effects was discovered for tri-n-butyl phosphate, bis-(2-ethoxy-
ethyl) ether, bromodichloromethane, and chlorodibromomethane. Information
on each of the other compounds is summarized in Table 14. Fifteen of
the 36 compounds identified in RTECS are listed as priority pollutants.
The 36 compounds were detected in concentrations ra~ging from
<1 ~g/l to 560 mg/l. Ten of these compounds were discharged to the
Kanawha River with concentrations ranging from 7 to 4,100 ~g/l. The
information presented in Table 14 shows that 24 compounds have demon-
strated human effects associated with them. The hazards of injecting
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, 6 of the compounds are known carcinogens,
benzene to humans and carbaryl, chloroform, ethanol, trichloroet~ene
and nickel to animals.
* This Registry is compiled annually by the National Institute for
Occupational Safety and Health.
** Toxline is a computerized bibliographic retrieval system for toxi-
cology.
-------
Table 14
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Chemical Other Toxicity Datab
Compound Name Molecular Abstracts Route of Type of Effectse Exposur~
Formula Service No. Aquatic Toxicitya Entry Species Dose Duration limits
Acetone C3H60 67-64-1 TLm 96:0ver 1000 Oral-human LDLo: 50 mg/kg OSHA
ppm Inhalation-human TCLo: 500 ppm Eye std (air):
Inhalation-man TCLo: 12.000 ppm 4H Central Nerv. TWA 1000 ppm
System
Oral-rat LD50: 9,750 mg/kg
Inhalation-rat LCLo: 64,000 ppm 4H
Inhalation-mouse LCLo: 110,000 mg/m3 62M
Intraperitoneal-mouse LD50: 1,297 mg/kg
Oral-dog LDLo: 24 g/kg
Intraperitoneal-dog LDLo: 8 g/kg
Subcutaneous-dog LDLo: 5 g/kg
Oral-rabbit LD50: 5,300 mg/kg
Skin-rabbit LD50: 20 gm/kg
Subcutaneous-guinea pig LDLo: 5,000 mg/kg
Acrylonitrile CaHaN 107-13-1d TLm96:100-10 ppm Oral-human LDLo:50 mg/kg OSHA std (air):
Oral-rat LD50:82 mg/kg TWA 20 ppm (skin)
Oral-rat TDLo:l,700 mg/kg 37WC Neoplastic
Inhalation-rat LCLo:500 ppm 4H
Inhalation-rat TCLo:80 ppm 6H/52W Neoplastic
Subcutaneous-rat LD50: 96 mg/kg
Parenteral-rat LDLo:200 mg/kg
Ora l-mouse LD50:27 mg/kg
Inhalation-mouse LCLo:900 mg/ma 60M
Intraperitoneal-mouse LDLo:lO mg/kg
Subcutaneous-mouse LD50:35 mg/kg
Inhalation-dog LCLo:110 ppm 4H
Ora 1- rabbi t LD50:93 mg/kg
Inhalation-rabbit LCLo:258 ppm 4H
Skin-rabbit LD50:280 mg/kg
Oral-guinea pig LD50:50 mg/kg
Inhalation-guinea pig LC50:576 ppm 4H
Benzene C6H6 71-43-2d TLm96:100-10 ppm Oral,-human LDLo: 50 mg/kg OSHA std (air):
Inhalation-human LDLo:20,OOO ppm 5M TWA 10 ppm;
Inhalation-human TCLo:,210 ppm Blood Cl 25
Inhalation-man TCLo:2,lOO mg/m3 4YI Carcino- Pk 50/10M/8H
genic
Oral-rat LD50:3,800 mg/kg
Inhalation-rat LC50:10,OOO ppm 7H
Intraperitoneal-rat LDLo:l,150 mg/kg
Ora l-mouse LD50:4,700 mg/kg
Inhalation-mouse LC50:9,980 ppm ~
Skin-mouse TDLo:1.200 gm/kg 49WI Neoplas- a
tic
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Chemical Other Toxicity Oatab
Compound Name Molecular Abstracts Route of Type of Exposur~
Formula Service No. Aquatic Toxicitya Entry Sped es Dose Duration Effectse Limits
Intraperitoneal-mouse L050:468 mg/kg
Subcutaneous-mouse TDLo:2,700 mg/kg 130 Terato-
(preg) genic
Oral-dog LOLo:2,OOO mg/kg
Inhalation-dog LCLo:146,OOO mg/m3
Inhalation-cat LCLo:170,OOO mg/m3
Intraperitoneal-guinea pig LOLo:527 mg/kg
Subcutaneous-frog LOLo:l,400 mg/kg
Inhalation-mammal LCLo:20,OOO ppm 5M
Benzene, Ethyl- CSH10 d Inhalation-human TCLo:100 ppm 8H Irritant OSHA std (air):
100-41-4 TLm96:100-10 ppm
Oral-rat L050:3,500 mg/kg TWA 100 ppm (skin)
Inhalation-rat LCLo:4,OOO ppm 4H
Ski n-rabbit L050:5,OOO mg/kg
Inhalation-guinea pig LCLo:10,OOO ppm
Biphenyl C12H10 92-52-4 Inhalation-human TOLo 4,400 ~g/m3 Irritant TLV (air):
0.2 ppm
Oral-rat L050: 3,280 mg/kg
Subcutaneous-mouse TOLo: 46 mg/kg Neoplastic OSHA std (air):
TWA 0.2 ppm
Oral-rabbit L050: 2,410 mg/kg
Butane, 1-ch1oro- C4HgC1 109-69-3 Oral-human LOLo:500 mg/kg
(l-chlorobutane) Oral-rat L050:2,670 mg/kg
Inhalation-rat LCLo:8,OOO ppm 4H
2-butanone C4HsO 78-93-3 TLm96:over Oral-human LOLo:500 mg/kg TLV(air):200 ppm
(methyl ethyl 1,000 ppm
ketone) Inhalation-human TCLo:100ppm 5M Irritant
Oral-rat L050:3,400 mg/kg OSHA std (air):
TWA 200 ppm
Inhalation-rat LCLo:2,OOO ppm 4H
Inhalation-rat TCLo:1,OOO ppm 6-150 Teratogenic
(preg)
Intraperitoneal-mouse L050:616 mg/kg
Skin-rabbit L050: 13 gm/kg
Butyl alcohol C4H100 71-36-3 TLm96:over Oral-human LOLo: 500 mg/kg TLV(air):50 ppm
(n-butanol) 1,000 ppm Inhalation-human TCLo: 25 ppm Irritant (skin)
Oral-rat L050: 790 mg/kg OSHA std (air):
Intraperitoneal-rat LOLo: 970 mg/kg TWA 100 ppm
Oral-mouse LOLo: 3,000 mg/kg """
Oral-rabbit LOLo: 4,250 mg/kg ~
Skin-rabbit L050: 4,200 mg/kg
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNOS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Compound Name
Molecular
Formula
Chemical
Abstracts Route of
Service No. Aquatic Toxicitya Entry
Species
Other Toxicity Oatab
Type of
Oose
Ouration
Effectse
Exposur~
Li mi ts
Butyl Carbitol
(Ethanol, 2-
2-butoxy ethoxy)-
Carbaryl
Chloroform
(Trichloromethane)
CsH1803
112-34-5 TLm96:100-10 ppm
Oral-human
Oral-rat
Intraperitoneal-mouse
Ski n-rabbit
Oral-guinea pig
Oral-man
C12HII02N 63-25-2
CHC13
TLm96:10-1 ppm
Oral-human
Oral-rat
Oral-rat
Inhalation-rat
Oral-rat
Intraperitoneal-rat
Implant-rat
Unknown-rat
Oral-mouse
Intraperitoneal-mouse
Oral-dog
Oral-rabbit
Oral-guinea pig
Oral-guinea pig
Oral-hamster
Oral-chicken
Oral-wild bird
d
67-66-3 TLm96:100-10 ppm
Oral-human
Inhalation-human
Inhalation-human
Oral-rat
Oral-rat
Inhalation-rat
Inhalation-rat
Oral-mouse
LOLo:500 mg/kg
L050:6,560 mg/kg
L050:850 mg/kg
L050:4,120 mg/kg
L050:2,OOO mg/kg
TOLo: 2,800 ~g/kg
LOLo: 50 mg/kg
L050: 400 mg/kg
TOLo: 5,700 mg/kg
LC50: 721 mg/kg
TOLo: 50 mg/kg
L050: 48 mg/kg
TOLo: 80 mg/kg
L050: 500 mg/kg
L050: 438 mg/kg
L050: 396 mg/kg
TOLo: 388 mg/kg
L050: 710 mg/kg
L050: 280 mg/kg
TOLo: 300 mg/kg
LOLo: 250 mg/kg
L050: 197 mg/kg
L050: 56 mg/kg
LOLo:140 mg/kg
TOLo:l,OOO mg/m3
TCLo:5,OOO mg/m3
L050:800 mg/kg
TOLo:70 gm/kg
LCLo:8,OOO ppm
TCLo:100 ppm
LOLo:2,400 mg/kg
Central
Nerv. Syst. OSHA std (air):
TWA 5 mg/m3
95 WI Carcinogenic
NIOSH recm std (air):
(9 or 100 Teratogenic TWA 5 mg/m3
preg)
Card nogeni c
(preg) Teratogenic
(preg) Teratogenic
lY
7M
OSHA std (air):
TWA 50 ppm
Systemic
Central
Nervous
System
78WI
Neoplas-
tic
NIOSH recm std
(air): Cl 2 ppm/60M
4H
7H Terato-
(6-15 0 preg) genic
*'"
N
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Chemical Other Toxicity Datab
Compound Name Molecular Abstracts Route of Type of Exposur~
Formula Service No. Aquatic Toxicitya Entry Species Dose Duration Effectse Limits
Oral-mouse TDLo:18 gm/kg 12001 Carcinogenic
Inhalation-mouse LC50:28 gm/m3
Intraperitoneal-mouse LD50:1,671 mg/kg
Subcutaneous-mouse LD50:704 mg/kg
Oral-dog LDLo:1,000 mg/kg
Inhalation-dog LC50:1DO gm/m3
Intraperitoneal-dog LD50:1,000 mg/kg
Intravenous-dog LDLo: 75 mg/kg
Inhalation-cat LCLo:35,OOO mg/m3 4H
Oral-rabbit LDLo:500 mg/kg
Inhalation-rabbit LC50:59 gm/m3
Subcutaneous-rabbit LDLo:3.0DD mg/kg
Inhalation-guinea pig LCLo:20,OOO ppm 2H
Inhalation-frog LCLo:6,OOO mg/m3
Inhalation-mammal LCLo:25.000 ppm 5M
p-creosol,2,6-di- C1sH240 128-37-0 Oral-rat LD50:2,450 mg/kg TLV (air):
tert-butyl- 10 mg/m3
Oral-mouse LD50:1,040 mg/kg
Intraperitoneal-mouse LDLo:250 mg/kg
Oral-cat LDLo:940 mg/kg
Oral-rabbit LDLo:2,100 mg/kg
Oral-guinea pig LD50:10,700 mg/kg
2-cyclohexen-l-one. CgH140 78-59-ld Inhalation-human TCLo:25 ppm Irritant OSHA std (air):
3.5,5-trimethyl- Oral-rat LD50:2,330 mg/kg TWA 25 ppm
(isophorone) Inhalation-rat LDLo:l,840 ppm 4H
Skin-rabbit LD50:1,500 mg/kg
Ethane, C2H4C12 107-06-2d TLm96:1.0DD-1DD Inhalation-human TCLo:4,DDD ppm H Central OSHA std (air):
l,2-Dichloro- ppm Nervous TWA 50 ppm
(Ethylene Dichloride) Sys tem Cl 100;
Pk 2DO/5M/3H
Oral-human TDLo:428 mg/kg
Oral-man LDLo:810 mg/kg
Oral-human LDLo:50D mg/kg
Oral-rat LD50:680 mg/kg
Inhalation-rat LCLo:1,OOO ppm 4H
Intraperitoneal-rat LDLo:60D mg/kg
Subcutaneous-rat LDLo:500 mg/kg
Oral-mouse LDLo:600 mg/kg NIOSH recm std (air):
Inhalation-mouse LCLo:5,OOO mg/m3 2H TWA 5 ppm;
Intraperitoneal-mouse LDLo:250 mg/kg Cl 15 ~
Subcutaneous-mouse LDLo:380 mg/kg w
Oral-dog LDLo:2,OOO mg/kg
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Chemical Other Toxicity Datab
Compound Name Molecular Abstracts Route of Type of Exposur2
Formula Service No. Aquatic Toxicitya Entry Species Dose Duration Effectse Limits
Intravenous-dog LOLo: 175 mg/kg
Oral-rabbit LD50:860 mg/kg
Inhalation-rabbit LCLo:3,OOO ppm 7H
Subcutaneous-rabbit LOLo:1,200 mg/kg
Inhalation-pig LCLo:3,OOO ppm 7H
Inhalation-guinea pig LCLo:1,500 ppm 7H
Intraperitoneal-guinea LDLo:600 mg/kg
pig
Ethane, 1,1,1- C2H3C13 71-55-6d TLm96:100-10 Oral-human LDLo:500 mg/kg
Trich1oro- ppm Inhalation-man LCLo:27 gm/m3 10M OSHA std (air):
(Methyl Chloroform) Inhalation-man TCLo:350 ppm Psycho- TWA 350 ppm
tropic
Inhalation-human TCLo:920 ppm 70M Central NIOSH recm std (air):
Nervous C1 350 ppm/15M
System
Oral-rat L050:14,300 mg/kg
Inhalation-rat LCLo:l,OOO ppm
Inhalation-mouse LCLo: 11 ,000 ppm 2H
Intraperitoneal-mouse L050:4,700 mg/kg
Oral-dog LD50:750 mg/kg
Intraperitoneal-dog L050:3,100 mg/kg
Intravenous-dog LDLo: 95 mg/kg
Oral-rabbit LD50:5,660 mg/kg
Subcutaneous-rabbit LD50:500 mg/kg
Oral-guinea pig LD50:9,470 mg/kg
Ethane, 1,1,2- C2H3C13 79-00-5d TLm:96:100-10ppm Oral-human LDLo:50 mg/kg OSHA std (air):
Trichloro- Oral-rat LD50:1,140 mg/gk TWA 10 ppm (skin)
Inhalation-rat LCLo:500 ppm 8H
Intraperitoneal-mouse DL50:994 mg/kg
Subcutaneous-mouse LD50:227 mg/kg
Ora 1-dog LDLo:500 mg/kg
Intraperitoneal-dog LDLo:450 mg/kg
Intraveneous-dog LDLo: 95 mg/kg
Subcutaneous-rabbit LDLo:500 mg/kg
Ethanol, 2-ethoxy- C6H1203 111-15-9 TLm:96:1000-100ppm Oral-human LDLo:500 mg/kg TLV (air):
acetate Oral-rat LD50:5,100 mg/kg 100 ppm (skin)
(Celloso1ve Inhalation-rat LCLo:1,500 ppm 8H
acetate) Intraperitoneal-mouse LD50:1,420 mg/kg OSHA std (air):
Skin-rabbit LD50:10,500 mg/kg TWA 100 ppm (skin)
Oral-guinea pig LD50:1,910 mg/kg .j:::o
.j:::o
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Chemical Other Toxicity Oatab
Compound Name Molecular Abstracts Route of Type of Effectse Exposur~
Formula Service No. Aquatic Toxicitya Entry Species Dose Duration Limits
Ether, diphenyl C12H100 101-84-8 Oral-rat LD50:3,370 mg/kg TLV (air):
(phenyl ether) 1 ppm (vapor)
OSHA std (air):
TWA 1 ppm
Ethyl alcohol C2HsO 64-17-5 TLm:96 over 1,000 Oral-child LDLo:2,OOO mg/kg TLV (air):
(ethanol) ppm Oral-human LDLo:500 mg/kg 1000 ppm
Oral-man TDLo:50 mg/kg Gastro-
intestinal
Oral-man TDLo:1,430 ~g/kg Central OSHA std (air):
Nervous TWA 1000 ppm
System
Oral-rat LD50:14 gm/kg
Intraperitoneal-rat LDLo:1,225 mg/kg
Intravenous-rat LD50:1,440 mg/kg
Oral-mouse L050:7,800 ~g/kg
Oral-mouse TDLo:340 gm/kg 57WI Carcinogenic
Intraperitoneal-mouse TDLo:7,500 mg/kg 90 (preg) Teratogenic
Intravenous-mouse LD50:1,973 mg/kg
Rectal-mouse TDLo:100 gm/kg 18WI Carcinogenic
Oral-dog LDLo:5,500 mg/kg
Intraperitoneal-dog LDLo:3,OOO mg/kg
Subcutaneous-dog LDLo:6,OOO mg/kg
Intravenous-dog LDLo:1,600 mg/kg
Oral-cat LDLo:6,OOO mg/kg
Intravenous-cat LDLo:3,945 mg/kg
Ora 1- rabbi t LD50:6,300 mg/kg
Skin-rabbit LDLO:20 gm/kg
Intravenous-rabbit LDLO:5,OOO mg/kg
Oral-guinea pig LD50:5,560 mg/kg
Intraperitoneal-guinea LDLo:4,OOO mg/kg
pig
Subcutaneous-frog LDLo:7,100 mg/kg
Ethylene, Tetra- C2C14 d Inh~lation-human TCLo:200 ppm Systemic OSHA std (air):
127-18-4 TLm96:100-10 ppm
chloro- (Tetra- Oral-human LDLo:500 mg/kg TWA 100 ppm;
chloroethene) Inhalation-man TCLo:280 ppm 2H Eye C1200;
Effects PK 300/5M/3H
Inhalation-man TCLo:600 ppm 10M Central
Nervous NIOSH recm std (air):
Sys tern TWA 50 ppm;
Cl 100 ppm/15M
Inhalation-rat LCLo:4,OOO ppm 4H +::0
Oral mouse LD50:8,850 mg/kg <..T1
Inhalation-mouse LCLo:23,OOO mg/m3 2H
-------
Table 14 (Cont' d.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Compound Name
Molecular
Formula
Chemical
Abstracts
Service No. Aquatic Toxicitya
Route of
Entry
Species
Other Toxicity Datab
Type of
Dose
Duration
Effectse
Exposur~
Limits
Ethylene, Trichloro- C2HC13
(Trichloroethene)
l-hexanol, 2-ethyl- CSH1SO
Isopropyl Alcohol
(Isopropanol)
C3HsO
79-01-6d TLm96:1000-100
ppm
104-76-7
67-63-0
TLm 96:1000-100
ppm
Intraperitoneal-mouse
Oral-dog
Intraperitoneal-dog
Intravenous-dog
Ora l-cat
Oral-rabbit
Subcutaneous-rabbit
Oral-human
Inhalation-human
Inhalation-human
Inhalation-man
Oral-rat
Inhalation-rat
Oral-mouse
Inhalation-mouse
Intravenous-mouse
Oral-dog
Intraperitoneal-dog
Intravenous-dog
Subcutaneous-rabbit
Oral-cat
Inhalation-cat
Inhalation-guinea pig
Oral-rat
, Ora l-mouse
Skin-rabbit
Inhalation-human
Ora'l-rat
Ora l-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Intravenous-dog
Intravenous-cat
Oral-rabbit
Skin-rabbit
Intravenous-rabbit
Subcutaneous-mammal
LD50:5,671 mg/kg
LDLo:4,000 mg/kg
LD50:2,100 mg/kg
LDLo:85 mg/kg
LDLo:4,OOO mg/kg
LDLo:5,OOO mg/kg
LDLo:2,OOO mg/kg
LDLo:250 mg/kg
TCLo:6,900 mg/m3
TCLo:160 ppm
TCLo:110 ppm
LD50:4,920 mg/kg
LCLo:8,000 ppm
TDLo:135 gm/kg
LC50:3,OOO ppm
LD50:34 mg/kg
LDLo:5,860 mg/kg
LD50:1,900 mg/kg
LDLO:150 mg/kg
LDLo:1,800 mg/kg
LDLo:5,864 mg/kg
LCLo:32,500 mg/m3
LCLo:37,200 ppm
LD50:3,200 mg/kg
LDLo:3,200 mg/kg
LD50:2,380 mg/kg
TCLo:400 ppm
LD50:5,840 mg/kg
LDLo:192 mg/kg
LD50:933 mg/kg
LDLo:6,000 mg/kg
LD50:6,150 mg/kg
LDLo:5,120 mg/kg
LDLo:l,963 mg/kg
LDLo:5,OOO mg/kg
LD50:16 mg/kg
LDLo:8,230 mg/kg
LDLo: 6 mg/kg
OSHA std (air):
10M Central TWA 100 ppm;
Nervous Cl 200;
System PK 300/5M/20
83M Central
Nervous
System
8H Irritant NIOSH recm std
(air): TWA 100
4H 150/10M ppmj
27WI Carcinogenic
2H PK llO/10m
2H
40M
Irritant
TLV (air):
400 ppm (skin)
OSHA std (air):
TWA 400 ppm
.:::-
0'\
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CD.
Compound Name
Molecular
Formula
Chemical
Abstracts
Service No. Aquatic Toxicitya
Route of
Entry
Species
Other Toxicity Datab
Type of
Dose
Duration
Effectse
Exposur!:
Umi ts
Methane, Dichloro- CH2C12
(Methylene Chloride)
N i c ke 1
Ni
Pentadecane, 2,6,10, C19H40
14,-tetramethyl-
(Pristane)
3-pentanone
(diethyl ketone)
CSHIOO
75-09-2d Tlm96:1,000-100
ppm
Inhalation-human
Oral-human
Inhalation-human
Oral-rat
Inhalation-mouse
Intraperitoneal-mouse
Subcutaneous-mouse
Oral-dog
Inhalation-dog
Intraperitoneal-dog
SUbcutaneous-dog
Intravenous-dog
Ora 1- rabbi t
Subcutaneous-rabbit
Inhalation-guinea pig
7440-02-0d
Inhalation-rat
Subcutaneous-rat
Intramuscular-rat
Intramuscular-rat
Intrapleural-rat
Parenteral-rat
Intratracheal-rat
Implant-rat
Intraperitoneal-mouse
Intravenous-mouse
Intravenous-dog
Implant-rabbit
. Oral-guinea pig
Inhalation-guinea pig
Intramuscular-hamster
Intraperitoneal-mouse
1921-70-6
96-22-0
Tlm96:1000-100
ppm
Ora 1- rat
Inhalation-rat
Intraperitoneal-rat
TClo:500 ppm
lDlo:500 mg/kg
TClo:500 ppm
lD50:945 mg/kg
lC50:14,400 ppm
lD50:1,500 mg/kg
lD50:6,460 mg/kg
lDlo:3,000 mg/kg
lClo:20,OOO ppm
lDlo:950 mg/kg
lDlo:2,700 mg/kg
lDlo: 200 mg/kg
lDlo:l,900 mg/kg
lDlo:2,700 mg/kg
lClo:5,000 ppm
TClo:15 mg/m3
TDlo:15 mg/kg
lDlo: 25 mg/kg
TDlo:l,OOO mg/kg
TDlo:l,250 mg/kg
TDlo:40 mg/kg
lDlo:12 mg/kg
TDlo:250 mg/kg
lD50:12 mg/kg
lDlo:50 mg/kg
lDlo: 10 mg/kg
TDlo:165 mg/kg
lDlo:5 mg/kg
TClo:15 mg/m3
TDlo:208 mg/kg
TDlo:1,300 mg/kg
lD50:2,140 mg/kg
lClo:8,OOO ppm
lDlo:1,250 mg/kg
lYI
OSHA std (air):
TWA 500 ppm; Cl
1,000; Pk 2,000/5M/2H
Central
Nervous
System
8H
7H
NIOSH recm std (air):
TWA 75 ppm;
Pk 500/15M
Blood
7H
2H
Carcinogenic OSHA std (air):
6WI Neoplastic TWA 1 mg/m3 (skin)
17WI Carcinogenic
22 WI Neoplastic
56WI Carcinogenic
Carcinogenic
2YI Neoplastic
91WI Carcinogenic
22W Carcinogenic
13WI Neoplastic
4H
~
.......,
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Chemical Other Toxicity Datab
Compound Name Molecular Abstracts Route of Type of Effectse . Exposur~
Formula Service No. Aquatic Toxicitya Entry Species Dose Duration Limits
Propane, 1,2- C3H6C12 78-87-Sd TLm96:100-10 ppm Oral-human LDLo:SO mg/kg
Dichloro- Oral-rat LDSO:1,900 mg/kg OSHA std (air):
Inhalation-rat LCLo:2,OOO ppm 4H TWA 7S ppm
Oral-mouse LDSO: 860 mg/kg
Oral-dog LDLo:S,OOO mg/kg
Skin-rabbit LDSO:8,7S0 mg/kg
Oral-guinea pig LDSO:2,OOO mg/kg
Propanen i tril e, C4H7N 78-82-0 Oral-rat LDSO:102 mg/kg
2-methyl- Inhalation-rat LCLo:1,OOO ppm 4H
(Isobutyronitrile) Skin-rabbit LDSO: 310 mg/kg
Subcutaneous-rabbit LDLo: 9 mg/kg
Subcutaneous-frog LDLo:4,800 mg/kg
Styrene CaHa 100-42-S TLm96:100-10 ppm Oral-human LDLo:SOO mg/kg TLV (air):
Inhalation-human LCLo:10,OOO ppm 30M 100 ppm
Inhalation-human TCLo:600 ppm Irritant OSHA std (air):
Inhalation-human TCLo:376 ppm Central TWA 100 ppmj
Nervous Cl 200j
System PK 600/SM/3H
Oral-rat LDSO:S,OOO mg/kg
Inhalation-rat LCLo:S,OOO ppm 8H
Oral-mouse LDSO:316 mg/kg
Inhalation-guinea pig LCLo:12 gm/m3 14H
Toluene C7Ha d Oral-human LDLo:SO mg/kg
108-88-3 TLm96:100-10 ppm
Inhalation-human TCLo:200 ppm Central OSHA std (air):
Nervous TWA 200 ppmj
System Cl 300j Pk SOO/10M
Inhalation-man TCLo:100 ppm Psycho- NIOSH recm std (air):
tropic TWA 100 ppm; Cl
Oral-rat LDSO:S,OOO mg/kg 200/10M
Inhalation-rat LCLo:4,OOO ppm 4H
Intraperitoneal-rat LDLo:800 mg/kg
In~alation-mouse LCSO:S,320 ppm 8H
Skin-rabbit LD50: 14 gm/kg
SUbcutaneous-frog LDLo:920 mg/kg
Zinc Zn 7440-66-6d Intraperitoneal-mouse LDSO:1S mg/kg
~
00
-------
Table 14 (Cont'd.)
TOXICITY OF ORGANIC COMPOUNDS
SOUTH CHARLESTON SEWAGE TREATMENT CO.
Abbreviations
(per Registry of Toxic Effects of Chemical
Substances - NIOSH - 1977 Edition)
Compound Name
Molecular
Formula
Chemical
Abstracts
Service No. Aquatic Toxicitya
Route of
Entry
Species
Other Toxicity Datab
Type of
Dose
Duration
Effectse
Exposur~
Limits
a Aquatic Toxicity: Tlm96 - 96-hour static or continuous flow standard protocol, in parts per millon (ppm).
b Other Toxicity Data: LD50 - lethal dose 50% kill
lOlo - lowest published lethal concentration
lC50 - lethal concentration 50% kill
LDlo - lowest published lethal dose
TOlo - lowest published toxic dose
TClo - Lowest published toxic concentration
TO - toxic dose
M - minute; H-hour; D-dayj W-weekj V-year
C - continuous
I - intermittent
NR - not reported
NIOSH - National Institute for Occupational Safety and Health
OSHA - Occupational Safety and Health Act of 1970
TWA - time-weighted average concentration
TLV - threshold limit value
Cl - ceiling
Pk - peak concentration
d' This chemical has been selected for priority attention as point source water-effluent discharge toxic pollutant (NRDC vs Train consent decree).
e Blood - Blood effects; effect on all blood elements, electrolytes, pH, protein, oxygen carrying or releasing capacity.
Carcinogenic - Carcinogenic effects; producing cancer, a cellular tumor the nature of which is fatal, or is associated with the formation
of secondary tumors (metastasis).
Central Nervous System - Includes effects such as headaches, tremor, drowsiness, convulsions, hypnosis, anesthesia.
Eye - Irritation, diplopia, cataracts, eye ground, blindness by affecting the eye or the optic nerve.
Gastrointentinal - diarrhea, constipation, ulceration.
Irritant - Any irritant effect on the skin, eye or mucous membrane.
Neoplastic - The production of tumors not clearly defined as carcinogenic.
Psychotropic - Exerting an effect upon the mind.
Systemic - Effects on the metabolic and excretory function of the liver or kidneys.
Teratogenic - Nontransmissible changes produced in the offspring.
c
Exposure limits:
"
~
~
-------
50
REFERENCES
1.
Ames, B.N., McCann, J., and Yamasaki, E., Methods for Detecting
Carcinogens and Mutagens with the Salmonella/Mammalian Microsome
Mutagenicity Test. Mutation Research, 31 (1975) 347-364.
2.
Commoner, B., Chemical Carcinogens in the Environment, Presentation
at the First Chemical Congress of the North American Continent,
Mexico City, Mexico, December, 1975.
3.
Commoner, B., Development of Methodology, Based on Bacterial
Mutagenesis and Hyperfine Labelling, For the Rapid Detection
and Identification of Synthetic Organic Carcinogens in Environmen-
tal Samples, Research Proposal Submitted to National Science
Foundation, Feb., 1976. .
4.
Commoner, B., Henry, J. I., Gold, J.C., Reading, M.J., Vithatil,
N.J., Reliability of Bacterial Mutagenesis Techniques to Distinguish
Carcinogenic and Non-carcinogenic Chemicals, Final Report to the
U.S. Environmental Protection Agency, EPA-600/1-76-022, Government
Printing Office, Washington, D.C., (April 1976).
5.
Hollander, A., ed., Chemical Mutagens, Principles and Methods
for Their Detection, Vol. 1, New York: Plenum Press, Chap. 9,
p. 267, 1971.
6.
on Microbial Assa
Procedures,
-------
APPENDIX A
CHAIN-OF-CUSTODY-PROCEDURES
-------
A-3
CHAIN-OF-CUSTODY PROCEDURES
(March 29, 1978)
Due t~ 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.
2.
It is in your actual possession, or
It is in your view, after being in your physical
possession, or
3.
/
It was in your physical possession and then you
locked it up 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.
-------
A-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 IICourier 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.
-------
A-5
3.
Whenever samples are split with a facility or government
agencYt 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 shipmentt and a copy will be re-
tained by the Project Coordinator.
5.
If sent by mailt the package will be registered with return
receipt requested. If sent by common carriert 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 airportt post officet etc. t 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.
-------
A-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.
-------
A-7
SAMPLE TAG
-'- ----
Proj. Code Station No. Sequence No. Mo.lDay/Yr. Time
Station Location Comp. Grab
o ENVIRONMENTAL PROTECTION AGENCY ~
/ P' , OFFICE OF ENFORCEMENT U1
. '... NATIONAL ENFORCEMENT INVESTIGATIONS CENTER C)
BUilDING 53, BOX 25227, DENVER FEDERAL CENTER ~
DENVER, COLORADO 80225
Samplers: (Signature)
'0- ~- -. ----.
... .
-
obverse
--
""""----- ---.- .
--. ----
Sample Type/Preservative(s)
1. General Inorganics/lce
2. Metals/HN03
3. Nutrients/H2SO. & Ice
4. Oil & Grease/H2S0. & Ice
5. PhenolicsjH.PO. & CuS04 & Ice
6. CyanidejNaOH & Ice
7. Organ ic 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. - Inorgc:nics/lce or Freeze
14. BioI. - Organics: Ice or Freeze
15. Source Filter/None
16. Probe Wash/None
17. III: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. BacteriologYI Ice .
23. Plankton/Formal; HgCI2; lugol's
24. Ch!orophylljlce or Freeze
25. PaUJOgenic Bacteria/Ice
26.
Remarks:
reverse
~GPO 777.941
-------
:::-
I
co
NATIONAL ENFORCEMENT INVESTIGATIONS CENTEI
Building 53. Box 25227. Denver Federal Center
Denver, Colorado 80225
ENVIRONMENTAL PROTECTION AGENCY
Office 01 Enlorcement
CHAIN OF CUSTODY RECORD
. .
Proj. No.
Project Name
SAMPLE TYPE
c
I D ~
:J .~ :J:J .- 11 D ;; ;;
.~ u 'c'c :i 'c .- n £ ... ~ g' ~
~ D ~~~ ~~~~~~~~f~ ~ _m
o ::) ~~... o...ocg-:;u'-oE ~ >.~
~ ~!~GO~~ ~'.~~g~~~~~i~~gt~
III " ., CJ 0 '0 .u - ... ... ... '" - CD G en ., oil( ., 0 ... .. 0 os
~i~~~li~~B~~~~~Di~~~~~~5!
~~~6f~o~~~~~~~~~~~~~~~f6:
~NM~~W~G~g~~~~~~~~~~~~~~~~~re
SAMPLERS: (Signa Iura}
en
rr ffi
w z
CDu.-
::;00{
~ ...
z z
o
u
STA. NO. SEO. NO. DATE
STATION LOCATION
TIME
Remarks
I
I
I
TOTAL NO. OF CONTAINERS
. Relinquished by; (Slgnatura)
Datefime
Daterlme
. Daterme
Received by; (Signatura)
Relinquished by; (Signa/ura)
Dateflme Received by; (Signatura)
Date/Time Received by Courier
"I " (Signatura)
Date/Time Received by Courier
." (Signatura)
Received lor Laboratory by:
(Signatura) ,
-
Relinquished by; (Signa Iura}
Received by; (Signatura)
Relinquished by: (Signatura)
Relinquished by Courier
,Slgnalura)
Recejved by MO,bile Lab
(Signatura) ,
Relinquished by Mobile Lab
(Signatura)
Method 01 Shipment:
Shipped by: (Slgnatura)
Courier Irom Airport
(Slgnatura)
Date/Time
I
ouoo
,,",
, .
".,' .
. ".."
. .'
." .'
." "":"; ;"".:
p"" .
,. . '-' "" "
Distribution: Original Accompanies Shlpm~nt: Copy to Co~rdinator Field Flies'
.'
-------
APPENDIX B
LITHIUM FLOW VERIFICATION PROCEDURES
AND SAMPLING PROCEDURES
-------
B-3
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:
,.
l~ . A conservative tracer.
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%.
2.
Metering the injected tracer solution with low flow
rate, high precision pumps.
During verification,
injection rate was checked at least ~/ice with a
graduated cylinder and stop watch.
-------
B-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 e~ch 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-
. toringthe diluted Li tracer on the discharge side.
Flow was calculated with the following equation:
Q= q Cq F
. . C-C
b
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-llter
-------
8-5 .
SAMPLING PROCEDURES
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 collection p~riodchemical preservatives were
added to the sample container prior to the start of the
'.
collection period.
Each of the sample aliquots were chemically
preserved upon collection.
At the end of the sampling period,
the chemically unpreserved po~tionof the samp1e 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
.
11'\
laboratory~Denver, Colorado.
Grab samples wey€ handled as discussed above with the
exception that the sample consisted of a single aliquot rather
than multiple samplings.
'.
-------
APPENDIX C
ANALYTICAL METHODS AND QUALITY CONTROL
/.
-------
C-3
CHEMISTRY ANALYTICAL METHODOLOGY AND QUALITY CONTROL
The analytical procedures used by the Chemistry Branch are described
in the following sections which are organized by working groups Inorganics)
Organics) and Trace Metals. The quality control procedures and data
used to verify the quality of the analytical data are also discussed.
INORGANICS
The samples from this study were analyzed for the following
inorganic parameters - BOD) TSS) COD) 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.
Parameter
Technique
Detection Limit)
mg/l
Reference
BOD
COD
TSS
NH3
Phenolics
TKN
Multiple bottle dilution
Dichromate reflux titration
Glass fiber filter filtration
Automated phenolate
4-AAP chlorimetric
Kjeldahl digestion)
Automated phenolate
Mercuric nitrate
2
5
1
0.05
0.001
0.2
1
Std. Methods) pg. 543
Std. Methods) pg. 550
Std. Methods) pg. 94
Std. Methods) pg. 616
Std: Methods) pg. 574
EPA -Manual) pg. 175
Std. Methods) pg. 616
Std. Methods) pg. 304
Chloride
Std. Methods - "Standard Methods for the Examination of Water and Wastewater",
14th edition (1975).
EPA Manual - "Methods for Chemical Analysis of Water and Wastes ") 1974.
Written methods prepared from "Standard Methodsll for BOD and TSS are
included as Attachments I & II. Additional precautions taken during the
analysis of the samples are discussed below by parameter.
BOD
The dissolved oxygen meter was calibrated by the azide modification
of the Winkler method ("Standard Methodsll) 14 edition) 1975) pg 443) to
assur~ accurate D.O. Measurements. Samples were seeded with seed material
that was acclimated to the specific waste being studied. The D.O. deple-
tions were normal for all dilutions of all samples.
-------
C-4
Quality control consisted of duplicate analysis of seven samples
and analysis of EPA reference sample #276-2 on six different days.
Additional quality control procedures are described in Attachment I.
Since two duplicate samples did not have valid dilutions, the precision
was calculated from five sets of data. The relative standard deviation
of the duplicate results is 25%. One reference sample result was
invalid because of'improper preparation. The mean accuracy of the
five valid reference sample results is 94.5%.
TSS
The analytical and quality control procedures described in Attachment
II were closely followed. The relative standard deviation of five
duplicate determinations is 3%. The mean accuracy of analysis of a
standard reference sample on four different days was 105%.
COD
All samples above and below 100 mg/l were analyzed using the high
and low level reagents, respectively. Four samples were analyzed in
duplicate with a mean RSD of 0.4%. Three samples were spiked with a
mean recovery of 107%. Two reference samples were analyzed with a
mean accuracy of 98%.
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
Two auto-analyzer method was adapted to 0-30 mg/l full scale by
adding a dilution loop onto the front end of the manifold. Two refer-
ence 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 RSD of the two pairs of data is 1.6%.
Phenolics
All absorbances were measured against a chloroform blank. Three
samples were spiked with a mean recovery of 98%. One reference sample
was analyzed with 92% accuracy.
-------
C-5
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 reference
sample was analyzed five times with 92% accuracy.
Metals
The samples from this study were analyzed for the following
metals: Al, As, Cd, Cr, Cu, Ni, Pb, Sn, and Zn. The samples consisted
of water samples, a primary domestic sludge sample, and an industrial
grit sample. Methods approved by the EPA for the NPDES program (40
CFR 136, Federal Register, December 1, 1976) were used in the analysis
of all water samples. The preparation techniques for the domestic
sludge sample and the industrial grit sample for all metals except
arsenic are based on that described in the Chemistry Laboratory Manual -
Bottom Sediments of the Great Lakes Region Committee on Analytical
Methods, 1969. The preparation and analysis techniques for the domestic
sludge sample and the industrial grit sample for arsenic were performed
using approved methods listed in the Federal Register of December 1,
1976 (40 CFR 136). The references to the methods used in the analysis
of the water samples for each metal and the detection limits for each
metal are listed in Table 1. The references to the methods used in
the analysis of the primary domestic sludge sample and the industrial
grit sample for each metal and the detection limits for each metal are
listed in Table 2. The detection limits in Table 1 for the water
samples are reported in units of milligrams per liter. The detection
limits in Table 2 for the primary domestic sludge sample and the
industrial grit sample are reported in units of micrograms per gram.
The detection limits in Table 2 assume a one gram dry weTght of sedi-
ment and a 100 ml digestion volume.
The methods listed in Tables 1 and 2 for each element were closely
followed. There were no significant deviations from the approved
methods. As an added precaution, all analyses were performed using
background correction procedures in order to preclude extraneous
signals from the sample matrix.
Water Samples
Aluminum: Sample replicates and spikes were analyzed for aluminum.
Only one sample replicate contained a detectable quantity of aluminum.
This replicate agreed with the original sample within 17%. The recoveries
for the sample spikes ranged from 80% to 100% with an average recovery
of 87%. This represents a slight negative bias in the aluminum results.
The EPA reference standard #3, lot 575, was analyzed. The experimental
value,was 0.9 mg/l while the true value was 0.904 mg/l aluminum.
Arsenic: Sample replicates and spikes were analyzed for arsenic.
Only one sample replicate contained a detectable quantity of arsenic.
This replicate agreed with the original sample within 12%. The recover-
ies for the sample spikes ranged from 110% to 150%, with an average
-------
C-6
recovery of 130%. This represents a positive bias in the arsenic
results. The EPA reference standards #2 and #3, lot 575, were analy-
zed. The experimental values were 0.11 and 0.16 mg/L, while the true
values wre 0.109 and 0.154 mg/l arsenic respectively.
Cadmium: Sample replicates and spikes were analyzed for cadmium.
None of the sample replicates contained detecta9le quantitites of
cadmium. The recoveries for the sample spikes ranged from 104 to
110%, with an average recovery of 106%. The EPA reference standard
#3, lot 575, was analyzed. The experimental value was 0.06 mg/L,
while the true value was 0.073 mg/l cadmium.
Chromium: Sample replicates and spikes were analyzed for chro-
mium. None of the sample replicates contained detectable quantities
of chromium. The recoveries for the sample spikes ranged from 102% to
104% with an average recovery of 103%. The EPA reference standard #3,
lot 575, was analyzed. The experimental value was 0.2 mg/l, while the
true value was 0.204 mg/l chromium.
Copper: Sample replicates and spikes were analyzed for copper.
Only one sample replicate contained a detectable quantity of copper.
This replicate agreed with the original sample within 26%. This
represents a difference in concentration of only 0.03 mg/l. The
recoveries for the sample spikes ranged from 96% to 104% with an
average recovery of 99%. The EPA reference standard #3, lot 575, was
analyzed. The experimental value was 0.1 mg/l, while the true value
was 0.102 mg/l copper.
Nickel: Sample replicates and spikes were analyzed for nickel.
The replicate results varied from 3% to 35% relative percent difference.
The 35% difference represents a concentration difference'-of only 0.03
mg/l. The recoveries for the sample spikes ranged from 102 to 110%
with an average recovery of 107%. The EPA reference standard #3, lot
575, was analyzed. The experimental value was 0.21 mg/l, while the
true value was 0.152 mg/l nickel.
Lead: Sample replicates and spikes were analyzed for lead. None
of the sample replicates contained detectable quantities of lead. The
recoveries for the sample spikes ranged from 92% to 134% with an
average recovery of 113%. This represents a slight positive bias in
the lead results. The EPA reference standard #3, lot 575, was analyzed.
The experimental value was 0.45 mg/l, while the true value was 0.352
mg/l lead.
Tin: Sample replicates and spikes'were analyzed for tin. None
of the sample replicates contained detectable quantities of tin. The
recoveries for the sample spikes ranged from 58 to 90% with a mean
recovery of 74%. This represents a negative bias in the determination
of tin. This is not surprising since tin is known to be unstable in
solution. The EPA reference standard #3, lot 575, does not contain
tin. Therefore, no AQC data is available for tin.
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C-7
Zinc: Sample replicates and spikes were analyzed for zinc. The
relative percent difference for the zinc replicates ranged from 0% to
29%. The 29% relative percent difference represents a concentration
difference of only 0.015 mg/l. The recoveries for the sample spikes
ranged from 152% to 168% with an average recovery of 159%. This
represents a positive bias in the zinc results. Laboratory contamina-
tion of the zinc spikes was investigated by determining the zinc
concentration of laboratory reagent blanks using the same acid that
was used to preserve the samples in the field. The laboratory reagent
blanks were found to contain no zinc. The EPA reference standard #3,
lot 575, was analyzed for zinc. The experimental value was 0.17 mg/l,
while the true value was 0.174 mg/l zinc. The fact that the experimen-
tal results for EPA reference standard #3, lot 575, were in good
agreement with the true value provided by the Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio, together with the fact that
the reagent blank contained no zinc, indicates that the water samples
were inadvertently spiked at a higher level than that which was expected.
The average value of the field blanks was 0.04 mg/l zinc. Sample
results having this approximate concentration are questionable.
Sediment Samples
Triplicate analyses for each metal contained in each of the two
sediment samples were performed.
Sludge: This sample contains all of the metals analyzed except
cadmium and tin at detectable concentrations. Aluminum is present at
a high level. Zinc, mercury, and lead are present at concentrations
which merit attention.
Sample replicates were analyzed for all metals. Th~ relative
standard deviation for the three replicates is listed for each metal
in Table 3. The relative standard deviations (RSD's) range from 5% to
29%. The high RSD for nickel is a result of the randomness introduced
in sampling plus the low precision due to the relatively low nickel
concentration (31 ~g/g) found in the sludge sample.
Grit: This sample contains all the
cadmium. Aluminum and nickel were found
Chromium, copper, mercury, lead and zinc
which merit attention.
metals analyzed except tin and
in high concentrations.
are present at concentrations
Sample replicates were analyzed for all metals. The relative
standard deviation for the three replicates is listed for each metal
in Table 3. The relative standard deviations range from 2% to 20%.
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C-8
Table 1
ANALYTICAL METHODS AND DETECTION LIMITS - WATER SAMPLES
Detection Limit,
Metal Technique mg/l Referencel
Al Flame Atomic Absorption 0.3 A, p. 92
As Flameless Atomic Absorption 0.002 B
Cd Flame Atomic Absorption . 0.03 A, p. 101
Cr Flame Atomic Absorption 0.04 A, p. 105
Cu Flame Atomic Absorption 0.04 A, p. 108
Ni Flame Atomic Absorption 0.06 A, p. 141
Pb Flame Atomic Absorption 0.2 A, p. 112
Sn Flame Atom~c Absorption 1.0 A, p. 150
Zn Flame Atomic Absorption 0.01 A, p. 155
lA - Methods for Chemical Anal sis of Water and Wastes, U.S. Environmental
Protection Agency, (1974 .
B - Atomic Absorption Newsletter, 14, 109 (1975).
Table 2
ANALYTICAL METHODS AND DETECTION LIMITS - PRIMARY DOMESTIC SLUDGE
SAMPLE AND INDUSTRIAL GRIT SAMPLE
Detect ion Li mit,
Element Technique (~g/g) Referencel
Al Flame Atomic Absorption 18 A; B, p. 92
As Flameless Atomic Absorption 0.3 C
Cd Flame Atomic Absorption 4 A;B, p. 101
Cr Flame Atomic Absorption 2 A;B, p. 105
Cu Flame Atomic Absorption 3 A;B, p. 108
Hg Flameless Atomic Absorption 0.01 A;B, p. 134
Ni Flame Atomic Absorption 6 A;B, p. 141
Pb Flame Atomic Absorption 55 A;B, p. 112
Sn Flame Atomic Absorption 200 A;B, p. 150
Zn Flame Atomic Absorption 2 A;B, p. 155
lA - Chemistry Laboratory Manual - Bottom Sediments, Great Lakes Region
Committee on Analytical Methods, U.S. EPA, Federal Water Quality
Administration, (December 1969).
B - Methods for Chemical Analysis of Water and Wastes, U.S. EPA (1974).
C - Absorption Newsletter, 14, 109 (1975).
-------
C-9
Table 3
RELATIVE STANDARD DEVIATION (%) FOR TRIPLICATE ANALYSIS OF
SLUDGE AND GRIT SAMPLES
Element Sludge Sample Grit Sample
Al 14 20
As 20 9
Cd N.D.! N.D.!
Cr 12 7
Cu 10 17
Hg 12 8
Ni 29 2
Pb 17 7
Sn N.D.! N.D.!
Zn 5 . 14
! N.D. - Not detectable.
ORGANICS
Several techniques for the analysis of organic compounds were
utilized for. the waste source evaluation, Union Carbide facilities and
South Charleston WWTP Survey. Identification of individual 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, volatiles, and selected samples were analyzed
for priority pollutants. Other samples, notably nonpurgeables, were
analyzed by direct aqueous injection analysis (DAI). Carbaryl was
analyzed by high pressure liquid chromatography (HPLC).
NEUTRAL EXTRACTABLE ANALYSIS
GC/MS Identification: Methylene chloride extracts of the water,
and acetone extracts of the sediment samples were concentrated to
small volumes and exchanged with isooctane and analyzed by GC/MS. The
initial identification was made using a manual search utilizing reference
spectra analyzed under the same instrumental conditions used for the
samples.
A library of standard spectra of the commonly occurring compounds
was made using a computer assisted evaluation program.! In those
instances where other than the commonly occurring compounds appeared,
a more complete search was made utilizing the complete computer library
and a follow up manual search.2.3'4.5
-------
C-10
Capillary Column Gas Chromatography: All the sample extracts
were analyzed by capillary column gas chromatography. Initial screen-
ing and quantitation were carried out on this gas chromatograph.
Compounds were identified by coincidence of retention times with
standards and quantitation was made using peak height measurement.
Packed Column Gas Chromatography: All the extracts were analyzed
by packed column gas chromatography using a computer controlled automatic
injector. Initial screening was carried out on this gas chromatograph.
REFERENCES
1.
"INCOS Data System - MSDS Operator's Manualt Revision 3".
Finnigan Instrumentst March 1978.
2.
"Eight Peak Index of Mass Spectra"t Mass Spectrometry Data
Centret Aldemastont Readingt UK. Second Edition 1974.
3.
"Registry of Mass Spectral Data"t Stenhagent Abrahamson and
McLaffertYt John Wiley & Sonst New York 1974.
4.
"Atlas of Mass Spectra Data" edited by: Stenhagent Abrahamson
and McLaffertYt John H. Wiley & Sonst New York 1969.
5.
Computer Assisted Evaluation of Organic Priority Pollutant
GC/MS Data - NEICt September 1978.
Quality Control: Quality control procedures consis~ed of analysis
of selected duplicate samplest analysis of solvent and procedure
blanks to identify interferencest and gas chromatographic analysis of
standards on a daily basis to confirm the integrity of the GC system.
For mass spectrometrYt a daily calibration was used to tune the mass
spectrometert and assure the integrity of the complete system. The
quality control procedures are documented in the attached methodologies
(Attachments 5t 6t 7t 8t 9t 10).
DIRECT AQUEOUS INJECTION ANALYSIS (DAI)
Selected samples were analyzed by DAI gas chromatography/mass
spectrometry (GC/M$). An aliquot of a sample is injected directly
into the inlet system of a gas chromatograph interfaced to a mass
spectrometer equipped with a computerized data system. GenerallYt low
boiling semi-volatile compounds that purge poorly are analyzed by this
method.
Quality Control: Blankst duplicate and spiked samples were
analyzed concurrently with the survey samples. None of the thirteen
selected DAI compounds were found in any of the three blank samples.
-------
C-ll
Five spiked samples representing eleven compounds were analyzed.
(One sample contained as many as three spiked compounds. Some compounds,
such as acetone were spiked into more than one sample). Of the eleven
discrete spikes the mean recovery was 116% with a Relative Standard
Deviation of 29%.
Two sets of replicates were analyzed with four compounds detected.
The average percent Relative Standard Deviation (% RSD) was 15. The
average percent difference of all sets of replicates was 22.
VOLATILES ANALYSIS
GC/MS Identification: An aliquot (5 ml) of a water samples was
purged with inert gas. The lower molecular weight purgable organic
compounds were stripped from the sample and trapped on a porous polymer.
These compounds were then desorbed from the column by reversing the
gas flow and rapidly heating the trap. The volatile organics released
were collected on an analytical GC column at room temperature. After
collection, the GC column oven was heated at a uniform rate and the
eluted compounds analyzed by the mass spectrometer. The common vola-
tile 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.!
The identification again was made using a computer assisted evaluation
program as for the neutral extractables.2 A library of standard
spectra was created by analyzing all the commonly occurring organics
in the Kanawha 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.
"Samples and Analysis Procedures for Screening of Industrial
Effluents for Priority Pollutants", u.S. EPA, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio, March
1977, revised April 1977.
2.
"INCOS Data System - MSDS Operator's Manual - Revision 3",
Finnigan Instruments, March 1978.
3.
Computer Assisted Evaluation of Organic Priority Pollutant
GC/MS Data - NEIC, September 1978.
-------
C-12
guality Control: Quality control procedures consisted of daily
routine calibration of the GC/MS, analysis of an organics free water
blank, and a standard mix at a concentration near midpoint of the
standard calibration curve. The calibration curve was previously
established by analyzing each standard over a typical working range of
20 to 200 ppb concentration, with response factors calculated relative
to an internal standard. Field blanks were analyzed with each set of ,
samples. Replicate analyses were run on at least two samples for every
set of twenty samples or less.
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 t 2 ~g/l.
Summary of blank results (~g/l)
Times Detn
Compound (15 samples) Range of Values Average
Methylene chloride 12 2-13 3 t 2
Toluene 2 2-5 nil
l,l,l-Trichloroethane 1 3 nil
Duplicates
Nine samples, six of them composites, were analyzed'_in duplicate. Ten
compounds of interest were determined in these analyses. The results are
summarized as follows:
Compound
Times Detn
(9 samples)
Deviation
Benzene
Bromodichloromethane
Carbon tetrachloride
Chloroform
1,2-Dichloroethane
Ethylbenzene
Methylene chloride
Tetrachloroethane
Toluene
1,1,I-Trichloroethane
2
1
1
6
1
1
6
1
2
1
t 8%
t 100%
t 50%
t 27%
t 20%
t 80%
t 45%
t 25%
t 48%
tl7%
-------
C-13
Recoveries
Four samples were spiked with standard mix to give each component
at a concentration of 200 ~g/l. Recoveries are listed below:
Compound
Percent Recovery
Benzene .
Bromodichloromethane
Bromoform
Carbon tetrachloride
Chlorobenzene
2-Chloroethylvinyl ether
Chloroform
Chlorodibromomethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-1,2-Dichloroethene
1,2-0ichloropropane
Ethylbenzene
Methylene chloride
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,~-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, Cincinnati,
was analyzed in triplicate. This QC sample, containing volatile organics,
was number 1276 WS.
-------
C-14
Analytical
Results Error
Compound ug/l IITruell Values %
Bromochloromethane (IS) 180 :t 20 200 10
Bromodichloromethane 13:t 2 12 8
Bromoform 13:t 1 14 8'
Carbon tetrachloride 9:t 1 13 31
Chloroform 60:t 7 68 12
Chlorodibromomethane 12:t 1 17 29
1,2-Dichloroethane 23:t 2 27 15
Tetrachloroethene 8:t 1 9 11
l,l,l-Trichloroethane 9:t 1 11 18
Trichloroethene 17:t 2 19 11
PRIORITY POLLUTANTS ANALYSIS
GC/MS Identification: Selected samples were analyzed for priority
pollutants by GC/MS using the recommended EPA procedure.! The volatiles
were measured using the same technique described previously for the volatiles
analysis, because both techniques are the same. The extractable organics
were analyzed for both acids, and neutrals, and bases combined as recommended. .
I
REFERENCES
'-
1.
IISampling and Analysis Procedures for Screening of Indus-
trial Effluents for Priority Pollutantsll, U.S. EPA, EMSL,
Cincinnati, Ohio, March 1977, revised April 1977.
2.
Computer Assisted Evaluation of Organic Priority Pollutant
GC/MS Data - NEIC, September 1978.
-------
".C-15 .
ATTACHMENT I
EIOCI!Ef.11 CAL OXYGEn DUil{/D - no PROBE PROCEDUP.E
(5 Days. 20oC)
STORET NO. 00310
1. . Scope and Application .
1.1 The biochemical oxygen demand test is a laboratory bioassay procedure
used'to estimate the quantity of oxyqen that is required to stabilize
. the biodeqradable matter in a wastewater.
1.2 The test ;las originally designed for and \'10rks most rel iably on ra\'/
and treated domestic wastes. The test can be applied to industrial
wastes .with careful attention to interferences and correct choice of
" bi~logical seed. . .
..
2.
Summary of ~ethod '. .
2.1 .An appropriate number of dilutions of each ~ample are prepared usinq
dilution water with added nutrients so that at least one dilution has
a depletion of at least 2 mg/l and a residual 00 of at least 1 mg/l .
after i ncuba ti on for 5 days in the dark at 21)0C. ' . :
2.2 'Dissolved oxygen is measured by a DO probe based On the polaro~raphic .
princip1e. The probe is calibrated \.rith air saturated \'tater at knm\'n
temperature and atffiospheri~ pressure.
3.
Sample Handlinq and Preservation'
3.( Samples should be stol"ed in ice or in,a refri!lerator at 'l0e andanalyz~d'
as soon as possible but no later than 24 hours after collection.
4.
ApPiu'atus
; -
. .
4.1 Glass or tin-lined stjll to produce distilled water.
4.2 Five gallon glass bottles wrapped with nylon tape to store dilution
water. ..
4.3 Incubation bottles, approximately 3~O m1, with standard ground qlass
tops and plastic caps to maintain water seals. The exact volume of
- each bottle is measured using water at 21)0C with class A volumetric
glassware and any that are not 300 + 5 ml are discarded.
4.4 An incubator with a continuous te~perature reco~der controlled at 2~0
+ lOCo A calibrated r:;ercur'y therr.:ol;]~tcr is. placed in the incubator
in a \'later-containing flask (!nd the temperature is checked daily.
4.5 A dissolved oxygen meter, autC':i1utically temperature co:npensated, if
possible, \'lith a self-stirring probe. .
4.6 A TC~:r.Iar SOT Tissue:lIizer \.tith variable 'speed control to homogenize
S,H'IP 1 es.
4.7 narof!let~r
-------
.,e, ..
'"
t:16 .'
, ,
5. ReJC)cnts
'.
, 5.1 Di s ti 11 ed \'la ter) free of orqani c contami nants as i nrli ca ted by t~~
Perman~}"::1ate Test as follm-/s:' Determine the conslImption of potassium
p:~rmannanate by adding 0.20 ml of Kr'1n04 solution (0.316 9/1) to 500 ml
or the distilled \-/ater and 1 ml of cone. H2S04 in a stoppered qlass '
bottle. The \'later has passed the test if the permanganate color does
not disappear l,'n less than 10 minutes upon standing at room temperature'l
Ideally, the color should be retained for 30 minutes. -
5.2' Phosphat~ buffer s6lution£ bissolve 8.5 q potassium di-hydroqen phos-
phate, KH2P04' 21.75 q dipotassium hydrogen phosphatc, K2HP04, 33.4 9
disodium hydrogen phosphate heptahydrate, NaZHP04.7HZO and 1.79 9
armlOnium chloride NH4Cl in about 500 ml distilled \'tater and dilute to ,
one liter. The pH of this buffer should be 7.2. Store in the refrif'jer-
ator and discard (including any of the follO\'ling reagents) .if there is
any sign of biological growth in the bottle.
5.3 Magnesium sulfate solution: Dissolve 22.5 9 MgS04'7H20.in distilled
water and dilute to one liter.
5.4 Calcium chloride solution: Dissolve 27.5 g anhydrous CaC12 in distilled
water and dilute to one liter. , -
5.5 Fe}'ric chloride solution: Dissolve 0.25 9 FeC13'6HZO in distilled \'/ater
and dilute to one liter.
5.6 1 N H2S04 and 1 NNaOH solutions.
5.7 Sodium sulfite solution, 0.028 N: Dissolve 1.77 9 anhydrous Na2S03 in
one lite~ distilled water. Prepare daily.
5.8 ~cagent grade potassium iodide., '
5.9 Starch indicator solution: Add a cold water suspension of 59 q soluble
starch to 800 ml of boiling water, \'lith stirring and boil for a few
minutes. Cool. dilute to approximately 1 liter and let settleover~
night. Use supernate and preserve \'lith 5 ml of chloroform.
5.10 Glucose-glutamic acid solutions: A) Dissolve 150 mg,~f each in dis-
tilled water and dilute to 1 litet~. B) Dissolve 100 mq 'of each in
distilled water and dilute to 1 liter. Split up each solution into 25 ml
bottles or tube. autoclave at 12loC for 1/2 hour, and store at 40C or
prepare fresh daily. .
5.11 Biological seed. '
6.
Glassware and Dilution Watcr Preparation
6.1 All dilution water and reagent storage bottles, BOn incubation battles,
and other ~lassware must be free of orq~nic contaminants and toxic
rr.etals. Ciean all qlass~'/are \-lith hot sOupy \'/atel~) rinse with 3 N HC1.
rinse three times \'lith hot tap water and twice with distilled water.
Any qlussware \'lith a film should not be uspd.
6.2 The distilled water should be cooled to 206C, saturated \'lith oxyqen by
bubbling air through the I'lilter and then stoi'E:,d at 20°C until usc. Just
prior to using the dilution \'/iltel', add 1 ml each of the magnesium
sulfate, calcium chloride, ferric chlodde, and phosphate buffer solution
solutions for each liter of water. Th~ biolonical s~cd should be added
(5 ml seed!l of dilution \-/ater) to the dilution \-late}' just before, use.
-------
10.
.
". C-l 7
7.
Sc 1 ec ti on of Seed
7.1 AJ J chlm-inatcd domestic Hastes and most industrial \'/aste:s require
seeding because of low microbial populations. The standard seed
material is primary treated se\'/iHle that has been stored at 200C for
2/l hours. Hm./ever) it is ir.\portant that, if possible, the seed to
.be used has been exposed to the waste that is being measured. There-
fore, an effluent from a tr~atrn2nt process or a receiving water co1-
le~ted below the outfall will sometimes be used as seed rnate~ial.
8. .
Interferences and Pretreatr:lent of Samples . ".
8.1 Blend samples containing non-homogeneous particulate matter \~ith the
Tekmar" SOT Tissuemizcr, Thirty seconds is usually adequate. .
8.2 Neutralize samples \'/ith a pH outside of the range 5-10 using the 1 H
acid or base. Host samples do not require neutralization because the
. buffering capacity of the dilution \'/ater and dilution of the samplr:s. .
8.3 Residual chlorine kills the seed organisms, All samoles except those
known not to contain residual chlorine should be checked as follows:
Add 5 ml of 1 N H2S0i!) 2 9 KI crystals and 1 ml of starch solution
to lao ml of sample. ( Add the 0.028 N sodium sulfite solution in
'0.1 ml increments until the purple color disappears. Each 0.1 ml .
increme~t corresponds to 1 mg/l C12' Add a proportional volume of
0.028 " sodium sulfite to an ~liquot of sample for testing. If there
. is any uncertainty) add an extra increment of sulfite, An excess of
sulfite solution of 1 ml/l sa~ple causes a BOD of less than 0.5 mg/l)
which is insignificant.
8.4 ~any organic compounds and trace metals are toxic to the seed organisms.
So:;,2times this interference can be eliminated by snlliple dilution.
~igher BOD values from the more dilute aliquots is evidence of iample
tC1xicity. These results should be carefully evaluated before beinq
reported. . .
8.5 Samples containing more than 9 mg!l 00 at 200C may b~ encountered during
winter months or in localities where alqae are qrowinq actively. To
prevent loss of oxygen during incubation of these samples) reduce the
DO to saturation by bringing the sample to about 200C.in a partly filled
bottle and agitating it by vigorous shaking. . " .
9.
Calibration of Dissolved Oxygen Meter
9.1 Carefully fill 3 BOQ bottles by use of a siphon with dilution water
(containing nutrients but not seed) that has been saturated with air
at 20°C. Using the table lrlthe DO meter manuCll) find the DO conCCn-
tration at the ambient atmospheric pressure and 20°C. Set the tem-
perature dial on the meter if necessa}~ to 20°C and adjust the cali-
bration knob until the meter reads the value determined from the tahlc. .
Save the otJ;~t. t~.:o bottles for checkirHJ the rr.etel~ during the analysis
9.2 [1j'j ft i na of the metet' response or a ve~y s 10\"1 responsc to 00 chan~JQs
is usually caused by a coated or torn electrode membrane.
Samplc Analysis Procedure .
rb-:-i Since most samples rcq:.rirc r.l:}rc then 7 mg/l of 02 for stabilization.
dilutions are req~ired beforc incu~ation. Prepare a sufficient nU~~er
of dilutions SG that at least one aliquot d2plctes at lcost 2 ~g/l and
has a r'csicu~l 00 of at least 1 mq!l after incubation. Usually thrce
t:ncJ so::::::ti[!:~s four dilutions are requircd. Oilutions UP to l~.~ are
r:Jde directly in the GOO bottles. A ~uid~ to sC!l:l~le size selection
fa 11 O~'/S :
-------
I .
, .',I'
o ~':18
r':~asuruble 1300
'. -.
Rl1nge
Sample Size, ml
Fac tor
% Dilution
4 - 12
B - 21}
1? 36
20 - 60
40 - 120
60 - 180
120 360
200 - 600
150
75
50
30
15
10
5
3
2.
"
6 .
10
20
30
60
100
50
25
16.67
10
5
3.33
1.67
.1
. .
'.
For dilutions less than 1%j) the sample is first diluted 1/10 or
1/100 with diluiion water and then the dilutions are cOffiQletcd in
the BOD bottles. . The samples should be homogenized. and shaken just
before a1iquots are taken. A graduate cylinder is used to measure
volumes of 15 ml or larger. large bore pipets are used for smalle~
volumes. One bottle per'dilution is prepared. Exercise care in
filling the bottles with dilution water so as not to have the water
into the neck of the bottl e more than 1/8". ... .
10.2 Prepare two bottles with seeded dilution water; Depletion of these
samples should be about 0.6 mg/l if ~omestic sewage is used for seed.
Blank values over 1.0 mg/l indicates contaminated dilution water or
incubation bottles. . .
10.3 Prepare one bottle wit~ 5 ml of glucose-glutamic acid standard A and
one bottle with 10 ml of standard B and fill with seeded dilution
water. The results for standards A and B shou1d be about 200 and
160 mg/l~ respectively.. .
.. 10.4 Measure the initial DO of all .samples~ being careful not to displace.
any of the dilution water. At the sa~e time the DO is measured> the.
probe mixes the samples. Wash the probe with distilled water between
each sample. After determinin9 the DO it may be necessary to add a
small amount of dilution \'later to prevent trappinq bubbles in the
bottle when stoppering. Place a.water seal in the neck of the bottle
and place a cap over ~he neck to maintain the. water seal.
10.5 Itis helpful to measure the DO of the samples after two days in order
to .judge the adequacy of the dilutions selected.. Pour off the water
seal before measuring the DO. Calibrate the no meter accordinQ to the
directions given in Section 9. Measure the DO of the most concentrated
dilution of each sa~ple. If there is less than 2 mg/) r~sidual DO,
increase the dilution factor's o.n subsequent days and mecisure the 00 in
the next most dilute sample. If the DO on the second sample is lcss
than 4 mq/l, re-aerate with an air stone attached to an air pump bQing
careful not to displace any of the water. Record the initial residual
and re-aerated DO values. Discard any sample with a residual 00 below
1 mg/l.. If there is less than a 2 mg/l depletion~ increase th~ strenqth
of the dilutions on subsequ2nt days.
10.6 The final DO measurcr:Jents are made \.,ithin " hours of 5 days of \.,hen
. the samples \'icr'C set up. Calibl"ate the 00 meter by the mcthod qiven
in .S2Ct;C(1 9. Any ciiiutions resulting in residual DO's that a)"(~
1 mg/l or greater and depletions that arc 2 mg/l rir greater are valid.
Calculate the BOD values by the following formula:
-------
"-C-19
nODS = F[(Di-Of)-f(B)]
where 0i = initial 00 of sample. mg/l
Of = final 00 of samrle. mg/l
B = the mean depletion of the two seeded dilution water blanks.
. mg/l
f = decimJl fraction of dilution water in sample'oottle
F = whole number dilution factor of sample,
For exa~ple. 30,ml ~f sample was used. the iniiial DO was 8.2 mg/l
and the final DO was 1.7 mg/l. The initial DO of both of the seeded
blanks was 8.1 mg/l and the final 00 was 7.3 mg/l
BOOS = 10[(8.2-1.7)-0~9(8.1-7.3)]
= 10[6.5-0.9(0.8)]
- 10[6.5-0.7J
= 10[5.8] ,
= 58 rl!g/l
10.7 Report the averag~ value of all of the valid dilutions to the nearest
whale number 0ith at most two significant figures. If the 00 deple-
tions increa$e \./ith increasing dilution. toxicity is indicated and'
the r~sults should be carefully evaluated before. bei~9 r~ported,
10,8 The results of the A&B glucose-qlutamic acid standards should be be-
tv/cen 160-240 and 130:-190 IiIg/l,' respectively, High results indicate
a very efficient seed or contaminated samples,' LOi'1 results indicate
a poor seed or blank values that were too hiqh. '
10,9 The mean of the seeded dilution water blank depletions should be be- .
low 1 mq/l. ideally 0.6 mg/1. High-values indicate contaminated
nutrients and minerals. dilution \':ater 01' nlass\./are. Correct any
problems before proceedin9- .
10.10 Report the nOD',vi1lues from different dilutions as duplicates on the'
AGC sheets. .
10.11 Attach the incub3tor temperature recordel' chart to the [100 Data/
Calculation Sheet. (attached).
Prepared hy 11. Carter 6/9/78
-------
800 Oata/C~1cula~ion.~heet~ Rev, 6/9/78.
.
.~
.'- ~
Analyst.
Study
, .'
O~te/Ti~e In ~
Qutc/iime nut 0
~~-) e tlo. i I
'.:iln~: 1 c pH I
.:::..:':.:.1... ml I
.,)mp 1 ~ \'01,
nn:TI\o0 , mq!l I I
~-d~-y O()~~rJ(1 I
:C-ilCri1te 00, mg!l I
111, ilT1Yo~li1qrr
;roj_s~_~cP., mq!l '.
B1i)nk Co r)' ., rnq/l -.
:ct 0, cI c pi" ~\(j 11 -
FlIetor
l301js, r.1~/l
lelln lWDS' mq(l
;i1mr,1c No.
;
-------
C-21
ATTACHMENT II
TOTAL SUSPE~DED SOLIDS
STORET NO. 0f)S3f)
1.
Scope and Application
1.1 The method is applicable to drinking~ surface
and to domestic and industrial wastes.
1.2 The detection limit of the method i5 1 mg/l.
and saline waters.
2.
Summary of ~iethod
2.1 A homogenized sample is filtered through a pre-washed glass fiber
filter. The residue retained on the filter is washed and then dried.
to constant weight at 10SoC and weighed to the nearest 0.1 milligram.
The TSS is calculated from the amount of residue per unit volume of
sample.
. 2.2 The fi 1 trate from thi s method may be used to determi ne the tota 1
dissolved solids.
3.
Sample Handlinq and Preservation
3.1 Samples should be stored at 40C and analyzed as soon as possible,
. but no later than 7 days after collection. .
4.
Apparatus
4.1 Whatman GF/C glass fiber filter discs, 43 mn.
.4.2 Millipore membrane filtering apparatus with reservoir and a coarse
fritted disc as a filter support. .
4.3 Aluminum drying pans, 50 mm and metal tray.
4.4 Tekmar SOT Tissuemizer.
4.5 Drying oven~ 1030-1050C.
4.6 Desiccator~ with Drierite indicating desiccant.
.4.7 Analytical "balance, 160 g capacity or larger~ sens;'tive" to 0.1 mg
and one weight equivalent to the optical range of the balance.
4.8 Graduate cylinder and Nide bore pipets. .
Balance Calibration
5.1 Using a balance with an optical range of 1.0 q, place a 1.0 Q (15%)
weight on the balance pan, set the weight control knob to 1.0 g,
release the balance and set the zero point with the optical zero
knob. With the balance released, slowly turn the weight control
knob back to zero. The optical scale should come to rest exactly
at 1.0 g. If the reading is more or less. than 1.0 Q. arrest the
balance, remova the top housing cover and adjust the sensitivity
weight. Repeat the calibration check.
5.
6.
Procedure
6.1 Preparation of qlass fiber filter disc: Place the glass fiber fil-
ter en the membrane fil~er apparatus with wri~k~2d surface up.
While vacuum is applied, wash the disc with 100 ml of distilled
water. Remove all traces of water by continuing to apoly vacuum
after water has passed through. Remove filter from membrane filter
apparatus. place in aluminum pan, and dry in .an oven at If)3-lf)SoC
for one hour. Remove to desiccator and store until neerled. Wei~h
in~edi~~e1y before use. After weighinq~ handle the filter with"
forceps only.
-------
£...22
6.2 Homogenize all non-uniform samples with blender and shake the
bottles before withdrawinq an aliquot to assure taking a represen-
tative sample.
. 6.3 Choose a maximum sample volume that will filter in 5 minutes or less.
Measure volumes smaller than 15 ml with wide bore pipets and larger
volumes with graduate cylinders. Discard any sam~le which does not
fiiter in 5 minutes and filter a smaller sample. volume.
6.4 Wash the graduated cylinder or pipet ana with the suction on, wash
the filter funnel \'1 a 1 1 , filter and residue \'lith b'/O t\o/enty-five ml
portions 'of distilled water allowing complete drainaqe between
washings. Remove all traces of water by continuing to apply vacuum
after water has passed. through.
6.5 Carefully remove the filter from the filter support. Place in an
aluminum pan and dry at least one hour at 103-1050C. Cool and weigh
immediately or place in a desiccator for later weiqhing. Re-dry and
re-weigh 10% or at least one filter per set of sam~les. If the in-
cremental weight loss is less than 0.5 mg, calculate the results
based on the original weights. If the weight loss exceeds 0.5 m~,
re-dry and re-weigh all of the filters and re-check 10% of the filters.
6.6 Analyze two blanks per set of samples by filtering 100 ml of distilled
water through t\'lO prepared filters. The amount of additional weight
loss after the filters have been prepared is nearly independent of
the volume of water filtered. Therefore, add the mean blank weight
loss to the residue weight for each sample. .
6.7 Analyze 10% or at least one sample per set in duplicate.
6.8 Analyze a standard sample with each sample set.
6.9 Calculate the results as follows:
TSS = (WG - WT) + B
Vs
w~ = r,ross weight of filter ana residue, mg
'."1
WT = Tare weight of filter~ mg
B = The mean of the two blank results, mg
Where B = B1 + B2
2
Bl = BT - BG
BT = Tare \'ei qht of fil ter ~ mg
BG = Gross weight of filterin~
Vs = Volume of sample filtered, 1
-------
T~TA"'CUL_N ~.
6/883
An a 1 ys t Study Date/Time Fi 1 ters in Oven
Date/Time Out .
S~mple No. r
Sarno 1 e Vo 1 ., 1
~e - chec k "/t. mq
i,ross "It., O1q :
tare "/t., mg
Kesidue 1.lt., mq
Blank Carr., mq
~orr. Res. I~t., mg
T55, mql1
Samole No.
Sample Vo 1., 1 .
Re-check In., mq
Gross '.It., mg
Tare \'It., mg
~ e sid u e ~I t., mq .
;31ank Co rr., mq
~Corr. Res. \..It., mq
ITSS, mq/l
i
!Sample No.
ISarnp 1 e Vo 1 ., 1
IRe-check 1~t. , mq
\-~ r 0 S S ~I t., mg
Tore I'lt., mq - ..-.--
rSi due \oIt.. mg
... - .1. Corr 19
..)10;;'. ., m
~ofr. Res. \~t., mg
TSS, r.lql1
..
Tare
Gress
Re-check
n
I
N
W
-------
,,: C-2A'
ATTACHMENT II I
J\:1-::llysis of Organic Pollutants in Hat:..:!" by Direct
J"queous Injection, Gas Chromatog}~aphy-r,1ass Spectrometry
MEIC - September 1978
1.0
Int i'oduct i on
Ma:1Y volatile organic compounds are soluble in water at concentrations
exceeding 1 mg/l. However, they are not suitable for Volatile Organics
Analysis (V.O.A.) due to their lml purgeability. This method is
suitable for GC/MS identification, confirmation, and quantitation of
the previously mentioned types of compounds. '
2.0 Summa ry of r~ethod
1.1
2.1
3.0
A sample' is injected into the inlet system of a gas chromatograph.
After vaporization, the aqueous s~nple is carried through a column
by an inert carrier gas. The sample components are partitioned
betHeen the carrier gas and a stationa}'y 1 iquid phase on an inert
solid support. The column effluent is introduced into a quadrupole
mass spectrometer by means of a glass jet separator. From the'
interface, the sample is passed into an electron impact ionization
source. The vari ous' i on fragments are fi ltered by a quadrupol e
mass filter and detected by a continuous dynode electron multiplier.
The signal is then fed to a computer controlled data system for
processing. Compounds are matched with standard spectra stored,
in a library and identified based upon thei}~ spectral similarity,
and relative retention times. Concentrations are calculated for
each identified compound based upon its relative response to an
, internal standard.' '.
Interferences
3.1
" - Particulate or suspended matter should be
. both plugging of syringes and formation of con-
Allowing particulates to settle before analysis
3.2
Pa rt i cul ate me; '-.
removed to pr~ .
densation nuc~: '
is acceptable.
Stability - Aqueous solutions of D-chloroform (CDC13) are unstable.
The CDC13 can exchange to CHC13. '
Stock standards of deuterochloroform (7500 ng/ul) that are prepared
24 hours prior to dosing and analysis, display large losses in response.
Even stock standards prepared 8 hours prior to dosing ,:ld analysis,
exhibit some loss of response. Stock standards of D-cL I oro,fonTI a!~e
prepared in vials that have approximately two ml. head srace. Vola-
tility losses occur in this head space. No losses are c,~::;ervable if
the stock standard solution is refrigerated and used vii' ,;11 four
hours of preparation.
-------
C-25
Identical Retention Times - It is possible with any given 'column
and operating conditions, to have two compounds that elute at
identical retention times. It is especially important to choose
an internal standard that does not coelute with another compound
(j:- interest. This problem is minimized by using GC/i'1S.
3.3
4.0 Apparatus
4.1
Finnigan 3200 Gas Chromatograph/Mass Spectrometer System with a
Finnigan INCOS data system and Revision 3.1 soft\'lare (1).
. .
5.0 Reagents and Haterials
5. 1
Purity of Reagents - All chemicals used for standards and internal
standards shall be of the highest purity available.
5.2 Purity of Water - All water.shall be of sufficient purity such that
no background is observed above the detection limit of the compounds
of interest. Filtration through activated carbon will eliminate any
interferences.
5.3 Carrier Gas - Only high purity helium shall be used.
5 . 4 Co 1 umn .
5.4.1
Column Tubing - Stainless steel, oil free.
x 20 I.
Dim2nsions'1/811 00
5.4.2 Solid Support - Chromosorb W acid washed 80/100 mesh.
5.4.3 Liquid Pha~e - Carbowax 20m - 5% loading.
'.
Internal Standard - Dilute 50 ul of deuterochloroform to 10 ml with
water. Shake well to assure all D-chloroform is in solution. The'
concentration of this solution is 7500 ng/ul.
5.5
5.5.1
5.6 Standards
5.6.1
5.6.2
Prepare this solution fresh every four hours and keep refrigerated.
Concentrated Standards - Prepare stock standards of each
compound of interest by weighing out 50 mg of pure compound
and diluting this with water to a volume of 50 ml. Stability
of stock solutions is enhanced by keeping the solutiuns
refrigerated. Stock solutions should be prepared fresh every
two \'Jeeks.
Analytical Standards for GC/MS - Dilute the concentrated
standards by adding 0.5 ml of each concentrate to a 12 ml
vial and bringing the volume to 10 ml. This working standard
should be prepared each day. Each ul of working standard is
equal to 50 ng (50 ng/ul).
-------
C-26
5.7 Masi Spectrometer Performance Standard - Prepare a 150 ng/ul
aqueous solution of Pentafluorobromobenzene and refrigerate until
ready for use. This solution is stable for one month.
6.0 Samples and Sampling Procedure
Sample Collection - Samples should be collected so that no air
remains in the bottle as a head space once the vial cap is tightened.
.6.2 Sample ContQiners - 1 oz. glass bottles equipped with Teflon lined
silicone septa and screw caps (Pierce #13074 and #12722 or equivalent).
Before sampling, wash used bottles with soap (Alconox or equivalent) . .
.andtap water, .rinse with tap water. New bottles require only washing
with tap water. Bake bottles at 2000e and septa at BOoe for 30 minutes.
Allow to cool in a desicator with charcoal adsorbant to maintain an
organics free atmosphere. Then cap the bottles and hold for sampling.
~ . 1
6.3 Sample Size for Analyses - The sample size must be small to prevent
(I'Jerloading of the column. . For aqueous analysis, a sample size of
5 ul is optimum.
6.4 Sample Storage - Storage time of samples should be kept to a minin1um.
If storilge cannot be avoided, the bacterial action, as well as vola-.
ti 1 ity .1 osses, shoul d be minimized by refri geration (2).
7.0 Procedure
7.1
Mass Spectrometer Calibration
7.1~lAdjust and calibrate the mass spectrometer according to the
manufacturers specifications.
,
7.1.2 Analyze a sample of pentafluorobromobenzene (PFBB).
7.1.3 Determine if the PFBB spectrum meets the performance criteria (3)
(Attachment 1). Proceed to analyses if it does or retune the
instrument to meet the performance criteria.
7.1.4
Analyze a standard mix of the compounds of interest and determine
if the response is \'/ithin an acceptable range of the pr--2viously.
established response factors. If not, determine the cause of
the problem, make the necessary corrections and reanalyze the
standa rd.
7.2 Sample Analysis
7.2.1
Equilib:" .2 the sample bottles to ambient temperature an~
pipette: .' ~ ml of sample into a 12 ml vial. Composite si;..:ples
may be pr"'~PQred by pipetting one ml volumes of each samp1e into,
a 12 ml vi~l. Dose the sample (composite) with 10 ul of internal
standard solution for each one ml of sample to yield an internal
standard concentration of 75 ng/ul. .
-------
7.3
7.2.3 Equilibrate the GC oven temperature to 70oC.
7.2.4
C-27
Inject 5 ul of the dosed sample, turn the vacuum diverter off
and immediately start collecting t1.S. data using the following
conditions:
-Mass Range 33 - 130 AMU
Scan Time - 3 seconds
After four minutes start the G.C. oven
(6o/min) oven max = 1800C .
program
7.2.5 Collect data until the last components have eluted from the
G.C. column. Typically this would be 320 scans or about 16
. minutes. .
Data Evaluation
7.3.1
After each analysis, collected data is analyzed by the procedure -
Computer Assisted Evaluation of Direct Aqueous Injection GC/NS
Data (4). ---
-------
C - 2.8 '
References
(1)
Finnigan INCOS Data System Operators f~anual, Revision 3; Finnigan 3200
GC/f'iS Systems ~1()nual, Finnigan Coy'poration, Sunnyv,:"le, CalifQ)~nia
(2) "Standclt'd Recommended Practi ce for t,1easuri ng Vol atil e Organic Hatter in
Hater by Aqueous-:Injection Gas Ch}~omatography~' ASH! 0-2908-74, P 480-487
(3)
Memo of J. Eichelberger and W. Budde, March la, 1978, Environmental
f'1onitoring and Support Laboratory, Ci ncinnati, Ohi 0 45268, Subject -
Pel'fl uorobl~omobenzene Reference Compound for Use "./ith Typi ca 1 Purge
and Trap Columns that Do Not Transmit DFTPP Readily.,
(4)
Computer Assisted Evaluation of Direct Aqueous Injection GC/t.1S Data -
ProcedU!~e Developed by the Chemistry Branch of the EPA, National Enforce-
ment Investigations Center, Denver, Colorado, September 1978 '
-- -- -- -_.-
-------
C-29
ATTACH~1ENT IV
Computer Assisted Evaluation of
Direct Aqueous Injection GC/MS Data
NEIC - September 1978
1.0 Introduction
1.1
This procedure is a slightly modified version of the priority
pollutant data evaluation procedure (1). Minor modifications
were made to enhance the handling of direct aqueous injection
(DAI) analyses data for the Kanawha River Valley project
(August 1978). .
2.0 Summary of Method
GC/MS data files are processed by location of an internal stan-
dard that is used for response reference. Compounds of interest
in a user library are reverse searched using an absolute retention
time window.. If a compound is located and passes the match cri-
teria, it is quantitated and the spectrum printed. Printed re-
sults are manually audited and the data verified or rejected.
3.0 Summary of Modifications
2.1
The compound detection routine (Detect) was changed to use
absolute retention times for location of the retention time
window. Only masses 41 through 125 were used in locating com- .
pounds due to the Argon background (m/e 40) in the system. .
3.2 The required spectrum match parameter limit (fit) in the compound
identification routine (Detec 2) was set to 450. This lower limit
was necessary due to the poor character of the spectra of the
DAI compounds. Poor character here means that the spectra con-
tain few ions and their response (sensitivity) is poor.
3. 1
3.3 The names of procedures used in both the DAI data evaluation and
the priority pollutant evaluation were changed to allow independent
operation of the two procedures.
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 flnot foundfl entry) \'/ill appear in the quantitation
report. The name and match rAsults will, however, appear in the
gualitative data report. .
-------
,JC-30~
4.2 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.
5.0 Apparatus
5.1 Finnigan INCaS data system software, Revision 3.1 or later. To
initially set up this procedure, the user must understand and be
~ proficient in the use of MSDA (2).
6.0 Procedure
6.1
Procedure Set Up
6.1.1
Create the procedures from the trace of EVDAI in Appendix I~
6.2 Library Set Up
6.2.1
Build a user library containing each compound of interest.
Appendix II is a library list of the 01 library. The first
entry must always be the internal standard and each entry
must include the quantitation parameters and retention times.
6.2.2 Execute EVDAI, edit the quantitation list for accuracy and
update the library parameters using commands in IIQUAN".
Using the "LIBR" program, generate hard copies of library
spectra for reference. Using the library list editor,
"EDLLII. generate summaries of the entries and-.quantitation
parameters as in Appendix II.
6.3 Routine Use
6.2.3
6.3.1
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.
6.3.2
6.3.3 Execute the procedure as follows:
EVDAI library. namelist. yes (no)
\~here :
library is the appropriate user library name.
namelist is the list containing the files to be processed.
yes (no) selects printout of the spectra at a peak that was
identified by the orocedure.
-------
C-3l
6.3.4 Appendix III is an example of PPEVAL output.
option was selected.
The "No"
7.0 Quality Control
7. 1
Each identification can be manually audited if the "yes" option
was selected. Inaccurate qualitative results may then be checked
. and manually corrected.
'7.2 Quantitation data accuracy is monitored by use of standard quality
control techniques such as daily standardization, replicate analysis
and spikes (3)-. Daily calibration of the method. can .be accommodated
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.
8.0 Precision and Accuracy
8.1
The.overal1 precision and accuracy is limited to the quality of the
raw data being processed.
9.0 References
(1)
"Computer Assisted Evaluation of Organic Priority Pollutant GC/~1S
Data", US EPA, Nat~ona1 Enforcement Investigations Center,
September 1978. .
(2)
"INCOS Data System - MSDS 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.
-------
, 'C-32'
..' .
APPENDIX Ia.
0"':'(
TRACE G~ PROCEDL~E ~VD~I
:;c ERAS:
'" :C~~~~ PRIORITY POLLUTANT EVALU~TIO~ ??~CEDU~E ~~~**]
'" :CTHIS PROCEDURE ~Y BE us::!) TO EVALUATE GC/MS tATA ]
'" ;CFOR PRIORITY POLLUTANT cEcA SECTION 337CA» COr:POUNDS ]
'" : C THE PROCEDURE UT!L!2SS ,:!r::2~!P.L STAND;~RDS /'HID REUITI'IE ]
'" :CRESPONSE FACTORS FOR OIJ~anTATlml. THE I"i3DS OPTION]
'" ;CSEARCH IS US:D TO LOCRT; F.ND ItENTIFY PE~~S. THE EPA ]
* ;CIDE~IT;FICATION C?ITERIA. E.G.. THRE: 10;-15 PER CCM?OU~!D ]
'" ; C. IS US:;:D TO LOCATE THE ':::::?OUND OF It1TE2"ST. MG:=.E I O;~S ]
'" :CHOWSVER i1AY mo USED AS 'n,,,, FIT OF THE SEARCH ROUTI!'JE WILLJ
'" :(YIE!..D mRc SPECIFICITY FeR T,..;: CCi":?,)U~ID. TriE FUL!.. ]
'" :(SPECTRUM IS OUTPUT IN OR')EP. TO ?~DVIDE CO~IFIR..tniGN OF ]
'" ; (TriE PRES::HCE 0;= THE COM?CIJNDS. ]
'" ; ( *:ICI<**:~*,iOI!<."""'~4<:~.!CICIOr.:~,~:!C_~:IC;o;cj'**'I:'I:****]
'" :(TO USE PPEVAL. BUILD A LIBRARY CONTAINING THE SPECTRA OF ]
'" :CTHE COMPOUNDS OF INTEREST. INCLUDE THE OUANTITATIVE DATA]
'" :CTHAT IS NECESSARY AS DESCRISED IN TriE MSDS ~ANUALS. ]
'" ;(CREATE A NAMELIST WITH THE NAMES OF THE FILES TO BE ]
'" ;(PROCESSED. EXECUTE THE PROCEDURE AS FOLLOWS: ]
'" :( FPEVAL LI!3?ARYNA~. NAI-:ELiST E.G. ?PSVAL vO.S';;?LE ]
"';( REVISED 38AUG73 O.J.L~GSDON II EPA-NEIC 3a3-234-4661 ]
'" :SETS PPSCAN;EDLL 'r'ESC-;3:W;E);EDLL NOC-:W:E)
'" ;SETN $2;SET4 SI:PPEV1;FEED;8EEP;aEE?;3EEP
'"
ERASE
SETS PPSCAN
EDLL YES (-;S;W;E)
EDLL NO C-:U;E)
SETN s2
SET4 SI
PPEVI
'" ERASE:
'" ; (PART OF PROCEDURE PPE'lAL
'" :(GET THE NEXT NI1i"IEL!ST EtlTRY AND CONTINUE PROCESSING
'" :(RT PPEV2
'" :GEn/;PPEV2;LOOP
'"
ERASE
GETN
PPEV2
'" ERASE
'" ;(PART OF PPEVAL. THIS FP.OCEDU~E SETS THE LI9~A~Y ENTRY ]
'" :(POIIITER TO THE FnST EnTRY. WHICH ~ST ALWAYS CE THE INTERNAL]
'" ;(STANDARD. LOCIS 13 THaI CMlLED AtlD THE INTERN:-\L FCUND ]
'" ;CTIiE: SPECTRUH NUI'3ER OF THE INTERNP.L STANDARD IS ]
'" ;(SiORED Itl ! IE! .FOR FUTUiI< ; C IS THEN RESET TO TH;: BEG INN ING. 101E DUAIITITHTIC~I LIST SET TO ]
'" ;(nIE FILE tlHt,=: All!) WPTI=:D ,OUT. DETECT:5 CALLED TO LOCATE EACH]
'" ;(COi"i?CUtlD (iF PRES=.nTJ. QUA~ IS TI!::N CALLED TO CA~CUlAT£ j
* ; (TIlE RE5UL TS ntl:J THE P:10CEDU;;::: RETURNS TO PFEV I TO GET THE ]
'" ; C tlEXT FILE TO PROCESS. ]
'" :FILECK PRIN.99/N;E)
'" ;EDLL PPLISTC-;W;E)
'" :SETJ ol:OIROC!;HI.90a.3E!E!:E);SET4 .1;LOCIS;SETlO !14:SET4 lOa
'" ;SETO SI;EDOLC-;W;E);EDSLC-:W;E);SETL 53;DETECT;OUANCI;H;E)
'" :EDLL PPLISTCD!I;E)
J
]
]
~ ;;':::,:LJ??j
;FILECC PRHI.99/t1.i"1: ;E)
; FEE:>
;BEEP
'"
'"
'"
'"
E~ASE
-------
..:' .. ":':~' .:.:<. ",.:"j
".,~" _.
APPENDIX lb.
'. -."'.... .-.". ..., -
.- .
C-33
. .
. .
-.
- .... . -- -_..."
.."'"
>i< ;(PHRT 0;= PPEVAI. J
'" ;(ROUTUE TO FIND Ali IHTERH~L STAHDA~D Iii A SAMPLE J
'" ;ruSE A REVE?SE SEARCH TO LOCATE THE IH~~HAL STAHDARD]
* ;SE;I4 f;f)
* ;SEAR/V(I;~;V25a3~Da;N2.Ia.4aa;~;D-60.6a;E)
.:1< ;LOCISI
'"
ERASE
SET14
SEAR (I;S:V25aaaaa;H2.la.4aD:~:D-6a.6a:E)/V
LOCISl
~ IF LOCIS1 . !14
'" ;(PART OF PPE,~L J
'" ;(1'10 IHTERNAL STANDARD FO'JHDJ
'" ;PR!N(QIS)
'" ; REiU PPEV2
'"
IF LOCISI.! 14
PRIN (9IS)
RETU PPEV2
114
SETHI
SET4
SEre $1
EDOL (-;W;E)
EDSL (-;W;E)
SETL 53
DETECT
'" ;(PART OF PPEVAL J
'" ;(TH!S ROUTItiE LOCATES COi"'.?G!.!NDS Iii THE J
* ;(SAMPLE FILE BY COMPARIHG THE SPECTRA Iii THE LIBRARY J
'" ;( WIrri THE SAi'?LE. RELATI'!E RETEHTIOH TIt':ES ARE USED J
'" ;(AND REFERiONCED TQ THE INTERliAL STANDARD FOUND EARLIER.J
'" ; (TIlE LIE:RARY PO !HTER IS aU!"'.::>ED AN!) TESTED TO J
* ; (SEE IF THE LAST L!BRARY ENTRY HAS SEEN PROCESSED. . J
>I< ; (THEN TIiE CURRENT SCAN tlUt13ER IS SET TO THE INT"RtiAL J
'" ;[STANDARD LOCATICa BY RECALLING n!E CONTENTS 0;:- 11::1. J
* ; (STORE THE SCAN NUI'SiOR OF J
'" ;(l1-!S BEST Mf'1TCH iN \~;:HHaLE 14 AND ALLOW ItHiOGRATIOH J
* ;[AT THAT S?ECTRU~ HUM3ER ONLY J
'" ;( IF TIlE COt'iPOUND IS tlOT FOU~iD. FLACE A HOT FOL:HD J
'" ;(EHTRY,INTO THE QUANTITATION LIST FOR LATER REFERENCE J
* ;SET4 !4...1
'" ;IF !24'>I.14
'" ;SET14 tta
* ;SETl Ila
'" ;EDLL PPLIST(5;W:E)
* ;SEAR/V(I:S:~:V2500aaa:M41.125:NI.la.l0;D-2a.2a:E)
'" ;f'R ItI/1
-------
" C-34'
0',',"'1
,..
APPENDIX Ie.
... ;CDATA IN THE OUANLIST ASSIGNED EARLIER.
... :CALSO CHECK AND PASS ONLY PEAKS WITH
... :CA FIT OF 758 OR GREATER
... ;IF DETECZ !16.DETEC2 ~4Sa
"':5ETI !14 '
... : CHRO S.3:G-4. 4; D-S. S;E)
... ;DETEC3
... ;RETU DETECI
...
IF DETEC2!16.DETEC2.4S8
SET! ! 14
CHRO CI:R:S:o:H!.3:A>S.3:G-4.4:D-S.S:E)
DETEC3
... IF !26 DETEC3.DETEC3
... :SPECCD:H:H:E)
,..
IF DETEC3!26.DETEC3
SPEC CD;N:H;E)
RETU DETEC I
EDOL (-:H;#;A;E)
LOOP
CUAH
-------
C-35
APPENDIX IIa.
HAM NUM: NAME
tJT FORMULA RET TIr.E BASE AREA U.P."I U.P.<>2
REL.?ET.T~~£/CAS* r..qSS ANT. REF. PEAK RESP.FILE RES?FACTOR
DI 1: D-CHLCROFORM.
119 7:27 84 91648. a.aaa a.aee
1.eaa B4.eea 75.a8 DI 1 :5 I.Ema
DI 2: ETHYL ETHER
74 C4.HI0.0 2:27 59 37312. a.aaa a.eaa
0.35B 45.00a 50.0a DI 1 :5 a.3:53
DI 3: ACETONE
58 C3.H6.0 3:27 43 175372. a.oaa a.eaa
a.584 43.oa8 50.0a DI 1 :5 1.2<'11
DI 4: METHYL ETHYL KETOHE
72 C4.HS.0 4:27 43 28224a. a.m:a a.aaa
0.659 43.0aa 513.00 DI 1 :5 1.682
DI 5: ACRYLONITRILE
53 C3.H3.N 6:57 53 262e9. a.eca a.aea
13.933 53.aaa 513.00 DI 1 :5 0.446
DI 6: STYRENE
1134 CB.H9 13:33 le4 63889. a.caa e.oaa
1.978 UJ4.eea 5a.ea DI 1 :5 0.951
DI 7: 1. 1 D I ~THOXYETHAHE
9a C4.H 1EJ.02 3:3a 59 134144. a.t!~<'1 B.Bee
a.47e 75. EJEJa sa. eo DI 1 :5 e.331
DI 8: ISOPROPAHOL
6a C3.HB.0 5: 15 45 84736. a.OOc a.e
-------
, C-Jb
APPENDIX IIb.
-.. .. ..-- .
HAM HUM: NAME
!.IT FORMULA RET TI!".E BASE AREA U.P.O\ U.?62
REL.RET.T,i~/CAS. MASS AMT. 'REF . PEAK RESP.FtLE RESP.FACTOR
DC 1: DCHLGROFORM
119 7: \5 84 1633<:3. B.B
-------
APPENDIX IlIa.
- .
. ..
. - -,-----------------------
CUAtlTITATlOIi REPORT
FILE: D91357SE
DRTR: D9EJ57eE.TI
e9/!J5/78 9:28:ee
SAM?LE: MIX D 5eliG/UL +15
COI'ms.: 70-180
FORr-:tJLA: G6/Mlt1
SU8~ITTED BY: JJS
I HSTRUMEliT: 3200EI
AHAL YST: JJS
WEIGHT: e.eoe
ACCT. 1'10.: J24a
AMOUNT-AREA * REF.AMNT/CREF.AREA* RESP.FACT)
-
liO NArE
I D-CHLOROFORM
2 RCRYLOHITP.ILE
3 I. 1 D I METHOXYETHAliE
4 ISOPROPAHOL
5 D : ETHYL KETONE
6 ISOBUTROHITRILE
7 !i-8UTAHOL
8 PRO?AHE.2.2'-OXYBIS
9 1.3-DIOXOLANE.2-METHYL
Ie BUTAliE.I-CHLORO
liO M/E SCAli TIME REF RRT t:E11-I RREA . AMOUNT "TOT
1 84 147 7:21 I 1.6m) A 88 652434. 75. eEJEJ liG/UL 14.29
2 53 137 6:51 1 e.932 A' BB 222688. 50.e8e liG/UL 9.52
3 75 69 3:27 1 e.469 A Ba 2eS334. 56. zao 1IG/UL 9.52
4 45 lEll 5:83 1 e.687 A 8B 552315. 5a.ElOa NG/UL 9.52
5 B6 130 6:36 I 8.834 A 89 1458S6. 56. m:o NG/UL 9.52
6 42 144 7: 12 I 8.9sa A SB 368eS6. 56.e;18 liG/UL 9.:52
7 55 222 11:06 I 1.510 A B8 72434. 50.e33 HG/UL 9.52
8 45 53 2:39 I 0.3:;1 A ea 512784. 5!.L oa
-------
C-'38
APPENDIX IIIba
..NAM NUM:
. - -...-------..---------------.
UT FORMULA
DI
DI
DI
DI
DI
DI
DI
DI
DI
DI
bl
DI
DI
DI
1:
2:
3:
4:
5:
6:
7:
B:
9:
18:
11:
12:
13:
14:
119
74 C4.HI8.0
5B C3.H5.0
72 C4.HB.0
53 C3.H3.N
184 CB.H8
913 C4.Hl0.02
613 C3.H8.0
86 C5.HI8.0
69 C4.H7.H
74 C4.HHJ.C
182 C6.HI4.0
88 C4.H8.02
92 C4.H9.CL
IDENTIFICATION REPORT
.. ~ .
NO SC~N
1 I~B
2 49
3 73
4 97
5 8
6 277
7 73
e 97
9 148
Ie 1:57
11 217
12 49
13 106
14 97
PURITY FIT
379 996
35 1 728
344 661
410 7413
8 8
26B 929
73 287
123 260
43 323
37 133
110 533
185 459
42 3613
164 329
NA;-E
D-CHLOROFORM
ET.~YL ETHER
ACETONE
METHYL ETHYL KETONE
ACRYLON ITR ILE
STYREHE
I, 1 D I MSTHOXYETHANE
ISOPROPANOL
DIETHYL KETONE
IS08UTRON ITR ILE.
l-I-aui~NOL
PROPANE,2,2'-OXYBIS
1,3-DIOXOLANE.2-METHYL
BUTAHE,I-CHLORO
FILE: D:E9857eE.TI
--------...
-------
C-39
ATTACHr.1ENT v
Methodology: Carbaryl Analysis
~'. . '. .
A liter of the sample was extracted serially with three 5U ml portions
of methylene chloride. The extracts were combined and passed through Na2S04
into a 250 ml round bottom flask. 50 ml of ethyl acetate was added to the
flask and the solvents were concentrated to 10 ml in a rotary evaporator at
450C. The extract was passed through a clean-up column of 3 cm Florisil
topped with 1 cm of Na2S04. The Carbaryl was eluted with 20 ml of ethyl
acetate. The 30 ml of etnyl acetate was concentrated to 10 ml on a hot
plate under a gentle stream of carbon filtered air.
The extract was analyzed on a Waters 204 liquid Chromatograph with a
M Bondapak C18 column. A methanol - 1% acetic acid gradient was used over
25 minutes at a flow rate of2.0 ml/min. The gradient was run from 0 to 80%
methanol. The dual channel UV detector was operated at wave lengths of 254
nm and 280 nm. .
Quality Control: A blank and a spike were analyzed along with the samples.
The blank did not contain any interferences at the retention time of Carbaryl
The spike was at a concentration of 250 ug/l of Carbaryl and the recovery
was 117%.
The presence of Carbaryl in the samples was established by the coin-
cidence of retention time and confirmed by the ratio of the ,254 to 280
response.
- - - . ..... . . -.
-------
C-4U
ATTACHMENT VI
Neutral Extraction Technique for Organics Analysis
September 1978
1.0 Scope and Application
This procedure is applicable for analysis 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 with CH2C12
(dich10ro~ethane) at a neutral pH. The extract is aried
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 source~ of
contamination. Therefore, at least one "Reagent B1ank"
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
tef10n stoppers and stopcocks. No stopcock grease ~sed.
Drying column: All glass 3 cm x 50 cm with attached
250 m1 reservoir.
6.2
-------
-------
C-4l
6.3 Concentrator: 250 or 500 ml Kuderna-Danish evaporative
concentrator equipped with a 5 or 10 ml receiver ampule
and a 3 ball Snyder column.
7.0 Reagents
Extraction solvent: Pesticide analysis grade CH C12
(dichloromethane) (Burdick and Jackson or equivafent)
7.2 Exchange solvents
7.1
7.2.1
Exchange solvent: Pesticide analysis grade
acetone (Burdick and Jackson or equivalent)
7.2.2
Exchange solvent: Iso-octane suitable for
pesticide analysis (Burdick and Jackson
or equivalent)
7.3
Drying agent: Analytical reagent grade granular
anhydrous Na2S04 (sodium sulfate). Washed with
CH2C12 prior to use.
7.4 Glas's wool that has been extracted with CH2C12
prior to use.
7.5 6N NaOH for pH adjustment.
7.6 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.
-------
C-42
8.4 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. AdQ~ml 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 tiansfer 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 l2ml 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 through the extraction
procedure, recoveries calculated and compared to literature
values (if available). . .
10.0 Calculations
9.1
10. 1
Solvent Recovery:
% recovery = Volume recovered (ml)*lOO/volume added (ml)
10.2 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.
---
-------
C-43
ATTACHMENT VII
Summary of Recovery Data
for Neutrals Extractable Organics
in Kanawha River Project
Background
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 method1s 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 I 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% OVI01.
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
I 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.
("")
I
.;:.
.;:.
Name
1 lextracti on - 2500 ug!l
% Recoverya
3 1 extraction 10 ug/l
% Recoveryb
methyl cellosolve acetate
79 :!: 9
16 :!: 0.3
styrene
anisole
99 :!: 1
167 :!: 25
119 1: 4
328 :!: 20
phenol
48 :!: 3
o
o-cresol
98 :!: 4
105 :!: 0.1
88c
N,N-dimethyl aniline
benzothiazole
108 :!: 5
butyl carbitol acetate-
86 :!: 69
27c
83c
103 :!: 4
2,6-dinitrotoluene
119 1: 53
217 1: 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 was observed.
-------
C-45
number of cases of no recoveries.
The limiting factor for detection is
most likely the use of packed column gas chromatography and could account
for a large part of the variation.
Recoveries at low levels, however, can
be expected to be more variable due to theclarger 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.
-- .. - --_..-- _..
-------
.' '\ C-f;.6
" \
ATTACH~~ENT VI-II
Sediments and Sludges Extraction Procedure---NEIC Aug. 1978
I.
SCOPE & APPLICATION
1.1- Solids which precipitate or sediment out from various waters
may be extracted for organic components analysis.
II.
SUMMARY OF METHOD
2.1- An aliquot of sample is allowed to air dry.
A portion of
.'-
this is oven dried for percent dry weignt calculation.
The remainder is ex-
tracted in a Soxhlet extraction apparatus with 1:1 acetone:hexane, then
concentrated/exchanged into iso-octane.
I I I.
SAMPLE HANDLING & PRESERVATION
3.1- Samples are collected as grabs in wide mouthed glass containers
with Teflon lined caps.
3.2- Samples are preserved by maintaining them at or below 40C
during shipment and storage.
3.3- Extracts are stored in glass bottles with Teflon lined caps
in explosion proof refrigerators at or below 4°C.
IV.
DEFINITIONS & COMMENTS
4.1- While this procedure should be adhered to as closely as possible,
sample characteristics (e.g., composition, amount available, and/or
concentration of organics extracted) may require some deviation.
v.
INTERFERENCES
5.1- Solvents and apparatus are potential sources of contamination.
-------
C-47
Therefore, at least one "Reagent Blankll must be prepared and processed
through the same analytical scheme as the associated samples.
5.2- Typical interferences from reagents include 4-methyl-4-hydroxy-
.2-pentanone (diacetone alcohol) from acetone, and phthalate esters from
sodium ~ulphate.
VI. ,APPARATUS
6.1- Heighing:
Mettler P1210N or equivalent, capable of taring 100
grams and weighing to ! 0.01 grams.
6.2- Glazed porcelain evaporating dishes for drying.
-
6.3- Laboratory oven capable of 105°C constant heat.
6.4- Soxhlet extraction apparatus with cellulose thimble.
6.5- Kuderna-Danish evaporative condensor fitted with a three-ball
Snyder column.
6.6- Drying column for extract.
6.7- Washing:
All glassware should be washed thoroughly with Alconox,
then rinsed with hot water and acetone.
VII.
REAGENTS
7.1- Pesticide analysis grade acetone, hexane and 2,2,4-trimethyl-
pentane (iso-octane).
7.2- Anhydrous sodium sulphate, washed with acetone just prior to use.
-'-
. .... - - - -' ..... .
VIII.
PROCEDURE
8.1.- Drying:
8.1.1- Place an aliquot of sample (approximately 50 grams dry-
...
weight) in a glass or glazed porcelain dish and allow to air dry in a
-------
C-'48
laboratory fume hood.
The material should be stirred frequently until a
free flow; ng pO\'Jdery so 1 ; d is obta i ned. .
8.1.2- Determining percentage dry weight:
Weigh out a S-lO gram
. (if available) aliquot of air dried sample into a tared evaporating dish.
Bake over night in an oven at 10SoC and rewei9h.
sample weight after oven drying
% dry weight = sample weight before oven drying x 100
8.2- Extraction:
8.2.1- Weigh out a 30 gram (if available) portion of air dried
sample and pulverize.
Add water to yield an estimated 15% moisture content
and mix thoroughly (average sludges will contain approximately 5% moisture
after air drying).
8.2.2- Place sample in a cellulose extraction thimble and plug
top with glass wool.
8.2.3- Extract using a Soxhlet extraction apparatus of appro-.
pr;ate size.
Extract with 1:1 acetone:hexane for a minimum of 25 siphoning
cycles.
8.3- Column Drying:
Dry the extract by passing through a 15 x 3 cm
column of acetone rinsed sodium sulphate.
Wash the coJumn into the filtrate
thereafter.
8.4- Concentration
8.4.1- Concentrate the resulting solution in a Kuderna-Danish
evaporative concentrator.
Exchange into 4 ml of iso-octane, bringing the
final volu;;;c up -;:0
5 ml iso-iJct~n2:.
8.4.2- Extracts containing suspected high concentrations of
organics may be concentrated to higher volumes to avoid precipitation.
Seyere precipitation may be alleviated by diluting resulting concentrate
w; th acetone.
_._-- ...--
-------
C-49
IX.
REFERENCES
9.1- "Draft Analysis of Sediment and Sludges for Priority Pollutants -
Organics Parameters", April 1978, EPA Region VII.
\.,. .: ,-:- I-
. .. .
.-. ___0'
-- --_.._-~--
-------
ATTACHMENT IX
August, 1978
C-50
METHODS: VOLATILE ORGANICS ANALYSES
Purge andlrap -~as Chromatography-Mass Spectrometry
This method is basically drawn from "Sampling and Analysis
Procedures for Screening of Industrial Effluents for Priority
Poll~tants", 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 pol1utants" 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-1; Tekmar
Company, P.O. Box 37202, Cincinnati, Ohio, 45222.
Special sorbent trap for lSC: stainless steel tube 1/8-
inch 0.0. by 17-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 l/8-inch 00 column packed with
0.2% Carbowax 1500 on 60/80 mesh Carbopack C; manufactured by
Supelco, Supe1co Park, Bellefonte, ~ennsylvania, 16823.
Standards
For liquid standards, a primary standard solution for each
compound was prepared from 10 u1 of the compound in 10 m1 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 m1 in methanol. Due to instability, acrolein
-------
and acrylonitrile were prepared in a separate standard mix. C-5l
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 u1 of this solution was diluted to
1.0 ml in water, and 10 ul of this preparation was added to
each 5 m1 sample aliquot, to give 200 ug/1 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 m1, and the syringe valve was closed. A 10 u1
aliquot of the internal standard (IS) mixture was introduced
into the sample by opening the valve and injecting the IS into
the syringe. An 8-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 ge1-Tenax trap at ambient temperature
( 20- 2 SO C ) .
'.1
.
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 12-minute p~rge time t~e 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 8 minutes; program at 80C/mm to 1700;
h~ld 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.
-------
C-52 .
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 perf1uoro~
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
1 2.8
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, bromochloromethane and 1,4-
dichlorobutane. These compounds represen~ early and late eluters
over the range of the Consent Decree compounds and are not oh
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
-------
C-53
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 jnterferences 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.
-------
.' .
C":S4
ATTACH~,1ENT X
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
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
3. 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.
4.2 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.
4.1
-------
5.0 Apparatus
C-55
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)
5. 1
6.0 Procedure
6.1.1
Procedure Setup
6. 1
Load the procedures listed in Appendix I into the system
disc or create the procedures from the trace of PPEVAL in
Appendix II.
6.2 Library Setup
6.2.1
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.
6.2.2 Execute PPEVAL, edit the quantitation list for accuracy and
update the library parameters using commands in IIQUANII.
6.2.3
Using the "LIBRII program, generate hard copies of 1 ibrary.
spectra for reference. Using the library list editor, .'
IIEDLLII, 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)
~lhere :
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-
taining one internal standard and one component. The "yes"
op~icn ~.;~s selected.
. ------
-------
C-56
7.0 Quality Control
Each identification can be manually audited if the "yes" option
was selected. Inaccurate qualitative results may then be checked
and manually corrected. .
7.2 Quantitation data accuracy ;s monitored by use of standard quality
control techniques such as daily standardization, replicate analysis
and spikes. (3) Daily calibration of the method can be accommodated
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.
7.1
8.0 Precision and Accuracy
. 8.1
The overall precision and accuracy is limited to the quality of the
raw data being processed.
9.0 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)
"INCOS Data System - MSDS 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.
/
--- -- -.----
-------
C-57
Appendicies
I. List of procedures, file names, and functions for PPEVAL
II.
Trace of PPEVAL
III. VOAs library list
IV. Base neutrals library list
V.
Phenols library list
VI. Example PPEVAL output
.---.. - -.. --
-------
REQUIRED PROCEDURES AND METHODS FOR OPERATION OF PPEVAL
C-5R
PROCEDURE OR METHOD
:t:-.fC:K*~::IC"',**::oIOI<'-ICIC:IC**:ICI<
PPEVAL
PPEVA
PPEV8
PPEVC
PPEVD
PPEVE
PPEVF
PPEVG
PPEVH
PR I~IP 1
PRINP2
FUNCT ION
)fOIO!<*****
II'I ITIAL IZATION
DATA FILE PROCESSING LOOP
DATA FILE PROCESSING
LOCATING THE INTERNAL STANDARD
INTERNAL STANDARD ERROR H~NDLER
COMPOUND LOCATER
NOT DETECTED ERROR HANDLER
IDENTIFICATION CHECK
SPECTRA PRINTING
IDENTIFICATiON REPORT HEADER
INTERNAL STANDARD ERROR MESSAGE
.. . -.- -
.
H
X
H
o
:z
I>J
p...
~
,
. . ....... -." '. -
-, . '- .
-------
C-59
APPENDIX IrA.
... '_.0.'''' ~..... ~... ......._..._-_....~_.......-
... ...., -.-
TRRCE OF PROCEDURE PPEVRL
* ERnSE
'" :[******** PRIORITY POLLUTRNT EVALUATION PROCEDURE ",~",]
'" :[THIS PROCEDURE MAY BE USED TO EVRLUATE GC/MS DATA ]
'" :[FOR PRIORITY POLLUTAHT CEPA SECTIOH 3a7CA» COMPOUNDS]
'" :[THE PROCEDURE UTILIZES INTERHAL STANDARDS AND RELATIVE ]
'" :[RESPONSE FACTORS FOR QUANTITATIOH. THE MSDS OPTION ]
'" :[SEARCH IS USED TO LOCATE AND IDENTIFY PEAKS. THE EPA ]
'" ;[IDENTIFICATION CRITERIA. E.G.. THREE IONS PER COMPOUND]
'" ;[.IS USED TO LOCATE THE COMPOUND OF INTEREST. MORE IONS]
'" ;[HOWEVER ~~Y BE USED AS THE FIT OF THE SEH~CH ROUTINE WILL]
'" :[YIELD MORE SPECIFICITY FOR THE COMPOUND. THE FULL ]
'" :[SPECTRUM IS OUTPUT IN ORDER TO PROVIDE CONFIRMATION OF ]
'" ;[THE PRESENCE OF THE COMPOUNDS. ]
'" ; ["'----"''''>I'-**'''~~****",***",'''~''''''''******'''*****'~****]
'" ; C TO USE PPEVAL. BU ILD A LI BRRRY CONTA IN WG THE SPECTRR 01" ]
'" ;CTHE COMPOUNDS OF INTEREST. INCLUDE THE OUANTITATIVE DATA]
'" :CTHAT IS NECESSARY RS DESCRIBED IN THE MSDS MANUALS. ]
'" :CCREATE R NA~LIST WITH THE NAMES OF THE FILES TO BE ]
* ;[PROCESSED. EXECUTE THE PROCEDURE AS FollOWS: 1
'" ;[ PPEVAL LIBRARYHAME. NAMELIST .YESCNO) ]
'" :[WHERE YESCNO) SELECTS PRINTED SPECTRA OF ACCEPTABLE]
'" :CMATCHES. E.G. PPEVAL va. SAMPLE
"';[ WRITTEN laAUG78 O.J.LOGSDON II EPA-NEIC 3a3-234-4661 ]
"';[ REVISED aSSEP78 O.J.LOGSDON II EPA-NEIC 3a3-234-4661 J
'" ;SETS PPSCAH:EDLL YESC-;$:U:E):EDLL HOC-:W:E)
'" :SETH S2:SET4 Sl:PPEVA;FEED:BEEP:BEEP:8EEP
'"
ERASE
SETS PPSCRH
EDLL YES C-;$:W;E)
EDLL HO C-:U:E)
SETH $2
SET4 $1
PPEVA
'" ERASE
'" :CPART OF PROCEDURE PPEVRL
'" ;CGET THE NEXT NAMELIST ENTRY AND CONTINUE PROCESSIHG
'" ;[AT PPEVB
* :GETH:PPEVB:LOOP
'"
ERASE
GETN
PPEVB
* ERASE
* ;[PRRT OF PPEVAL. THIS PROCEDURE SETS THE LIBRARY ENTRY ]
'" ;[POINTER TO THE FIRST ENTRY. WHICH MUST ALWAYS BE THE INTERNRL ]
* :CSTANDARD. PPEVC IS THEN CALLED AHD THE INTERHAL FOUND ]
'" :CTHE SPECTRUM HUMBER OF THE INTERNAL STANDARD IS ]
* ;CSTORED IN lie FOR FUTURE REFE~ENCE. THE LIBRARY POINTER]
* ;[ IS THEH RESET TO THE BEGItiNING. THE aUANTITATIOH LIST SET TO ]
'" ;CTHE FILE HAME AHD EMPTIED OUT. PPEVE IS CALLED TO lOCATE EACH]
'" :[COMPOUHD CIF PRESENT). CUAH IS THEN CALLED TO CALCULATE ]
'" : [THE RESULTS AND THE PROCEDURE RETURNS TO PPEVA TO GET THE ]
* :CNEXT FILE TO PROCESS. ]
'" :FILECK PRIN.99/N:E)
'" ;EDLL PPLISTC-:U:E)
'" :SETI *1;PARACI;H;E):CHROCI:HI.laSB.3SB;E):SET4 *I:PPEVC:SETIB 114:SET4 .a
'" ;SETO SI:EDOLC-:U:E):EDSLC-:W;E):SETL $3;PPEVE;CUANCI:H;E)
'" ;EDLL PPLIST(8!I:E)
'" ;:=;?l>
'" ;FILECC PRIH.99/N.N::E)
'" :FEED
* ;BEEP
*
ERASE.
FILE (K PRIN.99/H:E)
fDLL PPLIST (-;U:E)
SET! .1
PARA (I:H;E)
]
]
]
]
-------
. C-60
APPENDIX IIB.
.n. '.. ----...--" "",,'~-'-'._------ --.. ._--
CHRO CI;Hl.leSe.3S6;E)
SET4 01
PPEVC
* ERASE
* ;CPART OF PPEVRL J
* ;CROUTINE TO FIND AN INTERNAL STANDARD IN A SA~LE ]
* ;CUSE A REVERSE SEARCH TO LOCATE THE INTERNAL STANDARD]
* ;SETt4 06
'" ;SEAR/vCI;$;V2Seeeea;N2.16.6SEI;&;D-6E1.6E1;E)
'" ;PPEVD
'"
ERASE
SET! 4
SEAR
PPEVD
'" IF PPEVD . 114
'" ;CPART OF PPEVRL ]
'" ;CNO IHTERNAL STANDARD FOUND]
'" ;PRINC@P2)
'" : RETU PPEVS
'"
IF PPEVD.114
PRIN C@P2)
RETU PPEVB
SETtEl 114
SET4
SETO $1
EDOL C-;W;E)
EDSL C-;W;E)
SETL 53'
PPEVE
'" ;CPART OF PPEVAL J
'" ;CTHIS ROUTINE LOCATES COMPOUNDS IN THE '. ]
'" ;(SAM?LE FILE BY CO~PARING THE SPECTRA IN THE LIBRARY]
'" :CWITH THE SA~PLE. RELATIVE RETEHTION TIMES ARE USED]
'" ;CAND REFERENCED TO THE INTERNAL STANDARD FOUND EARLIER.]
'" ;CTHE LIBRARY POINTER IS BUMPED AND TESTED TO ]
'" ;CSEE IF THE LAST LIBRARY ENTRY HAS BEEN PROCESSED. ]
'" ;CTHEN THE CURRENT SCAN NUMBER IS SET TO THE INTERNAL]
'" ;( STAHDARD LOCATION BY RECALL ING THE CONTENTS OF 11E1. ]
'" ;CSTORE THE SCAN NUMBER OF ]
'" ;(THE BEST MATCH IN VARIABLE 14 AND ALLOW INTEGRATION J
'" ; C AT THAT SPECTRUM NUM8ER miL Y ]
'" ;(IF THE COMPOUND IS NOT FOUND. PLACE A NOT FOUND]
'" ;CENTRY INTO THE CUANTITATION LIST FOR LATER REFERENCE]
'" ;SET4 14..*1
"';IF 124"'1.14
'" ;SETt4 ...e
'" ;SETI lie
'" ;EDLL PPLISTC$;W;E)
'" ;SEAR/vCI;$;7.;V25BBBBB;NI.le.1B;D-2B.2e;EJ
* :PRIN/KXC!4~2; 114.6; 115.6; 116.7;C:E)
* ; PPEVF
'" ;LOOP
*
SET4 14..01
IF .1124.14
SETl4
SETI ItEl
EDLL PPLIST C$;W;EJ
C:~~; (!: s:.~ :\.1'25~~eec);N!.. !'3.. H~: D-'2~.. 2~:~) /'1
?R IN C 14.2; 1 14.6; I 15.6; 116.7 ;C;E)/KX
PPEVF
'" CPART OF PPEVAL]
'" ;(IF THE FIT IS LESS THAN OR ECUAL TO 759 J
'" ;(U~ITE A NOT DETECTED. NAMED ENTRY INTO THE]
'" ;(OUAHTITHTIOtJ LIST FOR FUTURE REFERENCE]
'" ;PPEVG
'" ;EDCL(-;N:.:A;E)
'"
CI;$;V2SeeeeEl;H2.1e.6ee;&;D-6E1.6e;E)/V
-------
APPEl-xDIX IIG °
... -...---.-......-...-.., -..--. ---....",.u ""'''---'''' ......... . .... . -.. . .. ",' .... .
. - ...- - - - .'" . . - '. ...
PPEVG
'" (PART OF PPEVAL
'" :CACCESS ANY. SCANS IDENTIFIED IN DETECT
* ;(AND INTEGRATE THEIR AREAS. RECORD THE
* ;(DATA IN THE OUANLIST ASSIGNED EARLIER.
'" ;(ALSO CHECK AND PASS ONLY PEAKS WITH
* :(A FIT OF 7se OR GREATER
* ;IF PPEVG !16.PPEVG 07ee
* :SETI 114
'" ;CHROCI;R;$;o;Nl.3:A)S.3:G-4.4;D-S.S;E)
* ;?P=VH
'" ; RETU PPEVF
*
IF PPEVGI16.PPEVGo70e
SET! 114
CHRO (I;R;$:O:NI.3;A)S.3;G-4.4;D-S.S:E)
PPEVH
* IF !26 PPEVH.PPEVH
* ;SPECco;N;H;E)
*
IF PPEVH!26.PPEVH
SPEC C":N;H:E)
RETU PPEYF
EDOL (-;N;o:A:E)
LOOP
OUAN CI; H; E)
EDLL PPL1ST (Bll;E)
PR IN (@P\)
FILE (C PRIN.99/H.M:;E)
FEED
BEeP
LOOP
FEED
BEEP
SE;:P
BEEP
.- ---
...-.,. ..
J
J
J
J
J
;J
C-61
-.. -........ --.' -... ''''''
-------
C-52
APPENDIX IID.
._---~-------------- --_. -- ......
PRINP2.ME
C;T;
C;T;
;E
= C20;T;
PRIORITY POLLUTANT EVALUATION;
NO INTERNAL STANDARD WAS FOUND HI SAMPLE; $1;
;D;F
, ..'~ ----- ..' ...-. ------------ ".-- -. .
PRINP1.ME = C2;T;IDENTIFICATION REPORT
;$1;C2;T;NO SCAN PURITY FIT
;C;E
FILE:
.".'-'"'' ..
- .,-- ---
-------
U_I.iE
r FORtULR
.RET. TlME/CRS.
RET" BRS"RRER~..I ...Z
MASS ANT. REF.PEAK RESP.FILE RESP.FACTOR
I_H4.L:"
a.
_aa.al8l
-
- U.~_U. VO ZB. 44 METHYLEHECHLORIDE <=>
O.eOB I z
z ..,
.., B4 C.HZ.CLZ a:a4 a4 a. a.aBa a.Baa '"
'"
3: a2 ACROLIEH ~ a.eBO B4. aBa2Ba. DB VO I vs I.aaa ~
; C3.H4.0 a:oa 56 a. a.aoa a.aoa
B.OOO 56.aBB20B.aa VO I vs I. BBB VO ZI: 47 BROMOFORM
Z5a C.H.BR3 3:B2 173 a. a..BBa a.Baa
4: a3 ACRYLOHITRILE a.aoa 173.aa020a.aa VO I VS I.eoa
3 C3.H3.H a:oo 53 a. a.aoo a.aaa
a.ooa 53.0aa2ao.oa VO I vs I.aaa VO Z2: 48 BROMODICHLOROMETHAHE
162 C.H.CLZ.BR 1:59 a3 a. a.aoo a.aoa
5: a4 BEHZEHE a.eao B3.aa02aa.aa VO I VS I. oaa
3 C6.H6 2: 19 7B a. a.aaa a.aaa
a.aao 7a.aaazao.oa VO I VS I.aoa .VO 23: 49 TRICHLOROFLUOROMETHA~E
136 C.CL3.F a: 19 lal a. a.aaa a.oaa
6: a6 CARBOHTETRACHLORIDE a.aaa la I. aa0200 .aa VO I VS I. aaa
2 C.CL4 1:45 117 a. a.aaa a.aaa
a.aoa 117. aoa2aa . aa VO I vs I. aaa VO 24: 51 DIBROMOCHLOROMETHAHE
2a6 C.H.CL.BR2 Z:32 129 a. a.aaa a.aBa
7: a6 CHLOROBEHZEHE o.aoa 129.aaazaa.aa VO I V5 I.aaa
2 C6.H5.CL 3:sa 112 a. a.oaa a.aea
o.aaa IIZ.oaozaa.aa VO I V5 I. aaa va 25: a5 TETRACHLOROETHEHE
164 C2.CL4 3:22 166 a. a.aoa a.aaa
a: la L 2-D I CHLOROETHAIIE a.aaa 129.aaazaa.aa va I VS I. aaa
'3 C2.H4.CL2 I:Z6 62 a. a.aaa a.aaa
a.ooa 62.000z00.aa va I vs I.aaa va 26: B6 TOLUEHE
92 C7.HB 3:29 91 a. a.aaa a.aaa
9: II I. I. I-TRICHLOROETHAlIE a.oaa 91.0ea2aa.aa VO I VS .. o~a
2 CZ.H3.CL3 1:41 97 a. a.aaa a.aaa
a.aoa 97.00azaa.aa VO I VS I.aaa va 27: a7 TRICHLOROETHEHE
13a C2.H.CL3 2:2a 1313 a. a.aoo a.aaa
10: 13 I.I-DICHLOROETHANE a.aaa 95.aaazaa.aa VO I V5 I.oaa
9 C2.H4.CLZ a:52 63 a. a.aao a.aaa
a.aoa 96.oea20a.aa va I V5 I. eaa
II: 14 I.I.Z-TRICHLOROETHAHE
'Z CZ.H3.CL3 Z:3Z 97 a. a.aaa a.aaa
o.ooa 03.aaazaa.aa va 1 V5 I.aaa
IZ: 15 I.I.Z.Z-TETRACHLOROETHAHE
.5 CZ.H2.CL4 3:Z7 a3 a. a.aaa a.aaa
a.aaa a3.eaazaa.aa VO I vs I.aaa
13: Z3 CHLOROFORM
8 C.H.CL3 1:2a B3 a. a.aaa a.aaa
a.aaa B3.aaazoa.aa va I vs I. aaa
14: Z9 I.l-DICHLOROETHEHE
6 CZ.HZ.CL2 a:z8 61 a. a.aaa a.aaa
a.ooo 96.aoazaa.aa VO I VS I. aaa
.,
15: 3a I.Z-TRRHS-DICHLOROETHEHE
:; CZ.H2.CLZ I:al 96 a. a.aaa a.aaa
a.aoa 96.aaa2aa.aa va I V5 I.aaa
16. 32 L Z-D ICHLOROPROPANE
l C3.H6.CLZ Z: II 63 a. a.aaa a.aaa
a.aaa 63.aaa2ea.aa va I V5 I.aaa
17: 33R 1.3-CIS-DICHLORO-I-PROPEHE
n
I
0'1
W
-------
01\....: "Ii..... 248 CI2.H9.0.0H J:~i:I ~~i:I U.
.... .+::- ....
2: 01 RCENRPHTHENE x 0.359 93.000 50.00 8t! I :5 0.586 x
: C12.H10 2:39 154 0. 0.000 0.000 .... ...
'"
0.710 154.000 20.00 Bt! I :5 0.586 '" Bt! 20: 53 HEXRCHLOROCYCLOPEt!TADIEHE 15
ffi
'" 270 C5.CL6 ..20 237 0. 0.000 0.000 '"
3: 05 8EHZIDINE ~ 0.000 237.000 20.00 8N I :5 L 000 ~
CI2.HI2.N2 5:00 184 O. 0.000 0.000
L 345 184.000 50.00 BN I :5 0.047 BN 211 54 ISOPHORONE
13B C9.HI4.0 1:09 82 0. 0.000 0.000
4: DB 1.2.4- TR ICHLOR08:IIZEtIE 0.3a9 B2.000 50.00 BH 1 :5 0.984
C6.H3.CL3 I: IB 180 O. 0.0ao 0.000
0.349 74.000 20.00 8H 1 :5 0.182 BH 22: 55 HAPHTHRLENE
128 C10.H8 1.25 128 o. o.oao 0.0011
5: 09 HEXRCHLOR08ElfZEtiE 0.379 128.0ao 20.00 8H I .5 L 287
C6.CL6 3:20 284 8. 0.000 0.000
0.893 2B4.000 20.00 8t! I :5 0.264 Bt! 23: 56 H ITROBEt!ZEHE
123 C6.H5.02.H 1:07 77 O. 0.0a0 0.000
6: 12 HEXACHLOROETHRtlE 0.300 77.000 511. 00 8H I :5 0.457
I C2.CL6 0:43 201 0; 0.000 0.000
0.192 117.0eo 20.00 8N I :5 0.398 8N 24: 62 H-NITROSODIPHEHYLRMIHE (HER5 A5 DIPHEHYLAMIHE)
169 CI2.HILH 3: 12 169 0. 0.0ao 0.008
7: IB 8IS(2-CHLOROETHYLIETHER 0.B57 169.000 20.08 BH I :5 8.145
C4.H8.0.CL2 8:37 93 O. o.ooa 0.000
0.165 93.000 50.00 Btl I :5 0.205 BN 25: 63 H-HITROSODIPROPYLAMIHE
130 C6.HI4.0.H2 0:55 78 0. 0.000 0.000
8: 20 2-CHLOROtiRPHTHALENE 0.247 130.000 50.00 BH 1 :5 0.05B
CI0.H7.CL 2: 12 162 O. 0.000 0.000
0.589 162.000 20.00 BH I :5 0.612 BN 26: 66 DI-(2-ETHYLHEXVLIPHTHALATE
390 C24.H38.04 5:44 149 O. 0.000 0.000
9: 25 1.2-DICHLOR08EHZENE \. 536 149.000 20.00 8H 1 :5 0.B41
; C6.H4.CL2 0:41 146 O. o.oeo 0.000
0.183 146.000 20.00 BN I :5 0.706 BH 27: 67 8UTVLBEHZYLPHTHALATE
312 CI9.H20.04 5:27 149 O. 0.000 0.000
101 26 J .3-DICHLOR08ENZEtiE \. 460 149.000 20.00 BH I :5 0.5BI
C6.H4.CL2 o:jl 146 O. 0.0130 0.000
0.138 14S.COO 20.00 8N I :5 0.519 8t! 28: 68 DI-H-BUTVLPHTHALATE
27B CI6.H22.04 4:06 149 8. 0.000 8.000
III 27 1.4-DICHLOR08EtlZEHE L 098 149.000 20.00 8H 1 ,5 \. 732
; C6.H4.CL2 0:34 146 O. 0.000 0.000
0.152 146.000 20.00 8H I :5 0.895 8N 29: 69 DI-OCTVLPHTHALATE
390 C24.H38.04 6:58 149 O. 0.000 0.000
12: 35 2.4-DIHITROTOLUENE 1.866 149.000 20.00 8N I :5 0.580
C7.H6.04.H2 2:59 165 O. 8.000 8.000
0.803 165.090 50.00 8N I :5 0.191 BH 30: 70 DIETHYLPHTHALATE
222 CI2.HI4.04 3:04 149 O. 0.000 0.000
13: 36 2.6-DINITROTOLUEHE 0.821 149.000 20.00 BN I :5 0.953
C7.H6.04.H2 2:46 165 0. 0.000 0.000
0.744 165.000 50.00 BN 1 :5 0.184 BH 31: 71 D I HETHYLPHTHALRTE.
194 CI0.HI0.04 2':40 163 O. 0.000 0.000
14: 37 1.2-DIPHEHYLHYDRRZIHE (HEAS. A5 AZOBEHZEHE) 0.714 163.000 20.00 Bt! I :5 0.817
CI2.HI0.H2 3:a6 77 O. 0.000 0.000
0.B34 77.00a 50.oa BN I :5 J. a66 8N 32. 72 8ENZO(R)RNTHRRCENE
" 22B CIB.HI2 6:14 228 a. 0.a0a a.oao
15: 39 FLUORAtlTHENE J. 670 228.aoo 20.00 8N I :5 0.120
C16.H10 4:34 202 o. 0.0ae 0.000
1.223 202.aoo 2a.ao 8N I :5 0."714 8H 33: 76 CHRYSENE
228 C18.H12 6: 14 228 o. o.aoo 0.080
16: 4a 4-CHLOROPHEtlYL PHEHYL ETHER 1.670 228.oao 28.00 BH .,1 :5 a.120
CI2.H9.0.CL 2:53 204 O. 0.000 0.000
a .799 2B4.a0e 20.ee 8N I :5 a.288 8N 34: 77 RCEHAPHTHYLEHE
152 CI2.He 2:33 152 o. e.000 o.eoo
17: 41 4-0ROMOPHEHYL PHEHYL ETHER e.6B3 154.000 20.00 BN I :5 0.003
"
-------
J- ANT,- - ~aa .a
C14.Hla 3.44 17B a.
I.aaa 17B.ooa 2a.ae BN I .S 1.433
36: Be FLUORENE
C13.Hle 3:ee 166 e. B.BOB B.aee
B.B04 166.eae 2e.Be BN I :S B.573 ~
...
37: BI PHENANTliREHE ><
CI4.HIB 3:44 17B B. B.aoe e.aee ...
1. 000 17B.000 20.ao 811 I .S I. 433 CI
z
W
0.
30: 84 PYREHE ~
C16.H10 4:3<1 202 B. B.ooe B.ooa
1.223 202.0::10 20.aD BII I :S 0.714
"
rU1- I'HII- - R- .. A!IIIU.P.~.P..;
MULA
REL.RET.TlME/CAS. MASS ANT. REF.PE SP.F P.FA
PH II Dla-ANTHRACENE (INTERNAL STANDARD)
IBB 2:43 IBa 44B64. B.aeo a.oaB
1.000 IBB.oae sa.ae PH I :S I.aea
. .;
PH 21 21 2. 4. 6-TR ICHLOROPHENOL x
196 C6.H3.0.CL3 1:46 196 a. B.aoo o.aoe ...
a.eoe 196 .aoawe .00 PH I :S 0.461 CI
z
W
0.
PH 31 22 4-CHLORO-3-METHVLPHENOL ?<
142 C7.H7.0.CL 2:06 142 B. 0.000 a.aae
0.000 142.aoolae.ao PH I .S 0.524
PH 4: 24 2-CHLOROPHENOL
12B C6.HS.0.CL B:27 12B a. a.aoe e.aae
a.eoe 12B.eoeloe.ae PH I :S 1.014
PH 5: 31 2.4-DICHLOROPHENOL
162 C6.H4.0.CL2 1113 162 B. B.oee B.eBa
a.aaa 162.aaalaa.aB PH I :5 a.714
PH 6: 34 2.4-DIMETHVLPHENOL
122 C8.Hla.0 \:11 122 a. a.aaa B.eaa
a.aaa 122.aoaIBa.Ba PH I :S B.617
PH 71 57 2-HITROPHENOL
139 C6.H5.03.N a:37 139 a. B.aaa a.aaa
B.aaa 139.BaaIBa.ao PH I .5 B.534
PH B: 58 4-NITROPHENOL
139 C6.H5.03.N S:BI 139 B. B.oaa a.BoB
a.BBD 65.aBBlaa.aa PH I :5 B.aDa
PH 9. 59 2.4-DINITROPHENOL
IB4 C6.H4.05.N2 2:53 184 543744. a.aaa B.BaB
I. DaD 184.BOa4
-------
C~60
A.
~.~~~.2~A: ~~
APPEJ.'IDIX VIA.
- . - ----' .
. ...----. ._-.
CUANTITATICN REPORT
FILE: 5MR$A
DATA: SMA$A. MI
e:oo:oo
SAMPLE: VOA STD MIX A
cor-ms.:
FORMULA:
SUBMITTED BY:
W/1.5. SEPT 3. 1978
INSTRUMENT: SYSIND
AH!=\LYST:
WE IGHT:
ACCT. NO.:
B.BeB
AMOUNT-AREA * REF.AMHT/(REF.AREA* RESP.FACT>
HO HAME
I I. 4-D ICHLOR08UTANE (INTERNAL STANDARD)
2 BROMO CHLOROMETHANE (IHTEKtIAL STANDARD)
3 B2 ACROLIEN
4 B3 ACRYLONITRILE
5 B4 8ENZENE
6 B6 CAR80NTETRACHLORIDE
7 B7 CHLOROBEHZENE
9 IB 1.2-DICHLOROETHANE
9 11 1.1.I-TRICHLOROETHAHE
Ie 14 1.1.2-TRICHLOROETHANE.
II 15 1.1.2.2-TETRACHLOROETHANE
12 19 2-CHLOROETHYLVINYLETHER
13 23 CHLOROFORM
14 3e 1.2-TRANS-DICHLOROETHENE
15 32 1.2-DICHLORO?ROPANE
16 38 ETHYL8EHZENE
17 44 METHYLENE CHLORIDE
18 47 8ROMOFORM
19 48 8ROMOD ICHLOROtlETHAHE
2e 51 DI8ROMOCHLOROMETHAHE
21 85 TETRRCHLOROETHENE
22 86 TOLUENE
23 87 TRICHLOROETHEHE
24 88 VINYL CHLORIDE
25 29 1.I-DICHLOROETHENE
HO WE SCAN TIME REF RRT METH AREA AMOUNT ?oTOT
I 55 251 4:11 I 1. eao A 88 1191ase. 2ee. OE!!! PP8 4.55
2 49 75 1:15 I e.299 A 88 1120880. 20a.ooa UG/L 4.55
3 HOT FOUND
4 HOT FOUND '
5 78 175 2:55 I a.697 A 89 1734110. 200.00a UG/L 4.55
6 117 139 2: 19 1 0.554 A 88 1242110. 2ee.eee UG/L 4.55
7 112 272 4:32 1 l.e84 A 89 194475e. 2eO.eaa UG/L 4.55
8 62 117 1 :57 1 0.466 A 88 111551e. 20e.eee UG/L 4.55
9 97 134 2: 14 1 e.534 A 88 125482e. 2eO.eoa UG/L 4.55
Ie 83 189 3:09 1 0.753 A 88 866289. 2eO.e66 UG/t. 4.55
11 83 247 4:07 1 e.984 A 88 1293270. 2ee.eea UG/L 4.55
12 le6 2EJE! 3:2EJ 1 0.797 A 88 119982. 2ee.eea UG/L 4.55
13 83 108 1:48 1 a.438 A 88 161275a. 2aa.e0a UG/L 4.55
14 96. 88 1:28 I 0.351 A sa 774512. 2ee.EJEJO UG/L 4.55
15 63 167 2:47 I e.665 A 88 le88563. 200.aoo UG/L 4.55
16 91 306 5:06 1 1.219 A B8 241971a. 20a.EJaO IJG/t. 4.55
17 84 45 0:45 I 8.173 A 88 . 56e556. 2eEJ.ooa UG/L 4.55
18 173 221 3:41 1 0.88B A 88 105498B. 2eO.eBB UG/L 4.55
19 83 153 2:33 1 O.61EJ A 89 1613148. 20a.000 UG/L 4.55
20 129 189 3:09 1 0.753 A B8 1452530. 20a.a08 UG/t. 4.55
.....' ....,.._.... ...--..--...-'.-"------'-" ..._---...-..~. .... ... ..
HO M/E SCAN TIME REF RRT METH AREA AMOUNT ?oTOT
21 129 243 4:03 I 0.968 A B8 1809630. 2aa.080 UG/L 4.55
22 91 251 4: 11 '1 l.ae9 A 88 187952a. 20a.000 UG/L 4.55
23 95 178 2:58 1 0.789 A BB 998815. 200.000 UG/L 4.55
24 HOT FOUND
25 96 63 I:EJ3 1 a.251 MXX 55884. 2EJO.EJOa UG/L 4.55?
(jJO fI/Vi flI"i7/i);V For- 7JI/J
. Cl}J/-1{OW,)j) N4NU1LLy ItDI)ED
o{l- ,
-------
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~~~.iF~~~~~": ';~f:i.~~t;;c~1 '" i~~~,j~~!':::i'~e.~A':y~~~>.
;., ~?r~~'Y~ i::';!;;.!.~ ...:.',~. - ~,~"?:..,~~:;-~,.;.~;~..;;:;:t~~>;r~~~.:E'
~"t:_~. .~~~~""-.!~ ~~~~1.. APPENDIX VIB.' ,...~~~;;:t'~':..-4..~.~~;t:&.~"'-2.~
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.:~~. b-<,... :C~~~':.: ~-.-t~~'T~'':'~?~''~'.~j,'~;::;:~~-':
...:;~,,:..1:.}~.:.... ...-v.,,;' "~'- ,,,,Q,7,;",",,,<....,,,-~p-.:~~.~;=;it~"r~~~
,.T..~~t~~.. '''':;4.'...~~~:;.:;~'.$$~~:;0~~.:[\.;.~.~-,..... -' ~~~"",.~~'"':~~,.....'.f>"'~~'
~ '- '~~~~~.,..,...~~~~~. ":""~K ..~£"-?t;-:;'<~''''''-i"''-~''''~''':':'~'?:>.''''
&....11..'."'.11
.t~~"'~ . J.;.,~ih':.91~ NAM NUM: WT FORMULA NAME .
~~ .~f VII: 126 C4.HB.Cl2 1.4-DICHlORG8UTANE (INTERNAL STANDAR
";2 VI 2: 128 C.H2.CL.8R 8ROMOCHlOROME:THANE (!NTE~NAl STANDAR
~ VI 3: 56 C3.H4.0 £12 ACROLIEN
~~.~ VI 4: 53 C3.H3.N £13 ACRYLONITRILE
,~ VI 5: 78 C6.H6 04 8ENZENE
VI 6: 152 C.CL4 06 CAR80NTETRACHlORIDE
VI 7: 112 C6.H5.Cl 06 CHlOROBENZENE
VI 8: 98 C2.H4.Cl2 lEI 1.2-DICHLOROEr.~ANE
VI 9: 132 C2.H3.CL3 11 1. 1. I-TRICHLOROETHANE
VI lEI: 132 C2.H3.Cl3 14 1. 1.2-TRICHLOROETHANE
VI \I: 166 C2.H2.CL4 15 1.1.2. 2-TET"ACHLORo=:r,.;ANE
VI 12: IEl6 C4.H7.0.Cl 19 2-CHLOROETHYLVINYLETHER
VI 13: 118 C.H.CL3 23 CHLOROFORM
VI 14: 96 C2.H2.Cl2 29 I.I-DICHLOROETHEHE
VI 15: 96 C2.H2.Cl2 3E1 1.2-TRANS-DICHLaROEr.~E:NE
VI 16: \12 C3.H6.CL2 32 1.2-DICHLOROPROPANE
VI 17: lE16 C8.Hle 38 ETHYLBENZENE
VI 18: 84 C.H2.CL2 44 HETHYLENECHLORIDE
VI 19: 25a C.H.8R3 47 BROMOFORM
VI 213: 162 C.H.CL2.8R 48 8ROMODICHLOROMETHANE
VI 21: 2136 C.H.Cl.8R2 51 DI8ROMOCHLOROMETHANE
Vt 22: 164 C2.CL4 as tEtRAtHLbROETHEHE
VI 23: 92 C7.H8 86 TOLUENE
VI 24: 133 C2.H.Cl3 87 TRICHLOi
-------
C-68
ATTACHr1ENT XI
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.
3.
4.
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.
Interferences
/
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.
3. 1
Apparatus
4.1
Finnigan Model 9500 gas chromatograph equipped with a glass
capillary column.
4.1.1
G,rob type injector for splitless injection.
4.1.2 Capillary glass column, 25 meters x 0.25 mm 10, OV-10l.
-------
4.2
Finnigan Model 3200 electron impact mass spectrometer.
C-69
4.2.1
Glass lined stainless steel tubing direct coupling
to gas chromatograph.
4.3 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 600C
and held for 1 minute after injection, then a temperature
program is initiated at 4oC/min. to a final temperature
of 2200C and held from 10 to 15 minutes. Column flow
is adjusted to give a nominal flow of 1.5 ml/min. at
100oC.
5.2 Mass Spectrometry
5.2.1
The following MS instrumental parameters are used:
Electron multiplier voltage
Lens voltage
Collector voltage
Extractor voltage
Ion Energy voltage
Electron Energy voltage
Emission Current
- 1600 volts
- 100 volts
.,. 35 volts
6 vo lts
10 volts
70 volts
- 0.5 ma
5.2.2 The following data acquisition parameters are used:
5.2.3
5.2.4
Scan time
Mass Range
Sensitivity
- 2 sec.
- 33-300
- 10-7 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.
.-.- -
-------
C-70
6.
Qua 1 i ty Control
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.
"
7.
References
(1)
"INCOS Data System - t1SDS Operators Manual - Revision 3",
Finnigan Instruments, March 1978.
-------
C-71
ATTACH~1ENT XI I
CCMPUTER ASSISTED EVALUATION OF
- ORGANICS CHARACTERIZATION GC/MS DATA
August 1978
L 0 This procedure is applicable to a:/llllS"data collected under constant
analytical conditions for qualitative data analysis.
2. 0 Surrrnary of Method
2.1 Ge;MS data files are processed by comparing spectra fran the
sample against spectra of known or suspected J?Ollutants con-
tainerl in a project related library.
If a spectrum matches
the project library spectrum sufficiently, an entry is made in
a table showing at what spect...'llffi number the match occured and
how good the match was.
After canpletion of the search for
each spectrum in the proj ect library, a list of the canJ?Ounds
searched for ani the matching results is printed as well as
each ?pectrum that was identified as a probable J?Ollutant.
-,
If
- - -
selected by the user, the procedure will then search the cur-
rent version of the NB (EPA!NIH/MSDC) library attempting to
identify unknown spectra fran peaks selected by the Bienann-
Billler algorithin in MAP.
3.0 Definitions and Camments
3.1
In some cases, canp:mnds may be identified by canparison to
external reference spectra only (1,2,3).
These "unconfirmed"
compourrl data may however be useful since the computer matching
still traces the presence of selected canJ?Ounds through each
sample analyzed.
Therefore, even these "unconfirmed" J?Ollu-
tants can serve to trace a Haste stream.
-------
C-72'
3.2
3.3
3.4
Quantitation of !,X)llutants identified is effected by locating
the corresponding GC pea.1.cs on GC/PID (flame ionization detector)
chromatograms.
The areas or pea..l< heights are measured and can-
pared to the res!,X)nse of known amounts of pure standard canp)unds.
The concentrations are then calculated.
Since this scheme uti-
lizes two chromatographic systems (GC/MS and G2/FID), :in sane
. cases, differences in thesesysterns will allow identification
by GC/MS but not allow quaptitation.
In such cases, "MS" is
rep)rted to signify a mass spectrcmeter identification.'
The identities of sane cOIrlfOnents are confi:i:med by the matching
of their mass spectra am GC retention times to the data ob-
tained fran the analysis of a pure standard com!,X)unds.
SUch
identities are indicated by "CF."
COJ'T'IfDnents not identified by mass spectranetry are rep)rted as
"NOli to denote not detected.
/
. ' ~
3.5 Analytical schemes may not allow measurement of some suspected
I
pollutants in all samples and the result is rep)rted as "NAil
or not analyzed.
4.0
Interferences
Since absolute GC reterition times are used for setting the search
4.1
windows, the windows must be wide enough to account for slight
variations in instrument conditions.
This could cause identi-
fication errors if comp)unds with slinilar spectra (isomers) are
in the winda.v.
t1anually checking each spectrum produced essen-
tially eleminates any error.
-------
C':'73
) Apparatus
5.1 Finnigan INCOS data system sofbvare running revision 3.1 or
later version.
To initially set up this procedure, the user
must understarrl and be proficient in the use of MSDS (4).
5.2
Th'COS "NEil mass spectra library (5).
J
Procedure
6.1 Procedure Setup
6.1.1 Load the procedures listed in appendjx 1 onto the sys-
ten disc or create the procedures fran the trace of OCEVAL
in Appendjx 2.
6.2 Library Setup
6.2.1 Obtain spectra of the ccrnp:>uros of interest by running
standards under the same analytical corditions to be
used for sample analysis.
6.2.2 Using the library editor, create a library containing
, .
the standard spectra with chemical names and retention
times.
Obtain a reference spectrum of each library
entry for a permanent record and reference via the li-
brary program:
G1i HSi G2i HSi... etc.
6.3
Routine use
6.3.1 Collect mass spectra of samples to be precessed Uhder
the same conditions as the standards were analyzed.
6.3.2
Using the namelist editor, create a name1ist containing
the names of the files to be processed.
6.3.3
Execu te the procedure:
-------
C:"74
OCFNAL library, namelist,- no (yes)
Where:
library is the user library name, namelist is
the file containing the names of the data files
to be processed and no or yes select a continued
search through the NB library.
If the user wants only to perform an NB search,
the procedure is initiated as follotNs:
OCEJAL NB, namelist
6.3.4 Appendix 3 is an e.,<:ample of OCf)l"P;L output consisting of
the following:
(1) The acquisition pararneter listing
(2) A chroma togram with peaks labeled by MAP
(3) A list of the cOIT1f:Ourds being searchE~j for and a
, summary of the search results.
(4) A collection of the spectra of peaks identified by
"
the precedure
(5) Library matching results for peaks found by MAP but
not identified in the user library.
7.0 Quality Control
7.1 Each identification is manually verified by catlp:iring the sam-
pIe spectrum to the reference spectrum in the user library.
In-
accurate computer results are re-evaluated and the correct data
reported .
8.0 Precision and Accuracy
8.1 The auto precessing routine I s accuracy for correctly identify-
ing compounds is lbnited by the quality of the original GC/r-lS
data.
-------
C-75
9.0
References
(1) "Eight Peak Inde..'{ of Hass Spectra," Mass Spectranetry Data Cen-
ter, Alderrnaston, Reading, UK. Second Edition 1974.
(2)
"Registry of Mass Spectral Data," Stenhagen, Abramsson ar.d
McLafferty; Wiley & Sons, New York, 1974.
(3 )
"Atlas of Mass Spectra Data," edited by:
stenhagen, Abrahams-
son and McLaffertv. Wiley & sons, New York, 1969.
(4) IITh"COS Data System - MSDS Operators Manual - Revision 3," Fin-
nigan Inst.....""UIDents, March 1978
(5) . liNES - NIH/EPA;MSOC Library - Revision 3," Finnigan Instruments,
March 31, 1978
-----.-. --
-------
C-76
APPENDIX I.
PROCEDURES k~ ~lliTHODS REQUIRED FOR OCEVAL
1. OCEW~
2. OCEVO
3. OCEV1
4. OCEV2
. 5. OCEV2A
6. OCEV2B
7. OCEV3
8. OCEV5
9. OCEV6
10. OCEV7
11. PRINO 1 .ME
12. PRIN02.ME
-------
C-77
APPENDIX II. a.
- ". .--. ."'~' --..",., ',' '. T"--.'
......-..........,.. .
...
TRACE OF PROCE!JtJ~E O:::E\'AL
>I< [:i<*** OCEVAL **,I<"A<:I~":.=:C:~!O:=::'<::"!<:'!( JULY 29.1978 -*'~]
:Ie ;[OCE'IAL PROVIDES TH~ C?E,~)TOR WITH A MEANS 0;= ]
* ;[LOCATING CO~~OU~DS THAT P.~E SUSPECT SASED ON ]
* ;(THEIR RETENTION T!i~SS ANi) SPECTRA. THESE]
* ;(COi"'.?OUiiD5 ARE SAVED IN HUSER LI8RARY FOR]
* ;[ACCESS BY OCEVRL. IF DESIRED. THE USER r~Y]
* ; [ALSO SELECT TI-IAT ALL OT.1::R PEAKS LC'CATED BY ~P.NS]
* ; [OF B ILLEP.-8 rEI~AtH1 Hi ~t~:> aE SEARCf-'SD AGA !NST THE]
* ;[1'18 LIBRARY. THE USS~ L!5~RP.Y r;UST CONTAIH)
>!C ;[SPECT!1A AND RETE:ITIO:I n;;;s. ALSO. ALL DATA ;=ILES]
* : (prOCESSSD tlUST HAVE SCA.;'> AVA ILABLE FRGM 25]
>!c. ;C8ELCLI TIlE EA?LIEST IOLUn:,G COMPOr:EI-tT (OR START AT 0)]
>I< ;(TO 2S AOGVE THE LATEST :::LUT:NG CO~:?OtIENT.]
:I< ;[TO USER TME ?ROCEDU~E. CP.E~TE A LI8RARY]
* ;(WITH THE SPECT~A AND :;!ST~NTiON Tm::S. CREATE A]
* ;(Nm~ELIST CONTAitilNG THE: ?ILE TO BE PROC:::SS::D.]
* ;[ ]
* ;[TriEN: >OCEVAL XV.li;:U.l::;L,:;T.I:OCYES)
* ;[ ] .
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APPENDIX: II. d.
Q~:~:~~: ~::~
CH~~FlCERIZATiON R~PQ~T
FILE:
HUM SPEC'}
PliRITY
FIT
, -
-------
C-81
APPENDIX III.
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ORGRNICS CHAR;:ICTE:;1IZRTlOti REPORT
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e/eo/EI!:J
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HAM HUM: UT FORr:t.ILA
39 1: 126 CO.Hl.:1.0
39 2: 144 C9.H20.0
39 3: 145 C6.H4.CL2
39 4: 130 ca.HIB.a
39 5: 13'3 C9.HI4.a
33 6: 162 CB.HIS.03
39 7: 0
39 B: 134 C9.Hle.a
39 9: 154 C 12.H 1a
39 10: 170 CI2.HIO.O
39 11: 222 CI2.HI4.04
39 12: 0
39 13: 220 C!5.HZ4.C
39 14: 96 C4.H4.0.HZ
39 15: e
39 16: e
39 17: a
39 18: 0
39 19: 0
39 28: 154 CB.HIO.03
39 21: 154 CI0.HI8.0
39 22: 266 CIZ.HZ7.04.P
39 23: 268 C19.H4a
39 24: 140 C9.HI6.0
39 25: 154 C9.HI4.02
39 26: 162 CB.H1e.03
39 27: 222 CI0.H22.05
NUM SPEC~ PURITY FIT
1 a 0 0
2 8 I) a
3 a 8 e
4 221 446 e55
5 e 0 e
6 e e e
7 a e e
B 0 8 e
9 a e 0
10 0 8 0
11 e 8 a
12 a I) 0
13 e e 0
14 e 8 e
15 696 411 e54
16 696 395 85h
17 92B 6~Z 97l~
18 8 a a
19 0 0 e
20 e 0 e
21 488 361 824
22 60Z 572 943
Z3 0 0 (J
~.1 0 8 iI
25 (3 a lJ
Z5 2G7 201 8::1
27 0 8 0
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NAI"E
2-ET'iYt. -2-HEX=:~IAL (liC)
2.5-DI~~TH\~-4-r.EPTANOL OR 5 HONA~OL (
D ICHLOROBE~IZEf!E ISOt'Ei=! eNC)
2-ETHYL-1-HE:
-------
APPENDIX D
Bacteriological Methods
-------
D-3
Bacteriological Methods
Bacteriological analyses of fecal coliform bacteria densities
were performed according to standard procedures using the Most
Probable Number technique*.
Using asceptic techniques, all samples
were collected in sterile bottles prepared by the accepted procedure.
Replicate analyses were performed for quality control purposes;
these data showed very good control and are available in the NEIC
laboratory files.
/
* Rand, M. et al, 1975.
Water andlWastewater.
Standard Methods for the Examination of
14th Ed. APHA - AWWA - SPCF, 1193 pp.
-------
APPENDIX E
Bioassay Methods
-------
E-3
BIOASSAY METHODS
Toxicity tests consisted of 96-hour bioassays performed according to
EPA standardized methods (EPA-600143-78-012).
A continuous flow
proportional diluter was used which provided a series of six effluent
concentrations and a 100% dilution water control.
Test chambers were
of all glass construction and of 8 liter capacity.
Flow rates were
regulated to provide a minimum of nine volumetric exchanges of test
solution for each chamber for each 24-hour period.
All concentrations
were done in duplicate with all test chambers containing ten fish.
The test fish used were young of the year fathead minnows (Pimephales
Promelas Refinesque) obtained from the Newtown Toxicology Laboratory
located at Cincinnati, Ohio.
The fish, approximately 4 cm long, were
acclimated for 96-hours prior to testing in Kanawha River water and
given prophylic treatment (25 mg/l Oxytetracycline HC1) to prevent
bacterial infection.
Dilution water was obtained from the Kanawha River at a point approx-
imately 3 km (2 River miles) upstream of the mouth of the Elk River.
The dilution water was stored in 1100 liter (300 gallon) epoxy-coated
wooden reservoirs and was replenished every 24-hours.
Test water for the South Charleston Sewage Treatment Company bioassay,
was pumped continuously and directly from outfall 001 to the bioassay
laboratory.
All test chambers were monitored daily for pH, temperature
and dissolved oxygen concentration (Table E-l).
In addition the high,
middle and low concentrations were analyzed for total alkalinity.
Water
temperature in the test chambers was maintained at 23.5°C + laC by use
-------
. 'E':4
of a constant temperature recirculating water bath.
Mortalities in each test chamber were recorded at 24-hour intervals.
The 96-hour LCSO value was calculated by computerized tape program based
on the Spearman-Karber probit technique.
-------
E-5
TABLE E-l
Physical-Chemical Characteristics
Union Carbide South Charleston Sewage Treatment Company Effluent
Augus t, 1978
Parameter Effluent Concentration (%)
Control 10 18 32 56 75 100
24-hour
DO mg/l 6.7 6.4 6.0 6.0 5.7 5.8 5.7
Temp. °C 23.3 23.2 23.2 23.2 23.3 23.2 23.5
pH 7.3 7.4 7.5 7.6 7.7 7.8 7.8
Total Alkalinity 34 206 331
48-hour
DO mg/l 6.5 6.1 6.0 6.0 5.5 5.5 5.3
Temp. °C 23.6 23.5 23.5 23.4 23.7 23.7 24.0
pH 7.2 7.3 7.4 7.5 7.6 7.7 7.7
Total Alkalinity 29 155 236
72-hour
DO mg/l 6.9 6.5 6.5 6.2 5.7 5.5 5.5
Temp °C 23.6 23.5 23.4 23.4 23.5 23.5 23.8
pH 7.2 7.5 7.6 7.6 7.7 7.8 7.8
Total Alkalinity 28 198 328
DO mg/l 7.6 7.3 7.0 6.7 6.0 5.9 5.8
Temp. °C 23.4 23.4 23.5 23.4 23.4 23.7 24.1
pH 7.2 7.4 7.4 7.5 7.6 7.7 7.7
Tota 1 A lka 1 i nity 30 225 357
-------
APPENDIX F
Mutagen Assay Methods
-------
F-3
Mutagen Assay Methods
I.
Sample Extraction
A 4:1 (80% benzene, 20% isopropanol) mixture of solvents was placed
in a clean, 1 gallon amber solvent bottle and continuously stirred
during the extraction procedure to assure adequate mixing.
For basic extractions, one-liter portions of sampleswere adjusted
above pH 12 with NaOH.
Each one liter aliquot was extracted three times
(5 minutes each) with 35 ml of fresh solvent.
The solvent fraction was
then separated, mixed with anhydrous sodium sulfate to remove any emulsion
and filtered into a one-liter round bottom flask.
The aqueous fraction
was retained for acidic extraction.
The combined solvent fractions (35 ml x 3 liters of sample extracted)
were evaporated to dryness at 50°C in a rotoevaporator.
The residue was
resuspended into 15 ml sterile dimethylsulfoxide (DMSO), labeled and
stored at 4°C until assayed by the Ames Procedure.
II.
Bacterial Mutagenicity Assay
The Standard Ames Bacterial Assay was performed using the plate
incorporation assay as described by Ames, et al.* Acidic and basic
sample extracts were screened with standard. Salmonella typhimurium
tester strains TA 98, TA 100, TA.1535 and TA 1537.
Samples were first
tested individually; if the sample demonstrated an elevated reversion
rate a dose-response relationship between concentration of sample ex-
tract and number of revertant colonies was determined for each responsive
....
tester strain.
Samples exhibiting a negative mutagenic response were
subjected to metabolic activation by addition of $-9 mix (supernated
from 9000 x g centrifugation rat liver homogenate).
The Bacterial Assay
was then repeated as discu~sed above.
* Ames, B.N., ~1cCann, J., and Yamasaki, E., Hethods for Detecting
Carcino ens and Muta ens with the Salmonellajt1ammalian-Microsome
Mutagenicity Test. Mutation Research, 31, 1975 347-364.
-------
F-4
III.
Quality Control
A three-liter volume of sterile distilled water was added to
a l-gallon amber glass bottle and treated as a sample.
This served
as a blank on the sample bottles, distilled water, extracting sol-
vents, emulsion removal, and the concentration process.
A DMSO blank
was tested to ensure that the material did not interfere with test
results.
The tester strains, TA 1535, TA 1537, TA 98 and TA 100, were
exposed to diagnostic mutagens to confirm their natural reversion
characteristics.
The strains were tested for ampicillin resistance,
crystal-violet sensitivity, ultra-violet light sensitivity, and
histidine requirement.
Spontaneous reversion rates were tested with
each sample analyzed.
Rat liver homogenate was tested with 2-aminofluorene against
strains TA 98 and TA 100 to confirm the metabolic activation process.
/
Sterility checks were performed on solvents, extracts, liver
preparation, and all culture media.
-------
APPENDIX G
TECHNICAL INFORMATION
DATA BASE DESCRIPTION
/
-------
G-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 Tox1ine data base cDntains over 650,000 records taken from
material published in primary journals.
It is part of the ~EDLINE
.:
file from the National Library of Medicine and is composed of ten
subfil es:
(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 )
Environme~ta1 Mutagen Information Center 1969-
(Dept. of Energy, Oak Ridge National Lab)
-------
G-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) Teratology 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 citations on the .health .
aspects of pesticides compiled by Dr. W. J. Hayes, Jr., EPA)
------- |