ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
EPA-330/2-77-013
EVALUATION OF CARBON TETRACHLORIDE DISCHARGES
AT
FMC CORPORATION, SOUTH CHARLESTON EAST PLANT
South Charleston, West Virginia •
June 1977
National Enforcement Investigations Center
Denver, Colorado
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CONTENTS
I SUMMARY AND CONCLUSIONS 1
II INTRODUCTION 2
III WASTEWATER DISCHARGE POINTS 5
IV MONITORING PROCEDURES ..... 7
V MONITORING RESULTS 11
APPENDICES
A March 15 Consent Order
B Chain of Custody Procedures
C Flow Measurement Techniques
D Analytical Quality Control
E Monitoring Results
/ .
iii
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I. SUMMARY AND CONCLUSIONS
1. From 0630 hours, April 13 through 0630 hours April 21, 1977 waste-
water discharges from Outfalls 018, 019, 022, the sulfur wash system
and the carbon adsorption unit at the FMC South Charleston, W. Va.
East Plant were monitored for the discharge of carbon tetrachloride.
Outfalls 018, 019 and 022 discharge to the Kanawha River. The sulfur
washwater and the water from the carbon adsorption unit are discharged
through Outfall 018. Flow was measured and the carbon tetrachloride
loads were calculated for each monitoring point. These discharge
points were monitored to determine if FMC was in compliance with the
March 15, 1977 consent order which limited the carbon tetrachloride
discharge from Outfall 018 to 68 kg (150 lb)/day.
i
2. During the eight-day survey, the maximum amount of carbon tetra-
chloride discharged from Outfall 018 was 7.7 kg (17 lb)/day. This
maximum discharge occurred durinci the sampling period 0630 April 13
to 0630 April 14. From April 14-19, the carbon tetrachloride discharge
from Outfall 018 was less than 2.7 kg'(6 lb)/day. On April 20, the
carbon tetrachloride discharge was 6.4 kg (14 lb)/day.
3. The maximum amount of carbon tetrachloride discharged from Outfall
018 during this survey was in compliance with the consent order.
4. From April 13 through April 19, the carbon tetrachloride discharged
from Outfall 019 was less than 0.45 kg (1.0 lb)/day. On April 20, the
carbon tetrachloride was 5.4 kg (12 lb)/day. The increase in the carbon
tetrachloride discharged from Outfall 019 was due to a spill outside
the spill containment system.
5. The discharge of carbon tetrachloride from Outfall 019 is not in
compliance with the consent order since such discharge is prohibited.
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2
II. INTRODUCTION
The FMC East Plant, at South Charleston, West Virginia, manufac-
tures carbon tetrachloride (CCI4) by reacting carbon disulfide with
chlorine. Both the carbon disulfide and chlorine are produced in
another portion of the East Plant. Waste water from the carbon tetra-
chloride manufacturing area is discharged from Outfalls 018, 019 and
*
022 to the Kanawha River [Figure 1].
In February 1977, excessive amounts of CC14 were found in the
Kanawha and Ohio Rivers and as a result, a temporary restraining order
requiring FMC to cease manufacturing CCI4 was issued March 9, 1977 by
the United States District Court for the Southern District of West
Virginia. Between March 9 and March 15, 1977, the Environmental Pro-
tection Agency and FMC negotiated a consent order [Appendix A] that
would allow FMC to resume manufacturing CCI4. This consent order was
signed by both parties March 15, 1977 and set a discharge limit of
68 kg (150 lb)/day for the discharge of CC14 from Outfall 018. No
other CCI4 discharges are allowed from the plant. In addition, the
carbon adsorption unit is to be designed to treat wastes, discharged
from the decanter unit, to levels of less than 4.5 kg (10 lb)/day of
CCI4.
On March 24, 1977, the Environmental Protection Agency, Region
III and Headquarters, requested that the National Enforcement Investi-
gations Center (NEIC) monitor CCI4 discharges from Outfalls 018, 019
and 022 to determine whether FMC was in compliance with the consent
order. On March 28, NEIC personnel visited the plant and FMC personnel
stated that the plant was not operating because of problems encountered
during attempted startups. During the period of March 28-April 15,
NEIC personnel made numerous visits to the plant, but these problems
*
NPDES Permit Numbers
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Figure 1
Sketch of Wastewater Discharges
From FMC CCI4 Area
From CI2 Unit
Carbon Uni.t
•3 ODDBDBDBSBBBOD QB
CCl* Tank Car
CCI/i Process
Water
Tank Car "
Wash Water
Ptt
Coolinr
Water
cci4
Mfg.
Area
Uni t
Effluent
From
NH-j Unit
Spill
Contain
ment
Pit
Spill Containment
Dikes
Water from D
¦ inside spill H
Q
contai nmervt-——*4
dikes 5
»3 B EB BS 83 B B8 D BBBQBBBN
eancBea
Suifur
Wash Unit
Sulfur Wash Effluent
Outfall 019
yOutfall 018
Outfall
122
Q- Denotes sample point
CO
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continued until April 9, consequently, the NEIC survey did not begin
until April 13, continuing until April 21. Outfalls 018, 019, 022,
the discharge from the carbon adsorber and the sulfur wash discharge
were monitored during the survey. The carbon adsorber and sulfur
waste discharges are discharged through Outfall 018.
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5
III. WASTEWATER DISCHARGE POINTS
The wastwater containing carbon tetrachloride that is discharged
through Outfall 018 [Figure 1], originates from two areas within the
carbon tetrachloride plant. The first stream originates in the CCI4
purification section of the plant and consists of wash water. Currently,
this wash water is treated to remove most of the CCI4 by routing the
wash water through two decanters in series and then through an acti-
vated carbon column before discharging it through Outfall 018. The
flow rate of this stream ranges from 0.20 and 0.60 m (50 and 150 gal)/
min. The second CCl^ containing source originates in the sulfur re-
covery portion of the plant and consists of wash water from washing
the sulfur. This sulfur wash water, containing CCI4, is currently
discharged to Outfall 018 without treatment. By January 1978, a treat-
ment system will be installed to remove the CCI4 from sulfur wash water.
The flow rate from the sulfur wash system ranges from 0.90 and 1.70 m3
(250 and 450 gal)/min. The total discharge rate from Outfall 018 is
3 3
approximately 122 m (32,000 gal)/min. The major portion [119 m
(31,500 gal)/min] of this waste water originates in the chlorine manu-
facturing area.
The discharge through Outfall 019 is once-through, non-contact
cooling water, used in about 15 to 20 heat exchangers within the CCI4
plant and this flow rate ranges from 26 and 32 m3 (6,800 and 8000 gal)/
min. There should be no CCI4 in this, but since most heat exchangers
leak, small amounts of CCI4 are found. This stream is discharged with-
out treatment. FMC has installed a monitoring system to detect CCI4
at several locations (about 20) where the cooling water discharges to
the collection header. Five of these monitoring locations feed samples
to an ARCAS total hydrocarbon analyser that monitors the sample for
total hydrocarbons. The results of this analysis are transmitted to
the carbon tetrachloride control room and printed out on a strip chart.
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6
If the total hydrocarbons for any of the five waste streams exceeds
4 ppm, the operator manually diverts the contaminated waste from
Outfall 019 into a spill containment system. All water discharged
into the spill containment system is treated by the activated carbon
column and discharged through Outfall 018 into the Kanawha River.
The hydrocarbon analyzer samples each of the five streams about every
5-6 minutes.
The other approximately 15 monitoring points are conductivity
cells. These conductivity cells send a signal to the process control
room and, when the conductivity of a stream changes by a certain
amount (amount of conductivity change unknown), this stream is manu-
ally diverted from Outfall 019 to a spill containment system. Any
water entering the spill containment system is subsequently treated
by the activated carbon column and discharged via Outfall 018.
The majority of the wastewater discharged from Outfall 022 orig-
inates in the ammonia plant and should be free of CCl^. Tank cars
used for shipping CCI4 are washed in this area and this wash water
containing CCI4 was formerly discharged via Outfall 022. FMC has
modified this system so that all tank car wash water is now discharged
through Outfall 018. Even though the tank car wash water is not cur-
rently being discharged to Outfall 022, small amounts (100 to 300 ppb)
of CCI4 are present in this discharge.
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7
IV. MONITORING PROCEDURES
During the period April 13 through April 20, 1977, samples for
CCI4 analysis were collected and flows were measured at Outfalls 018,
019, 022, the sulfur wash effluent, and the carbon adsorption unit.
Chain-of-custody procedures [Appendix B] were followed for the col-
lection of all samples and field data and for laboratory analyses.
Samples were collected by FMC personnel at the same time and locations
as the NEIC samples were collected.
FLOW DETERMINATIONS AND MONITORING LOCATIONS
Outfall 018
The sampling location for Outfall 018 was at the company-installed
collar-pipe tap just above the point at which the pipe became submerged
in the Kanawha River. Flows were determined by the dilution technique
using Lithium Chloride as a tracer [Appendix C]. Company personnel
measured the flow using a potassium dichromate solution as the tracer
for the dilution technique. Flows were also measured by NEIC (using
the Lithium method) at a manhole approximately 15 m (50 ft) upstream
of the 018 sample point. This flow measurement was used as a check
on the flow from Outfall 018. The concentrated lithium chloride solu-
tion was injected into the waste stream approximately 90 m (300 ft)
upstream of the 018 sampling site.
> r
Sulfur Wash Discharge
The sampling location for the sulfur wash area discharge was at
a hole in the 20 cm (8 in) pipe about 1.5 m (5 ft) upstream of the
entrance to the 018 conduit. Flow determinations were made using
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8
lithium chloride. The concentrated lithium chloride solution was in-
jected into the waste stream near the sulfur wash area, about 90 m
(300 ft) upstream of the sampling site.
Carbon Adsorption Unit Discharge
The sampling location for the effluent from the carbon adsorption
unit was a tap located in the discharge line just downstream from the
unit flowmeter. Flows were measured using the company-installed turbo-
flowmeter and digital totalizer. Both are direct read-out units. A
calibration of these units was not possible; however, the flow deter-
mined by the flowmeter was in agreement with the totalizer flow.
Outfall 019
The sampling location for Outfall 019 was located in a rectangu-
lar concrete channel near the bank of the river. Instantaneous flow
determinations were made using the Dye-Dilution technique (April 13)
and using a Marsh-McBirney velocity meter (April 14 to 20). [Appen-
dix C]. The dye injection station was located at a 90° bend in the
channel, approximately 20 m (65 ft) upstream of the 019 sample site.
Velocity traverses with the Marsh-McBirney flowmeter were performed
at the sample site.
Outfall 022
Outfall 022 was sampled at the entrance to the company-installed
3-in. Parshall flume prior to where the wastewater is discharged to
the river. Flows were measured using the Parshall flume and recorded
continuously (April 13-17) by a Manning dipper flowmeter. Instanta-
neous head measurements at the Parshall flume were also recorded hourly
and converted to flow (April 13-20).
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9
FLOW MEASUREMENT PROCEDURES
Beginning at 0730 on April 13, flow measurements were made every
four hours at Outfalls 018 and 019, each flow corresponding to a CCI4
composite sample (see following section). For example, the 0730 flow
corresponds to composite No. 1 (0630-0930), the 1130 flow to No. 2
(1030-1330), etc. At Outfall 022 and the carbon adsorption unit, the
hourly instantaneous flows were averaged in six groups of four to
correspond to the six CCI4 composite samples. Flows for the sulfur
wash effluent were determined three times daily, i.e. once per shift,
at 1130, 1930 and 0330, with each flow corresponding to two of the
six CCI4 composites (1130 to No. 1, and No. 2, etc.).
SAMPLE COLLECTION PROCEDURE
Beginning at 0630 on April 13, individual grab samples were col-
lected hourly (on the half-hour to coincide with company procedure)
from each of the five monitoring locations. All samples were stored
in ice and shipped to the NEIC laboratory in Denver, Colorado at the
end of each 24-hour period. The CCI4 samples were composited on an
equal volume basis to correspond to the flow measurement frequency
for Outfalls 018 and 019 (i.e. every four hours). For example, the
hourly samples collected between 0630 and 0930 were combined equally
into the No. 1 composite sample, those collected between 1030 and 1330
into No. 2, etc., yielding six composites per location per day. All
samples were analyzed in accordance with EPA approved analytical pro-
cedures [Appendix D] which are in accordance with the methods of anal-
ysis specified in the consent order [Appendix A]. Samples were not
collected at the carbon adsorption unit while the unit was down, 1230
April 20 to 0330 April 21.
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The loads [kg(lb)/day] of carbon tetrachloride discharged from
each sample point were calculated using the average flow rate for
each four-hour period and the carbon tetrachloride analysis from the
corresponding four-hour composite. These six calculated loads were
summed to determine the total load for each 24-hour period.
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11
V. MONITORING RESULTS
Monitoring results are summarized by sampling locations [Table 1]
and discussed below. Complete physical and chemical data for each
sample location are found in Appendix E.
Outfall 018
The March 15 consent order [Appendix A] specifies that the carbon
tetrachloride discharge from Outfall 018 be less than 68 kg (150 lb)/
day. During the eight day survey, April 13-20, 1977, the maximum
amount of carbon tetrachloride discharged from this Outfall was 7.7 kg
(17 lb)/day April 13. From April 14-19, the discharge of carbon tetra-
chloride was less than 2.7 kg (6 lb)/day. On the final,day of the
survey, April 20, the carbon tetrachloride discharge was 6.4 kg (14 lb)/
day.
The maximum carbon tetrachloride discharge rate of 7.7 kg (17 lb)/
day is in compliance with the March 15 consent order.
Outfall 019
The March 15 consent order specified that carbon tetrachloride
shall not be discharged from any outfall other than 018. During the
eight days of the NEIC survey, carbon tetrachloride was discharged
daily from Outfall 019. From April 13 through April 19, the carbon
tetrachloride in the wastewater discharge was 0.45 kg (1.0 lb)/day
or less [Table 1]; however, on April 20 the carbon tetrachloride dis-
charged from Outfall 019 was 5.4 kg (12 lb)/day. This increase in
the carbon tetrachloride discharge was due to a spill that was dis-
charged via Outfall 019. The March 15 consent order does not allow
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Table 1
SUMMARY OF tlONITORINR RESULTS
FMC CORPORATION
April 13-21, 1977
DATE a/13 V14 4/15 4/16 4/17 4/18 4/19 a/20
S7ATI0M nVday kq/day m^/day kq/day m^/day kq/day ni^/day kq/day m^/day kq/day m^/day kq/day m^/day kg/day n^/day kq/day
x 1000 x 1 COO x 1000 x 1000 x 1000 x 1000 x 1000 x 1O00
(trqd) (lb/day) (mad) (lb/day) (mqd) (lb/day) (irqd) (lb/day) (mgd) (lb/day) (mnd) (lb/day) (r^d) (lb/day) (mod) (lb/day)
0:8
146
7.9
160
2.0
171
2.5
117
1.3
152
0.83
170
0.90
172
2.5
170
5 4
(38.6)
(17.0)
(42.3)
(4.4)
(45.1)
(5.5)
(30.9)
(2.8)
(40 1)
(1.8)
(45.0)
(2.0)
(45.4)
(5.5)
(£4 8)
(14.0)
r S
(flow only)
174
170
144
151
161
ICi
15=1
u"stream
(45.9)
(45 0)
(38.0)
(40.0)
(42.4)
(43.4)
(42.0)
Carbon**
0 27
<0.81*
0.27
<0.82*
0.31
<0.92*
0.30
<0.90*
0.28
<0.84*
0.27
<0.82*
0 27
<0.82*
0.91
0.89
sosos ;t:on Urn t
(0.071)
<(1.8)
(0.071)
<(1.8)
(0.021)
<(2.0)
(0.079)
<(2.0)
(0.074)
<(1.9)
(0 072)
<(1.8)
(0 072)
<(1.8)
(0.024)
(2.0)
Sul fur 'Jash
1.2
0.78
1 .2
2.6
1 1
2 5
1 2
? 0
1.2
1.2
1.2
1.1
1 3
2.1
1.2
2.0
(0.32)
(1.7)
(0.32)
(5.3)
(0 29)
(5 6)
(0.31)
(4.5)
(0.11)
(2.5)
(0.32)
(2.5)
(0 34)
(4.6)
(0.31)
(a-4)
019
37.2
<0.30*
40.9
<0 26*
41.1
<0J5*
39 3
<0 23*
40 2
<0.21*
38.7
0.25
3°.2
0.47
43.1
<5.6*
(9.8)
<(0.56)
(10.3)
<(0.57)
(10.9)
<(0.33)
(10.4)
<(0 62)
(10.6)
<(0.46)
(10.2)
(0.55)
(10.4)
(1.0)
(11.*)
<(12.0)
022
1 0
0.22
1 0
0.19
2.7
0.28
2.4
0 17
1 .9
0.21
i 8
0 ^4
0.90
0.13
0.45
0.10
(0.26)
(0.49)
(0 26)
(0.42)
(0.68)
(0.62)
(0 62)
(0 37)
(0.49)
(0.46)
(0.47)
(0 32)
(0 22)
(0 28)
(0.12)
(0.22)
~Indicates tnat one or rro^e o 6 daily 4-hour comoosites was less than detectable limit of 3 ppb; thus, load is shown as "less than."
**Locas for carbon adsorption are in qrans/day and 10~3 lb/day
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13
any carbon tetrachloride to be discharged from Outfall 019, FMC was
not in compliance with the consent order. In addition, the spill on
April 20 was not in compliance with the consent order.
Outfall 022
The carbon tetrachloride discharge from Outfall 022 ranged from
0.10 to 0.28 kg (0.22 to 0.62 lb)/day [Table 1] during the survey.
The March 15 consent order does not allow any carbon tetrachloride
to be discharged from Outfall 022; FMC was not in compliance with
the consent order.
OTHER MONITORING POINTS
i
The discharge from the sulfur wash system was monitored during
this survey as a partial check on the 018 discharge. The sulfur wash
wastewater contains the majority of the carbon tetrachloride that is
discharged through Outfall 018. The maximum amount of carbon tetra-
chloride discharged via the sulfur wash system was 2.6 kg (5.8 lb)/
day [Table 1]. The amount of carbon tetrachloride in the sulfur wash
stream was approximately equal to the carbon tetrachloride in Outfall
018 except on April 13 and April 20. The difference in the loads
from the sulfur wash stream and Outfall 018 for April 20 is explained
by the carbon adsorption unit not being in operation on this date,
but the large difference detected on April 13 cannot be explained.
f
The average carbon tetrachloride discharge from the carbon ad-
sorber was very low, less than 0.0009 kg (0.002 lb)/day, [Table 1]
during the survey. The maximum carbon tetrachloride concentration
3
in this wastewater stream was 19 ppb with a flow rate of 0.09 m
(25 gal)/min. This is a maximum load of 0.003 kg (0.006 lb)/day.
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The March 15 consent order requires that the carbon column effluent
contain less than 4.5 kg (10 lb)/day carbon tetrachloride; therefore,
the discharge from the carbon adsorber was in compliance with the
consent order.
SPILL CONTAINMENT SYSTEM
The consent order required that a spill containment system be
installed around the carbon tetrachloride process area before the
process was put into operation and this system was completed prior
to any attempted start-ups. The spill containment system was in
compliance with the consent order.
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APPENDIX A
March 15 Consent Order
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1
UKITE3 STATES DISTRICT CCJJ'T tOR 1iIE
SOUTHS?.!; L'lCiRICT OF WI.ST V1IGISIA
KUKTINGTO!?
unxtj:d si aits or ay-trica,
Plaintiff,
V. CIVIL ACTIO:i \0.
PilC CORPORATION,
Defendant.
\
co:>ti;n? opdur
The complaint h&vir.y fccsn filed on .'larch 9, 1577, er.d
with plaintiff and defendant by thc.ir respective attorneys hcviny
cor.f?mtcd without trial or adjudication of any icsua of feet cr
Iz-i heroin to ths entry of this Order, end v/ithcut thia Crd«vr
constituting r.r.y cvidcr.co or adL-.ission by any pirty hjirsto with
respect to &-iy issua of fnct or law horeint
HOW, TL'tKZFCKJS, before cha taking of ai.y testii:.or.y, upon
the pleacinrs, end without adjudication of any issue of fact or
lav: hc-rcin, and upon th3 consent of thn parties hereto, it ia
CiOLPJiO, ADJUDGED and DiCRIZD so follcv3t
I
This Court ha3 jurisdiction of tho siiLjt-ct rstter end of
' ' S
tho parties consent Jtivj hereto*
<*
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II
Tha provisions of this Crdor shftll ap^ly to and bo birJiny
upon the defendant, its officials, dirc-ctore, &c;ent3, servants, em-
ployers, successors and assigna c.r.d ell pcrsor.3, fir:.3 cud. corporations
acting ur.dor, through or for it and upon these persons, fir.^3
and corporations in active concert or participation with it.
Ill
Tha defendant (hereafter T: 1C") way co:.-,;ncc and
continue tha operation of it3 cnlff chlorine reaction cystcJa
at its South Charleston, Kcst Virginia pl-int (the "Plant")
when and eo lcr.g as it hnsi
r
A. Erected a containment system sufficient to contain
approximately 21,000 L-allcna, around tho snifcf chlorine reaction
systers and plugged all savers, conduits, pipes or other con-
veyances fron within the contained area in a tanner desicjneJ
to prevent any spill3, leaks or ot^ar types of discharges frora.
che enlff chlorine 3yetaa from reaching the Kanawha liivtr or
oth?r waters of tho United Statesj
D. Frovided twenty-four (24) I.our visual survsillar.es
to detect And eliminate the presence of ar.y g^1113, l«a).s or ar.y
other type of discharge of carbon tetrachloride into tho contained
area; and
-2-
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C. >Jada adequate prevision# including but not United
to twenty-four (24) hour visual observation, for tho storare,
transport, and disposal of the first stage carbon tetrachloride
product mix produced thereby in a manner designed to prevent any
spill, leaJ; or other discharge into tho mnavha River or other
waters of the United States and so stores, transports, and dis-
poses of such product .-nix. Transfer of cuch product nix to
temporary storage shall only occur during daylight hours ar.d shall
bo in a "batch" iroaa and under continuous visual surveillance.
IV
FflC ray commence and continue the manufacture of '
carton tetrachloride at tho Plant vhen and so long as it hacx
A. Installed treatment facilities on the discharge
lino frora the decanter unit designed to treat wastes discharged
thersfroa to level3 less than 10 pounds of carbon tetrachloride
on a single cay, provided however, thati
1. The treatment facilities shall consist of a
single stage activated carbon column system with the apourte-
nanccs required for trcati.tent of all process waste vatcrs dischAr^vd
froa the decanter unit;
2. Tho tre&trar.t facilities shall be operated at
t T
all tiues to iiininize the discharge of carbon tetrachloride.
-3
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3. FIIC shall c.or.itor carbon tetrachloride! in tho
discharge from the treatment facilities by taking flow proportioned
composited samples at least onco every four hours, shall average
tha amounts of carbon tetrachlorides in all composited camples taken
during each day, shall split samples with r.?A on request, shall
analyze the samples using the analytical procedure attached hereto
as Exhibic A, sfinll submit the results of such analysis to E?.\
weekly, and shall allow l?A or its contractor to ironitcr carbon
tetrachloride in the discharge from the treatment facilities.
4* Whenever, after the completion of tha second
charge of carbon to the tre^tiicnt facilities, the treatment
facilities have bsen operated for a period of ten consecutive
days such the total discharge during any one day of that period
does not exceed the average of the daily discharges of all of thz tc
days during that period by r.ore than 100ft, an effluent 1 irrita-
tion Is thoxety established ecjucl to twice tha cverago of the
daily discharges on all of the ten day3 during that p^rioi.
FKC shall thereafter not discharge vaste3 fron the decanter
unit containing carbon tetrachloride in OKcec3, on any cay, of
the effluent limitation so established; and
5. FKC r.ay, at any tiiro, replaco the treatment
facilities with alternative tr
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tetrachloride equal to or less than tho air.ounts established In
paragraph IV-A-4 herein for the discharge of carbon tetracMorico
froa the decanter unit treated vccte water stream and cJ.c discharge
limitations eBt&bliahod in paragraph IY-.V-4 herein shall be modified
accordingly to a lessor number.
U. Erectad a containment systnn around the entire carton
tetrachloride production facility at the Plant r.nd plugged all
severe, conduits, pipes or other conveyances from within tho
contained area# excopt into outfall 013, in a ::cnr.er designed
to prevent any spills, leaks, or other types of discharges fro:i
tbo carbon tetrachloride production facility frora reaching tho
Kanawha River or other waters of the United State3.
V
A. PMC shall operate its trcatme.it facilities at all
tiisaa to RinirJlzci the discharge of carbon tetrachloride and In no
i
event shall It discharge carton tetrachloride fro= cutfall C13 at
the Plant to tho Kanawha *ivor in ur.ccc3 of 150 rounds on any
single day (tho "total discharge allowed"); provided, however,
that t
1. On or before January 1, 1973, r;;C shall install
a dual stage carbon treatment syster. on the discharge Una froa
the sulfur wash unit designed to treat v.'a3tcs discharged thcre-
fron to lovola less than 15 pounds per day.
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2. Fi1C ehill monitor carLon tetrachloride in tha
discharge from tho treatcont facilities by tahir.g flovf proportioned
coja£-ooitod oci=?lca at least onco every four hours, shall avcra«jo
the amounts of carbon tetrachloride in all co-.pcsited senrplas t-Ken
during each day, shall s;lit sor-plcs vith LFA on request, shall
finalyzo tho samples using the analytical procedure attached hereto
as Exhibit A, shall 3ubnit the results of such analysis to LTA
voekly, and shall allow TFA or its contractor to monitor carbon
tetrachloride in tha discharge froa tho treatment facilities.
3. Whenever, after tha thirtieth '-ay Collo'.?iny the
instillation of tho treatment facilities on tha discharge lina
fronj the sulfur wash unit, the treatment facilities havo been
oporatod for a period of ten consecutive days such that tho total
discharge during any or.a day of that period Joes not exceed tha
average of tho daily c'iechargts of all of the ten clays during
that period by coro than 100%, an effluent limitation is thereby
established equal to twice tho avera?® of th'a daily discharges on
all of the ten days curing that period. FKC shall thereafter not
diEchar^c vaste vatero frora the sulfur vash unit containing carbon
tetrachloride in excess, on any diy, of the effluent limitation
so established.
4. Whenever an effluent liritution io established
under paragraph V ,\-3 heroin, an effluent limitation shall bo
' ¦ >
established on outfall 013 at the Plant equal to tho sun of
-------
tho effluent limitation on tho dioch£.rgo froa the decanter
unit cGtabliched under paragraph IV A-4 harein and tho e-ffluo:it
limitation on tho discharge from tho sulfur wash unit established
under paragraph V .*-3 heroin. r^C shall thercaftcr not discharge
carbon tetrachloride frcra the Plant in excess, on any cay, of
that effluent limitation.
5. In tho event that the flow of tho Kc.r.cvha I'.Lv cr
at tho Charleston gau^e ia less than 2fcSd cubic f-cot per second
("cfs") prior to the tise that tha treatnent facilities required
by paragraph V horoin aro installed and operating, F:*.C shall
cea.sc discharging csrbcn tetrachloride fro:n the Plint until such
tins &a tha flov of the Kanwaha River cxcueds 2S20 cfs at the
Charleston gauge.
f
B. FKC shall discharge all process waste vatcrs containing
carbon tetrachloride froa the Plant through outfill 013. Vhcro
shall be no spill, leak, or any other type of discharge of carbcn
tetrachloride froa tho Plant other than as epscificd in this
paragraph V. In the ovent that any discharge other than a3
eet forth hazrein shall occvr, F.'!C shall not be relieved fron
liability under thia Order, unless and until F.iC dcr-cr.strite?
by clear and convincing proof to the satisfaction of this Court
that circumstances beyond its control, including enployea
negligence, which could not ba prevented or foreseen, caused
cuch discharge.
-7-
-------
C. l.'otvithstanding any other provision of this Order,
in tho event that carbon tetrachloride i3 spilled, leaked or
otherwise discharged to the Kanawha .Hivor froci tho Plant other
than as specified in this paragraph V, or appears likely to ba
discharged, P.'iC shall irnediati'ly take all steps necessary to
KLiniirJ.no or, if possible, elirtir.ato the quantity do spilled,
leaked or otherwise discharged. In the event of such a spill,
leak or ctl.er discharge, F!'C shall irr-ediately notify I A'A end
shall relate to it the circumstances leading to the event and
the rerc-dial nca^urcs tafcen. Compliance with the provisions
of t'ni3 Crder shall not relieve rl-iC fron legal liability for
any spill, leaX or other discharge.
VI
At cotrcDcncor.'.ent of tho nanufacture of carbon tetra-
chloride at the Plant, FHC shall coTjrenco continuous conitorir.g
of carbon tetrachloride (1) in the vaste discharge lice froa
the treatment sy3ten following the decanter unit; (I) in the
waste water discharge line from the sulfur wash system (after
treatment, or.ee treatment is installed); and (3) in the water
discharged fron outfall 015 to tho Kanawha Kiver and shall report
the results of cazta to EPA o.sca a veok. until /.fril 15, 1&77, and
once a nonth thereafter. Continuous cea:.3 aacpling at least
once ovory hour. Reports shall bo in terr-o of pounds of carbon
/ r
/
tetrachloride discharged per day.
-------
VII
F.MC shall, within 14 days of the effective date of
thia Order, rotoin the services of an outside engineering fira
utilizing registered professional engineers vjho c.ro competent
to per~om a detailed survey of the carbon tetrachloride unit
at the Plant. This firm will evaluate the physical integrity
of all tanhs, vessels, punps, piping and related equipment containing
carbon tetrachloride in the carbon tetrachloride unit. *he con-
tractor will further review the concept, design and installation
of x;er7r.an'-int faciliti_s for the prevention, containment and control
of accidental carbon tetrachloride discharges. l:pon completion of
this study the contractor will scbr.it a written report reco.Tu'renii^g
corrections of any conditions which could result in a cischargo
of carbon tetrachloride to the river. FitC will take action on
such recozurendutio.ns to correct the deficiency. Findings of tho
contractor er.d F.S'C'a progress on necessary rer.tdial action vill
bo transmitted to l;P.\.
VIII
Ff'.C will prcvido rerrcsc-ntativt23 of the Unviron.-.ental
Protection Agency access at all tiz^cs to the Plant in accordance
with the following procedure!
A. Tha representatives shall call tho rain riant
t 7
telephone r.ur&er* They shall idantify thor.&olvea
and during the hour3 of 8jC0 A.n. to 5:00 p.m.
-9-
-------
ahall oak for tho resident plant t.anagur or hio
designee. During tho hour3 of 5*.00 p.n. to 8:00 a.n
they shall only identify thenselvcG to tho operator.
After identifying themselves they shall armounco
the area of tha L'lant to vhich they oosire acceas.
Access to the carbon tetrachloride area shall be
accorded within thirty ninutes fron tha tica the
area to ba ins^ectod is Ocsisriitctd* Access to
other areas of tha Plant shall hz accorded within
sixty pir.utca fron the tine tho aroa ia designated.
B. ri1C Corporation reserves the right to clc-ny acccs
to sach representatives in tho evynt that circur.star.
vould endanger tho health or Uvea of such represent
tivo9. In such event, FJ-'C Corporation shall advise
the representstive3 in detail of such circ.ir.stances.
Iraediately after tho removal or passage of such
circumstances, acccss shall bo granted to such
representatives.
IX
This Order is not and shall not bj interpreted to
bo a pemit under section 402 of the Federal irater Pollution
Control Act (33 U.S.C. Sac. 1342), r.or shall it in any vray
relieve tho defendant of any obligation imposed by the
/ r
Federal l.'ftter Pollution Control Act or in ar.y jernit issued
-------
thereunder, nor shall it in any way relievo tho defendant
of its obligation to comply with er.y other local, state or
federal lew in ar.y way related to tho subje.ct of thin Order.
of enabling cither party to this Order to apply to the Court at
any tiac for such further Ozdero or directions as nay be a^propriri
for the construction or carrying out of this Order or for tho
modification of t!ie terr.3 of any of tha provisions hereof or
for the enforcement or dissolution hereof.
X
Jurisdiction ic retained by the Court for the purpose
Va hereby consent to the entry of thi3 COl.'SJ.N? CaDEH
without further noticet
UK I TED CCATiS C? AFRICA
VMr* Cnr->nr.i >• i nr»
Judgment entered in cccorcance with tha forc-coir.9 Conccn
Order, this
-------
Industrial Chemical Division
Technical Department
Control Laboratory
SC South Charleston
Technical
Analytical Method SC11-21 (3-77)
Waste Water
Method for CCL4 (Gas Chromatograph)
Based On:
This procedure is based on work done at ICRD, Princeton,
New Jersey and at South Charleston, West Virginia.
Carbon tetrachloride in water is measured by direct
injection of the aqueous sample into a chromatograph equipped
with an electron capture detector. Familiarity with the instru-
ment and detector is assumed.
Calibra tion:
Prepare four solutions containing
p9/9 CCL4 in methanol. Caution: All glassware must
be cleaned with soap and water, rinsed with pure water, and baked
in an over at 400°C for 2 hours. Store in a clean desiccator
until ready to use. Prepare a series of about ten hypo bottles
(50 ml) equipped with teflon lined rubber seals and aluminum crimp
caps or with mimert valves. Fill the bottle completely full
(no air bubbles), seal and weigh. 1
Inject microliter quantities from the strong standards
and mix well. Glass beads or a teflon stir bar facilitate the
mixing. These aqueous standards should be prepared to cover a
range of 1 ppb to 1 ppm.
Inject 5 pi from each standard into the chromatograph
and calculate a response factor from the average. This factor
is programmed into the calculator-integrator in accordance
with the manufacturers instructions.
I
Procedure:
Inject 5 jjl of samples and read the ppb CCL4 from the
integrator print out.
LA Suttle
SCll-^i \i-ii)
-1-
Princeton
Central Research-
Attachment
"EXHIBIT A"
-------
!
Attachment No. 1
Instrumental Conditions
Hewlett-Packard (Model 5738) Gas-Liquid Chromatograph
with ECD Detector - Nickel63 15 m Ci.
Column, 8 feet glass 6 mm ID packed with Tenax 60/80 inesh.
i
Carrier Gas - 5% methane in argon 60 PSI 60 mls/min flow.
Injector - on column 250°C.
Column - 165°C.
Detector - 300°C vented to hood with exhaust fan.
Integrator-recorder Hewlett Packard S3380A programmed per
instruction manual.
HA Martin
-------
APPENDIX B
Chain of Custody Procedures
-------
ENVIRONMENTAL PROTECTION AGENCY
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
CHAIN OF CUSTODY PROCEDURES
dune 1 , 1975
GENERAL
The evidence gathering portion of a survey should be characterized by the minimum'
number of samples required to give a fair representation of the effluent or water body
from which taken. To the extent possible, the quantity of samples and sample loca-
tions will be determined prior to the survey.
Chain of Custody procedures must be followed to maintain the documentation necessary
to trace sample possession from the time taken until the evidence is introduced into
court. A sample is in your "custody" if:
1. It is in your actual physical possession, or
2. It is in your view, after being in your physical possession, or
3. It was in your physical possession and then you locked it up in a manner so
that no one could tamper with it.
All survey participants will receive a copy of the survey study plan and will be
knowledgeable of its contents prior to the survey. A pre-survey briefing will be held
to re-appraise all participants of the survey objectives, sample locations and Chain
of Custody procedures. After all Chain of Custody samples are collected, a de-briefing
will be held in the field to determine adherence to Chain of Custody procedures and
whether additional evidence type samples are required.
SAMPLE COLLECTION
1. To the maximum extent achievable, as few people as possible should handle
the sample.
2. Stream and effluent samples shall be obtained, using standard field sampling
techniques.
3. Sample "tags (Exhibit I) shall be securely attached to the sample container
at the time the complete sample is collected and shall contain, at a minimum,
the following information: station number, station location, data taken,
time taken, type of sample, sequence number (first sample of the day -
sequence No. 1, second sample - sequence No. 2, etc.), analyses required and
samplers. The tags must be legibly filled out in ballpoint (waterproof ink).
4. Blank samples shall also be taken with preservatives which will be analyzed
by the laboratory to exclude the possibility of container or preservative
contamination.
5. A pre-printed, bound Field Data Record logbook shall be maintained to re-
cord field measurements and other pertinent information necessary to refresh
the sampler's memory in the event he later takes the stand to testify re-
garding his actions during the evidence gathering activity. A separate
set of field notebooks shall be maintained for each survey and stored in a
safe place where they could be protected and accounted for at all times.
Standard formats (Exhibits II and III) have been established to minimize
field entries and include the date, time, survey, type of samples taken,
volume of each sample, type of analysis, sample numbers, preservatives,
sample location and field measurements such as temperature, conductivity,
-------
2
DO, pH, flow and any other pertinent information or observations. The
entries shall be signed by the field sampler. The preparation and conser-
vation of the field logbooks during the survey will be the responsibility
of the survey coordinator. Once the survey is complete, field logs will be
retained by the survey coordinator, or his designated representative, as a
part of the permanent record.
6. The field sampler is responsible for the care and custody of the samples
collected until properly dispatched to the receiving laboratory or turned
over to an assigned custodian. He must assure that each container is in his
physical possession or in his view at all times, or locked in such a place
and manner that no one can tamper with it.
7. Colored slides or photographs should be taken which would visually show the
outfall sample location and any water pollution to substantiate any con-
clusions of the investigation. Written documentation on the back of the
photo should include the signature of the photographer, time, date and site
location. Photographs of this nature, which may be used as evidence, shall
be handled recognizing Chain of Custody procedures to prevent alteration.
TRANSFER OF CUSTODY AND SHIPMENT
1. Samples will be accompanied by a Chain of Custody Record which includes the
name of the survey, samplers' signatures, station number, station location,
date, time, type of sample, sequence number, number of containers and analy-
ses required (Fig. IV). When turning over the possession of samples, the
transferor and transferee will sign, date and time the sheet. This record
sheet allows transfer of custody of a group of samples in the field, to the
mobile laboratory or when samples are dispatched to the NEIC - Denver labora-
tory. When transferring a portion of the samples identified on the sheet to
the field mobile laboratory, the individual samples must be noted in the
column with the signature of the person relinquishing the samples. The field
laboratory person receiving the samples will acknowledge receipt by signing
in the appropriate column.
2. The field custodian or field sampler,, if a custodian has not been assigned,
will have the responsibility of properly packaging and dispatching samples
to the proper laboratory for analysis. The "Dispatch" portion of the "Chain
of Custody Record shall be properly filled out, dated, and signed.
3. Samples will be properly packed in shipment containers such as ice chests, to
avoid breakage. The shipping containers will be padlocked for shipment to
the receiving laboratory.
4. All packages will be accompanied by the Chain of Custody Record showing iden-
tification of the contents. The original will accompany the shipment, and a
copy will be retained by the survey coordinator.
5. If sent by mail, register the package with return receipt requested. If sent
by common carrier, a Government Bill of Lading should be obtained. Receipts
from post offices, and bills of lading will be retained as part of the perma-
nent Chain of Custody documentation.
6. If samples are delivered to the laboratory when appropriate personnel are not
there to receive them, the samples must be locked in a designated area within
the laboratory in a manner so that no one can tamper with them. The same per-
son must then return to the laboratory and unlock the samples and deliver
custody to the appropriate custodian.
-------
3
LABORATORY CUSTODY PROCEDURES
1. The laboratory shall designate a "sample custodian." An alternate will be
designated in his absence. In addition, the laboratory shall set aside a
"sample storage security area." This should be a clean, dry, isolated room
which can be securely locked from the outside.
2. All samples should be handled by the minimum possible number of persons.
3. All incoming samples shall be received only by the custodian, who will in-
dicate receipt by signing the Chain of Custody Sheet accompanying the samples
and retaining the sheet as permanent records. Couriers picking up samples at
the airport, post office, etc. shall sign jointly with the laboratory custodian.
4. Immediately upon receipt, the custodian will place the sample in the sample
room, which will be locked at all times except when samples are removed or
replaced by the custodian. To the maximum extent possible, only the custo-
dian should be permitted in the sample room.
5. The custodian shall ensure that heat-sensitive or light-sensitive samples,
or other sample materials having unusual physical characteristics, or re-
quiring special handling, are properly stored and maintained.
6. Only the custodian will distribute samples to personnel who are to perform
tests.
7. The analyst will record in his laboratory notebook or analytical worksheet,
identifying information describing the sample, the procedures performed
and the results of the testing. The notes shall be dated and indicate who
performed the tests. The notes shall be retained as a permanent record in
the laboratory and should note any abnormal ties which occurred during the
testing procedure. In the event that the person who performed the tests is
not available as a witness at time of trial, the government may be able to
introduce the notes in evidence under the Federal Business Records Act.
8. Standard methods of laboratory analyses shall be used as described in the
"Guidelines Establishing Test Procedures for Analysis of Pollutants,"
38 F.R. 28758, October 16, 1973. If laboratory personnel deviate from
standard procedures, they should be prepared to justify their decision dur-
ing cross-examination.
9. Laboratory personnel are responsible for the care and custody of the sample
once it is handed over to them and should be prepared to testify that the
sample was in their possession and view or secured in the laboratory at all
times from the moment it was received from the custodian until the tests
were run.
10. Once the sample testing is completed, the unused portion of the sample to-
gether with all identifying tags and laboratory records, should be-returned
to the custodian. The returned tagged sample will be retained in the sample
room until it is required for trial. Strip charts and other documentation
of work will also be turned over to the custodian.
11. Samples, tags and laboratory records of tests may be destroyed only upon the
order of the laboratory director, who will first confer with the Chief,
Enforcement Specialist Office, to make certain that the information is no
longer required or the samples have deteriorated.
-------
EXHIBIT I
EPA, NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Station No.
Dato
Time
Scquonco No.
8
o
*
Station Location
-Grab
-Comp.
_BOD
-Solids
_COD
_Nutricnts
Samplers.
_MetaIs
.Oil ancl Grease
_D.O.
_Bact.
-Other
Remarks / Preservative:
Front
I
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
J*""*
p ^ \
J?
Back
-------
z 52
i ^
m y
79 Z
1
r
r
(A
-4
o
z
o
22
"V
o
z
TOTAL VOLUME
TYPE CONTAINER
TJ
JO
m
m
TO
2
rj
<
NUTRIENTS
BOD
COD
TOC
TOTAL SOLIDS
SUSPENDED SOLIDS
ALKALINITY
DO
pH*
CONDUCTIVITY*
TEMPERATURE*
TOTAL COLIFORM
FCCAL COLIFORM
TURCIDITY
OIL AND GREASE
METALS
BACTI
PESTICIDES
HERB
TRACE ORGANICS
HHTNOL
-------
E IT
Samplors:
FIELD DATA RECORD
STATION
NUMBER
DATE
TIME
TEMPERATURE
°C
CONDUCTIVITY
/tmhos/cm
PH
S.U.
D.O.
mg/l
Goge HI.
or Flow
Ft. or CFS
-
•
t
I
-------
I
EXHIBIT IV
ENVIRONMENTAL PROTECTION AGENCY
Office Of Enforcement
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Building 53, Box 25227, Denver Federal Center
Denver, Colorado 80225
CHAIN OF CUSTODY RECORD
SURVEY
SAMPLERS: (Signature)
STATION
NUMBER
STATION LOCATION
DATE
SAMPLE TYPE
TIME
Woler
Comp Grab
Afr
SEO
NO
NO OF
CONIAINERS
ANALYSIS
REQUIRED
Relinquished by: (stature)
Received by: (Signature;
Dale/Time
Relinquished by: (s.gnatmc)
Received by: (Signoture/
i r ;
Date/Time
1
Relinquished by: (S.gnoiurej
Received by: (stature)
Date/Time
Relinquished by: (Signature)
Received by Mobile Laboratory for field
analysis: (Signature)
Date/Time
Dispatched by: (Signature)
Date/Time
1
Received for Laboratory by:
Date/Time
1
Melhod of Shipment:
Distribution: Orig. — Accompany Shipment
1 Copy—Survey Coordinator Fiold Files
-------
APPENDIX C
Flow Measurement Techniques
-------
FLOW MEASUREMENT USING LITHIUM CHLORIDE
Flow determinations at two monitoring locations (Outfall 018 and
the sulfur wash effluent) were made using the lithium chloride tracer
method. In this technique a solution of lithium chloride of known
concentration is injected at a constant rate an adequate distance up-
stream of the sampling point to insure complete mixing. Samples are
then collected at the monitoring location to determine the lithium
concentration in the waste stream. The flow is then calculated from
the known injection rate, the concentration of the injected lithium
and the lithium concentration after mixing in the wastewater.
Samples were analyzed for lithium at the NEIC laboratory in Denver
on a Perkin-Elmer Model 403 Atomic Absorption spectrophotometer. Cali-
bration of the instrument was performed daily using lithium standards
of known concentration. Frequent checks were made during the day to
insure accuracy.
A preliminary study of the two monitoring locations whose flows
were measured by lithium chloride tracer was conducted prior to the
start of the survey. In this study, samples from these two sites were
analyzed for background levels of lithium to determine the concentra-
tion necessary for the injected lithium and the appropriate injection
rate. During the initial set-up period in the field, and after one
week of sampling, these studies were repeated with similar results.
The preliminary field study also tested each outfall to determine the
injection time required for development of the concentration plateau.
A factor of safety was then included in the collection time'at each
station to insure that sampling occurred after the concentration pla-
teau had been reached. Background samples were taken with each flow
sample prior to injection of the lithium and the concentration of lith-
ium in each flow sample was corrected for the background concentration.
Also, a sample of the injected lithium solution was taken with each
-------
flow sample and analyzed to obtain the concentration. Other quality
control procedures included: 1) measurement of pump injection rates
at least 4 times per day, 2) a check to determine the length of time
required for the lithium concentration to return to background concen-
trations after the injection pumps were shut off.
DYE DILUTION TECHNIQUE FOR FLOW MEASUREMENT
Flow determinations were made at Outfall 019 (April 13-14) using
the dye dilution technique with fluorometric detection. In this pro-
cedure, a fluorescent dye is introduced into the flow stream, and the
concentration of the dye is monitored downstream at the sampling point.
The dye injection station is located far enough upstream to insure
complete mixing at the sampling site. The dye is premixed gravimetri-
cally to a known concentration and is injected at a known and constant
rate. The flow at the sampling point is determined from the injection
rate, the known concentration of the dye, and the measured concentra-
tion of the dye in the flow stream.
The dye used in this technique is Rhodamine WT, which exhibits
high sensitivity, a low sorptive tendency, and stability under varying
pH conditions. The fluorescence assay equipment consists of the G.K.
Turner Model 111 fluorometer, with a far UV lamp, a high sensitivity
kit, a standard door and a matched set of cuvettes. The fluorometer
is calibrated once per day by measuring the fluorescence of gravimetri-
cally prepared standards of known concentrations.
f 7
A preliminary study of the Outfall was conducted during the in-
itial set-up period of the survey. Samples were taken and analyzed
for background fluorescence. A background sample was also taken with
each flow sample, and the fluorescence of the flow sample was corrected
for the fluorescence of the background sample. Quenching and sorption
studies were also conducted, and results indicated no significant loss
-------
of dye through chemical change or physical adsorption. When low pH
values quenched the fluorescence of a sample, the sample was neutra-
lized to pH 7 (with a powdered buffer to insure no concentration
change) to recover the fluorescence, and then reanalyzed.
Other quality control measures included: 1) measurement of dye
injection rate at each station at least 4 times per day; 2) a mixing
check at the sampling site to insure a complete mix; 3) use of poly-
ethylene gloves when handling concentrated dye to reduce the possibil-
ity of contamination; 4) frequent fluorometer reference to zero using
a dummy cuvette; and 5) triple-rinsing of cuvettes with distilled
water before each use.
-------
FLOW MEASUREMENT USING THE MARSH-McBIRNEY
ELECTRO-MAGNETIC FLOW METER
The flow meter is provided with a Faraday type electro magnetic
flow sensor which has two perpendicular axes so that both X and Y
directional vectors can be measured. The operator can obtain from
the measurement both the direction and magnitude of the water velocity.
All sensors are cylindrically shaped and have no moving parts which
are susceptible to clogging or fouling.
The sensor consists of a cylinder containing an electro-magnet
internally and two pairs of external electrodes in contact with the
water. Flow around the cylinder probe intersects magnetic flux lines
causing voltages to be generated which are linearly proportional to
the water velocity. The voltages are detected by the electrodes,
processed at the signal conditioner and presented as analog voltages
linearly proportional to the X and Y components of the velocity vector.
The accuracy of an electro-magnetic sensor includes linearity,
zero drift, and absolute calibration. Linearity allows direct read-
ing without a correction chart and accurate recording of steady flow
in the presence of fluctuations. All Marsh McBirney instruments are
accurate to at least + 2% of reading or + 0.07 feet per second,
whichever is larger.
-------
APPENDIX D
Analytical Quality Control
-------
ANALYTICAL QUALITY CONTROL SUMMARY
FOR FMC CC14 SURVEY ANALYSES
Quality control consisted of measurement of three parameters to
monitor the accuracy, repeatability and limit of detectability. Also,
the method was evaluated and found to be linear over a working range
of 0 to 200 ppb CCI4 and checked occasionally during the analyses of
samples.
Accuracy
No accuracy data from measurement of independently prepared stan-
dards are available. However, stock standard solutions were prepared
daily by addition of 6.3 }j1 of pure CC14 from a 10 pi syringe to 1
liter of reagent water to yield a solution of 10 mg CCI4/I. The amount
of CCI4 delivered from the syringe was measured as 9.88 mg with a rela-
tive standard deviation (RSD) of 1.31 percent for 10 determinations.
These data show a negative bias of 1.2% on the accuracy of the standard
and thus a 1.2% positive bias of the results.
Repeatability
Positive calibration of the analyses was performed using a 200 ppb
CCI4 in reagent water standard. The standard was prepared daily and
run at least three times during the sample analysis runs that day. The
daily results of these analyses are shown below: fT
Sampling Date
£
mean
Percent RSD
April 13-14
3
197
11
April 14-15
4
201
6.7
April 15-16
5
202
3.7
April 16-17
5
203
5.2
April 17-18
5
200
4.3
April 18-19
7
196
7.9
April 19-20
9
194
8.4
April 20-21
4
201
3.0
-------
Duplicate analyses of samples were performed occasionally to
supplement the above data. Results for three duplicate analyses are
comparable with the % RSD data shown above.
Limit of Detectabi1ity
Detection limits were determined as two times the standard devi-
ation of blank at the retention time of CCl^. Initial limits were set
from analysis of six reagent water blanks. The standard deviation was
1.2 ppb and the detection limit calculated to be 3 ppb (rounded up
from 2.4 ppb for convenience of reporting data). Reagent water blanks
were measured daily during analyses and were 3 ppb or less.
Initial
186 ppb
27 ppb
25 ppb
Second
199 ppb
30 ppb
23 ppb
Percent Deviation
6.5
10
8.7
f .
-------
ANALYTICAL METHOD AND EVALUATION FOR MEASUREMENT OF CC14
The analyses for carbon tetrachloride (CCI4) were performed using the
direct aqueous injection technique described by FMC in the consent
decree dated 15 March 1977. This technique was evaluated to determine
detection limits, linear range, and precision at NEIC prior to use for
this survey. Occurrances of high concentrations of CCI4 were confirmed
by combined gas chromatography-mass spectrometry.
The direct aqueous injection technique for CCla described by FMC in the
consent decree of 15 March 1977 was evaluated for use by NEIC. The only
significant deviations from the FMC method was that 2 vil in instead of
5 y1 injections were made and that standards were prepared daily in
aqueous solution.
Instrument Conditions
GC:
Column:
Carrier Gas:
Injector:
Column:
Detector:
Peak Measurement:
Linearity:
Detection Limit:
Precision:
Hewlett Packard (HP) Model 5738 with 15 mCi Nickel
63 detector
8 feet by 1/8 inch stainless steel packed with 60/80
mesh Tenax GC
10% methane in argon, 60 psig and 60 ml/min flow rate
250°C
165°C
300°C
Either peak height or area integration with HP3352
data system
Standard solutions of CCI4 in water over a range of
0-600 ppb were analyzed. Figure 1 shows that above
200 ppb the response is no longer linear. This is
probably due to the large amounts of CCI4 causing
the detector to recover slower, thus increasing the
area. To minimize errors, samples above 200-250 ppb
CCI4 were diluted with distilled water and reanalyzed.
Figure 2 shows that linearity is maintained at the
low end of the analysis range. Peak height measure-
ments yield comparable results.
Six distilled water samples were analyzed. At the
retention time equivalent to CC14, the baselines were
measured to determine the detection limit.. The stand-
ard deviation (a) was 1.2 ppb. The detection limit
(2a) was averaged up to 3 ppb.
The average percent standard deviation for the 200 ppb
CCI4 standard was 5.3 for 7 days of analyses and 5 to 6
measurements of the standard per day.
? r
-------
0
So too zoo $00
pph CC/y
Fl^ufte i , HigH L)A/F4c/7-y
Hoo
Soo
6co
Ficjuav Z,
3o
ppbCd/y
Lou* RAKtye LiAivA^try
-------
APPENDIX E
Monitoring Results
-------
Table A
MONITORING RESULTS
OUTFALL 018
FMC CORPORATION
April 13-21, 1977
Date Composite Time Flow CC1 a
Number ni /dny mqd ppb
x 1000
4/13
a/14
4/15
4/16
4/17
1
0730
1?01/
1 51—
39 6
15
2
11 30
40.0
13
3
1530
152
40.1
3/
300
4
1930
129 ,
1 42—
?A. 2
5
2330
37' 4
9 1
6
0330
154
16017
40 6
5.2
1
0730
42.2
5.4
2
1130
165
43.7
7.1
3
1530
200
52.9
8.3
4
1930
104
145—
27.5
5.1
5
2330
38.3
5.9
6
0330
186, .
49.1
35
1
0730
1831/
48.4
17
2
nyj
181
1871'
47.7
8.6
3
1510
49.3
8.0
4
19 ''O
192
50.9
7.9
5
2330
137
1451'
36 2
17
\y
0330
30.2
34
0730
152
40 2
18
2
1110
l'o
38 5
8.0
3
1530
Si/
19 b
5 8
4
1930
21 2
6.0
5
2330
86
22 7
4.9
fi2/
0330
163
43.0
14
1-
0730
116
30 6
"6 6
2
1130
151
39 9
5.9
3
1530
147
41 5
6.5
4
1930
164
43 4
4.2
5
2330
170
44 9
5 4
6
0330
153
40.5
4.8
W Lithiun s?Pole lost or contaminated, flow is averaae of preceding and followina flows
2/ 1 bottle broken; composite consists of 3 samples.
3/ Corfirred by mass spectrometry.
CCl*
kq/day
CC14
1b/day
018 Upstream Flo,-;
m->/day mqd
x 1000
2.4
5.3
2 0
4.3
1 8
4 0
39
85 6
1 3
2.8
0.8
1 a
0.9
1.9
168
44.4
1 2
2 6
191
50.4
1.7
3 7
231
60.9
0 53
l 2
153
40 4
0.86
i 9
144
3S. 1
6 7
15
157
41 .4
3.1
6 9
177
46 7
1 6
3 4
162
42 S
1 5
3.3
155
41.2
1.5
3.4
186
49.2
2 3
5.1
4.9
11
2.7
6.0
142
37.4
1.2
2 6
138
36 5
0 43
0 S5
138
36 4
0.48
1 1
1^8
39.0
0.42
0 93
156
41 .3
2 3
5 0
1 -2
37 5
0.76
1 7
0.89
2.0
165
43 7
1.0
2 3
142
37 5
0.69
1 5
1-6
3 6
0 92
2 0
151
39 8
0.74
1.6
153
40.4
-------
Table A (continued)
MONITORING RESULTS
OUTFALL 018
FfiC CORPORATION
April 13-21, 1977
Date
Composite
Time
Flow
CC14
opb
CCI4
CCI4
018 Hostream
Flow
N'juber
mJ/day
x 1000
mgd
kg/day
lb/day
m-Vdav
x 1000
mgd
4/18
1
0730
170
45 9
5.5
0.93
2 1
154
43.4
2
1130
159
41.9
5.5
0.87
1 9
131
34.5
3
1530
169
44.6
5 4
0.91
2.0
161
<2.5
4
1930
157
£1.5
5 6
0 88
1.9
178
*"6 9
5
2330
191
17a!7
50 5
4 5
0.86
1 9
173
<5.7
6
0330
45.4
5.5
0 97
2.1
1 58
<1 7
4/19
1
0730
160
4 2.3
4.4
0 70
1 6
157
41 5
2
1130
174
*6 0
8.8
1 5
3 4
165
43.9
3
IS 30
169
7
12
2 0
4 5
170
<5 0
4
1930
161
42.4
20
3.2
7.1
154
40 6
5
2330
171
45.2
17
2.9
fi 4
155
41 .0
6
0330
197
51 9
21
4.7
10
18'
<3.5
4/20
1
0730
182
48 2
30
5.5
12
166
13.8
2
1130
10n
4* 5
I 30
22
48
157
A\ C
3
1530
177
^6.7
17
3 0
6 6
170
<5 0
4
1930
161
42 5
15
2.5
5 7
157
41.5
5
2330
154
40.7
11
1.7
3 7
155
41 .2
6
0330
174
45.7
22
3.8
8 4
147
33.8
Litmui sa-ole lost or contaminated; flow is average of preceding and following flows.
2/ 1 bottle Droken; coTDOsite consists of 3 samoles.
-------
Table I)
until tohii.t. hishlts
OUI I7\LL 010
rut conr'TJAr i on
Apt 11 13-21, 19/7
Dote
Com|iosUe
Number
T i r.ie
n 0 :
m^/tlov
x loon
mod
Cfl/]
opb
CC1„
kfj/dci y
cn„
lb/day
1/13
4/14
4/15
4/16
4/17
4/18
4/19
4/20
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1/
1/
0730
1130
1530
1030
2330
0330
0730
1130
1530
1930
23f0
0330
0730
1130
1530
1930
2330
0330
; 730
1130
1530
1930
2330
0330
0730
1130
1530
1930
2330
0330
0730
1130
1530
1930
2330
0330
0730
1130
1530
1^30
2330
0330
0730
1130
1530
1930
2330
0330
33 2
34.8 ,
36 3U
37.8
34.1
42 4
?0 5
3R 7
41.3
45.0
45.8
47.3
38.2
31.8
37 5
46.2
46 2
47.3
35.2
35 6
3r) 7
45 8
43 5
39.0
34.1
37"82/
40 2Z!
42.8
43.5
42.8
35 6
34.8
34.1
40.9
44.3
42 4
36.0
34.4
37.3?/
40.1
41 6
45.8
37 1
38.2
37.8
53.3
50.7
41 6
10.1
9.2
9. (/-¦
10.0
9.0
11.2
7 8
9 7
10.9
11 9
12.1
12.5
10 1
8.4
9.9
12 2
12.2
12.5
9 3
9.4
9.7
12.1
11.5
10.3
9 0
10.0
10.6
11.3
11.5
11 3
9.4
'9.2
9 0
10.8
11.7
11.2
9.1
9 1
9.8
10.6
11 0
12.1
9.8
10 1
10.0
14.1
13.4
11 0
2/
16
<3
<3
5 9
9.8
9.8
5.1
<3
3 7
5 3
14
5 0
8.0
<3
<3
<3
<3
6.5
7.0
18
<3
5 3
5.0
4.9
5.1
3.2
v-3
7.6
7.3
5.2
4.2
7.1
12
5 5
6.0
5.2
3.7
fi.l
20
35
3.1
4 2
11
5.9
<3
400
160
87
0.61
<0 10
<0.11
0.22
0.33
0.4?
0.15
<0.11
0 15
0 2/1
0.64
0.2^
0.11
<0.095
<0.11
<0.14
<0.U
0.31
0 25
0.64
<0.11
0.24
0.22
0.19
0.17
0.12
<0 12
0.33
0.32
0.22
0 15
0.25
0.41
0.22
0 27
0.22
0.13
0.21
1.75
1.4
0 13
0.19
0.41
0 23
<0.11
21
8 1
3.6
1.3
0 23
0.24
0 4Q
0 74
0.92
0 33
0 24
0 34
0 53
1.4
0.52
0.25
0 21
0.25
0.31
0.31
0 68
0 54
1.4
0 24
0.54
0.48
0.42
0.38
0 28
0 27
0 72
0.70
0 49
0.33
0.55
0.90
0.50
0.59
0 49
0.29
0.46
1.6
3.1
0.28
0.42
0.90
0.50
0.25
'4-7 ,
18
8.0
T7 nTdtlle broken; comnosite consists of 3 samples.
2/ now measurement not taken due to toxic atmosphere, flow is averaqe of preceding
and following flows
-------
Tnblc C
honiTorino fir'.uirs
on IT All IV/?.
rnr coijpokah n:i
Apnl 13-21, 1')//
Do to
Compos 11.0
Time
now
CCK
pph
! '*2 c~)
\ o
<
CCI4
lb/day
Number
in Vtiny
x 1000
iiuid
1/13
1
0730
0 89
0 236
220
0 20
0 43
?
1130
0 93
0 246
240
0 22
0 49
3
1530
1.0
0 27?
200
0 21
0 15
4
1930
1.0
0 272
230
0 24
0 52
5
2330
1.1
0.281
,240
0 26
0 56
4/1/)
6
0330
1.1
0.283
190
0.20
0 45
4/14
1
0730
0 98
0 ?59
220
0 22
0 48
2
1130
0.91
0 240
190
0 17
0 38
3
1530
0 93
0 247
240
0 2?
0 49
4
1930
0.98
0.2G0
210
0 21
0 46
5
2330
1 0
0 269
170
0 17
0 38
6
0330
1.0
0 268
160
0 16
0 36
4/15
1
0730
0 G9
0.236
160
0.14
0 32
2-1/
1130
2 5
0 673
250
0 64
1 4
3
1530
2 8
0 749
60
0 17
0.38
4
1930
3 0
0 802
94
0 29
0.63
5
2330
3 2
0 83b
79
0 25
0.55
6
0330
3 0
0 781
68
0 20
0.14
4/16
1
0730
2 9
0.759
64
0.18
0.41
2
1130
2.9
0.765
54
0 16
0.34
3
1530
2 4
0 6-16
72
0 18
0 39
4
1930
1.9
0.508
91
o i;
0.39
5
2330
2 0
0 530
90
0 18
0 40
6
0330
1.8
0.48
-------
To hic D
Mounou'.r, remits
suiiu'' rrri ulnt
rnr coworcAno'i
April 13-21, 1977
Date
Composite
Tune
Qow_
CCl/j
cn4
CC1,
Kumbci
m^/day
x 1000
mgd
ppb
kg/day
lb/cl,
1/13
1
0730
i.zl'
1600
2
1130
0.32
1300
1.7
3 8
3
1530
1 ^
1300
4
1930
0.32
490
1.1
2 4
5
2330
1 ?y
420
6
0330
0.32
600
0.61
1.3
4/14
1
0/30
1.2^
1300
2
1130
0.32
1 a00
1 6
3.6
3
1520
i.^
1400
4
1930
0.32
1300
1 6
3 6
5
2330
1 2-'
1400
6
0330
0.32
6400
4.7
10
4/15
1
0730
3300
2
1130
0.61
0.16
1700
1.5
3 4
3
1530
1900
4
1930
1.4
0.37
1500
2.4
5.2
5
2330
2300
6?/
0330
1.3
0.35
5100
3.7
8.2
4/16
0730
3200
2
1130
1.3
0.34
1200
2.9
6.3
3
1530
1100
4
1930
1.1
0.29
1200
1-3
2.8
5
2330
6?0
6
0330
1 2
0.31
2500
1.9
4.1
4/17
1
0730
1S00
2
1130
1.2
0.32
1100
1.6
3.4
3-w
1530
990
43/
1930
1.1
0.29
650
0.90
2.0
5
2330
740
6
0330
1.2
0.31
840
0.95
2.1
4/18
1
0730
1.2-'
.
960
2
1130
0.31
1300
1.4
3.0
3
1530
1100
4
1930
1.2
0.31
850
1.2
2.6
5
2330
}.2-
620
6
0330
0.34
620
0.80
1.8
4/19
1
0730
1.3 -
430
2
1130
0.31
530
0 62
1.4
3
1530
1600
4
1930
1.4
0.38
3300
3.4
7.6
5
2330
3100
6
0330
1.2
0.31
510
2.2
4.8
4/20
1
0730
760
2
1130
1.2
0.32
2900
.2.
4.8
3
1530
1300
/ 7
4
1930
1.2
0.31
2300
0 92
2.0
5
2330
750
6
0330
1.2
0.30
3900
2.8
6.2
TJ Flows not measured with Li CI for April 13-14, flow used is averaqe of April 15-21
flows.
2/ Lithium Srfmple lost or contaminated, flow is averaqe of preceding and following.
3/ 1 bottle broken, composite consists ol 3 samples.
-------
Tabic t
MOD 11 OR ll.". Krsill TS
CARROI AUSd'ilM Ki'l IJN11
WiC ami'oi'Aiiou
April 13-21 , 19/7
Date
Co.nposi le
Number
11 MIC
I ow
m-Vday
x 1000
nnjtl
CCI4
pob
CC1/,
g/diiy
Cri/|
lh/fl.iy
ylO-3
1/13
4/14
4/15
4/16
4/17
4/18
4/19
4/20
1
0730
0.27
0 0/2
<3
<0.8?
<1.8
2
1130
0 ?6
0 008
<3
<0 78
<1 7
3
1510
0.27
0 07?
<3
<0.8?
<1 8
4
1930
0.27
0 07?
<3
<0 82
<1 8
5
?330
0 27
0.072
<3.
<0.82
<1 8
6
03 )
0.27
0 070
<3
<0 80
<1 8
1
O/'.O
0.27
0.072
<3
<0 82
<1 8
2
1130
0.33
0 038
<3
<1.0
<2.2
3
1530
0.27
0 072
<3
<0 8?
<1.8
4
1930
0 2/
0 070
<3
<0.80
<1 8
5
2330
0.25
0 065
<3
<0.74
<1.6
6
0330
0.25
0 065
<3
<0.74
<1 6
1
0730
0.27
0 070
<3
<0 80
<1 8
2
1130
0.36
0 095
<3
<1.1
<2 4
3
1530
0 34
0 090
<3
<1.0
<2 2
4
1930
0.30
0.078
<3
<0.89
<2.0
5
2330
0.29
0 076
<3
<0.86
<1 9
0330
0.30
0.079
<3
<0.90
<2 0
ll/
0730
0.27
0.072
<3
<0.82
<1 8
2
1130
0.35
0 094
<3
<1.1
<2 4
3
1530
0.32
0 085
<3
<0.96
<2 1
4
1930
0.27
0 07?
<3
<0 8?
<1.8
5
2330
0.27
0 072
<3
<0.82
<1 8
6
0330
0.29
0.078
<3
<0.88
<1.9
1
0730
0.27
0.072
<3
<0.82
<1.8
2
1130
0.31
0.083
<3
<0.94
<2.1
3
1530
0.27
0.072
<3
<0.82
<1.8
4
1930
0.26
0 068
<3
<0 78
<1 7
5
2330
0.27
0 072
<3
<0.82
<1.8
6
0330
0.28
0.074
<3
<0 84
<1 9
1
0730
0.27
0.072
<3
<0.82
<1.8
2
1130
0.27
0 072
<3
<0.82
<1.8
3
1530
0.27
0 072
<3
<0 82
<1.8
4
1930
0.27
0 072
<3
<0.82
<1 8
5
2330
0.27
0.072
<3
<0 82
<1.8
6
0330
0.27
0 072
<3
<0 82
<1 8
1
0730
0.27
0 072
<3
<0.82
<1.8
2
1130
0 27
0.072
<3
<0.82
<1 8
3
1530
0.27
0.072
<3
<0.82
<1.8
4
1930
0.27
0.072
<3
<0 82
<1.8
5
2330
0.27
0.072
<3
<0.82
<1.8
6
0330
0.27
0.072
<3
<0.82
<1.8
1
0730
0.27
0.072
3 4
0.93
2.1
2
1130
0.14
0.036
13
1.8
4 0
3
1530
0
0
-
0
4
1930
0
0
-
0
0'
5
2330
0
0
-
0
0
6
0330
0.014
0.036
19
2.6
5.7
77 1 bottleTroken; composite consists of 3 samples.
-------
Table F
SUMMARY OF FIELD MEASUREMENTS -
FMC CORPORATION
April 13-21, 1977
4/13
4/14
4/15
4/16
4/17
4/18
4/19
4/20
Station
PH
Temp
pH
Temp
pH
Temp
pH
Temp
pH
Temp
pH
Te-np
PH
Temp
P'H
Temp
OlS
3.1
22
10.3
22
10.4
22
10.5
23
10.4
24
10.0
25
8.7
25
6.1
25
10.6
25
11 0
25
11.7
24
12.0
25.5
11.6
26
10.8
26
10 0
26
11.4
25.5
Carbon
Absorption
12.5
35
12 2
32
12.5
25
12.3
33
12.5
27
12.6
28
12 0
21
12.0
29
Uni t
13.0
43
12.7
39
13.0
40
13.0
43
12 9
38
12.8
41
12.9
33
12 5
33
Sulfur Wash
1 .4
15
2.4
15
0 5 -
18
1.2
17
2 8
18
1.4
22
1.1
22
2 6
19
2.5
23.5
7.5
20
2.9
26
3 7
25
3.7
21
3.1
23
4 4
23
a 0
23
OlS
6.4
14
7.6
14
7 6
17
7.3
16
7.4
17
6 5
19
4.0
17
7.6
19
9.7
18
9 1
17
9.4
20
9 9
20
8.4
18
9 3
22
9 1
19
9.9
20
022
10.?
14
9.7
14
8 8
14
9.6
14.5
9.8
16
10.2
17
8.8
13
9.7
1 £
11.3
16
11.0
16
12.4
25
10.3
16.0
10.2
11
10 7
17-
10 5
19
10.4
19
1/ pH anG temperature are
presen
ted in ranges of
S.U. and
°C
------- |