ENVIRONMENTAL PROTECTION AGENCY
-OFFICE OF ENFORCEMENT
EPA-330/2-76-031
Compliance Monitoring
and
Wastewater Characterization
NL Industries, Inc.
St. Louis, Missouri
(June 1976)
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
DENVER, COLORADO
rf1**8*^
AND /A
REGION VII, KANSAS CITY, MISSOURI
OCTOBER 1976
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Environmental Protection Agency
Office of Enforcement
COMPLIANCE MONITORING AND WASTEWATER CHARACTERIZATION
OF
NL INDUSTRIES, INC.
ST. LOUIS, MISSOURI
(June 1976)
October 1976
National Enforcement Investigations Center - Denver, Colorado
and
Region VII - Kansas City, Missouri
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CONTENTS
I INTRODUCTION 1
II SUMMARY AND CONCLUSIONS 4
III NPDES PERMIT CONDITIONS 13
IV MONITORING PROCEDURES 15
V MONITORING RESULTS 17
OUTFALL 001 18
OUTFALL 002, 005, 007 26
OUTFALL 003 27
OUTFALL 004 29
OUTFALL 006 36
OUTFALL 008 40
OUTFALL 009 and Oil 42
OUTFALL 010 51
OUTFALLS 012 and 013 52
OUTFALL 014 53
OUTFALL 015, 016, 018 and 019 57
OUTFALLS 017, 020, 021 and 022 59
RIVER INTAKE WATER 59
PROPOSED TREATMENT FACILITIES 60
VI EFFLUENT TOXICITY 62
OUTFALL 001 62
OUTFALL 009 63
OUTFALL Oil 66
REFERENCES 68
APPENDIX
A NL INDUSTRIES RECONNAISSANCE REPORT . 71
B NPDES PERMIT LIMITATIONS 105
C FIELD STUDY METHODS 121
D CHAIN OF CUSTODY PROCEDURES 131
E ANALYTICAL PROCEDURES,
QUALITY CONTROL 143
F DAILY MONITORING DATA 147
G INDIVIDUAL pH AND TEMPERATURE
MEASUREMENTS 173
H COMPARISON OF LITHIUM CHLORIDE AND
PARSHALL FLUME FLOWS - OUTFALL 001 . 245
I BIOASSAY TEST PROCEDURES 257
iii
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Tables
1 Summary of NPDES Permit Interim Effluent Limitations 14
2 Average Daily TSS and Iron Loads, Composite, 001 22
3 Average Daily TSS and Iron Loads, Grab, 001 24
4 Average Daily Gross and Net TSS Loads, Composite, 004 .... 32
5 Average Gross and Net Iron Load, Composite, 004 33
6 Average Daily TSS and Iron Loads, Grab, 004 35
7 Average Daily Gross and Net TSS Load, Composite, 006 38
8 Average Daily TSS Load, Grab, 006 39
9 Average Daily TSS and Iron Loads, Composite, 009 45
10 Average Daily TSS and Iron Loads, Composite, Oil 46
11 Average Daily TSS and Iron Loads, Grab, 009 48
12 Average Daily TSS and Iron Loads, Grab, Oil 49
13 Average Daily Gross and Net TSS Loads, Composite, 014 .... 55
14 Average Daily Gross and Net Titanium Loads, Composite, 014 .. 56
15 Average Daily TSS and Titanium Loads, Grab, 014 58
16 Acute Toxicity of Outfall 001 and Associated Chemical Data . . 64
17 Acute Toxicity of Outfall 009 and Associated Chemical Data . . 65
18 Acute Toxicity of Outfall Oil and Associated Chemical Data . . 67
Figures
1 Plant Layout 2
2 Rutile Process 19
3 SOL Process 28
4 Intake Hater Flow Diagram 28
5 Initial Process 30
6 Anatase and N.P. Process 43
IV
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I. INTRODUCTION
NL Industries, Inc.* was formed in 1891 by the merger of 25 separate
manufacturers of white lead. Today the Company makes more than 200
categories of products. Titanium dioxide, manufactured by the Titanium
Division, is the whitest and brightest inorganic pigmentary substance in
the world. This pigment is used as an additive to paints, porcelain
enamels, plastics, paper, and other products. NL operates titanium
dioxide plants in the United States and several foreign countries.1
The St. Louis, Missouri plant manufactures titanium pigments by the
sulfate process using Mclntyre ilmenite ore shipped from upper New York
State and slag purchased from Quebec Iron and Titanium (QIT). The
ilmenite ore is used to produce the rutile and non-pigmentary (NP)
grades of titanium dioxide, while the slag is used to produce the anatase
grade. Prior to 1972, the St. Louis plant produced calcium pigment,
approximately 70% calcium sulfate (CaSOJ and 30% titanium dioxide
(TiOp). Paint manufacturers changed to latex formulations and the plant
was converted in 1972 to 100% TiOg pigments; customers now add the
extenders. Sulfuric acid is also manufactured by the contact process
for in-plant use.
The plant is on 99 hectares (40 acres) adjacent to the Mississippi
River [Fig. 1]; an additional 99 hectares was purchased from the U. S.
Government at the end of World War II and is used to store raw ore and
slag, coal, and "gangue" mud (solids remaining after metallic salts have
been removed from the ore or slag).
* Formerly, National Lead Company
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Briefly, the pigment manufacturing process consists of digesting
pulverized ore or slag with concentrated sulfuric acid. The resulting
sulfates of titanium, iron, and other metals are leached from the inert
cake with recycled process streams and clarified river water; any ferric
salts present are reduced to the ferrous form by treatment with powdered
iron to prevent coloration of the final titanium dioxide product. The
resulting solutions are clarified, cooled, and concentrated (the solution
from the ilmenite ore process is crystallized prior to concentration to
remove copperas). The titanyl sulfate in the concentrated solution is
hydrolyzed; the resulting precipitate is washed several times and calcined
to produce titanium dioxide. The calcined product is cooled, ground,
and bagged or slurried for shipment. A detailed process description is
summarized in the Reconnaissance Report for NL Industriest St. Louis3
Missouri [Appendix A].
Waters used in processing and for cooling purposes are pumped from
the river through a single intake and are discharged untreated to the
Mississippi River from 22 outfalls. Outfalls 001, 004, 006, 009, Oil,
and 014 contain the majority of the process wastewaters. The remaining
16 outfalls contain cooling water, filter backwashes, boiler blowdown
wastes, or are only used in emergencies. All sanitary wastewaters are
discharged to the Metropolitan Sewer District sewers for treatment at
the Lemay primary wastewater treatment plant.
On March 8, 1976, the National Enforcement Investigations Center
(NEIC) was requested by Region VII, EPA, to characterize the major
wastewater discharges and to determine compliance of all the discharges
with the interim NPDES* permit effluent limitations. Monitoring of all
outfalls was conducted June 1 to July 1, 1976. This report summarizes
the results of this survey.
National Pollutant Discharge Elimination System
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II. SUMMARY AND CONCLUSIONS
1. During the period June 1-July 1, 1976, NEIC monitored all waste-
water discharges from NL's St. Louis plant to a) characterize the
major process discharges and b) determine the compliance status of
all discharges with the interim NPDES permit effluent limitations.
2. Prior to the survey, Company officials predicted that production
would be approximately 95% of the average production rate. This
latter production rate was used to establish the NPDES permit
effluent limitations. According to the Company officials, the raw
material processed would consist of approximately 70% Mclntyre ore
and 30% of QIT slag. However, shortly after the survey commenced,
production was reduced. Mclntyre ore was not processed and total
production was reduced to 82% of the average rate.
Company officials admitted that process modifications were made to
bring the wastewater loads in compliance with the permit limitations,
Therefore the wastewaters discharged from the process outfalls when
ore processing ceased were not typical of previous wastewater
discharges.
3. The wastewaters discharged from outfall 001 consist of strong and
weak acid filtrates, clarified river cooling water, weak caustic
filtrates, acidic wastes from the DeLore division of NL Industries,
and cleanup water.
o
On a composite basis, the flow averaged 8,000 m /day (2.12 mgd),
the pH ranged from 0.2 to 3.6 and the temperature ranged from 25 to
42.5°C. The discharge violated the pH limitation (0.5) on two days
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and the temperature exceeded the limitation of 37.8°C (100°F) on 82
of 360 measurements. The total suspended solids (TSS) and iron
loads averaged 5,100 and 20,600 kg (11,250 and 44,500 lb)/day,
respectively, and complied with the interim effluent limitations.
There were major differences in the constituents of the wastewater
before and after the changeover to slag. Prior to and during the
changeover, the iron load averaged 28,120 kg (62,010 lb)/day; after
the changeover, the iron load averaged 17,880 kg (28,100 lb)/day,
or a 48% reduction.
Although not limited by the permit for this outfall, the titanium
load was seven times the limit established for outfall 014.
The permit requires that the pH be monitored by one grab sample per
hour for 24 hours twice a week. The Company monitors pH only when
samples are collected, once a week.
On a grab sample basis, the iron load averaged 21,280 kg (46,950
1b)/day, approximately 75% of the effluent limitation. The average
total suspended solids load [7,120 kg (15,720 lb)/day] exceeded the
permit limitation by 36%. On June 25, the total allowable load for
the month (effluent limitation x 30 days) was exceeded.
Outfalls 002, 005 and 007 discharge excess flow (untreated river
water) from the condenser recirculating system. Outfalls 005 and
007 were inactive during the survey and according to Company
personnel have been inactive for the past six years. The the pH is
limited to a range of 6 to 9 and the temperature to 35.6°C (96°F).
On June 25, the pH was 4.6 and on June 26 the pH was 5.8. Since
acidic wastes are discharged upstream of the river intake, and the
intake water pH on these two days was less than 6.0, this may have
accounted for the low pH of the discharge on these two days. The
temperature ranged from 25 to 34°C.
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5. Outfall 003 contains the backwash water from seven gravity sand
filters. The discharge is intermittent as the filters are back-
washed once a day for 10 to 12 minutes. The permit limits the TSS
concentration to 70 mg/1 and the pH to a range of 6.0 to 12.5. On
two days, the effluent pH was below 6.0 (5.3 on June 2 and 5.7 on
June 30). The TSS concentrations exceeded the interim limitation
on 28 of the 30 days. The NPDES permit prohibits the discharge of
pollutants that have been removed in the treatment of water.
6. The 004 discharge consists of untreated river water, clarified
river water used in washing the Shriver presses, and the blowdown
of clarified river water used as scrubbing media in the digester
air pollution control equipment. On a composite sample basis, the
gross TSS and iron loads averaged 23,410 and 2,590 kg (51,470 and
5,720 lb)/day, respectively. The TSS load exceeded the permit
limitation by a factor of 2.4 and the iron load exceeded the
limitation by 400%.
Once Mclntyre ore processing ceased, the iron load averaged 1,200
kg (2,640 lb)/day which exceeded the limitation by almost 100%;
prior to the conversion, the iron load averaged 6,570 kg (14,490
lb)/day, or five times greater than the load after the conversion
to slag.
Based on grab samples, the effluent exceeded the interim limitations
for TSS and iron for 21 days and 26 days, respectively. The effluent
pH was less than the lower limitation of 6.0 for a total of 113 of
359 measurements made. The low pH values were due to the acid
content of the wash filtrates from the Shriver presses.
7. Outfall 006 receives the underflow from the three Accelator clarifiers
plus non-acidic wastes from the DeLore operation. In a meeting
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with EPA, Company officials stated that net limitations should be
applied to this outfall. However, the NPDES permit prohibits the
discharge of pollutants that are removed in the treatment of water.
The gross and net TSS loads on a composite basis for June 1-17
averaged 21,570 kg (47,560 lb)/day and 19,090 kg (42,000 lb)/day,
respectively. These loads exceeded the permit limitation of 3,070
kg (6,750 lb)/day by 700 and 620%, respectively.
Grab samples were collected daily June 1 to 17 and on June 23 and
28 (to comply with monitoring requirements). The TSS load averaged
29,370 kg (64,800 lb)/day June 1 to 17 and 19,190 kg (42,360 lb)/day
over the 30-day period. The load discharged in June exceeded the
interim limitation by 625%.
The effluent pH is limited to 6.0 to 9.5. The pH exceeded 9.5 for
27 of 192 measurements.
8. The outfall 008 discharge originates in the powerhouse and from the
zeolite softeners and demineralization units. The six zeolite
softeners and four cationic demineralizers are regenerated once a
day while the three anionic demineralizers may be regenerated more
frequently. The regeneration cycles produce alternating streams of
highly caustic and acidic wastewaters. The permit limits the
effluent pH to a range of 1 to 11; the pH must be monitored continuously.
The Company does not monitor the pH continuously. The effluent was
monitored by NEIC personnel on a continuous basis. The strip chart
(on file at NEIC) showed that both the upper and lower pH limitations
were exceeded daily.
9. The sewer lines comprising outfalls 009 and Oil are interconnected
upsewer of the discharge locations. According to ML personnel,
under normal operating conditions only a small portion of the 009
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8
flow enters the Oil sewer. Prior to the survey, plant personnel
removed the non-process flow from Oil and rerouted this flow to
outfall 013. Outfall Oil contained only the overflow from 009.
Outfall 009 (and therefore Oil) contained process wastewaters,
floor washings, and storm water.
The 009 and Oil flows averaged 7,540 and 3,080 m /day (1.99 and
0.81 mgd), respectively. ML personnel reported that flows from
outfall 009 ranged from 10,970 to 16,275 m3/day (2.9 to 4.3 mgd).
The higher flows reported by NL may have been due to the higher
production levels experienced prior to the survey; however, the
higher flows are probably due to errors in measurements with the
potassium tracer, used by plant personnel.
On a composite sample basis, the TSS and iron loads from 009
averaged 3,680 and 25,700 kg (8,130 and 56,670 lb)/day, respectively,
The TSS load was 70% of the interim limitation, but the iron load
exceeded the limit by a factor of 1.2.
The TSS and iron loads discharged from Oil complied with the
interim limitations.
The titanium loads discharged from outfalls 009 and Oil averaged
6,190 and 1,100 kg/day (13,650 and 2,430 lb)/day, respectively.
These loads exceed the interim limitation for outfall 014 by 700%
and 125%. Limitations for titanium have not been established for
outfalls 009 and Oil.
The permit requires that 009 and Oil be monitored for temperature
once a day and pH continuously. The Company does not comply with
these requirements. For each outfall, the temperature limitation
was not exceeded in June. For outfall 009, the pH of the effluent
was less than 0.5 (lower limit) on 26 of 360 measurements; for
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outfall Oil, 148 pH measurements out of 360 observations were less
than 1.0 (lower limit). The Company cannot meet the Oil pH limitation
since it rerouted the condensate and cooling waters to outfall 013.
On a grab sample basis, the effluent discharged from 009 had
average TSS and iron loads of 6,190 and 26,010 kg (13,660 and
57,360 lb)/day. These loads exceeded the interim limitations by
17 and 25%, respectively. For outfall Oil, the TSS load averaged
1,150 kg (2,560 lb)/day, and did not exceed the limitation. The
iron load averaged 13,920 kg (30,700 lb)/day and complied with the
limitation.
10. Outfall 010 contains non-contact cooling water from the acid plant.
Temperature and pH are limited by the permit; the pH is to be
monitored continuously. Plant personnel stated that pH is not
monitored continuously. The temperature complied with the permit
for all observations and the pH was less than the lower limit for
one measurement only.
11. Prior to the NEIC survey, outfalls 012 and 013 contained condensate
from sulfuric acid production, floor washings, and storm water.
The Company rerouted the condensate and cooling water from outfall
Oil to outfall 013. Additional process flow from 014 may enter the
013 sewer through a cross-connection.
Composite samples collected from 013 June 9 to 16 indicated that
process wastewaters were being discharged. TSS, iron and titanium
concentrations were much higher than the intake levels. On May 27,
the effluent was grayish in color (similar to the color of the 014
effluent), also indicating the presence of process wastewaters.
The effluent temperature exceeded the permit limitation on three
observations.
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10
The permit requires the pH of both outfalls to be continuously
monitored and recorded; NEIC personnel observed that the Company
does not monitor continuously. The effluents discharged from both
outfalls complied with the permit limitations.
On 14 of the 15 days that flow occurred in outfall 012, the tempera-
ture exceeded the permit limit by about 30°C.
12. Process wastewaters from calcining, grinding, milling, of
washdown and air pollution control scrubber wastewaters, and
barometric condenser water are discharged from outfall 014. The
untreated river water used in the barometric condenser is metered
and recorded and comprises about 50% of the flow. Company officials
in a meeting with the EPA stated that net effluent limitations
should be applied to this outfall. The permit limits TSS and
titanium on a gross basis.
On a composite sample basis, the gross average TSS load exceeded
the permit limitation by 42%, however the net average TSS load was
54% of the limitation. Gross and net average titanium loads
exceeded the limitations by 220 and 200%, respectively. On a grab
sample basis, the average gross TSS and titanium loads exceeded the
limitations by 60 and 230%, respectively.
The pH of the effluent was less than 2.0 (lower limit) for 8 of 360
measurements; the temperature complied with the permit limitation.
13. Outfalls 015, 016, 018, and 019 contain non-process wastewaters and
are limited to a pH range of 6.0 to 9.0. Outfall 015 was inactive.
The pH limitation was exceeded by outfall 016 on one day, on two
days for outfall 018, and on 4 days for outfall 019.
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11
14. Non-process wastewaters are discharged from outfalls 017, 020, 021
and 022. The permit limits the pH to 6.0 to 11.5 and the temperature
to 99°C (210°F), and requires daily monitoring. Plant personnel
stated that monitoring is not conducted daily. There was no flow
in outfalls 017, 020 and 022. The effluent discharged from outfall
021 complied with the temperature limitation and exceeded the pH
limitation on one day when the pH was 5.8.
15. The intake water was monitored on a 24-hour composite basis and a
grab sample basis. The intake concentrations of TSS, iron and
titanium varied daily and on most days there was no correlation
between grab sample and composite sample concentrations. Credit
for intake levels for net calculations therefore can only be
determined by 24-hour flow-weighted composite samples.
16. During the reconnaissance and field survey, no work was being done
in the "boat yard" to prepare the site for construction of the
proposed treatment facilities. However, the old acid plant was
being dismantled during June. The Schedule of Compliance in the
permit specifies that construction was to commence by June 30, 1975
and completed by December 31, 1976. This latter deadline cannot be
met.
17. The proposed treatment facility is conceptually designed to treat
an effluent flow of 151 m3/min (40,000 gpm) or 218,000 m3/day (57.6
mgd). Total process wastewaters discharged during June were less
than 50% of this flow. Since only process wastewaters require
neutralization, the total sludge volume [2,720 m. tons (3,000
tons)/day] produced in neutralization will be significantly re-
duced, thus decreasing treatment and disposal costs.
18. Bioassays were conducted on the effluent discharged from outfalls
001, 009, and Oil. The wastewaters from all three outfalls were
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12
acutely toxic to channel catfish. The 96-hour LCcn values were
bU
0.65, 0.46, and 0.63%, respectively. High concentrations of iron
and low pH levels caused mortality of the test fish.
The levels of toxicity for outfalls 001 and 009 were similar to
levels recorded in 1972. Toxicity of outfall Oil was calculated to
be approximately ten times greater in 1976 than reported in 1972.
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III. NPDES PERMIT CONDITIONS
On April 10, 1974, NPDES permit No. MO 0000451 was issued to NL
Industries, Inc., Titanium Pigment Division for the facility located at
Carondelet Station, St. Louis, Missouri. The permit, authorizing
industrial wastewater discharges to the Mississippi River, will expire
at midnight, April 9, 1979.
Interim limitations were established for 22 outfalls for the period
beginning on the effective date of the permit and lasting through the
date the interceptor and single outfall designated 023 is built and
operable. At this time, all discharges from the present 22 outfalls
will be discontinued and all wastewater will be discharged from outfall
023. Initial limitations were established for outfall 023 for the
period beginning on the date the interceptor and single outfall 023 is
built and operable and lasting through June 30, 1977. Final limitations
for outfall 023 were established beginning June 30, 1977 and lasting
through the expiration date. The Schedule of Compliance set the completion
of construction by December 31, 1976, and for the treatment facility to
be operational by June 30, 1977.
The interceptor and the single outfall have not been constructed;
therefore the interim effluent limitations for the 22 outfalls were
effective during the NEIC survey. Interim, initial, and final effluent
limitations are contained in Appendix B. Interim limitations are
summarized in Table 1. Self-monitoring for total suspended solids,
iron, and titanium are to be conducted on a grab basis once a week.
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Table 1
SUMMARf OF NPDES PERMIT INTERIM EFFLUENT LIMITATIONS
NL INDUSTRIES, ST. LOUIS, MO.
Outfall
No. Total Suspended Solids
Daily Average
kg/day 1 b/day
001 5,220 11,500
002, 005, 007 NA
003 70 mg/1
004 9,710 21,400
006 3,070 6,750
008 NA
009 5,310 11,700
010, 012, 013 NA
Oil 5,310 11,700
014 3,900 8.500
015, 016, 018,
019 NA
017, 020, 021,
022 NA
Discharge Limitations
Total Iron
Daily Average
kg/day 1 b/day
28,650 63,100
NA
NA
635 1,400
NA
NA
21,000 46,100
NA
21,000 46,100
NA
NA
NA
Titanium
Daily Average
kg/day 1 b/day
NAf
NA
NA
NA
NA
NA
NA
NA
NA
870 1 ,920
NA
NA
pH Range Temperature
Dally Maximum
°F
0.5-9.0
6.0-9.0
6.0-12.5
6.0-9.0
6.0-9.5
1.0-11.0
0.5-9.0
2.0-9.0
1.0-9.0
2.0-9.0
6.0-9.0
6.0-11.5
100
96
NA
NA
NA
110
130
100
130
160
NA
210
t «4 - Not Applicable
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IV. MONITORING PROCEDURES
All of the active outfalls were sampled on a grab basis during the
30-day period June 1 to July 1, 1976, to comply with the monitoring
requirements of the NPDES permit. In addition, the six outfalls containing
the majority of the process wastewaters and the intake were monitored on
a composite basis for the same period to characterize the quantity and
quality of the wastewater discharges. The intake was also monitored on
a grab basis.
Outfalls 005 and 007 (cooling water overflow), 015 (cooling water),
017 (normally dry), and 020 (boiler blowdown) were not discharging
during the survey. Intermittent outfalls 012 (condensate from acid
production) and 019 (cooling water from steam ejector) were sampled only
on days when a flow occurred. Outfall 006 (underflow from Accelators,
DeLore effluent) was sampled daily on a composite basis June 1 to 17,
after which samples were collected weekly on a grab basis to comply with
the NPDES permit monitoring requirements. Outfall 013 (condensate from
acid production) was sampled on a grab basis June 1 to 9 and June 16 to
30, and on a composite basis June 9 to 15.
Samples for TSS, iron and titanium were collected at the six major
process outfalls (001, 004, 006, 009, Oil, 014) and the intake, and com-
posited on a flow-weighted basis. Instantaneous flows for each outfall
and the intake were measured every two hours when a sample aliquot was
collected. The dye dilution technique was employed for outfalls 004,
006 and 014 (for June 1 to 4*). Lithium chloride was used as the flow
measuring tracer at outfalls 001, 009, Oil and 014 (June 5 to July 1*).
Appendix C
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16
NEIC personnel installed a depth sensing device on the Company's 9-
inch Parshall flume permanently installed on outfall 001. Flows were
read each time a sample was collected. At the intake, flows are measured
by an in-line orifice plate and recorded on a Hays recorder (circular
chart).
Details on NEIC sampling procedures and flow measurement techniques
are contained in Appendix C. Chain-of-custody procedures [Appendix D]
and analytical quality control procedures [Appendix E] were followed.
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V. MONITORING RESULTS
Prior to the NEIC survey, NL Industries officials indicated that
production was scheduled at a rate approximately 95% of the average
production rate until October 1, 1976.2 Of the total amount of raw
material processed, approximately 70% would consist of Mclntyre ore and
30% of QIT slag.* The average production rate had been used to establish
the NPDES permit effluent limitations. After the survey commenced,
production was reduced to 82% of the average production rate and the
processing of ore ceased. NEIC personnel were not notified of the
changes until the modifications were almost completed. The changeover
to slag as the exclusive raw material was completed by June 9.3 The
average amount of slag processed was more than twice the Company's
estimate.
In a conference in Kansas City, Mo. between EPA and NL Industries,
NL officials admitted that the process modifications were made to bring
the wastewater loads in compliance with the permit limitations. Because
the slag is richer in titanium than the ore (71% vs. 47%),u the process
effluents would contain less iron (limited by the permit for outfalls
001, 004, 009, and Oil) when slag is processed exclusively. Therefore,
the wastewaters discharged from process outfalls after the conversion to
slag were not typical of the wastewaters discharged under previous (or
normal) processing conditions.
Monitoring results are tabulated by individual sampling location
and are discussed by individual outfall.
* NL has requested that production rates and the quantities of raw material
be kept confidential.
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18
OUTFALL 001
The wastewaters discharged from this outfall consist of strong and
weak acid wash filtrates from the Moore Leaf Filter operation [Fig. 2],
clarified river water used for the cascade cooler in the rutile process,
weak caustic filtrates from the SOL* process [Fig. 3], acidic wastes
from the DeLore** Dorr tank (about 10 to 20% of the total effluent
discharged from 001), cleanup water from sinks and floor washings, and
storm water from roof and ground runoff. Since all cooling and process
waters have been clarified, gross limitations apply to this outfall.
The NPDES permit states that samples of the effluent discharged
from outfall 001 should be collected immediately prior to the Parshall
flume. The Company monitors the effluent in the acid brick-lined wet
well about 30 m (100 ft) downstream of the Parshall flume. The wet well
location was also used by NEIC (samples were collected from the flow
entering the wet well effluent pipe) because the No. 22 Dorr tank effluent
flows into the 001 sewer about 30 m (10 ft) upstream of the flume.
Wastewater samples collected at the flume may not be representative
because mixing may not be adequate. Moreoever, the flume is located
inside an acid brick-lined sump limiting the access, and the acid mists
from the wastewaters constituted a safety hazard for NEIC personnel.
The wastewater discharged from 001 was characterized for flow, pH,
temperature, TSS, iron, and titanium on a composite sample basis [Table
* Ti02, which is iron-free but not calcined, is reacted with 50% NaOH,
washed in a filter to remove sodium, and reacted with HCl. The material,
termed SOL, is added to the rutile pigment to yield highly reflective
properties for special orders.
** The DeLore operation, a division of NL, produces barytes (barium sulfate)
by grinding, bleaching, washing, filtering, and drying. The DeLore
Division operates independently of the titanium plant; however, the
titanium plant is responsible for their wastewater discharges and
provides utilities for processes.
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WOOD PIBRB H»°
MOORE LEAP
FILTERS
TO SOL PROCESS
Figurf 2. ftutife Prec*t« N 1 Indutlrlo*, Si. Levin, Mo.
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20
5O% NaOH
STRIKE
TANK
H2O
L
ROTARY
FILTER
STRONG
FILTRATE
STEAM HEAT
HCI
I
PEPTIZATION
TANK
WEAK FILTRATE
-*-DIGESTER SCRUBBER
+-OO1
SOL
OO4
WASTE
CAUSTIC
TANK
_r
WET MILLING
TREATMENT TANKS
Figure 3. SOL Process N L Industries, St. Louis, Mo.
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21
F-l, Appendix F*]. The flow averaged 8,000 m /day (2.12 mgd), the pH
ranged from 0.2 to 3.6, and the temperature ranged from 25 to 42.5 °C,
The TSS and iron loads averaged about 5,100 and 20,600 kg (11,250 and
44,500 lb)/day, respectively [Table 2],
There were major differences in the constituents of the wastewater
during the changeover to slag and after the conversion was completed.
The average iron load discharged June 1 to 8 was 28,100 kg (62,000 lb)/day;
the average load for June 9 to 30 was 17,880 kg (38,100 lb)/day, or a
38% reduction. The NPDES permit limits iron to 28,650 kg (63,100 lb)/day.
This limit was exceeded on 5 days during the first half of June (i.e.,
the period when wastewater from ore processing was being discharged).
Although not limited by the NPDES permit for this outfall, the
concentration of titanium averaged 750 mg/1 which corresponds to an
average load of 6,000 kg (13,200 lb)/day. This load is about seven
times the limit established for outfall 014 of 870 kg (1,920 lb)/day.
The NPDES permit requires that the TSS, iron, flow, and temperature
be monitored at least once a week with grab samples, and pH be monitored
twice a week by one grab sample/hour/24 hours. The Company does not
comply with the pH monitoring requirements. According to plant personnel,
temperature and pH are only measured when grab samples for TSS and iron
are collected. Due to the amount of time required to collect effluent
samples from all outfalls, NEIC personnel measured pH (and temperature)
every 2 hours/24 hours over the 30-day period [Table G-l, Appendix G**].
Grab samples for TSS and iron were collected daily by NEIC personnel
[Table F-2].
The effluent pH was less than 0.5 (lower pH limitation) on 2 days.
On June 1, the pH at 7:15 a.m. was 0.4; on June 26 the pH was 0.3 at
* Appendix F contains the daily monitoring data for all outfalls.
** Appendix G contains the individual pH and temperature measurements
for all outfalls.
-------
22
Table 2
AVERAGE DAILY TSS AHD IKON LOADS (24-HR COMPOSITE SAMPLES)
OUTFALL 001
HL INDUSTRIES, ST. LOUIS, MO.
June 1-July 1, 1976
DateT
Total Suspended Solids
Cumulative Load it
kg
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
t
tt
ttt
Composit
3
7
12
15
20
23
27
32
34
37
38
41
50
58
61
63
70
76
83
87
91
99
107
112
123
130
133
140
146
152
e s
Cumulative
Average
,010
,900
,440
,420
,980
,540
,020
,080
,630
,110
,920
,500
,200
,380
,380
,510
,290
,440
,020
,480
,150
,350
.910
,160
,120
,380
,900
,790
,150
,870
antples
load =
Ib
6,640
17,420
27,430
33,990
46,250
51,910
59,580
70,750
76,380
81 ,860
85,850
91,550
110,730
128,770
135,390
140,090
155,060
168,620
183,130
192,980
201,070
219,170
238,050
247,420
271,580
287,600
295,370
310,580
322,400
337,220
correspond
Lj + Lz + ,
Average Load ttt
kg/day
3,010
3,950
4,140
3,850
4,190
3,920
3,860
4,010
3,840
3,710
3,530
3,450
3,860
4,170
4,090
3,960
4,130
4,240
4,360
4,370
4,340
4,510
4,690
4,670
4,920
5,010
4,950
5,020
5,040
5,090
to the
I- + ..
load = L- + £„ + t. + . . . L
4 6 O
Ib/day
6,640
8,710
9,140
8,500
9,250
8,650
8,510
8,840
8,480
8,180
7,800
7,630
8,510
9,190
9,020
8,750
9,120
9,360
9,630
9,650
9,570
9,960
10,350
10,310
10,860
11,060
10,940
11,090
11,110
11,240
production
. L.. where
,„ where If
Iron
Cumulative Loadtt
kg
25,000
55,660
70,640
94,740
114,010
134,870
173,620
224,990
253,270
279,560
305,850
337,880
360,590
389.280
411,240
430,610
439,950
445,490
456,800
470,000
484.510
502.290
519,970
532,000
541 ,040
555,950
571,930
587,120
604,190
618,360
day, 7 a.
L is the
Ib
55,130
122,740
155,780
208,920
251,410
297,400
382,860
496,140
558,500
589,560
647,530
718,160
768,240
831 ,500
879,740
922,470
943,080
955,310
980,250
1,007,150
1,039,150
1,078,360
1,117,360
1,143,890
1,163,820
1,196,690
1,231,920
1,265,420
1,303,070
1,334,320
m. -7 a.m.
daily load
is the total number
Average Loadttr
kg/day
25,000
27,830
23,540
23,680
22,800
22,470
24,800
28,120
28,140
27,950
27,800
28,150
27,730
27,800
27,400
26,900
25,880
24,750
24,040
23,500
23,070
22,830
22,600
22,170
21,640
21,380
21,180
20,970
20,830
20,600
1 b/day
55
61
51
52
50
49
54
62
62
58
58
59
59
59
58
57
55
53
51
50
49
49
48
47
46
46
45
45
44
44
,130
,370
,920
,230
,280
,560
,690
,010
.050
,950
,860
.840
,090
,390
,650
,650
,470
,070
.590
,350
,480
,000
,580
,660
,550
.020
.620
,190
,930
,470
discharged
of days
SZ + N2 + N3 * ' ' ' ^N
-------
23
11:08 a.m. and 0.2 at 1:11 p.m., 3:09 p.m. and 5:10 p.m. The temperature
of the effluent exceeded the permit limitation of 37.8 °C (100 °F) on
June 1, 10, 12 to 15, and 22 to 30. Over the 30-day period, 82 of 360
temperature measurements exceeded 38°C.
On a grab sample basis, the iron load averaged 21,280 kg (46,950
lb)/day, approximately 75% of the permit limitation [Table 3]. On 5 of
the 30 days, the summation of the daily discharges divided by the number
of days the measurements were made, exceeded the permit limitation. For
June 1 to 8, the iron load averaged 25,840 kg (56,930 lb)/day, or 90% of
the permit limitation. For June 9 to 30, the iron load averaged 19,600
kg (43,070 lb)/day, or 68% of the effluent limitation. Based on the
first 8 days' data, it is highly probable that the effluent limitation
for iron would have been exceeded if Mclntyre ore and slag were processed
at average production levels.
The TSS load exceeded the permit limitation of 5,220 kg (11,500
lb)/day on 10 days [Table 3]. On the first day of monitoring, the TSS
load was 5,530 kg (12,200 lb); however, from June 2 to 21, the average
daily load was less than the permit limitation. On June 25, the total
load for the month* was exceeded and therefore the average daily load
for June 25 to 30 exceeded the limitation. For the 30-day period, the
average TSS load of 7,120 kg (15,720 lb)/day exceeded the limitation by
36%.
During the survey, NEIC personnel observed that the solids content
of the effluent varied during the day. Therefore, beginning on June 21,
more than one grab sample of the effluent was collected to determine if
there was a correlation between the flow rate and the TSS and iron
concentrations. There was no correlation between the magnitude of the
* Total load is equal to permit limitation, 5,220 kg/day, multiplied by
days in month, 30, which equals 156,600 kg (345,000 lb}.
-------
24
Table 3
AVERAGE DAILY TSS AND IRON LOADS (CRAB SAMPLES)
OUTFALL 001
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Total Suspended Solids
Date
Cumulative Load
kg
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5
7
11
14
16
17
19
27
29
30
31
34
35
40
44
45
66
75
78
83
92
118
132
142
167
181
184
192
209
213
,530
,070
,910
,360
,930
,800
,620
,870
,010
,530
,110
,210
,160
,190
,430
,120
,750
,870
,190
,180
,620
,710
,410
,930.
,400];
.260];
,750];
,820];
,470!
,690T
Ib
12
15
26
31
37
39
43
61
64
67
68
75
77
88
98
99
147
167
172
183
240
261
292
315
369
399
407
425
462
471
.200
,590
,270
,670
,340
,260
,290
,500
.020
,380
,660
,500
,600
,690
,050
,570
,260
,370
,500
,510
,330
,840
,050
,250.
,200*
,780];
,470];
.720?
,430^
,750f
Average Load
kg/day
5,530
3,530
3,970
3,590
3,380
2,960
2,800
3,480
3,220
3,050
2,830
2,850
2,700
2,870
2,960
2,820
3,920
4,210
4, 110
4,160
4,410
5,390
5,750
5,950
6,690
6,970
6,840
6,880
7,223
7,120
Ib/day
12,200
7,790
8,750
7,910
7,460
6,540
6,180
7,680
7,110
6,730
6,240
6,290
5,970
6,330
6,530
6,220
8,860
9,300
9,080
9.170
9,730
11,900
12,690
13,130
14,760
15,370
15,090
15,200
15,940
15,720
Iron
Cumulative Load
kg
33,
56,
71,
102,
114,
131,
174,
206,
236,
266,
345,
362,
389,
406,
427,
445,
461,
466,
474,
487,
505,
524,
536,
561,
568,
582,
592,
609,
631,
638,
930
570
030
350
700
560
900
720
600
390
480
540
030
590
690
430
350
000
220
790
180
770
050
000
030
640
300
200
600
640
Ib
74,820
124,740
156,630
225,690
252,920
290,090
385,670
455,850
521,740
587,430
761 ,830
799,460
857,870
896,600
943,120
982,250
1,017,370
1,027,630
1,045,760
,075,690
,114,040
,157,230
,182,110
,237,130
,252,640
,284,880
,306,190
,343,470
,392,880
1,408,420
Average Load
kg/day
33,930
28,280
23,670
25,580
22,940
21,920
24,980
25,840
26,290
26,640
31 ,400
30,210
29,920
29,042
28,500
27,840
27,140
25,890
24,950
24,390
24,050
23,850
23,300
23,370
22,720
22,410
21 .930
21 ,760
21 ,780
21 .280
1 b/day
74,820
62,370
52,210
56,420
50,580
48,340
55,090
56,980
57,970
58,740
69,250
66,620
65,990
64,040
62,870
61,390
59,840
57,090
55,040
53,780
53,050
52,600
51,400
51,550
50,100
49,410
48,380
47,980
48,030
46,950
t Exceeds NPDES pern-it limitation for the total load for June.
-------
25
flow and the concentrations of the pollutants [Table F-2]. This clearly
demonstrates the need for flow-weighted composite samples to determine
the characteristics of the effluent and compliance with permit limitations.
The toxicity of the effluent was evaluated, using channel catfish,
in flow-through bioassays. Concentrations of less than }% wastewater
mixed with Mississippi River water were acutely toxic. The results of
the bioassays are discussed in Section VI.
NL personnel stated that a 9-inch Parshall flume is used to determine
flow through outfall 001.2 Instantaneous flows are determined by measuring
the depth of flow at the stilling well and determining the flow from
standard flume tables. Continuous flow measurement is not conducted.
Potassium hydroxide is also used as a tracer by plant personnel to
confirm the flume flow data and also to provide flows for the Discharge
Monitoring Reports (DMR). Plant personnel stated that the flows measured
by both methods agreed closely. However, they stated that they felt the
flume data were not reliable. The NEIC flow data for the flume were
compared with the flows measured with lithium chloride [Table H-l,
Appendix H*]. The individual comparisons show that the Parshall flume,
as presently installed, does not provide reliable flow data. If the
obstructions are removed from the throat and upsewer and downsewer of
the flume, and if the approach conditions are changed to meet flume
design and installation specifications, the device could provide reliable
flow data.**
According to the DMR's, the flow from outfall 001 for the first
quarter of 1976 averaged 10,900 m /day (2.9 mgd).l» Plant personnel
stated that the potassium hydroxide tracer did not appear to provide
* Appendix H contains the individual 2-hour lithium chloride and
Parshall flume flow measurements.
** NEIC personnel did not determine if the flume was installed levelt or
if all critical dimensions corresponded to standard specifications.
-------
26
reliable flow data since the potassium concentration measured in the
effluent after a concentrated potassium hydroxide solution had been
injected frequently could not be detected above background levels. This
contradicts the previous Company statement that the tracer flows and
Parshall flume flows were in close agreement. Higher flows would be
calculated than were actually occurring and the DMR data would be
inaccurate. Since potassium levels are fairly high in the effluent, 3
to 10 ppm, and the levels after injection range from 5 to 35 ppm,2 the
tracer is not suitable for this wastewater. A tracer should be used
which is present in trace amounts, and the tracer should be injected at
a rate and concentration which results in levels at least five times
greater than the background levels.
Comparing water usage for the first quarter of 1976 and for June
1976 on a production basis, the Company used about 16$ more water per
ton of ore and slag digested for the first quarter than in June. Water
usage should be related to production. However, that does not appear to
be the case since hoses are allowed to flow uncontrolled onto the floors
and the water is subsequently discharged from 001, thus preventing the
comparison of water usage on a production basis.
OUTFALLS 002, 005, 007
Four constant-speed centrifugal pumps are used to withdraw Mississippi
River water through a single 137 cm (54 in) diameter intake line.
o
Approximately 218,000 m /day {57.6 mgd) are pumped for use in the power
house condensers or for once-through cooling water. The condenser water
is returned to a concrete holding basin and the cooling water is discharged
back to the river. Approximately 32,700 m /day (8.6 mgd) of the condenser
water are introduced into the water treatment system for clarification
prior to use in the processes. The excess condenser water in the concrete
basin overflows into outfall 002. Outfalls 005 and 007 receive the
-------
27
condenser water overflow when outfall 002 is out of service. According
to plant personnel, outfalls 005 and 007 have not been used in the past
6 years.
The NPDES permit limits the pH to a range of 6 to 9 and the tem-
perature to 35.6 °C (96 °F) [Table 1]; these parameters are to be
monitored once a week on a grab sample basis.
NEIC monitored outfall 002 once a day for pH and temperature [Table
F-3]. Outfalls 005 and 007 were inactive. The pH ranged from 4.6 to
7.5 and the temperature from 25 to 34°C. On June 25, the pH was 4.6 and
on June 26, 5.8; both values were below the allowable lower limif'of
6.0. Since outfall 001 discharges acidic wastewaters upstream of the
intake, the pH of the river water was depressed below 6.0 [Table F-21]
and may have accounted for the low pH of the condenser water.
OUTFALL 003
The powerhouse condenser water used for process water is treated
in three clarifiers. The overflow from the clarifiers passes through
seven gravity, mixed bed sand filters. An additional eleven mixed bed
pressure filters are used only when all process lines are operational.
During the reconnaissance, it was verbally reported that there were 4
gravity filters and 7 pressure filters used for the overflow. The
pressure filters have not been used for a long time and would require
considerable rehabilitation to become operational. The seven gravity
filters are backwashed once a day for 10 to 12 minutes at a rate of 1.3
to 1.4 m3/min (3,400 to 3,600 gpm); the backwash is discharged from
outfall 003 [Fig. 4].
The NPDES permit limits TSS to 70 mg/1 and the pH to a range of 6.0
to 12.5. The Company monitors once a week on a grab basis as required
-------
LIME OR FERRIFLOC
OUTFALL OO2
ONCE THRU COOLING
RIVER WATER
INTAKE
TOWER
\
POWER HOUSE
CONDENSERS
|
COOLING
BASIN
^•^MB^BI
1
(AS NEEDED)
/ACCELAT
M -ORS
i \
POWER HOUSE
REGENERANT TO OO8
BACKWASH TO OO3
UNDERFLOW TO 006
EMINER\ POWER MOUSE
AND PROCESS
PROCESS
Figure 4. fnfoke Wafer Flow Diagram, N L Indusfr/of, SI. Louis, Mo.
ro
CO
-------
29
by the permit. NEIC personnel sampled the effluent daily except for
June 1 [Table F-4]. The filters had been backwashed by the time NEIC
personnel were prepared to collect the samples.
The pH ranged from 5.3 to 8.9 and the TSS from 14 mg/1 to 970 mg/1.
On June 2 and June 30, the pH was 5.3 and 5.7, respectively; this is
below the effluent limitation range. The TSS concentrations exceeded
the permit limitation on 28 of the 29 days that samples were collected.
The TSS concentrations varied considerably over the 30-day period.
This was expected since filter backwash TSS concentrations are extremely
high during initial backwashing and decrease rapidly as the suspended
material is flushed from the filters. It is not possible for the
effluent to meet the 70 mg/1 limitation without treatment.
During the reconnaissance, NL plant personnel stated that the
limitations should be applied on a net basis. However, most of the
suspended matter has been removed in the clarification process, aided
with lime, as the main coagulant, and ferrifloc. The NPDES permit
prohibits the discharge of pollutants once it has been removed in the
treatment of water. This would apply to removal of solids by sand
filtration.
OUTFALL 004
According to NL plant officials, most of the wastewater discharged
from 004 consists of untreated river water from barometric condensers
serving the copperas vacuum crystallization process, and condensers
serving the steam bayonet concentrators. The remainder of the flow
consists of clarified river water used in the washing sequence of the
Shriver presses and the blowdown of clarified river water used as the
scrubbing media in the digester air pollution control equipment [Fig. 5],
-------
N*OM
f
SLOWDOWN
SLOWDOWN
•OO4
.^/SCRUBJ
STORAOC '
| WATER VAPOR
I 1 !
ORE A] W6T I
• l»-i —*• DRIER —»•
SLAG SILO
i r —~ ~~~~
\ / PRI\
BOELL | 1 BUFLL RAW RIVER iL^^Ar.guftX
DRV ESP "*"" | OR V ESP *~| WATER \ BER /
*ee U I fj; ^- p
WATER VAPOR 1 2 1 i D ,„
i2i !«> 5
( | 1 J l_ MAftCV 4 5 ^^
\ BER /
or slag dlgeatlan only)
f Add ad Jn a«par«t« tan*)
S|LO — * DRIER *-)S|LO —£-} BALL •'SLASSIFIER *• B|N j MaSO. IRON SOLIDS
| 1 | 1 U,LL | 1 ^ \^^^
1 WITT HOPOPRX/ / \
COARSE T / \
^ r f DiQESTERl
M,O 1
AIR
FILTER T
| .'.
j PRECOAT
M,0 M.° *~*"
PRECIPIT
TAN
DOW FLOC
•f DORR 1 •»«.•.«*.
1 THICK-] TANK '
SPNER/
\/
4 .i___— . B»»<
SLAQ
1
*
fCONCEN-\
MEAT ^\^_^/
f VAC
FATION ^~V»_M,0
"* ' SV
T\EJECTOf
«-" I BARO C
OO4
TO PIOMENT PROCESS
,
t
JAT
t &
ONO
H,0
5HRIVER
PRESS
FINAL WASH
TO O04
i • -»TO N P
ORE
RAW
/^XRIVER
S<^"
VACl\
t EJECTOR
VACUUM * BARO
COND
CRVSTALLIZER
,
HORIZONTAL
t— H.O
FILTER
COPPERAS
'
SILO
(DRV)
Figure 5. Initial Proton, N t Induitriei, St. Louit, Ma.
SLURRY
CO
o
-------
31
Company personnel believe that the effluent limitations should be
applied on a net basis due to the amount of untreated river water discharged
from the outfall.5 To receive credit for intake pollutant concentrations,
the intake and the effluent must be monitored on a flow-weighted composite
sample basis. A grab sample cannot be used for net limitations because
of the time the intake water requires to pass through the plant and
because the characteristics of the effluent and influent change over the
day. The best representation of pollutant concentrations is collected
via composite samples.
The wastewater was characterized for flow, pH, temperature, and TSS
and iron on a composite sample basis [Table F-5]. For net load calculations,
it was assumed that the entire flow from 004 was eligible for credit for
intake concentrations. The gross TSS load discharged in June averaged
23,410 kg (51,470 lb)/day while the net TSS load was 5,290 kg (11,670
lb)/day [Table 4]. The gross load exceeded the permit limitation* by a
factor of 2.4 while the net load was about 55% of the limitation. The
gross average iron load averaged 2,590 kg (5,720 lb)/day and exceeded
the limitation* by 400%; the net average iron load of 1,960 kg (4,340
lb)/day exceeded the limitation by 300% [Table 5].
Because the Mclntyre ore was removed from processing, the character-
istics of the effluent were altered significantly, especially for iron.
Copperas is a byproduct of the ore and when the copperas process was
shut down, the iron concentration was reduced significantly. After the
ore was eliminated, both TSS and iron concentrations were equivalent to
intake levels on 11 and 8 days, respectively. The net iron load after
the conversion to slag, except for one day, was within the permit
limitation. The gross iron load after the conversion averaged 1,200 kg
(2,640 lb)/day, which exceeded the limitation by almost 100%. Prior to
the conversion to slag, the gross iron load averaged 6,570 kg (14,490
lb)/day, more than five times greater than the load after the conversion
* Permit limits TSS and iron on a. gross basis.
-------
32
Table 4
AVERAGE DAILY CROSS AND NET TSS LOAD (24-HR COHPOSITE SAMPLES)
OUTFALL 004
NL INDUSTRIES, ST. LOUIS, MO.
June 1-July 1, 1976
Date*
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Total Suspended
Cumulative Load ~t
kg
45,560
88,470
120,320
154,140
189,480
236,990
263,730
282,110
301 ,550
317,870
328,950
334,480
341 ,520
347,840
357,760
365,640
371 ,230
379,250
392,530
412,360
447,050
503,470
550,510
582,530
616,830
635,350
659,420
678,460
688,360
702,310
Ib
100,470
195,100
265,340
339,920
417,850
522,610
581,570
622,110
664,970
700,960
725,400
737,590
753,130
767,060
788,930
806,310
814,200
831 ,890
861,180
904,920
981 ,420
1,105,710
1,209,430
1,280,030
1,355,660
1,396,500
1,449,580
1,491,570
1,513,400
1,544,170
Solids (GrossJ
Average Load
kg/day
45,560
44,230
40,100
38,530
37,900
39,500
37,670
35,260
33,500
31 ,780
29,900
27,870
26,270
24,840
23,850
22,850
21 ,830
21,070
20,650
20,610
21 ,280
22,880
23,930
24,270
24,670
24,430
24 ,420
24,230
23,730
23,410
1 b/day
100,470
97,550
88,440
84,980
83,570
87,100
83,080
77,760
73,880
70,100
65,940
61 ,460
57,930
54,790
52,590
50,390
47,890
46,210
45,320
45,240
46,730
50.260
52,580
53,330
54,220
53,710
53,680
53,270
52,180
51,470
Total
Suspended
Solids (Net)
Cumulative Load ttt Average Load
kg Ib
17,570
37,800
55,030
72,520
90,190
107,320
112,330
113,640
119,910
126,540
128,120
128,120
130,460
130,460
135,010
140,070
143,650
148,900
151,960
154,200
154,200
154,200
154,200
154,200
158,850
158,850
158,850
158,850
158,850
158,850
38,750
83,360
121,360
159,930
198,890
236,670
247,720
250,610
264,430
279,050
282,540
282,540
287,720
287,720
297,750
308,920
316,810
328,400
335,150
340,100
340,100
340,100
340,100
340,100
350.370
350,370
350,370
350,370
350,370
350,370
kg/day
17,570
18,900
18,340
18,130
18,030
17,880
16,040
14,200
13,320
12,650
11,640
10,670
10,030
9,310
9,000
8,750
8,450
8,270
8,000
7,710
7.340
7,000
6.700
6,420
6,350
6,100
5,880
5,670
5,470
5,290
1 b/day
38,750
41 ,680
40,453
39,980
39,770
39,440
35,380
31,320
29,380
27,900
25,680
23,540
22,130
20,550
19,850
19,300
18,630
18,240
17,630
17,000
16,190
15,450
14,780
14,170
14,010
13,470
12,970
12,510
12,080
11,670
t Composite samples correspond to the production day, 7 a.m.-? a.m.
tt TSS cumulative load exceeded total load for month from June 9-July 1, thus exceeding
the permit limitations on all days after June 8.
ttt Iron cumulative load exceeded total load for month from June 2-July 1, thus exceeding
the permit limitations on all days after June 1.
-------
33
Table 5
AVERAGE GROSS AND NET IRON LOAD (34-HR COMPOSITE SAMPLES)
OUTFALL 004
NL INDUSTRIES, ST. LOUIS, MO.
June 1-July 1, 1976
J,
Datet
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Iron (Gross)
Cumulative Load
kg
3,630
9,270
36,370
41,610
45,000
47,800
50,020
52,580
61,730
62,340
63,070
63,390
64,030
64,660
65,590
66,260
66,550
66,550
66,610
67,580
68,440
70,370
71,480
72,400
74,550
75,380
76,150
76,950
77,280
77,770
Ib
8,020
20,450
80,210
91,770
99,260
105,440
110,350
115,990
136,170
137,510
139,130
139,830
141,250
142,640
144,690
146,180
146,830
146,830
146,970
149,110
151,020
155,280
157,730
159,760
164,520
166,350
168,050
169,830
170,550
171,630
Average Load
kg/day
3,630
4,630
12,120
10,400
9,000
7,960
7,140
6,570
6,850
6,230
5,730
5,280
4,920
4,610
4,370
4,140
3,910
3,690
3,500
3,370
3,250
3,200
3,100
3,010
2,980
2.900
2,820
2,740
2,660
2,590
Ib/day
8,020
10,220
26,730
22,940
19,850
17,570
15,760
14,500
15,130
13,750
12,640
11,650
10,860
10,180
9,640
9,130
8,630
8,150
7,730
7,450
7,190
7,050
6,850
6,650
6,580
6,400
6,220
6,060
5,880
5,720
Iron (Net)
Cumulative Load™
kg
2,440
7,040
33,830
39,050
42,190
44,560
46,000
47,310
55,780
55,840
56,120
56,130
56,190
56,240
56,640
56,950
57,150
57,150
57,150
57,630
57,630
57,630
57,630
57,630
58,980
58,980
58,980
59,020
59,020
59,060
t Composite samoles correspond to the production day, 7 a.
tt The iron cumulative load exceeded the total load for the
thus exceeding the
permit limitation
on all days
Average Load
Ib /• kg/day
5,
15,
74.
86,
93,
98,
101,
104,
123,
123,
123,
123,
123,
124,
124,
125,
126,
126,
126,
127,
127,
127,
127,
127,
130,
130.
130,
130,
130,
130,
380
530
610
130
050
280
470
360
050
180
800
830
970
080
980
670
130
130
130
200
200
200
200
200
180
180
180
280
280
370
m. -7 a.m.
month from
2
3
11
9
8
7
6
5
6
5
5
4
4
4
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
1
,440
,520
,270
,760
,430
,420
,570
,910
,200
,580
,100
,670
,320
,010
,770
,550
,360
,170
,000
,880
,740
,610
,500
,400
,350
,260
,180
,100
,030
,960
Ib/day
5
7
24
21
18
16
14
13
13
12
11
10
9
8
8
7
7
7
6
6
6
5
5
5
5
5
4
4
4
4
June 3-July
,380
,760
,870
,530
,610
,380
,490
,040
,670
,310
,250
,310
,530
,860
,330
,850
,410
,000
,630
,360
,050
,780
,530
,300
,200
,006
,820
,650
,490
,340
2*
after June 2.
-------
34
to slag, and the net iron load averaged 5,910 kg (13,030 lb)/day. The
net iron load was 9.3 times greater than the effluent limitation.
The NPDES permit requires that flow, TSS, and iron be monitored at
least once a week on a grab basis. NEIC personnel measured pH (and
temperature) every 2 hours over the 30-day period [Table G-2]. Grab
samples for TSS and iron were collected daily and instantaneous flows
were measured each time a grab sample was collected [Table F-6]. T-he pH
is limited to a range of 6.0 to 9.0. The pH of the effluent was below
the lower limit in 10 of 31 measurements made when grab samples were
collected and a total of 113 measurements out of 359 pH measurements
during the 30-day period were less than 6.0. The TSS and iron loads
averaged 22,130 and 1,530 kg (48,810 and 3,390 lb)/day, respectively,
which exceeded the corresponding effluent limitations by 228 and 240%
[Table 6]. From June 1 to 8, the TSS and iron loads averaged 32,960 and
3,350 kg (72,700 and 7,390 lb)/day, after the conversion to slag, the
TSS and iron loads averaged 18,190 and 870 kg (40,120 and 1,930 lb)/day,
respectively. Although the TSS load was not significantly reduced after
the conversion to slag, the iron load was decreased by 75%.
The total allowable monthly load for TSS was exceeded on June 10
and for iron on June 5. Therefore, the average daily permit limitation
for TSS was exceeded on 21 days and for iron on 26 days. The pH violations
were due to the acid content in the wash filtrates from the Shriver
presses and the wastewaters discharged from the copperas process.
During the reconnaissance, the plant personnel reported that the
flow from 004 ranged from 43,600 to 65,400 m3/day (11.5 to 17.3 mgd).
Flow is measured by Company personnel on an instantaneous basis using
the tracer method with potassium hydroxide as the trace material.
During the survey, the flow ranged from 27,700 to 77,900 m3/day (7.3 to
20.6 mgd). The average flow was 50,000 m3/day (13.2 mgd). As discussed
-------
35
Table 6
AVERAGE DAILX TSS AND IKON LOADS (CRAB SAMPLES)
OUTFALL 004
SL INDUSTRIES, ST. LOUIS, MO.
June 1978
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Total
Suspended Solids (Gross)
Cumulative Load f
k9
56,950
99,040
138,510
164,940
188,940
228,290
245,760
263,750
283,380
296,180
308,500
313,100
319,200
325,920
339,560
346,820
352,620
358,180
361,570
376,820
413,250
469,970
523,090
562,560
585,250
599,500
621,220
641,910
650,710
664,070
Ib
125,570
218,380
305,410
363,690
416,610
503,390
541,910
581 ,580
624,860
653,080
680,250
690,390
703,850
718,680
748,730
764,750
777,540
789,800
797,290
830,930
911,270
1,036,340
1,153,490
1,240,540
1 ,290,580
1,322,010
1,369,910
1,415,530
1,434,930
1,464,400
Average Load
kg/day
56,950
49,520
46,170
41,230
37.780
38,040
35,100
32,960
31 ,480
29,610
28,040
26,090
24,550
23,280
22,630
21,670
20,740
19,890
19,030
18,840
19,670
21,360
22,740
23,440
23,410
23,050
23,000
22,920
22,430
22,130
Ib/day
125,570
109,190
101,800
90,920
83,320
83,900
77,410
72,700
69,420
65,300
61,640
57,530
54,140
51,330
49,910
47,800
45,730
43,870
41,960
41 ,540
43,390
47,100
50,150
51 ,680
51,620
50,840
50,730
50,550
49,480
48.810
Iron (Gross)
Cumulative Load ++ Average Load
kg
4,300
6,100
7,250
8,780
19,630
22,300
23,520
26,810
30,800
31 ,980
32,500
32,680
33,260
33,780
33,780
34,280
34,500
34,920
35,020
35,740
36,930
38,580
41 ,200
42,440
43,280
43,800
44,660
45,250
45,550
46,020
Ib kg/day
9,480 4,300
13,450 3,050
15,990 2,410
19,380 2,190
43,320 3,920
49,200 3,710
51,900 3,360
59,170 3,350
67,970 3,420
70,590 3,200
71,750 2,950
72,150 2,720
73,440 2,550
74,590 2,410
74.590 2,250
75,710 2,140
76,200 2,020
77,140 1,940
77,360
78,950
81,580
85,220
91,010
93,750
95,610
96,770
98,660
99,970
100,640
101,680
,840
,780
,750
,750
,790
,760
,730
,680
.650
,610
,570
,530
Ib/day
9,480
6,720
5,330
4,840
8,660
8,200
7,410
7,390
7.550
7,050
6.520
6.010
5,640
5,320
4,970
4,730
4,480
4,280
4,070
3,940
3,880
3,870
3,950
3,900
3,820
3,720
3,650
3,570
3,470
3,390
f The TSS cumulative load exceeded the total load for the month from June 10-30,
thus exceeding the permit limitation on all days after June 9.
ft The iron cumulative load exceeded the total load for the month from June 5-30,
thus exceeding the permit limitation on all days after June 4.
-------
36
previously, the potassium tracer is not suited for flow work at this
facility due to the high background levels. Although the Company flows
fall within the range measured by NEIC, the flows measured by the
Company may not be representative of actual conditions.
OUTFALL 006
The intake water from the concrete basins is treated in three
Accelator clarifiers, operated in parallel. Lime is used as the main
coagulant, although a coagulant aid is sometimes used to promote clari-
fication. The underflow from the Accelators is discharged directly to
the river via outfall 006 [Fig. 5]. In addition, non-acidic process
wastewaters from the DeLore operation, floor drains, and storm runoff is
discharged from 006. The DeLore wastewaters comprise about 2 to 10% of
the total flow from 006, according to plant officials.
NL personnel believe that the effluent limitations should be
applied on a net basis.5 As in the case of outfall 004, to receive
credit for intake pollutant concentrations, the intake and the effluent
must be monitored on a flow-weighted composite sample basis. The net
concentration would be calculated by subtracting the intake concentration
from the effluent concentration. Credit could not be given to the
intake load since all of the water is not treated in the Accelators.
Similarly, credit could not be allowed for the load treated by the
clarifiers since the material is physically separated from the water and
discharged while the treated water is used elsewhere in the plant and
subsequently discharged from other outfalls. The practice of discharging
removed pollutants back into the receiving water is prohibited by the
NPDES permit.
The wastewater was characterized June 1 to 17 for flow, pH, temper-
ature, and TSS on a composite sample basis [Table F-7]. For net load
-------
37
calculations, it was assumed that the entire flow from 006 was eligible
o
for intake concentration credit. The flow ranged from 6.85 x 103m to
13.62 x 103m3/day (1.8 to 3.6 mgd) and averaged 10.28 x 103m3/day (2.7
•3
mgd). NL personnel stated that the flow ranged from 7.19 x 103m to
11.7 x 103m3/day (1.9 to 3.1 mgd) [Appendix A]. The gross and net TSS
loads discharged over the 16-day period averaged 21,570 and 19,090 kg
(47,560 and 42,000 lb)/day, respectively [Table 7]. These loads exceeded
the permit limitation* of 3,070 kg (6,750 lb)/day by 700 and 620%,
respectively.
The NPDES permit requires that flow, pH, and TSS be monitored at
least once a week on a grab basis. NEIC personnel monitored pH (and
temperature) every 2 hours June 1 to 17. Grab samples for TSS were
collected and instantaneous flows measured daily June 1 to 17 and on
June 23 and 28 (to comply with monitoring requirements)[Table F-8]. The
pH is limited to a range of 6.0 to 9.5; the pH of the effluent exceeded
9.5 on 3 days when grab samples were collected. However, the pH exceeded
the upper limit 27 of 192 measurements made during the survey [Table G-3],
The TSS load averaged 29,370 kg (64,800 lb)/day over the 16-day
period and 19,190 kg (42,360 lb)/day over the 30-day period [Table 8].
The load discharged for June exceeded the NPDES permit limitation by
625%.
The underflow from the Accelators is designed to carry a high
concentration of solids; therefore, without treatment, the effluent
cannot meet the interim limitations. The effluent should be routed
to the proposed treatment facilities and the solids recovered. The
wastewater would not have to be neutralized.
* Permit limits TSS on a gross basis.
-------
38
Table 7
AVERAGE DAILY CROSS AND NET TSS LOAD (24-HR COMPOSITE SAMPLES)
OUTFALL 006
NL INDUSTRIES, ST. LOUIS, MO.
June 1-17, 1976
4
DateT
1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
Total Suspended Solids (Gross)
Cumulative Load TT
19
64
102
124
154
189
215
225
246
260
274
285
296
311
326
345
kg
,070
,030
,630
,270
,720
,680
,220
,240
,730
,430
,730
,650
,350
,540
,070
,140
t Composite samples
tt The 0r<
oss and net
Ib
42
141
226
274
341
418
474
496
544
574
605
629
653
686
719
761
,050
,180
,290
,000
,150
,250
,570
,680
,080
,280
,830
,900
,490
,990
,030
,080
correspond
TSS
Average Load
kg/day
19,070
32,010
34,210
31,060
30,940
31,610
30,740
28,150
27,410
26,040
24,970
23,800
22,790
22,250
21,730
21,570
to the
Ib/day
42,050
70,590
75,430
68,500
68,230
69,700
67,790
62,080
60,450
57,420
55,070
52,491
50,260
49,070
47,930
47,560
production
cumulative loads exceeded
Total
Suspended
Cumulative LoadrT
14
54
89
107
135
166
187
195
214
226
239
249
259
272
286
305
day,
the
kg
,510
,420
,420
,870
,380
,210
,770
,080
,310
,700
,650
,090
,150
,670
,370
,440
7 a.m
total
Ib
32,010
120,030
197,200
237,890
298,560
366,550
414,090
430,210
472,630
499,960
528,520
549,340
571,520
601 ,340
631,520
672,170
i. -7 a.m.
load for
Solids (Net)
Average
kg/day
14,510
27,210
29,800
26,960
27,070
27,700
26,820
24,380
23,810
22,670
21 ,780
20,750
19,930
19,470
19,090
19,090
the month
Load
Ib/day
32,010
60,000
65,730
59,470
59,710
61 ,090
59,150
53,770
52,510
49,990
48,040
45,770
43,960
42,950
42,100
42,010
from
June 3-17 and from June 4-17, respectively, thus exceeding the permit limitation
on all days after June 2 (gross) and June 3 (net).
-------
39
Table 8
AVERAGE DAILY TSS LOAD (GRAB SAMPLES)
OUTFALL 006
NL INDUSTRIES^ ST. LOUIS, MO.
June 1976
Date Total Suspended Solids
Cumulative Load* Average Load
kg lb kg/day Ib/day
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
23
28
39,960 88,120
126,240 279,320
154,770 342,240
188,790 417,260
220,170 486,470
272,010 600,770
323,220 713,670
369,140 814,870
389,620 860,030
400,290 883,560
414,420 914,720
424,910 937,850
436,560 963,550
444,930 982,000
450,380 994,010
469,930, .1,037,120. .
491,910;;i,085,580l;
537,520TTl,186,080tt
39,960 88,120
63,120 139,600
51,590 114,000
47,190 104,300
44,030 97,290
45,330 100,100
46,170 101,900
46,140 101,800
43,290 95,550
40,030 88,350
37,670 83,150
35,400 78,150
33,580 74,110
31,780 70,140
30,020 66,260
29,370 64,820
21,380;!! 47,200;;;
19,190™* 42,360ftt
t The TSS cumulative load exceeded the total
load for the month from June 2-16, 23, and
28, thus exceeding the permit limitation on
all days after June 1.
tt Loads discharged on June 17-22 and 24-2?
were not used in calculating the cumulative
load since the effluent was not sampled
on this date.
ttt Average load for 23rd and 28th was cal-
culated from the cumulative load divided
by the total number of days, e.g. 491,910
kg * 22 days = 21,380 kg/day.
-------
40
OUTFALL 008
All of the wastewater discharged from 008 originates in the power
house from the zeolite softeners and the demineralization units used to
produce deionized water for steam production [Fig. 5]. The six zeolite
softeners and the four cationic demineralizing units are regenerated
once a day while the three anionic demineralizing units may be regenerated
more frequently if necessary. There are three 2.44 m (8 ft) and three
1.8 m (6 ft) diameter zeolite softeners. The units are regenerated on
the following schedules.2
Zeolite Softeners
8-ft Units 6-ft Units
Surface Wash 15 min @ 220 gpm 10 min @ 85 gpm
Backwash 30 min @ 250 gpm 30 min & 155 gpm
Brine (10%) 23 min @ 72 gpm 18 min (P 72 gpm
Slow rinse 45 min @ 55 gpm 45 min @ 55 gpm
Fast rinse 45 min @ 380 gpm 45 min @ 215 gpm
Cation Demineralizers
Surface Wash 15 min @ 125 gpm
Backwash 30 min @ 250 gpm
Acid, 1st stage (2% H?SOJ 25 min @ 150 gpm
Acid, 2nd stage (5% H-SO?) 30 min @ 155 gpm
Acid displacement 5 min @ 150 gpm
Rinse 46 min @ 400 gpm
Anion Demineralizers
Backwash 10 min @ 180 gpm
Caustic (5% NaOH) 90 min @ 24 gpm
Displacement 70 min @ 20 gpm
Rinse 60 min @ 300 gpm
-------
41
The regeneration cycles produce alternating streams of highly
caustic and acidic wastewaters. The caustic wastes contain high
concentrations of sodium salts of the various anions removed, while the
acidic wastes contain the cations removed from the treated water.
According to plant personnel, there is a continuous flow from the outfall,
but the regeneration flows are intermittent. Based on the data above,
the minimum regeneration flow from 008 is approximately 1,400 m /day
(0.37 mgd), or 580 m3/day (0.153 mgd) from the zeolite softeners, 560
3 3
m /day (0.147 mgd) from the cation units, and 260 m /day (0.07 mgd).
3
NL plant personnel estimated that the total flow averages 4,360 m /day
(1.15 mgd). Flows were not measured by NEIC to confirm the Company
estimate.
The NPDES permit limits the temperature of the effluent to 43°C
(110°F) and the pH to a range of 1 to 11. The pH is to be monitored
continuously, and temperature once a week. NEIC personnel observed
during the survey that NL plant personnel do not monitor the pH con-
tinuously. NEIC monitored the pH and temperature daily* on a grab
basis; in addition, the pH was continuously monitored over the 30-day
period. Instantaneous pH and temperature measurements [Table F-9] show
that seven pH values exceeded the upper limitation, and one pH value was
less than the lower limitation over the 30-day period; the temperature
did not exceed 43°C. The continuously recorded pH strip chart (on file
at NEIC) showed that both the upper and lower pH limitations were
exceeded daily.
Since basic and acidic wastes are discharged, this wastestream
should be neutralized prior to discharge.
Except June 12 when measurements were not made.
-------
42
OUTFALLS 009 and Oil
The sewer lines comprising outfalls 009 and Oil are interconnected
upsewer of the discharge locations. According to NL personnel, under
normal operating conditions, only a small portion of the flow in the 009
sewer flows into the Oil sewer, but at high river levels, additional 009
flow may be diverted to Oil.
Outfall 009 contains wash filtrates from the non-pigmentary (NP)
and anatase systems [Fig. 6], floor washings, and storm water. During
the reconnaissance, outfall Oil contained condensate from the steam
turbine in the acid plant, untreated river water used for non-contact
cooling water in the barometric condenser serving the steam turbine,
surface drainage, and the overflow from outfall 009. After the recon-
naissance and prior to the survey, the condensate from the steam turbine
and barometric condenser cooling water were rerouted to outfall 013.
The only flow from outfall Oil, according to plant personnel, was the
overflow from the 009 sewer.
The wastewaters discharged from both outfalls were characterized
for flow, pH, temperature, TSS, iron and titanium on a composite sample
basis [Tables F-10 and F-ll]. The flow from outfall 009 ranged from
6,240 to 10,370 m3/day (1.65 to 2.74 mgd). NL personnel reported the
flow to range from 10,970 to 16,275 m3/day (2.9 to 4.3 mgd) [Appendix
A]. The higher flows reported by NL personnel may have been character-
istic of the flows at the higher production levels experienced prior to
the survey. However, the higher flows are probably due to the previously
discussed inherent error associated with using potassium hydroxide as
the tracer material in the NL flow measurement method.
NL reported the flow from outfall Oil to range from 10,970 to
13,620 m /day (2.9 to 3.6 mgd); however, because most of the flow v
diverted to outfall 013, the flow data cannot be compared with the
-------
TO RUTIUE A NP
PRI SCRUBBERS
1
PROM .
MVOROLVSIS
SEPARAN
1 WEAK FILTRATE
»f"DORR \ * 0<>* WEAK
UNER J Al DUST F1LTR
X^X H,SO. 2n OUST
IPROCESS "a° u f Mif M
STREAM £ X
ROTARY ,j DLtAtll gE{, WASH
" FILTER *" TANK"1^ FILTER
SCRUBBINS
MEDIUM
t*
ATE J
"'?>• KOH^
icl-U
1 CONDITION
"*" TANK
1 L-
STRON3 ACID FILTRATE
TO DIQESTER WEAK FILTRA
,
rErROTARY
/PHI \ I
_/SCRUB\ WET
\ BER /~ VENTURI
loox "3" . .°,VEPSIZE_..,_ ,..
r — { T
20H{ !•*• x^x
1 1 ROTARY . COOL.NS ^Q—^\ „ CLAOOir .^ U
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SLURRY
UNOCRSIZC
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CAR \J
BAOOINQ PROCESS
Figure 6. Analas* and N.P. Proc«i», N I Industries, St. Lowii, Me.
u>
-------
44
o
survey data. During June, the flow averaged about 3,080 m /day (0.81
mgd) and ranged from 1,750 to 5,820 m3/day (0.46 to 1.54 mgd).
The TSS and iron loads discharged from outfall 009 averaged 3,680
and 25,700 kg (8,130 and 56,670 lb)/day, respectively [Table 9]. The
TSS load was about 70% of the effluent limit, however the iron load was
1.2 times greater than the effluent limitation. The total load for the
month was exceeded on June 23-24, therefore exceeding the permit limitation
from June 23-July 1.
The TSS and iron load discharged from outfall Oil averaged 1,090
and 16,930 kg (2,410 and 37,320 lb)/day, respectively [Table 10]. These
loads were significantly less than permit limitations. However, for
June 1 to 19, the iron load did exceed the daily average permit limitations.
Since the slag was used exclusively during the last portion of the
survey, it is highly probable that the permit limitations for iron would
have been exceeded had ore and slag been processed the entire month.
The concentration of titanium ranged from 290 to 1,760 mg/1 in the
009 effluent and from 90 to 730 mg/1 in the effluent discharged from
Oil. The titanium loads discharged from 009 and Oil averaged 6,190 and
1,100 kg (13,650 and 2,430 lb)/day, respectively. Titanium is limited
by the permit only for outfall 014. The titanium loads discharged from
009 and Oil exceed the limitation established for 014 by 700% and 125%,
respectively. Since titanium is an NL product, the discharge of this
material represents a loss of product. NL should improve their house-
keeping procedures and take the appropriate steps to reduce spills.
The NPDES permit requires that outfalls 009 and Oil be monitored
for temperature once a day and pH continuously (or one 24-hour composite
pH measurement for outfall Oil). NEIC personnel observed that the
temperatures are not measured daily by NL personnel and the pH is not
-------
45
Table 9
AVERAGE DAILY TSS AND IRON LOADS (24-HR COMPOSITE SAMPLES)
OUTFALL 009
NL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
DateT
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30- July 1
t
*
Total Suspended Solids
Cumulative Load
kg
3,860
5,690
8,010
12,380
14,460
16,810
19,170
20,790
23,070
26,870
28,560
36,590
49,050
52,040
60,440
62,160
63,200
70,820
72,770
74,450
77,210
83,650
87,380
91,710
94,040
96,870
98,600
101,900
105,060
110,550
Composite samples
Ib
8,510
12,550
17,670
27,300
31 ,890
37,090
42,310
45,890
50,930
59,330
63,060
80,770
108,250
114,830
133,350
137,150
139,450
156,270
160,570
164,280
170,360
184,560
192,780
202,330
207,470
213,710
217,530
224,820
231,800
243,910
correspond
The cumulative load exceeded
limitation on all
days after
Average Load
kg/day
3,860
2,840
2,670
3,090
2,890
2,800
2,730
2,590
2,560
2,680
2,590
3,050
3,770
3,710
4,020
3,880
3,710
3,930
3,830
3,720
3,670
3,800
3,800
3,821
3,760
3,720
3,650
3,630
3,620
3,680
to the
Ib/day
8,510
6,270
5,890
6,820
6,370
6,180
6,040
5,730
5,650
5,930
5,730
6,730
8,320
8,200
8,890
8,570
8,200
8,680
8,450
8,210
8,110
8,380
8,380
8,430
8,300
8,210
8,050
8,020
7,990
8,130
production
Iron
Cumulative Load
kg
27
57
68
100
149
197
238
277
303
335
360
387
401
418
447
469
502
521
529
544
556
581
607
638
662
679
701
719
743
771
day,
,170
,120
,030
,870
,760
,760
,270
,190
,900
,820
,100
,560
,200
,590
,290
,990 1
,590 1
,420 1
,430 1
,780 1
,660 1
,750 1
,350 1
,440*1
,500*1
,810*1
,130*1
,400*1
,820*1
,090*1
Ib
59,910
125,960
150,010
222,430
330,230
436,030
525,370
611,200
670,100
740,500
794,030
854,580
884,670
922,950
986,240
,036,300
,108,190
,149,720
,167,390
,201,250
,227,460
,282,780
,339,230
,407,800*
,460,850*
,499,030*
,546,040*
,586,340*
,640,190*
,700,320*
Avoraqe Load
kg/day
27,170
28,560
22,670
25,210
29,950
32,960
34,030
34,640
33,760
33,580
32,730
32,290
30,860
29,900
29,810
29,370
29,560
28,960
27,860
27,230
26,500
26,440
26,400
26,600
26,500
26,140
25,960
25,690
25,640
25,700
1 b/day
59
62
50
55
66
72
75
76
74
74
72
71
68
65
65
64
65
63
61
60
58
58
58
58
58
57
57
56
56
56
,910
,980
,000
,600
,040
,670
,050
,400
,450
,050
,180
,210
,050
,920
,740
,760
,180
,870
,440
,060
,450
,300
,220
,650
,430
,650
,260
,650
,550
,670
7 a.m.-? a.m.
the total load for the month, thus exceeding
the permit
June 23-24.
-------
46
Table 10
AVERAGE DAILY TSS AND IRON LOADS (24-HR COMPOSITE SAfifPLES)
OUTFALL Oil
Nl INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Date*
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Total Suspended Solids
Cumulative Load
kg
760
1,330
6,610
6,890
7,530
8,560
11,330
12,240
12,360
13,330
14,320
14,760
15,380
15,890
16,540
17,670
18,930
20,140
20,570
20,870
21,200
22,520
23,240
24,220
24,750
25,520
27,690
28,600
30,570
32,820
Ib
1,680
2,940
14,580
15,210
16,620
18,910
25,020
27,020
27,280
29,420
31,600
32,580
33,950
35,070
36,510
39,010
41,790
44,460
45,410
46,070
46,800
49,720
51,320
53,500
54,680
56,390
61,180
63,190
67,530
72,500
Average Load
kg/day
760
660
2,200
1,720
1,500
1,420
1,610
1,530
1,370
1,330
1,300
1,230
1,180
1,130
1,100
1,100
1,110
1,110
1,080
1,040
1,000
1,020
1,010
1,000
990
980
1,020
1,020
1,050
1,090
Ib/day
1,680
1,470
4,860
3,800
3,320
3,150
3,570
3,370
3,030
2,940
2,870
2,710
2,610
2,500
2,430
2,430
2,450
2,470
2,390
2,300
2,220
2,260
2,230
2,220
2,180
2,160
2,260
2,250
2,320
2,410
Iron
Cumulative Load
kg
53,940
72,950
95,510
109,710
140,010
194,130
259,110
293,610
297,150
320,980
337,110
340,630
342,040
344,080
358,840
364,040
374,850
383,480
386,000
391,770
394,600
409,410
421,460
435,630
447,050
460,360
468,590
479,380
496,920
508,040
Ib
118,800
160,720
210,470
241,780
308,600
427,800
570,900
646,900
654,700
707,250
742,810
750,570
753,690
758,190
790,740
802,210
826,050
845,100
850,670
863,390
869,640
902,300
928,880
960,130
985,320
,014,670
,032,830
,056,630
,095,310
,119,840
Average Load
kg/day
53,940
36,470
31,830
27,420
28,000
32,350
37,010
36,700
33,010
32,090
30,640
28,380
26,310
24,570
23,920
22,750
22,050
21 ,300
20,310
19,580
18,790
18,600
18,320
18,150
17,880
17,700
17,350
17,120
17,130
16,930
Ib/day
118,800
80,360
70,150
60,440
61,720
71,300
81,550
80,860
72,740
70,720
67,520
62,540
57,970
54,150
52,710
50,130
48,590
46,950
44,770
43,160
41,410
41,010
40,380
40,000
39,410
39,020
38,250
37,730
37,760
37,320
t Composite samples correspond to the plant production day, 7 a.m.-? a.m.
-------
47
continuously recorded (24-hr composite samples are not collected by NL
personnel for outfall Oil). Flow, TSS, and iron are to be monitored
once a week on a grab sample basis at each outfall by the plant personnel
NEIC personnel measured pH and temperature every 2 hours over the
30-day period [Tables G-4 and G-5]. For outfall 009, the pH of the
effluent was below the lower limit of 0.5 on 26 of 360 measurements; the
temperature never exceeded 54°C (130°F). For outfall Oil, 148 of 360 pH
measurements were lower than the permit limitation 1.0; the temperature
did not exceed the permit limitation. Since the turbine condensate and
cooling water were rerouted to outfall 013, there is no non-process
wastewater in outfall Oil to neutralize the acidic effluent; therefore
the Company will not be able to meet the interim pH limitation. Since
outfalls 009 and Oil contain the same wastewaters, the same limitations
should apply. Currently, outfall 009 is limited to a range of 0.5 to
9.0 and outfall Oil to a range of 1.0 to 9.0.
The effluents discharged from 009 and Oil were also monitored daily
for TSS and iron on a grab sample basis [Tables F-12 and F-13]. The TSS
loads discharged from outfalls 009 and Oil averaged 6,190 and 1,150 kg
(13,660 and 2,560 lb)/day, respectively, [Tables 11 and 12] and were 11
and 22% of the permit effluent limitations. The average TSS load
exceeded the limitation on the last 2 days of the survey for outfall
009, while the Oil TSS load never exceeded the limitation. The summation
of the TSS loads from both outfalls averaged 7,340 kg (16,220 lb)/day,
or about 40% greater than the individual outfall limitation. These data
support the 24-hr composite data and the limitation for TSS should apply
as the summation of the loads from each outfall.
Iron loads discharged from outfalls 009 and Oil averaged 26,010 and
13,920 kg (57,360 and 30,700 lb)/day, respectively, on a grab sample
basis. The permit limitation was exceeded from June 23-30 for outfall
-------
48
Table H
AVERAGE DAILY TSS AND IKON LOADS (GRAB SAMPLES)
OUTFALL 009
HL INDUSTRIES, ST. LOUIS, MO.
June 1976
Total Suspended Solids
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Cumulative Load
kg
3,200
5,430
10,620
13,340
14,070
15,680
16,990
18,090
32,690
33,530
34,420
45,500
50,790
53,330
72,820
77,170
77,460
115,630
117,230
121,700
125,680
133,200
137,870
141,710
143,160
144,300
145,200
147,990.
164,400;
185,810t
lb
7,070
12,000
23,440
29,440
31 ,050
34,600
37,490
39,930
72,130
73,990
75,950
100,390
112,060
117,680
160,670
170,280
170,920
255,080
258,610
268,490
277,280
293,860
304,160
312,640
315,840
318,350
320,340
326, 490^
362,690];
409,910t
Average Load
kg/day
3,200
2,710
3,540
3,330
2,810
2,610
2,420
2,260
3,630
3,350
3,120
3,790
3,900
3,800
4,850
4,820
4,550
6,420
6,170
6,080
5,980
6,050
5,990
5,900
5,720
5,550
5,370
5,280
5,660
6,190
Ib/day
7,070
6,000
7,810
7,360
6,210
5,760
5,350
4,990
8,010
7,390
6,900
8,360
8,620
8,400
10,710
10,640
10,050
14,170
13,610
13,420
13,200
13,350
13,220
13,020
12,630
12,240
11,860
11,660
12,500
13,660
Iron
Cumulative Load
kg lb
24,150 53,250
62,160 137,060
70,540 155,540
110,800 244,330
132,790 293,120
180,350 397,920
222,810 491,550
249,770 550,950
313,340 691,050
340,580 751,110
364,230 803,260
399,830 881,770
430,390 949,170
448,170 988,400
476,300 1,050,430
505,290 1,114,350
515,440 1,136,730
545,410 1,202,830
555,290 1,224,630
568,160 1,252,750
581,270 1,281,660
604,010 1,331,800
628,430M,385,660t
659,750M,454,720t
681,560M,502,820!;
697, DOOM, 536, 870t
714,840n, 576,220*
730, 1201- 1,609, 920*
752,560M,659,400t
780,460M,720,940t
Average Load
kg/day
24,150
31 ,080
23,510
27,700
26,550
30,050
31 ,830
31 ,220
34,810
34 ,050
33,110
33,310
33,100
32,010
31,750
31,580
30,320
30,300
29,220
28,400
27,670
27,450
27,320
27,480
27,260
26,800
26,470
26,070
25,950
26,010
Ib/day
53,250
68,530
51,840
61,080
58,620
66,320
70,220
68,860
76,780
75,110
73,020
73,480
73,010
70,600
70,020
69,640
66,860
66,820
64,450
62,630
61,030
60,530
60,240
60,610
60,110
59,110
58,370
57,490
57,220
57,360
The cumulative load for the month was exceeded; thus, tlie permit limitation IMS
exceeded on all succeeding days.
-------
49
Table IS
AVERAGE DAIW TSS AND IKON WADS (GRAB SAWLES)
OUTPALL Oil
SL INDUSTRIES, ST. LOUIS, MO.
June 19?G
Total Suspended Solids
Date
1
2
3
4
5
6
7
8
9
10
n
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Cumulative Load
kg Ib
540
1,590
3,230
3,580
3,770
7,580
8,990
9,060
9,110
10,780
11,020
11,830
12,120
12,250
13,090
13,990
14,470
15,260
16,580
16,880
17,520
18,880
29,200
30,110
30,890
31 ,330
32,150
32,490
33,530
34,790
1,190
3,520
7,150
7,930
8,350
16,760
19,880
20,040
20,160
23,840
24,370
26,160
26,800
27,090
28,940
30,920
31 ,990
33,730
36,640
37,320
38,750
41,750
64,520
66,520
68,250
69,220
71,030
71 ,790
74,100
76,890
Average Load
kg/day
540
790
1,070
890
750
1,260
1,280
1,130
1,010
1,070
1,000
980
930
870
870
870
850
840
870
840
830
850
1,260
1,250
1,230
,200
,190
,160
,150
,150
Ib/day
1,190
1,760
2,380
1,980
1,670
2,790
2,840
2,500
2,240
2,380
2,210
2,180
2,060
1,930
1,920
1,930
,880
,870
,920
,860
,840
,890
2,800
2,770
2,730
2,660
2,630
2,560
2,550
2,560
Iron
Cumulative Load
kg
50,040
64,620
76,650
96,070
96,580
167,890
203,480
228,000
230,410
240,430
263,110
266,140
267,550
268,500
279,120
284,160
287,600
299,620
304,270
308,920
311,230
324,290
337,440
352,450
365,020
375,310
383,550
391,210
406,700
417,850
Ib
110,200
142,360
168,890
211,720
212,850
369,850
448,250
502,370
507,690
529,800
579,810
586,500
589,630
591,720
615,150
626,250
633,860
660,370
670,640
680,900
686,010
714,810
743,820
776,920
804,630
827,330
845,510
862,400
896,570
921,170
Average Load
kg/day
50,040
32,310
25,550
24,010
19,310
27,980
29,060
28,500
25,600
24,040
23.910
22,170
20,580
19,170
18,600
17,760
16,910
16,640
16,010
15,440
14,820
14,740
14,670
14,680
14,600
14,430
14,200
13,970
14 ,020
13,920
Ib/day
110,200
71,180
56,290
52,930
42,570
61 ,640
64,030
62,790
56,410
52,980
52,710
48,870
45,350
42,260
41,010
39, 140
37,280
36,680
35,290
34,040
32,660
32,490
32,340
32,370
32,180
31 ,820
31,310
30,800
30,910
30,700
-------
50
009 [Table 11]. The instantaneous iron load discharged from 009
exceeded the limitation by as much as 300%, and over the 30-day period
it exceeded the limitation by an average of 25%. The maximum instantaneous
iron load discharged from Oil exceeded the limitation by 340%.
Static and continuous flow bioassays were conducted on both outfalls
to determine the toxicity of the effluents. A mixture of Mississippi
River water and 1% effluent was toxic to all channel catfish in less
than 4 hours. The results of the bioassays are discussed in Chapter VI.
NL personnel measure instantaneous flows for both outfalls by the
tracer method, using potassium hydroxide. Except for the previously
discussed problems caused by using the potassium solution as a tracer,
the method is satisfactory for outfall 009 since the solution is added
to the sewer containing flowing wastewater. The injection location for
outfall Oil is in a wet well or surge basin where the wastewater must
flow into the Oil sewer; there is no direct access to the sewer.
Therefore, the tracer solution must completely mix with the wastewater
in the wet well and reach an equilibrium condition before samples can be
collected from the river location for flow calculations. The minimum
time, determined by NEIC, required for the tracer to reach a steady
state value at the outfall was 10 minutes. Since the Company uses a
constant head (Mariotte) bottle and injects for 5 to 10 minutes before
the bottle is emptied, there is considerable doubt as to whether steady
state conditions are met and if flows measured are representative. Low
concentrations yield high calculated flows which, in turn, increase the
calculated pollutant load. If NL desires to use this method in the
future for flow measurement, the injection solution should be changed to
a material present in trace amounts, and the injection period should be
extended to ensure steady-state conditions.
During the survey, the effluents from 009 and Oil changed color on
numerous occasions from a light clear green to an opaque, milky-white
-------
51
light green. Since this condition did not seem to be normal, the plant
personnel were asked about the change in appearance. The opaque effluent
occurs if there is a spill or when a leak develops. (The physical
changes in appearance of the effluents discharged from outfalls 001,
013, and 014 were also observed during the survey.) Since the discharge
is not observed continuously or frequently, the spill or leak could
occur for several hours (the change in color did occur for several hours
during the survey). Better and improved housekeeping practices should
be instituted into the process operation.
OUTFALL 010
In the sulfuric acid process, hot, concentrated sulfuric acid
passes through cast iron coils which are cooled by passing untreated
river water over the exterior coil surface. The river water is dis-
charged via outfall 010. A conductivity sensor with a readout device
has been installed in the acid facilities to detect leaks in the coils.
An alarm is activated if a leak occurs, but the flow is not automatically
neutralized or stopped.
Only pH and temperature are limited by the permit [Table 1]. The
pH is to be monitored continuously and the temperature measured once a
week. During the reconnaissance, plant personnel stated that the pH is
not monitored continuously.
Temperature and pH were monitored daily by NEIC [Table F-14]. On
June 13, the pH of the wastewater was 1.6 which was less than the lower
pH limitation. The pH and temperature complied with the permit limitations
for all other observations.
-------
52
OUTFALLS 012 and 013
Prior to the NEIC survey, outfalls 012 and 013 contained condensate
from the sulfuric acid production, floor washings, and storm water. In
addition, a cross-connection exists between the sewers serving outfalls
013 and 014 and process wastewaters from the 014 sewer could flow into
the 013 sewer. However, by May 28 both the condensate from the steam
turbine in the acid plant, and non-contact cooling water in the barometric
condenser serving the steam turbine, previously discharged from outfall
Oil, were rerouted to the 013 sewer. Additional flow from the acid
plant was also routed to the 013 outfall. The flow in outfall 012 was
not changed.
The NPDES permit limits only the pH and temperature in both out-
falls [Table 1]; the temperature is to be monitored once a week and the
pH continuously. During the reconnaissance, plant personnel stated that
the pH is not continuously monitored.
The effluent from outfall 012 was monitored once a day by NEIC
[Table F-14]. On 15 days, no flow was observed.* On 14 of 15 days that
flow occurred, the temperature exceeded the permit limit by approxi-
mately 30°C. The effluent complied with the pH limitations.
Although only pH and temperature are limited by the permit, the
effluent from outfall 013 was characterized both on a 24-hour composite
sample basis [Table F-15] and a grab sample basis [Table F-16] for TSS,
iron and titanium. The effluent was monitored on a 24-hour basis for
one week, June 9 to 16; daily grab samples were collected June 1 to 9
and June 16 to 30. The pH of the effluent is limited to 2.0 to 9.0;
although the effluent complied with the limitation, the pH of the
* NEIC personnel re-checked the outfall every 2 hours when there Das
no flow. Flow could have occurred during periods between the checks.
-------
53
effluent was not always characteristic of untreated river water which
the plant personnel had reported as the only flow in the sewer. The pH
dropped to as low as 2.6 [Table G-6] during June 9 to 16. According to
plant personnel, years ago there was an acid spill in the sulfuric acid
production area and the acid has remained trapped underground. NL plant
personnel stated that the low pH of the 013 flow was due to the trapped
acid seeping into the 013 sewer. The source was backtracked by plant
personnel during the survey.
The temperature exceeded the permit limitation for three observations:
June 10, 11 and 20. The maximum temperature measured was 41.5°C.
For June 9 to 16, net loads discharged from 013 were computed to
determine if process wastewaters were present. The data indicate that
process wastes were discharged on June 10 to 11 since TSS, iron and
titanium concentrations were much higher than intake levels. The grab
sample data for June 1 to 9 also indicate that process wastes were
present. On May 27 the effluent was grayish in color, similar to the
color of the 014 effluent, instead of brown which is characteristic of
the intake water; this also indicated the presence of process wastes.
It is highly probable that process wastes were periodically entering the
013 sewer by the interconnection with the 014 sewer. Since cooling
water is the only flow permitted to be discharged from this outfall, the
sources of process wastes entering the 013 sewer should be isolated and
eliminated.
OUTFALL 014
Process wastewaters from the calcining operation, grinding of
pigment, steam milling, wash down and scrubbers, and barometric con-
denser water constitute the majority of the flow from 014 [Fig. 2]. The
largest sources of waste material are the overflow of the pigment
settling basins after grinding, and spills from various operations. The
-------
54
titanium dioxide is reduced in size by particle-to-particle grinding in
the micronizer. Untreated river water is used in the barometric condenser
serving the micronizer; this flow is measured by means of a standard
orifice plate, 14.98 cm (5.897 in) in diameter, and recorded on a
Foxboro recorder. Because the river water comprises over 50% of the
total flow, the NL plant personnel feel that net limitations should be
applied to 014.5
The Company has installed a weir box and a V-notch weir at the end
of the pipe to measure flows; however, the box was overflowing and the
V-notch weir could not be used to determine the flow. The Company uses
the potassium hydroxide tracer method to determine the flow.
The wastewater discharged from 014 was characterized for flow, pH,
temperature, TSS, and titanium on a composite sample basis [Table F-17].
3 1
The total flow averaged 15,500 m /day (4.08 mgd); about 8,650 m /day
(2.3 mgd) was untreated river water [Table F-18]. The gross TSS load
averaged 5,520 kg (12,180 lb)/day and the net TSS load averaged 2,100 kg
(4,640 lb)/day [Table 13]. The gross load exceeded the permit limitation
for TSS by 42% (the permit limitations apply to the gross loads);
however, the net load was only 54% of the limitation. Gross and net
titanium loads averaged 1,910 and 1,830 kg (4,150 and 4,040 lb)/day,
respectively [Table 14]. The average gross load was 220% of the titanium
load limitation and the average net load was over twice the limitation.
The pH of the effluent was less than 2.0 (lower pH limitation) for
8 of 360 measurements and the temperature complied with the permit
limitation [Table 6-7].
The permit requires that TSS and titanium be monitored once a week
on a grab sample basis. Grab samples were collected daily by NEIC
[Table F-19]. The average TSS and titanium loads exceeded the permit
-------
55
Table 13
AVERAGE DAILy CROSS AND NET TSS LOADS (24-M COMPOSITE SAMPLES)
OUTFALL 014
NL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
4.
Date1
Total Suspended Solids (Gross)
Cumulative Load
kg
June 1-2'ft 8,780
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
t
tt
12,
16,
24,
28.
33,
37,
43,
46,
48,
52,
53,
56,
59,
61.
64,
66,
68,
73,
79,
89,
101,
115,
124,
130,
136,
147,
153,
156,
160,
Composite
One al
•iquo
250
880
510
640
200
630
550
390
730
230
770
410
300
860
660
780
960
470
350
680
920
600
290*
100*
210*
780*
050*
290*
160*
samples
t eampl
Ib
19,370
27,010
37,220
54,040
63,150
73,210
82,980
96,030
102,300
107,470
115,190
118,590
124,420
130,790
136,450
142,630
147,300
152,110
162,050
175,030
197,820
224,820
255,000
274,170*
287,000*
300,470*
325,980*
337,600*
344,750*
353,290*
Average Load
kg/day
8,780
12,250
8,440
8,170
7,160
6,640
6,270
6,220
5,790
5,410
5,220
4,880
4,700
4,560
4,410
4,310
4,170
4,050
4,080
4,170
4,480
4,850
5,250
5,400
5,420
5,440
5,680
5,660
5,580
5,520
correspond to the
e in the <
Composite
Ib/day
19,370
27,010
18.610
18,010
15,780
14,640
13,830
13,710
12,780
11,940
11,510
10,780
10,360
10,060
9,740
9,500
9,200
8,940
9,000
9,210
9,890
10,700
11,590
11,920
11,950
12,010
12,530
12,500
12,310
12,180
Total
Suspended Solids (Net)
Cumulative Load
kg
4,800
8,940
10,950
16,540
19,210
21,230
22,630
26,080
27,060
27,660
29,550
29,550
31,490
32,810
34,490
36,820
38,450
39,710
41,530
43,020
45,720
47,600
50,570
52,960
54,350
55,370
61 >090
61 ,090
61 ,090
61,090
Ib
10,580
19,720
24,180
36,490
42,390
46,850
49,950
57,560
59,720
61,050
65,220
65,220
69,500
72,410
76,120
81 ,270
84,880
87,660
91 ,670
94,960
100,920
105,060
111,600
116,880
119,950
122,210
134,830
134,830
134,830
134,830
plant production day, 7 a.m. -7
mas added
in an incorrect propt
Average Load
kg/day
4,800
8,940
5,480
5,510
4,800
4,240
3,770
3,720
3,380
3,070
2,950
2,680
2,620
2,520
2,460
2,450
2,400
2,330
2,300
2,260
2,280
2,260
2,290
2,300
2,260
2,210
2,340
2,260
2,180
2,100
a.m.
•>rtion,
Ib/day
10
19
12
12
10
9
8
8
7
6
6
5
5
5
5
5
5
5
5
4
5
5
5
5
4
4
S
4
4
4
thus
,580
,720
,090
,160
,590
,370
,320
,220
,460
,780
,520
,920
,790
,570
,430
,410
,300
,150
,090
,990
,040
,000
,070
,080
,990
,880
,180
,990
,810
,640
this
composite sample for TSS may not be representative. Therefore, the composite sample
fov June 1-2 uas not used in determining the cumulative or average load,
The gross cvmila.ti.ve load exceeded the total load for ths month, thus exceeding
the permit limitation on all succeeding daye.
-------
56
Table 14
AVERAGE DAILY CROSS AND NET TITAHIUU LOADS (24-HR COMPOSITE SAWLES)
OUTFALL 014
KL INDUSTRIES, ST. LOUIS, MO.
June-July 19?'6
j.
Date1
Titanium (Gross)
Cumulative Loader
kg
June l-2ttt 1,300
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
t
tt
8,260
9,470
11,780
13,710
14,690
18,830
23,050
24,470
28,220
31,720
36.040
37,340
39,300
40,640
42,420
43,200
43,700
44,570
45,890
47,150
48,280
49,520
50,440
51,120
51 ,620
54,230
54,680
55,190
55,600
Composite samples
The gr
•oss and net
1b
2,870
18,220
20,900
26,000
27,930
30,100
39,240
48,560
51,690
59,960
67,680
77,210
80,090
84,420
87,390
91,310
93,030
94,130
96,050
98,980
101,760
104,260
107,000
109,040
110,540
111,640
117,410
118,400
119,540
120,460
Average Load
kg/day
1,300
8,260
4,730
3,920
3.420
2,930
3,130
3,290
3,050
3,130
3,170
3,270
3,110
3,020
2,900
2,820
2,700
2,570
2,470
2,410
2,350
2,300
2,250
2,190
2,130
2.060
2,080
2,020
1,970
1,910
Ib/day
2,870
18,220
10,450
8,660
6,980
6,020
6,540
6,930
6,460
6,660
6,760
7,010
6,670
6,490
6,240
6,080
5,810
5,530
5,330
5,200
5,080
4,960
4,860
4,740
4,600
4,450
4,510
4,380
4,260
4,150
Titanium (Net)
Cumulative Loadti-
k9
1,200
8,210
9,400
11,670
12,530
13,490
17,560
21,720
23,090
26,730
30,180
34,450
35,670
37,550
38,770
40,500
41,260
41,740
42,590
43,880
45,040
46,120
47,310
48,200
48,850
49,310
51,890
52,300
52,780
53,130
Ib
2,660
18,100
20,720
25.730
27,620
29,730
38,700
47,870
50,890
58,920
66,540
75,950
78,650
82,800
85,490
89,310
90,990
92,040
93,920
96,760
99,330
101,710
104,330
106,300
107,740
108,760
114,450
115,360
116,430
117,410
correspond to the plant production day, 7 a.m.-?
cumulative
load
both exceeded
the total load for
Average
kg/day
1,200
8,210
4,700
3,890
3,130
2,690
2,920
3,100
2,880
2,970
3,010
3,130
2,970
2,880
2,760
2,700
2,570
2,450
2,360
2,300
2,250
2,190
2,150
2,090
2,030
1,970
1,990
1,930
1,880
1,830
a. fit.
the month
Load
Ib/day
2,660
18,100
10,360
8,570
6,900
5,940
6,450
6,830
6,360
6,540
6,650
6,900
6,550
6,360
6,100
5,950
5,680
5,410
5,210
5,090
4,960
4,840
4,740
4,620
4,480
4,350
4,400
4,270
4,150
4,040
from
June 10-July I, thus exceeding the permit limitation on all days after June 9-10.
tt+ One aliquot sample in the composite uas added in an incorrect proportion, thus
this composite sample for titanium may not be representative. Therefore, the
composite sample for June 1-2 uas not used in determining the cumulative or average
load.
-------
57
limitations on 10 and 26 days, respectively [Table 15]. The average
daily TSS load exceeded the limitation by 60% and the average daily
titanium load was 230% of the limitation. The solids and titanium in
the effluent represent product lost to the sewer.
During the survey, Company employees were observed cleaning hydraulic
forklifts and similar equipment next to an open manhole on the 014
sewer. The solids, lubricants, and oils were flushed into the sewer.
The Company should designate a cleaning area for equipment and install
treatment facilities to collect the pollutants.
OUTFALLS 015, 016, 018 and 019
Outfall 015 contains the backwash water from the concrete cooling
basin traveling screens used to remove trash from the river water before
it is pumped to the barometric condensers. Outfall 016 is a standby for
015 and is normally dry; however, during the survey 016 was in use and
015 was dry. Outfall 018 contains packing gland drainage from the five
booster pumps used to increase the plant's water pressure. A vacuum
system removes ashes from the ash silo, and a steam ejector pulls the
vacuum. A barometric condenser serves the steam ejector, and clarified
river water from the condenser is discharged from 019 along with steam
condensate and fines from the steam.
These outfalls are limited to a pH range of 6.0 to 9.0 and must be
monitored once a month. NEIC monitored the discharges daily [Table F-
20]. The pH was less than 6.0 on June 25 for outfall 016, and on June
24 and 26 for outfall 018. The pH of the 019 effluent was greater than
9.0 on 4 days during the survey.
-------
58
Table 15
AVERAGE DAILy TSS AND TITANIUM LOADS (GRAB SAMPLES)
OUTFALL 014
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Total Suspended Solids
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
IS
19
20
21
22
23
24
25
26
27
28
29
30
Cumulative Load1"
kg
12,480
36,090
42,260
46,040
49,020
53,900
59,450
62,970
66,200
75,350
79,410
81,410
85,150
85,710
87,950
91 ,650
94,050
100,330
104,020
108,430
120,920
134,200
150,930
161,190
166,510
171,890
178,310
182,810
185,360
189,790
Ib
27,530
79,600
93,210
101,550
108,120
118,900
131,150
138,930
146,060
166,240
175,200
179,620
187,870
189,100
194,040
202,210
207,500
221,360
229,500
239,220
266,730
296,020
332,920
355,550
360,870
372,730
386,900
396,830
402,470
412,240
Average Load
kg/day
12,480
18,040
14,080
11,510
9,800
8,980
8,490
7,870
7,350
7,530
7,210
6,780
6,550
6,120
5,860
5,720
5,530
5,570
5,470
5,420
5,750
6,100
6,560
6,710
6,660
6,610
6,600
6,520
6,390
6,320
Ib/day
27,530
39,800
31 ,070
25,380
21,620
19,810
18,730
17,360
16,220
16,624
15,920
14,960
14,450
13,500
12,930
12,630
12,200
12,290
12,070
11,960
12,700
13,450
14,470
14,810
14,430
14,330
14,330
14,170
13,870
13.740
Titanium
Cumulative Loadt+ Average Load
kg
1,990
19,420
20,500
21,390
22,430
23,710
26,950
29,130
30,560
36,660
39,130
41 ,800
43,780
44,710
46,320
50,620
50,870
52,220
53,450
54,370
55,790
56,910
58,730
59,220
59,610
59,960
60,540
60,670
60,900
61.350
Ib
4,400
42,850
45,250
47,210
49,520
52,350
59,490
64,300
67,470
80,920
86,370
92,270
96,640
98,700
102,250
111,730
112,290
115,270
118,000
120,020
123,160
125.640
129,660
130,750
131,610
132,400
133,680
133,970
134,470
135,480
kg/day
1,990
9,710
6,830
5.340
4,480
3,950
3.850
3.640
3,390
3,660
3,550
3,480
3,360
3,190
3,080
3,160
2,990
2,900
2,810
2,710
2,650
2,580
2,550
2,460
2,380
2,300
2,240
2,160
2,100
2,040
lb/
-------
59
OUTFALLS 017. 020. 021. and 022
The boiler blowdown water is discharged from outfall 020, and
outfall 021 is the drain in a concrete basin housing a tank which
receives boiler blowdown wastewater (020). Outfall 022 is used to
discharge water which collects in a sump in the coal pit. This outfall
has not been used in several years and outfall 017 is not used at all.
The wastewaters discharged from these outfalls are limited to a pH
range of 6.0 to 11.5 and a temperature of 99°C (210°F). The pH and
temperature must be monitored once a day. During the reconnaissance,
plant personnel stated that these effluents are not monitored daily.
NEIC monitored the effluents discharged from 021 daily for pH and
temperature [Table F-20]; outfalls 017, 020, and 022 were dry. On June
3, the pH of the effluent was 5.8; the effluent complied with the permit
limitations on all other days.
RIVER INTAKE WATER
o
Four Peerless vertical centrifugal pumps [3 @ 66 m /min (17,500
q
gpm) and one at 38 m /min (10,000 gpm)] deliver river water through the
137-cm (54-in) diameter intake line to four Allis-Chalmers centrifugal
3 3
booster pumps [two at 19 m /min (5,000 gpm) and two at 38 m /min (10,000
gpm)]. A portion of the raw water is used directly from the intake
line, by passing the booster pumps.
The river intake water was sampled on a composite and grab basis
during the survey [Tables F-21 and F-22, respectively]. The intake flow
o
averaged 198,000 m /day (52.2 mgd); the instantaneous flows averaged
200,000 m3/day (53 mgd).
-------
60
Intake concentrations of TSS, iron and titanium varied daily, and
the concentrations of the grab samples were not equivalent to the
concentrations of the composite samples on most days. Therefore, if net
limitations are established for outfalls which qualify, the intake water
and effluents must be sampled on a 24-hour composite flow-weighted basis
on the same monitoring day. Credit for the intake levels cannot be
determined with grab samples due to the varying concentrations.
The intake is influenced by the outfalls immediately upstream.
Outfalls 001 and 004 discharge acidic wastewaters with high concen-
trations of iron. The data show that the pH of the intake water was
depressed to low levels and iron concentrations are substantially
greater than concentrations found in surface waters.
PROPOSED TREATMENT FACILITIES
According to the NPDES permit compliance schedule, a neutralization
treatment plant is scheduled to become operational in 1977. The treatment
facilities will be located in the boat yard area and in the area where
the old acid plant units are situated. There are concrete piers buried
in the boat yard which must be removed before construction can commence.
During the reconnaissance, plant personnel stated that the piers
were being removed by an outside contractor. During the June survey,
periodic inspection of the boat yard by NEIC personnel indicated that
there was no work being done on the concrete piers. However, the old
acid plant was being dismantled during the survey.
The Schedule of Compliance specifies that construction was to
commence by June 30, 1975. The construction is to be completed by
December 31, 1976. The treatment facilities cannot be constructed in
time to meet the December 31, 1976 deadline or the June 30, 1977 deadline.
Therefore, the Company will not be in compliance with the NPDES permit.
-------
61
According to plant personnel during the reconnaissance, all outfalls
are to be intercepted and the entire waste load discharged from a single
outfall. Many of the oufalls contain non-process cooling water and this
flow should not be introduced into the proposed treatment system.
Instead, all sources of process wastewaters should be isolated and
collected into a single sewer and treated.
The total process wastewater flow from outfalls 001, 004, 009, Oil,
and 014 averaged 84,180 m3/day (22.24 mgd), or 58 m3/min (15,400 gpm)
o
which is considerably less than the effluent flow of 151 m /min (40,000
gpm) reported by Ryckman, Edgerley, Tomlinson, and Associates, Inc.
o
(RETA).* Assuming that another 19 m /min (5,000 gpm) of process waste-
water is discharged from the remaining outfalls, the total flow requiring
3 3
neutralization would be about 76 m /min (20,000 gpm) or 52,500 m /day
(13.9 mgd). This is one-half the flow that RETA used to calculate the
total'tons of sludge produced by neutralization. Therefore, by only
treating the process wastewaters, and blending the neutralized effluent
(after solids recovery) with the non-process wastewaters (if desirable),
the total amount of sludge produced in neutralization predicted by RETA
[2,260 to 2,720 m.tons (2,500 to 3,000 tons)/day] could be reduced
significantly (by almost 50%) which would decrease treatment and disposal
costs.
* Report titled "An Environmental Report on the Impacts of Neutral-
izing the Wastewater Effluent from the St. Louis Titanium Plant,"
Novembert 1975.
-------
VI. EFFLUENT TOXICITY
In 1972, EPA evaluated the toxicity of wastewater discharges into
the Mississippi River from NL Industries.6 Three wastewater discharges
were reported to be acutely toxic to test fish as indicated by 96-hour
bioassays. Concentrations of effluent lethal to 50% of the exposed test
fish (LC5Q) during the 96-hour tests were calculated to be 0.63% for
outfall 001, 0.60% for outfall 009 and 7.5% for outfall Oil.
In June 1976, NEIC re-evaluated the toxicity of outfalls 001, 009
and Oil. A series of range-finding static bioassays indicated that
concentrations of less than 1% wastewater from any of the three outfalls
were acutely toxic to channel catfish (ictdlurus punctatus). Continuous-
flow bioassays were conducted to determine the 96-hour LCgQ of wastewaters
discharged from outfalls 001, 009 and Oil. Methods of testing are
described in Appendix I and the fish bioassay results for each outfall
are discussed below.
OUTFALL 001
Wastewater from NL Industries' outfall 001 was diluted in Mississippi
River water to concentrations ranging from 0.075 to 0.75%. Channel
catfish were exposed to each concentration during a 96-hour bioassay.
Within 24 hours all the test fish died in the 0.75% concentration of
wastewater. No mortalities occurred in the lower concentrations (0.075
to 0.56%) during the remainder of the bioassay test. The 96-hour LC5Q
for channel catfish was calculated to be 0.65%.
Chemical analyses of the 0.75% concentration test water strongly
indicated that mortality was caused by a combination of iron (16 mg/1)
-------
63
and low pH (4.2). Doudoroff and Katz7 have reported that acute toxic
conditions prevail when more than 2 mg/1 iron is present in water with a
pH level of less than 5.8. The pH of the lower test concentrations
(0.075 to 0.56%) were above 5.8 [Table 16].
Results recorded during this 1976 study for wastewater chemistry
and toxicity of outfall 001 were similar to results reported by the EPA
following the 1972 survey of NL Industries.
OUTFALL 009
Bioassay tests to determine the toxicity of the effluent from
outfall 009 were conducted using a series of dilutions of wastewater in
Mississippi River water. Wastewater concentrations evaluated during the
test ranged from 0.2 to 2.0%. Within 15 minutes, test fish showed
stress and began to hemorrhage in the 2.0% wastewater concentration. In
less than two hours all test fish died in wastewater concentrations of
1.12% and higher. Mortality continued and at 24 hours all test fish
were dead in wastewater concentrations of 0.64% and higher. No fish
died in the lower concentrations (0.20 to 0.36%) during the 96-hour
bioassay. The toxicity (96-hr LC5Q) of the effluent discharged from
outfall 009 to channel catfish was calculated to be 0.46%.
Analyses of the lethal test waters revealed iron concentrations
ranging from 11 to 35 mg/1 and pH values of 2.3 to 4.1. These conditions
appeared to cause the observed fish mortalities. Investigators8 have
reported that fish cannot survive in waters with such low pH levels.
Furthermore, the presence of iron salts in the acidic test water is
known to substantially increase toxicity.7 In the lower test dilutions
(0.20 to 0.36%), pH was at environmentally safe levels (6.0 to 6.6)
[Table 17].
-------
Table 16
ACUTE TOXICITY OF OUTFALL 001 AND ASSOCIATED CHEMICAL
NL INDUSTRIES, ST. LOUIS* MO.
June 12-16, 1976
Parameter
(mg/1 )
pH (units)
Iron
Titanium
% Survival
24 hr
48 hr
72 hr
96 hr
0.
A
4.2
16
1.9
0
0
0
0
75%
Bft
4.2
16
1.9
0
0
0
0
0.
A
6.3
12
1.4
100
100
100
100
56%
B
6.3
12
1.4
100
100
100
100
0.
A
6.3
9
1.0
100
100
100
100
42%
B
6.3
9
1.0
100
100
100
100
0.24%
A
6.8
5
0.60
100
100
100
100
B
6.8
5
0.60
100
100
100
100
0.
A
6.9
3
0.32
100
100
100
100
,13%
B
6.9
3
0.32
100
100
100
100
0.
A
6.9
2
0.17
100
100
100
100
.075%
B
6.9
2
0.17
100
100
100
100
Control
(receiving
water)
A B
8.1
1
<4
100
100
100
100
8.2
1
<4
100
100
100
100
t Chemical values of the diluted effluent are calculated (undiluted effluent value x effluent test
concentration).
tt Letters A & B signify duplicate bioassay tests.
CTl
.£»
-------
Table 17
ACUTE TOXICITY OF OUTFALL 009 AND ASSOCIATED CHEMICAL DATA^
NL INDUSTRIES, ST. LOUIS, MO.
June 20-243 1976
Parameter
(mg/1 )
pH (units)
Iron
Titanium
% Survival
24 hr
48 hr
72 hr
96 hr
2.
A
2.3
35
5.0
0
0
0
0
00%
Bft
2.3
35
5.0
Ottt
0
0
0
1.
A
2.5
26
3.7
0
0
0
0
50%
B
2.5
26
3.7
Ottt
0
0
0
1.
A
2.9
20
2.8
0
0
0
0
12%
B
2.7
20
2.8
Ottt
0
0
0
0.64%
A
4.0
11
1.6
0
0
0
0
B
4.1
11
1.6
0
0
0
•o
0.
A
6.0
6.3
0.90
100
100
100
100
36%
B
6.0
6.3
0.90
100
100
100
100
0.
A
6.6
3.5
0.50
100
100
100
100
,20%
B
6.5
3.5
0.50
100
100
100
100
Control
(receiving
water)
A
7.4
28
<4
100
100
100
100
B
7.4
28
<4
100
100
100
100
t Chemical values of the diluted effluent are calculated (undiluted effluent value x effluent test
concentrations ).
tt Letters A & B signifn duplicate bioassay tests.
ttt All fish were dead in 2 hours.
a*
-------
66
Comparison of survey results reported by EPA in 1972 with results
reported here showed that calculated toxicity values and the chemistry
of wastewater from outfall 009 were similar during both the EPA surveys.
OUTFALL Oil
The toxicity of the effluent discharged from outfall Oil was
evaluated through a series of fish bioassays using concentrations of
wastewater ranging from 0.15 to 1.5%. Tests showed that wastewater
concentrations of 0.84% and higher were acutely toxic to channel catfish.
All test fish died in these wastewater concentrations within 4 hours.
At lower concentrations (0.15 to 0.48%) no mortalities occurred, and the
96-hour LC,-n was calculated to be 0.63%.
b(J
Test water in which fish mortalities were observed was chemically
analyzed. Results showed a pH range of 2.7 to 3.4 and iron concen-
trations of 15 to 28 mg/1. Toxicity of outfall Oil appeared to be
related primarily to low pH since these levels have been reported to be
lethal to all fish species within a few hours.8 Iron concentrations
contributed to the toxicity through synergistic action with the low pH.7
In the non-lethal test water (0.15 to 0.48%) pH was at environmentally
safe levels (5.8 to 6.9) [Table 18].
Results of this study were compared with results recorded by the
EPA during the 1972 survey. In 1976, outfall Oil had an increased
hydrogen ion concentration (lower pH) and the wastewaters were approxi-
mately ten times more toxic than in 1972.
-------
Table 18
ACUTE TOXICITY OF OUTFALL Oil AND ASSOCIATED CHEMICAL
NL INDUSTRIES, ST. LOUIS, MO.
June 20-24, 1976
Parameter
(mg/1)
pH (units)
Iron
Titanium
% Survival
24 hr
48 hr
72 hr
96 hr
1.5%
A Btf
2.7 2.7
28 28
4.0 4.0
o om
0 0
0 0
0 0
1.
A
2.9
21
3.0
0
0
0
0
12%
B
3.0
21
3.0
Ottt
0
0
0
0.
A
3.4
15
2.3
0
0
0
0
84%
B
3.4
15
2.3
Ottt
0
0
0
0.48%
A
5.8
8.8
1.3
100
100
100
100
B
5.9
8.8
1.3
100
100
100
100
0.27%
A
6.9
5.0
0.73
100
100
100
100
B
6.9
5.0
0.73
100
100
100
100
0.15%
A
6.9
2.8
0.40
100
100
100
100
B
6.9
2.8
0.40
100
100
100
100
Control
(receiving
water)
A B
7.0
28
<4
100
100
100
100
7.0
28
<4
100
100
100
100
t Chemical values of the diluted effluent are calculated (undiluted effluent value x effluent test
concentvations).
tt Letters A & B signify duplicate bioassay tests.
ttt All fish were dead in 4 hours.
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68
REFERENCES
1. "National Lead Company," a brochure printed by the National Lead
Company, 111 Broadway, New York, N.Y. 10006, March 1967.
2. Letter - May 17, 1976 with attachments from Mr. Jeffrey E. Silver,
Counsel for Environmental Affairs, NL Industries, Inc., to Mr. Earl
J. Stephenson, Director, Enforcement Division, U.S. Environmental
Protection Agency, Region VII, Kansas City, Mo.
3. Letter - August 17, 1976 with attachment from Mr. Jeffery E. Silver,
Counsel for Environmental Affairs and Mr. F. R. Baser, Director,
Environmental Control Department, NL Industries, Inc., to Mr.
Carroll Wills, U. S. Environmental Protection Agency, National
Enforcement Investigations Center, Denver, Colo.
4. Letter - August 10, 1976 with attachments from Mr. Jeffery E.
Silver, counsel for Environmental Affairs, NL Industries, Inc., to
Mr. Earl J. Stephenson, Director, Enforcement Division, U.S. Environ-
mental Protection Agency, Region VII, Kansas City, Mo.
5. Conference held March 4, 1976 in Kansas City, Mo. between USEPA,
Region VII and NL Industries, Inc.
6. Industrial Survey, NL Industries Carondelet Plant, St. Louis, Mo.,
October 16-21, 1972. NFIC-Cincinnati, 48 p.
7. P. Doudoroff, and M. Katz. 1953. Critical review of literature on
the toxicity of industrial wastes and their components to fish (2).
The metals as salts. Sewage and Industrial Wastes 25:802-839.
8. Committee on Water Quality Criteria, Environmental Studies Board,
National Academy of Science, National Academy of Engineering, 1972.
Water Quality Criteria 1972. USEPA R3-73-033. Washington, D.C.
594 p.
9. Committee on Methods for Toxicity Tests with Aquatic Organisms,
1975. Methods for acute toxicity tests with fish, macroinvertebrates,
and amphibians. USEPA - 660/3-75-009. Corvallis, Oreg. 61 p.
10. American Public Health Association, 1971. Standard Methods for the
Examination of Water and Wastewater. 13th ed. New York, 874 p.
11. D.I. Mount, and W. A. Brungs. 1967. A simplified dosing apparatus
for fish toxicological studies. Water Res. 1:21-29.
-------
69
APPENDICES
A NL Industries Reconnaissance Report
B NPDES Permit Limitations
C Field Study Methods
D Chain of Custody Procedures
E Analytical Procedures and Quality Control
F Daily Monitoring Data
6 Individual pH and Temperature Measurements
H Comparison of Lithium Chloride and
Parshall Flume Flows - Outfall 001
I Bioassay Test Procedures
-------
71
Appendix A
NL Industries Reconnaissance Report
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73
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, BOX 25227. DENVER FEDERAL CENTER
DENVER, COLORADO 80225
DATE
RECONNAISSANCE REPORT FOR N. L. INDUSTRIES, ST. LOUIS, MISSOURI
Date of Reconnaissance: April 7-8, 1976
Attendees: N. L. Industries - Ivan B. Lampe, Plant Manager
0. J. "Bud" Gewinner, Project Engineering
Superintendent
NEIC-Denver - James L. Hatheway
Art N. Masse
Bruce A. Binkley
Barrett E. Benson
BACKGROUND
The St. Louis plant was purchased by National Lead in July, 1923, from
the Mineral Refining and Chemical Company. The plant, located on the
Mississippi River at the confluence of the River Des Peres (channel
used to convey storm water to the river), manufactures titanium pigments
by the sulfate process from ilmenite ores from upper New York State and
slag purchased from Quebec Iron and Titanium (QIT). Sulfuric acid is
also manufactured by the contact process for in-plant use. The plant
operates 24 hours/day, seven days/week.
Prior to 1972, the plant produced calcium pigment, approximately 70%
CaS04 and 30% Ti'02- Paint manufacturers changed to latex formulations
and the plant converted in 1972 to 100% Ti02 pigments; the customers now
add the extenders. Due to the conversion, much of the equipment has been
taken out of service.
The plant is located on 40 acres adjacent to the river; an additional
40 acres adjacent to the plant on the south was purchased from the U. S.
-------
74
Government. The southern area, known as the "boat yard" was to be used for
testing military watercraft during World War II and large concrete piers
were constructed. However, the war ended before the testing area was
completed and the government abandoned the area. N. L. has contracted
a local firm to remove these piers as this area will be used for the pro-
posed neutralization treatment facility.
All process and cooling waters are pumped from the river through a
single intake. A portion of the water is treated for process use, the rest
is used for once-through cooling purposes. All process wastewaters and
cooling waters are discharged untreated to the Mississippi River from
22 outfalls. Outfalls 001, 004, 006, 009, Oil and 014 contain the majority
of the process wastewaters. The remaining 16 outfalls contain cooling water,
filter backwashes, boiler blowdown wastes, or are dry (outfalls 005, 007,
013, 016, 017 and 021 are only used in emergencies). Water used in the
processes are either recycled to other processes or are discharged to
the river. The Company tries to recycle the strong acid filtrates and
washes wherever possible. A list of the waste sources and the estimated
flow for each outfall is listed in Table 1. All sanitary wastewaters are
discharged to the Metropolitan Sewer District's sewers for treatment at
the Lemay primary wastewater treatment plant.
DISCHARGE LIMITATIONS
NPDES Permit No. MO 0000451, issued on April 10, 1974, expires on
April 9, 1979. Initial effluent limitations apply to the 22 outfalls
until the outfalls are intercepted and the wastewaters discharged through
a single outfall, no. 023. The initial permit limitations and the final
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75
TABLE ONE
WASTEWATER SOURCES AND ESTIMATED FLOWS
N. L. INDUSTRIES, ST. LOUIS, MO. PLANT
Estimated*
Outfall Flow (MGD) Wastewater Sources Discharging to Outfall
001 2-3 Wash filtrates from rutile process, SOL
effluent, Delore acidic effluent, plant
washdowns.
002 6-9 Cooling water overflow from power house
condensers.
003 6-13 Backwash from gravity and pressure sand
filters.
004 6-9 Barometric condenser cooling water from
crystallization process; wash water from
Shriver filters (about 1% of total flow);
scrubber water blowdown from digester
scrubbers; concentrator and crystallizer
barometric condenser cooling waters.
005, 007 6-9 Used only when the cooling basin outfall
(002) is out of service; the overflow is
split between 005 and 007.
006 1.9-3,1 Sludges from accelators, Delore non-acidic
effluent.
008 0.25-1.2 Backwashes from demineralizer and zeolite
beds regeneration. Alternating stream of
highly caustic and acidic discharges.
009 2.9-4.3 Wash filtrates from NP and anatase systems,
floor washings, storm water. Connected
with outfall Oil.
010 8.6-12.9 River water used for coil cooling in the
H2S04 plant.
Oil 2.9-3.6 Condensate from steam turbine in acid
plant, untreated river water used for
non-contact cooling in barometric con-
denser serving steam turbine, surface
drainage, overflow from outfall 009.
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76
TABLE ONE (Continued)
WASTEWATER SOURCES AND ESTIMATED FLOWS
Estimated*
Outfal 1 Flow (M6D) Wastewater Sources Discharging to Outfall
012, 013 0.07 Storm water, condensate from H2S04 pro-
duction.
014 3.6-4.7 Effluent from wet grinding, steam milling,
river water from the micronizers1 baro-
metric condensers.
015 0.3 Cooling basin traveling screen wash water
(traveling screen used to remove trash
sending water to the barometric condensers).
016 Not Used Standby for 015.
017 Not Used Dead outfall.
018 Packing gland drainage from the five
booster pumps used to increase plant
water pressure.
019 0.03 Steam ejector (pulls vacuum on ash silo)
barometric condenser river water (clarified),
and fines from the steam and steam condensate.
020 0.1 Boiler blowdown.
021 Not Used Drain for concrete basin housing tank
which receives boiler blowdown wastes
(020).
022 Not Used Water from coal pit sump.
* Flows supplied by N. L. Industries St. Louis Plant personnel during the
reconnaissance, and 1974 EPA monitoring (Region VII).
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77
limitations for outfall no. 023 are listed in Appendix A. According to the
Compliance Schedule, the interceptor sewer, outfall no. 023, and a wastewater
treatment facility are to become operational on July 1, 1977.
SELF-MONITORING
A quarterly summary of the DMR's submitted for 1975 indicate that the
initial limitations are not being met [Table Two]. All monitoring is done
on Monday or Tuesday. Instantaneous flows are determined by injecting
potassium hydroxide for ten minutes upsewer and collecting one sample from
the waste stream at a predetermined time after injection. The tracer method
is used on outfalls 004, 006, 009, Oil and 014. Outfall 001 is equipped with
a 9-inch fiberglass Parshall flume, however a stilling well or flow recording
device have not been installed. There are periods when the flume is sub-
merged and flow measurements cannot be made. Company personnel determine
the depth of flow in the flume with a ruler and calculate the instantaneous
flow from standard tables. The flow from outfall 002 is determined by sub-
tracting various water meter readings from the intake flow. The flow from
outfall 003 is intermittent and is determined from the backwash pumping
rates for the sand filters. The remaining flows are estimated by the
Company personnel.
HATER INTAKE AND TREATMENT FACILITIES
Four constant speed electric pumps (three rated at 15,000 gpm each and
one rated at 10,000 gpm) are used to withdraw river water through a single,
54-inch diameter intake line. An orifice plant has been installed in the
intake line; flows are recorded and totalized on a Hays recorder. The
orifice is at least 20 years old; the flow recorder is calibrated infrequently.
-------
TABLE TWO
QUARTERLY SUMMARY OF 1975 DMR'S
N. L. INDUSTRIES, ST. LOUIS, MO.
«sJ
00
Outfall
001
002
003
004
006
008
Quarter
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
PH
Limit Reported
0.5-9.0 1.2-1.6
1.2
1.1
0.8-2.3
6-9 6.7-7.4
6.9
7.2
5.8-7.6
6-12.5 6.7-7.4
6.7
6.7
6.6-8.5
6-9 6.4-7.5
6.4
7.0
3.3-8.7
6-9.5 7.4-9.3
8.1
9.3
3.3-9.9
1-11.0 11.6-12.4
4.6
1.4-12.7
1.3-13.6
Temp (°F)
Limit Reported
100 82
95
104
78
96 59
81
87
68
110 68
75
91
70
TSS Ub/day)*
Limit Reported
11,500 22,500
32,570
72,033
16,905
70 mg/1 418 mg/1
590
707
273
21,400 23,100
73,620
57,252
13,986
6,750 45,020
101,710
70,159
35,595
Iron (Ib/day) Titanium (Ib/day)
Limit Reported Limit Reported
63,100 78,400
58,796
49,456
20,791
1 ,400 1 ,960
3,903
3,683
2,102
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TABLE TWO (Continued)
Outfall
009
010
on
012
013
014
Quarter
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
Jan. 1975
2nd
3rd
4th
PH
Limit Reported
0.5-9.0 1.1-2.1
1.8
0.7-1.6
1.3-7.2
2-9 2.7-6.6
7.1
7.2-10.6
3.2-8.6
1-9 5.0-6.3
3.0
1.2-2.8
0.7-8.4
2-9 5.6-7.8
5.6
6-8.6
0.7-8.5
2-9 1.4-3.2
3.8
1.9-6.5
3.3-7.5
2-9 2.6-6.9
6.4
4.8-9.1'
6.1-8.9
Temp ("¥)
Limit Reported
130 88
104
105
78
100 70
86
97
73
130 58
88
101
77
100 163
170
90
133
100 70
78
90
73
160 86
108
108
88
TSS (Ib/day )i
Limit Reported
11,700 15,700
38,531
24,865
13,454
11,700 3,470
26,663
24,501
7,506
8,500 4,010
18,340
16,913
9,443
Iron (Ib/day)
Limit Reported
46,100 86,000
198,674
109,536
49,274
46,100 287
8,495
6,614
6,583
Titanium (Ib/day)
Limit Reported
1,920 951
3,786
4,704
3,382
vo
-------
00
TABLE TWO (Continued) °
Outfall
020
Quarter
Jan. 1975
2nd
3rd
4th
PH
Limit Reported
6-11.5 10.8-11.4
1113
10.9-12.3
10.9-11.4
Temp («F)
Limit Reported
210 208
185
204
202
TSS (Ib/day) 1 Iron (Ib/day) Titanium (Ib/day)
Limit Reported Limit Reported Limit Reported
1 Outfall 003 is limited on a concentration basis.
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81
The circular chart reads in gpm and has a factor of 1,000; the integrator
is 3,600.
A schematic of the water treatment process is shown in Figure 1. Raw
water is screened at the river with traveling screens (the screenings are
discharged to the river without treatment from an unpermitted outfall).
Approximately 40,000 gpm of water is pumped for use in the power house
condensers or for once-through cooling water. The condenser water is
returned to a concrete basin. About 6,000 gpm of this water is introduced
into the treatment system, the excess water overflows to outfall 002. The
river water, heated in the power house condensers, is used as process water
because the treatment efficiency is improved. The river water from the
concrete basin is treated in three Accelator clarifiers operated in parallel.
Lime is used as the main coagulant, although a ferrifloc is sometimes used
to aid clarification. The underflow from the Accelators is discharged
directly to the river via outfall 006. The overflow goes to 11 sand
filters. Presently four gravity, mixed bed* filters are used to treat all
of the overflow; there are an additional seven pressure sand filters (mixed
bed)* which are used when all process lines are operational. Each gravity
filter has a capacity of 600 gpm and each pressure filter is rated at 500
gpm. The filters are backwashed once/shift, via outfall 003. After fil-
tration, the water is chlorinated; plant personnel thought that the chlorine
residual was 5-20 mg/1, but were not sure when it was pointed out that the
concentration of 5-20 mg/1 chlorine was toxic.
* Filter media consists of a coal material and gravel of varying sizes.
-------
00
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TRW
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RNt*
LIKE OR
UNDERFLOW BACKWASH
70 006 To 00?
PROCESS
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N.L.
5T LDOiS, MO
-------
83
After disinfection, the water is used in the processes and for boiler
makeup water. The water used in the high pressure boilers is demineralized
in four cation and four anion units. These units are regenerated with
caustic or acidic solutions. Water for the low pressure boilers and the
waste heat boiler in the acid plant is softened in three zeolite filters.
All regenerants are discharged via outfall 008.
PROCESS DESCRIPTION AND HASTE SOURCES
A. Preparation. Digestion. Concentration, and Hydrolysis [Figure Two]
The two raw materials, QlT slag and Mclntyre ilmenite ore, are pro-
cessed separately, although some of the equipment is used for both pro-
cesses. The slag contains about 70% Ti02 while the ilmenite contains only
47% Ti02. Therefore the process streams are never mixed. The ilmenite ore
comprises about two-thirds of the raw material. The ilmenite ore is used
to produce the rutile and non-pigmentary (NP) grades of titanium dioxide
while the slag is used for the anatase grade. Rutile is used as the pig-
ments for paints and has a long, flat crystalline structure. Anatase, a
"blob" type of crystals, is used for coating paper. The NP grade is used
for frit enamel pigment which is used in the porcelain enamels for appliances.
The processing sequences for the two raw materials are almost identical
and are discussed concurrently.
The two raw materials are received at the plant in a wet or moist form.
The materials are either placed in wet silos or stockpiled in the boat yard.
The plant can store from 60 to 90 days supply of raw material. There is one
wet silo for the ilmenite and one wet silo for the slag. The material is
dried in a gas fired, continuous rotary drier at 300°F. Oil is used for
-------
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-------
85
drying when gas is not available. The dryer has a capacity of 50 tons/hour.
After drying, the material is stored in dry silos. The Company drys over an
8-hour period for each ore as it requires from four to five hours to convert
the drier to process the other raw material. The only emission from the
drying operation is water vapor which is not controlled. Dusts from the
dry silos are collected in a Buell dry electrostatic precipitator (ESP) and
are returned either to the dry silos or to the digesters (if the particles
are fine enough).
The dried material is sent to five Marcy iron ball mills for grinding;
the ball mills are fed continuously 24 hours/day. Each mill is rated from
5 to 12 tons/hour, depending upon the type of ore processed. Usually two or
three mills are operational under normal process conditions. The mills grind
to a particle size of +4%, 200 mesh, or about 4% of the particles are larger
than 1/400-inch diameter. The ground material is then classified; all coarse
material is returned to the ball mills while the fines are sent to seven
surge bins for storage prior to processing. A Buell dry ESP collects all
dusts from the ball mills. The ESP is automatically rapped every 15 minutes
and the dusts are returned to the classifier.
The dried, ground material is transferred from the bins to a wet hopper
before being placed in the digester tanks. There are 36 digesters at the
plant, but only 27 are in service since the 1972 conversion. The contact
digestion step, a batch operation, requires about 16 hours for completion.
Sulfuric acid, 66°Be', is added to the ground material in the digesters,
mixed with air and the solution heated. During the reaction, a cake is
formed consisting of titanyl, ferrous and ferric sulfates. The titanyl and
iron sulfates are dissolved from the inert cake with clarified river water,
-------
86
which requires about 12 hours of the total digestion period. Powdered iron
is added to the mixture to react with the excess sulfuric acid to produce
hydrogen which reduces all of the ferric iron to the ferrous form. A small
amount of quadrivalent titanium is also reduced to the trivalent state to
prevent oxidation of the ferrous iron at a later step in the process. The
reduced titanium is lost from the process.
Fumes from the digestion reaction are treated in scrubbers for St^. SO-j,
particulate and vapor control. There are nine primary scrubbers which use
untreated river water as the scrubbing media. The countercurrent scrubbers
were designed by N. L. Industries and are 8 feet in diameter and approximately
55 feet in depth. About 9,000 gpm of the scrubbing water is recycled through
the scrubbers and approximately 5,000 gpm of the water is blown down for a
10-nrinute period via outfall 004. The scrubbers are only operated for 15-30
minutes, during the reaction period. The fumes from the reactions involving
the ilmenite ore are only scrubbed in the primary scrubbers since the fumes
are low in 502* however an acid mist is emitted during reaction. The emissions
from the QIT slag digestion process are sequentially treated in primary and
secondary scrubbers since the slag is rich in SOo. For both emissions, the
acid mists are removed in the primary scrubber, the S02 is removed in the
secondary scrubber. The secondary scrubbers serve two primary scrubbers.
The secondary scrubber consists of a HEIL packed tower with interlocking
saddles as the media. A waste caustic solution (2-3% sodium hydroxide),
which occurs in their SOL process, is used as the scrubber liquid. The
caustic solution is recycled continuously during digestion only. The blow-
down rate is controlled by the pH of the caustic solution which is maintained
between 7-7.5. About 50-60 gpm is blown down to outfall 004.
-------
87
After digestion and reduction, the mixture is clarified in two 50 foot
diameter Dorr Oliver clarifiers. There are eight additional Dorr clarifiers,
however these are only used for surge purposes. An organic coagulant, Dow
Floe 7402, is added in liquid form to improve sedimentation. The underflow
from the thickeners, is pumped to the mud clarification building. The solids
are dewatered on a large, Ametek Filter Co., rotary vacuum filter. A dia-
tomaceous earth precoat is added to the solids. From 5-10 gpm of clarified
river water is sprayed on the rotary filter to recover additional TiSO^.
(The reduced titanium in the solids is soluble.) The filtrate is returned
to the process. The filter cake or gangue mud is trucked to the boat yard
on the southern part of the plant and placed on a limestone pad to neutralize
the acid. The limestone pad is on top of a clay pad to prevent percolation;
the area is diked to contain all runoff. The gangue mud is moist enough to
prevent fugitive dusts. Approximately 70 tons of solids are produced daily;
there is sufficient storage area for another four to five years. An alternate
disposal site has not been found.
The Dorr clarifier overflow is sent to a surge tank for additional solids
removal before treatment in the Shriver presses. There is only one surge tank,
which is only used for the ilmenite ore process due to the volume processed.
The QIT slag solution is sent directly to the presses.
There are five Shriver presses which are plate and frame filters, using
a cloth media and filter paper. The solutions are fed under pressure to the
presses; a filter aid, either diatomaceous earth or Pearlite, is added as a
precoat. The press cycle time ranges from 8 to 20 hours. The solids or
filter cake are washed off the presses and are sent to the mud treatment
building. The final wash on the filter cloth, using clarified river water,
is discharged via outfall 004.
-------
The filtrate from the presses are sent directly to the concentrators
for the QIT slag process while the ilmenite ore process filtrate is sent
to the crystallization operation to remove iron. About 25% of the ilmenite
ore filtrate is diverted to the NP process.
The crystallization process is operated on a batch basis. There are
four Swenson crystallizers, operated under a vacuum of 29 inches of mercury
at 13°C (evaporative cooling). The iron become supersaturated and ferrous
sulfate (copperas) crystals are formed. The titanyl sulfate remains in
solution. The vacuum is obtained with three steam ejectors and two baro-
metric condensers operated in series. The third ejector is vented to the
atmosphere. Raw river water is used in the barometric condensers. The
wastewaters are discharged via outfall 004.
After crystallization, the mixture is discharged to two horizontal
table filters to remove the titanyl sulfate (and some ferrous sulfate) from
the crystals. Clarified river water is used to wash the crystals in the
winter months. Well water is used in the summer due to the increase tem-
perature of the river water. The clear copperas crystals are transported
by belt conveyer to a storage silo or are dissolved in water, and sold.
The filtrate from the table filters is sent to the concentrators.
There are three Mantius Steam Bayonet Tube type concentrators which
are operated under a vacuum of 27" Hg to remove water at a lower temperature.
The temperature of the solution is maintained at 96°C. Two of the concen-
trators are used for the ilmenite ore process. The vacuum is pulled with
air ejectors. There is a barometric condenser on each of the concentrators
which discharge via outfall 004. After the concentration process, the Ti02
content is about the same for each raw material.
-------
89
The hot concentrate is dribbled into heated (90-95°C) water which
causes the precipitation of Tit^ as a titanium dioxide hydrate crystal.
The next processes are for soluble iron removal by a series of dilution,
filtering and washing steps using countercurrent water flow. The anatase
and NP processes are identical and differ from the rutile process.
B. Anatase Process (NP Process is Identical to Anatase Process) [Figure Three]
In the anatase process, the QIT slag solution is sent to seven Dorr
thickeners (there are three additional standby Dorr thickeners). An organic
coagulant, SEPARAN No. 273, is added to the material entering the thickener.
The overflow from the thickeners, termed weak filtrate, is discharged via
outfall 009 and contains 36% H2S04. The total flow from the seven thick-
eners is approximately 1,163 gpm. The TSS are about 1 mg/1 and the pH is
less than 1.0. The overflow is high in iron. The underflow becomes the
process stream and contains 20% solids. The underflow is sent to seven
rotary drum filters where clarified water is added for additional washing.
The strongacid filtrate is sent back to the digestion process. The filter
cake is transferred to the bleaching tanks. There are two bleach tanks in
service and an additional bleach tank for a spare. Small quantities of
sulfuric acid and aluminum or zinc dusts (reductants) are added to the
bleach tanks. The ferric iron is reduced to the ferrous form. The bleached
solution is sent to a secondary wash filter. The weak acid filtrates are
returned to the Dorr thickeners. The dewatered cake containing about 40%
solids from the secondary wash filter are sent to the calcination process.
-------
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M.L.
-------
91
C. Rutile Process [Figure Four]
In the rutile process, the ilmenite ore solution is sent to cascade
cooling coils (using clarified river water) and cooled from 96°C to 60°C.
The cooled solution is sent to the Moore Leaf filter operation. There are
ten filter frames and thirteen tubs which receive the frames. Eight of
the tubs are used for primary filtering and five for secondary filtration.
In the primary filtering process, the filter leaves are precoated with wood
fibre. There are 35 leaves/filter which are covered with a cloth media. A
vacuum is applied to the frames to dewater the solids. The primary frame
is washed with clarified river water and the cake is removed in the bleaching
operation prior to secondary filtration. Sulfuric acid and aluminum or zinc
dusts are added to the bleach tanks. The cake is then transferred to the
secondary filter tubs. The weak filtrate from the secondary tubs is sent
to a Dorr thickener. The overflow from the thickener, containing 5% HgSO^,
is discharged via outfall 001. The underflow is sent to a tub between the
cascade cooler and the primary pickup tub. The strong filtrate from the
primary tub is sent to a Dorr thickener; the overflow from the thickener is
returned to the digestion process. Excess overflow is discharged via outfall
001. There is always an excess overflow, about 33 gpm containing 23% l^SO^.
After the second filtration step, the cake is transferred to a dump tank
prior to conditioning. The weak filtrates from the pickup and wash tubs
are returned to the Dorr thickener containing the weak filtrates.
D. Conditioning and Calcination [Figures Three and Four]
The anatase and rutile materials are then slurried with clarified river
water to the conditioning area where PgOs, potassium hydroxide and other
-------
FIGURE
RUTIUE PROCESS
N.L.
4T L0» IS MO
CGOUNb \NKTCtt.
DM. HiO
HzO I
VO
ro
-------
93
additives are mixed with the materials. The NP materials are not conditioned.
The conditioned anatase and rutile slurries and the NP slurry are dewatered
in the same rotary vacuum filter (process streams are not mixed). The
filtrate is sent back to the weak filtrate Dorr thickener.
The washed hydrates are then sent to the calcination process. Although
there are 11 calciners, units nos. 5, 6, 7 and 8 are out of service. Calciners
nos. 1, 2 and 3 are used for rutile material, with unit no. 4 in the standby
status. Calciner no. 10 is used for the NP material; unit no. 9 is maintained
as a spare. The largest calciner, no. 11, is used for the anatase material.
In the calcination process, the water of hydration is removed in rotary
kilns (calciners) heated to approximately 1,000°C. The NP material from the
rotary kiln comes off in a dry form. The large particles are pulverized,
screened, pumped to a dry bin and bagged in 50-pound bags which are stored
in the warehouse.
The anatase material from the kiln is cooled to less than 100°C in a
cooling barrel, then screw conveyed to four Raymond roller mills for crushing.
The crushed particles are classified, with the undersize either bagged as dry
product or slurried with demineralized water from the power house or with
condensate water to railroad tank cars for shipment. The slurry contains
about 75% solids. The oversize particles are returned to the Raymond mills.
From the rutile calciners, the material is cooled in cooling barrels
and conveyed to nine Raymond roller mills (only five mills are in operation).
The pulverized product is repulped with water, dispersed with monoisopropylamine
to make the product pumpable, and passed over a magnetic separator to remove
iron. The product is then ground in the pebble mill, which uses Belgium
-------
94
flint rock (to prevent contamination with iron) to reduce the particle size,
and classified in Dorr Clones. The coarse or heavy particles from the Dorr
Clones are returned to the pebble mill and the fine particles (product) are
sent to treatment tanks. Here the product is separated into different process
streams for treatment into different grades. Conditioners are added in the
treatment process before final drying. Silica dioxide, aluminum sulfate
(alumina), sodium aluminate, and sodium silicate are used as conditioners.
Because alumina is acidic, caustic sodium aluminate is also added to obtain
a neutralized alumina. The Company manufactures the sodium aluminate and
aluminum sulfate for process use. After treatment, the various grades are
washed with demineralized water to remove sodium ions (from the sodium
aluminate conditioner). The product is dewatered in rotary filters (two
primary and two secondary) (wash water is added to the filters) and dried
on two P&S steam heated, traveling belt driers. The filtrate from the rotary
filters is sent to Dorr thickeners. A coagulant aid, SEPARAN, is added to
the thickener. The underflow is sent back to the treatment tanks and the
overflow is sent to the micronizer mill. After drying, the product is con-
veyed by elevator to the micronizer mill where particle to particle grinding
occurs due to pressure and steam. The ground material is passed through a
cyclone separator which removes about 95% of the pigment to the bagging
operation where it is packaged in 50-pound bags.
The exhaust gases from the 11 calciners contain S02> 803, Ti02> particulate
matter and products of combustion. Approximately 20% of the exhaust gases are
recycled to the kiln to recover the heat. The gases from each calcination
process (anatase, NP and rutile) are exhausted to a primary scrubber which
-------
95
removes the TK^ from the gas stream. The scrubbers are 15 feet in diameter,
and 35 feet in depth. The scrubbers serving the rutile and NP calciners use
clarified river water as the scrubbing medium. The no. 11 calciner scrubber
for the anatase process uses the secondary wash filtrate as the scrubbing
medium. After primary scrubbing, the gas streams pass through a wet Venturi
scrubber (Chemical Construction Co.) for acid mist removal. Clarified river
water is used in the wet Venturi scrubbers which then is sent to the primary
scrubbers. The blowdown from the scrubbers is sent to the Dorr clarifiers.
Each calcining system is equipped with the two scrubbers. The weak filtrate
used in the no. 11 calciner primary scrubber is sent to the seven Dorr
thickeners (units which follow the hydrolysis process); the overflow from
the thickeners is discharged via outfall 009. The blowdown from the NP
scrubbers is sent to the two Dorr thickeners (units v/hich follow the hydro-
lysis process) which overflow to outfall 009. The blowdown from the rutile
scrubbers flows to a single Dorr clarifier (there are no Dorr thickeners
following the hydrolysis process). The overflow is discharged via outfall
009 and the underflow is sent to the Dorr thickener following the Moore
Leaf filter process; the overflow from the latter thickener is discharged
to outfall 001.
The cyclone separator (serving the micronizer) is served by a primary
scrubber to control the 5% fraction of the product stream which is not re-
covered by the cyclone. The scrubbing solution is the effluent from the
Dorr thickeners which serve the rotary filters following the rutile condi-
tioning process. The scrubbing solution is returned to the Dorr thickeners.
The steam from the scrubber is sent to a contact barometric condenser (3-4
inches of Hg, vacuum); raw river water is used for cooling and is discharged
via outfall 014. Excess overflow from the Dorr thickeners cited immediately
above is also discharged to outfall 014.
-------
96
E. SOL Process [Figure Five]
Sodium titanate, which is sometimes used in the rutile process as a
promoter, is made from slurried TiC^ which is removed from the rutile process
after the secondary Moore Leaf filter washing step (iron free, but not cal-
cined). The TiOg is reacted with 50% sodium hydroxide in a strike tank which
is steam heated. The mixture is washed in a filter to remove the sodium.
The filtrate is discharged via outfall 001, is also used in the digester
scrubber, and is used in the wet mill operation for alumina. The washed
material is reacted with hydrochloric acid and is termed SOL. The HC1
peptizes the material or activates the product. The SOL is added to the
rutile pigment for special orders for highly reflective properties.
SULFURIC ACID PRODUCTION
Sulfuric acid is produced by two contact H2S04 units. Molten sulfur
is barged from the Gulf Coast up the Mississippi and stored in insulated,
steam heated tanks on plant property. The only effluent from the process
is once through river water used for cooling. The water is passed over
cast iron cooling coils containing concentrated sulfuric acid. The cooling
water is discharged via outfall 010. Conductivity cells have been installed
in the cooling water discharge to detect leaks in the cast iron coils. The
conductivity cells are equipped with an alarm.
DELORE OPERATION
The Delore operation, a division of N. L. Industries, operates inde-
pendently of the Ti02 plant. However, the St. Louis plant provides treated
water for the Delore operation and accepts and is responsible for their
wastewaters. The Delore operation grinds barium sulfate (barytes), then
-------
97
STRIKE
HEAT
I
ROTARY
FlLTfcfc
HCl
WSAX FILTRATE
W^ST€
JT
W6T
'SOL
SOL
N.L.
ST
-------
98
bleaches the barytes with sulfuric acid to dissolve impurities. The material
is washed, filtered and dried. The acid rinses and filtrates are sent to a
Dorr clarifier. The overflow is discharged via outfall 001 and comprises
from 10 to 20% of the total discharge from the outfall. The effluent from
the grinding operation, floor washings and from a flotation operation is
discharged via outfall 006. This discharge is non-acidic and comprises from
2 to 10% of the total outfall flow.
PLANNED TREATMENT FACILITIES
A neutralization treatment plant is scheduled to become operational
in 1977 according to the NPDES permit. Plant personnel would only discuss
the treatment process in general terms. The acid liquors will be pumped
to holding tanks and then into continuous reaction tanks where a calcium
carbonate slurry will be added for neutralization. The overflow from the
reaction tanks will be sent to aeration ponds to precipitate ferric hydro-
xide. If the solids cannot be discharged, they will be sent to a thickener
followed by filters, or will be sent to ponds. The Company wants to dis-
charge the solids slurry after neutralization because they do not have
space for ponds. The ferric hydroxide would be discharged with the solids
slurry.
All research and pilot testing is being done at the New Jersey Sayer-
ville plant.
EFFLUENT GUIDELINES
The Development Document for Proposed Effluent Limitations for Major
Inorganic Products Segment of the Inorganic Chemicals Manufacturing, August
1973 describes Best Practicable Control Technology Currently Available (BPCTCA)
-------
as neutralization with lime or caustic, removal of suspended solids with
settling ponds or clarifier-thickener, and recovery of by-products. BATEA
is the same as BPCTCA plus additional clarification and polishing. The
effluent limitations are as follows:
Parameter BPT (kg/kkg)+ BAT (kg/kkg)+
Flow 90,500 1/kkg 90,500 1/kkg
TSS 2.2 1.3
Fe 0.036 0.036
Pb 0.014 0.014
Total Other Metals* 0.015 0.015
The guidelines are not broken down for specific processes.
t Monthly average values.
* V, Al, Si, Cr, Mn, Nb and Zr.
Based on the daily average production of 232 ton/day, the total allow-
able discharges from the St. Louis plant would be as follows:
Parameter Allowable Discharge
Flow 19 X 106 liters/day (5 mgd)
TSS 463 kg/day (1,020 Ib/day)
Fe 7.6 kg/day (16.7 Ib/day)
Pb 2.9 kg/day (6.5 Ib/day)
Total Other Metals 3.2 kg/day (7 Ib/day)
-------
100
The amounts of pollutants discharged from the process outfalls* for 1975
(quarterly basis), excluding water treatment sludges and solids were as
follows:
Parameter
TSS, Ib/day
Fe, Ib/day
Ti, Ib/day
Jan.
68,800
166,600
951
2nd 1/4
189,700
269,900
3,786
3rd 1/4
195,600
169,300
4,704
4th 1/4
61 ,300
78,750
3,382
The Effluent Guidelines have been challenged by the industry and new
limitations are expected to be promulgated later this year.
* Outfalls 001, 004, 009, Oil and 014.
-------
APPENDIX A
NATIONAL LEAD INDUSTRIES, INC.
101
Effluent limitations from effective date of Permit through the date the
interceptor and the single outfall No. 023 is built and operable.
Outfall 001
E'Cuent Characteristic
Flow-m3(Day (MGD)
Total Suspended
Solids
Iron
lenperature
Outfall 002, 005
EJGuent Characteristic
Floirtn3/Day (MGD)
Temperature
Outfall 003
Effluent Characteruti:
Flow-ns/Day (MGD)
Suspended Solids
Outfall 004
Effluent Characteristic
Flow-m3/Day (MGD)
Total Suspended
Solids
Iron
Pbch..-*
kg/day (Ibs/day)
Daily Avg Daily Max
NM N/ft
5220(11500) N/A
28650(63100) N/A
N/A N/A
and 007
• Lir.iitationi
O til <:r Units (Specify)
Daily Avg Daily Max
N/A N/A-
N/A N/A
N/A N/A
N/A 100° P
Discharge Limitations
kg/day (Ibs/day)
Daily Avg Daily Max
N/X N/K
N/A N/A
kg/day Cbs/dew
Dally Avg Daily Max
N/A NM
N/A N/A
Other Units (Specify)
Daily Avg Daily Max
N/S TR/7C
N/A 96° F.
! Limitations
OLier Units (SpeeUy)
Daily Avg Daily Max
N/A N/A
70 Bg/1 N/A
Dischirge Limitations
*2/day (Ibs/df-y)
Daily Avg Daily Max
N/S NAT
9710(21400) N/A
635(1400 ) N/A
Diner Uniti (Specify)
Daily Avg Dally Max
NAs: N7r
N/A N/A
N/A N/A
Monitoring Rwplre.Tijnlj
Measurement Sample
Frequency Type
I/week N/A
I/week grab
1/veek grab
I/week Observations
Monitorln? TUquireaer.ts
Measurement Sample
Frequency Type
1/veek N/A
I/week Observations
Measurement Sample
Frequency Type
I/week N/A
1/veek grab
Monitoring Requires enta
Measurement Sample
Frequency Type
1/veek N/A
I/week grab
I/week grab
-------
102
Outfall 006
Effluent Charzctonsti:
Flow-ra3/Day (MGD)
Total Suspended
Solids
Outfall 008
Effluent Characteristic
Flow-m3/Day (MGD)
Tenperature
Outfall 009
Effluent Qiaractaristh
Flow-m3/Day (MGD)
Total Suspended
Solids
Iron
Temperature
OutfalTOlO, 012
Effluent Characteristic
Flow— m3/Day (MGD)
Temperature
Outfall Oil
Effluent CharneUristi:
Flow-m3/Day (MGD)
Total Suspended
Solids
ITOQ
Temperature
Discharge Limitations
kg/day (Sbs/dsyJ Other Units (Specify)
Daily Avg Daily Max Daily Avg Daily Mas
N/ft N/* N/flr N/A-
3070(6750) N/A N/A N/A
Discharge Limitations
kg/day (lbs/da"yl Olher Units (Specify)
Daily Avg Daily Max Daily Avg Daily Max
N/A~ N/A- N/A- N/A-
N/A N/A N/A 110° S?.
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg Daily Max Daily Avg Daily Max
N/A N/X N/X N/K"
5310(11700) N/A N/A N/A
21000(46100) N/A N/A N/A
N/A N/A N/A 130° P
and 013
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Dally Avg Daily Max Daily Avg Daily Max
N/A~ N/A~ N/A~ N/A~
N/A N/A N/A 100° F.
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg Daily Max Daily Avg Daily Max •
NM N/A NM N/*
5310(11700) N/A N/A N/A
21000(46100) N/A N/A N/A
N/A N/A N/A 130° F
Monitoring Requlrem tntj
Measurement Sample
Frequency Type
I/week N/A
I/week grab
Monitoring Requirements
Measurement Sample
Frequency Type
I/week N/A
I/week Observation
Monltoria; Requirements
Measurement Sample
Frequency Type
1/weck K/A
I/week grab
I/week grab
I/day Observation
Monitoring Requirements
Measurement Sample
Frequency Type
I/week N/A
I/week Observation
Monitorial; Requirements
Measurement Sample
Frequency Type
I/week N/A
I/week grab
I/week grab
I/day Observation
-2-
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103
Outfall 014
Effluent Chuccteriitic
Flow— ma/Dsy (MCD)
Total Suspended
Solids
Titaniua
Temperature
Outfall 015, 016
Effluent Characteristic
Flow-m3/Day (MGD)
Outfall 017, 020
Effluent Characteristic
Flow-m3/Day (MGD)
Tenperacurc
Effluent limitat
No. 023 is built
Outfall 023
Effluent Characteristic
Flow-nj3/Day (MGD)
Total Suspended
Solids
Total Iron as Fe
Tenperature
Discharge Limitation*
J^/dny
-------
105
Appendix B
NPDES Permit Limitations
-------
A. EFFLUENT LIMITATIQT MONITORING REQUIREMENTS , „„!.«> IT
the effective date the date the interceptor and the single outsell
During the period beginning Of this permit and lasting through No. 023 is built and operable
the permittee is authorized to discharge from outfall(s) serial number(s) 001.
Such discharges shall be limited and monitored by the permittee as specified below:
EIGuent CharactersUc Discharge Limitations
kg/day (lbs/d'«y) Other Units (Specify)
Flow-m3/Day (MGD)
Total Suspended
Solids
Iron
Temperature
Daily Avg
NM
5220(11500)
28650(63100)
N/A
Daily Max
Daily Avg
N/*
Daily Max
Monitoring Requirements
Measurement
Frequency
I/week
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
100° F
I/week
I/week
I/week
Sample
Type
N/A
grab
grab
Observations
The pH shall not be less than 0.5 standard units nor greater than 9.0 standard units and shall be monitored
by one grab sample per hour for 2-'» hours twice per week.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements r :cified above shall be taken at the following location(s):
immediately prior to the Parshall flurae.
r»
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O
O
O
O
O
O
-•J
-------
A. EFFLUENT LIMITATIONS AND MONITORING REQUIREMENTS
on the effective date the date the interceptor and the single outfall
During the period beginning Of this Eernit and lasting through No. 023 is built and operable
the pcrmitlce is authorized to discnarge from outfall(s) sarial number(s) 002, 005 and 007.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluent Characteristic
Flow-m3/Day (MGD)
Temperature
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg
N/A
N/A
Daily Max
N/S
N/A
Daily Avg
N/Z
N/A
Daily Max
N/3T
96° F.
Monitoring Requirements
Measurement
Frequency
I/week
I/week
Sample
Type
N/A
Observations
The pH shall not be less than 6.0 standard units nor greater than 9.0 standard units and shall be monitored
at the discharge point.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following locatdon(s):
at the discharge point.
'2.
O
O
O
O
O
5
37
H
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A. EFFLUENT LIMITATIONS AND MONITORING REQUIREMENTS
on the effective date the date the interceptor and single outfall
During the period beginning of this perait and lasting through No. 023 is built and operable
the permittee is authorized to discharge irw.i outfall(s) serial number (s) 003.
Such discharges shall bo limited and monitored by the permittee as specified below: •
Effluent Characteristic Discharge Limitations
kg/day (Ibs/dayj Other Units (Specify)
Flow-m3/Day (MOD)
Suspended Solids
Daily Avg
N/A
N/A
Daily Max
N/A
Daily Avg
N/A
70 mg/1
Daily Max
N/A
Monitoring Requirements
Measurement
Frequency
I/week
I/week
Sample
Type
N/A
grab
The pH shall not be less than 6.0 standard units nor greater than 12.5 standard units and shall be monitored
by one grab sanple per hour for 24 hours twice per week.
There shaU be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following location(s):
at the discharge point.
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A. ETmSE^mrarATOSS AKD MOTTPKimC REQUIREMENTS
on the elective date the date the interceptor and si'-Vgle wtfall
During the period begirjr:mg Op this perait and lasting through No. 023 is built and operable
the permittee is authorized to discharge from outfall(s) serial number(s) 004.
Such discharges shall be limited and monitored by the permittee as specified below:.
Effluent Characteristic
Flow-in3/Day (MOD)
Total Suspended
Solids
Iron
Discharge Limitations
Monitoring Requirements
kg/day (Ibs/day)
Daily Avg Daily Max
N/H
9710(21400)
635(1400 )
N/S
N/A
N/A
Otner Units
Daily Avg
«/*
N/A
N/A
(Specify)
Daily Max
N/ST
N/A
N/A
Measurement
Frequency
I/week
I/week
I/week
Sample
Type
N/A
grab
grab
The pH shall not be less than
at the discharge point.
standard units nor greater than 9.0 standard units and shall be monitored
There shall be no discharge of floating solids or visible foam in other than tnce amounts.
Samples taken in compliance with the monitoring requires: mis specified above shall be taken at the following location(s):
at the discharge- point.
5
a
o
o
o
o
i»
VJ1
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A. ITFLUENT LIMITATION AND MONITORING REQUIREMENTS
on the effective date the date the interceptor and single outfall
During the period beginning Of t^s pern-.it and listing through No. 023 is built and operable
tho permittee is authorized to discharge from outfall(s) serial number^) one.
permittee is autnonzed to discharge from outfall(s) serial number(s) 006.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluent Ciaractoristic
Flow—m3 /Day (MGD)
Total Suspended
Solids
Discharge Limitations Monitoring Requirements
kg/day (Ibs/day) Other Units (Specify)
Measurement Sample
Daily Avg Daily Max Daily Avg Daily Max Frequency Typj
3070(6750)
N/ff
N/A
N/A
N/A
I/week
I/week
N/A
grab
The pH shall not be less than 6.0 standard units nor greater than 9.5 standard units and shall be monitored
one grab sample per day.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following location(s):
at the discharge point.
o
o _,
o
o
o
o
-------
ro
A. EFFLTJENT LIMITATIONS AND MONITORING REQUIREMENTS
on the effective date the date the interceptor and single outfall
During *r.G period beginning of this pomit and lasting through Ko. 023 is built and operable
the j. :.T i.ttee is authorized to discharge from otftfall(s) serial numbcr(s) 008.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluor.t Characteristic
Flow-n3/Day (MOD)
Temperature
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg Daily Max Daily Avg Daily Max
N/A"
N/A
N/A"
N/A
N/A"
N/A
110° F.
Monitoring Requirements
Measurement
Frequency
1/veek
I/week
Sample
Type
N/A
Observation
The pH shall not be less than 1.0 standard units nor greater than 11.0 standard units and shall be monitored
continuously.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance v/ith the monitoring requirements specified above shall be taken at the following location(s):
at the discharge point.
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o
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A. EFFLUENT LIMITATIONS" AND MONITORING REQUIREMENTS
on the effective date the date the Interceptor and single outfall
During the period beginning 0£ this permit and lasting through No. 023 is built and operable
the permittee is authorized to discharge from outfall(s) serial r.umber(s) 009.
Such discharges sha!! be limited and monitored by the permittee as specified below:
Effluent Characteristic
Discharge Limitations
Monitoring RequLrements
kg/day (Ibs/day)
Daily Avg Daily Max
FIow-ra3/Day (MGD)
Total Suspended
Solids
Iron
Teaperature
NA
5310(11700)
21000(46100)
N/A
N/X
N/A
N/A
N/A
Other Units (Specify)
Daily Avg Daily Mas
N/X
N/A
N/A
N/A
N/T
N/A
N/A
130° F
Measurement
Frequency
I/week
I/week
I/week
I/day
Sample
Type
N/A
grab
grab
Obser
The pH shall not be less than' 0.5 standard units nor greater than 9 • 0 standard units and shall be monitored
continuously.
There shall be no discharge of floating solids or visible fon**1 in other than trace amounts.
Samples teien in compliance with the monitoring requirements specified above shall be taken at the folio wing location (s):
;:: t".:'j cif-c^arge point.
T:
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O
O
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A. EFFLUENT LIMITATIONS'AND MONITORING REQUIREMENTS
the date the interceptor and single outfall
^ on the effective date,
.During the penod beginning of this pex-r.it and lasting through No. Q23 is built and operable
the permittee is authorized to discharge from outfall(s) senal number(s) Q10 Q12 and 013.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluent Characteristic
Flow—m3/Day (MGD)
Temperature
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg
N/A~
N/A
Daily Max
N/A"
IT/A
Daily Avg
N/A~
N/A
Daily Max
N/A~
100° F.
Monitoring Requirements
Measurement
Frequency
I/week
I/week
Sample
Type
N/A
Observation
The pH shall not be less than 2 . 0 standard units nor greater than 9 . 0 standard units and shall be monitored
continuously.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following location^:
at the discharge point.
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A. EFFLUENT LIMITATIONS AND MOiMTORING REQUIREMENTS
on the e~-Active date the date the interceptor and single outfall
During the period beginning of this pt,.-r.i- and lasting through Ho. 023 is built and operable
Ithc permittee is authorized to discnige from outfall(s) serial numbtr(s) Oil.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluent Characteristic
Discharge Limitations
kg/day (Ibs/day)
Daily Avg Daily Max
Flovr— m3 /Day (MOD)
Total Suspended
Solids
Iron
leap era Cure
NM
5310(11700)
21000(46100)
N/A
NM
N/A
N/A
N/A
Other Units (Specify)
Daily Avg Daily Max
NM
N/A
N/A
N/A
NM
N/A
N/A
130° F
Measurement
Frequency
I/week
I/week
I/week
I/day
Sample
Type
N/A
grab
grab
Obser
The pH shall not be less than 1.0 standard units nor greater than 9.0 standard units and shall be monitored
continuously or one 24-hour composite.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with' the monitoring requirements specified above shall be taken at the following location(s):
at the discharge point.
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A. EFFLUENT LIMITATION? AND MONjTOKNG REQUIREMENTS
on the affective date the date the interceptor and single outfall
During the period beginning Of thia permit and Isz'r-xg through No. 023 is built and operable
'the permittee is authorized to discharge from ov.^!f3(fi) serial numbcr(s) 014.
Monitoring Requirements
Such discharges sbdl be limited and monitored by the permittee as specified below:
Effluent Characteristic
Discharge Limitations
kg/day fibs/day)
Daily Avg Daily Max
Flow— m3 /Day (MGD) KM N/A
Total Suspended
Solids
Titanium
Temperature
3900(8500)
870(1920)
N/A
N/A
N/A
N/A
Other Unite (Specify)
Daily Avg Daily Max
N& N/A
N/A
N/A
N/A
H/A
N/A
160°P
•^
Measurement
Frequency
I/ week
I/week
I/week
I/week
Sample
Type
I/week
I/week
I/week
I/week
The pH shdl not be less than 2.0 standard units nor greater than 9.0 etendard units and shell be monitored
One grab sanple per day.
There shall be no duchanjs of floating eolids or visible foam In other then trace amounts.
Samples taien ic compliance Trith the monitoring requirements specified above chcll be taken at the following location (a):
at the discharge point.
7
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X
-------
A. EFFLUENT LIMITATIONS" AND MONITORING REQUIREMENTS
on the effective d? '::: the date the interceptor and the single outfall
During the period beginning of this permit -TriJ lasting through No. 023 is built and operable
the permittee is authorized to discharge from outfall(s) serial number(s) 015, 016, 018 and 019.
Such discharges shall be limited and monitored by the permittee" as specified below:
Effluent Characteristic
Flow—m3 /Day (MOD)
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg
N/A~
Daily Max
N/A—
Daily Avg
N/A-
Daily Max
N/A—
Monitoring Requirements
Measurement
Frequency
I/month
Sample
Type
N/A
The pH shall not be less than 6.0 standard units nor greater than 9-0 standard units and shall be monitored
cnce per month.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following location(s):
at the discharge point.
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00
A. EFFLUENT LIMITATIONS AND MONITORING REQUIREMENTS
on the effective date the date the interceptor and single outfall
During the period beginning of this permit and lasting through No. 023 is built and operable
i'.ie pern!"tee is authorized to discharge from outfall(s) serial number(s) 017, 020, 021 and 022.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluent Characteristic
Flow-m3/Day (MGD)
Tenperature
Discharge Limitations
kg/day (Ibs/day) Other Units (Specify)
Daily Avg
N/A-
N/A
Daily Max Daily Avg
N/A-
N/A
N/A-
N/A
Daily Max
N/A-
210 F.
Monitoring Requirements
Measurement
Frequency
I/week
I/day
Sample
Type
N/A
Grab
The pH shall not be less than 6.0 standard units nor greater than 11.5 standard units and shall be monitored
by one grab sample per day.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples :?xcr. in compliance with the monitoring requirements specified above shall be taken at the following locationfs):
at the discharge point.
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A. EFFLUENT LIMITATIONS AND MONITORING REQUIREMENTS
on the date the interceptor and single outfall No.
Dvring the period beginning and operable r.nd lasting through June ju, i*//
ithe permittee is authorized to discharge from outfall(s) serial number(s) 023.
Such discharges shall be limited and monitored by the permittee as specified below:
023 is built
EfDuent Characteristic
Flo
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ro
A. EFFLUENT LIMITATION AND MONITORING REQUIREMENTS
During the period beginning June 30,1977' and lasting through expiration1 date
the permittee is authorized to discharge from outfall(s) sarial number(s) 023.
Such discharges shall be limited and monitored by the permittee as specified below:
Effluent Characteristic Discharge Limitations
Monitoring Requirements
Flow-m3/Day (MOD)
Total Suspended
Solids
Total Iron as Fe
Titanium as TiOo
kg/day Obs/day)
Daily Avg Daily Max
NM N/£
2590(5700) 3885(8550)
775(1700) 1165(2550)
454(1000) 680(1500)
Other Units (Specify)
Daily Avg Daily Max
"*
N/A
N/A
N/A
,/*
N/A
N/A
N/A
Measurement
Frequency
Continuous and
recorded
I/day
I/day
I/day
Sample
Type
N/A
24 hr
24 hr
24 hr
All limitations expressed above on this page are the difference between the quantity and quality of
the intake water and the quantity and quality of the discharge. The intake water shall be monitored for
each parameter as specified above.
The pH shall not be less than 6 standard units nor greater than 9.0 standard units and shall be monitored
continuously and recorded at the discharge from final manhole.
There shall be no discharge of floating solids or visible foam in other than trace amounts.
Samples taken in compliance with the monitoring requirements specified above shall be taken at the following !ocation(s):
monitoring station built into discharge 023 and sufficient room to allow accessability.
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121
Appendix C
Field Study Methods
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123
FIELD STUDY METHODS
FLOW DETERMINATIONS AND MONITORING LOCATIONS
Intake
The intake flow is measured in the intake line by the differential
across a segmented orifice plate extending from the top of the line to
23.07 cm (9.084 in) below the center line, with pressure taps 137 cm
(54-in) upstream of and 94 cm (37 in) downstream from the orifice plate.
Differential is sensed by a Hays 245 C transmitter of 0-200 inches water
range, and transmitted electrically to a Hays circular chart recorder/
integrator. Meter calibration is not routinely checked, but was last
done by NL personnel on May 15, 1976 with a mercury column attached to
the transmitter input. NEIC samples were collected from a valve
connected directly to one of the booster pumps.
001
The sampling location for outfall 001 was at the concrete flood
control box or wet well, approximately 30 m (100 ft) upsewer of the
discharge into the river. The Company also samples at this point, using
a QCEC automatic sampler. Inspection by NEIC personnel revealed that
the samples are not preserved with ice. Flows were determined by the
Lithium Chloride Tracer Method (see heading following titled "Dye Dilution
Technique for Flow Measurement"). A Company 9-inch Parshall flume has
been installed at a point approximately 30 m (100 ft) upsewer of the
sampling point; however, there was no recording device to measure the
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124
flow. The flume was inspected by NEIC personnel and found to have
obstructions upstream of, in, and downstream from, the throat. A Wesmar
model SLM 9 Ultrasonic Level Monitor was installed at the flume by NEIC
personnel and a level reading was taken each time a sample was collected.
A comparison of the flows from the flume readings with the flows obtained
from the lithium tracer technique indicated that the obstructions rendered
that device inaccurate. Lithium chloride solution was injected at a
mixing box approximately 60 m (200 ft) of the sampling site.
004
The sampling location for outfall 004 was at the concrete box
manhole at the discharge end of a 0.78 m (30 in) inside diameter wooden
pipe, approximately 45 m (150 ft} upstream of the river discharge point.
The Company has a QCEC automatic sampler 2 m (6 ft) upstream of the NEIC
sampling site, but the samples are not preserved by ice. Instantaneous
flows were determined using Rhodamine WT fluorescent dye in the dye-
dilution technique (see heading following titled "Dye Dilution Technique
for Flow Measurement"). The dye v/as injected into the flow stream in
the wooden pipe approximately 75 m (250 ft) upsewer of the sampling
site.
006
The sampling location for outfall 006 was in a concrete box manhole
directly across the street from the intake booster pump house and approxi
mately 60 m (200 ft) upstream of the partially submerged river outfall.
The Company also samples at this point. Instantaneous flows were deter-
mined using the dye dilution method. The dye injection station was
located in a concrete box manhole approximately 12 m (40 ft) upsewer of
the sampling site.
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125
009
The sampling location for outfall 009 was in a concrete manhole/
flood control box or wet well on the river side of the main office
building, approximately 60 m (200 ft) upsewer of the river discharge
point. The Company also samples at this location. Instantaneous flows
were determined by the Lithium Chloride Tracer Method. Since outfall
009 sometimes overflows into outfall Oil at an upstream point, the
injection station for the concentrated lithium solution was located
downstream from the junction of the two sewers. This injection point
was approximately 60 m (200 ft) upstream of the sampling point, at the
opposite end of the building.
on
The sampling location for outfall Oil was in a concrete manhole/
flood control box or wet well on the river side of the railroad tracks,
about 30 m (100 ft) upstream of the river discharge point. The Company
also samples at this location. Instantaneous flows were determined by
the Lithium Chloride tracer method. The concentrated lithium solution
was injected into a concrete box manhole, downstream of the junction
with 009 sewer and about 200 m (650 ft) upstream of the sampling site.
014
The sampling location for outfall 014 was in a concrete manhole/
flood control box on the plant side of the railroad tracks, approximately
45 m (150 ft) upstream of the river discharge point. The Company also
has a QCEC automatic sampler at this location; the samples are not
preserved with ice. Instantaneous flows were determined using the
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126
dye-dilution technique (June 1-4) and the lithium chloride tracer method
(June 5-July 1). When low pH values were found in the waste stream, the
dye method was replaced by the lithium method to insure no tracer loss.
Both the dye and lithium injection stations were located at a manhole
near the southwest corner of the calcination building, about 90 m (300
ft) upstream of the sampling point.
002, 003. 005, 007, 008, 010, 012. 013, 015-022
Outfalls 005, 007, 015, 017, 020 and 022 were dry during the 30-day
monitoring period. Outfalls 002, 003, 008, 010, 012, 016, 018, 019 and
021 were sampled on a grab basis only and no flow measurements were made
at these locations. The sampling locations for these outfalls are as
follows:
002 - outfall from the concrete cooling basin
003 - manhole or flood control box, about 30 m (100 ft)
upsewer from the river outfall
008 - in between the railroad tracks in the effluent
channel next to the coal pile for the power house
010 - at the flood control box, about 30 m (100 ft)
upsewer of the river outfall
012 - in the manhole next to a maintenance building, about
120 m (400 ft) upsewer of the river outfall
016 - at NPDES site
018 - at NPDES site, inside the booster pump house
019 - at the NPDES site
021 - at the NPDES site
The sampling location for outfall 013 was a concrete manhole/flood
control box on the plant side of the railroad tracks about 60 m (200 ft)
north of the sampling site for 014. Flows were measured at this outfall
for a period of 7 days (June 9-16) by the dye-dilution technique. The
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127
injection station was located at a manhole in the parking lot about 75 m
(250 ft) upstream from (west of) the sampling point.
FLOW MEASUREMENT USING LITHIUM CHLORIDE
Flow determinations at four outfalls (001, 009, Oil, 014) were made
using the lithium chloride tracer method. In this technique a solution
of lithium chloride of known concentration is injected at a constant
flow rate an adequate distance upstream of the sampling point, to insure
mixing. Downstream samples are collected to determine the lithium
concentration in the waste stream. The flow is then calculated from the
known injection rate, the injected lithium concentration 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.
Calibration of the instrument was accomplished daily using lithium
standards of known concentration. Frequent checks were made during the
day to insure accuracy.
A preliminary study of the four outfalls whose flows were measured
by lithium chloride tracer was conducted prior to the start of the
survey. In this study, samples from these four outfalls were "spiked"
with a known amount of lithium and analyzed. The results showed 100%
recovery of lithium. Also, the samples were analyzed for background
levels of lithium to determine the concentration 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
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128
included in the collection time at each station to insure that sampling
occurred after the concentration plateau had been reached. Background
samples were taken with each flow sample prior to injection of the
lithium and the concentration of lithium 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 for complete
mixing of the injected lithium solution at each sampling point, and 3) a
check to determine the length of time required for the lithium concentration
to reach background concentrations after the injection pumps were shut
off.
DYE DILUTION TECHNIQUE FOR FLOW MEASUREMENT
Flow determinations were made at four outfalls (004, 006, 013, 014)
using the dye dilution technique with fluorometric detection. In this
procedure, 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 gravimetrically
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 concentration 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 6. K.
Turner Model III fluorometer, with a far UV lamp, a high sensitivity
kit, a standard door and a matched set of cuvettes. The fluorometer is
-------
129
calibrated once per 12 hour shift by measuring the fluorescence of
gravimetrically prepared standards of known concentrations.
A preliminary study of the four outfalls was conducted during the
initial set-up period of the survey. Samples were taken from each of
the outfalls 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
neutralized to pH 7 (with a powdered buffer to insure no concentration
change) to recover the fluorescence, and then placed in the fluorometer.
Other quality control measures included: 1) measurement of dye
injection rate at each station at least 2 times per shift; 2) a mixing
check at each sampling site to insure a complete mix; 3) use of poly-
ethylene gloves when handling concentrated dye to reduce the possibility
of contamination; 4) frequent fluorometer reference to zero using a
dummy cuvette; and 5) triple-rinsing of cuvettes with distilled water
before each use.
SAMPLE COLLECTION PROCEDURE
Twenty-four-hour Composite Samples
Beginning at 7 a.m. on June 1, individual grab samples were collected
every 2 hours from outfalls 001, 004, 006, 009, Oil, 014 and the intake.
The intake samples were composited continuously on a flow-weighted basis
and stored at 4°C. The samples from the outfalls whose flows were
measured by dye dilution [004, 006 and 014 (June 1-4)] were stored at
4°C and composited in the field on a flow-weighted basis at the end of
each 24-hour period. The samples from outfalls whose flows were measured
-------
130
by the lithium tracer technique [001, 009, Oil and 014 (June 5-July 1)]
were stored at 4°C and shipped to Denver at the end of each 24-hour
period. There they were analyzed for lithium concentrations and com-
posited on a flow-weighted basis.
Because it had greatly exceeded the permit limitations, outfall 006
was sampled on a composite basis only until 7 a.m. June 17, after which
samples and flow measurements were taken weekly on a grab basis. The
five other major outfalls and the intake were monitored on a composite
basis until 7 a.m. July 1. Outfall 013, which the Company claimed to
consist only of river water, was monitored on a composite basis for 7
days (June 9-16) when June 1-8 grab sample data indicated characteristics
other than river water.
Grab Samples
Grab samples for TSS and metals were collected at least once per
day at outfalls 001, 004, 009, Oil, 013, 014 and the intake, preserved
and/or stored at 4°C, and shipped to Denver. Daily grab samples for TSS
were collected at outfall 006 until June 17 after which weekly grabs
were taken. Daily grabs for TSS were also taken at outfall 003. Samples
were collected daily and analyzed only for pH and temperature at the
following outfalls: 002, 008,* 010, 012, 016, 018, 019 and 020.
Outfalls 012 and 019 discharged intermittently.
Outfall 008 was continuously monitored for pH.
-------
131
Appendix D
Chain of Custody Procedures
-------
ENVIRONMENTAL PROTECTION AGENCY
Office Of Enforcement
NATIONAL ENFORCEMENT fNVESTIGATIONS CENTER
Building 53, Box 25227. Denver Federal Center
Oonvor, Colorodo 80223
July 24, 1974
CHAIN OF CUSTODY PROCEDURES
€eneral:
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 quan-
tity of samples and sample locations 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
1s 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, date 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).
-------
134
Chain of Custody Procedures (Continued)
Sample Collection (Continued)
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 main-
tained to record field measurements and other pertinent infor-
mation necessary to refresh the sampler's memory in the event
he later takes the stand to testify regarding his action's
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, DO, pH,
flow and any other pertinent information or observations. The
entries shall be signed by the field sampler. The preparation
and conservation 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 lab-
oratory 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 sub-
stantiate any conclusions of the investigation. Written documenta-
tion 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 also 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 analyses required (Fig. IV),
When turning over the possession of samples, the transferor and
transferee will sign, date and time the sheet. This record sheet
-------
135
Chain of Custody Procedures (Continued)
allows transfer of custody of a group of samples in the field,
to the mobile laboratory or when samples are dispatched to the
NFIC - Denver laboratory. 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 pack-
aging 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
1ce 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 identification of the contents. The original will accom-
pany the shipment, and a copy will be retained by the survey
coordinator.
5. If sent by mail, register the package with return receipt request-
ed. 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 permanent Chain of Custody documentation.
6. If samples are delivered to the laboratory when appropriate person-
nel 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 person must then return to the
laboratory and unlock the samples and deliver custody to the
appropriate custodian.
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 indicate receipt by signing the Chain of Custody Record Sheet
-------
136
Chain of Custody Procedures (Continued)
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
Y/hen samples are removed or replaced by the custodian. To the
maximum extent possible, only the custodian should be permitted
1n the sample room.
5. The custodian shall ensure that heat-sensitive or light-sensitive
samples, or other sample materials having unusual physical
characteristics, or requiring 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 abnormalities which occurred during the testing
procedure. In the event that the person who performed the tests
1s 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 during 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 theiir 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 together 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.
-------
137
Chain of Custody Procedures (Continued)
11. Samples, tags and laboratory records of tests may be destroyed
only upon the order of the laboratory director, v/ho will first
confer with the Chief, Enforcement Specialist Office, to make
certain that the information is no longer required or the samples
have deteriorated.
-------
138
EXHIBIT I
EPA, NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
Station No.
Dalo
Time
Sequence No.
Station Location
_BOD
.Solids
_COD
.Nutrients
.Metals
.Oil and Groaso
.D.O.
.Bad.
-Other.
Samplers:
.Grab
_Comp.
Romarks/Prosorvalivo:
Front
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF ENFORCEMENT
NATIONAL ENFORCEMENT INVESTIGATIONS CENTER
BUILDING 53, DOX 25227, DENVER FEDERAL CENTER
DENVER, COLORADO 80225
Back
-------
EXHIBIT II
rOR
SURVEY, PHASE.
DATE
FYPE OF SAMPLE.
ANALYSES REQUIRED
STATION
NUMBER
i
STATION DESCRIPTION
TOTAL VOLUME |
TYPE CONTAINER
PRESERVATIVE
NUTRIENTS I
O
O
CO
O
8
u
0
to
O
O
01
<
0
SUSPENDED SOLIDS |
ALKALINITY |
O
o
i
i
a
[ CONDUCTIVITY* |
1 TEMPERATURE' |
| TOTAL COLIFORM |
| FECAl COLIFORM |
| TUFBIDITY |
UJ
in
<
UJ
CXL
O
0
z
<
6
| S1V13VY I
u
CO
•
| PESTICIDES |
c:
a:
aj
X
•
| TKACE ORGANICS 1
0
Z
HI
REMARKS
co
-------
EXHIBIT III
Sampler*:,
FIELD DATA RECORD
STATION
NUMBER
DATE
TIME
TEMPERATURE
«C
CONDUCTIVITY
ft mhos/cm
PH
S.U.
D.O.
mg/l
Gcge Hi.
or Flow
Fl. or CFS
-------
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
141
SURVEY
STATION
NUMBER
STATION LOCATION
DATE
Relinquished by: (Signoiuie)
Relinquished by: (s.gnoiure;
Relinquished by: (s.gnoturej
Relinquished by: (Sgnorurej
Dispatched by: (Signaiun)
Method of Shipment:
Date,
TIME
SAMPLERS: |s,gno»Ure)
SAMPLE TYPE
Wolcr
Comp
Grab
Air
SEQ
NO.
NO OF
CONTAINERS
ANALYSIS
REQUIRED
Received by: (Signature)
Received by: /s.gnoiurej
Received by: (Sgaaiute)
Received by Mobile Laboialory for field
analysis: is,3,,oiuie}
(lime
Received for Laboratory by:
Dale/Time
Date/Time
Date/Time
Dale/Time
Dale/Time
Distribution: Oiig.—Accompany Shipment
1 Copy—Survey Coordinator Fiold File*
OPO
-------
Appendix E
Analytical Procedures and Quality Control
-------
145
Analytical Procedures and Quality Control
Samples collected during this survey were analyzed, where appro-
priate, according to procedures approved by EPA* for the monitoring
of industrial effluents as shown in the following table.
Parameter Method Reference
Li, Fe, V, Ti Atomic Absorption EPA Methods for Chemi-
cal Analyses of Water
and Wastewater 1971,
pg. 83
TSS Gravimetric ibid., page 278
The procedure for preparing samples for titanium analysis was
modified in order to solubilize the TiOg. An appropriate sample
aliquot with 3 ml concentrated sulfuric acid was evaporated on a
hot plate until $03 fumes appeared. The sample was then fused with
10 grams potassium pyrosulfate and dissolved in 80 ml of 10% (by
volume) sulfuric acid. An excess of potassium fluoride was added to
complex the dissolved titanium and the sample brought to 100 ml with
more 10% sulfuric acid.
The solubility of iron and vanadium did not depend upon the
presence of hydrochloric acid in the sample; therefore the step re-
quiring the addition of HC1 to the samples was omitted. This was not
a substantive deviation from the approved method, and was done to
protect the analytical instrument from the corrosive effects of a
mixture of nitric and hydrochloric acids.
The Perkin-Elmer model 403 atomic absorption spectrophotometer
was calibrated daily using standard lithium solutions. Frequent
*Federal Register, Vol. 40, No. Ill, June 9, 1975
-------
146
checks of the standards were performed during each run. A Perkin-
Elmer model 306 AAS was used in the analysis for iron, vanadium and
titanium. Similar quality control checks were performed for the
elements.
Reliability of the analytical results was documented through an
active Analytical Quality Control Program. As part of this program,
replicate analyses were normally performed with every tenth sample to
ascertain the reproducibility of the results. In addition, where
appropriate, every tenth sample was spiked with a known amount of the
constituents to be measured and reanalyzed to determine the percent
recovery. These results were evaluated in regard to past AQC data on
the precision, accuracy, and detection limits of each test. On the
basis of these findings, all analytical results reported for the sur-
vey were found to be acceptable with respect to the precision and
accuracy control of this laboratory.
-------
147
Appendix F
Daily Monitoring Data
-------
Table F-l
sinmm OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS (24-HR COMPOSITE SAMPLES)
OUTFALL 001
NL INDUSTRIES, ST. LOUIS, MO.
June—July 1976
Date*
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Flow
m /day
x 103
6.85
8.28
7.57
6.92
3.97
8.02
7.91
8.59
6.54
8.28
7.87
6.47
9.15
9.19
9.38
7.91
8.81
8.66
9.27
8.59
8.74
9.12
9.31
8.02
6.85
7.57
7.83
8.21
8.25
8.09
mgd
1.81
2.19
2.00
1.83
1.05
2.12
2.09
2.27
1.73
2.19
2.08
1.71
2.42
2.43
2.48
2.09
2.33
2.29
2.45
2.27
2.31
2.41
2.46
2.12
1.81
2.00
2.07
2.17
2.18
2.14
pH Range
S.U.
0.4-1.7
0.5-1.7
0.7-1.8
0.5-1.8
0.7-1.5
0.8-2.5
1.4-2.4
1.0-3.6
1.0-1.6
0.9-1.6
1.2-1.6
0.9-1.3
0.8-1.5
1.1-1.7
1.3-1.8
1.1-2.4
0.6-1.6
1.2-1.8
1.0-1.6
0.8-2.5
0.7-1.6
0.7-1.6
0.9-1.7
1.0-2.0
0.7-1.5
0.2-1.8
0.9-1.7
0.9-1.7
0.9-1.7
0.8-1.4
Temp.
Range
°C
32-39.5
31-38
30-35
34-37
25-38
26-36
33-36
30-38
32-38
32-41
33.5-36
26-41
32-42.5
37-41
35-40
32-38
33-38
34-37.5
32.5-36
31-39
28-40
34-40
34-40
33-41
36-40
32-40
35.5-42
36.5-40
35-41
33-42
Total
mg/1
440
590
600
430
1,400
320
440
590
390
300
230
400
950
890
320
270
770
710
710
520
420
900
920
530
1,600
960
450
840
650
830
Suspended Solids
kg/day
3,010
4,890
4,540
2,980
5,560
2,560
3,480
5,060
2,550
2,480
1,810
2,580
8,700
8,180
3,000
2,130
6,780
6,150
6,580
4,460
3,670
8,200
8,560
4,250
10,960
7,260
3,520
6,890
5,360
6,720
Ib/day
6,640
10,780
10,010
6,560
12,260
5,660
7,670
11,170
5,630
5,480
3,990
5,700
19,180
18,040
6,620
4,700
14,970
13,560
14,510
9,850
8,090
18,100
18,830
9,370
24,160
16,020
7,770
15,210
11,820
14,820
mg/1
3,650
3,700
1,980
3,480
4,850
2,600
4,900
5,980
4,320
1,700
3,340
4,950
2,480
3,120
2,340
2,450
1,060
640
1,220
1,420
1,660
1,950
1,900
1,500
1,320
1,970
2,040
1,850
2,070
1,750
Iron
kg/day
25,000
30,660
14,980
24,100
19,270
20,860
38,750
51 ,370
28,280
14,080
26,290
32,030
22,710
28,690
21 ,960
19,370
9,340
5,540
11,310
13,200
14,510
17,780
17,680
12,030
9,040
14,910
15,930
15,190
17,070
14,170
Titanium
Ib/day
55,130
67,610
33,040
53,140
42,490
45,990
85,450
113,280
62,360
31 ,060
57,970
70,630
50,080
63,260
48,420
42,730
20,610
12,230
24,940
26,900
32,000
39,210
39,000
26,530
19,930
32,870
35,230
33,500
37,650
31,250
mg/1
.840
840
920
630
1,240
760
1,140
840
1,020
1,040
1,140
1,120
650
1,430
780
680
500'
900
660
700
520
520
490
300
700
520
400
490
700
380
kg/day
5,750
6,960
6,960
4,360
4,920
6,090
9,010
7,210
6,670
8,610
8,970
7,240
5,950
13,150
7,320
5,370
4,400
7,800
6,110
6,010
4,540
4,740
4,560
2,400
4,790
3,930
3,130
4,020
5,770
3,070
Ib/day
12,680
15,350
15,350
9,620
10,860
13,440
19,880
15,910
14,720
19,000
19,780
15,980
13,120
28,990
16,140
11 ,850
9,720
17,200
13,490
13,260
10,020
10,450
10,050
5,300
10,570
8,670
6,900
8,870
12,730
6,780
t Samples uere collected from ? a.m. to 7 a.m. to correspond with the plant production day.
the time period 7 a.m. to midnight June 1 and midnight to 7 a.m. June 2.
The date June 1-2 indicates
vo
-------
Table F-2
SUMMARY Of FIELD MEASUREMENTS AtlD AtlALTTICAl RESULTS (CRAB SAMPLES)
OUTFALL 001
KL IHDUSTKIES, ST. LOUIS, MO.
June 7976
Date Time of
Collection
June 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
17
18
19
20
21
21
22
22
23
23
24
24
24
25
25
25
26
26
27
27
27
28
28
28
29
29
30
1510
1115
1120
1100
0125
1105
1105
2335
1712
2108
1110
1926
1110
2117
1005
2118
0722
1315
1710
1713
1715
0400
1310
131*5
0519
1314
0720
1114
1315
0915
1313
1512
0909
1931
0135
0910
1312
0716
1112
1310
1114
1513
0909
Instantaneous
Flow
m3/day
x TO3
7.91
6.69
7.34
7.91
5.14
6.24
8.70
11.01
6.35
7.26
8.32
6.20
10.59
7.98
7.45
7.68
10.14
9.91
9.31
7.75
9.04
8.65
9.50
6.24
8.09
8.55
8.06
11.99
7.94
9.42
6.66
7.00
5.45
6.51
9.46
6.35
7.26
6.96
10.71
7.79
8.13
7.68
7.98
10.06
mgd
2.09
1.77
1.94
2.09
1.36
1.65
2.30
2.91
1.68
1.92
2.20
1.64
2.80
2.11
1.97
2.03
2.68
2.62
2.46
2.05
2.39
2.29
2.51
1.65
2.14
2.26
2.13
3.17
2.10
2.49
1.76
1.85
1.44
1.72
2.50
1.68
1.92
1.84
2.83
2.06
2.15
2.03
2.11
2.66
pH
S.U.
0.8
1.4
1.0
1.5
0.9
2.5
2.0
1.0
1.4
1.6
1.5
1.2
1.2
1.1
1.8
1.3
0.6
1.0
1.2
1.4
1.3
1.7
1.6
1.2
0.9
1.0
.4
.0
.9
.5
.5
0.7
.5
.8
.2
0.8
1.7
1.0
1.7
1.2
1.1
0.9
1.1
1.5
Temperature
°C
37
32
31
35
34
30
36
32
37.
41
33.5
38
40*
38
40+
36
33
37
35
36
35
38
35
391
40+
38
36
35.
40!
40
37.
40*
37
37
35,
39. 5+
39'
37+
39;
40
401
41 '
39'
Total Suspended Sol Ids
mg/1 kg/day Ib/day
700
230
660
310
500
140
210
750
180
210
70
500
90
630
570
90
160
4,200
980
300
530
600
1,700
440
3,700
2,600
1,700
220
2.100
300
410
4,900
6,600
470
850
4,800
510
470
720
840
1.300
3,400
900
420
5,530
1,5*0
4,840
2,450
2,570
370
1,820
8,250
1,140
1,520
530
3. ICO
950
5,030
4,240
690
1,620
41,640
9,120
2,320
4,790
5,200
16.140
2,740
29,950
22,220
13,700
2,630
16,690
12,260
3,130
34.300
35.960
3.050
8,040
30,510
3.700
3.270
7.110
6.540
10.570
26.120
7,180
4,220
12,200
3,390
10,680
5.400
5,670
1.920
4,030
18,210
2,520
3,360
1.280
6.840
2,100
11.090
9.350
1.520
3,570
91,820
20,110
5,130
10,570
11,460
35,600
6,050
66,030
49,000
30,210
5,810
36,800
27,010
6,900
75.640
79.310
6.740
17,730
67.290
8,170
7.210
17,000
14.440
23.320
57,590
15,840
9,320
mg/1
4,290
3,380
1,970
3,960
2,400
2,700
4,980
2,890
4,700
4,100
9,500
2.750
2.500
2,200
2,830
2.310
1,460
1.720
500
1,060
2,120
920
2,170
2,270
2,200
2,500
1,400
1.430
2,400
4,100
650
1,650
960
1,230
1,640
3,200
1,070
1,660
1.100
2,230
2,650
3,600
2,150
1,020
Iron
kg/day
33.930
22,640
14.460
31 ,320
12,350
16,660
43.340
31 ,820
29,880
29,790
79,090
17,060
25,490
17.560
21.100
17,740
14,800
17,050
4,650
8,220
19,170
7.970
20.610
14,170
17,810
21,370
11,280
17,150
19,070
33,630
4,320
11,550
5,230
8.000
15.510
20.340
7.770
11,550
11,780
17,380
21 ,560
27.650
17,160
7,040
Ib/day
74,820
49,920
31 .890
69,060
27,230
37.170
95,580
70. ISO
65,390
65,690
174,400
37.630
53,00
38.730
45.520
39,130
32,650
37.600
10,260
18,130
42,280
17,580
45,450
31,250
39,260
47,120
24,830
37,830
42,050
85,190
9,540
25,470
11,530
17,650
34.210
44,860
17,140
25.480
25,970
38.330
47,5*0
60.930
37,830
15.540
t Exceeds the IfPDES per-nt limitation of 37.3"C (100"P)
-------
151
Table F-3
TEMPERATURE AND pH ANALYSES
OUTFALL 002
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Time
1310
1025
0855
0745
0920
0950
0726
1340
0912
0955
0745
0920
0933
1540
0735
0750
1330
0740
0950
1125
1115
0730
1325
1350
1333
1535
1335
0804
0947
1354
pH Temp
S.U. °C
7.0 28
7.4 25
7.5 25
7.4 30
6.9 31
7.3 26.5
6.5 26.5
7.1 30
7.1 29
6.8 32
7.2 30
7.2 30
6.5 31.5
6.7 31
6.5 30
6.5 31.5
6.7 30.5
7.4 32
6.0 34
6.9 31
6.6 33
6.3 31
6.4 32.5
6.1 31.5
4.6 31
5.8 32
6.5 32
6.3 31.5
6.3 32.5
6.3 31
-------
152
Table F-4
TEMPERATURE, pff, AND TOTAL SUSPENDED SOLIDS ANALYSES
OUTFALL 003
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Time
NSf
1030
0740
0740
0730
0730
0750
0800
0745
0745
0750
0740
0740
0740
0755
0740
0750
0815
0735
0730
0740
0710
0745
0910
0800
0747
0745
0815
0725
0745
PH
S.U.
5.3
6.3
7.0
6.6
6.6
8.1
8.5
6.4
6.8
7.3
7.0
6.6
6.4
6.5
6.2
6.7
7.0
8.9
6.6
6.4
5.6
6.4
NRft
6.9
6.0
6.4
6.3
6.5
5.7
Temp.
°C
23
23
26
23
25
25
25
25
26
27
27
27
28
28.5
27.5
27
28.5
27.5
27.5
28
27
27
25
27
27
26
28
28
28
TSS
mg/1
14
200
310
130
480
660
240
440
970
600
680
500
80
260
130
130
180
620
430
520
860
470
390
670
120
170
320
310
290
t NS = Not Sampled
tt NR = Hot Recorded in field book
-------
Table F-5
SWUARJ OF FIELD HEASVREHEOTS AKD ANALYTICAL RESULTS (24-HB COMPOSITE SAMPLES)
OUTFALL 004
IIL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Date1"
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-K
14-15
15-15
16-17
17-18
16-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Flow
n3/day
x 103
65.10
61.31
52.23
58.32
67.97
77.89
55.71
65.66
62.71
51.02
52.80
39.51
58 74
52.68
53.36
56.32
37.32
27 66
34.05
37.43
43 37
51.18
42.77
43.85
42.35
37.81
42.99
47.61
36.67
41.04
mgd
17.20
16.20
13.80
15.41
17.95
20.58
14.72
17.35
16.57
13.48
13.95
10.44
15.52
13.92
15.42
14.88
9.86
7.31
9.00
9.89
11.46
13.54
11.30
11.59
11.19
9.99
11.36
12.58
9.69
10.84
pH Range
S.U.
6.4-10.2
3.6-8.5
5.5-7.0
3.1-7.2
3.4-7.0
6.1-6.8
3.4-6.8
5.4-6.8
4.0-6.9
2 5-6.8
2.9-7.2
2.8-6.9
1.7-7.0
6.0-7.4
4.0-6.8
6.3-7.1
3.4-7.9
2.1-7.0
1.3-7.2
1.8-7.2
2.9-6.9
3.8-6.8
2.4-6-8
2.4-6.3
1.7-7.1
1.5-6.2
2.6-6.4
2.3-6.1
2.7-6.4
3.9-6.2
Temp.
Range
°C
24-27.5
23-28
22-29
25-32
24-32
24-28
24-29
25-28
25-29
22-37
27-35
29-30
28.5-32
28-31
26.5-29.5
27-31
25-32
25-30
25-32
26-32
27-33
25-30
24-28
25-30
25-29
24 5-30.5
25-32
28-33
26.5-30
26-29
Total
mg/1
700
700
610
580
520
610
480
280
310
320
210
140
120
120
170
140
150
290
390
530
800
1.100
1,100
730
810
490
560
400
270
340
Suspended Solids
(Gross)
kg/day
45,560
42,910
31,850
33,820
35,340
47,510
26.740
18,380
19,440
16,320
11,080
5,530
7,040
6,320
9,520
7,880
5.590
8,020
13,280
19,830
34,690
56,420
47,0
-------
en
Table F-6
SUMMARY OF FIELD MEASUREMENTS AND A11ALYTICAL RESULTS (CRAB SAMPLES)
OUTFALL 004
BL INDUSTRIES, ST. LOUIS, MO.
June 1976
Instantaneous
Date Time of
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
22
23
24
25
26
27
28
29
30
t
tt
Collection
1530
1130
1150
1130
1130
0920
1110
2322
1730
2115
1330
1932
1125
2130
0735
2130
mo
2315
0730
1710
0330
0325
1310
1725
1338
1525
2315
1525
0924
1525
0920
Exceeds NPDSS
U.S. = sample
Flow
m /day
x 103
79.10
62.83
56.00
58.74
57.15
70.28
30.65
74.98
65.44
45.72
44.01
32.85
61.05
61.16
68.16
60.55
44.62
18.54
33.98
38.15
54.39
49.62
53.51
53.67
54.08
44.51
30.99
45.26
45.98
33.85
39.32
mgd
20.90
16.60
14.90
15.52
15.10
18.57
8.10
19.81
17.29
12.08
11.63
8.68
16.13
16.16
18.01
16.00
11.79
4.90
8.98
10.08
14.37
13.11
14.14
14.18
14.29
11.76
8.19
11.96
12.15
8.94
10.39
pH Temperature Total Suspended Solids
S.U.
6.5
7.0
6.2
6.9
6.9
6.3
6.6.
5.4*
6.2
6.2
4.0*
6.9
6.9
6.7.
5.8*
6.8
7.5.
2.2*
7.1
7.2.
2.6*
6.7
6.5.
2.5*
2.4*
3.1*
6.2
6.4.
2.7*
6.4,
5.2*
°C
24
27
26
25
25
28
27
25
29
28
30
30
30
29.5
27.5
29.5
30
25
25
28
32
28
27
27
30
26
26
32
30
28
29
mg/1
720
670
700
450
420
560
570
240
300
280
280
140
100
110
200
120
130
300
100
400
670
1,100
1,100
990
730
510
460
480
450
260
320
kg/day
56,950
42,090
39,470
26,430
24,000
39,350
17,470
17,990
19,630
12,800
12,320
4,600
6,100
6,720
13,640
7,260
5,800
5,560
3,390
15,250
36,430
54,570
58,870
53,120
39,470
22,690
14,250
21,720
20,690
8,800
13,360
Ib/day
125,570
92,810
87,030
58,280
52,920
86,780
38,520
39,670
43,280
28,220
27,170
10,140
13,460
14,830
30,050
16,020
12,790
12,260
7,490
33,640
80,340
120,340
129,800
117,150
87,050
50,040
31,430
47,900
45,620
19,400
29,470
mg/1
54.4
28.7
20.5
26.2
190.0
38.0
40.0
44.0
61.0
26.0
12.0
5.6
9.6
8.6..
N.st*
8.4
5.0
23.0
3.0
19.0
22.0
29.0
35.0
49.0
23.0
19.0
17.0
19.0
13.0
9.0
12.0
Iron
kg/day
4,300
1,800
1,150
1,530
10,850
2,670
1,220
3,290
3,990
1,180
520
180
580
520
500
220
420
100
720
1,190
1,430
1,870
2,620
1,240
840
520
860
590
300
470
Ib/day
9,480
3,970
2,540
3,390
23,940
5,880
2,700
7,270
8,800
2,620
1,160
400
1,290
1,150
1,120
490
940
220
1,590
2,630
3,170
4,120
5,790
2,740
1,860
1,160
1,890
1,310
670
1,040
permit limitation
not sent
to UEIC lab
-------
155
Table F-?
SUMMARY OF FIELD MEASUREMENTS AND TOTAL SUSPENDED SOLIDS (24-HR COMPOSITE SAHPLES)
OUTFALL 006
NL INDUSTRIES, ST. LOUIS, MO.
June 1-17, 1976
Date*
Flow
m /day mgd
1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
x 103
10.59
13.62
12.86
11.39
11.27
10.59
10.21
10.44
10.74
6.85
7.53
8.66
7.98
9.80
9.08
12.71
2.80
3.60
3.40
3.01
2.98
2.80
2.70
2.76
2.84
1.81
1.99
2.29
2.11
2.59
2.40
3.36
pH Range
S.U.
6.8-10.0
10.1-8.9
8.9-9.7
6.1-10.2
6.6-9.7
6.7-10.9
6.8-10.2
7.2-10.9
8.3-10.4
7.5-9.6
7.6-9.6
6.8-8.1
6.6-7.7
6.6-8.5
6.7-8.1
6.4-9.5
t Samples were collected from 7 a.m.
dati
2 June
1-2 indicates the time p
Temp.
Range
°C
20-26
21-25
23.5-26
25-28
24.5-27
24-26
24-26
25-27
26-32
26-29
27-29
28-32
28-30
25-30
28-30
27-29
to 7 a.
>eriod 7
Total
mg/1
1,800
3,300
3,000
1,900
2,700
3,300
2,500
960
2,000
2,000
1,900
1,260
1,340
1,550
1,600
1,500
Suspended
(Gross)
kg/day
19,070
44,960
38,600
21,640
30,450
34,960
25,540
10,020
21,490
13,700
14,300
10,920
10,700
15,190
14,530
19,070
Solids
Ib/day
42
99
85
47
67
77
56
22
47
30
31
24
23
33
32
42
,050
,130
,110
,720
,140
,iqo
,320
,110
,400
,200
,550
,070
,590
,500
,040
,050
m to correspond with the plant
a.m. to n
ridnight June
1 and mu
Total
mg/1
1,370
2,930
2,720
1,620
2,440
2,910
2,110
700
1,790
1,810
1,720
1,090
1,260
1,380
1,508
1,450
Suspended
(Net)
kg/day
14,510
39,910
35,000
18,450
27,510
30,830
21,560
7,310
19,230
12,390
12,950
9,440
10,060
13,520
13,700
18,430
production day.
Jnight
to 7 a.m.
Solids
Ib/day
32,010
88,020
77,170
40,690
60,670
67,990
47,540
16,120
42,420
27,330
28,560
20,820
22,180
29.820
30,180
40,650
The
June 2.
-------
156
Table F-8
SUMMARY OF FIELD MEASUREMENTS AND TOTAL SUSPENDED SOLIDS
(CRAB SM1PLES)
OUTFALL 006
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
23
28
Time of
Collect.
1545
1150
1200
1100
0200
0940
1120
2307
1745
2130
1545
1943
1550
2140
1740
2145
1415
1450
Instantaneous
Flow
m /day
x 103
12.49
22.71
10.97
10.97
14.26
10.37
15.06
11.20
9.31
8.89
7.06
8.74
7.72
11.96
5.45
13.96
9.15
19.83
mgd
3.30
6.00
2.90
2.90
3.77
2.74
3.98
2.96
2.46
2.35
1.86
2.31
2.04
3.16
1.44
3.69
2.42
5.24
pH
S.U.
8.8
9.5
9.0
8.8
7.8
8.6.
10. OT
9. a*
8.3
9.3.
9.6*
7.6
7.1
7.2
7.1
7.7
6.2
9.2
Temp.
°C
25
23
24
25
26.5
24
£4
26
29
27.5
29
30
30
30
30
29
27
27.5
Total
mg/1
3,200
3,800
2,600
3,100
2,200
5,000
3,400
4,100
2,200
1,200
2,000
1,200
1,510
700
1,000
1,400
2,400
2,300
Suspended Solids
kg/day
39,960
86,280
28,530
34,020
31,380
51,840
51,210
45,920
20,480
10,670
14,130
10,490
11,650
8,370
5,450
19,550
21,980
45,610
Ib/day
88,120
190,200
62,920
75,020
69,210
114,300
112,900
101,200
45,160
23,530
31,160
23,130
25,700
18,450
12,010
43,110
48,460
100,500
t Exceeds NPDES permit limitations
-------
157
Table F-9
INSTANTANEOUS pH AND TEMPERATURE MEASUREMENTS
OUTFALL 008
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date Time pH Temp.
S.U. °C
1
2
3
4
5
6
7
8
9
10
n+*
12tt
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
1245
1010
0815
1000
1005
1000
1010
1420
1440
1430
1045
_
1000
1600
1805
1400
1350
1350
1145
1145
1135
0746
1745
1418
1355
1604
1405
1545
1557
1408
7.5 32
7.8. 24
0.21 35
11. 6T 27
2.2. 28
ll.r 25
10.9 25
2.3. 27
11. r 30
8.9 28
9.9 28
_ _
7.2 29
8.2 29
7.1 29
8.2 31
7.9. 30
11. 51" 32
1.6. 30
11. 5T 28
2.2 28
1.2 28
10.3 30
10.2. 27
12.6T30.5
2.5 30
10.6 29.5
2.0 28
1.6. 31
12. 61" 42
t Exceeds NPDES permit
limitations
tt Measurements not made.
-------
Table F-I0
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS (24-HP COMPOSITE SAMPLES)
OUTFALL 009
NL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Date1"
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Flow
m /day
x 103
7.57
7.34
7.04
6.24
7.19
8.13
7.64
6.51
7.38
6.92
6.51
7.30
6.96
6.81
7.00
6.39
6.54
7.94
6.73
6.73
7.07
8.36
8.47
9.42
7.07
7.87
8.66
8.70
9.04
10.37
mgd
2.00
1.94
1.86
1.65
1.90
2.15
2.02
1.72
1.95
1.83
1.72
1.93
1.84
1.88
1.85
1.69
1.73
2.10
1.78
1.78
1.87
2.21
2.24
2.49
1.87
2.08
2.29
2.30
2.39
2.74
pH Range
S.U.
0.3-1.4
0.3-1.4
0.3-0.9
0.4-0.9
0.2-1.2
0.3-0.9
0.1-1.2
0.8-1.7
0.1-1.7
0.3-1.2
0.5-1.6
0.5-1.3
0.1-1.3
0.8-1.4
0.9-1.4
0.4-1.8
0.6-1.3
0.5-1.7
0.8-1.6
0.7-1.3
0.9-1.5
0.9-1.5
0.9-1.8
0.7-1.7
0.8-1.6
0.9-1.5
0.9-1.5
1.2-1.5
0.7-2.1
0.9-1.7
Temp.
Range
°C
36-41
36-42
36-42
38-42
36-41
39-45
36-46
36-42
38.5-43
38-42
39.5-44
41-45
39-45
38-43
38-43
40.5-43
39-45
43-46
38-44
41-45
42-45
42-45
42-48
35-45
38-49
40-48
45-48
43-48
42-43
42-46
Total
mg/1
510
250
330
700
290
290
310
250
310
550
260
1,100
1,790
420
1,200
270
160
960
290
250
390
770
440
460
330
360
200
380
350
530
Suspended Solids
kg/day
3,860
1,830
2,320
4,370
2,080
2,350
2,360
1,620
2,280
3,800
1,690
8,030
12,460
2,990
8,400
1,720
1,040
7,620
1,950
1,680
2,760
6,440
3,730
4,330
2,330
2,830
1,730
3,300
3,160
5,490
Ib/day
8,510
4,040
5,120
9,630
4,590
5,200
5,220
3,580
5,040
8,400
3,730
17,710
27,480
6,580
18,520
3,800
2,300
16,820
4,300
3,710
6,080
14,200
8,220
9,550
5,140
6,240
3,820
7,290
6,980
12,110
mg/1
3,590
4,080
1,550
5,260
6,800
5,900
5,300
5,980
3,620
4,610
3,730
3,760
1,960
2,440
4,100
3,550
4,980
2,370
1,190
2,280
1,680
3,000
3,020
3,300
3,400
2,200
2,460
2,100
2,700
2,630
Iron
kg/day
27,170
29,950
10,910
32,840
48,890
48,000
40,510
38,920
26,710
31,920
24,280
27,460
13,640
17,390
28,700
22,700
32,600
18,830
8,010
15,350
11,880
25,090
25,600
31 ,090
24,060
17,310
21,320
18,270
24,420
27,270
Titanium
Ib/day
59,910
66,050
24,050
72,420
107,800
105,800
89,340
85,830
58,900
70,400
53,530
60,550
30,090
38,280
63,290
50,060
71 ,890
41,530
17,670
33,860
26,210
55,320
56,450
68,570
53,050
38,180
47,010
40,300
53,850
60,130
mg/1
960
820
690
1,140
970
1,010
1,760
700
1,000
920
800
1,400
1,910
1,400
1,400
920
520
1,260
440
460
860
640
380
580
460
420
320
290
350
450
kg/day
7,260
6,020
4,850
7,110
6,970
8,210
13,450
4,550
7,370
6,370
5,200
10,220
13,300
9,970
9,800
5,880
3,400
10,010
2,960
3,090
6,080
5,350
3,220
5,460
3,250
3,300
2,770
2,520
3,160
4,660
Ib/day
16,020
13,270
10,700
15,690
15,370
18,120
29,660
10,040
16,270
14,040
11,480
22,540
29,320
21,960
21,610
12,970
7,500
22,080
6,530
6,830
13,420
11,800
7,100
12,050
7,170
7,290
6,110
5,560
6.980
10.280
t Samples were collected from ? a.m. to 7 a.m. to correspond with the plant production day. The date June 1-2 indicates
the time period 7 a.m. to midnight June 1 and midnight to 7 a.m. June 2.
-------
Table F-ll
SUKHAR7 OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS (24-HR COMPOSITE SAMPLES)
OUTFALL Oil
UL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Date1"
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Flow
m /day
x 103
4.76
3.00
3.77
3.59
5.82
3.46
3.79
2.52
1.74
3.47
3.41
2.23
2.08
2.32
3.26
2.99
3.08
2.63
2.05
2.15
1.75
3.89
2.60
2.91
2.55
3.24
2.55
2.60
4. BO
3.17
mgd
1.26
0.79
0.99
0.95
1.54
0.92
1.00
0.67
0.46
0.92
0.90
0.59
0.55
0.61
0.86
0.79
0.81
0.70
0.54
0.57
0.46
1.03
0.69
0.77
0.67
0.86
0.68
0.69
1.27
0.84
pH Range
S.U.
0.5-1.3
0.4-1.3
0.3-0.8
0.4-1.6
0.4-1.3
0.2-0.9
0.6-1.4
0.6-1.7
1.0-1.8
0.1-1.0
0.3-1.5
0.9-1.4
1.1- .8
1.2- .8
0.6- .6
0.1- .5
0.4- .5
0.5- .9
0.7- .4
0.5- .4
1.0- .9
0.7-1.5
0.3-1.4
0.9-1.5
0.6-1.4
0.6-1.7
0.8-1.6
0.7-1.7
0.7-1.9
0.4-1.4
Temp.
Range
°C
34-46
37-42.5
41-50
35-44
35-52
37-45
35-45
35-46
35-44
41-46
41-48
.38-44.5
33-49
35-39
37-43
40-46
33.5-45
40-48
35-40
35-40
32-42
38-48
38-48
40-48
40-50
35-48
42-48
42-48
42-48
45-62
Total
mg/1
160
190
1,400
80
no
300
730
360
70
280
290
200
300
220
200
380
410
460
210
140
190
340
280
340
210
240
850
350
410
710
Suspended Solids
kg/day Ib/day
760
570
5,280
280
640
1,030
2,770
910
120
970
990
440
620
510
650
1,130
1,260
1,210
430
300
330
1,320
720
980
530
770
2,170
910
1,970
2,250
1,680
1,260
11,640
630
1,410
2,290
6. 110
2,000
260
2,140
2,180
980
1,370
1,120
1,440
2,500
2,780
2,670
950
660
730
2,920
1,600
2,180
1,180
1,710
4,790
2,010
4,340
4,970
mg/1
11,300
6,320
5,980
3,950
5,200
15,700
17,100
13,800
2,030
6,860
4,720
1,580
680
880
4,520
1,740
3,510
3,280
1,230
2,680
1,620
3,800
4,630
4,870
4,480
4,100
3,220
4,140
3,650
3,500
Iron
kg/ day
53,940
19,010
22,550
14,200
30,300
54,120
64,980
34,500
3,540
23,830
16,130
3,520
1,410
2,040
14,760
5,200
10,810
8,630
2,520
5,770
2,830
14,810
12,050
14,170
11,420
13,310
8,230
10,790
17,540
11,120
Ib/day
118,800
41 ,920
49,750
31,310
65,820
119,200
143,100
76,000
7,800
52,550
35,560
7,760
3,120
4,500
32,550
11,470
23,840
19,050
5,570
12,720
6,250
32,660
26,580
31,250
25,190
29,350
18,160
23,800
38,680
24,530
mg/1
180
200
730
680
150
210
510
250
90
90
480
150
150
130
330
590
240
320
200
320
210
410
580
510
560
400
480
430
420
540
Titanium
kg/day
850
600
2,750
2,440
870
720
1,930
630
150
310
1.640
330
310
300
1,070
1,760
730
840
410
6SO
360
1,590
1,510
1,480
1,420
1,290
1,220
1,120
2,010
1,710
Ib/day
1,890
1,320
6,070
5,390
1,920
1,600
4,260
1,390
340
680
3,610
730
680
660
2,370
3,830
1,630
1,850
900
1,510
810
3,520
3,320
3,270
3,140
2,860
2,700
2,470
4,450
3,780
Samples uere collected from 7 a.m. to 7 a.m. to correspond with the plant production day.
the time period 7 a.m. to midnight June 1 and midnight to 7 a.m. June 2.
The date June 1-2 indicates
in
-------
Table F-12
SVlStARI OF FIELD MEASUREl-!SilTS A'!D AUALTTICAL RESULTS (CRAB SAMPLES)
OUTFALL 003
HL INDUSTRIES, ST. LOUTS HO.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
14
15
16
17
18
19
20
20
21
21
21
21
22
22
23
23
24
24
25
26
27
28
29
29
30
Time of
Collect-tor
1512
0915
1317
1330
0136
0920
1110
2126
1727
2115
1520
2030
0934
0735
1333
0928
0917
0918
0723
1515
0914
1530
0110
1118
1326
1522
0310
0726
0310
1320
0455
2310
1320
2310
0925
2110
1520
2310
0921
Instantaneous
Flow
1 m3/day
x 103
8.0Z
7.98
7.98
7.57
5.63
8.06
7.72
6.92
8.59
7.04
6.35
7.34
7.45
5.18
6.32
6.96
7.26
5.63
9.31
6.95
6.35
7.72
7.07
7.15
7.87
7.07
6.85
8.32
9.95
8.06
8.55
9.15
6.92
7.60
7.53
7.75
8.70
8.89
11.39
mgd
2.12
2.11
2.11
2.00
1.49
2.13
2.04
1.83
2.27
1.86
1.68
1.94
1.97
1.37
1.67
1.84
1.92
1.49
2.46
1.84
1.68
2.04
1.87
1.89
2.03
1.87
1.81
2.20
2.63
2.13
2.26
2.42
1.83
2.01
1.99
2.05
2.30
2.35
3.01
PH
S.U.
0.7
1.4
0.7
0.7
0.7,
0.31
0.3f
1.4
0.1*
0.9
0.6
0.9
0.9
1.2
1.0
1.1
1.2
1.2
1.0
0.8
1.1
1.1
1.0
1.4
1.2
.5
.4
.1
.1
.2
.6
.5
.3
.3
.4
.3
.2
0.7
0.9
Temperature Total
"C
38
36
41
41
42
41
37
42
42.5
42
44
41
43
43
41
38
40.5
39
43
44
41.5
42
44
43
42
42
45
42
45
35
45
46
42
46
45
47
47
43
45
mg/1
400
280
650
360
130
200
170
160
1,700
120
140
1,510
710
240
610
2,600
600
52
4,100
230
160
1,400
230
370
870
350
600
1,200
850
120
980
420
210
150
120
360
95
3.600
1,880
Suspended Solids
kg/day
3,200
2,230
5.190
2,720
730
1,610
1,310
1.100
14,600
840
890
11,080
5,290
1,240
3.B50
19,490
4,350
290
38,170
1,600
1,010
10,800
1,620
2,640
6,840
2,470
4,110
9,990
8,460
960
8,380
3,840
1,450
1,140
900
2,790
820
32.010
21.410
Ib/day
7,070
4,930
11.440
6,000
1,610
3,550
2,890
2,440
32,200
1,860
1.960
24,440
11,670
2,740
8,500
42,990
9,610
640
84,160
3,530
2,240
23,830
3,580
5,830
15,100
5,460
9,060
22,030
18.650
2.130
18.480
8,480
3,200
2,510
1.990
6.150
1,820
70.590
47,220
mg/1
3,010
4,760
1,050
5,320
3,900
5,900
5,500
3,390
7,400
3,870
3,720
4,850
4,100
3,060
3,120
4,040
3,990
1,800
3,220
,420
,820
,900
,700
,620
,730
2,000
2,080
3,200
2,750
2,750
3,120
3,420
3.150
2,030
2.370
1,970
2.500
2,600
2.450
Iron
kg/day
24.150
38,010
8,380
40.260
21,990
47,560
42,460
26,960
63.570
27,240
23,650
35,600
30,560
15,850
19,710
28.130
28,990
10,150
29,970
9,880
11.570
14.660
12.400
11.590
13,610
14,140
H.240
26,640
27,360
22.160
26,680
31.320
21.810
15,440
17.840
15,280
21,760
23.120
27.900
Ib/day
53,250
83.810
18.480
88.790
48.490
104,800
93,630
59,400
140,100
60,060
52,150
78,510
67,400
34,980
43.430
62,030
63,920
22,380
66,100
21 ,800
25,510
32,340
25,520
25,540
30,010
31.190
31,390
58,740
60,310
48,880
58,840
69,060
48,100
34.050
39,350
33.703
47,980
50.980
61.540
t Exceeds BPOES permit limtatione
-------
Table F-13
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS (CRAB SAMPLES)
OUTFALL Oil
KL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
21
22
22
23
24
24
25
26
27
28
29
30
Time of
Collection
1525
0735
1325
1340
0146
0925
1115
2207
1735
2145
1724
1730
0940
1128
0930
0925
0923
1955
1519
0920
0149
1524
0348
1725
1330
0343
2346
1325
2335
0935
2142
1525
0927
Instantaneous
Flow
m /day
x 103
4.50
2.46
2.83
4.46
0.87
3.93
3.29
1.77
1.18
3.88
3.48
1.93
1.82
1.90
3.82
3.60
1.32
2.93
3.30
1.94
2.03
1.46
0.88
2.90
2.42
2.85
3.14
2.61
2.46
2.57
2.16
4.76
3.33
mgd
1.19
0.65
0.75
1.18
0.23
1.04
0.87
0.47
0.31
1.02
0.92
0.51
0.48
0.50
1.01
0.95
0.34
0.77
0.87
0.51
0.54
0.39
0.23
0.76
0.64
0.75
0.83
0.69
0.65
0.68
0.57
1.26
0.88
pH Temperature
S.U. °C
0.8T
1.1.
0.4!
0.5f
1.0.
o.st
0.5f
1.4
1.2.
0.9*
O.S1"
1.2
1.2
1.3
1.4
1.2
1.4.
0.8f
1.0
1.0.
0.8T
1.5
1.3.
0.8*
0.6f
1.1
1.4
1.3
1.0
1.1.
0.9T
1.2.
0.9T
42
40
47
42
36
41
40
39
35.5
43
48
38
36.5
38
38
41.5
35
45
36
36
36
33
35
41
41
46
47
44
48
45
49
42
45
! Total
mg/1
120
430
580
80
220
970
430
43
47
430
70
420
160
70
220
250
370
270
400
78
230
230
1,100
470
410
6,900
290
300
180
320
160
220
380
Suspended
kg/day
540
1,050
1,640
350
190
3,810
1,410
70
50
1,670
240
810
290
130
840
900
480
790
1,320
150
460
330
960
1,360
990
19,660
910
780
440
820
340
1,040
1,260
Solids
Ib/day
1,190
2,330
3,630
780
420
8,410
3,120
160
120
3,680
530
1,790
640
290
1,850
1,980
1,070
1,740
2,910
330
1,030
740
2,130
3,000
2,190
43,350
2,000
1,730
970
1,810
760
2,310
2,790
mg/1
11,100
5,930
4,240
4,350
590
18,100
10,800
13,800
2,040
2,580
6,500
1,570
780
500
2,780
1,400
2,610
4,100
1,410
1,040
3,580
2,440
1,210
4,500
3,730
6.060
4,780
4,800
4,180
3,200
3,540
3,250
3,350
Iron
kg/day
50,040
14,580
12,030
19,420
510
71,310
35,590
24,520
2,410
10,020
22,680
3,030
1,410
950
10,620
5,040
3,440
12,020
4,650
2,020
7,230
3,570
1,060
13,060
9,0^0
17,260
15,010
12,570
10,290
8,240
7,660
15,490
11,150
Ib/day
110,200
32,160
26,530
42,830
1,130
157,000
78,400
54,120
5,320
22,110
50,010
6,690
3,130
2,090
23,430
11,110
7,600
26,510
10,270
4,460
16,070
7,880
2,350
28,800
19,950
38,070
33,100
27,710
22,700
18,180
16,890
34,170
24,600
t Exceeds 1IPDES permit limitations
-------
162
Table F-14
SUMMARy OF pH AND TEMPERATURE MEASUREMENTS
OUTFALLS 020 AND 012
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Outfall
Time of
Measurement
1340
1035
1040
0845
0855
1005
0852
1434
1446
1359
1040
1345
1405
1200
1800
0955
1340
0955
1340
1150
1145
0756
1510
1414
1350
1558
1400
1543
0940
1405
010
pH
s.u.
7.5
7.4
7.2
6.8
7.2
0.8
6.7
6.2
6.8
6.8
7.2
3.0.
1.6f
6.1
7.2
6.9
7.1
7.1
7.2
6.9
6.6
7.6
5.5
5.3
6.7
5.8
6.7
6.0
6.3
6.0
Temp.
°C
28.5
28
29
30
30
29
25
26
27
27
28
28
30
30
29
28
28.5
28.5
28
30
26
34
34
31
28.5
32
33.5
34
32
31.5
Outfall
Time of
Measurement
1400
1020
1030
0850.
NFt1"
0850
0850
NF
1630
1355
NF
NF
NF
1150
NF
NF
1340
0950
1335
1152
1136
0800
NF
NF
NF
NF
NF
NF
NF
NF
012
PH
S.U.
9.0
8.0
8.0
7.4
7.1
6.7
6.3
6.6
2.7
5.3
6.3
4.7
6.0
4.8
6.8
Temp,
°C
68!
72
7°I
681'
•
70f
70'
67
72
28
4.
73!
72I
67I
65!
66I
T
65T
t Exceeds NPDES permit limitations
tt No flow observed
-------
Table F-JS
SUMKAXT OF FIELD MEASUREMENTS AND ANAUtTICAL RESULTS
24-HR COHPOSITE SAMPLES
OUTFALL 013
HI, INDUSTRIES, ST. LOUIS, HO.
June 9-16, 1976
Date*
9-10
10-11
11-12
12-13
13-14
14-15
15-16
Flow
m /day ragd
xlO3
8.02 2.12
5.67 1.50
6.92 1.83
8.17 2.16
8.25 2.18
8.81 2.33
8.89 2.35
PH
Range
S.U.
2.6-3.7
3.4-6.5
2.8-6.2
3.3-5.4
5.9-6.5
5.4-6.5
5.8-6.6
Temp.
Range
"C
32.5-37
34-41.5
34-39
32-36
27-37
32-37
25.5-36
Total Suspended
Sol Ids (Gross)
rag/1
220
260
150
90
88
140
130
kg/day
1,760
1,470
1,030
730
720
1,230
1.150
Ib/day
3.880
3.250
2,290
1,620
1,600
2,700
2,540
Total Suspended
Solids (Net)
ng/1
10
70
0
0
8
0
38
kg/day
80
390
0
0
60
0
330
Ib/day
170
870
0
0
140
0
740
Iron
(Gross)
mg/1 kg/day Ib/day
32 255 565
42 235 525
18 120 270
12 95 215
12 95 215
11 95 210
13 115 250
Iron
(Net)
mg/1 kg/day
21.2 170
31.2 175
9.4 65
4.3 35
2.1 15
0 0
4.0 35
Titanium
(Gross)
Ib/day
370
390
140
75
35
0
75
ng/1
<2
24
9
9
9
8
9
kg/day
15
135
60
70
70
70
80
Ib/day
35
300
135
160
160
155
175
Titanium
(Net) '
rag/1
0
12
4
3
0
0
0
kg/day
0
65
25
20
0
0
0
Ib/day
0
150
60
50
0
0
0
Samples aerg collected from 7 c..m, to 7 a.m. to correspond uith the plant production day.
nidnight June 1 and midnight to 7 a.m. Jung 2.
The date June 1-2 indicates the time period 7 a.ia. to
CO
-------
164
Table F-16
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS
(GRAB SAMPLES)
OUTFALL 012
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Date
1
2
3
4
5
6
7
8
9
t
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Time of
Collect.
1410
1045
1000
0900
0815
0840
0835
1440
1805
1540
0948
1930
1550
0950
0125
0330
1540
2325
1340
1925
0950
2125
"1540
0950
PH
S.U.
6.5
6.3
6.2
6.6
6.6
6.8
6.7
4.2
2.8
6.1
6.2
6.4
6.7
6.5
6.5
6.2
2.3
7.0
6.5
6.6
6.1
6.3
5.6
5.7
Temp.
°C
38
33
34
32
34
26
31.5
33.5
34.5
35
36.5
35
36,.
39ft
36
34
29
34
35
35
35
37
36
37
TSS
1,500
600
560
470
440
540
530
270
260
140
110
220
360
580
970
210
990
690
550
390
540
350
260
340
Iron
mg/1
38
26
28
20
26
15
27
45
36
12
6
5.2
7
13
25
29
28
17
20
15
13
12
14
7
Titanium
3
8
13
14
<2
10
<2
8
9
8
4
4
4
6
8
12
<4
<4
4
4
<2
<4
<4
9
t Composite samples collected June 9-16, 2976
tt Exceeded NPDES permit limitation
-------
Table F-l?
SUMMARI OF FIELD MEASUREMENTS AtlD ANALYTICAL RESULTS (24-HR COMPOSITE SAKPLES)
OUTFALL 014
NL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Date*
June 1-2**
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-H
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
Flow
m3/day
x 103
16.27
14.76
12.18
23.12
12.52
12.33
14.30
16.91
15.82
15.63
19.45
15.44
15.55
14.45
16.04
16 50
16.31
15.5?
15.55
15.10
17.52
17.75
15.55
14.49
14.19
13.89
13.77
15.06
12.98
14.91
mgd
4.30
3.90
3.22
6.11
3.31
3.26
3.78
4.47
4.18
4.13
5.14
4.03
4.11
3.82
4.24
4.36
4.31
4.12
4.11
3.99
4 63
4 69
4.11
3.83
3.75
3.67
3.64
3.98
3.43
3.94
pH Range
S.U.
2.7-6.5
1.1-7.1
2.2-6.0
1.4-6.8
0.2-5.5
1.9-7.1
1.2-5.6
2.7-6.1
3.0-6.4
1.9-7.1
5.9-6.9
6.3-7.2
6.1-7.0
6.1-7.4
5.3-6.6
2.1-7.0
3.5-6.7
2.2-6.8
6.4-7.4
2.8-6.7
4.1-6.7
2.1-6.6
2.0-6.8
2.0-7.3
2.0-6.9
2.2-6.9
2.3-7.3
2.1-6.7
2.1-5.9
2.2-5.6
Temp.
Range
°C
31-45
37-48
38-46
30-50
38-54
38-50
40-51
34-46
39-48.5
37-48
44-59
40-48
46-58
42-53
37-54
46-55
38-51
37-53
43-50
45-55
44-56
42-52
39-54
34-50
43-56
49-56
42-53
44-49
38-43
41-50
Total Suspended Solids
(Gross)
mg/1
540
830
380
330
330
370
310
350
ISO1
150
180
100
170
200
160
170
130
140
290
390
590
690
880
600
410
440
840
350
250
260
kg/day
8,780
12,250
4,630
7,630
4,130
4.560
4,430
5,920
2,840
2.340
3.500
1.540
2,640
2,890
2,560
2.800
2,120
2,180
4,510
5.880
10.330
12,240
13.680
8,690
5,810
6.110
11,570
5,270
3,240
3,870
Ib/day
19,370
27.010
10.210
16,820
9,110
10,060
9,770
13.050
6.270
5,170
7,720
3,aQO
5,830
6.370
5,660
6,180
4,670
4,810
9.940
12.980
22.790
27,000
30,180
19,170
12,830
13,470
25,510
11,620
7,150
8,540
Total
mg/1*
290
600
160
240
210
160
100
200
60
40
100
0
120
90
100
140
100
80
110
100
150
100
190
160
100
70
410
0
0
0
Suspended Solids
(Net)"
kg/day
4,800
8.940
2,020
5,580
2,670
2.020
1.400
3.450
980
600
1,890
0
1,940
1,320
1,680
2.330
1,630
1,260
1,820
1,490
2,700
1,880
2,970
2,390
1,390
1,020
5,720
0
0
0
Ib/day
10.580
19,720
4,460
12.310
5,900
4,460
3,100
7,610
2.160
1,330
4,170
0
4,280
2.910
3,710
5,150
3,610
2.780
4,010
3,290
5.960
4.140
6,540
5,230
3,070
2,260
12,620
0
0
0
mg/1
80
560
100
100
70
80
290
250
90
240
180
280
84
136
84
103
48
32
56
83
72
64
80
64
48
36
190
30
40
28
Titanium
(Gross)
kg/day
1,300
8,260
1,210
2,310
870
980
4,140
4,220
1,420
3,750
3,500
4,320
1,300
1.960
1.340
1,780
780
500
870
1,320
1,260
1,130
1,240
920
630
500
2,610
450
510
410
Ib/day
2,870
18.220
2,680
5,100
1,930
2.170
9,KO
9,320
3,130
8,270
7,720
9,530
2.830
4,330
2,970
3.920
1,720
1,100
1,920
2,930
2,780
2,500
2,740
2,040
1,500
1.100
5,770
990
1,140
920
Titanium
(Net)
mg/1*
70
550
100
100
70
70
280
240
80
230
170
180
80
130
70
100
40
30
50
83
60
60
60
60
40
33
180
30
40
20
kg/day
1.200
8.210
1.190
2.270
850
960
4.070
4.160
1.370
3.640
3. <50
4.270
1.220
1,830
1.220
1.730
760
430
850
1.290
1.160
1,030
1,190
890
650
460
2,580
410
480
350
Ib/day
2.650
18.100
2.620
5.010
1.S90
2,110
8.S70
9.170
3,020
8.030
7,620
9.410
2.700
4,150
2,600
3,820
1,630
1.050
1.830
2. SCO
2.570
2,330
2,620
1,970
1,4^0
1,020
5.690
910
1,070
980
The date June 1-2 indicates the time period 7 a.n.
. — i-- • • — to 7 a.m. to correspond with the plant production day.
to -.idnigr.t June 7 and nidright to 7 a.m. June 2.
tt Cross discharge minus the mi.cror.izer diacharge (Table F-18) equals net discharge.
* Calculated from net load
in the composite UOB added in an incorrect proportion, therefore thie composite sample for TSS and Titanium may not be
in
-------
166
Table F-18
UNTREATED RIVER WATER CONTRIBUTION FROM MICRONIZER TO OUTFALL 014*
NL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Datetf Flow*
m /day mgd
x 103
June 1-2*** 9.27 2.45
2-3 8.93 2.36
3-4 9.31 2.46
4-5 7.30 1.93
5-6 5.60 1.48
6-7 6.51 1.72
7-8 7.75 2.05
8-9 9.50 2.51
9-10 8.89 2.35
10-11 9.15 2.42
11-12 8.93 2.36
12-13 8.93 2.36
13-14 8.78 2.32
14-15 9.23 2.44
15-16 9.61 2.54
16-17 9.31 2.46
17-18 8.93 2.36
18-19 9.19 2.43
19-20 8.97 2.37
20-21 9.34 2.47
21-22 9.42 2.49
22-23 9.42 2.49
23-24 8.93 2.36
24-25 8.28 2.19
25-26 6.32 1.67
26-27 9.08 2.40
27-28 8.85 2.34
28-29 8.74 2.31
29-30 7.94 2.10
30-July 1 8.89 2.35
Total Suspended Solids Titanium
mg/1** kg/day Ib/day mg/ kg/
1** day
430 3,980 8,790 10 90
370 3,300 7,280 6 50
280 2,600 5,740 3 25
280 2,040 4,510 5 35
260 1,450 3,210 3 15
390 2,530 5,590 4 25
390 3,020 6,670 10 75
260 2,470 5,440 7 65
210 1,860 4,110 6 50
190 1,740 3,830 12 110
180 1,600 3,540 5 45
170 1,510 3,340 6 50
80 700 1,540 9 75
170 1,570 3,460 9 80
92 880 1,950 13 125
50 460 1,020 5 45
54 480 1,060 2 15
100 920 2,020 2 15
300 2,690 5,930 2 15
470 4,390 9,680 4 35
810 7,630 16,830 10 90
1,100 10,360 22,850 6 55
1,200 10,710 23,630 6 50
760 6,300 13,880 4 30
700 4,420 9,750 4 25
560 5,080 11,210 4 35
660 5,840 12,880 4 35
740 6,460 14,260 4 35
410 3,250 7,180 4 30
440 3,910 8,620 4 60
lb/
day
200
115
60
80
35
55
170
145
115
240
100
115
170
180
275
100
40
40
40
80
205
125
115
70
55
80
80
80
70
135
t Data used to cumpute net load discharged from outfall 014
(Table F-17).
tt Composite samples correspond to the plant production day.
7 a.m.-? a.m.
* Micronizer flow taken
** Intake concentration
*** One aliquot sample in
proportion, therefore
June 2-2.
from NL Industries' charts.
the composite was added in an incorrect
sample may not be representative for
-------
Table F-19
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS (GRAB SAMPLES)
OUTFALL 014
HL INDUSTRIES, ST. LOUIS, m.
June 1976
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
22
23
24
25
26
27
28
29
30
Time of
Collection
1545
0945
1345
1405
0215
0945
1145
2152
1845
1800
1157
2136
1145
1419
1543
0957
0950
1001
1555
0955
0130
0355
1410
1425
2330
1350
2128
1000
2130
1540
1000
Instantaneous
Flow
m /day
x 103
24.98
18.16
18.16
11.12
8.06
12.86
15.44
16.80
17.97
16.95
17.67
16.72
16.27
14.00
14.95
14.83
16.01
16.12
11.92
15.40
12.71
17.83
15.63
15.21
15.55
14.00
14.95
14.61
13.24
12.79
15.29
mgd
6.60
4.80
4.80
2.94
2.13
3.40
4.08
4.44
4.75
4.48
4.67
4.42
4.30
3.70
3.95
3.92
4.23
4.26
3.15
4.07
3.36
4.71
4.13
4.02
4.11
3.70
3.95
3.86
3.50
3.38
4.04
pH
S.U.
6.4.
1.1*
5.8
6.6
5.6
6.4.
1.2t
6.1
5.4
7.1
6.2
6.6
6.8
6.9
6.4
2.4
6.7
2.9
6.7
6.5
6.4
6.2
6.3
5.8
7.3
2.0
6.7
5.6
6.4
2.2
5.5
Temperatun
°C
38
41
40
40
49
41
50
34
47.5
43.5
54
46
58
46
38
53
40
41.5
45
45
55
53
44
42
49
45
55
52
45
44
48
Total Suspended
e Solids (Gross)
mg/1
500
1,300
340
340
370
330
360
210
180
540
230
120
230
40
150
250
150
390
310
350
270
700
850
1,100
660
380
360
440
340
200
290
kg/day
12,480
23,610
6,170
3,780
2,980
4,880
5,550
3,520
3,230
9,150
4,060
2,000
3,740
560
2,240
3,700
2,400
6,280
3,690
5,390
3,430
12,490
13,280
16,730
10,260
5,320
5,380
6,420
4,500
2,550
4,430
Ib/day
27,530
52,070
13,610
8,340
6,570
10,780
12,250
7,780
7,130
20,180
8,960
4,420
8,250
1,230
4,940
8,170
5,290
13,860
8,140
11,880
7,570
27,510
29,290
36,900
22,630
11,730
11,860
14,170
9,930
5,640
9,770
Titanium (Gross)
mg/1
80
960
60
80
130
100
210
130
80
360
140
160
122
67
108
290
16
84
104
80
48
80
72
120
32
28
24
40
10
18
30
kg/day
1,990
17/.30
1,080
890
1,040
1,280
3,240
2,180
1,430
6,100
2,470
2,670
1,980
930
1,610
4,300
250
1,350
1,230
1,230
610
1,420
1,120
1,820
490
390
350
580
130
230
450
Ib/day
4,400
38,450
2,400
1,960
2,310
2,830
7,140
4,810
3,170
13,450
5,450
5,900
4,370
2,060
3,550
9,480
560
2,980
2,730
2,710
1,340
3,140
2,480
4,020
1,090
860
790
1,230
290
500
1,010
t Exceeded HPDES permit limitations
-------
Table F-20
SOMiART OF pf! AND TEMPERATURE MEASUREMENTS
OUTFALLS 016, 018, 019 and 021
NL INDUSTRIES, ST. LOUIS, MO.
June 1976
Outfall 016
Date
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
36
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Time of
Collect.
1315
1030
0900
0740
0910
0955
0728
1^14
1515
1050
0750
0940
0936
1545
0745
0750
1335
0750
0955
1128
1117
0732
1410
1352
1336
1539
1338
0806
0951
1356
pH
S.U.
6.8
7.0
7.2
7.2
6.8
7.1
6.7
7.1
7.1
6.8
7.3
7.4
6.5
6.8
6.4
6.8
7.0
7.5
7.2
7.3
6.7
6.5
6.5
6.3.
5.6f
6.0
6.0
6.3
6.9
6.3
Temp.
°C
20
22
21
22
22
23
21
23
24
23
24.5
25
25.5
26
25
27.5
25.5
25
25
22
24
23
21
24
24
25
25
25
25
24
Outfall 018
Time of
Collect.
1600
0945
1100
0815
1000
0830
0810
1403
1805
1343
1145
1350
1355
1140
1730
0940
1345
1337
1005
1134
1124
0741
1400
1400
1340
1546
1344
0810
0955
1341
pH
S.U.
7.3
7.1
7.2
7.0
7.0
6.2
6.9
7.0
6.6
6.9
7.4
7.4
6.8
6.7
6.9
6.8
6.2
7.5
7.2
7.3
7.1
6.6
6.8X
5.6*
6.4.
5.8*
6.5
6.5
6.5
6.1
Temp.
°C
24
21
23
24
24
24
23
24
24.5
25.5
26
26
26
27
27
24.5
25.5
25.5
23,5
24
22
24
24
25
24
27
29
28
27.5
24.5
Outfall 019
Time of
Collect.
1250
0950
1045
1005
1145
1010
1000
1013
No
1345
1150
0955
0948
No
0920
1545
1540
1340
1345
1138
1130
0746
1557
1408
1414
1523
1355
1535
1550
1318
PH
S.U.
9.2J
9.7f
7.8
6.8
7.5
7.1
6.7
7.6
flow
8.6
7.4
8.0
7.5
flow
8.6
8.8
7.7
9.2f
8-5
8.3
8.1.
9.5*
6.8
8.2
9.0
7.1
7.4
7.6
6.0
9.0
Temp.
°C
57
59
51
6G
53
50
61
51
62
36
60
43.5
60
72
37
60
61
60
48
40
37
49
64
37
38
62.5
28
39
Outfall 021
Time of
Collect.
1255
0955
1050
1010
1150
1012
1005
1020
1435
1350
1155
1000
0950
1745
0922
1135
1545
1345
1010
1132
1131
0743
1550
1405
1410
1550
1356
1533
1553
1346
PH
S.U.
9.9
10. 4^
5.8'
10.4
10.8
8.8
10.9
10.3
10.7
9.9
9.5
9.7
8.4
10.5
9.7
10.2
9.3
9.8
10.1
7.9
9.2
7.4
7.1
9.4
8.1
6.4
8.5
8.4
7.3
6.5
Temp.
ec
40.5
47
42
32
54
47
53
50
59
44
37
37
59
46
48
52
40
47
47.5
25
38
29
57
40
48
34
36
35
31
57
t Exceeds IJPDSS permit limitations
-------
169
Table F-21
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS
(24-HR COMPOSITE SAMPLES)
RAW WATER INTAKE
NL INDUSTRIES, ST. LOUIS, MO.
June-July 1976
Date1"
Flow1"1"
m /day mgd
pH Range
S.U.
Temp. Range
°C
TSS Iron Titanium
mg/1
x 103
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
t
tt
204
212
212
221
206
205
201
205
204
200
201
196
185
190
189
188
184
182
188
198
201
193
196
198
193
198
193
193
195
196
54.0
56.0
56.1
58.3
54.4
54.1
53.1
54.1
53.8
52.8
53.0
51.9
49.0
50.1-
49.9
49.8
48.6
48.1
49.6
52.3
53.1
51.0
51.8
52.3
51.1
52.4
51.0
51.0
51.5
51.8
6.0-7.6
6.3-8.1
6.5-7.5
6.5-7.0
6.1-6.9
6.7-7.4
6.4-7.5
6.0-7.9
6.5-7.1
6.5-6.9
6.9-7.4
6.6-7.1
6.1-6.9
6.3-6.9
5.9-6.9
5.8-6.8
2.1-7.1
6.0-7.0
6.4-7.8
3.7-7.3
5.7-6.9
6.0-6.8
5.2-6.6
5.2-6.8
5.7-7.1
5.5-6.8
5.5-6.6
5.7-6.4
5.8-6.3
5.0-6.2
Composite samples correspond to
Data from integrator
on intake
22-23
21.5-24
22-24
23-25
22-24
23-24
21-24
22-24
23-25
24-25
24.5-26
25-26
25-27
25-27.5
25.5-26
24.5-26
25-26
25-26
24-26
22-25
23-25
23.5-25 1
20-24 1
23-24
24-25
24-25
25-27
25-26
25-26
24-25
430
370
280
280
260
390
390
260
210
190
180
170
80
170
92
50
54
100
300
470
810
,100
,200
760
700
560
660
740
410
440
plant production day.
flow recorder
18.4
16.9
5.9
<0.3
3.8
5.5
14
19
10.8
10.8
8.6
7.7
9.9
11
9
6.4
2.3
2.8
8.9
13
26
42
28
21
19
22
18
16
13
11
7 a.m.
10
6
3
5
<3
4
10
7
6
12
5
6
9
9
13
5
<2
<2
<2
4
10
6
6
<4
<4
<4
<4
<4
<4
7
-7 a.m.
-------
170
Table F-22
SUMMARY OF FIELD MEASUREMENTS AND ANALYTICAL RESULTS
(GRAB SAMPLES)
RAW WATER INTAKE
NL INDUSTRIESt ST. LOUIS, MO.
June 1976
Date Time of
Collection
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
21
22
22
23
24
25
26
27
28
29
30
1540
1145
1210
1045
0150
1000
1130
2305
1800
2130
1535
1943
1530
2145
0810
2140
1140
2305
0800
0320
0310
1330
1740
1543
1555
2305
1545
0945
1340
1000
Instantaneous
Flow
m /day
x 103
218
218
218
218
218
218
212
204
207
207
202
196
180
180
180
191
196
185
185
207
207
191
199
202
193
202
204
196
196
199
mgd
57.6
57.6
57.6
57.6
57.6
57.6
56.2
54.0
54.7
54.7
52.3
51.8
47.5
47.5
47.5
50.4
51.8
49.0
49.0
54.7
54.7
50.4
52.6
53.3
51.1
53.3
54.0
51.8
51.8
52.6
pH
S.U.
7.6
7.0
6.9
6.5
6.9
7.0
6.9
6.2
6.5
6.7
7.1
6.5
6.9
6.7
6.4
6.8
6.9
6.1
6.9
6.6
6.3
6.0
5.5
6.1
6.5
6.0
6.4
6.0
5.8
5.6
Temp.
°C
22
22
23
23
24
23
24
24
25
24
26
25.5
27
27.5
25.5
25.5
25.5
25
24.5
25
24
25
24
24.5
24
25
27
26
26
24
TSS
410
400
350
250
300
750
320
250
230
190
190
130
t
120
170
110
no
96
160
640
970
900
980
750
680
430
500
680
260
380
Iron
mg/1
17.7
17.7
7.6
<0.3
5.1
4.9
18
13
8.5
9.2
9.8
7.7
13
5.7
11
8.8
4.2
3.0
3.7
19
27
41
28
24
14
20
12
13
33
15
Titanium
6
4
5
4
<3
3
11
7
7
16
<3
9
8
10
14
4
<2
<2
<2
4
18
2
8
<4
4
<4
<4
4
4
<4
t Sample not sent to NEIC laboratory.
-------
171
Table F-23
OF VANADIUM CONCENTRATIONS
(24-HR COMPOSITE SAMPLES)^
NL INDUSTRIES, ST. LOUIS, MO.
June 2976
Date Outfall Outfall Outfall
00V • 009TT Oil T
June 1-2
2-3
3-4
4-5
5-6
6-7
7-8
8-9
9-10
10-11
11-12
12-13
13-14
14-15
15-16
16-17
17-18
18-19
19-20
20-21
21-22
22-23
23-24
24-25
25-26
26-27
27-28
28-29
29-30
30-July 1
15
20
20
18
21
22
24
20
18
20
33
66
66
48
39
48
33
17
43
53
60
7
62
41
37
55
36
61
69
64
59
57
58
70
71
79
54
45
53
64
58
80
84
94
72
81
95
90
60
71
82
13
115
108
97
76
81
• 80
85
84
27
17
31
20
13
25
27
22
17
135
126
41
22
20
102
110
97
124
119
71
72
16R
146
146
136
134
104
114
105
104
t By Mr. James D. Vieregg's letter of May IS, 1976,
Mr. Jeffrey E. Silver, Environmental Counsel^
NL Industries, Inc., uas notified that NEIC
would not test for vanadium during the Compliance
Monitoring Survey at NL. Laboratory personnel
were so informed. Due to an apparent communication
breakdown, vanadium analyses were run as specified
in the original Study Plan, from the metals samples
collected from the intake a>id outfalls 001, 009,
Oil and 013. These samples were also used to
test for iron and titanium. The above data has
not been utilized in any manner in drawing con-
clusions contained in this report.
tt All concentrations in mg/l. Intake and outfall
013 concentrations were <1 mg/l each day.
-------
173
Appendix G
Individual pH and Temperature Measurements
-------
175
Table G-l
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
001
Date
JLINC i
JU*}£ 2.
J1ME3
•
Time of
Collection
07/6-
0130
//o7
/300
JStO
/705"
/926~
2 US'
2.3/5"
SS"
0730
/3/o
/5~20
'''I'H,
23/&
OH?
03/&
OtfS'S'
07 or
0900
//30
/320_
/7oo
/
-------
176
Table G-l (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lf 1976
Outfall
OOi
Date
J<.tve i
JQNZ 6"
Time of
Collection
Olio
03/8
oys&
07(0
O X tS~
//oo
'1*1
/ s O $
/ & j ^-
2. S/S~
2.3*0
03/3"
oyfj
07/5-
07/S"
///s~
/ ZtO
/ 5~/O
/7/tf
/7-2 6
2/22
2 3/O~
Temperature
°C
32'5""
3X-0
3J~O
$6\O
36.0
$$-.o
3/.0
3$,0
•33:0
3s:o
^* **
3f.O
3 '*,0
pH
S.U.
l.o
J.'JL
0. 7
/, J"
i.8
/'?
/.t
0.7
Q.S~
/,o
cc
0,S~
O.S
/.y
/.5"
/.^
X.J"
0, 7
/.£.
0.1
o.7
t Exceeds NPDES Permit Limitations
-------
177
Table G-l (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June I - July I, 1976
Outfall
001
Date
J^hif 6
JUV* 7
Time of
Collection
OUST
03/0
05'07
07/0
J//0
X3AT
/rso
/73C
/93-f
23-25"
0136
03*6'
OS'tS'
C 7'S"
C7/S"
//&3~
/300
• /Sot*
/ 7 °S"
/?f7
-2120
Temperature
°C
26.0
26-O
3,6'. O
26.0
33,0
36.0
1V.O
T>y.0
Sf.O
3/.O
3y.o
33.5-
35-. j-
33.0
3/0
36.0
36.0
36.0
36.0
3
-------
178
Table G-l (Continued)
TEMPERATURE AND pfl MEASUREMENTS
It. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
OOl
Date
Jc/A/eT H
Jt/AJtr 9
Time of
Collection
0/
o/s/
03-/S
OS'S, o
0700
O'foo
///o-
/cT/?
/7/^
2 bo?
13/3
Temperature
°C
33. f
33. S"
Sy.s'
3o,o
33. o
38 0
36.0
3/0
36.0
36. o
32.0
35Ttf
^J v3* ^?
*J O / j
52.^>
36.0
3^, o
3X ^
37.^
3/,^?
PH
S.U.
2,3
2.3
2,y
2,b
3-^
/*-
/' ff
2.3
/.o
/.£>
/. 6
/<5"
/<&
/. 3
J.O
/./
/, y
/f-
t Exceeds NPDES Permit Limitations
-------
179
Table G-l (Continued)
TEMPERATURE AND pff MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
col
Date
^iifje to
\J(/AJ£ //
Time of
Collection
O//0
O33y
OS03
072. t
o?//
///0
Jf/S
/7/2
/9o?
3./0/"
23/7
C//3
03/7
OS 03
///O
/S'O
/?/y
2//7
23/3
Temperature
°C
36-0
36,0
3«5"O
33. o
32. 0
37. 0,
3'/o
Y/. o^
-------
180
Table G-l (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July 1, 1976
Outfall
Date
Time of
Collection
Temperature pH
°C S.U.
661
/Z
/3
on 7
2305'
0//6
03/7
072 0
33.5'f
37,6*"
33.0
32.0.
/,
A •*•
A 2
/.O
t Exceeds NPDES Permit Limitations
-------
181
Table G-l (Continued)
TEMPERATURE AND pH frfEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
001
Date
Jl/AJf /5~oo
<57/^
///o
/3/5
/5"o^
/^f?
a//3
23/0
Temperature
°C
y/^i-
^o,o|
37,"
^o.'o*
^/O, t) ^
^'ot"
5^x o Y
33to^
3?.o
yo Ol
fO O^
fl>,0 t
35:^^
3'/*°
3cT^
3/T
-------
182
Table G-l (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
0&I
Date
Ji/Aj£ /6
w? ;?
Time of
Collection
o/oo
63 /&
0720
//05~
/3/0
/£/€>
/7//
3?//S
3 3/O
O///
03/3
o so 8
Q7J-2.
GJ22.
// /5~
'/*fo
'%?3
2/33~
2.3/7
Temperature
°C
J^o
i?,o
35.0
3
-------
183
Table G-l (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
001
Date
-"*"* /S
^»e,1
Time of
Collection
O/3G
0336
OS'S O
07/3
a 7/5"
/ ^}/ff
/ £^f £>
/7/o
/9/3
3./33~
Z33f
0/27
0330
OS" (7
07 ) 7
Oej2S'
// 2 0
/3/-S~
' / JV 0
J7/3
s?yo
2.33-S-
Temperature
°C
3^,o
36,^3
•36.0
3&,5~
37/ o
37.0
3S%
3C;0
3&,o
3S.O
36.0
3&o
' 3l/*0
33. sr
3f/ 0
33". o
36-, o
32.5"
3^o
3^ ^
PH
S.U.
/,S~
/, o
/ y'
/.z
/. 7
» ' J
y ^
/.t
/.I
/,*-
/J
t.JL
/. V
/ 5"
/, 6
/.3
X6
/. y
A V
Ad)
t Exceeds NPDES Permit Limitations
-------
184
Table G-l (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1076
Outfall
00/
Date
Ji/AfcT 3. Q
.
£ y.1
Time of
Collection
0/31-
033O
OS jZ o
0 7/ 0
07/7
///,-s-
/&?
/7/5"
/*? BS~
it yj~
1337
O/yo
oyoo
O$'3.5'
07 tl-
0*7/2.
//06
,/3/o
V^'i-S"
/ 7yy
2/33
Temperature
°C
3^. fl
3JJ, 0
35-7 ^j
35/, O
3?, o
37. o
19.0*
35",o
3^.0
3$,e>
32,o
3S.o
3-P, o
'37. 5", d?
^J'.o
3?'of
tj/^fc O
^J 6* O
PH
s.u.
/. 2
/,3.
/ /
/$
C,3
/,/
/.S
/J
///
A6
/a
2,5-
X 7
/ 6
/, 3
A 6
/ 3
/. 6
/ y
/a
0,7
t Exceeds NPDES Permit Limitations
-------
185
Table G-l .(Continued)
TEMPERATURE AND pH MEASUREt-lENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
00]
Date
*JL//Uf 2.2.
jyve .23
Time of
Collection
o/3?
07/0
//oS~
/3/-S-
/^/o
Ii
0/3e>
63*?
OS/*}
<>7/7
09//
// of
J3SV
/7/o
2/^7
Temperature
°C
11' o^
3S.O
37,S
yo,&*
39, o
§?'
38.0
3V.o
32, o
3 6, o
?>7,S-
3& 0
5-^V
^ T
y&+ o
PH
s.u.
/'I
/;f
/^~
^7
d,7
/3
£>, ?
S.3
/ ^
/. /
/.7
/,y
/.2-
/.o
A 9
o.?
t Exceeds NPDES Permit Limitations
-------
186
Table G~~l (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July 1, 1976
Outfall
QOl
Date
ji/vc 2 y
JQKJG as-
Time of
Collection
&/?
36, o
pH
S.U.
/,y
//o
•*'?
/V
a?
o,$
/- ii
X /
/:•/
/.o
/,J
'•^
°/.s-
/.y
O.7
/,s~
0,7
/.o
t Exceeds NPDES Permit Limitations
-------
187
Table G-l (Continued)
TEMPERATURE AND pH MEASUREMENTS
. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
00 /
Date
vV/l/0
O?//
07/0
//o*
/3/:3-
'w
Temperature
°C
3P, o
33.6
37. o4
32.0
3,7. o
37.0
3Zf
36, o
33*0
3s: o
35To
Yo, o'
33.0
38, o
3.r.S-
3?,3"^
-------
188
Table G-l (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
66/
Date
Jt/fle 2 b
JcJAJf 2?
Time of
Collection
O/2. ?
63 Z/
G5~6$
07/fc
07/f
///z
/3/0
/o/y
/7/o
/93?
3>sys"
2 333
0/32
632.3.
ay&3
/7/0
/?y/
1/23
23*3
Temperature
°C
39"- c*
39. o*
3 ?. a*
37,6
33. o
39. o[
yb, o*"
36xV
3 9. of"
37, of
39, or
37, ot
37,cT
JSxO
'57, ^)
3^5"^ o
$^0, o '
«/o, ot
-------
189
Table G-l (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
OOI
Date
JVAtf 3&
Jf/Ly /
Time of
Collection
CJ3 o
6330
67?>S-
0907
//o£"
/3/3
/7/9
S132-
2/2?
•23*3-
012 9
03 /f
Temperature
°C
37, o
3JT.O
3?. o
37. 0^
33,0
36,0
*%?<>*•
38>°
38,6,
37,0*
35T o
3 6, o
PH
S.U.
//2
/.2-
/J
/,£•
/, 2_
/,3
/J
///
/' /
0.8
L'JL
t Exceeds NPDES Permit Limitations
-------
190
Table G-2
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lf 1976
Outfall
00 H
Date
«Jf«<2 /
1 « «s 9
J«A;eJ
•
Time of
Collection
0730
//so
/i oo
I73c
2/34
23S6
0.3 3 S
Q6'3*>
0750
0925
1/30
/325
/ •6", 7 £>
173o
/73S
2/36
2J34T
0/2S
&33 °
O^/o
II CO
/3*/3
/630
1724
2/30
233$
Temperature
°C
25,0
26, 0
26, o
2*'C
2&S-
2£,6
j£ u?s £}
O & ^t
27,5
23,6
26, o
27-0
27*
•2.8.0
27* 6
26-.S
<^ v / O
rt ^y ^-
27,6
25,0
*22,o
2C,,o
2C, o
28,0
26. 0
2.s',$
2V, 5
PH
S.U.
7,0
6.7
f"f ' ft
\&c 5
(cito
6*9
/6V 2 r
6*3
6/^>
6,2
6r^
7,0
7,2
J«6-f
ft5
6/ CJ~
^*5"
6,g
^/
6r^
(,,O
(ye 2
7,0
6,0
frS" -f
cf/7 -/-
6c/
t Exceeds NPDES Permit Limitations
-------
191
Table G-2 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lf 1976
Outfall
0 0 */
Date
JtVe *y
Ju/oe 5"
JvUC t>
Time of
Collection
0A?;5-
0335
05/0
07y<5
OQVO
1 130
1620
1 725
/9J5
2/26
omo
0330
06fO
o 7*10
O9V0
Il3o
/32o
I62o
1720
/9o*5
2t36
232 f
OlZS
OJA3"
05IO
07 VO
OQ20
11 25
/33S-
1525
mo
21/S
Temperature
°C
29.0
28.5-
2^5
27,0
26,0
26 tO
3o-o
27,0
32,0
3o ,6
%*'?
2
6.9
& 2 +
3° A./ f-
6,0
ffftl
6c3
6r3
6>. 6>
£"£
6r J
6, 3
(s> i (0
(o t &
(ffc i
(0* i
G.fi
t Exceeds NPDES Permit Limitations
-------
192
Table G-2 (Continued)
TMIPERATURE AND pfl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 197G
Outfall
00 H
Date
Jut)? 7
JO NJfr &
Jo u& _
2120
2325
Temperature
°C
25, o
2&.O
26>, O
26.0
2C, 5
27fo
Ztf/a
27,0
26c4
Z7,0
2^0
2C..O
25.5
IS, 5
ZS'O
2%,%
2 <*>, ®
26,o
Z8. o
28* o
29,o
25 o o
25e5-
25.0
26,0
23, 0
££• O
27,0
28rS
27,0
23,0
26' o
27,0
PH
S.U.
6e 7
bo 7
(c,t 7
(otZ
Sr.'ii-
(ot d,
J'8 +
(e<8
for 5
(PC 6
for*/
6,5
fcc '/
G.-1/
(yi O
6*5
Csc 7
r <5
5c^ 1-
(cf 3
6e */
6,8
d>c *"/
fi X^ f.
(01 c)
6>e8
6.*/
6r2
6cv3
G,Z
t Exceeds NPDES Permit Limitations
-------
193
Table G-2 (Continued)
TEMPERATURE AND pU MEASUREfifENTS
W. I. INDUSTRIES, ST. LOUIS, MO.
June 1 -July lt 1976
Outfall
OOH
Date
w nif 1 0
JL' tic. II
«-k/t/c? /^
•
Time of
Collection
ONI
0320
O3/0
0736'
03Zo
1 122
/J2f?
/530
f7,Z0
/
'/£*
',*7/0
Z/29
2J/S
Temperature
°C
2&.o
Z7.0
Z7,o
37.0
Z7.0
28,5
29o 5
2,8'C
25.6
29/0
ZQ.O
Z7.0
28-o
27,5
22,0
2*7° &
Z7-0
Z7-0
3 6,0
•27-5
3S,&
\JY'0
27,0
JK&
28~£
c6
/o c O *
0^5 T"
Z'Q +
& 6 4-
fcc 2
C0 f G
(o* 3
G? c 2
6c2
Goc/
6, 3
6>,8
2.. 6
6- 7
^/. ^ ?
tt** V
6/ 7
^O ^^
t Exceeds NPDES Permit Limitations
-------
194
Table G-2 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
coy
Date
Jc/A'e /J
" /
/e 7 /*
(ec 6
(o, 9
6r 6-
6*8
u>f 2
&>* 7
^/fi
£t,7
7,0
&r*/
6c2
t',3
6*Z
£>* 7
r/V
7o/
6,8
1'J /
(fr &
*/.v -t
6-, 6
6, 7
6,3
6* 7
Ge> v?
Exceeds NPDES Permit Limitations
-------
195
Table G-2 (Continued)
TEMPERATURE AND pfl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
oo y
Date
JcA/e. /&
Jjue /7
Jtl/Jc /?
•
Time of
Collection
O/eo
0325
0507
07/6
O906
//to
/^7
/707
/?33
2/30
2320
0//S
e>3/&
OS//
0&0f
O920
///O
/6f?3
/726~
/"?-3 &
2/0 ff
0//0
0<30ff
0y>S3r
°7\?0
&*?£&
//£&
X \JrV
f&S*&
/& 5? *?"
Temperature
°C
0 , 0
ze< o
Of *C
>u \0t \J
2 7t o
28,0
-30, O
3/,0
28?a
7 r* ^
A /* &
29*6
2#.o
2 <#.a
27e$
27,o
28* 5"
3o i o
£2,&
•30, 0
•J7^7/ 0
20.0
29.0
28, o
25. o
27, f
2&c g
29,0
29. 0
29*5
i;l
PH
S.U.
0,0.
6*$
6,3
6>t<5
7*f
6*9
6^3
'f-r /
7 -t
^y
-------
196
Table G-2 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 2, 1976
Outfall
&0y
Date
Jvve / 9
Jove 2 6
( , , 9;
vjc1 fJ & £ '
Time of
Collection
tf//y
0308
OSo 1
0730
O<3 2&
11/5
/S/O
/ 7/3
it/7
2//3
2320
03/o
O<5 30
Olos
O108
/ f& 8
/3<2 Q
iS/Z
21 \5
232 o
01 25
03 3o
05/5
0705
0^0 7
1106
/3
*3&t o
3o f o
3c>fC>
32«o
2o.o
2. 5, o
28,0-
28r6
2 G>, 0
3 O, O
2S,o
lf',0
30,0
28,0
2'7,#
32r O
2%.o
&7'&
Z7* f
2*7 o
2B.o
26,o
28,6
2CfeO
30,0
27-3
PH
S.U.
Zt2 f
GeO
2e.i +
7r> /
7e 2
7e/
/ '}
(or *-•
6*3
toe 9
f>f P
6, 8
H«o -t-
(~ 3
7, /
fer O
7*2
/eg i
2,2 f
V* i
T o
/C £t
lr,l
2*1 -f-
^ H
2t6 +
lot
(pt Ce
6, 7
^r?
f 3
*/<= 3 +
2*3 l~
«/J
t Exceeds NPDES Permit Limitations
-------
197
Table G-2 (Continued)
TEMPERATURE AND pi! MEASUREMENTS
N, 1. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
oo H
Date
Jc'/ue 22
V/L- Me 2 J
Jc>jue2€>
'Z7,e>
27e O
27r o
2. 7t£i
2SrO
28,0
3o.0
21>O
2<1,0
2.5,0
28,0
26,o
PH
S.U.
" Cy i-
G*,7
&. 7
3,9 +
6>e O
6,8
(ff(* s^
& c /
3,0 f
<£>*<"!
60 /
3, ? -y-
6>c7
(ar /
6<5
2Jn f
6r &
2« 7 +
6e/
2*$- +
3°c6 +
&c3 y-
3^5 f-
Cf-tf 4
<5"- 3 -*•
6", 8
5. «t f
5, 6 +
2r 'V +
2,7 f
6«- 8
?o f/ -f
6«- 0
^^ ^
+ Exceeds NPDES Permit Limitations
-------
198
Table G-2 (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
004
Date
vA>A>c' 2-5
dove 26
Jc'we. 27
•
Time of
Collection
OI20
0315
05OO
0930
H20
/J27
'f?l?G
2/20
23'f
Oizo
0315
OS 00
0732
Ocf2 O
/i/6
/3~2°£
i'72&
/q 2-S
2/2e>
23 f 5
O/2S
O3I5
CJi2& £/
rt *7 ? *•*)
£/ s j£ £•*
0720
///y
/3 22
/&'2 $
/
28^0
28,0
27,0
27,o
?~7,o
27,o
2% 5
27- 0
2-0
1-6,0
25,o
28-0
30 ?0
*S/, 0
^/o 6
•32,0
^c,o
25 <&
PH
S.U.
6/6
6r 7
t'l j
JV7 /
tfV- 7 •*•
'/^ /
ij f
1'fi +
2,6 +
2,2 +
/*7 +
'icO f
2.7 +
\}e 6 -f-
Z t O
£n 4/
/ r7
CPr ^
$« 7
t Exceeds NPDES Permit Limitations
-------
199
Table G-2 (Continued)
TEMPERATURE AND pti MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
Jtme 1 - July 1, 197S
Outfall
ooy
m
Date
J<.>*Je 2.8
Jove 27
duve 3o
•
Time of
Collection
0/20
33/5
072 e
#9 Z-
Z//5
23/3
Of 20
Q$ZO
O$oo
O7/-5
0^2.0
//fo
/ 3 2&
/$23
/?/&
^//^
23/5
Temperature
°C
2o
28*5
<3o, o
•3C.S
33, 0
rt O £
2& 5
2*?! O
33,0
2<3,o
28,0
28,0
28,0
26*5
27.0
*3tf, o
*} g} ^+^
•2.8.0
*3o,o
28,0
28.o
3o,o
28.0
28.0
2.^,0
2>7i&
27fo
28,0
28.0
Zt.O
2.^,0
PH
S.U.
^J +
•5e& +
6*8 +
6.6
V.VJ-
f^a / T
&t. 2
3,0 +
•3^4
2*8 +
20 3 +
& Cj L
£-# O T"
6,1
£. \
G>to
^O j-y
, ft
1.0
G'O
&9
6r 2
2.8 +
6,8 +
-------
200
Table G-2 (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
COH
Date
Jtjfy 1
'
Time of
Collection
0120
0315
0500
Temperature
°C
27.0
26,0
27,0
PH
S.U.
6? < e.
*7 *~> i
O* / ~t
t Exceeds NPDES Permit Limitations
-------
201
Table G-3
TEMPERATURE AND p!I MEASUREMENTS
II. I. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
s.u.
X/C//VC /
JQ/uf 3
/s yo
2 ooo
2/-TO
6 JOS'
nys
JL2 00
-------
202
Table G-3 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 13 1976
Outfall
606
Date
Jwe y
Ji/AtcT £
Time of
Collection
c/SS"
OZVO
OS22
63 6 Q
3 5^ o
PH
S.U.
-------
203
Table G-3 (Continued)
TEMPERATURE AND pH MEASUREt-IENTS
It. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
00(0
Date
Ji/Me &
JCJM£ 7
Time of
Collection
0135-
03' 30
0323'
%?0l
/5V o
/7/0
/9os-
2 // 0
23/0
6/Jt>
03/6
SAT
o?ro
S32 o
'/**?
/9/o
/9S3
23 «7
Temperature
°C
sy.r
25", 0
2*f
25". 0
2 y^'
2 (>,o
Zf.o
2S. o
2S,o
2f,Q
25". o
"X *,b
X 7f^
•J (J /)
IX' o
2 6, o
26.0
2 t,°
PH
S.U.
1.7*
7,3
6,7
/!'!*•
7./
6.8
? £
3.1
9, /
9,3
7/y
7.3f
76 f
/SAf
-------
204
Table G-3 (Continued)
TEMPERATURE AND p!l MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
OQL,
Date
>/i/A/c S
,/ LI ME 9
Time of
Collection
0 II £~
03/2
oyso
o rsy
/oos-
/yof
/ 73$
/ J '3. o
2./C7
3.3*7
o/l o
0*0°
5S
/35"<5
/5^y6
/ ? yi" "
O 7 O ?
^4 / •< x5
Temperature
°C
26.0
23"< °
2 6, 0
25: o
2<$, o
2 (>. o
2.7,0
2£, 0
26,0
36,o
26, o
2<=.b
27.0
2.8.6
2?,*
^1,0
3-7, o
27, 0
33,o
PH
S.U.
&>,$
7.S
7,£
9-0
7.'± ^
/7^
r}, £ ^
79^
95*
• O \
7.X
Z,l
9.9
/iy*
8, 6
?, 7
3-3
r.t
o -^ •
o ^ O
0 * /
t Exceeds NPDES Permit Limitations
-------
205
Table G-3 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
006
Date
Jt/Nt /O
Time of
Collection
0130
CS/'^L
£>Sol>
Oc/3^~
//$/Q
/ 3y &
/^T£"
/?yo
/?•£?
JL /3 0
233o
03.ro
67/0
//yo
/SI
X/27
2330
Temperature
°C
37x0
lS.°o
3. 7-0
az.0
3.3,0
27. S
2.8,0
2 7.$
2?,*
a 7.5-
28,4
2.3, 6
\7°o
a?£
29.0
Z.i.0
27,0
PH
S.U.
I'l
^'o
S.7
f, d
7.3~
7,3-
9//1
t '•*•*.
9, 6
?>3
-------
206
Table G-3 (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 13 1976
Outfall
**
Date
(/i/we* 13.
JQM& /3
Time of
Collection
0332
flSVO
O IS'O
// yd
/3/o
/7VQ
/75"c> 7
CloS*
o 7y^~
//£2.
/35~o
/ s5~0
/ 7SQ
/9A2
2/33
233 0
Temperature
°C
2^, o
2&S-
Hi
27, o
2.7,0
J.%0
3&.0
'3.3.Q
*S,Q
3.3,0
30.o
33., o
J? &* o
23,a
3 o, C
27, o
2,6,0
A 7.o
3O,(}
27, 0
27, o
pH
S.U.
*/
V, o
7.V
72.
?./
7.S-
7,6
6, J"
7i
7V
7 ^
&S
6^6
7 /
6>
'?>*/
7.1
7 /
7,^
7//
7,3
t Exceeds NPDES Permit Limitations
-------
207
Table G-S (Continued)
TEMPERATURE AND ptl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
ObC,
Date
jQtJG /y
juue ,r
Time of
Collection
0/30
Cf//°
o7.ro
//3-S"
/3#f
/7?0
3S-/0
Z330
0/30
033 o
Sf/o
Otis'
//So
ysso
/S35~
/?yo
/930
233J-
Temperature
°C
^.0
%''f
23"'o
29.0
3o. o
3 o, o
fo?o
3 0,0
30,0
29.o
29.0
3.2,0
3.8,o
I9,o
3o.o
3 0,0
30,0
*-? S\ /\
PH
S.U.
7.2.
7,2
6>.6>
6,7
6.8
£-T
22.
7,5-
7,2.
6,7
6,7
6,7
7, y
7.1
8- /
7./
7,6
t Exceeds NPDES Permit Limitations
-------
208
Table G-3 (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUTS, MO.
June 1 - July 1, 1976
Outfall
0*1
Date
Ji/^'b
JquE 17
JUN*C 23
Jowc 28
Time of
Collection
0/00
03^0
0s~/y
o8os~
0737
'sir
/?3f
2/*r
^ 3^--s-
o/yj-
C32S~
OSl o
J4I5
Temperature
°C
2 £, o
55,tf
^7,o
2
-------
209
Table G-4
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Ooi
Date
Jc ue \
Jcue. 2
Juue. 3
Time of
Collection
O8ZS
/\ 0 ^ jf
€J i ^O
HOC
J326
/S/2
'7/3
/1 3 2.
2// 9
2.32V
0/2V
4327
06/3
0
io.o
**'**
%°o
*4*o
*fo •&
•3G.O
y|^
30.0
38°o
PH
S.U.
/•o
Oe3 +
Qoy +
Gt 7
Ot 7
0«
-------
210
Table G-4 (Continued)
TEMPERATURE A^D pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 2 - July 1, 1976
Outfall
ooy
Date
Jt U<3 Ll
Jove. S
vuue (o
Time of
Collection
0127
0320
0720
OV20
I /
133 o
15ZZ
/ 7/6'
(730
Z//7
23Z2
C /3 £>
0 3J5
O 7/0
0 7Z6
/ / 2£>
' '3.Z0
/^%
/*?<30
2/26
2322
°'*/
0^72
0723
0*2*
'/3Z5
'fffs*
%l
Temperature
°C
37co
•3c,. o
•S^'O
38-0
3&.0
46,0
*S/' O
4^ o
3*1,0
*/6iO
•*//* 0
*//• 0
•*z»c
^9°
V6,%>
y/^^j
*/&tO
If.o
37<0
*37<0
*30,a
36,o
3%c
^8?v
*/&,&
W*£>
16,0
<
/*2
1,0
Qr i 1-
°i*2 '
0'3 +
0*6
Co 2 *
O.f
&'<•£
Oo$
Oc 3 4
Oe3 +
0*7
O»7
t Exceeds NPDES Permit Limitations
-------
211
Table G-4 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July lf 1976
Outfall
Date
Time of
Collection
Temperature
°C
pH
S.U.
00*3
8
•Olll
0323
07/5
0920
///O
/3 2.0
/3/6
zj/y
#7? S
2/26
23/0
O//8
0920
2//S
t Exceeds NPDES Permit Limitations
, o
•Slo.O
72*6
*//*$
a 7
7
5
/o Z
0-8
/•
0
li
/,y
A 7
0,7
G'/ *
-------
212
Table G-4'(Continued)
TEMPERATURE AND pit MEASUREMENTS
. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
009
12
A3/0
0923
2//S
23/6
6-302
0-727
// 22
0933
2320
t Exceeds NPDES Permit Limitations
/0* 6
/,0
I' f
Of 7
0*6
-------
213
Table G-4 (Continued)
TEMPERATURE AND pf! MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
CO1?
0306
///y
/62S
0/f-l
0312.
S333
Z3 /o
Oil /
O730
09 2&
2/08
23/6
t Exceeds NPDES Permit Limitations
e)
O
J 8<0
a
fff
-------
214
Table G-4 (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July ly 1976
Outfall
Date I Time of
Collection
Temperature
°C
pH
s.u.
009
/7
O/IZ
03 to
07/6
C<7/7
/S/J
2//G
Z3/2
&//0
OSQO
°73 &
0^/8
2//O
23/0
G723
ft/8
V3.0
/, O
6'
Or
I* 5"
I" I
/* O
Or V
/e>6
/*/
/f O
ted
/•• J
/<> 2
/«• 2
&<•
-------
215
Table G-4 (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
'2C
Jove il
OJ/c
/// 9
S3
Z//0
23/6
0116
07/9
2//e
Z&6
Of 10
07Z6
S32&
S7/7
Z//0
0
V3.0
/*&
o. 8
i\z
/*/
lot
/*/
/o /
/e O
/• 6
1* O
0.7
/^y
/•I
Exceeds NPDES Permit Limitations
-------
216
Table G-4 (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July lf 1976
Outfall
GO*?
Date
Untie 22
JvfjQ 23
JvveZ'/
Time of
Collection
Ot /O
O3/0
6V 36
0726
C
£>*/*&
67/3
/32o
/^?^
/*?/ f)
2.//O
2-3/6
Temperature
°C
46,0
fy3, 0
^6,0
'to' c'j
^3,3
*%°6
%£
%%%
16,6
*/£•&
6
'/£*<)
42,0
35,0
'JOiG
•^S1?' o
*/*/• o
35,0
y3>o
440
^£%>
-Sff'O
ii'°
38,0
^7*0
y?i0
V6.0
PH
S.U.
/c 3
/* V
/^ 2
/•/
/*/
^0
t.O
tag
f*s
tc I
1,1
fa 7
Off/
Oe
-------
217
Table G-4 (Continued)
TEMPERATURE AND pll MEASUREt-fENTS
N. L.' INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
PH
S.U.
J (jftc 27
C//6
03/0
6720
//ZO
2//0
O//G
O3/
2,3
/'o
/'.#
-------
218
Table G-4 (Continued)
TEMPERATURE AND pU MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 2976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
28
O720
J-72O
23/0
&//0
t'3/O
0725
0320
/3Z2,
/7/eT
'23/0
O//0
67/7
23ZZ
V
<*-/£,&
0
46,0
13,0
A V
/,. 6
**2
/-£
f*3
/A
* V-
JcS
/*$
A 7
2.1
h2
0,7
IcS
6,7
t.O
1,0
Id
1*1
t Exceeds NPDES Permit Limitations
-------
219
Table G-4 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
0 0*?
Date
Jjy I
Time of
Collection
O//5~
63/5
Temperature
°C
^6 "/ 0
PH
S.U.
AV
/c 7
t Exceeds NPDES Permit Limitations
-------
220
Table G-5
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 2976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
0030
1350
1625
C3SC,
ofts
/I 27
2327
0733
// ZO
2/3?
Z330
-///<&
0,0 /•
0.7 +
Or S "T
A/
hZ
CSS +
C<,f?-i-
1*3
/oO
0,53 +
O<7 +
0>£ +
4
A-
Of*/ f
Exceeds NPDES Permit Limitations
-------
221
Table G-5 (Continued)
TEMPERATURE AND pU MEASUREMENTS
. L. INDUSTRIES, ST, LOUIS, MO.
June 1 - July lt 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
0730
0925
1/30
23.2?
2./J5
2333
OS/6
0730
2/2
t Exceeds NPDES Permit Limitations
-3s, o
*/£>>&
0»H
/*(
/<*
0,7 /
0* 'y.*~
6*7+
0,6 f
o.e f-
0<8 -f
0"6 •/•
O. 7
-------
222
Table G-5 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
Jufiie
0/23
/32S
2/36
07-30
O730
1730
22*7
2337
0734
SJJ2
t Exceeds NPDES Permit Limitations
?,O
^37*4
38.0
. 0
yz.o
43,0
G*9 +
/c2
0.7 *-
d,-7t-
/,C
c>7
1*7
A V
/, 7
/.&
-------
223
Table G-5 (Continued)
TEMPERATURE AND ptl MEASUREtJENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July I, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
//
Jt
t/US
23J 7
0/39
0J36
0730
073 2
//*?
0320
07W
00/6
38,0
0,8
0& +
0,7 +
f
O. 3 +
0,8 *-
0,8 ^
o.*}
t Exceeds NPDES Permit Limitations
-------
224
Table C-5 (Continued)
TE14PERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
fS"
03'/O
0522
07J?
OW&
Illo
07?/
tr'Z8
/3J8
'72 8
0337
CXTS8
0733
09*30
//Z5
t Exceeds NPDES Permit Limitations
37 4*
-------
225
Table G-5 (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
Jime 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
Jo/we 17
0322
/lie
SS2o
JVJS
2333
OS 2 Z
2338
0337
O5/0
J/23
/'/JS
t Exceeds NPDES Permit Limitations
43.6
6
O
MO
f.O
Co 7
/a 2
tc 2
leO
O'l
0*8-t
/ £ \j
x^ C/ ^
1*5
a-/ y-
O>5 /
(?r^ -f
•/
-------
226
Table G-S (Continued)
TEMPERATURE AND p// MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
0//
Date
Ju/ue /7
Jutfe 2o
June 21
•
Time of
Collection
G/J8
CS23
0730
O323
1 125
1323
IS iq
1730
/931?
2133
2337
0/37
0338
052 o
Q722
Off 2o
H3o
\ -3 u? <-?
1724
W38
2138
2337
Oi*/7
0338
O520
0728
0320
IIZO
1330
1438
2/3 7
2336
Temperature
°C
4^2
W0
<37c$
<3$r °
J6o5"
3^1 O
36. O
3&7 -t
le 3
/c5
Ic5
hi
1*5
7^7
A#
X'7
t Exceeds NPDES Permit Limitations
-------
227
Table G-S (Continued)
TEMPERATURE AND pH MEASUREMENTS
J7. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July 1, 1976
Outfall
0 II
Date
June 22
Jt>N<2 23
Ji>ne 24
•
Time of
Collection
OI3S
0318
0522
0730
OV20
II IG
1328
I62*/
1725
1138
2137
OHH
f)yi^Lf
0520
0725
0923
U25
1330
15 i5
17 25
ItftjO
ZlVO
2338
0/J9
£L? ' yj
O522
07Z0
w
2/33
/) y j/S
£*\3* ^f&
Temperature
°C
3^'O
35.0
H2iO
y/«<9
39,6
V2.o
^A 'v/ f+
AJ^J s*\
IJleO
15.0
tfS'O
tj5<0
H&.o
HSiO
38.0
*jO*O
t/2ef>
*/5,O
tfOiO
3&.O
#3*0
tfH>O
J/6'O
V0.0
w-e
Jf6 .0
ys • 0
ty£. O
*%£>
^/7"0
pH
S.U.
ist
/*3
ho
OoQ f-
Or 7+-
l c 3
O,.8 +
0<.
-------
228
Table G-5 (Continued)
TEMPERATURE AND p!I MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
25
03J&
0725
O723
1123
1323
2/30
2333
0/10
Q320
({23
'l/2-3
2335
QS30
0723
2333
WO
30.0
37*5
', O
0
/-
/**/
lf 2
/.o
O.8 +
/f 7
/.O
A /
O* 7>
Q.8-*
A/
/cO
/,&
1,0
t Exceeds NPDES Permit Limitations
-------
229
Table G-S (Continued)
TEMPERATURE AND pfl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July I, 1976
Outfall
Date
Time of
Collection
Temperature
PH
s.u.
26
Q6ZO
07Z5
/123
Jove 2?
033f
0620
&925
/123
2335
0520
0727
092?
2325
t Exceeds NPDES Permit Limitations
^2.0
46,0
a
hi
/* 7
/•2
L-2
I*/
A-2
O« 7-t
&8 i-
tcl
-------
230
Table G-5 (Continued)
TEMPERATURE AND ptl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 -July 2, 1976
Outfall
0/J
Date
Jv/y /
Time of
Collection
S-iT
as/o
Temperature
°C
*£*
PH
S.U.
tfr 9 A
t Exceeds NPDES Permit Limitations
-------
231
Table G-6
TEMPERATURE AND pfl f>!EASUREt-!ENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
O'J
6325
//60
/fy/
2323
0323
0810
J/3S
2/33
C/36
O9&O
2./30
2330
36. 0
3. C
tf/f 5 -
, 6
O
2f 7
2*')
2,8
2*8
2,8
3*3
3*3
3,7
3,7
6.2
&-2
<$•?
£7
O** ^f
&«6
6*2
3,0
2,8
6,8
6.2
t Exceeds NPDES Permit Limitations
-------
232
Table G-6 (Continued)
TEMPERATURE AND pH MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
PH
S.U.
0/3
C/t/A/C? fi
Jvue t5
2/30
£>73o
S3 2 7
2/25
2328
C/2S
0328
O6Z5
2/26
2323
O
3 2.. 6'
36. o
36', a
27<&
35.O
?,&
36, &
3,7
3.8
C-.6
6.2
6,3
b.Z
&. I
3.8
t Exceeds NPDES Permit Limitations
-------
233
Table G-6 (Continued)
TEMPERATURE AND pfl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
//3d
23 2 a
C/3e
032J
+ Exceeds NPDES Permit Limitations
27,0
27,0
33*0
36,0
35.G
5.8
-------
234
Table G-?
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
2/52
ogoo
2.336
V/V3
03 <&
231*
33,0
•33.0
38,0
, a
48,0
5
t Exceeds NPDES Permit Limitations
6,O
a/5"
*•?
3c2
Ir ( +
J*Z
3.-&
2,8
<$.&
^.o
2*3
-------
235
Table G-7 (Continued)
TEMPERATURE AND pfl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U
<-/
03V3
X5-/7
2003
t Exceeds NPDES Permit Limitations
38-O
,o
o
Vc.o
32,0
3*2
2.6
2.6
OcZ f-
J< 7
/',<-/ +
2*6,
3*2
-------
236
Table G-'f (Continued)
TEMPERATURE AND pi! MEASUREMENTS
N. 1. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
s.u.
e 8
C/37
2332
*w/
08/0
/&/&
2./30
233Z
t Exceeds NPDES Permit Limitations
o
3',C
3, /
/
•3, Z
3*3
2,7
£,•2
He. 6
3,6
j;/
-------
237
Table G-7 (Continued)
TEMPERATURE AND pf! MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
jo
12
0328
05 IS"
6830
loos'
1353
7
02-02
C$30
0827
2/36
Z33
0732
0820
//62
I 735
2336
t Exceeds NPDES Permit Limitations
-37,0
*3,0
G
&<&
Cr< 8
G>f£
-------
238
Table G-7 (Continued)
TEMPERATURE AMD pH MEASUREMENTS
N. 1. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
tie
/5
03Z 7
03/5
6803
232?
£33/
#625
//53
/3V/
#328
OBC8
1000
Z/26
23/7
t Exceeds NPDES Permit Limitations
£2,6
,0
3 7s
3 to
38,6
(o'efa
Cn (o
7.0
&.£>
6.2
£s
6.8
6, f
Cot &
6*2
6/y
-------
239
Table G-7 (Continued)
TEMPERATURE AND pH MEASUREf-IENTS
IT. L. INDUSTRIES, ST. LOUIS, MO.
June I - July lt 1976
Outfall
Date
Time of
Collection
Temperature
PH
S.U.
June
J*A><3 /*?
IQ
0332
03/3
G73-0
Z/27
232?
O33O
Of/2
2/32
2329
0327
OSr-z
0755
//if/
$3.0
53.0
O
38,0
W<0
$0-0
. o
37*5
39,0
•37*5-
37,0
&*o
2*4
6,0
7,0
(a* O
6. 7
5*3
^C" C3
\s * ^7
2,9
&.o
2,S.
t "Exceeds NPDES Permit Limitations
-------
240
Table G-7 (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
o/y
/9
2o
2i
0/27
0321
OS 10
1936
2/20
2329
O/28
O5/3
0742
2/2S
232B
O328
000o
0938
//V5
2/2$
2327
6'3.o
0
?
.0
18,6
*/&'. 0
&r 7
6.G
/Of 6
6,0
J«8
2,8
6,5
t Exceeds NPDES Permit Limitations
-------
241
Table G-7 (Continued)
TEMPERATURE AND pfl MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July lt 1976
Outfall
Date
Time of
Collection
Temperature
PH
S.U.
a/*/
22
X/we 23
Of '2V
//3S
MS
I76'Z
233Z
0/32
0333
W4T
2330
0/30
2/27
Z330
t Exceeds NPDES Permit Limitations
£2,0
3*3,o
52,6
WO
32.0
48,0
£2,0
S/.a
33,6
WO
6.3
6,-Z
3,7
6c3
&,t>
2.7
6,8
2,0
6*6
2,3
3.3
i,8
%2
-------
242
Table G-7 (Continued)
TEMPERATURE AND plf MEASUREMENTS
S. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 2976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
Jt/tfe 27
G/30
#330
2/30
23/7
03/3
/$
-------
243
Table G-7 {Continued)
TEMPERATURE AND pH MEASUREl-fENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June 1 - July 1, 1976
Outfall
Date
Time of
Collection
Temperature
°C
PH
S.U.
28
6328
OS/3
Jo
2333
C328
09V3
2/2$
232$
07SZ
t Exceeds NPDES Permit Limitations
18,0
z/2.0
38,0
2,3
2,6
£/
2*3
6.S
6,7
•' •?
u, £
2.1
^. 7
3,8
2*3
-------
244
Table G-7 (Continued)
TEMPERATURE AND pll MEASUREMENTS
N. L. INDUSTRIES, ST. LOUIS, MO.
June I - July 1, 1976
Outfall
0/*-/
Date
July f
Time of
Collection
out
0523
Temperature
°C
^7^
PH
S.U.
JV2
3,2
t Exceeds NPDES Permit Limitations
-------
245
Appendix H
Comparison of Lithium Chloride and Parshall Flume Flows
Outfall 001
-------
247
Table ll-l
COl-tPARISON OF LITHIUM CHLORIDE AND PAHSHALL FLUME FLOWS
NL INDUSTRIES, INC. 3 ST. LOUIS, MO.
June 1976
Date
1-2
2-3
3-4
Time
O700
0900
1100
I30O
1500
1700
1300
21 OO
25OO
oioo
0300
0500
O70O
1 100
1 300
1 5OO
\70D
l^oo
2100
2300
OICO
O300
0500
0700
1100
1300
1500
1700
1900
2100
2^20
0100
03DO
0500
Pars ha 11 Flume Flow
mgd
1.8(0
1 95
2.05
2.42
I.Sfo
2.14
1.84
U78
1.95
?J05
2.14
1.95
1.95
.8k
.86
. 6fe
T5
2.05
.1 8
.70
2.05
2.05
Z.05
1.95
1.95
2.05
2.05
2/>5
1 &£>
l!-78
2.O5
1.7B
1.93
Lithium Chloride Flow
mgd
1.57
1.17
2.Z4
2.09
2.11
1.67
2.OI
1.44
I.4&
1.19
2.4)7
3.t>3
1.71
2.14
1.88
1.89
2.03
1.9O
2.31
1.90
1.74
2.39
1.99
2.»5
194
2.05
1.97
2.10
2.55
l.fe>&
1 5
-------
248
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PARSHALL FLUME FLOWS
NL INDUSTRIES, INC., ST. LOUIS, MO.
June 1976
Date
4-5
5-6
6-7
Time
O700
090O
1100
1300
1500
1700
1200
2100
2300
OIOO
0300
O700
1 100
1 300
\700
1200
2100
2300
OIOO
O300
0500
0700
O900
1100
1300
1500
1700
l^OO
2100
2500
OIOO
03DO
0500
Pars hall Flume Flow
mgd
2.05
2.01
2.02
2.05
1.93
2.0Z
1.76
l.feO
\.9S
\.b9
\.t>9
2.05
2.05
Z.13
2A-^J
IQfc,
1.78
2.05
1.95
l.8o
1.93
1 fi4
1. O*T
U78
1.76
\.&b
\.95
1.75
\.~15
1.84
2.05
2.33
1.95
Lithium Chloride Flow
mgd
?.5ft
l.5fo
2.09
1.82
\.es
2.0T
\.(o2>
1.53
1.92
l.34>
1.64
I.Ob
1.01
1.08
1.38
LIZ
O.9I
0.90
O.VC0
fl Qft
1.03
2.02
\.9Z
1.95
2.34
l.feS
1-77
1.89
2.31
2.94
2.ft7
2.12
-------
249
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PARSHALL FLUME FLOWS
NL INDUSTRIES, INC., ST. LOUIS, HO.
June 1976
Date
-7-8
8-9
9-10
Time
0700
09OO
1100
1300
1500
1700
1500
2IOO
2300
OIOO
0300
0500
O700
o^oo
1 IOO
1 300
1500
noo
1500
2100
2300
OIOO
0300
0500
0700
O20Q
1100
1500
1500
1700
1900
2100
2500
OIOO
0300
0500
Parshall Flume Flow
mgd
iet>
2.05
2.11
Z.U
I.Bfe
2.11
1.84
f.04
2.33
—
™*
2.05
2.52
f.93
I.8t>
7.14
£05
2.05
2.H
l.0b
1 86
2.14
l.fcb
2 14
1.95
1.78
\.Bh
2.14
1.78
l.fcfe
l.ftfe>
2.23
l.feO
l.^fe>
Lithium Chloride Flow
mgd
1.3$
1.97
2.3O
1.93
2.54
1.03
2.36
2.4^
l(c>9
•" IMr ^
I.7S
Z.62
2."71
I.9Z
• • ^ *•
2.0O
2.34
2.15
2.71
2.91
1.70
2.04
2.15
1.74
1.4b
1.92
181
1. (03
1.1^8
1.52
l.(e»Z
2.3ft
Z.29
1.2^
1.45
-------
250
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PAPSHALL FLUME FLOWS
NL INDUSTRIES, INC., ST. LOUIS, MO.
June 1976
Date Time Parshall Flume Flow
mgd
10-11 0700
O9OO
1100
1300
1 500
1700
1200
2100
2300
O\OD
(9300
0QOO
IH2 O700
O9OO
l 100
1300
1500
noo
l9oo
2100
2300
oioo
0300
0500
12- ft 0700
O900
1 100
1500
I50D
1700
1900
2100
2500
0100
03DO
0500
2.20
Z "39
2.32
1.95
1 &fe
1.95
1.93
1.78
1.84
2.05
2.11
l.5>5
1.95
2.14
7. OS
1.84
1.75
1.8k
1.95
2.05
I.fe9
2.14
1.95
2.05
2.05
2.11
2.11
2J05
1.53
t.93
l.bO
L78
l.(j>9
1.93
1.55
Lithium Chloride Flow
mgd
2.44
2.foO
2.IZ
2.08
2.30
1.94
1.89
1.92
2.32
2.05)
2.48
2.12
2.05
2.01
U>l
1 "73
•• • ^
2.1&
2.01
1.98
2.0}
2.05
2.5*
2.64
2.05
2.68
2.11
••• • •
1.74
1.60
1.74
nt
1.84
2.59
1.15
1.05
-------
251
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PARSMLL FLUME FLOWS
NL INDUSTRIESt INC., ST. LOUIS, HO.
June 1976
Date
13-14
W-15
15-lfe
Time
O700
09OO
UOO
1300
1500
1700
1300
2100
2300
0IOD
03OO
05OO
O700
O90O
1 100
1300
1500
noo
|$oo
2100
2300
CM DO
0300
0600
0700
O900
1 100
1300
1500
1700
1900
2100
2500
0100
03DD
0500
Parshall Flume Flow
mgd
1.84
Ml
2.05
1.95
1.95
1.6t>
1.78
2.05
2.14
2.02
Z.05
2.H
2.49
239*
•* • ••^
213
^»*»^
2.05
2.11
2.23
2.14
2.52
239
2.Z3
2/5Z
2.14
2.33
2.59
z.u
2.05
2.39
\(o9
i.\\
—
l.64>
2.6?2.
Lithium Chloride Flow
mgd
2.11
•f • •
2.41
2.60
1.15
Z36
2.73
Z.07
2.01
2.97
3. SO
2.U7
2.55
7.15
23?
2.77
2.38
2.11
2.40
2.42
2.33
2.37
2.90
Z.4J
1.97
242,
*•• »^fc»
1.99
2.75
?!2O
2.12
-»
Z.IA
2.9ft
-------
252
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AW PARSHALL FLUt-JE FLOWS
NL INDUSTRIES, INC., ST. LOUIS, MO.
June 1976
Date
ife-n
n-ia
\B-19
Time
O70O
09OO
MOO
1300
1500
1700
1500
21 CD
2300
OIOO
0300
0500
O700
O900
) IOO
1 300
1500
HOD
l9oo
2100
2500
OIOO
0300
0500
07OO
O900
1100
1300
1500
noo
»90o
2100
2300
OIOO
03W>
0500
Parshall Flume Flow
mgd
2.11
2.33
2.4Z
2.Z9
2.14.
2.42,
233
Z.Z3
Z.42
2.62
2.Z3
2.42
2.20
2.29
2.20
2.49
2.49
2.fe2
2.52
2.73
2.73
2.fo2
2.52
2.4Z
2.39
3.10
2.6>2
2.52
2'.6>2
2.42
2.S2
2.23
2.42
2.52
Lithium Chloride Flow
mgd
2,89
^4 *r ^^
1.95
3.74
2.30
2.H
Z.Z6
2.03
2.12
6.08
0.10
2.^8
2.6)8
2.Z9
Z eo
•K • »^^™^
I.9S
1.91
2.17
2,54
2.54
1.93
2.48
2.2^
1 Bl
• • *^»
3.35
2.4b
2.Z7
2.4b
2.03
^ • ^F
I.9O
2.19
2*o^
2.09
-------
253
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PARSUALL FLUME FLOWS
ML INDUSTRIES, INC., ST. LOUISA MO.
June 1976
Date
19-20
2o-zi
21-21
Time
O7OO
09OO
1100
I30O
1500
1700
1500
2100
2300
01 DO
0300
0500
O700
o^oo
1 100
1300
\ 50O
noo
1900
2100
2300
oioo
O300
0500
0700
O9OO
1 100
1300
I50D
noo
1500
2100
2300
OIOO
0300
0500
Parshall Flume Flow
mgd
2.fe9
2.93
2 to2
2.42
2.33
2.52
2.t>2
2.S2.
2.6Z
2.23
233
2.SZ
2.faZ
2.^2
2.b2
7.42.
2.39
2.82.
2.52
2.33
2.(e>2.
2.62
2.33
2.49
2 ^2
2.62
273
2.79
2.52
2.^2
2.73
Z.fr2
2.49
•—
Lithium Chloride Flow
mgd
3.43
3.01
2.09
1.98
1.97
2.05
2.01
3.00
3.57
2.09
2.11
2.0&
2.98
4.07
2.89
3.SZ
4.00
4.07
4A3
Zlb
6.32,
3.3b
4.23
5.25
2.02
I 91
• 9f •
1.77
2.5/
2.^3
2.O3
1.53
2.49
l.9d
I.Co3
2.Z&
-------
254
Table H-l- (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PARSIIALL FLUME FLOVS
NL INDUSTRIES, INC., ST. LOUIS, MO.
June 1976
Date
22-25
23-24
24-25
Time
0700
09OO
1100
I30O
1500
I70O
1200
2100
2300
OIOO
0300
05OO
O700
0500
I 100
1 300
1500
noo
1500
2100
2300
OIOO
O300
0500
0700
O900
1100
1300
J50D
noo
1900
2100
2300
OIOO
03 DO
0500
Parshall Flume Flow
mgd
2.C02
2.52
2.52
2.73
2.73
2.73
2.52
259
2.19
2.42
2.79
2.6>2
2,93
2.52
2.73
2,62
2.62
2.42
2.42
2.33
2.42
2.42
2.52
2fe2
2.59
229
*'*i
2.52
2.20
233
2.39
2.20
2.20
2.14
2.14
2.39
Lithium Chloride Flow
mgd
2.61
2.04
2.22.
2.14
2.63
2.10
3.10
2.21
2.4$
1.94
3.04
2.2to
3.41
2.2(*
229
2ft
272
3.30
2.53
2.12
I.4P
2.2to
2.b9
2.2t>
3.17
2.27
2.10
2.49
2.74
2.27
2.05
1.19
1.77
1.53
1.53
\.7fc
-------
255
Table H-l (Continued)
COMPARISON OF LITHIUM CHLORIDE AND PARSHALL FLW1E FLOWS
NL INDUSTRIES, INC., ST. LOUIS, MO.
June 1976
Date
25-26
2fc-27
27-28
Time
0700
09OO
1100
1300
1500
1700
1200
21 OO
2300
OlOO
0300
0500
O700
O^oo
I too
1 300
l^oo
noo
1900
2IO&
2300
OIOO
O300
osoo
0700
O900
1100
1300
1500
noo
1500
2100
2500
OIOO
03PO
0500
Parshall Flume Flow
mgd
3.00
2.20
2.14
2.49
2.29
2.29
2.33
2.29
2 loL
2.33
2.14
2.23
2.20
2.45
2.14
2.14
2.11
2.39
273
Z&2
2.19
2.11
til
262
2.3?
2.20
2.20
2.29
2.29
2.20
259
*»• ^^
2.20
2.33
2.52
Z.fl
Lithium Chloride Flow
mgd
2.93
1.7k
l.4fe
I.&5
1.44
1.8O
1.89
2.0Z
2 (to
1.73
1.58
1.12.
2-?I
1.12
1.43
l.7ft
l.&>0
7.07
2.50
2.4>l
3.2b
I. foo
1.51
1.60
2.57
1.92
1.83
1.84
£02
2.5b
1.78
1.84
2.23
I* iO^V
-------
256
Table H-l (Continued)
C014PARISON OF LITHIUM CHLORIDE AND PARSHALL FLUF4E FLOWS
NL INDUSTRIES, INC.,, ST. LOUIS, MO.
June 1976
Date
28-Z9
29-30
2H*
Time
O7CO
O9OO
HOC
1300
1500
1700
I530O
21 OO
2300
OIOO
0300
05OO
O700
O?oo
I 100
1 300
1500
noo
1900
2100
2300
01 OO
OcJOO
0500
0700
O9DO
I I 00
1300
1500
nco
1900
2100
2300
OIOO
03CO
0500
Pars hall Flume Flow
mgd
2.59
Z29
2.33
2.42
2.39
2.39
2.20
2.29
2.11
2.49
2.19
2.4*9
2&2
ioo
219
2.35
2.23
2.11
2.49
2.20
2.14
2.20
2.52
2.49
2.14
2.33
2.33
2.49
2.39
2.02
2.29
2.20
2.23
2.33
2.23
2.02
Lithium Chloride Flow
mgd
2.53
I.&4
2.O(o
2.15
2.4»3
l.bl
1.B2
I.Wp
I.fc3
2.23
2.07
332
2.95
1.94-
Z.03
2.49
2.\l
lib
2.4&
2.13
1.90
I.&2
2.19
1.77
».fc2
2 fe>fe»
2.70
2.40
2.2b
l.9b
2.04
2.05
2.00
2.52
l.fcfc
1.5S
-------
257
Appendix I
Bioassay Test Procedures
-------
259
BIOASSAY TEST PROCEDURES
Detailed descriptions of the static and continuous-flow bioassay
procedures are presented in Methods for Acute Toxicity Tests with Fish,
Macroinvertebrates, and Amphibians8 and Standard Methods for the Exam-
ination of Water and Wastewater.9
The test fish were young-of-the-year channel catfish about 9 cm
(3 1/2 inch) in total length and approximately 5 gm in wet weight. The
fish were obtained from two sources: the Tishomingo National Fish
Hatchery, Tishomingo, Oklahoma; and the Cedar Bluff National Fish
Hatchery, Ellis, Kansas. Fish from each hatchery were acclimated to
dilution water in separate compartments of an acclimation tank, for two
days prior to testing. During this time the fish showed no stress and
the mortality observed was less than 5%.
Dilution water was obtained from the Missouri shoreline of the
Mississippi River north of the central St. Louis area, upstream from NL
Industries discharges [Fig. 1-1]. This water supported test fish as
evidenced by their survival in the acclimation tank during acclimation
and in the control chambers during the bioassays [text Tables 16-18].
Chemical characteristics of this water are presented in Tables 16-18.
Static Bioassays
Range-finding static bioassays were performed in the mobile
laboratory and in a locked room in the main building at the LeMay Sewage
Treatment Plant [Fig. 1-1],
-------
260
HUMBOLDT BOAT DOCKS
(Site of Dilution Water
for B io ass ay s)
ST LOUIS, MISSOURI
LeMay WWTP
(Lo cation of
Mobile Lab)
NATIONAL LEAD
INDUSTRIES
MILES
Figure 1-1. Location Map, BSoassay Survey
NL Industries
St. Louis, Missouri, June 1976
-------
261
In the first series of rangefinding tests, three fish each were
placed into effluent concentrations of 100, 50, 10, 5, 1, 0.5 and 0.1%
for 24 hours. Tests indicated that wastewater concentrations of less
than 1% were toxic to channel catfish. To refine the toxicity range, a
second series of static bioassays was conducted. Duplicate concen-
trations of 1, 0.56, 0.32, 0.18 and 0.10% were made up for each effluent
in individual 37.5-liter (10-gal.) glass aquaria using a 24-hour composited
effluent sample and dilution water from the Humboldt boat dock. Total
volume of solution in each aquarium was 36 liters. Ten fish were
introduced into each of the test solutions and 96-hour static bioassays
were performed. Fish survival was monitored closely after the start of
the test and at 24-hour intervals thereafter. Results indicated that
continuous-flow bioassay ranges should be 0.07 to 0.75% for outfall 001,
0.2 to 2.0 for 009 and 0.15 to 1.5 for Oil.
Continuous-flow Bioassays
Continuous-flow bioassays were conducted to provide specific
toxicity information. The type of flow-through system used is a
modification of the Mount proportional diluter.10 Two diluter systems
are housed in the mobile laboratory. Each consists of 6 replicate
testing chambers and replicate control chambers. Effluents supplied to
the two systems were retained in separate 562-liter (150-gal.) stainless
steel tanks mounted in the mobile laboratory. Dilution water was
contained in two 937-liter (240-gal.) plastic lined wooden tanks. The
test chambers were glass aquaria holding 8.5 liters of test solution.
Fresh solutions were gravity fed to the top of each aquarium from the
diluters, and older solution was discharged through a "U" tube located
near the bottom of the aquarium. The average turnover rate of test
solutions in each chamber for the three continuous-flow bioassays was
4.9 per day.
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262
From June 12 to 16, 1976, a continuous-flow bioassay was conducted
using a 24-hour composited sample from outfall 001. Wastewater concentrations
ranged from 0.075 to 0.75%. From June 20 to 24, 1976, continuous-flow
bioassays were conducted on 24-hour effluent composites from 009 and Oil
outfalls. For the 009 bioassay, concentrations ranged from 0.2 to 2.0%
while for the Oil bioassay concentrations ranged from 0.15 to 1.555.
Daily throughout these continuous-flow bioassays, fish survival was
monitored. New solutions of effluents were made up periodically in both
holding tanks using the original 24-hour composited samples which had
been refrigerated.
Ninety-six-hour LC50's for the three bioassays were computed from
straight-line graphical interpolation of the survival data.
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RECOMMENDATIONS
NL INDUSTRIES, INC.
ST. LOUIS, MISSOURI
1. Until the proposed treatment facility is operational, it is
recommended that the NPDES permit interim limitations be modified
as follows to reflect the actual discharge conditions:
Outfall pH Temperature
No. °F
001
002
005,
003
004
006
008
009
010,
on
013
014
015,
018,
017,
021,
0.2-9.0
007 4.5-9.0
5.0-12.5
1.0-10.0
6.0-12.0
0.2-13.0
0.1-9.0
012 1.5-9.0
0.1-9.0
Non-contact cool
shall not exceed
2.0-9.0
016 4.5-12.5
019 4.5-12.5
020 6.0-12.5
022 6.0-12.5
113
NAf
NA
NA
NA
110
145
120
145
TSS Iron Titanium
Ib/day
17,000-20,000 63,100
NA NA
1 ,000 mg/1 NA
15,000t+ 3,600tft
55, 000-60, 000+t NA
NA - NA
15,000-18,000 80,000
NA NA
15,000-18,000 80,000
15,000
NA
NA
NA
NA
NA
15,000
NA
5,000
ing water only. Discharge concentrations
intake concentrations.
160 8,500+t NA 4,000+t
NA
NA
210
210
NA NA
NA NA
NA NA
NA NA
NA
NA
NA
NA
t Not applicable
tt Net load
ttt QIT slag only
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In addition, it is recommended that flow-weighted composite samples
be collected at least weekly for process outfalls 001, 004, 009,
Oil, and 014, to determine compliance with permit conditions.
2. NL Industries be required to modify their flow measuring techniques
to provide representative flow data for all process outfalls.
3. Solids removed in intake water treatment be disposed of properly,
according to the NPDES permit requirement, and not be discharged
into the Mississippi River.
4. NL Industries comply with the interim permit pH monitoring re-
quirements for outfalls 001, 008, 009, 010, Oil, 012, 013, 017,
020, 021 and 022.
5. The monitoring location for outfall 001 be changed from the present
NPDES designated site at the Parshall flume to the wet well,
approximately 30 m (100 ft) downsewer of the flume.
6. NL Industries treat only process wastewaters in the waste neutral-
ization facility. All non-process wastewaters should be monitored
and discharged directly to the river (except wastewaters generated
in the treatment of the intake water).
7. The NPDES permit limitations include a provision that compliance
with the daily average limitation can be determined by a minimum of
four samples collected and analyzed during any calendar month, for
all process outfalls.
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