United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
Research ana Development
Analysis of Priority
Pollutants at a
Primary Aluminum
Production Facility
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further deveJopment and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8, "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-79-087
April 1979
ANALYSIS OF PRIORITY POLLUTANTS AT
A PRIMARY ALUMINUM PRODUCTION FACILITY
by
9
G. D. Rawllngs and T. J. Hoogheem
Monsanto Research Corporation
Dayton, Ohio 45U07
Contract Mb. 68-03-2550
Project Officer
A. B. Craig, Jr.
Metals and Inorganic Chemicals Branch
Industrial Environmental Research, Laboratory - Cincinnati
U. S. Environmental Protection Agency
Cincinnati, Ohio 4 5268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 1*5268
-------
DISCLAIMER
This report has been reviewed by the Industrial Environmental
Research Laboratory-Cincinnati, U.S. Environmental Protection
Agency, and approved for publication. Approval does not signify
that the contents necessarily reflect the views and policies of
the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use. «
ii
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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our
environment and even on our health often require that new and
increasingly more efficient pollution control methods be used.
The Industrial Environmental Research Laboratory - Cincinnati
(lERL-Ci) assists in developing and demonstrating new and
improved methodologies that will meet these needs both efficiently
and economically.
This report evaluates the removal efficiency of the 129 priority
pollutants due to existing wastewater treatment technology at a
single Soderberg-type primary aluminum plant. A brief process
description and a detailed description of sampling, analytical,
quality assurance, and treatment plant assessment are presented.
Results of the investigation will enable EPA to identify which
priority pollutants are being emitted by industry and to determine
the ability of wastewater treatment technologies to remove
priority pollutants. Questions or comments regarding this report
should be addressed to the Metals and Inorganic Chemical Branch
of the Industrial Environmental Research Laboratory in Cincinnati.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii
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ABSTRACT
As a result of the 1976 consent decree resulting from the
National Resources Defense Council et al., v Train suit, EPA is
obligated to identify which of the 129 priority pollutants are
present in industrial wastewaters and to determine the ability
of various wastewater treatment technologies to remove these
priority pollutants. This project investigated the source of
priority pollutants, assessment of the wastewater treatment
plant, and priority pollutant removal efficiency for a single
Soderberg-type primary aluminum plant.
Forty-eight hour composite samples were collected from the
following streams: 1) plant intake water; 2) wastewater from
the primary air pollution control system (gas stream cooling
water and wet EPS's); 3) secondary air pollution control system
(room ventilation wet scrubber liquor); 4) paste plant briquette
cooling water; and 5) final effluent after the wastewater
treatment plant.
Wastewater from the primary air pollution control system entered
a conventional chemical coagulation (using slaked lime)-
clarification plant. Clarified water from the clarifier was
combined with the other three wastewater streams and flowed into
a settling lagoon with a 20-hr hydraulic retention time.
Clarified lagoon water was finally discharged to the river.
The principal source of organic compounds in the wastewater was
from the primary and secondary air pollution control systems and
results from the volatilization of petroleum coke and pitch in
the Soderberg anode. Wastewater treatment plant removal
efficiencies of greater than 85% were achieved for the majority
of the organic priority pollutant species detected.
IV
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.CONTENTS
Page
Foreword ill
Abstract iv
Figures vi
Tables vii
1. Introduction 1
2. Summary 2
3. Source Description 6
Process Description 6
Wastewater Treatment Plant 10
4. Sampling and Analysis Protocol 12
Sampling Procedure 12
Analytical Procedures 15
5. Results and Conclusion 21
Analytical Results 21
Wastewater Treatment Plant Performance 23
References 27
Appendices
A. Recommended List of Priority Pollutants 28
B. Priority Pollutant Analysis Fractions 34
Conversion Factors and Metric Prefixes 37
v
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FIGURES
Number Page
1 Schematic drawing of a vertical stud Soderberg
aluminum reduction cell 7
2 Primary air pollution control system 9
3 Wastewater treatment plant 11
4 MRC bottle label for sample identification. ... 14
5 Analytical scheme for volatile organics analysis. 17
6 Sample processing scheme for nonvolatile organics
analysis 19
VI
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TABLES
Number Page
1 Treatment Plant Removal Efficiencies for
Priority Pollutants 4
2 Sampling Logistics for Priority Pollutants. ... 13
3 Analysis of Organic Priority Pollutants and
Cyanide 22
4 Metals Concentrations in Water and Wastewater
Streams Analyzed by Atomic Absorption Method. . 23
5 Mass Flow Rates and Treatment Plant Removal
Efficiencies for Metals 24
6 Treatment Plant Removal Efficiencies for Priority
Pollutants 25
vii
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SECTION 1
INTRODUCTION
On 7 June 1976 the U.S. District Court of Washington, D.C.,
issued a consent decree (resulting from Natural Resources Defense
Council et al., v Train) requiring EPA to enhance development of
effluent standards for 21 industrial point sources, including
nonferrous metals manufacturing. Among other requirements, the
court mandate focused federal water pollution control efforts on
potentially toxic and hazardous chemical compounds. As a result,
a list of 129 surrogate chemicals, known as priority pollutants,
was established. The consent decree obligates EPA to identify
which priority pollutants are present in industrial wastewaters
and to determine the ability of various wastewater treatment
technologies to remove priority pollutants.
Therefore, the objective of this project was to provide accurate
data on the concentration of the 129 priority pollutants in
wastewater samples collected from a single primary aluminum
plant equipped with a well designed wastewater treatment plant.
In addition, the removal efficiency for priority pollutants wa$
evaluated.
This report provides a brief process description and a detailed
description of the sampling, analytical, and quality assurance
procedures employed. Analytical results and evaluation of the
treatment plant are then presented.
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SECTION 2
SUMMARY
The purpose of this project was to provide accurate data on the
concentration of the 129 priority pollutants in intake water and
wastewater samples collected from a single primary aluminum plant
equipped with an examplary wastewater treatment plant. Data were
then used to evaluate treatment plant removal efficiencies for
priority pollutants.
Fortyeight hour composite samples were collected from the follow-
ing streams: (1) plant intake water; (2) wastewater from primary
air pollution control system (gas stream cooling water and wet
ESP's); (3) secondary air pollution control system (room ventila-
tion wet scrubber liquor); (4) paste plant briquette cooling
water; and (5) final effluent. The sample collection technique
followed that recommended by EPA for priority pollutant analysis,
with a few modifications designed to better insure sample integ-
rity, chain of custody, and to address site specific requirements.
Because of the way the wastewater treatment plant was constructed,
a grab sampling technique was used instead of using automatic
samplers. A sample was collected from each stream every hour for
48-hr using a Teflon -lined, 3-gal stainless steel bucket.
Aliquots were removed from the bucket with glass beakers and
placed in appropriate sample containers. By maintaining the
proper preservatives, this technique allowed field composite
samples for total cyanide and total phenol instead of a single
grab sample as EPA recommended. Sample containers were labeled,
sealed, packed in ice, and airfreighted to MRC for analysis.
The priority pollutant analysis scheme divides the compounds into
eight fractions for analysis: volatile organics, base/neutral
organics, acid organics, pesticides and PCB's, metals, cyanide
(total), phenol (total), and asbestos.
It is important to realize that some of the organic priority
pollutant analysis procedures are still under development and
require further verification and validation. Therefore the data
presented for organic species serve to identify which of the 129
pollutants were present and to indicate the general concentration
ranges within a factor of two.
-------
Two chemical species were not analyzed in this project: 2,3,7,8-
tetrachlorodibenzo-p-dioxin (TCDD) as recommended by EPA because
of the hazard involved in preparing laboratory standard solu-
tions; and asbestos. However, samples for potential future
asbestos analysis were collected, preserved, and stored at 4°C.
Since there are no sources of pesticides in aluminum production,
the pesticide analysis fraction was also eliminated.
A summary of the analytical results is presented in Table 1.
Only those organic compounds detected in the samples are pre-
sented in the table. Values in Table 1 are reported in mass
flow rate units (g/day) to eliminate apparent dilution effects
when reporting values in stream concentration units. Mass flow
rate was determined by multiplying species concentration by the
appropriate stream flow rate.
From the mass flow rate data, the removal efficiency for priority
pollutants by the wastewater treatment plant were calculated.
This value was calculated by subtracting the sum of the values
in columns two through four from the value in column five and
dividing the difference by the sum of columns two through four.
The wastewater treatment plant was a conventional chemical coag-
ulation-clarification plant. Slaked lime (CaO) was added to
the wastewater stream from the primary air pollution control
system. This stream then went to a 1.09 x 106 £ clarifier with a
hydraulic retention time of two hours. Sludge was sent to
sludge holding lagoons which had no resulting wastewater dis-
charged. Clarified water from the clarifier was combined with
the other wastewater streams and flowed to a settling lagoon
with a 20-hr hydraulic retention time. Clarified water from
the lagoon was finally discharged to the river.
The principal source of organic compounds in the wastewater
was from the volatilization of petroleum coke and pitch in the
Soderberg anode. These oil and tar vapors were subsequently
collected in the primary and secondary air pollution control
equipment. Wastewater resulting from gas stream cooling, wet
ESP's, and wet scrubber liquor was discharged to the treatment
plant.
Based on the values in Table 1, removal efficiencies of greater
than 85% were achieved for the majority of the organic priority
pollutant species detected. Organic species with lower removal
efficiencies included bis(2-ethyl hexyDphthalate, acenaphthene,
pyrene, fluoranthene, and total phenol.
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TABLE 1. TREATMENT PLANT REMOVAL EFFICIENCIES FOR PRIORITY POLLUTANTS
Mass flow rate in stream, g/day
Primary pollutant
Bis(2-ethyl hexyl) phthalate
Naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Pyrene
Fluoranthene
Chxysene
Benzo (a) anthracene
Benzo (b) f luoranthene
Benzo (k) Fluoranthene
Benzo (a) pyrene
Dibenzo ( a , h) anthracene
Indeno ( 1 , 2 , 3 -cd ) pyrene
Benzo (1,2, 3-cd) perylene
Phenol
Methylene chloride
Toluene
Benzene
Phenol (total)
Antimony (total)
Copper (total)
Nickel (total)
Zinc (total)
Intake
water
1,470
_b
_
_
_
-
30
70
70
-
150
-
220
150
-
-
-
—
150
150
-
290
2,200
400 ± 50
590 ± 100
2,100 ± 150
Primary Secondary
control system control system
65
260
650
50
650
230
1,960
2,870
4,170
3,000
2,350
3,390
2,740
7,440
1,430
4,570
1,960
910
100
40
80
3,590
5,800
400
14,700 ± 1,100
1,500
1,560
_
40
_
_
-
.520
2,590
5,700
1,560
2,070
-
—
2,070
—
100
100
—
-
-
-
8,190
2,600
1,100
<260
2,400
Paste Final
plant discharge effluent
30
-
3
-
3
15
15
70
80
80
80
-
110
100
-
20
20
—
10
5
-
170
50
14 ± 1
<8
60
670
-
670
470
70
-
200
2,660
5,330
600
530
-
470
670
-
70
70
—
-
-
-
7,730
2,700
600 ± 90
330
2,300 ± 130
Percent
removal
32
100
3
_c
89
100
91
52
46
87
88
100
84
93
100
99
97
100
100
100
100
37
68
60 ± 3
98 ± 2
42 + 2
aValue calculated by subtracting the sum of columns 2 through 4 from the value in column 5 and dividing the
difference by the sum of columns 2 through 4 and converting into percent.
Blanks indicate species not present in stream sample.
CNondeterminable—value in effluent greater than sum of input values.
-------
Of the thirteen priority pollutant metals only four were detected
above instrument detection limits: antimony, copper, nickel, and
zinc. Removal efficiency data indicated the treatment plant was
very effective at removing nickel and moderately effective at
removing antimony, copper, and zinc.
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SECTION 3
SOURCE DESCRIPTION
PROCESS DESCRIPTION
Large scale, economic production of primary aluminum became
possible when, in 1886, Charles Martin Hall and Paul Heroult
independently invented the electrolytic process. The Hall-
Heroult process has remained essentially unchanged since its
inception, except for equipment design modifications and
improvements in operating practice, and is employed in all com-
mercial United States production of primary aluminum (1).
In general, the process involves passing a continuous current
through an electrolytic cell containing alumina (A1203) dis-
solved in molten cryolite (AlFa'SNaF) which is maintained at
940°C to 980°C (2). As electrolysis proceeds, aluminum settles
to the bottom of the cell at the cathode and is periodically
tapped and drained.
Oxygen is evolved at the carbon anode at the top of the cell and
reacts with the carbon to produce a mixture of carbon monoxide
(CO) and carbon dioxide (CO2), thus consuming the carbon anode.
Primary aluminum plants in the United States are classified by
the method used to replace carbon anodes. The two methods are
referred to as the prebaked anode (intermittent replacement)
and the Soderberg anode (continuous replacement). The plant
sampled in this study used the Soderberg anode type cells with
vertical anode studs for carrying current (Figure 1). This
type of plant is referred to as a vertical stud Soderberg
design.
(1) Thompson, G. S., Jr. Development Document for Effluent
Limitations Guidelines and New Source Performance Standards
for the Primary Aluminum Smelting Subcategory of the Aluminum
Segment of the Nonferrous Metals Manufacturing, Point Source
Category. EPA-440/l-74-019d (PB 240 859), U.S. Environmental
Protection Agency, Washington, D. C., March 1974. 142 pp.
(2) Kirk-Othmer Encyclopedia of Chemical Technology, Volume I.
John Wiley and Sons, Inc., New York, New York, 1963.
pp. 931-944.
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ANODE STUDS
CARBON ANODE
SKIRT
EXPOSED
CELL SURFACE
MOLTEN CRYOLITE
MOLTEN ALUMINUM
PRIMARY
CONTROL SYSTEM
BURNER
GAS AND TAR BURNING
ALUMINA
Figure 1. Schematic drawing of a vertical stud Soderberg aluminum reduction cell (1)
-------
For the plant sampled, anode preparation began in the anode paste
plant, where petroleum coke and solid pitch were hot blended.
The anode paste was then formed into briquettes. Hot briquettes
are then dropped into a trough of water for cooling. Briquette
cooling water was discharged to the wastewater treatment plant
at a flow rate of 13 £/s to 19 £/s (200 to 300 gpm) and neutral
pH.
For the Soderberg anode design, briquettes were fed batchwise
into the top of the carbon anode. As the briquettes settled and
approached the hot bath, the paste was baked in place to form
the anode. Tars and oils characteristic of anode baking were
evolved as a fume at the cell.
The plant sampled contained 300 electrolytic cells, or pots,
electrically connected in series to form two potlines arranged
in two and one-half potrooms, with two potlines per room.
Continuous evolution of gaseous reaction products from each
aluminum-reduction pot results in a large volume of fume which
consists of CO, CC>2 / volatile fluoride compounds, fine dust
consisting of cryolite, aluminum fluoride, alumina, and carbo-
naceous material and organic compounds from the coke and pitch
used to make anode briquettes. These air emissions were con-
trolled, as shown in Figure 1, by installing a skirt around
the edge of the anode, at the interface between molten electro-
lyte and Soderberg anode, Figure 2. A gas burner was designed
in the vent line to burn organic vapors before venting to the
primary air pollution control device. Spray chambers were
installed between the fan and control device to lower the gas
temperature (90°C to 150°C) to 27°C to 38°C.
The air flow rate from each pot was 0.19 to 0.24 standard m3/s
(400 to 500 scfm). At the plant sampled, wetted-wall electro-
static precipitators (ESP) were used to control primary air
emissions. Eight ESP's, each controlling emissions from 30
pots, and four ESP's each controlling 15 pots were used. Each
of the eight larger ESP's had an air flow rate of 5.7 standard
m3/s (12,000 scfm) and each of the four smaller ESP's had an
air flow rate of 2.8 standard m3/s (6,000 scfm). Exit gas tem-
perature from the ESP's was about 27°C.
Two sources of wastewater were created by the primary air pollu-
tion control system-spray cooling water and ESP's. The total
volume of water discharged from the primary air pollution con-
trol system was 151 £/s (2,400 gpm). For an ESP collecting gas
from 30 pots, 4 to 6 %,/s (60 to 100 gpm) of cooling water and 9
to 11 £/s (140 to 180 gpm) of water from the ESP were combined
and discharged to the wastewater treatment plant.
-------
vo
SODERBERG
ANODE
ELECTROLYTIC
CELL
RIVER
WATER
fflft-
I
GAS COOLING
WATER
4T06I/S
VENTED TO
RIVER ATMOSPHERE
WATER AIMUY
I
ESP
ESP DRAIN
9 TO lll/s
-TOWASTEWATER
TREATMENT PLANT
151/s
Figure 2. Primary air pollution control system.
-------
The plant was also equipped with a secondary air pollution con-
trol system to collect pollutants which escaped into the potroom.
Each of the five potrooms was equipped with a room ventilation
system and two spray-chamber wet scrubbers. A total of 40 ven-
tilation fans were used with four fans per scrubber unit. Each
fan pulled 142 standard m3/s (300,000 scfm) and each scrubber,
therefore, treated 566 standard m3/s (1,200,000 scfmj of room
air.
Each spray-chamber wet scrubber was equipped with four banks of
spray nozzels, a screen, one bank of nozzels, and a mist elimi-
nator. Each of the secondary scrubbers used 60 £/s (950 gpm)
of once-through river water, totalling 600 £/s (9,500 gpm) of
scrubber water discharged to the wastewater treatment plant at
pH 6.1.
WASTEWATER TREATMENT PLANT
As described, there were three primary wastewater streams flowing
to the treatment plant:
• Combined ESP wash water and gas stream spray cooling
water (pH 2.8) at 151 i/s,
• Secondary scrubber system from room ventilation (pH 6.1)
at 600 Jl/s, and
• Briquette cooling water from the paste plant (pH 7) at
13 £/s to 19 £/s.
Storm water runoff was piped into the paste plant wastewater
line, but no rainfall occurred during the sampling period. The
plant's sanitary wastewater was treated in a separate activated
sludge treatment plant and discharged into the main chemical
treatment plant at a flow rate of 1.0 £/s (20 gpm).
A flow diagram of the wastewater treatment system is shown in
Figure 3. Slacked line, CaO, was added to the ESP wastewater
at a rate of 30 g CaO per kilogram of aluminum produced per day
in order to remove fluorides. During the sampling period, the
plant produced 203.2 metric tons of aluminum per day.
This limed stream then went to a standard clarifier with a
hydraulic retention time of about 2 hr. Settled solids, prin-
cipally calcium fluorides, were pumped to sludge holding ponds.
No wastewater was discharged from these ponds.
Clarified water (pH 7) was combined with secondary scrubber
water and paste plant cooling water and sent to a settling
lagoon with a 20 hr hydraulic retention time. The combined
outfall of 771 H/s (16 mgd) was discharged to a river.
10
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RIVER WATER
850 l/s
PRIMARY CONTROL
SYSTEM - WET
ESP
LIME-*
30 s/kg Al
SECONDARY
CONTROL SYSTEM •
WET SCRUBBERS
151 l/s
PH2.8
TREATED SANITARY
WASTEWATER
1.0 l/s
600 l/s
SUMP
OVERFLOW pH 7
SLUDGE TO
SLUDGE LAGOON
13 TO
19 l/s
BRIQUETTE
COOLING WATER
DISCHARGE
TO RIVER
771 l/s
Figure 3. Wastewater treatment plant.
11
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SECTION 4
SAMPLING AND ANALYSIS PROTOCOL
SAMPLING PROCEDURE
Collection Technique
Wastewater sample collection techniques followed those recom-
mended by EPA in Reference 3, with a few modifications designed
to better insure sample integrity, chain of custody, and reflect
site specific requirements. Since the plant operated 24-hr/day,
7 days/week at full production and since the wastewater stream
flow rates varied by less than 10%, 48-hr composited samples
were collected at'the following locatipns:
• Plant intake river water,
• Primary control system (ESP's and gas cooling water),
• Secondary control system,
• Paste plant wastewater (anode briquette cooling water),
• Final effluent.
Samples of the treated sanitary wastewater were not collected
because of its low flow contribution (1.0 H/s compared to 771
H/s) and because the sanitary treatment plant was oversized and
reduced the total organic load to a biochemical oxygen demand
(BOD) of less than 5 mg/1.
Because of the way the wastewater treatment system was con-
structed, it was not possible to use automatic samplers and
still guarantee sample integrity. Therefore, 48-hr grab samples
were collected once every hour with a 3-gal Teflon®-lined,
stainless steel bucket. Aliquots were removed from the bucket
using glass beakers and placed in the appropriate sample con-
tainers. Care was always taken to insure the sample remained
homogenous while in the bucket. It took approximately 5 min
to remove all aliquots from the bucket and place them in the
containers.
(3) Draft Final Report: Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority Pollutants.
U.S. Environmental Protection Agency, Cincinnati, Ohio,
April 1977. 145 pp.
12
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Sampling logistics for subsequent priority pollutant analysis are
shown in Table 2 (3, 4). Before sampling began, bottle labels
were filled out and affixed to appropriate sample bottles. Fig-
ure 4 shows the bottle label designed by MRC for sample identi-
fication. Once applied to the bottle, clear tape was put over
the label to prevent water damage to the label.
TABLE 2. SAMPLING LOGISTICS FOR PRIORITY POLLUTANTS
Analysis fraction
Container, per
sampling point
Preservatives
required (3, 4)
Volatile organics
4-40 ml glass vials
w/TefIon-lined
septa
Nonvolatile organics 1-1 gal amber glass
(base/neutral, acid, pharmaceutical jug
pesticide, & PCB's) w/TefIon-lined cap
Metals
Cyanide (total)
Phenol (total)
1-500 ml plastic
1-500 ml plastic
1-500 ml glass
Keep at 4°C, if residual
chlorine is present (KI
paper turns blue) then add
0.03 ml of 10% sodium thio-
sulfate to each bottle.
j
Keep at 4°C
In the lab add 5 ml of redis-
tilled HNO3/ keep at 4°C
Adjust pH £ 12 w/lON NaOH,
keep at 4°C
0.5 g CuSO^ at beginning,
adjust pH < 4 w/H3POit
(100 ml con H3PC>4. to 1
liter of water) keep at
4°C
Asbestos
1-1 liter plastic
1.0 ml of HgCl solution
(2.71 g HgCl in 100 ml
distilled water), keep at
4°C
Four samples, collected every twelve hours, were collected for
volatile organics analysis, as opposed to the one grab sample
recommended in Reference 3. Each of the four samples per stream
were hermetically sealed immediately after collection and placed
in ice at 4°C and were laboratory composited for one analysis
per wastewater stream. Since there was no free chlorine,
(4) Manual of Methods for Chemical Analysis of Water and Wastes.
EPA-625/6-76-003a (PB 259 973). U.S. Environmental Protec-
tion Agency, Cincinnati, Ohio, 1976. 317 pp.
13
-------
Job
Sample or Run No..
Sample Location
Type of Sample
Analyze for
Preservation
Comments _
Log No. Date
Initials
Figure 4. MRC bottle label for sample identification.
14
-------
tested by potassium iodide (KI) paper, in any of the wastewater
streams, preservatives were not required in the volatile organic
sample (3) .
The grab sampling technique had the added advantage of field com-
positing samples for total cyanide and total phenol analyses as
opposed to the one grab sample method described in Reference 3.
Proper preservatives were added to these bottle in the beginning
and proper preservation pH maintained throughout the 48-hour
sampling period.
Asbestos samples were collected, preserved, and stored at 4°C
for possible future analysis.
Sample Container Preparation
All glass containers and beakers were thoroughly cleaned with
strong acid (50% sulfuric acid -t- 50% nitric acid) , rinsed in
distilled water, and heated in a glass annealing oven at 400°C
for at least 30 minutes. Once the bottles cooled to room tem-
perature, Teflon-lined caps were applied.
Plastic bottles were thoroughly cleaned by washing in nitric
acid and rinsing several times in distilled water.
During the first grab sampling period, each sample container was
seasoned by rinsing with the appropriate wastewater sample and
discarding the rinse.
Sample Shipping Procedure
At the completion of the 48-hour sampling period, all containers
were checked to insure proper preservation. Then each bottle
cap was taped to the bottle to prevent leakage during shipment.
All glass bottles were wrapped with plastic glass packing
material.
Sample containers were placed in plastic ice chests and filled
with ice to maintain sample temperature at 4°C. Each ice chest
was taped closed and appropriate shipping labels applied.
Samples were then taken to the airport and shipped via commercial
air freight to Dayton for analysis. No sample containers were
destroyed during transport to MRC.
ANALYTICAL PROCEDURES
Recommended analytical procedures (3) developed by EPA were used
throughout this project. It is important to realize that some of
the procedures are still under development and require further
verification and validation. Therefore, the data presented serve
to identify which of the 129 priority pollutants (Appendix A)
15
-------
were present and to indicate the general concentration ranges
within a factor of two.
Two of the 129 chemical species were not determined in this
project: 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and asbestos.
EPA-Environmental Monitoring and Support Laboratory (EMSL)
recommended that TCDD should be omitted because of its extreme'
toxicity and potential health hazard involved in preparing
standard solutions in the laboratory from the pure compound (3).
Asbestos samples were collected, preserved, and stored at 4°C.
for possible future analysis. Also, due to the source of waste-
water in the primary aluminum industry, pesticides were also not
analyzed in the samples. The only source of pesticides would be
the river intake water.
The analytical procedure (3) divides the 129 priority pollu-
tants into six basic catagories: volatile organics, nonvolatile
organics, metals, cyanide, phenol, and asbestos. Appendix B
lists the chemical species which belong to each category. The
following sections outline the analytical procedures and MRC
modifications for analyzing each group of priority pollutants.
Volatile Organics
The recommended method for volatile organic analysis was designed
by EPA to determine those chemical species which were amenable
to the Bellar purge and trap method (3). Appendix B lists those
priority pollutants classified as volatile organics.
Four hermetically sealed 40-ml glass vials collected from each
of the five sampling points were composited in the laboratory
for one analysis. Two composited solutions were used, one for -
analysis and one as a backup sample. Figure 5 is a simplified
diagram of the analytical scheme for volatile organics analysis*
An internal standard of 1,4-dichlorobutane was added to 5 ml of
the composited sample and the sample sparged with helium onto a
Tenax GC-silica-packed sample tube. Two tubes were prepared,,
one for analysis and one duplicate. Tenax tubes were then
sealed in glass under a nitrogen atmosphere and stored in a
freezer at -18°C until analyzed.
Analyses were carried out using a Hewlett Packard 5981 GC-Mass
Spectrometer with 5934 Data System. Sample tubes were heated to
180°C over a 1-minute period and held at that temperature for
4 minutes to desorb the compounds onto a Carbowax 1500 column
held at -40°C. For compounds with boiling points below room
temperature, cryogenic trapping at -40°C (liquid nitrogen •
cooling) was found to give better reproducibility of retention ;
time than using the suggested temperature of 30°C. After desorp-
tion, the GC column temperature was raised 8°C/minute to 170°C.
16
-------
COMPOSITE
4 VIALS
INTERNAL
STANDARD
ADDED
SPARGE 5 ml SAMPLE
WITH HELIUM
ONTO TENAX-SILICA TUBE
STORE ?
NO
THERMALLY
DESORB
ONTO GC COLUMN
COLLECT AND
ANALYZE MS
CHROMATOGRAM
YES
SEAL TUBE
IN GLASS
UNDER NITROGEN
AND STORE AT-18 °C
Figure 5. Analytical scheme for volatile organics analysis,
17
-------
Qualitative identification of a compound was made using three
criteria listed in the protocol (3): 1) retention time must
coincide with known retention times, 2) three characteristic
masses must elute simultaneously, and 3) intensities of the char-
acteristic masses must stand in the known proper proportions.
Quantitation of volatile organics were made using response
ratios to the 1,4-dichlorobutane internal standard.
Nonvolatile Organics
Nonvolatile organics are divided into three groups for analysis:
base/neutral fraction, acid fraction (phenols), and pesticides
and polychlorinated biphenyls (PCB). A list of compounds that
are classified as nonvolatile organics is given in Appendix B.
Due to the sources of wastewater in aluminum manufacturing,
pesticides were not analyzed in the samples.
The analytical procedure is described in Reference 3. Figure 6
depicts the sample processing scheme for the base/neutral and
acid fractions. The sample solution, 2 fc, was made alkaline
(pH greater than 11) with sodium hydroxide, and then extracted
three times with methylene chloride. The wastewater samples
formed emulsions upon extraction with methylene chloride. The
problem was resolved by drawing off small amounts of separated
solvent and pouring the extract through the sample in the
separatory funnel. Separation was also enhanced by slowly drip-
ping the emulsion onto the wall of a slightly tilted flask.
Extracts were dried on a column of anhydrous sodium sulfate, con-
centrated to 1.0 ml in a Kuderna-Danish (K-D) evaporator with
a Snyder column, spiked with deuterated anthracene, sealed in
septum capped vials, and stored at 4°C until analyzed. Analyses
were performed on the GC-MS system using SP 2250 and Tenax GC
columns for base/neutral and acid samples, respectively (3).
Metals
In addition to the volatile and nonvolatile organics, the 129
chemical species include 13 metals, measured as the total metal.
All metals were quantified by conventional flame and flameless
atomic absorption techniques (4, 5).
(5) Standard Methods for the Examination of Water and Waste-
water, Fourteenth Edition. American Public Health
Association, Washington, D.C., 1976. 874 pp.
18
-------
ADJUST SAMPLE pH TO
pH>ll
W/SODIUM HYDROXIDE
METHYLENE CHLORIDE
EXTRACTION
BASES & NEUTRALS
ACIDS (PHENOLS), UNEXTRACTABLES
BOTTOM LAYER
TOP LAYER
DRIED ON
ANHY. SODIUM SULFATE
CHANGE pH< 2
W/HYDROCHLORICACID
CONCENTRATE
IN K-D EVAP.
TO 1ml
METHYLENE CHLORIDE
EXTRACTION
ACIDS
AQUEOUS
DRIED ON ANHY.
SODIUM SULFATE
SAVE 25 ml
DISCARD REMAINDER
GC/MS
IDENTIFICATION &
QUANTITATION
CONCENTRATED
IN K-D EVAP.
TO 1ml
GC/MS
IDENTIFICATION &
QUANTITATION
Figure 6.
Sample processing scheme for
nonvolatile organics analysis,
19
-------
Five milliters of redistilled nitric acid were added to the
metals samples in the laboratory and allowed to sit for two hours
before removing aliquots for analysis. Due to the higher solids
loading of the wastewater from the primary air pollution collec-
tion system, this sample was vacuum filtered with 0.45-pin filters
and both the filtrate and filter paper analyzed for metals.
The filter paper sample was parr bombed with nitric acid and the
resulting solution diluted to 100 ml with distilled deionized
water. Filter paper and reagent blanks were also prepared and
analyzed.
The five sampling locations resulted,in six samples for metals
analysis because one sample required filtration and analysis
of filtrate and filter. Three of the samples were split and
analyzed as blind repeats. A certified National Bureau of
Standards trace elements in water sample and two MRC standards,
one in the 10 mg/1 concentration range and one in the 0.05 mg/1
range were used to calibrate the atomic absorption instrument.
Two filter paper blanks, a nitric acid/water, and a distilled
water blank were included in the analysis scheme.
Asbestos
Asbestos samples were collected at each of the five sampling
points and presented with a HgCl solution (3). Samples were then
stored at 4°C for possible future analysis. No asbestos samples
were analyzed for this project.
Cyanide (Total) s
Total cyanide was analyzed according to the procedure in Refer-
ence 3. One blind repeat and one spiked sample were included
with the five samples for quality assurance.
Phenol (Total)
In addition to specific phenolic compounds and phenol measured by
GC-MS, total phenol was also measured by typical wet chemistry
techniques (3-5). ;
Phenol samples were preserved in the field by adding 1.0 g
maintaining the pH to less than 4 with HsPO^ and storing the
sample at 4°C. Recent research has indicated this preservation
technique is adequate for at least 8 days (6) . All phenolic
samples collected in this study were analyzed within 5 days of
collection.
(6) Carter, M. J. and M. T. Huston. Preservation of Phenolic
Compounds in Wastewaters. Environmental Science and
Technology, 12(3) : 309-313, 1978.
20
-------
SECTION 5
RESULTS AND CONCLUSION
ANALYTICAL RESULTS
Organics
Results of the organic priority pollutant analyses are shown in
Table 3. Compounds presented in the table are those found in
the base/neutral, acid, and volatile organics fractions. Pesti-
cides were not analyzed due to the nature of the wastewater
sources.
Of the list of compounds, the majority of the species were detec-
ted in the base/neutral fraction. Only phenol and 2,4-dimethyl
phenol were detected in any of the acid fractions. Methylene
chloride, toluene, and benzene were the only priority pollutant
organics detected in the volatile fractions.
In order to fully understand the quantity of organic species
present in each stream and the distribution of the species
through the treatment system, the concentration values in Table 3
were multiplied by the appropriate wastewater stream flow rate.
This technique shows the difference between simple dilution
effects and removal effects, since stream dilution is not an
acceptable form of pollution control technology.
Since the plant was producing 203.2 metric tons of aluminum per
day, discharge values are also reported as grams of pollutant
per metric ton of product produced.
Total Cyanide and Phenol
Samples were also analyzed by conventional wet chemistry tech-
niques to total cyanide and total phenol (4). Results of these
analyses are also shown in Table 3. No cyanide was detected in
any of the samples below the detection limit of 4 yg/Jl. The
detection limit for total phenol was 5 yg/A.
Metals
The thirteen priority pollutant metals were analyzed by conven-
tional atomic absorption and the results are shown in Table 4.
21
-------
TABLE 3. ANALYSIS OF ORGANIC PRIORITY POLLUTANTS AND CYANIDE
Stream and flow rate
Intake river water, 850 &/s
Primary control system, 151 i/s
Secondary control system, 600 t/s
Paste plant (briquette cooling), 19 l/s
Final effluent, 771 i/s
Concentration,
Priority pollutant observed us/I
BisU-ethyl hexyDphthalate
Anthracene
Fluoranthene
Pyrene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo Ik) £ luoranthene
Hethylene chloride
Toluene
Cyanide (total)
Phenol (total)
Naphthalene
Acenaphthene
Acenaphthylene
BisU-ethyl hexyljphthalate
Fluor ene
Phenanthrene
Anthracene
Pyrene
Fluoranthene
Chrysene
Benzo (a) anthracene
Benzo (b) f luoranthene
Benzo(k) f luoranthene
Benzo (a) pyrene
Dibenzo(a ,h) anthracene
Indeno (1,2,3 -cd) pyrene
Benzo (g ,h ,i) perylene
Phenol
Nethylene chloride
Toluene
Benzene
Cyanide (total)
Phenol (total)
BisU-ethyl hexyDphthalate
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (g ,h , i) perylene
Indeno (1 , 2, 3-cd) pyrene
Cyanide (total)
Phenol (total)
BisU-ethyl hexyDphthalate
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo (a) anthracene
Benzo (k) f luoranthene
Benzo (a) pyrene
Indeno (1,2, 3-cd) pyrene
Benzo (g , h , i ) perylene
Hethylene chloride
Toluene
Cyanide (total)
Phenol (total)
BisU-ethyl hexyDphthalate
Acenaphthylene
Fluorene
Acenaphthene
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (g,h , i) perylene
Indeno (1,2, 3-cd) pyrene
Benzo (k) f luoranthene
Cyanide (total)
Phenol (total)
20
0.4
1
1
2
2
3
2
2
<4
<5
20
50
4
5
50
230
150
220
320
230
180
260
210
S70
110
350
150
70
8
3
6
<4
725
30
0.7
10
110
50
30
40
40
8
8
<4
158
20
2
2
9
9
50
40
50
50
70
60
10
10
8
3
<4
102
10
7
1
10
3
BO
40
9
8
10
.1
1
7
<4
116
Mass rate,
g/day
1,470
30
70
70
150
150
220
150
150
<290
<370
260
650
50
65
650
3,000
1,960
2,870
4,170
3,000
2,350
3,390
2,740
7,440
1,430
4,570
1,960
910
100
40
80
<50
3,600
1,560
40
520
5,700
2,590
1,560
2,070
2,070
100
100
<210
8,200
30
3
3
15
15
80
70
80
80
110
100
20
20
10
5
<7
170
670
470
70
670
200
5,330
2,660
600
530
670
70
70
470
<270
7,730
Discharge factor,
g/metric ton Al
7.2
0.1
0.3
0.3
0.7
0.7
1.1
0.7
0.7
<2
<2
1.3
3.2
0.2
0.3
3.2
15
9.6
14
21
15
12
17
13
37
7.0
22
9.6
4.5
0.5
0.2
0.4
<0.3
18
7.7
0.2
2.6
28
13
7.7
10
10
0.5
0.5
<1
40
0.1
0.01
0.01
0.07
0.07
0.4
0.3
0.4
0.4
0.5
0.5
0.1
0.1
0.05
0.02
<0.1
0.8
3.3
2.3
0.3
3.3
1.0
26
13
3.0
2.6
3.3
0.3
0.3
2.3
<1
38
22
-------
TABLE 4. METALS CONCENTRATIONS IN WATER AND WASTEWATER
STREAMS ANALYZED BY ATOMIC ABSORPTION METHOD
Metals concentration by stream, yq/t.
Metal
Antimony
Arsenic
Beryllium
Cadfftium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Intake water
30
<10
<10
<5
<10
5.5 ±0.7
<50
<2
8.0 ± 1.4
<1
<2
<50
28 ± 2
Primary
control system
450
<10
<10
<20
<20
31
<100
<4
1,130 ± 85
<2
<4
<90
117
Secondary
control system
50
<10
<10
<10
<10
21
<50
<2
<5
<1
<2
<1
47
Paste plant
30
<10
<10
<10
<10
8.5 ± 0.7
<10
<2
<5
<1
<2
<1
34
Final effluent
40
<10
<10
<10
<10
9.0 ± 1.
<50
<2
5
<1
<2
<1
35 ± 2
4
Values indicated with the less than sign (<) indicate the metal
concentration is below the stated detection limit. Samples were
analyzed in duplicate and on two separate days. Fluctuations in
concentrations are noted by the plus or minus standard deviation
values.
The mass flow rate, given in g/day, of each metal in each of the
five streams is given in Table 5. Values were calculated by
multiplying the metal concentration (Table 5) by the appropriate
stream flow rate value, shown in Figure 3, and converting to
g/day.
WASTEWATER TREATMENT PLANT PERFORMANCE
The principal source of organics in the wastewater was from the
volatilization of petroleum coke and pitch in the Soderberg
anode. These organic vapors were subsequently collected in the
air pollution control system and the resulting wastewater dis-
charged to the treatment plant.
Of the metals detected, above instrument detection limits,
antimony, copper, nickel, and zinc were discharged at the same
rate as the amount coming in with the intake water. There was
no gain in metals due to the aluminum plant.
In order to evaluate the removal efficiency of the wastewater
treatment plant for priority pollutants, the mass flow rate
values were used and are presented in Table 6. Removal effi-
ciencies were calculated by summing the quantity of species in
the primary control system stream, secondary control system
stream, and paste plant stream and comparing this value to the
quantity in the final effluent. Since cyanide, arsenic,
23
-------
TABLE 5. MASS FLOW RATES AND TREATMENT PLANT REMOVAL EFFICIENCIES FOR METALS
N)
Metals mass flow rate by stream, g/day
Metal
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
Intake water
2,200
<700
<700
<360
<700
400 ± 50
<3,600
<150
590 ± 100
<70
<150
<3,600
2,100 ± 150
Primary Secondary Paste
control system control system plant
5,800
<130
<130
<260
<260
400
<1,300
<50
14,700 ± 1,100
<30
<50
<1,200
1,500
2,600
<500
<500
<500
<500
1,100
<2,600
<100
<260
<50
<100
<50
2,400
50
<20
<20
<20
<20
14 ± 1
<20
<3
<8
<2
<3
<2
60
Final
effluent
2,700
<670
<670
<670
<670
600 ± 90
<3,300
<130
330
<70
<130
<70
2,300 ± 130
Percent
removal
68
b
b
b
b
60 ±
b
b
98 ±
b
"b
~b
42 ±
3
2
2
Value calculated by subtracting the sum of columns 2 through 4 from the value in column 5
and dividing the difference by the sum of columns 2 through 4 and converting into percent.
Since all concentrations were below instrument detection limits, percent removal values
were not calculated.
-------
TABLE 6. TREATMENT PLANT REMOVAL EFFICIENCIES FOR PRIORITY POLLUTANTS
Ui
Mass flow rate in stream, g/day
Primary pollutant
Bis(2-ethyl hexyl) phthalate
Naphthalene
Acenaphthene
Acenaphthylene
Fluorene
Phehanthrene
Anthracene
Pyrene
P luor anthene
Chrysene
Benzo (a) anthracene
Benzo (b) f luor anthene
Benzo (k) Fluoranthene
Benzo (a) pyrene
Dibenzo (a,h) anthracene
Indeno (1 , 2 , 3-cd) pyrene
Benzo (1,2, 3-cd) perylene
Phenol
Methylene chloride
Toluene
Benzene
Phenol (total)
Antimony (total)
Copper (total)
Nickel (total)
Zinc (total)
Intake
water
1,470
_b
-
-
-
-
30
70
70
-
150
—
220
150
-
-
-
—
150
150
-
290
2,200
400 ± 50
590 ± 100
2,100 ± 150
Primary Secondary
control system control system
65
260
650
50
650
230
1,960
2,870
4,170
3,000
2,350
3,390
2,740
7,440
1,430
4,570
1,960
910
100
40
80
3,590
5,800
400
14,700 ± 1,100
1,500
1,560
-
40
-
-
_
520
2,590
5,700
1,560
2,070
-
-
2,070
-
100
100
—
-
-
-
8,190
2,600
1,100
<260
2,400
Paste Final
plant discharge effluent
30
-
3
—
3
15
15
70
80
80
80
—
110
100
—
20
20
-
10
5
-
170
50
14 ± 1
<8
60
670
-
670
470
70
—
200
2,660
5,330
600
530
-
470
670
-
70
70
-
-
_
-
7,730
2,700
600 ± 90
330
2,300 ± 130
Percent
removal
32
100
3
-c
89
100
91
52
46
87
88
100
84
93
100
99
97
100
100
100
100
37
68
60 ± 3
98 ± 2
42 ± 2
aValue calculated by subtracting the sum of columns 2 through 4 from the value in column 5 and dividing the
difference by the sum of columns 2 through 4 and converting into percent.
Blanks indicate species not present in stream sample.
GNondeterminable—value in effluent greater than sum of input values.
-------
beryllium, cadmium, chromium, lead, mercury, selenium, silver,
and thallium were not detected in any stream, efficiency values
could not be determined.
Based on the values in Table 6, removal efficiencies of greater
than 85% were achieved for most organic species detected.
Organic chemical species with lower removal efficiency values
are bis(2-ethyl hexyl) phthalate, acenaphthene, pyrene, fluor-
anthene, and total phenol.
The treatment plant is moderately effective at removing antimony,
copper and zinc, and very effective at removing nickel.
26
-------
REFERENCES
1. Thompson, G. S., Jr. Development Document for Effluent
Limitations Guidelines and New Source Performance Standards
for the Primary Aluminum Smelting Subcategory of the Aluminum
Segment of the Nonferrous Metals Manufacturing, Point Source
Category. EPA-440/l-74-019d (PB 240 859), U.S. Environmental
Protection Agency, Washington, D. C., March 1974. 142 pp.
2. Kirk-Othmer Encyclopedia of Chemical Technology, Volume I.
John Wiley and Sons, Inc., New York, New York, 1963.
pp. 931-944.
3. Draft Final Report: Sampling and Analysis Procedures for
Screening of Industrial Effluents for Priority Pollutants.
U.S. Environmental Protection Agency, Cincinnati, Ohio,
April 1977. 145 pp.
4. Manual of Methods for Chemical Analysis of Water and Wastes.
EPA-625/6-76-003a (PB 259 973). U.S. Environmental Protec-
tion Agency, Cincinnati, Ohio, 1976. 317 pp.
5. Standard Methods for the Examination of Water and Waste-
water, Fourteenth Edition. American Public Health
Association, Washington, D.C., 1976. 874 pp.
6. Carter, M. J. and M. T. Huston. Preservation of Phenolic
Compounds in Wastewaters. Environmental Science and
Technology, 12(3):309-313, 1978.
7. Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76e, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 p.
27
-------
APPENDIX A
RECOMMENDED LIST OF PRIORITY POLLUTANTS
TABLE A-l. RECOMMENDED LIST OF PRIORITY POLLUTANTS
Compound name
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzidine
Carbon tetrachloride (tetrachloromethane)
Chlorinated benzenes (other than dichlorobenzenes)
Chlorobenzene
1,2,4-Trichlorobenzene
Hexachlorobenzene
Chlorinated ethanes (including 1,2-dichloroethane,
1,1,1-trichloroethane and hexachloroethane)
1,2-Dichloroethane
1,1,1-Trichloroethane
Hexachloroethane
1,1-Dichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
Chloroethane
Chloroalkyl ethers (chloromethyl, chloroethyl and
mixed ethers)
Bis(chloromethyl) ether
Bis(2-chloroethyl) ether
2-Chloroethyl vinyl ether (mixed)
Chlorinated naphthalene
2-Chlor©naphthalene
(continued)
28
-------
TABLE A-l (continued).
Compound name
Chlorinated phenols (other than those listed elsewhere;
includes trichlorophenols and chlorinated cresols)
2,4,6-Trichlorophenol
p-Chloro-m-cresol (4-chloro-3-methylphenol)
Chloroform (trichloromethane)
2-Chlorophenol
Dichlorobenzenes
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichlorobenzidine
3,3'-Dichlorobenz idine
Dichloroethylenes (1,1-dichloroethylene and
1,2-dichloroethylene)
1,1-Dichloroethylene (vinylidine chloride)
1,2-Trane-dichloroethylene
2,4-Dichlorophenol
Dichloropropane and dichloropropene
1,2-Dichloropropane
1,3-Dichloropropylene
(ais and trans-l,3-dichloropropene)
2,4-Dimethylphenol
Dinitrotoluene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
I,2-Diphenylhydrazine
Ethylbenzene
Fluoranthene —
(continued)
29
-------
TABLE A-l (continued).
Compound name
Haloethers (other than those listed elsewhere)
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
Bis(2-chloroisopropyl) ether
Bis(2-chloroethoxy) methane
Halomethanes (other than those listed elsewhere)
Methylene chloride (dichloromethane)
Methyl chloride (chloromethane)
Methyl bromide (bromomethane)
Bromoform (tribromomethane)
Dichlorobromomethane
Trichlorofluoromethane
Dichlorodifluoromethane
Chlorodibromomethane
Hexachlorobutadiene ;
Hexachlorocyclopentadiene
Isophorone (3,5,5-trimethyl-2-cyclohexen-l-one)
Naphthalene
Nitrobenzene
Nitrophenols (including 2,4-dinitrophenol
and dinitrocresol)
2-Nitrophenol
4-Nitrophenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
Nitrosoamines
N-nitrosodimethylamine
N-nitrosodiphenylamine
N-nitroso-di-n-propylamine
Penta chlorophenol
Phenol
(continued)
30
-------
TABLE A-l (continued).
Compound name
Phthalate esters
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Polynuclear aromatic hydrocarbons
Benz(a)anthracene (1,2-benzanthracene)
Benzo(a)pyrene (3,4-benzopyrene)
3,4-Benzofluoranthene
Benzo(k)fluoranthene
(11,12-benzofluoranthene)
Chrysene
Acenaphthylene
Anthracene
Benzo(ghi)perylene (1,12-benzoperylene)
Fluorene
Phenanthrene
Dibenz(ah)anthracene
(1,2,5,6-dibenzanthracene)
Indeno(1,2,3-cd)pyrene
(2,3-o-phenylenepyrene)
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl chloride (chloroethylene)
Pesticides and metabolites
Aldrin
Dieldrin
Chlorodane (technical mixture and metabolites)
DDT and metabolites
4,4'-DDE (p,p;-DDX)
4,4'-ODD (p,p'-TDE)
31
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TABLE A-l (continued).
Compound name
Endosulfan and metabolites
ct-Endosulfan
3-Endosulfan
Endosulfan sulfate
Endrin and metabolites
Endrin
Endrin aldehyde
Heptachlor and metabolites
Heptachlor
Heptachlor epoxide
Hexachlorocyclohexane
a-BHC
B-BHC
X-BHC (lindane)
6-BHC
Polychlorinated biphenyls (PCB)
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Toxaphene
Elements
Antimony (Total)
Arsenic (Total)
Asbestos (Fibrous)
Beryllium (Total)
Cadmium (Total)
Chromium (Total)
Copper (Total)
Cyanide (Total)
Lead (Total)
(continued)
32
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TABLE A-l (continued).
Compound name
Elements (continued)
Mercury (Total)
Nickel (Total)
Selenium (Total)
Silver (Total)
Thallium (Total)
Zinc (Total)
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
33
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APPENDIX B
PRIORITY POLLUTANT ANALYSIS FRACTIONS
TABLE B-l. VOLATILE COMPOUNDS
Compound
Compound
Chloromethane
Dichlorodifluoromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Trichlorofluoromethane
1,1,-Dichloroethylene
1,1-Dichloroethane
trans-1,2,-dichloroethane
Chloroform
1,2-Dichloroethane
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodichloromethane
Bis(chloromethyl) ether
1,2-Dichloropropane
trans-1,3-dichloropropene
Trichloroethylene
Dibromochloromethane
Cis-1,3-dichloropropene
1,1,2-Trichloroethane
Benzene
2-Chloroethyl vinyl ether
Bromoform
1,1,2,2-Tetrachloroethylene
1,1,2,2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Acrolein
Acrylonitrile
34
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TABLE B-2. BASE NEUTRAL EXTRACTABLE COMPOUNDS
Compound
Compound
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachloroethane
1,2-Dichlorobenzene
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
1,2,4-Trichlorobenzene
Naphthalene
Bis(2-chloroethyl) ether
Hexachlorocyclopentadiene
Nitrobenzene
Bis(2-chloroethoxy) methane
2-Chloronaphthalene
Acenaphthylene
Acenaphthene
Isophorone
Fluorene
2,6-Dinitrotoluene
1,2-DiphenyIhydrazine
2,4-Dinitrotoluene
N-nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene
Anthracene
Diethyl phthalate
Dimethyl phthalate
Pluoranthene
Pyrene
Di-n-butyl phthalate
Benzidine
Butyl benzyl phthalate
Chrysene
Bis(2-ethylhexyl) phthalate
Benz (a)anthracene
Benzo(b)fluoranthene
Benzo (k)fluoranthene
Benzo(a)pyrene
Indeno (1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
N-nitrosodimethylamine
N-nitroso-di-n-propylamine
4-Chlorophenyl phenyl ether
3,3'-Dichlorobenzidine
2,3,7,8-Tetrachlorodibenzo-
p-dioxina
Bis-(chloromethyl) ether
This compound was specifically listed in the consent decree.
Because of TCDD's extreme toxicity, EPA recommends that labora-
tories not acquire analytical standards for this compound.
TABLE B-3. ACID EXTRACTABLE COMPOUNDS
2-Chlorophenol
Phenol
2,4-Dichlorophenol
2-Nitrophenol
p-Chloro-m-cresol
2,4,6-Trichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
4-Nitrophenol
Pentachlorophenol
35
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TABLE B-4. PESTICIDES AND PCB
Compound
0-Endosulfan
a-BHC
Y-BHC
B-BHC
Aldrin
Heptachlor
Heptachlor epoxide
ot-Endosulf an
Dieldrin
4,4'-DDE
4,4'-ODD
4,4'-DDT
Endrin
Endosulfan sulfate
6-BHC
Chlordane
Toxaphene
PCB-1242 (Aroclor 1242)
PCB-1254 (Aroclor 1254)
PCB-1221 (Aroclor 1221)
PCB-1232 (Aroclor 1232)
PCB-1248 (Aroclor 1248)
PCB-1260 (Aroclor 1260)
PCB-1016 (Aroclor 1016)
TABLE B-5. METALS AND OTHER COMPOUNDS
Metals,
total Others
Antimony Asbestos
Arsenic Cyanide
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
36
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CONVERSION FACTORS AND METRIC PREFIXES (7)
To convert from
CONVERSION FACTORS
TO
Degree Celsius (°C) Degree Fahrenheit (°F)
Kilogram (kg)
Liter /s
Meters 3/s (m3/s)
Pound-mass (avoirdupois)
Gallon (U.S. liquid) /min
(gpm)
Footvmin (cfm)
Multiply by
= 1.8 toc + 32
2.205
1.585 x 101
2.119 x 103
Prefix
Kilo
Milli
Micro
Symbol
k
m
y
METRIC PREFIXES
Multiplication factor
10 3
ID'3
10~6
Example
5 kg = 5 x 103 grams
5 mg = 5 x 10"3 gram
5 mg = 5 x 10"3 gram
(7) Standard for Metric Practice. ANSI/ASTM Designation:
E 380-76£, IEEE Std 268-1976, American Society for Testing
and Materials, Philadelphia, Pennsylvania, February 1976.
37 p.-
37
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TECHNICAL REPORT DATA
(Please read Ins true tioni on the revene before completing}
1. REPORT NO.
EPA-600/2-79-087
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Analysis of Priority Pollutants At A Primary Aluminum
Production Facility
6. REPORT DATE
April 1979 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Gary D. Raw!ings and Thomas J. Hoogheem
B. PERFORMING ORGANIZATION REPORT NO
MRC-DA-861
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, OH 45407
10. PROGRAM ELEMENT NO.
1BB610
1^CONTRACT/GRANT NO.
68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 3/78-1/79
14. SPONSORING AGENCY CODE
EPA/600/12
IS. SUPPLEMENTARY NOTES
16. ABSTRACT
This project investigated the source of priority pollutants, assessment of the waste-
water treatment plant, and priority pollutant removal efficiency for a single Soderberg-
type primary aluminum plant. Forty-eight hour composite samples were collected from
the following streams: 1) plant intake water; 2) wastewater from the primary air
pollution control system (gas stream cooling water and wet EPS's); 3) secondary air
pollution control system (room ventilation wet scrubber liquor); 4) paste plant
briquette cooling water; and 5) final effluent after the wastewater treatment plant.
Wastewater from the primary air pollution control system entered a conventional chemical
coagulation (using slacked lime)-clarification plant. Clarified water from the
clarifier was combined with the other three wastewater streams and flowed into a
settling lagoon with a 20-hr hydraulic retention time. Clarified lagoon water was
finally discharged to the river. The principal source of organic compounds in the
wastewater was from the primary and secondary air pollution control systems and
results from the volatilization of petroleum coke and pitch in the Soderberg anode.
Wastewater treatment plant removal efficiences of greater than 85% were achieved for
the majority of the organic priority pollutant species detected.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Aluminum industry
Wastewater
Priority Pollutants
b.IDENTIFIERS/OPEN ENDED TERMS
Wastewater treatment
Wet Scrubber Liquor
Soderberg Byproducts
COSATI Field/Group
68D
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
44
20. SECURITY CLASS (Thispage/
22. PRICE
Unclassified
EPA Form 222O-1 lt-73)
38
iHJSGPO: 1979 — 657-060/1661
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