United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
EPA 600 2 79 093
Apr,i 1979
Research ant) Development
&EPA
Analysis of Priority
Pollutants at a
Primary Zinc
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-600/2-79-093
April 1979
ANALYSIS OF PRIORITY POLLUTANTS AT A
PRIMARY ZINC PRODUCTION FACILITY
by
T. J. Hoogheem and G, D. Rawlings
Monsanto Research Corporation
Dayton, Ohio 45407
Contract No. 68-03-2550
Project Officer
A. B. Craig, Jr.
Metals and Inorganic Chemicals Branch
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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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.
11
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FOREWORD
t
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 primary zinc 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 pollut-
ants are being emitted by industry and to determine the ability
of wastewater treatment technologies to remove priority pollut-
ants. 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
111
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ABSTRACT
As a result of the 1976 consent decree (Natural Resources Defense
Council et al. v Train suit), EPA is obligated to identify which
of the 129 priority pollutants are present in industrial waste-
waters and to determine the ability of various wastewater treat-
ment technologies to remove these pollutants. This project
investigated the source of priority pollutants, assessment of the
wastewater treatment plant, and priority pollutant removal
efficiency for a single primary zinc manufacturing plant.
Forty-eight hour composited samples were collected from the
following streams: 1) plant intake water, 2) sanitary discharge,
3) gas scrubber wastewater, 4) lagoon wastewater, and 5) plant
effluent.
The plant treats all process, sanitary, and storm run-off waste-
water in a lime precipitation/solids clarification treatment
plant.
Results indicate high levels of zinc, cadmium, and chrome being
generated but being removed to acceptable state requirements by
the treatment plant. Low levels of several priority pollutant
organics were found, originating either in the city water supply
or being generated chemically within the manufacturing plant.
IV
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CONTENTS
Page
Foreword iii
Abstract iv
Figures vi
Tables vii
1. Introduction 1
2. Summary 2
3. Source Description 4
General 4
4. Sampling and Analysis Protocol 12
Sampling Procedure 12
5. Results and Conclusions 21
Organics , 21
References 30
Appendices
A. Recommended List of Priority Pollutants 31
B. Priority Pollutant Analysis Fractions 37
C. Plant Production and Treatment Plant Data 40
Conversion Factors and Metric Prefixes 45
v
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FIGURES
Number Page
1 Zinc plant process flow diagram 5
2 Zinc plant waste treatment system 10
3 MRC sample bottle label design 14
4 Analytical scheme for volatile organics analysis. 17
5 Sample processing scheme for nonvolatile organics
analysis 19
VI
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TABLES
Number Page
1 Net Effluent Factors for Sampled Zinc Plant ... 3
2 Removal Efficiencies for Sampled Zinc Treatment
Plant 3
3 Monthly Water Usage by Division for Sampled
Plant (February 1978) 7
4 Sampling Logistics for Priority Pollutants. ... 13
5 Organic Priority Pollutants in Zinc Plant Water
Streams 22
6 Metals Analysis - AA 24
7 Metal Mass Loadings and Removal Efficiencies for
Waste Treatment Plant (AA Basis) 25
8 Metal Effluent Factors for Sampled Zinc Plant
(AA Basis). 26
9 Metal Effluent Factors for Sampled Zinc Plant
(Gas Scrubber/HaSOiJ 26
10 Net Metal Mass Effluent Factors for Sampled Zinc
Plant 27
11 Data Collected for Plant Discharge 28
vxx
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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 zinc plant
equipped with a well designed wastewater treatment plant. In
addition, the removal efficiency for priority pollutants was
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
A primary zinc plant was sampled for the 129 priority pollutants
from 8 March 1978 to 10 March 1978. The sampled plant produces
on an average 189,000 kilograms of cathode zinc and 600 kilograms
of cadmium per day. The plant operates 24 hours a day, 7 days
per week utilizing both zinc sulfide and zinc oxide in producing
high grade zinc and zinc alloys.
The plant treats all wastewater, both process and cooling, and
rainfall runoff in a central physical/chemical waste treatment
plant. The average wastewater flow treated per day is 2,540
kiloliters. Sources of wastewater to the treatment plant are
gas scrubber wastewater from the roasting operation and holding
lagoon wastewater. The lagoon collects all other plant generated
wastewater including a sanitary discharge that has received pri-
mary treatment and chlorination.
Five locations in the plant were sampled for priority pollutants.
These were:
• city water supply
• sanitary discharge
• gas scrubber wastewater
• lagoon wastewater
• plant effluent
Sampling techniques followed EPA protocol.
Results indicate low levels of several priority pollutant
organics, either entering the plant in the city water supply or
generated chemically within the plant. Metals analysis indicates
high levels of zinc, cadmium, and lead, being generated but being
removed to acceptable state requirements by the treatment plant.
The plant operates effectively but is currently overloaded with
solids. Net effluent factors for the plant discharge and metal
removal efficiencies are presented in Tables 1 and 2.
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TABLE 1. NET EFFLUENT FACTORS FOR
SAMPLED ZINC PLANT
Total Net effluent factor,
metal (AA) _ E£/]SSL ?J
Silver 0.10
Beryllium -a
Cadmium 0.29 ± 0.05
Chromium 2.1 ± 0.1
Copper 0 . 14
Nickel -a
Lead -a
Antimony -a
Zinc 11
Arsenic -a
Mercury -a
Thallium -a
Selenium 0.6 ± 0.01
Net effluent factor cannot be
calculated since the metal con-
centration in both samples was
below instrument detection
limits.
TABLE 2. REMOVAL EFFICIENCIES FOR SAMPLED
ZINC TREATMENT PLANT
Total
metal (AA)
Silver
Beryllium
Cadmium
Chromium
Copper
Nickel
Lead
Antimony
Zinc
Arsenic
Mercury
Thallium
Selenium
Removal efficiency,
percent
94
_a
100
93
100
94
100
_a
100
99
99
_a
85
Removal efficiency cannot be
calculated since the metal con-
centration in all samples was
below instrument detection
limits.
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SECTION 3
SOURCE DESCRIPTION
GENERAL
The sampled plant produces special high grade electrolytic zinc,
99.99 percent pure, in two separate operating departments.
The sulfide department treats zinc sulfide (ZnS) concentrates
from mines in Honduras and Nicaragua.
The oxide department produces zinc oxide (ZnO) fume from the
company's lead smelter in Texas. Zinc fume from the company's
Montana smelter is also deleaded at the plant's Texas lead
smelter before being sent to the sampled plant for processing.
In general, the operation of the oxide plant is similar to that
of the sulfide plant. The oxide plant was built as a separate
operation, however, because the sulfide plant could not treat
relatively large quantities of germanium contained in some of
the fume being processed.
The oxide plant has a production capacity 50 percent greater
than the sulfide plant, producing about 4,900 metric tons of zinc
per month compared to about 3,269 metric tons per month produced
by the sulfide plant. Total zinc production in 1977 was 69,000
metric tons or 5,750 metric tons per month. Thus, zinc produc-
tion at the sampled plant in 1977 was 70.4 percent of capacity.
Process Description
A flow diagram of the zinc refining operations at the sampled
plant is shown in Figure 1.
Zinc sulfide concentrates are first converted to zinc oxide cal-
cine by roasting. The calcine is leached in spent electrolyte
containing 15-20 percent sulfuric acid to form a zinc sulfate
(ZnSO^) solution containing copper, cadmium, and other
impurities in addition to zinc. Remaining in the residue are
lead, silver, gold, iron, and other insolubles. Each metric ton
of calcine yields from 200 to 250 kilograms of residue.
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TO MARKET
> TO MARKET
TO OFF-SITE
LEAD SMELTER
* Oxide plant flow chart is similar to that ot suttide plant ex-
cept in the following details:
• Saw material Consists ol zinc oxide fume (ZnO) which
requires no roasting.
• Associated sulturic acid plant not required
* Oxide circuit functions at SOOv DC. 20.000 amperes
and contains 29 anodes (•¥) and 26'- } rof ftotfgs pw
cell,
• A portion ot metal from me oxide plant melting lurnace
is transferred to another lurnace for alloying.
Figure 1. Zinc plant process flow diagram.
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Most of the impurities in the solution (principally copper and
cadmium) are precipitated in two purification stages using Zinc
dust as the cementing agent. Copper precipitates from the first
purification are removed by filtration and sent to the Texas lead
smelter for further treatment. Cadmium precipitates from the
second purification stage are processed in the plant to produce
the metal which is cast as balls and sticks-
In the electrolytic department, the purified zinc sulfate solu-
tion is added to a sulfuric acid-base electrolyte circulating
through 280 of a total of 320 electrolytic cells. Responding to
a charge of direct current, the zinc in solution plates out on
the aluminum cathodes.
The zinc is stripped from the cathodes every 24 hours and
charged into a reverbatory furnace for melting and casting into
25 kilogram slab and 1,090 kilogram ingot for market.
Zinc for the alloy melting furnace is taken molten from the
melting furnace serving the oxide plant. Various percentages of
magnesium, aluminum, copper, and nickel are added to the molten
zinc to produce various high quality die alloys. The alloys are
cast as 9 kilogram bars.
Plant produced zinc alloys are used principally in the manufac-
ture of automobile grills, trim, and carburetor and fuel-pump
housings. Large quantities are also used in household appliances,
toys, and general hardware.
Zinc sulfate power, produced as a by-product, is made by drying
purified zinc sulfate solution. It is used by the makers of
insecticides and fertilizers and by the mining industry as .a
flotation reagent. The plant can produce 227 metric tons a
month of this chemical. The yearly production capacity of this
chemical is 2,724 metric tons.
Cadmium, also as a by-product, is removed as a precipitate in
the second purification stage. Retreated, it is made into
refined metal. It is sold to electroplaters for use in plating
steel to protect it against rust and for use in surfacing
bearings. Monthly capacity for cadmium metal is 27 metric tons.
Total 1977 production of cadmium at this plant was 218 metric
tons. Thus, cadmium production in 1977 at the sampled plant was
67 percent of total capacity.
Using sulfur dioxide from the roasting of sulfide ores, the
plant produces up to 6,820 metric tons of sulfuric acid per
month. A small amount is used as makeup in the leach process
and the balance is sold. Total 1977 production of sulfuric acid
at this plant was 59,474 metric tons. Thus, sulfuric acid
production at the sampled plant was 73 percent of total
capacity.
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Water Usage
All water used in the sampled plant is bought and originates
from the city water treatment plant. The water is taken from a
freshwater surface supply by the city and softened with lime and
a polyelectrolyte, filtered, and chlorinated before arriving by
pipe at the zinc plant for in-plant uses. In 1977, the zinc
plant purchased 1,406,377 kiloliters from the city. Based on this
figure, the monthly average was 117,198 kiloliters, the daily
average 3,853 kiloliters, and the hourly average 160 kiloliters.
The plant operates 24 hours per day, 7 days per week.
The plant reas or operations using water and their estimated
usage rates are shown in Table 3. The usage rates were
estimated using plant supplied data for 1 February 1978 to 28
1978.
TABLE 3. MONTHLY WATER USAGE BY DIVISION FOR
SAMPLED PLANT (FEBRUARY 1978)
Division
Water usage
monthly total Daily average
(kiloliters) (kiloliters/day)
Waste-heat boilers
Process boilers
Roasting (cooling)
Laboratory
Change house (sanitary)
ZnS leaching
ZnO leaching
ZnS purification
ZnO purification
ZnS cell division
ZnO cell division
ZnS casting (contact cooling)
ZnO casting (contact cooling)
Pilot plant
Air compressor cooling
Demineralizer3
Zinc duct (mixing)
ZnSOij purification
ZnO die casting (contact cooling)
Cadmium (contact cooling)
Acid plant (scrubbing)
TOTALS :
7,658
10,496
17,245
469
1,249
2,854
2,706
2,078
1,556
2,388
2,596
1,764
1,764
466
1,529
38,871
76
223
337
337
12,180
108,892
273
375
616
17
45
102
97
74
56
85
93
63
63
17
55
1,388
3
8
12
12
435
3,889
Does not include waste-heat and process boiler water which is
also demineralized.
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The major water demand in the zinc plant is for demineralized
water. Of the 38,871 kiloliters per month demineralized
(excluding boiler feed water), approximately 18,420 kiloliters
is used as part of two scavenger processes in the purification
areas. An additional 6,828 kiloliters per month is used as wash
water in the leaching operations. The remaining 16,623 kilo-
liters per month is used for regeneration of the demineralizers
and for dilution water in the production of sulfuric acid. The
regeneration water requirements account for approximately
80 percent of this remaining 16,623 kiloliters per month.
Sources of Wastewater
All water used within the zinc plant is eventually treated by
the plant's waste treatment system before being discharged to a
surface waterway. This includes any rainwater runoff up to 12.7
centimeters of rain in 24 hours. The major exceptions to this
are 1) demineralized water leaving as dilution water in plant
produced surf uric acid (98 percent I^SOit) , 2) demineralized
water lost as steam from the plant boilers, 3) cooling tower
drift and evaporation, 4) evaporation from the treatment plant
holding lagoon, and 5) water leaving the waste treatment plant
in sludge residues.
All wastewater, including rainfall runoff within the plant
boundaries is sent to the treatment plant holding lagoon except
for the gas scrubber wastewater from the roasting operation
which enters the treatment plant in a separate pipe. This gas
scrubber wastewater results from the scrubbing of the roaster
smoke stream for particulate removal. The scrubber treats the
smoke immediately after a Cottrell electrostatic precipitator
system. During the sampling period, the gas scrubber wastewater
flow averaged 170 liters per minute but on the previous month
averaged 295 liters per minute. This waste stream travels to
the treatment plant in polyvinyl chloride plastic pipe.
As mentioned, the holding lagoon collects all other wastewater
generated within the zinc plant. The major source of wastewater
is noncontact cooling water. All cooling water receives 5.7
liters of scale, corrosion, and foaming inhibitors, approximately
8.2 kilograms of chromate, and 8.2 kilograms of chlorine per
day. Contact cooling water from zinc and cadmium casting also
is sent to the holding pond. Noncontact cooling water is both
used on a once-through (roasting) and closed loop (all other
plant cooling) basis. Cooling tower blowdown and contact
cooling flow rates to the holding lagoon are not measured by the
plant and thus actual flow to the lagoon is not known.
Another source of wastewater to the holding lagoon is regenerate
waste from the demineralizers. Again, actual flow to the lagoon
is not measured and is thus unknown. Regenerates used are sul-
furic acid and caustic.
8
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Another source of wastewater is process water from the zinc
oxide and zinc sulfide leaching, purification and electrolytic
operations. Cell house washing and spent solution wastage (none
under normal operating conditions) are two examples of wastewater
sources from these operations. Again, actual flow to the lagoon
is not measured and is unknown.
Sanitary wastewater from the change (shower) house and other
plant buildings receives minimal primary treatment with clori-
nation (1.4 kilograms per day) to a residual of 1.5 to 3.0 mg/&
combined chlorine before being sent to the holding lagoon. An
overflow wier allowed a measurement of flow during the sampling
period for this source. Flow varied from 110 to 276 liters per
minute and average 227 liters per minute.
As mentioned previously, all plant rainwater runoff is also sent
to the lagoon. No rain was experienced during the sampling
period and no runoff entered the lagoon.
Two minor sources of wastewater to the holding lagoon come from
plant laboratory and pilot plant activities.
Wastewater Treatment Plant
The sampled plant has a physical/chemical waste treatment plant
as shown in Figure 2. Wastewater enters the system from two
sources. These are the gas scrubber and the holding lagoon.
The holding lagoon has a design capacity of 22,710 kiloliters
with a detention time of 7 days. Due to solids accumulation
for which the lagoon was not designed for, current actual
capacity is estimated to be 40 to 50 percent of design. The
reason for this situation is discussed in the results and con-
clusion section of this report.
Both sources of wastewater to the treatment plant first enter
the flash mixing tank, where they are contacted with slaked lime.
Although the plant does not measure lime usage on a day-by-day
basis, the lime slaker (when running) ran at 100 percent of the
design rate of 11.35 kilograms per minute as CaO during the
sampling period. The flash mixer has a 28 kiloliter capacity.
Diffused air is also pumped into the mixer for agitation and
mixing enhancement. The limed wastewater next enters the
reactor clarifier. Immediately before entering the clarification
section, a flocculant is added to aid in flocculation. Again,
the plant does not measure an addition rate but daily usage
amounted to approximately 22.7 kilograms. The clarifier, itself,
is radial feed, central overflow in design. It has a capacity
of 1,506 kiloliters, a design detention time of 6 hours, and a
maximum design overflow rate of 3,936 liters per minute. During
the sampling period, the clarifier had a clear depth (distance
from water surface to sludge blanket) of 0.5 to 0.9 meters. The
clarified wastewater overflows the clarifier and is discharged to
the channel.
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V^/-!1—' SCRI
SANITARY
WASTE TREATMENT
ACID
SCRUBBER WATER
J) INTAKE WATER
LIME SLURRY \J
o SAMPLE POINTS
6 MILLION
GAL. LAGOON I
LIME
SLAKER
CITY WATER
VACUUM
DRUM FILTER
FLOCCULANT
(POLYMER)
SOLIDS
SUPERNATANT TO
LAGOON IN
EMERGENCY
PLANT
DRAINAGE
DIVERSION IFpH<90R>ll
—xjJL-x
SHI P CHANNEL-^PARSCHELL FLUME (METERED)
Figure 2. Zinc plant waste treatment system.
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Effluent pH was in the 10-11 range during sampling but requires
no adjustment due to applicable state standards for pH.
Solids leave the bottom of the clarifier and are pumped to a
sludge thickener. Supernatant (overflow) off the thickener was
designed to be discharged to the flash mixing tank but is
currently recycled back to the lagoon. The thickener has a
174 kiloliter capacity, detention time of 10-11 hours, and
design overflow rate of 102 liters per minute. Thickened solids
(5-10 percent by volume) are pumped from the thickener bottom to
a vacuum filter. Filtrate off the vacuum filter was designed to
flow to the thickener at a rate of 45 liters per minute but
currently is sent to the flash mixer. Filter cake (15 to 30
percent solids by volume) is pumped to drying beds on the plant
site. Dried solids are shipped to a registered solid waste
disposal site, for an annual fee paid by the plant.
During the sampling period (48 hours), the treatment plant dis-
charged 5,800 kiloliters or 2,900 kiloliters per day. During
1977, the treatment plant discharged 927,000 kiloliters or
2,500 kiloliters per day. Allowing for scheduled maintenance
and other down time during 1977, the amount of wastewater
treated during the sampling period is considered representative
of normal plant operation.
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 1, with a few modifications designed
to better insure sample integrity, chain of custody, and site
specific requirements. Since the plant operated 24-hours/day,
7 days/week, 48-hour flow-proportioned samples were collected at
the following locations:
• City water supply at the waste treatment plant labora-
tory sink,
• holding lagoon water approximately 15 meters from where
it enters the waste treatment plant flash mixing tank,
• gas scrubber wastewater approximately 1.5 meters from
where it enters the waste treatment plant flash
mixing tank, and
• plant effluent approximately 18 meters downstream from
the waste treatment plant reactor clarifier.
All four points were composited over a 48-hour period, from
10:00 A.M. March 8 to 10:00 A.M. March 10, 1978. The city water
supply was the only sample point not flow proportioned.
Because of the way the wastewater treatment system was con-
structed (pres'surized pipe flow) , it was not possible to use
automatic samplers and still guarantee sample integrity. There-
fore, 48-hour grab samples were collected once every hour with a
11.3 liter Teflon®-lined stainless steel bucket. Aliquots were
removed from the bucket using glass beakers and placed in the
appropriate sample containers. Care was always taken to insure
the sample remained homogeneous while in the bucket. It took
(1) 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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approximately 5 minutes to remove all aliquots from the bucket
and place them in the containers. For flow proportioning, the
flow was first checked each hour, the bucket filled, and the
appropriate volumes measured out.
A fifth sampling location was added on the second day of the 48-
hour sampling period. After discussions with plant personnel,
it was decided to run a 24-hour composite on the sanitary treat-
ment plant effluent before it enters the holding lagoon. Due to
both minimal soluble organics removal in the sanitary treatment
plant and the addition of chlorine to the waste stream, it was
felt that sufficient potential for trihalomethane formation
existed to warrant an individual sample of this stream. Thus
for a 24-hour period, samples were composited on a flow-
proportioned basis in the same manner as the previously described
four points.
Sampling logistics for subsequent priority pollutant analysis
are shown in Table 4 (1, 2). Before sampling began, bottle
labels were filled out and affixed to appropriate sample bottles.
Figure 3 shows the bottle label designed by MRC for sample
identification. Once applied to the bottle, clear tape was put
over the label to prevent water damage to the label.
TABLE 4. SAMPLING LOGISTICS FOR PRIORITY POLLUTANTS
Analysis fraction
Container, per
sampling point
Preservatives
required (1, 2)
Volatile organics
Nonvolatile organics
(base/neutral, acid,
pesticide, and PCB's)
Metals
Cyanide (total)
Phenol (total)
Asbestos
4-40 ml glass vials
w/Teflon-lined septa
1-3.785 liter amber glass
pharmaceutical jug w/
Teflon-lined cap
1-500 ml plastic
1-500 ml plastic
1-500 ml glass
1-1 liter plastic
Keep at 4"C, if residual
chlorine is present (KI
paper turns blue) then
add 0.03 ml of 10%
sodium thiosulfate to
each bottle.
Keep at 4°C.
In the lab add 5 ml of
redistilled HNO3,
keep at 4°C.
Adjust pH > 12 w/lON
NaOH, keet at 4"C.
0.5 g CuSOi, at beginning,
adjust pH < 4 w/H3PO,,
(100 ml con H3?0it to 1
liter of water) keep
at 4°C.
1.0 ml of HgCl solution
(2.71 g HgCl in 100 ml
distilled water), keep
at 4°C.
(2) 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
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Job
Sample or Run No..
Sample Location
Type of Sample
Analyze for
Preservation
Comments _
Log No. Date
Initials
Figure 3. MRC sample bottle label design.
14
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Four samples, collected every twelve hours, were collected for
volatile organics analysis, as opposed to the one grab sample
recommended in Reference 1. Each of the four samples per stream
were immediately hermetically sealed 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, tested by
potassium iodide paper, in any of the wastewater streams, preser-
vatives were not required in the volatile organic sample (l).a
The time for volatile organic sample collection was as follows:
• 48-hour (lagoon, scrubber, city water, effluent) -
12:00 A.M. 8 March, 12:00 P.M. 8 March, 12:00 A.M.
9 March, and 12:00 P.M. 9 March.
• 24-hour (sanitary) - 4:00 P.M. 9 March, 12:00 P.M.
9 March, and 8:00 A.M. 9 March.
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 1.
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.
The pH of each sampling point was noted each hour from either
automatic monitors or treatment plant operator measurements.
The pH of the sanitary treatment plant discharge was not taken.
The temperature of the discharge from tne zinc treatment plant
was recorded hourly from an automatic monitor.
The flow of the gas scrubber waste stream and the plant discharge
was recorded hourly from an automatic monitor. The flow of the
holding lagoon waste stream was estimated for flow proportioning
needs by difference between the treatment plant discharge flow
and the gas scrubber waste stream flow. The sanitary treatment
plant discharge flow was recorded hourly by measuring a 60°
V-notched overflow wier. City water flow was not measured.
aThe city water supply and sanitary wastewater should have
tested positive for free chlorine but did not. Free residual
in the city supply had evidently dissipated by the time it
reached the tap and the sanitary discharge was evidently very
high in chlorine demand.
15
-------
Sample Container Preparation
All glass containers and beakers were thoroughly cleaned with
strong acid (50% sulfuric acid + 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 Procedure
Recommended analytical procedures (1) 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)
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 (1).
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 zinc industry, pesticides were also not
analyzed in the samples. The only source of pesticides would be
the city water supply.
16
-------
The analytical procedure (1) 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 (1). Appendix B lists those
priority pollutants classified as volatile organics.
Four hermatically 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 4 is a simplified
diagram of the analytical scheme for volatile organics analysis.
COMPOSITE
4 VIALS
SPARGE 5 ml SAMPLE
WITH HaiUM
ONTO TENAX-SILICA TUBE
Figure 4. Analytical scheme for volatile
organics analysis.
17
-------
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.
Qualitative identification of a compound was made using three
criteria listed in the protocol (1): 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 zinc manufacturing, pesti-
cides were not analyzed in the samples.
The analytical procedure is described in Reference 1. Figure 5
depicts the sample processing scheme for the base/neutral and
acid fractions. The sample solution, 2 &, 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 analysed. Analyses
were performed on the GC-MS system using SP 2250 and Tenax GC
columns for base/neutral and acid samples, respectively (1).
Ifi
-------
ADJUST SAMPLE pH TO
pH > 11
W/SODIUM HYDROXIDE
METHYLENE CHLORIDE
EXTRACTION
BASES & NEUTRALS
ACIDS (PHENOLS), UNEXTRACTABIES
BOTTOM LAYER
DRIED ON
ANHY. SODIUM SULFATF.
CONCENTRATE
IN K-D EVAP.
TO 1ml
GC/MS
IDENTIFICATION &
QUANTTTATION
TOP LAYER
Figure 5,
CHANGE pH < 2
W/HYDROCHLORICACID
METHYLENE CHLORIDE
EXTRACTION
ACIDS
AQUEOUS
DRIED ON ANHY.
SODIUM SULFATE
SAVE 25-: |
DISCARD REW.DEPj
Sample processing scheme for non-
volatile organics analysis.
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 (3, 4).
(3) Standard Methods for the Examination of Water and Waste-
waters. Fourteenth Edition, American Public Health
Association, Washington, B.C., 1976. 874 pp.
(4) Carter, M. J. and M. T. Huston, Preservation of Phenolic
Compounds in Wastewaters. Environmental Science and
Technology, 12(3):309-313, 1978.
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 gas scrubber and lagoon waste-
streams, this sample was vacuum filtered with 0.5 ym 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 seven samples for metals
analysis because two samples required filtration and analysis
of filtrate and filter. Three of the sampled 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 preserved with a HgCl solution (1). Samples were
then stored at 4°C for possible future analysis. No asbestos
samples were analyzed for this project.
Cyanide (Total)
Total cyanide was analyzed according to the procedure in
Reference 1. 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 (1-3).
Phenol samples were preserved in the field by adding 1.0 g
CuSOtf, maintaining the pH at less than 4 with H3POtf and storing
the sample at 4°C. Recent research has indicated this preserva-
tion technique is adequate for at least 8 days (4). All
phenolic samples collected in this study were analyzed within 5
days of collection.
20
-------
SECTION 5
RESULTS AND CONCLUSIONS
ORGANICS
The types and concentrations of organic priority pollutants
found in the five water streams sampled are listed in Table 5.
Five compounds in the effluent can be directly traced to the
city water supply. These are methylene chloride, toluene,
bis(2-ethyl hexyl)phthalate, bromodichloromethane and anthracene.
Confirmation of the existence of these compounds in the city
water supply from the city treatment plant is not possible at
this time as no analysis by the city is available (samples have
been taken by state authorities but data is not yet available).
Trichlorofluoromethane in the effluent can be traced to the gas
scrubber wastewater but is not added by the plant directly. The
compound is either originating from the scrubbing operation on
the roasting smoke stream or is forming at the scrubbing water
temperature from chlorine in the water supply and flourine in
the smoke stream. Trichloroethylene in the effluent can be
traced to the scrubber wastewater, the holding lagoon, and the
sanitary discharge. No trichloroethylene is used at the plant.
Therefore, the compound is forming in these waste streams.
Chlorine exists in cooling water going to the holding lagoon,
city water going to the scrubber, and city water used for sani-
tary purposes. The compound is forming within the plant as it
does not appear in plant intake water.
The phthalates found in all sample water streams can originate
from the city water supply, as previously mentioned, PVC pipe
used to transport the gas scrubber water and holding lagoon
water to the treatment plant and gloves used during sampling in
handling the wastewater. Fluoranthene in the lagoon water can
also be traced to the city water supply although none was found
in the effluent. Pyrene and benzo(a)pyrene found in the holding
lagoon do not appear in the plant effluent.
The only compound in the plant discharge not appearing in any
water stream going to the treatment plant is chloroform. As the
plant does not chlorinate the effluent, this compound cannot be
accounted for unless it exists in the slaked lime or flocculant
added to the wastewater during precipitation/clarification.
21
-------
TABLE 5. ORGANIC PRIORITY POLLUTANTS IN ZINC
PLANT WATER STREAMS
Water source
Organic priority
pollutant identified
Concentration,
Plant intake (city water)
Gas scrubber wastewater
Holding lagoon wastewater
Sanitary discharge
Plant effluent
Methylene chloride
Toluene
Bromoform
Dibromochloromethane
Bromodichloromethane
4-Chlorodiphenyl ether
N-Nitrosodiphenylamine
Bis(2-ethyl hexyl)phthalate
Pluoranthene
Benzo(a)anthracene
Anthracene
Methylene chloride
Toluene
Trichlorofluoromethane
Trichloroethylene
Bis(2-ethyl hexyl)phthalate
Methylene chloride
Toluene
Trichloroethylene
Diethyl phthalate
Bis(2-ethyl hexyl)phthalate
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Methylene chloride
Toluene
Trichloroethylene
Diethyl phthalate
Bis(2-ethyl hexyl)phthalate
Methylene chloride
Toluene
Trichlorofluoromethane
Chloroform
Bromodichloromethane
Trichloroethylene
Bis(2-ethyl hexyl)phthalate
Anthracene
1.3
2.7
5.3
7.7
9.3
2.4
4.6
8.6
5.4
2.4
0.1
224
57
4.8
4.2
22
3,3
8.0
2.6
0.9
8.7
2.2
2.2
2.0
1.2
0.7
17
1.2
3.6
10
2,610
8.8
101
53
7.3
7.2
107
0.5
22
-------
Analytical workup for organic priority pollutants involves the
use of methylene chloride for extraction purposes. The high
levels found in the gas scrubber waste stream and the plant
effluent can be explained by possible contamination during
analytical workup.
Collectively, except for the methylene chloride concentration in
the plant effluent and scrubber wastewater, the levels equal or
are less than 100 yg/£. The majority are below 10 yg/£. It
should be emphasized that this analysis most importantly indi-
cates the presence of the particular compound. Additional
analysis is needed to more accurately quantify the actual con-
centrations. No mass loadings or effluent factors were calcu-
lated for these organics.
Finally, it should also be emphasized that none of the compounds
identified is directly added by the plant. Compounds identified
are either being formed chemically within the plant, being
picked up as stream contaminants from pumps, pipes, or quench
operations, or coming to the plant in the city water supply.
Metals
Priority pollutant metals found in the five sample locations are
presented in Table 6. Mass loadings into and out of the treat-
ment plant with removal efficiencies are shown in Table 7.
It should be noted that with solids overflow from the thickener
re-entering the lagoon, metals concentrations are higher than if
no recycle was occurring. Thus, mass loadings for the lagoon
are higher than the true loadings originating from plant waste-
waters. Each individual waste stream entering the lagoon would
have to be measured to get actual mass loadings for plant
wastewater going to the treatment system. Metals removal is in
general quite good for this treatment plant. This fact is
expected for the amount of lime being added and the pH of the
discharge. By keeping the pH high, metals are remaining
insoluble and thus increasing removal efficiency.
Metal effluent factors for the sampled waste streams and plant
effluent are given in Table 8. In addition, effluent factors
for the gas scrubber waste stream based on E^SO^ production are
given in Table 9.
Net metal effluent factors are given in Table 10. These factors
account for metal concentrations not added by the plant but
present in the incoming city water supply. Production figures
and water usage rates used as a basis for calculations are pre-
sented in Appendix C.
23
-------
TABLE 6. METALS ANALYSIS - AA
Metal
(total)
Silver
Beryllium
Cadmium
Chromium
Copper
Nickel
Lead
Antimony
Zinc
Arsenic
Mercury
Thallium
Selenium
Gas scrubber
liquid, mg/1
0.
<0.
42
0.
24
0.
17
01
02
11
01
Gas
scrubber
solids
mg/g
11
<0
12
0
4
0
210
.10
.11
.5
.05
<1.5 <8.4
78
<2.
<0.
0.
0.
6
01
32
35
60
<0
11
<0
12
.11
.53
mg/1
0.73
<0.01
0.83
<0.007
0.31
0.04
15
<0.59
4.1
<0.01
1.00
<0.04
0.83
Lagoon
liquid ,
mg/1
0.09
<0.02
8.1
2.2
6.2
0.08
8.5
<1.5
2,100
0.84
0.02
<0.09
0.17
Lagoon
mg/g
0.62
<0.04
2.9
<0.04
2.1
<0.02
26
<3.0
36
0.45
0.65
<0.19
0.09
solids
mg/1
0.11
<0.01
0.51
<0.01
0.44
<0.01
4.4
<0.52
6.2
0.08
0.11
<0.03
0.01
Sanitary ,
mg/1
0.01
<0.01
7.0
<0.01
0.69
<0.01
0.57
<0.8
110
0.05
<0.02
<0.05
<0.01
City
water ,
mg/1
<0.01
<0.01
<0.01
<0.01
0.02
<0.01
<0.05
<0.8
0.38
<0.01
<0.01
<0.05
<0.01
Effluent,
mg/1
0.02
<0.01
0.02
0.14
0.03
<0.01
<0.05
<0.8
1.1
<0.01
<0.01
<0.05
<0.04
-------
TABLE 7. METAL MASS LOADINGS AND REMOVAL EFFICIENCIES FOR
WASTE TREATMENT PLANT (AA BASIS)
Metal
(total)
Silver
Beryllium
Cadmium
Chromium
Copper
to .
en Nickel
Lead
Antimony
Zinc
Arsenic
Mercury
Thallium
Selenium
Gas scrubber
liquid,
kg/day
0.003
<0.005
10
0.027
6.00
0.002
4.07
<0.37
19
0.64
0.001
0.08
0.08
Gas scrubber
solids,
kg/day
0.18
<0.002
0.20
0.002
0.08
0.009
3.5
<0.14
1.0
<0.002
0.24
<0.01
0.20
Lagoon
liquid,
kg/day
0.25
<0.05
21
5.8
16
0.21
22
<4.0
5,500
2.2
0.04
<0.24
0.45
Lagoon
solids,
kg/day
0.29
<0.02
1.3
<0.02
1.2
<0.001
12
<1.4
17
0.21
0.30
<0.09
0.04
Plant
effluent,
kg/day
0.04
<0.3
0.06
0.41
0.10
<0.01
<0.14
<2.3
3.3
<0.03
<0.006
<0.14
0.12
Removal
efficiency,
percent
94
-a
100
93
100
94
100
_a
100
99
99
_a
85
aRemoval efficiency cannot be calculated since the metal concentration in all samples
was below instrument detection limits.
-------
TABLE 8. METAL EFFLUENT FACTORS FOR SAMPLED ZINC PLANT (AA BASIS)
Effluent factor, mq/kq of cathode zinc
Metal
(total)
Silver
Beryllium
Cadmium
Chromium
Copper
Nickel
Lead
Antimony
Zinc
Arsenic
Mercury
Thallium
Selenium
Gas scrubber
liquid
0.02
<0.03
54
0.14
32
0.01
21
<2.0
100
3.4
0.005
0.41
0.45
Gas scrubber
solids
0.95
<0.01
1.07
0.01
0.40
0.05
19
<0.74
5.3
<0.01
1.3
<0.05
1.1
Lagoon
liquid
1.3
<0.28
113
31
87
1.1
119
<21
29,000
12
0.24
<1.3
2.4
Lagoon
solids
1.5
<0.08
7.1
<0.09
6.1
<0.01
62
<7.30
88
1.1
0.06
<0.45
0.21
Plant
effluent
0.23
<0.15
0.34
2.2
0.53
<0.07
<0.74
<12
17
<0.15
<0.03
<0.77
0.61
TABLE 9. METAL EFFLUENT FACTORS FOR SAMPLED ZINC PLANT
(GAS SCRUBBER/H2SO4)
Effluent factor,
rag/kg of H2SO4
Atomic adsorption basis
(AA)
Metal
Gas scrubber
liquid
Gas scrubber
solids
Silver
Beryllium
Cadmium:
Chromium
Copper
Nickel
Lead
Antimony
Zinc
Arsenic
Mercury
Thallium
Selenium
0.02
<0.03
63
0.16
36
0.01
25
<2.3
117
3.9
0.01
0.48
0.53
1.1
<0.01
1.2
0.01
0.47
0.05
22
<0.86
6.2
<0.01
1.5
<0-06
1.2
26
-------
TABLE 10. NET METAL MASS EFFLUENT FACTORS
FOR SAMPLED ZINC PLANT
Metal
(total)
(AA)
Silver
Beryllium
Cadmium
Chromium
Copper
Nickel
Lead
Antimony
Zinc
Arsenic
Mercury
Thallium
Selenium
Net effluent factor.
Plant
effluent
0.23
<0.15
0.34
2.17
0.53
<0.07
<0.74
<12
17
<0.15
<0.03
-------
These data show the treatmhnt plant to be effectively reducing
all metals added to city water during plant use to acceptable
and applicable state discharge requirement levels.
Flow, pH, Temperature
Temperature and pH measurements taken during the sampling period
for the plant effluent are shown in Table 11. Additional pH
measurements and flow measurements are presented in Appendix C.
TABLE 11. DATA COLLECTED FOR PLANT DISCHARGE
Sampling Point:
Sampling Period:
Plant Discharge
10:00 A.M. March 8, 1978 to
10:00 A.M. March 10, 1978
Hour Temperature , c
3/8/78
10
11
12
1
2
3
4
5
6
7
8
9
10
11
12
3/9/78
1
2
3
4
5
6
7
8
9
10
11
12
1
2
3
4
5
6
7
8
9
10
11
12
3/10/78
1
2
3
4
5
6
7
8
9
64
64
64
64
64
65
65
64
64
64
65
65
64
64
64
64
64
64
63
63
62
60
62
64
64
65
66
66
67
67
67
68
68
69
69
70
70
71
72
71
71
71
71
71
71
71
72
73
T pH
10.3
10.3
10.3
10.3
10.3
10.1
10.1
10.0
10.0
10.0
9.9
9.9
9.9
10.0
9.9
9.8
9.9
9.9
9.9
9.9
9.9
9.9
9.9
9.8
9.9
9.9
9.9
9.9
9.9
9.9
9.9
9.8
9.9
9.8
9.8
9.8
9.7
9.7
9.7
9.7
9.7
9.7
9.7
9.6
9.7
9.6
9.6
9.6
28
-------
Total Phenol and Total Cyanide
Cyanide concentrations in all samples were below the detection
limit of .002 mg/1. Phenol concentrations in all samples were
below the detection limit of .002 mg/1 except for the sanitary
discharge. This point had a phenol concentration of .007 mg/1.
Waste Treatment System
The waste treatment system at the sampled plant utilized the
best design parameters available as originally conceived.
However, as currently operated, the plant is less than 100 per-
cent efficient.
During the sampling period, the plant was experiencing a solids
overloading of both the reactor clarifier and the sludge
thickener. During the sampling period no more than a 0.9 meter
clear depth in the reactor clarifier was observed and inter-
mittent overflow of solids from the sludge thickener back to the
holding lagoon was a common occurrence. The treatment system
was originally designed to have the clear overflow from the
thickener discharged to the flash mixing tank. Due to the
solids overloading, this overflow is now returned to the holding
lagoon. The lagoon was not designed to handle any solids and
thus two undesigned operating conditions currently exist.
First, the lagoon has over a period of time accumulated solids
from the sludge thickener overflow so that a majority of the
holding lagoon capacity has been lost. Second, a dredge has
been placed in the lagoon to pump solids back to the treatment
plant for settling and removal. However, this operation has
strained the system even further. In short, the treatment plant
is producing more solids than the thickener/vacuum filter can
remove. Solids are simply being recycled within the treatment
system and the lagoon.
By increasing vacuum filter capacity, this problem could
potentially be reduced.
A water balance of this treatment plant (with current design
modifications) is presented in Appendix C.
29
-------
SECTION 6
REFERENCES
1. 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.
2. 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.
3. Standard Methods for the Examination of Water and Waste-
waters, Fourteenth Edition, American Public Health
Association, Washington, D.C., 1976. 874 pp.
4. Carter, M. J. and M. T. Huston. Preservation of Phenolic
Compounds in Wastewaters. Environmental Science and
Technology, 12 (3):309-313, 1978.
5. 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 pp.
30
-------
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
1i1i1-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-Chloronaphthalene
(continued)
31
-------
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'-Dichlorobenzidine
Dichloroethylenes (1,1-dichloroethylene and
1,2-dichloroethylene)
1,1-Dichloroethylene (vinylidine chloride)
1,2-Trans-dichloroethylene
2,4-Dichlorophenol
Dichloropropane and dichloropropene
1,2-Dichloropropane
1,3-Dichloropropylene
(cis and trans-1,3-dichloropropene)
2,4-Dimethylphenol
Dinitrotoluene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
1,2-Diphenylhydrazine
Ethylbenzene
Fluoranthene
(continued)
32
-------
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 dinitrocresql)
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)
33
-------
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'-DDT
4,4'-DDT
4,4'-DDE (p,p'-DDX)
4,4'-DDD (p,p'-TDE)
(continued)
34
-------
TABLE A-l (continued).
Compound name
Endosulfan and metabolites
a-Endosulfan
6-Endosulfan
Endosulfan sulfate
Endrin and metabolites
Endrin
Endrin aldehyde
Heptachlor and metabolites
Heptachlor
Heptachlor epoxide
Hexachlorocyclohexane
a-BHC
6-BHC
A-BHC (lindane)
6-BHC
Polychlorinated bipnenyls (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)
35
-------
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)
36
-------
APPENDIX B
PRIORITY POLLUTANT ANALYSIS FRACTIONS
TABLE B-l. VOLATILE COMPOUNDS
Compound
Compound
Chloron;? thane
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
37
-------
TABLE B-2. BASE NEUTRAL EXTRACTABLE COMPOUNDS
Compound
Compound
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachloroethane
1,2-Dichlorobenzene
Bis {2-chlorois6propy1) 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-Diphenylhydrazine
2,4-Dinitrotoluene
N-nitrosodiphenylamine
Kexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene
Anthracene
Diethyl phthalate
Dimethyl phthalate
Fluoranthene
Pyrene
Di-n-butyl phthalate
Benzidine
Butyl benzyl phthalate
Chrysene
Bis(2-ethylhexyl) phthalate
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Eenzo (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-DimethyIphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
4-Nitrophenol
Pentachlorophenol
38
-------
TABLE B-4. PESTICIDES AND PCB
Compound
B-Endosulfan
a-BHC
Y-BHC
B-BEC
Aldrin
Heptachlor
Heptachlor epoxide
a-Endosulfan
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
39
-------
APPENDIX C
PLANT PRODUCTION AND TREATMENT PLANT DATA
Table C-l presents data taken by the treatment plant operators
during sampling. The data is in English units. Table C-2 is
plant production data for 1977. Figure C-l is a water balance
of the waste treatment plant.
40
-------
TABLE C-l. LOG SHEET WASTEWATER TREATING UNIT
affluent flow
(gal/day)
affluent pH
effluent temperature,
•f
Effluent suspended
•olid*
Reaator well pH
Reactor meter pH
Neutralization pH
Iiime feed manual/
automatic
time feed rate
£•> Lime a laker water rate
L_J
SOj scrubber water
flow (gpm)
802 scrubber water
pH
Lagoon water pH
Reaator well
% eolide
R-C mid-level
% eolide
Clear depth olarifier,
ft.
3 in. Denver mud pump
Filter on/off
C-D mud pump on/off
600 gpm on/off
500 gpm on/off
8:00 m
937,500
10,2
6S«
0
8.06
8.3
-
Auto.
8/100
4,820
30
1.2
2.4
85
88
3
On
On
On
On
Off
loioo m
850,000
10,3
64'
0
10.3
10.8
-
AutO.
8/100
Off
30
1.3
2.54
85
88
2
On
On
On
On
Off
12:00 AH
575,000
10.2
64«
0
9.65
9.8
-
Auto.
8/100
4,820
30
1.3
2.6
85
90
1-1/2
On
On
On
On
Off
2:00 PM
837,500
10.1
«•
0
10.0
10.4
-
AUtO.
8/100
Off
30
1.35
2.36
80
85
1-3/4
On
On
On
On
Off
4:00 PM
837,500
10.1
65"
0
9.63
6.7
-
AutO.
8/100
4,820
24
1.38
2.2
84
80
1-1/8
On
On
On
On
Off
6tOQ PM
926,250
10.0
64°
0
10.30
10.4
-
AutO.
8/100
Off
24
1.32
1.84
82
86
3
On
On
on
On
Off
8:00 PM
1,225,000
10.0
64°
0
8.5
9.8
-
AUtO.
8/100
4,820
24
1.20
1.32
82
86
2
On
On
On
On
Off
10:00 PH
1,275,000
9.9
65'
0
9.65
10.0
-
AUtO.
8/100
4,820
24
1.04
2.24
82
88
4
On
On
On
On
Off
13:00 PM
750,000
9.9
64"
0
8.6
8.9
-
AUtO.
8/100
Off
24
1.2
1.9
84
90
1-3/4
On
On
On
On
Off
2:00 AH
750,000
9.9
64°
0
10.4
10.5
-
AutO.
8/100
Off
24
1.3
2.0
85
90
3
On
On
On
On
Off
4:00 AM
987,500
9.9
63°
0
9.0
9.0
-
Auto.
8/100
4,820
24
1.2
2.2
84
92
3-1/2
On
On
On
On
Off
6:00 AM
887,500
9.9
63»
0
9.6
10.2
-
Auto.
8/100
Off
24
1.2
2.1
84
92
3-1/2
on
On
On
On
Off
(continued)
-------
TABLE C-l (continued).
Effluent flow
(gal/day)
Effluent pH
Effluent temperature,
Effluent suspended
solids
Reactor well pH
Reactor meter pH
Neutralization pH
Lime feed manual/
automatic
Lime feed rate
Lime slaker water rate
802 scrubber water
flow (gpm)
S02 scrubber water
pH
Lagoon water pH
Reactor well
* solids
R-C mid-level
» solids
Clear depth clarifies?,
ft
3 in. Denver mud pump
Filter on/off
(3-D mud pump en/off
600 gpm on/off
500 gpm on/off
8:00 AM
962,500
9.9
62°
0
8.2
8.4
-
Auto.
8/100
4,820
24
l.SO
1.63
70
80
3-3/4
on
On
Oft
on
Off
10:00 AH
800', 000
9.9
64°
0
11.32
11.6
-
AUtO.
8/100
Off
24
1.60
9.53
85
85
4
Off
On
On
Off
Off
12:00 AH
950,000
9.9
64°
0
8.5
8.0
-
Auto.
8/100
4,820
24
1.52
6.76
90
94
4
Off
On
On
Off
Off
2:00 PM
900,000
9.8
66°
0
9.5
9.5
-
Auto.
8/100
4,820
,4
1.5
6.47
92
92
3-3/4
Off
on
On
Off
Off
4:00 PH
375,000
9.9
67°
0
9.6
9.9
-
AUtO.
8/100
Off
20
1.4
6.5
92
94
5
On
On
Off
off
Off
6:00 PM
825,000
9.8
68°
0
9.6
9.4
-
Auto.
8/100
4,820
0
_
6.5
88
as
2-1/2
Off
Off
Off
Off
Off
8:00 PM
650,000
9.8
69°
0
9.9
10.3
-
Auto.
8/100
Off
10
1.1
9.9
87
90
2
On
On
On
Off
Off
10:00 PH
537,500
9.7
70°
0
10.4
10.7
-
AUtO.
8/100
Off
10
1.0
7.6
80
81
1-1/2
On
On
On
Off
Off
12:00 PH
525,000
9.7
71°
0
9.9
10.0
-
Auto.
8/100
Off
0
_
2.8
82
90
2
on
On
On
On
Off
2:00 AM
487 , 500
9.7
71°
0
11.0
11.5
-
AUtO.
8/100
Off
20
1.1
3.0
95
90
2
On
On
On
On
Off
4:00 AM
475,000
9.7
71°
0
7.9
8.2
-
Auto.
8/100
4,820
20
1.2
2.8
89
95
2
On
On
On
On
Off
6:00 AM
450,000
9.6
71°
0
10.0
10.5
-
Auto.
8/100
Off
0
-
2.7
90
95
2
On
Off
Off
On
Off
-------
TABLE C-2. PRODUCTION FIGURES FOR SAMPLED PLANT (1977)
Total production
Cathode zinc:
Cathode cadmium:
H2SOIJ production:
Water usage
City water:
City water demineralized:
Water treated from gas scrubber water:
Water treated from holding lagoon:
Total water treated:
Dry residue from treatment plant:
69,008 metric tons
218 metric tons
59,474 metric tons
(98% HjSO^)
1,406,377 kilo-
liters
506,293 kiloliters
98,410 kiloliters
828,915 kiloliters
927,325 kiloliters
2,906 metric tons
at 20% by volur.e
solids
43
-------
11.35KIIOGRAMS/MIN^aO
FLOCCULANT
22.7 KILOGRAMS/DAY
4190 LPM MAX. DESIGN
3936 LPM MAX. DESIGN
4228 LPM MAX. CURRENT
3974 LPM MAX. CURRENT
76 LPM
VACUUM FILTER
37.8 LPM
IN SLUDGE
SOLIDS
DESIGN
MODIFICATION
38 LPM
REACTOR CLARIFIER
1506430 LITERS
254 LPM
37.8LPM DESIGN
0 LPM CURRENT
MLPM DESIGN
102 LPM CURRENT
SLUDGE THICKENER
174110 LITERS
151 LPM
TO LAGOON
(DESIGN
MODIFICATION)
• FLASH TO
"MIXING TANK
(DESIGN)
DISCHARGE
Figure C-l. Water balance for treatment plant design and current operation.
-------
CONVERSION FACTORS AND METRIC PREFIXES (5)
To convert from
CONVERSION FACTORS
To
Degree Celsius (°C) Degree Fahrenheit (°F)
Kilogram (kg)
Liter/s
Meters3/s (m3/s)
Pound-mass (avoirdupois)
Gallon (U.S. liquid)/min
(gpm)
Foot3/min (cfm)
Multiply by
t°F = 1.8 t°C + 32
2.205
1.585 x 101
2.119 x 103
Prefix
Kilo
Milli
Micro
Symbol
k
m
y
METRIC PREFIXES
Multiplication factor
103
io-3
10~6
Example
5 kg
5 mg
5 mg
= 5 x 103 grams
10~3 gram
1 (\~ 3 rn-aTn
= 5
5 x xu " gram
x 10~3 gram
(5) 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 pp.
45
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
REPORT NO.
EPA-600/2-79-093
3. RECIPIENT'S ACCESSION NO.
. TITLE AND SUBTITLE
Analysis of Priority
Production Facility
Pollutants At A Primary Zinc
5. REPORT DATE
April 1979
6. PERFORMING ORGANIZATION CODe
issuing date
r. AUTHOR(S)
Thomas J. Hoogheem and Gary D. Raw!ings
8. PERFORMING ORGANIZATION REPORT NO.
MRC-DA-862
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
1515 Nicholas Road
Dayton, OH 45407
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
68-03-2550
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory-Cin,
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
15. SUPPLEMENTARY NOTES
16. ABSTRACT
As a result of the 1976 consent decree (Natural 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 pollutants. This project investigated the
source of priority pollutants, assessment of the wastewater treatment plant, and
priority pollutant removal efficiency for a single primary zinc manufacturing plant.
Forty-eight hour composited samples were collected from the following streams:
(1) plant intake water, (2) sanitary discharge, (3) gas scrubber wastewater, (4) lagoon
wastewater, and (5) plant effluent.
The plant treats all process, sanitary, and storm run-off wastewater in a lime
precipitation/solids clarification treatment plant.
Results indicate high levels of zinc, cadmium, and chrome being generated but being
removed to acceptable state requirements by the treatment plant. Low levels of
several priority pollutant organics were found, originating either in the city water
supply or being generated chemically within the manufacturing plant.
17.
KEY WORDS AND DOCUMENT ANALYSIS
a.
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS
c. COSATl Field/Group
Pollution
Zinc Industry
Metals
dastewater
Priority Pollutants
Pollution
Wastewater
68b
18. DISTRIBUTION STATEMENT
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
Release to Public
20. SECURITY CLASS (Thispage)
Unclassified
.56-
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
ft U.S. Gcmrmrant Printing Office 1979 — 4S7-060/S322
46
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