United States
Environmental Protection
Agwcy
Industrial En
UalHa
Utaritory
Cincinnati OH 45268
EPA-600-2-79-039
January 1979
mi Development
Characterization of
Priority Pollutants
from a Secondary
Lead and Battery
Manufacturing
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 development 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-600/2-79-039
January 1979
CHARACTERIZATION OF PRIORITY
POLLUTANTS FROM A SECONDARY
LEAD AND BATTERY MANUFACTURING FACILITY
by
Eugene J. Mezey
Battelle's Columbus Laboratories
Columbus, Ohio 43201
Contract No. 68-03-2552
T2006
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, 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 contains an assessment of waterborne emissions from a facility
in which secondary lead is produced and lead storage batteries are manufactured.
The study has been conducted to provide a better understanding of the sources,
nature, and control of emissions from such facilities. Particular attention
has been given to the presence and control of the priority pollutants. Further
information on this subject may be obtained from the Metals and Inorganic
Chemicals Branch, Industrial Pollution Control Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii
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ABSTRACT
A plant site at which secondary lead is produced from old batteries was
sampled utilizing the U.S. EPA protocol for the priority pollutants. The
waste treatment plant at this site uses lime and settle techniques to remove
pollutants from the wastewater before it is discharged into a stream.
The results of the study show that the concentrations of benzene and
cyanides were below their detection limits in all of the streams sampled.
Further, the concentrations of phenols were below their detection limit in
both the influent and effluent of the treatment plant.
The results of the study also show that the lime and settle treatment
practiced at this site removes in excess of 90 percent of the lead, mercury,
and zinc. The technique is slightly less effective for copper and cadmium
because of their low concentrations in the influent to the treatment plant.
Nevertheless, in excess of 70 percent of both copper and cadmium was removed.
Because of the extremely low concentrations of antimony, chromium, and nickel
in the influent to the treatment plant, the effectiveness of the lime and
settle treatment for the removal of these metals could not be evaluated with
any degree of confidence.
IV
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CONTENTS
Foreword ..... .,..............,,.,, ill
Abstract ...... iv
Figures , vi
Tables ......... vi
1. Introduction ........... . ... 1
2. Summary , , 2
3- Source Description . ....... 4
Process Description , 4
Wastewater Treatment 6
4. Sampling and Analytical Approach for
Verification Testing of Priority Pollutants .... 9
Sampling Procedures 9
Flow Measurement 12
Analytical Procedure , 14
5- Discussions of Effectiveness of Lime and Settle
Treatment for the Removal of Priority Pollutants 22
Waste Loads Per 24-Hour Periods 22
Removal Efficiencies 22
Conclusion ..... 26
Bibliography 27
Appendix
Identification Log of Samples Collected 28
v
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FIGURES AND TABLES
Figure Number Page
1 Sources and Sample Code for Wastewater Streams 5
2 Wastewater Treatment Plant for a Secondary Lead-
Battery Manufacture Mix 7
Table Number
1 Efficiency of the Removal of Metals from Wastewater
Produced in a Secondary Lead and Battery Plant 2
2 Daily Flow Rates for Secondary Lead-Battery
Manufacture Mix 13
3 Water Balance During Sampling Period - Secondary
Lead-Battery Manufacture Mix 14
4 Analytical Survey Results - Secondary Lead-Battery
Manufacture Mix * 16
5 Quality Assurance for Pollutant Analyses 18
6 Metals by Direct and Addition Method 19
7 Duplicate Analyses for Metals 20
8 Waste Load of Priority Pollutants in 24-Hour
Period - Secondary Load-Battery Manufacture Mix 23
9 Waste Load of Classical Parameters in 24-Hour Period .... 24
10 Comparison of Waste Load in Treatment Plant Influent
to Load Measured at Sumps and the Removal Efficiency
Based on the Effluent Waste Load 25
vi
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SECTION 1
INTRODUCTION
The Effluent Guidelines Division (EGD), Office of Water Planning and
Standards, of the U.S. Environmental Protection Agency (EPA) has been charged
with the responsibility for conducting tests to determine the presence of
129 priority pollutants in wastewater from facilities which manufacture non-
ferrous metals. Specifically, the EPA is obligated to identify toxic priority
pollutants and the effectiveness of various treatment processes for removing
them from wastewaters generated in the various types of smelters and refineries,
including secondary lead plants. The EGD is required to review the effective-
ness of various technologies and to propose and promulgate effluent limitations.
Battelle's Columbus Laboratories (BCL) undertook the preliminary evalu-
ation of facilities and conducted the sampling arid analyses of waste streams
at one facility. The data were collected for the Office of Research and
Development (ORD) in support of the EGD. The information developed herein is
to be used to augment the data base supporting a regulation. These data also
will be utilized by the ORD to substantiate a metals precipitation manual which
is under preparation. Plant operating data are to be used to qualify the
performance of the system and to identify factors influencing the character-
istics of the samples collected. The activity for this task deals with
wastewater discharges from a facility in which secondary lead smelting and
battery manufacturing are conducted.
This report describes the process, the wastewater treatment facility, and
the sampling and analytical protocol, and presents the results and conclusions.
The conclusions are based on the sampling program, which showed how effective
the wastewater treatment was in removing not only the 129 priority pollutants,
but also those tentatively listed as pollutant parameters in effluent guide-
lines for secondary lead plants.
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SECTION 2
SUMMARY
A plant site, at which secondary lead is manufactured from old batteries,
including battery cracking, was sampled using EPA protocol procedures for the
priority pollutants.^ The plant uses a lime and settle wastewater treatment
before discharging to a stream. This same plant is used to treat wastewater
from the manufacture of industrial batteries, automotive batteries, and lead
oxide. All of the waste streams discharging into the treatment plant were
sampled (according to protocol) upstream at sumps serving the facilities.
The influent as well as the effluent of the wastewater treatment plant was
sampled over a 46-hour period. The samples were analyzed for the priority
pollutants.
Of the priority pollutants, it was determined that the concentrations of
benzene and cyanide were below their detection limits in all of the streams
sampled. The concentration of phenol also was determined to be below the
detection limit in the influent and effluent water of the treatment plant.
The daily waste loads calculated for the priority pollutants and the
efficiencies of their removal are shown in Table 1.
TABLE 1. EFFICIENCY OF THE REMOVAL OF METALS
FROM WASTEWATER PRODUCED IN A SECONDARY
LEAD AND BATTERY PLANT
Influent
Priority Load Concentration,
Pollutant kg/day mg/£
Copper (Cu)
Zinc (Zn)
Lead (Pb)
Antimony (Sb)
Cadmium (Cd)
Chromium (Cr)
Nickel (Ni)
Mercury (Hg)
0.
0.
3.
1.
0.
0.
0.
0.
250
960
907
250
172
141
219
001
0.
0.
11.
0.
0.
0.
0.
0.
16
58
70
80
11
09
14
66
Effluent
Load Concentration, Removal Efficiency,
kg/day mg/Jt %
0
0
0
1
0
0
0
.062
,078
.202
.383
.047
.140
.233
__
0
0
0
0
0
0
0
-------
as practiced in this facility is Very effective in removing zinc, lead, and
mercury and slightly less effective for copper and cadmium because of the low
concentrations encountered. The effectiveness of this method in removing
nickel» chromium, and antimony could not be evaluated with confidence because
the low concentrations in the influent to the treatment plant are probably near
solubility limits at pH 8*5.
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SECTION 3
SOURCE DESCRIPTION
PROCESS DESCRIPTION
At the plant site, lead compounds, lead, and lead alloys from secondary
sources are smelted and refined. In addition, lead oxide and automotive and
industrial batteries are manufactured on site. The plant consists of the
following areas:
• blast furnaces to melt or reduce the lead or lead
oxide scrap,
• a reverberatory furnace in which lead scrap is melted
and refined,
• a baghouse and lime-water scrubber serving the furnaces,
• a continuous casting line for ingots,
• a large receiving yard where the materials for charging
the blast furnace (i.e., coke, scrap iron, rerun slag,
reverb slag, limestone, plastic battery cases, antimony
ore and dross, flue dust and scrap, and lead battery
plates) are stored mainly under roof,
battery breaking operations,
industrial battery manufacturing operations,
automobile battery manufacturing operations,
lead oxide manufacturing operations,
a wastewater treatment plant, and
a landfill.
The relationship of each area of operation to the wastewater load to the
treatment plant is shown in Figure 1.
The blast furnace, reverberatory furnace, and ingot line noncontact
cooling water discharge into a sump which also is used to gather roof and
plant runoff for treatment.
Used batteries containing spent electrolyte (sulfuric acid, etc.) are
processed on site. The tops of batteries are sheared off and contents
dumped. The lead and lead compounds are separated from the electrolyte which
is mixed with wash water. This wastewater is a major effluent. It is pre-
treated by settling before being pumped to the treatment plant from the sump
serving this facility.
In the manufacture of industrial and automobile batteries, wastewater is
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Waste water
Sources from
Manufacturing Operations
Sources from
Secondary Smelting Operations
008
Industrial Battery Manufacture
Acid Washdown, Forming and
Pasting Washdown and Cooling
009
012
Automotive Battery Manufacture (SLI)
Battery Case Washing Area
Washdown and Pasting Machinery
and Site Runoff
010
Oxide Manufacturing
Oil and Grease Related
Remote Plant Waste
Limed and Hauled In
011
Lagoon
Leachate from
Stream Enclosure
and Plant Runoff
003
Holding
Tank
002
Treatment Plant
(Lime and Settle)
Battery Breaking
Spent Eldctrolyte
006
Blast Furnace, Smelter and
Ingot Noncontact Cooling
and Site Runoff
005
Landfill Leachate
Solids from Scrubber,
Treatment Plant and
Battery Breaking
004
001
. To Creek
FIGURE 1. SOURCES AND SAMPLE CODE FOR WASTE WATER STREAMS
(Secondary Lead-Battery Manufacture Mix)
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generated from the washdown of sulfuric acid spills that occur during battery
filling and the washdown of the stations where lead oxide pasting and forming
are done. Contact cooling wastewater from the manufacture of lead oxide
contains oil and grease.
Although the blast and reverberatory furnaces emissions are scrubbed with
lime water, the wastewater is recycled. The solids formed during the scrubbing
are disposed of in the landfill along with the solids produced during waste-
water treatment. The leachate from this landfill is collected and contributes
to the wastewater treatment load.
In order to prevent any leachate originating from the plant area from
polluting the stream passing under the plant site, the leachate is collected
outside an enclosure surrounding the stream and pumped to the wastewater treat-
ment plant. The wastewater treatment plant also receives pretreated (limed)
wastewater brought in by tanker truck from a nearby plant where automobile
batteries are manufactured.
WASTEWATER TREATMENT PLANT
The treatment plant receives wastewater from eight collection sumps
located throughout the plant in four holding tanks, as shown in Figure 2. The
wastewater is pumped from the holding tanks to the primary reaction tank where
it is mixed with dry lime. The slurry is then gravity fed to the secondary
reaction tank where a 0.1 percent solution of flocculating agent (CALGON
Wt-3000) is added at a rate of about 3.8 £/min (1 gal/min) to promote floccu-
lation and crystal growth. The wastewater is sent on to two clarifiers and
the clarifier overflow enters a series of three lagoons for settling before
being discharged to the stream. The pH of the discharge from the treatment
plant is 7 to 8.5. The underflow from the clarifiers is pumped to a thickener
where further separation of liquid and solid occurs. The underflow, containing
about five percent solids, is trucked to the landfill. The overflow from the
thickener is returned to the secondary reaction tank via a receiving lagoon.
This lagoon also receives the limed wastewater brought from a plant in a
nearby city four times a day (about 5000 gallons per load). The underflow
from the receiving lagoon is recycled to the thickener. All the lagoons are
cement lined.
The limed wastewater received from the remote plant contains Thrifty
Foam* and Duponal^ as well as excess lime.
3
About 1550 m /day (410,000 gpd) of wastewater from the holding tanks was
treated during the sampling period.
Plant production during the sampling period appears on page 8.
DuBois Chemical Company, Sharonville, Ohio.
E. I. DuPont, Dye and Chemical, Wilmington, Delaware.
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8,269 kgpd
3,738 Ibpd
1,554 m3 pd
Dry Lime
Feed
!Ui
n c =£
« CM O
i 5f
^
Flocculant
Solution
6.00 m3 pd
(1,600 gpd)
Influent = 410,500 + 1,600 + 22,000 = 434,100
Effluent = 412,100 + 22,000 = 434,100
I
Underflow to
Land Fill
83.0 m3 pd
( 22,000 gpd)
Remote Plant
Wastewater-Trucked In
83.0 m3 pd
( 22,000 gpd)
(41
^, Holding
^. Tanks
t {4)
*.
0,500 gpd)
I.,
Primary Reaction ~
Tank
(Neutralization)
1
Secondary Reaction
Tank
(Crystalization)
i
Overflow
Lagoon
Underflow to
Thickener
Underflow
Overflow
to Secondary
Reaction Tank
Overflow
Three
Lagoons
^ Stream
1,560 m3 pd
(412,100 gpd)
Lagoon
Recycle
FIGURE 2. DIAGRAM OF WASTEWATER FLOW IN A WASTE WATER TREATMENT
PLANT FOR A SECONDARY LEAD-BATTERY MANUFACTURE FACILITY
Sampling Sites; See Figure 1 for Greater Detail)
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Plant production during the sampling period:
Industrial Batteries* On-Site Auto Battery Manufacturing
41.2 kkg/day -x-6,540 batteries/day
(37.4 tons/day)
Oxide Production Remote Auto Battery Manufacturing
44 kkg/day '\/7,500 batteries/day
(40 tons/day)
Lead Smelter
198 kkg/day
(180 tons/day)
* Industrial battery production is designated by weight rather than number
because of the variability in their size.
8
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SECTION 4
SAMPLING AND ANALYTICAL APPROACH FOR
VERIFICATION TESTING OF PRIORITY POLLUTANTS
An approach was developed which is used for sampling and analysis for
verification testing to determine the presence or absence of priority pollu-
tants in wastewater discharges from a secondary lead smelting plant. Waste
streams before commingling at the treatment plant, as well as the commingled
influent and effluent, were sampled because of the mix of the smelting
operation waste streams with battery manufacture waste streams. Five streams
related to smelting operations were sampled according to the protocol for the
priority pollutants. Five additional streams from battery manufacture were
also sampled. Samples were also analyzed for total suspended solids, metals
(As, Cd, and Pb), sulfates, and oil and grease.
The precautions taken to meet stringent quality assurance guidelines in
the sampling procedure, field flow measurements, and analytical procedures
(i.e., sampling and analytical protocol) are described in this section of the
report.
SAMPLING PROCEDURES
Presampling Preparation
All presampling activity was directed at assembling, cleaning, and
storing sample containers to be used in the field according to the procedures
outlined in "Appendix III, Collection of Samples for Screening Analysis, of
the Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants.1 Sample containers were cleaned, rinsed with
organic-free water, drained and air- or oven-dried at 100°C as appropriate.
Sampling Sites
During an initial survey of the plant, sampling sites were identified.
The sampling points were located at the influent to the treatment plant
(between the holding tanks and the primary reaction tank) and at the effluent
being discharged from the last lagoon. Upstream sampling points were sumps
receiving the wastewater from the industrial operations noted in Figure 1.
The sampling sites and the coding used in the field to identify the samples
and record information on the progress of the sampling in a permanent record
book* are given in Figure 1. The only difference between the presampling
* BCL Notebook 33888.
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survey sites and the final sites sampled was the additipn of a sump which
collects battery case washings in the automotive battery manufacturing area
(012). Organic-free "blank" water supplied by BCL was identified as 000 and
the source water at the site as 007 (city water)f
Collection Techniques
Three areas assumed to be critical in the overall was,tewater collection
and treatment facility were sampled in duplicate composites:
• The influent to the treatment plant (002) wag composited
over a 46-hour period by a constant drip rate method
Cv>3 m£/min) and also manually. The manual collection
took place every 2 hours using a 600-mJl beaker filled
to 400 mA. Both composites were collected in 10,000-m£
bottles (Pyrex) kept at ice temperature,
• Two 10,000-mA composites of treatment plant effluent (001)
were collected in a 46-hour period. One was collected
with an ISCO* automatic sampler taking constant volume
samples every 20 minutes, and the other was collected
manually every 2 hours using a beaker, as described above.
Again, all samples were kept iced during and after the
sampling period.
• Two composites of the battery breaker sump (006) also were
prepared. One was prepared with the ISCO sampler and the
other manually.
In those cases were the ISCO unit was used, it was given a field "blank"
water treatment and an operational sampling using "blank" water.
Samples from the remaining process wgstewater sumps were composited
during the 46-hour sampling period manually using beakers to remove the
500-m£ samples from the sump. Each site had its own sampling beaker and each
beaker was protected from dust and dirt between sampling periods. All were
kept at ice temperature during and after sampling (ambient air was near
freezing).
Grab samples for phenol, cyanide, and organics were taken once between
1500 and 1600 hours, when maximum production activity was evident, and again
at low plant activity at 2100 and 2330 hours:
• Each sample for cyanide analysis was collected in a
1-liter amber polyethylene bottle and preserved with
0.6 gram of ascorbic acid and at least 2 m& of ION
NaOH; final pH = 10.
* ISCO = Model 1680, ISCO, Lincoln, Nebraska,
10
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• Each sample for phenol was collected in a 1-liter
glass bottle and preserved with 2 m£ H~SO, (cone,),
if pH was greater than 4.
• Samples for benzene (organics) were collected in an
8-oz glass bottle with extra precautions taken during
filling to eliminate entrapped air bubbles at the
Teflon/silicone septa cap.
• Each set of grab samples had its own "blank" water
sample prepared.
All sampling events were recorded in a permanent record book and specially
prepared labels were marked with waterproof markers and affixed with water-
proof tape. A log of the 71 daily grab samples and eighteen 10-liter
composites was prepared and is appended to this report.
Sample Shipping
The collected samples were kept at ice temperature while being transported
from the plant site to BCL by truck (overnight). Once at BCL, the samples
were stored in a cooler set at 4°C until split (a period of 2.5 days during
the weekend).
Sample Splitting
The composited samples were split according the recommendations cited in
the "Collections of Samples for Screening Analyses of Priority Pollutants"'-*-';
that is, by syphoning into five clean bottles after magnetic stirring of the
composite using a Teflon stirring bar. Polyethylene tubing equipped with a
Viton rubber tip was used to make the transfers. The system was washed
thoroughly and rinsed with "blank" water between uses. The bottles were
cleaned using IN HNO and at least triple rinsed with "blank" water (Milli-Q-
water), drained, heated to 200°C, and cooled in a dust-free area to room
temperature. Caps also were cleaned and lined with close-fitting Teflon liners.
The bottles were labeled and coded in sets of five (one 16-oz bottle and four
32-oz bottles), to match the composite being split. The five samples were to
be used for the following purposes and were identified as such:
Metals (MET)
Pesticides, PCB, and asbestos (P&P)
Gas chromatography/mass spectroscopy (GC/MS)
Classic parameters (CP)
Company's sample.
The remainder of the composite was stored at 4°C for further use if needed.
In each case, the composites selected for splitting were all manually
composited samples. The composites prepared by automatic sampling were
reserved as backup and stored at 4°C without splitting. This approach
provided an opportunity for comparison of similarly collected composites if
needed.
11
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The coding used to identify the split samples matched that used to
identify the streams sampled in the field (i.e., 000 through 012).
All of the samples split from the composite were stored at 4°C until
their submission for analysis. Custody of these samples was transferred for-
mally to the analytical team with a list of their identity, origin, and analyses
required.
Probable Qualifications
Regarding Sampling
(1) The failure of the automatic samplers to perform
uniformly in the field made the composite less likely
to be representative than the manually composited
samples. The failure was caused by collapse of the
thin-walled Teflon tubing supplied with the unit. If
it had not been for the precaution of parallel manual
sampling, the quantity of sample collected would have
.fallen short of that required for samples.
(2) A 28-hour composite from the battery case wash and rinse
water stream (automotive battery production, 012) was
collected since this sump was not discovered until 18
hours into the sampling period. However, since the
flow of this stream was steady rather than intermittent,
the 28-hour composite is believed to be comparable to a
46-hour composite.
FLOW MEASUREMENT
Both the flow rate of the effluent from the treatment plant and the
influent from the holding tanks are measured through a weir and recorded in
the control room of the treatment plant. The wastewater from the sumps is
discharged via pumps (usually in pairs) to the holding tanks. For pumps
equipped with on-time clocks, the amount of flow from the sumps was calculated
from their capacity and their period of operation. Those without clocks were
equipped with electric clocks by the sampling team and plant personnel before
the sampling was started to provide measure of on-time. One weakness in this
method is that the capacity of the pump is given against a fixed hydrostatic
head which may or may not be the head it is working against. In this case the
estimations of flows were reasonably accurate.
Flow rates for the sampling period for each of the wastewater streams
sampled are given in Table 2. A water balance for the sampling period is
presented in Table 3. Based on the estimates made from the pump capacity
and the pump clock on-time, the value for volume of the wastewater pumped to
the holding tanks from the sumps per day agrees very well with the volume
entering the treatment plant from the holding tanks. The volume used for
waste load calculations was 1550 m3/day (409,500 gpd). The volume of source
process water was slightly less than that calculated as pumped from the sumps
from operations known to use process water directly, but the difference was not
considered significant. In order to bring the flows near balance it was
12
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TABLE 2. DAILY FLOW RATES FOR SECONDARY
LEAD-BATTERY MANUFACTURE MIX
Wastewater
Stream Code Process
001
002
003
004
005
006
007
008
009
Treatment Plant
Effluent
Treatment Plant
Influent
Stream Enclosure
Leachate
Landfill Leachate
Furnace Noncontact
Cooling
Battery Breaker
Process Water
Industrial Battery
Manufacturing
Automotive Battery
Method of
Measurement
Weir-Meter
Readings
Weir-Recorded
Continuously
Pump Capacity/
On-Time Clock
Pump Capacity/
On-Time Clock
Pump Capacity/
On-Time Clock
Pump Capacity/
On-Time Clock
Meter Reading
for Period
Pump Capacity/
On-Time Clock
Pump Capacity/
24-Hour
Flow Rate
m /day (gpd)
1563.00 (412
1554.00 (410
75.44 ( 19
197.46 ( 52
138.72 ( 36
69.83 ( 18
1040.88 (275
306.59 ( 81
190.27 ( 50
,850)
,580)
,930)
,170)
,650)
,450)
,ooo)(a)
,000)
,270)
010
Oil
012
Manufacturing Site
Leachate and Runoff
Lead Oxide Production
Remote. Plant Trucked
In Wastewater
Automotive Battery
Manufacturing Wash
and Rinse
On-Time Clock
Pump Capacity/ 286.15 ( 75,600)
On-Time Clock
Weight of Load
(b)
83.45 ( 22,050)
Pump Capacity/ 287.05 ( 75,840)
On-Time Clock
(a) Usage measurement for period by plant.
(b) The volume of load was estimated from the weight of the load and the
specific gravity of the liquid (assuming the same specific gravity as that
of H00).
13
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TABLE 3. WATER BALANCE DURING SAMPLING PERIOD
SECONDARY LEAD-BATTERY MANUFACTURE MIX
Daily flow to holding tanks
during sampling period:
E 003, 004, 005, 006, 008, 009, 010, 012 * 1550 nu/day (409,500 gpd)
Influent, 002, to treatment plant = 1550 m /day (409,500 gpd)
Daily wastewater flow related to
process source water flow during
sampling period:
Wastewater E 005, 006 less electrolyte,
008, 010, 012 = 1380 nu/day (372,540 gpd)
Source water, 007 plant data^ = 1041 m /day (275,000 gpd)
(a) Metered water only.
necessary to correct the wastewater flow from the battery breaking operation,
Sample 006, for the volume of spent electrolyte introduced into the
system. This amount was estimated to be about 1.9 liters per battery for the
approximately 8000 batteries processed per day during the sampling period.
ANALYTICAL PROCEDURE
Only those priority pollutants specific to the secondary lead/antimony
segment of the nonferrous metals category were determined in accordance with
the work plan. These were handled as follows:
Collect, Analyze, and Collect and Preserve
Preserve Samples Sample Only
Antimony (Sb) Asbestos, pesticides
Cadmium (Cd) Dimethyl phthalate
Chromium (Cr) Diethyl phthalate
Copper (Cu) _ Di-n-butyl phthalate
Cyanides (CN ) Bis (2-ethyl hexyl) phthalate
Lead (Pb) Butyl benzyl phthalate
Mercury (Hg)
Nickel (Ni)
Zinc (Zn)
Phenols
Benzene
In addition to those waste streams related to secondary lead production,
analyses for priority pollutants also were made of the wastewaters generated
in industrial battery manufacturing, automotive battery manufacturing, and
lead oxide production. These streams were also analyzed for oil and grease.
14
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All the wastewater streams also were analyzed for pH, total suspended solids
(TSS), sulfate, and other pollutant parameters related to secondary lead
manufacture.
The analytical results are summarized in Table 4. The sample numbers in
Table 4 are the base numbers recorded in Battelle Record Book No. 33888 (see
section on sample splitting). Quality assurance information for the data in
Table 4 for oil and grease, benzene, total cyanide, soluble sulfate, and
phenols is summarized in Table 5. Similar information for trichloroethylene
and metals is presented in detail.
Trichloroethylene
Because a chromatographic peak can be the result of one or more compounds,
confirmation analysis by mass spectrometry was needed to positively
identify these peaks which were identified as benzene by retention time.
The first confirmation was run on Sample 007 which comes from the city water
supply. Treating the process water in a manner sensitive enough to detect 78
ng of benzene by mass spectrometry, only a trace was detected. However, a
very strong pattern of trichloroethylene was present. (It is not uncommon
to find chlorinated hydrocarbons in water supplies that have been chlorinated.)
Mass spectrometer confirmation analysis on Samples 002, 003, and 010
showed they all contained trichloroethylene as the major component and only
a trace of benzene (<--0.1 ppb) . Since the source of the trichloroethylene was
the city water supply and all other samples not yet confirmed showed lesser
amounts, it was not believed to be necessary to confirm the other samples,
except for Sample Oil whose origin was another plant site. This sample also
contained trichloroethylene but no benzene. A trichloroethylene standard
was run and used to calculate the values for trichloroethylene reported in
Table 4.
/
Sample 003, which contained the highest amount of trichloroethylene, was
run in triplicate with the following results: 63.1 yg/£, 57.3 yg/£, and
55.0 ug/£. The maximum deviation from the average was 4.6 yg/£ or about 8
percent from the average. Sample 007 gave values of 6.29 and 6.60 yg/£
which averages 6.45 yg/£, or about 2.4 percent deviation from the average.
Duplicate analyses on Sample 001 gave values of 6.1 and 6.5 yg/£.
Metals
A Perkin Elmer Model 305B atomic absorption spectrophotometer was used
for the metal analysis. The conventional air-acetylene flame method was used
for all metals except mercury. A flameless method was used for the mercury
analysis.
The insoluble metals are those that can be filtered from the sample,
and the soluble metals remain and are analyzed in the filtrate.
The mercury analyses were done with the flameless cold vapor techniques
in which the mercury is reduced, amalgamated onto silver wool, and then
released into the absorption cell by heating the silver wool.
15
-------
TABLE 4. ANALYTICAL SURVEY RESULTS - SECONDARY LEAD-BATTERY MANUFACTURE MIX
Sample No. Sample Location 011&6rease
mg/t
000
001
002
003
004
005
006
007
008
009
010
on
012
Blank Water Taken to Site 1.4
Wastewater Treatment Plant
Effluent
Wastewater Treatment Plant
Influent
Stream Enclosure Leacnate
Landfill Leac hate-Smelter Area
Furnace and Ingot Cooling,
(no contact)
Battery Breaker Sump
Process Water-City Water
Industrial Battery Manufacturing 0.7
Auto Battery Manufacturing Area
Leachate and Runoff <0.1
Lead Oxide Manufactured Plant 21.3
Remote Auto Battery Plant 2.1
Auto Battery Manufacturing/Washer 1 .6
and Rinse
Total
Benzene Cyanide
vg/l mg/i
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
<0.1 <0.01
Soluble
Sulfate
mg/nu
<0.0001
3.5
4.7
0.68
3.2
0.51
40.3
0.05
5.9
0.40
0.06
1.9
37.2
Suspended Soluble
Sol Ids Phenols Copper
mg/£ xig/fc fng/Ji
<0.01
0.01
0.05
<0.01
0.08
0.04
0.20
<0.01
0.05
<0.01
0.01
7.6
0.14
<4
<4
<4
6
5
<4
<4
<4
5
<4
<4
<4
33
<0.01
0.04
0.16
0.08
0.20
0.01
1.8
0.01
0.14
0.02
<0.01
0.03
0.35
Insoluble
Copper
mg/u
0.01
<0.01
<0.01
<0.01
0.01
0.05
<0.01
<0.01
<0.01
<0.01
<0.01
0.05
<0.01
Soluble Insoluble
Z1nc Z1nc
mq/l rag/ 1
.03
0.05
0.58
0.28
0.94
0.30
7.6
0.10
0.20
0.20
0.05
0.06
0.59
<0.01
0.01
<0.01
<0.01
0.02
0.05
0.03
<0.01
<0.01
<0.01
<0.01
0.12
<0.01
Trichloro-
ethylene
ug/l pH
<0.1
1.8
3.3
59
2.9
0.4
2.6
6.5
2.9
1.3
6.0
6.4
1.9
6.4
8.3
1 .4
2.6
4.5
6.9
0.6
7.6
2.9
1.4
7.9
7.5
0.7
Milligrams per liter (mq/i.) = parts per million
Mlcrograms per liter (ug/J.) • parts per billion
Milligrams per mllllliter (mg/mi) « weight percent x 0.1
(continued)
-------
TABLE 4. (Continued)
Soluble
Sample No. Sample Location Lead
rng/n
000
001
002
003
004
005
006
007
008
009
010
on
012
Blank Water Taken
to Site
Wastewater Treatment
Plant Effluent
Wastewater Treatment
Plant Influent
Stream Enclosure
Leachate *
Landfill Leachate
Smelter Area
Furance and to
Ingot Cooling,
(No Contact)
Battery Breaker Sump
Process Water-City
Water
Industrial Battery
Manufacturing
Auto Battery Manu-
facturing Area
Leachate & Runoff
Lead Oxide Manufac-
turing Area
Remote Auto
Battery Plant
Auto Battery Manufac
turing Case Washer
<0.05
0.13
2.5
1.8
4.5
0.31
4'. 2
0.16
2.4
0.87
0.15
0.65
2.4
Insoluble
Lead
V3/1
<0.05
0.14
9.2
<0.05
7.9
3.7
88.
0.05
4.23
<.05
1.6
15
3.3
Soluble
Antimony
mg/Jl
<0.33
0.89
0.80
<0.33
0.35
<0.33
18.0
<.33
<0.33
<0.33
<0.33
<0.33
0.43
Insoluble Soluble
Antimony Cadmium
mg/J> mg/d
<0.33
<0.33
<0.33
<0.33
<0.33
<0.33
0.41
<0.33
<0.33
<0.33
<0.33
<0.66
<0.33
<0.01
0.03
0.11
<0.01
0.08
0.08
3.0
<0.01
<0.01
-------
TABLE 5. QUALITY ASSURANCE FOR POLLUTANT
ANALYSES
Analysis
Oil and grease
Benzene
Total cyanide
Soluble sulfate
Phenols
Sample
Standard
Standard
008
Calibration
003
007
009
000
000
006
009
Material
Added
1.5 mg oil
2 . 1 mg grease
4.8 mg oil
4.2 mg grease
7.8 mg oil
4.9 mg grease
1.42 yg
51.4 yg/£
5.50 yg/£
2.6 mg/£
48 . 0 mg/m£
4.71 yg/£
18.8 yg/£
9.4 yg/£
Material
Found
3.7 mg
8.9 mg
11.9 mg
1.36 yg
48.0 mg/£
4.8 yg/£
2.4 yg/£
47.2 mg/m£
3.77 yg/£
17.0 yg/£
10.8 yg/£
Recovery ,
percent
102.7
98.9
93.7
96
93.4
87.3
92.7
98.3
80
90.4
115
18
-------
The addition method was used as a cross-check for the direct analysis
method for all metals except mercury. In this method, known quantities of the
metal being tested are added to aliquots or dilutions of the sample. The
absorbance of these solutions and of sample solutions with no metal added are
plotted on the vertical axis of a graph, with the concentration of the known
standard plotted on the horizontal axis. When the resulting line is extra-
polated back to zero absorbance, the absolute value of the x-intercept gives
the concentration of the unknown. Conventional spiking of samples is not used
when the method of addition is used.
The results obtained by the method of addition compared to the direct
method are shown in Table 6. Most of the results are for soluble metals
because most insoluble concentrations were very low. The result of the
addition method, versus the direct method of analysis, for insoluble copper
shows a 16.6 percent deviation at the 0.06 mg/£ level. For the soluble metals,
the greatest deviation is 13.6 percent for antimony.
TABLE 6. METALS BY DIRECT AND ADDITION METHOD
Metal
Copper
Zinc
Lead
Antimony
Cadmium
Chromium
Nickel
Sample
008
005
007
008
008
009
001
006
004
012
002
003
006
012
Soluble (S)
or Insoluble (I)
S
I
S
S
S
S
S
S
S
S
S
S
S
S
Method, mg/£
Direct
0.14
0.05
0.10
0.20
2.43
0.87
0.89
17.9
0.08
0.02
0.09
0.15
0.94
0. 39
Addition
0.16
0.07
0.12
0.23
2.78
0.90
1,17
17.3
0.08
0.02
0.10
0.16
1.04
0,48
% Deviation
from Average
6.7
16.6
9.1
6.9
6.7
1.7
13.6
1.7
0
0
5.3
3.1
5.3
10.3
The mercury samples were spiked in the conventional manner instead of
using the method of addition. Samples 006 and 003 for soluble mercury were
spiked with 100 nanograms of mercury each with 105 percent and 108 percent
recovery, respectively. Samples 006 and 003 for insoluble mercury were
spiked with 100 nanograms of mercury. Recovery on these were 95 and 105
percent, respectively.
19
-------
Duplicate analyses were run for all metals, except mercury, and these
data are shown in Table 7. Excellent agreement was obtained for all metals
except in Sample 006 for antimony which showed 15.7 percent deviation from
the average result of 0.415 mg/£. The rest of the values show less than
5 percent deviation from the average.
Summary of Quality Assurance Program
The quality assurance data discussed above for each compound reported,
except pH values, were based on duplicate analyses, spikes, method of-addition
for metals, and mass spectrometer confirmation of gas chromatography analysis.
These quality assurance data showed excellent results for duplicate runs,
spikes, the method of addition versus direct method for metals and GC/MS con-
firmations.
The recovery of three spikes for the phenol analysis showed the greatest
range of deviation at recoveries of 80.0, 90.4, and 115 percent of the amount
added. The largest percent deviation from the average for the metal analysis
was 16.6 percent for the insoluble copper and 13.6 percent for soluble antimony.
These are good reproducibilities at these low levels using two different methods
of analysis.
TABLE 7. DUPLICATE ANALYSES FOR METALS
Metal
Sample
Soluble, mg/£
Run 1
Run 2
Insoluble, mg/£
Run 1 Run 2
Copper
Zinc
Lead
Antimony
Cadmium
Chromium
Nickel
003
006
003
006
003
006
003
006
003
006
003
006
003
006
0.08
1.82
0.28
7.75
1,84
4.18
<0.33
17.9
<0.01
3.03
0.15
0.41
0.13
0.94
0.08
1.75
0.27
7.50
1.81
4.33
<0.33
17.9
<0.01
2.98
0.14
0.41
0.13
0.94
<0.01
<0.01
<0.01
0.03
<0.05
87.5
<0.33
0.35
<0.01
<0.01
<0,01
0.02
<0.04
<0.04
<0.01
<0.01
<0.01
0.03
<0.05
87.5
<0.33
0.48
<0.01
<0.01
<0.01
0.02
<0.04
<0.04
Note: Mercury samples were spiked instead of direct duplicate analysis,
text for results.
See
20
-------
SECTION 5
DISCUSSIONS OF EFFECTIVENESS OF LIME AND SETTLE
TREATMENT FOR THE REMOVAL OF PRIORITY POLLUTANTS
WASTE LOADS PER 24-HOUR PERIODS
The analytical results and the average daily flow rates measured for the
sampling period were used to calculate the waste loads of both the priority
pollutants and the classical parameters for each of the waste streams sampled.
Priority Pollutant Loads
The mass flow of the priority pollutants entering and leaving the waste-
water treatment plant daily are given in Table 8. Since benzene and cyanide
concentrations were below detection limits, they were assumed to be absent
and were not included in the loading calculations. Whenever concentrations of
pollutants in a wastewater stream were found to be below detection limits,
loadings were not calculated since such values would be meaningless. For
example, phenols were found in sufficiently high concentration in the enclosure
leachate (003), landfill leachate (004), and the industrial and automotive
battery manufacture wastewater streams (008 and 012) to be measured, but
because of dilution by the other streams, the concentration was below the
detection limit in the influent and effluent. Concentrations of mercury and
the insoluble forms of metals suggest similar behavior.
Classical Parameters Loads
The loads of pollutants given in Table 9 were selected as those para-
meters likely to be used for the development of effluent limitations for the
secondary lead segment of the nonferrous metals point source category. Oil
and grease was not one of these parameters, but probably would be one for the
battery manufacturing or lead oxide manufacturing category. Since no samples
were taken for oil and grease of the influent and effluent and no past history
of such measurements being made at this plant exists, the data serve only to
identify a loading for the two industries that must be removed by treatment.
Sulfate is not one of the parameters for the secondary lead industry either.
It was measured, however, to demonstrate its prevalence in the wastes from
this type of manufacturing mix.
REMOVAL EFFICIENCIES
In Table 10, the waste load entering the treatment plant as the influent
from the holding tank is compared with the load calculated from the sum of the
21
-------
TABLE 8. WASTE LOAD OF PRIORITY POLLUTANTS IN 24-HOUR PERIOD, SECONDARY LOAD—BATTERY MANUFACTURE MIX
Priority Pollutant Load, kg/day
Waste Stream
and Code
Treatment Plant
Effluent, 001
Influent, 002
Enclosure Leachate, 003
Land Fill Leachate, 004
Noncontact Cooling, 005
Battery Breaker, 006
Process Water, 007
Ind.Bat. Mfg, 008
Auto Bat. Mfg, 009
Lead Oxide Mfg, 010
Remote Plant, Oil
Auto Bat. Mfg Wash, 012
Trichloro(a)
Phenols ethylene
0.0028
0.0052
0.0005 0.0045
0.0010 0.0006
0.0001
0.0002
0.0068
0.0015 0.0009
0.0003
0.0017
0.0005
0.0095 0.0006
Copper
Sol Insol
0.062 —
0.250
0.006
0.039 0.002
0.001 0.007
0.126
0.010
0.043 —
0.004
--
0.003 0.004
0.100 00
Zinc
Sol Insol
0.078 0.016
0.906 —
0.044
0.186 0.004
0.042 0.007
0.531 0.002
0.104 —
0.061 --
0.038 —
0.014
0.005 0.010
0.169 —
Lead Antimony
Sol
0.202
3.907
0.136
0.889
0.043
0.293
0.167
0.736
0.166
0.043
0.054
0.689
Insol Sol Insol
0.218 1.383
14.376 1.250
—
1.560 0.069 --
0.513
6.145 1.257 0.029
0.052 —
1.297
_-
0.458 —
1.252 —
0.947 0.123 --
Cadmium
Sol Insol
0.047
0.172
__
0.016
0.006
0.086 —
—
—
—
—
0.002 —
0.006 —
Chromium
Sol Insol
0.140
0.141
0.011 —
0.014 0.004
0.006
0.029 0.001
0.031
0.015 —
0.008 --
0.009 —
0.004 —
0.238 0.003
Nickel
Sol
0.233
0.219
0.098
0.053
0.015
0.066
—
—
_
—
0.010
0.112
Mercury
Insol Sol Insol
— 0.0010
_
0.0001
__
— 0.00003 —
— — —
— 0.0013
_
_ —
0.012 — 0.00005
0.00009
(a) Benzene and cyanide concentration were below detection limits and.not included in the waste load. Trichloroethylene was not one of the listed
priority pollutants.
(b) Concentration of the pollutants was below detection limits in those waste streams marked with dash (—).
-------
(a)
TABLE 9. WASTE LOAD OF CLASSICAL PARAMETERS IN 24-HOUR PERIODV '
Secondary Load - Battery Manufacture Mix
N>
Pollutant Load, kg/day ^b'
Waste Stream
and Code
Treatment Plant
Effluent, 001
Influent, 002
Enclosure Leachate, 003
Land Fill Leachate, 004
Noncontact Cooling, 005
Battery Breaker, 006
Process Water, 007
Ind Bat Mfg, 008
Auto Bat Mfg, 009
Lead Oxide Mfg, 010
Remote Plant, Oil
Auto Bat Mfg Wash, 012
Oil &
pH Grease
8.3
1.4
2.6
4.5
6.9
0.6
7.6
2.9 0.133
1.4
7.9 6.095
7.5 0.175
0.7 0.459
Soluble
Sulfate
5.439
7.344
0.051
0.632
0.071
2.814
0.052
1.809
0.076
0.017
0.159
10.678
Lead
TSS
0.016
0.078
—
0.016
0.006
0.014
—
0.015
—
0.003
0.634
0.040
Sol
0.202
3.907
0.136
0.889
0.043
0.293
0.167
0.736
0.166
0.043
0.054
0.689
Insol
0.218
14.376
—
1.560
0.513
6.145
0.052
1.397
—
0.458
1.252
0.947
Cadmium
Sol Insol
0.047
0.172
__
0.016
0.011
0.086
—
—
__
__
0.002
0.006
(a) Classical parameters include the pollutants parameters selected for development of effluent limitations
of the secondary lead segment of the nonferrous metals point source category, i.e., pH, TSS, As, Cd
and Pb.
(b) Concentration of the pollutants were below detection limits in those waste streams marked with dash
-------
TABLE 10. COMPARISON OF WASTE LOAD IN TREATMENT PLANT INFLUENT TO LOAD MEASURED
AT SUMPS AND THE REMOVAL EFFICIENCY BASED ON THE EFFLUENT WASTE LOAD(a'
Waste Treatment Sum
of Pollutants Waste Treatment
x.s Plant Influent from Sumps Plant Effluent
Pollutant
Phenol
Trichloroethylene
Copper: Sol.
Insol.
Zinc: Sol.
Insol.
Lead: Sol.
Insol.
Antimony: Sol.
Insol.
Cadmium: Sol.
Insol.
Chromium: Sol .
Insol .
Nickel: Sol.
Insol
Mercury: Sol.
Insol.
Oil & Grease
Sulfate
(a) Retention time
kg/day
_<0
0.0052
0.250
—
0.906
—
3.907
14.376
1.250
—
0.172
—
0.141
—
0.219
—
—
0.001
(d)
7.344
in holding tanks (144,100
originates from holding tank into which
(b) Benzene and cyanide concentrations were
(c) Concentrations
(d) Oil and grease
kg/day
0.0125
0.0162
0.332
0.013
1.194
0.023
3.216
12.224
1.449
0.029
0.121
— -
0.365
0.008
0.354
0.012
0.00003
0.0015
6.862
16.359 (5.681)(e)
g) is about 8.4 hours
sumps are discharged.
below detection limit.
kg/day
_»
0.0028
0.062
—
0.078
0.016
0.202
0.218
1.383
—
0.047
—
0.140
—
0.233
—
—
—
(d)
5.439
at collection
Removal Efficiency, %
Based on
Influent
—
46
75
—
91
0
95
98
0
—
73
--
0.7
—
0
--
—
100
(d)
26
rate of 410,580
Based on
£ Sumps
100
83
81
100
93
30
94
98
5
100
61
—
62
100
34
100
100
100
(d)
33
g/day. Influent
of the pollutants were below the detection limits for those marked with dash ( — ) .
not measured in influent
or effluent.
(e) The value of 5.681 kg/day is the amount of sulfate less that contributed by the waste stream 012 (10.678 kg/day),
-------
pollutant load in each waste stream sump. As mentioned earlier, because of
the dilution of pollutants upon mixing of the waste streams in the holding
tanks, their concentration ends up below the detection level (e.g., phenol
and insoluble metals). There are discrepancies in the weight of soluble
copper, antimony, chromium, nickel, and mercury which may be attributable to
the dilution effect. The fact that the load of sulfate in stream 012 of 10.678
kg/day alone exceeds the load in the influent to the treatment plant of 7.344
kg/day suggests that some event in the production of automotive batteries
contributed to this disparity. These variations also may be caused by the
eight-hour retention time in the holding tanks, which would delay detection
of gross variations in concentration. The holding tanks would also tend to
average out extremes in concentration.
The efficiency for the removal of the priority pollutants by the technique
of lime and settle (pH = 8.5) is also given in Table 9. The efficiency was
calculated by the following method:
[(kg/day). ,. - (kg/day) -,.] x 100 = Removal Efficiency, Percent.
(kg/day).nf
For comparison, the removal efficiency based on the load calculated from the
sumps instead of the influent also is also presented.
Of the priority pollutants, lead, mercury, and zinc are removed 90
percent or better. Cadmium and copper are removed 70 percent or better.
Efficiencies based on the summation of the sump loads are all better effi-
ciencies based on the influent loadings except for lead and cadium. However,
these values may have less meaning than the efficiencies calculated from the
influent and effluent.
CONCLUSION
The lime and settle technique for the removal of metals at this secondary
lead manufacturing plant is only 90 percent effective for zinc and lead, 70
percent effective for copper and cadmium, and ineffective for antimony and
nickel. Benzene and cyanide are not present in detectable amounts, while
phenol, although present in some streams, is reduced to below detection limits
after treatment.
25
-------
BIBLIOGRAPHY
(1) Sampling and Analysis Procedures for Serening Industrial Effluents for
Priority Pollutants. Staff of the Environmental Monitoring and Support
Laboratories, U.S. EPA, Cincinnati, Ohio, March, 1977 (rev. April, 1977.
26
-------
APPENDIX
IDENTIFICATION LOG OF SAMPLES COLLECTED*
46-HR COMPOSITE SAMPLES
Secondary Lead Smelter Wastewater Streams**
March 21 (1655 hr) to March 23 (1508 hr), 1978
,ISCO
nni
001
Comp Plant effluent - collected by ISCO auto sampler -
programmed to collect 70 m£/20 m£ (Note: VL liter
of effluent collected from 1655 to 0700 - expected
nniB ISCO _, .
001 Blank
__.. Manual
001 Comp
002
^-r-
002
Drip
Comp
Comp
Manual
003
__,Manual „
004 Comp
_ _ ..Manual „ >
005 Comp
006
ISC°
Comp
_n,B ISCO „
006 Comp
3 £ of blank water in a 1-gallon jug
Plant effluent collected manually 394 m£/2 hrs -
24 collection periods
Treatment plant influent collected by constant drip
rate 3 m£/min
Treatment plant influent collected 394 m&/2 hrs -
24 collections periods (CP)
Creek enclosure leachate; collected 394 mfc/2 hrs -
24 CP
Landfill dump leachate and smelter runoff - collected
394 mil 2 hrs - 24 CP
Blast furnace and smelter cooling water - 394 m£/2
hrs - 24 CP
Battery breaker - acid and wash - ISCO auto sampler
70 m£/20 min (Note: Only 1 £ of sample collected in
first 16 hours)
3 £ of blank water rinsed through auto sampler
(continued")
* From Battelle Record Book No. 33888
** Manual composite collected every 2 hours - total volume 10 9, (2.5 gal.);
auto composite collected every 20 minutes - total volume 10 £ (2.5 gal).
27
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006 nua Comp Battery breaker - collected manually - 394 m£/2 hrs -
24 CP
OQ7Manual Comp process water (city water) - 394 m£/2 hrs - 24 CP
(Note: Spring water line was broken during sampling
period.)
Battery Manufacturing Area*
March 21 (1655 hr) to March 23 (1608 hr) , 1978
oogManual Comp industrial Battery Division - 394 m£/2 hrs - 24 CP
OQ9Manual CQ^ Automobile Battery Mfg., runoff and leachate -
394 m£/2 hrs - 24 CP
Automobile Battery Mi
394 m£/2 hrs - 24 CP
Automobile Battery Mi
500 m£/2 hrs - 15 CP
010 anua Comp Automobile Battery Mfg., lead oxide manufacture -
012 anua Comp Automobile Battery Mfg., battery wash and rinse -
011Manual Comp Remote - Auto Battery Mfg. plant (treated with lime)
1500 m£/truck load - 5 truck loads
000 Blank 9,5 £ of blank water - BCL - Milli-Q Water
GRAB SAMPLES FOR CYANIDES**
Secondary Lead Smelter Wastewater Streams
March 21, 1978 (2100 - 2300)
001 CN Wastewater treatment plant effluent
002 CN Wastewater treatment plant influent
003 CN Runoff and leachant surrounding creek enclosure
004 CN Landfill leachant and smelter area runoff
005 CN Blast furnace and lead ingot cooling water (city
water, non-contact)
006 CN Battery breaker sump
007 CN Process water (city water)
* Manual composite collected every 2 hours - final volume 10 £ (2.5 gal).
** Each sample collected in a l-£ amber polyethylene bottle, and preserved
with 0.6 gm (1/4 level teaspoon) of asborbic acid and at least 2 m£ of
ION NaOH. Final pH = 10.
28
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Battery Manufacturing Area
March 21, 1978 (2100 - 2300)
008 CN Industrial battery manufacturing
009 CN Automobile battery manufacturing area leachate
and runoff
010 CN Automobile battery manufacturing lead oxide
manufacturer
012 CN Automobile battery manufacturing battery case washer
Oil CN Remote auto battery plant
000 CN BCL's Milli-Q Water Blank
Secondary Lead Smelter Wastewater Streams
March 22, 1978 (1500 - 1600)
001 CN Wastewater treatment plant effluent
002 CN Wastewater treatment plant influent
003 CN Runoff and leachate surrounding creek enclosure
004 CN Landfill'leachate and smelter area runoff
005 CN Blast furnace and lead ingot cooling water (city
water, non-contact)
006 CN Battery breaker sump
007 CN Process water (city water)
Battery Manufacturing Area
March 22, 1978 (1500 - 1600)
008 CN Industrial battery manufacturing
009 CN Automobile battery manufacturing area leachate and
runoff
010 CN Automobile battery manufacturing lead oxide manu-
facturer
012 CN Automobile battery manufacturing battery case washer
29
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Oil CN Remote auto battery plant
000 CN BCL's Milli-Q Water Blank
GRAB SAMPLES FOR PHENOLS*
Secondary Lead Smelter Wastewater Streams
March 21, 1978 (2100 - 2330)
001 PH Wastewater treatment plant effluent
002 PH Wastewater treatment plant influent
003 PH Runoff and leachate surrounding creek enclosure
004 PH Landfill leachate and smelter area runoff
005 PH Blast furnace and lead ingot cooling water (city
water, non-contact)
006 PH Battery breaker sump
007 PH Process water (city water)
Battery Manufacturing Area
March 21, 1978 (2100 - 2330)
008 PH Industrial battery manufacturing
009 PH Automobile battery manufacturing area leachate
and runoff
010 PH Automobile battery manufacturing lead oxide manu-
facturer
012 PH Automobile battery manufacturing battery case washer
Oil PH Remote auto battery plant
000 PH BCL's Milli-Q Water Blank
Secondary Lead Smelter Wastewater Streams
March 22, 1978 (1500 - 1600)
001 PH Wastewater treatment plant effluent
* Each sample collected in a 1 £ glass bottle and preserved with 2 mH H-SO,
(cone.), if pH was greater than 4.
30
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002 PH Wastewater treatment plant influent
003 PH Runoff and leachate surrounding creek enclosure
004 PH Landfill leachate and smelter area runoff
005 PH Blast furnace and lead ingot cooling water (city
water, non-contact)
006 PH Battery breaker sump
007 PH Process water (city water)
Battery Manufacturing Area
March 22, 1978 (1500 - 1600)
008 PH Industrial battery manufacturing
009 PH Automobile battery manufacturing area leachate and
runoff
010 PH Automobile battery manufacturing lead oxide manu-
facturer
012 PH Automobile battery manufacturing battery case washer
Oil PH Remote auto battery plant
000 PH BCL's Milli-Q Water Blank
GRAB SAMPLES FOR ORGANICS*
Secondary Lead Smelter Wastewater Streams
March 21, 1978 (2100 - 2330)
001 OR Wastewater treatment plant effluent
002 OR Wastewater treatment plant influent
003 OR Runoff and leachate surrounding creek enclosure
004 OR Landfill leachate and smelter area runoff
005 OR Blast furnace and lead ingot cooling water (city
water, non-contact)
006 OR Battery breaker sump
* Samples collected in an 8-oz, glass bottle filled with a Teflon/silicone
septa. Extra caution was taken to eliminate entrapped air bubbles at septa.
31
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007 OR Process water (city water)
Battery Manufacturing Area
March 21, 1978 (2100 - 2330)
008 OR Industrial battery manufacturing
009 OR Automobile battery manufacturing area leachate and
runoff
010 OR Automobile battery manufacturing lead oxide manu-
facturer
012 OR Automobile battery manufacturing battery case washer
Oil OR Remote auto battery plant
000 OR BCL's Milli-Q Water Blank
Secondary Lead Smelter Wastewater Streams
March 22, 1978 (1500 - 1600)
001 OR Wastewater treatment plant effluent
002 OR Wastewater treatment plant influent
003 OR Runoff and leachate surrounding creek enclosure
004 OR Landfill leachate and smelter area runoff
005 OR Blast furnace and lead ingot cooling water (city
water, non-contact)
006 OR Battery breaker sump
007 OR Process water (city water)
Battery Manufacturing Area
March 22, 1978 (1500 - 1600)
008 OR Industrial battery manufacturing
009 OR Automobile battery manufacturing area leachate and
runoff
010 OR Automobile battery manufacturing lead oxide manu-
facturer
32
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012 OR Automobile battery manufacturing battery case washer
Oil OR Remote auto battery plant
000 OR BCL's Milli-Q Water Blank
GRAB SAMPLES FOR OIL AND GREASE*
Secondary Lead Smelter Wastewater Streams**
March 21, 1978 (2100 - 2330)
001 O&G Wastewater treatment plant effluent
002 O&G Wastewater treatment plant influent
003 O&G Runoff and leachate surrounding creek enclosure
004 O&G Landfill leachate and smelter area runoff
005 O&G Blast furnace and lead ingot cooling water (city
water, non-contact)
006 O&G Battery breaker sump
007 O&G Process water (city water)
Battery Manufacturing Area
March 21, 1978 (2100 - 2330)
008 O&G Industrial battery manufacturing
009 O&G Automobile battery manufacturing area leachate and
runpff
010 O&G Automobile battery manufacturing lead oxide manu-
facturer
012 O&G Automobile battery manufacturing battery case washer
Oil O&G Remote auto battery plant
000 O&G BCL's Milli-Q Water Blank
Secondary Lead Smejlter Wastewater Streams**
March 22, 1978 (1500 - 1600)
001 O&G Wastewater treatment plant effluent
* Each sample bottle contained 2 mH H2SO, (cone,), before sample was collected.
** No special samples collected for this group.
33
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002 O&G Wastewater treatment plant influent
003 O&G Runoff and leachate surrounding creek enclosure
004 O&G Landfill leachate and smelter area runoff
005 O&G Blast furnace and lead ingot cooling water (city
water, non-contact)
006 O&G Battery breaker sump
007 O&G Process water (city water)
Battery Manufacturing Area
March 22, 1978 (1500 - 1600)
008 O&G Industrial battery manufacturing
009 O&G Automobile battery manufacturing area leachate
and runoff
010 O&G Automobile battery manufacturing lead oxide manu-
facturer
012 O&G Automobile battery manufacturing battery case washer
/
Oil O&G Remote auto battery plant
000 O&G BCL's Milli-Q Water Blank
34
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TECHNICAL REPORT DATA
(flease read Instructions on the reverse before completing)
. REPORT NO.
EPA-600/2-79-039
3. RECIPIENT'S ACCESSIOr+NO.
4. TITLE AND SUBTITLE
Characterization of Priority Pollutants from a Secondar;
Lead and Battery Manufacturing Facility
5. REPORT DATE
January 1979 issuing date
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S)
8. PERFORMING ORGANIZATION REPORT NO.
Eugene J. Mezey
G-66l7-0601
9. PERFORMING ORGANIZATION NAME AND ADDRESS
BATTELLE'S COLUMBUS LABORATORIES
505 King Avenue
Columbus, Ohio 1*3201
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
68-03-2552 (T2006)
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research La"b.
Office of Research and Development
U. S. Environmental Protection Agency
Cincinnati, Ohio ^5268
- Cinn. OH
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
SPA/600/X2
15. SUPPLEMENTARY NOTES
16. ABSTRACT
A plant site at which secondary lead is produced from old batteri-es was sampled
utilizing the U. S. EPA protocol for the priority pollutants. The waste treatment
plant at this site uses lime and settle techniques to remove pollutants -from the
wastewater before it is discharged into a stream.
The results of the study show that the concentration of benzene and cyanides
were below their detection limits in all of the streams sampled. Further, the
concentrations of phenols were below their detection limit in both the influent and
effluent of the treatment plant.
The results of the study also show that the lime and settle treatment practiced
at this site removes in excess of 90 percent of the lead, mercury, and zinc. The
technique is slightly less effective for copper and cadmium because of their low
concentrations in the influent to the treatment plant. -Nevertheless, in excess of 70
percent of both copper and cadmium was removed. Because of the extremely low con-
centrations of antimony, chromium, and nickel in the influent to the treatment plant,
the effectiveness of the lime and settle treatment for the removal of these metals
could not be evaluated with any degree of confidence.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COS AT I Field/Group
Pollution
Wastewater
Treatment
Pollution control
Stationary source
Secondary lead
Battery manufacturing
Lime and settle treatment
Priority pollutants
13B
13. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)'
UNCLASSIFIED
21. NO. OF PAGES
Ul
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
35
* U.S. GOVERNMENT FRWTMG OFFICE: 1979 -657-060/1588
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