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

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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

-------
                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

-------
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

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                    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

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                                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

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                                  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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