EPA/600/A-132/019
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Control Technologies for Defunct Lead Battery Recycling Sites -
Overview and Recent Developments
Michael D. Royer
U.S. Environmental Protection Agency
Superfund Technology Demonstration Division
Edison, New Jersey
Ail Selvakumar and Roger Gaire
Foster Wheeler Enviresponse, Inc.
2890 Woodbridge Avenue
Edison, New Jersey
Abstract
This paper condenses and updates the information presented in the EPA technical resource
document (TRD) entitled "Selection of Control Technologies for Remediation of Lead Battery Recycling
Sites". That document provides federal remedial project managers (RRMs) and their supporting contractors
with the following information to facilitate the selection of treatment alternatives and cleanup services at lead
battery recycling sites (LBRS): (1) description of operations commonly conducted, and wastes generated
at LBRS; (2) technologies implemented or selected for LBRS remediation; (3) case studies of treatability
studies on LBRS wastes; (4) past experience regarding the recyclability of materials that are found at LBRS;
and (5) profiles of potentially applicable innovative treatment technologies.
Background
A defunct LBRS is where battery breaking, secondary lead smelting, or both were performed for the
purpose of reclaiming lead from spent lead-acid batteries. Twenty-nine defunct LBRS are or have been
addressed under the Superfund Program. Of the 29 LBRS, 20 are battery breaking sites, where the
operations consisted principally of battery breaking, draining the spent acid and separating the battery cases
from the lead. The other 9 LBRS were integrated battery breaking/lead smelting sites, where batteries were
riot only taken apart to remove the lead, but the lead was remeited and subjected to further processing to
produce lead alloys for subsequent reuse.
LBRS are likely to contain a variety of wastes such as lead contaminated soil, metallic lead and lead
compounds, spent sulfuric acid with metals in solution, battery case fragments (ebonite, hard rubber, or
1
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polypropylene), smelting residuals (slag, matte, etc.) and pollution control residuals.
Lead Battery Recycling Site Characterization
Lead contaminated media at LBRS can be classified into four main groups:
o Soils, sediments, and sludges - includes soils and particulate matter intermixed with water or other
aqueous components,
o Waste piles - by-products from battery recycling operations.
o Water - includes groundwater, surface water and contaminated wash water or process waters from
soils, sediments, and sludges treatment processes,
o Buildings, structures and equipment - includes all process structures, buildings and equipment.
An example of a LBRS conceptual model for potential pathways of exposure is presented in Figure
1.
Lead is the primary contaminant found in soils, sediments, and sludges at LBRS. Concentrations
ranging up to 7% have been noted. Lead (Pb), lead sulfate (PbS04), lead oxide (PbO), and lead dioxide
(PbOj) are the predominant lead species found at a LBRS. Sites with carbonate soils generally contain lead
carbonate (PbCOj), hydrocerussite (PbjtCO^OHJj), or lead hillite (Pb4S04 (COa)a(OH)a). Other heavy
metals such as antimony, arsenic, cadmium, and copper are sometimes present, but normally relatively low
concentrations.
Soil cleanup goals vary depending on site specific factors such as exposure routes and location of
humans and sensitive environmental receptors. In spite of this site to site variability, two common cleanup
goals do tend to recur. One of these includes reduction of lead concentrations in the soil, sediment, or
sludge to the point that the leachate yields less than 5 mg/L of lead when subjected to an EPA-mandated
leaching procedure (i.e., EP Toxicity or TCLP tests). Soils with TCLP leachates above 5 mg/L lead art
considered to be hazardous waste, which means that it generally cannot be landfilled until it has been
treated to yield a leachate less than 5 mg/L lead when subjected to the EP Toxicity leaching procedure
(Federal Register, 1990). A second common cleanup goal is the reduction of the total lead content In
residential soil to a level of 500 to 1000 mg/kg. In accordance with EPA Office of Solid Waste and
Emergency Response (OSWER) Directive #9355.4-02, an interim soil cleanup level of 500 to 1,000 mg/kg
total lead was adopted for protection from direct contact at residential settings. OSWER is in the process
of revising this directive to account for the contribution of various media to total lead exposure and t" 3
2
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Figure 1, A lead battery recycling site conceptual model.
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produce a strong scientific basis for choosing a soil lead cleanup level for a site. OSWER believes that the
best available approach is to use the EPA uptake biokinetic model (USEPA, 1991 a).
Lead is generally not very mobile in the environment, and tends to remain relatively close to its point
of initial deposition following its escape from the recycling process. Soils strongly retain lead in their upper
few centimeters; they are the major sinks for pollutant lead. The capacity of soil to adsorb lead increases
with increasing pH, cation exchange capacity, organic carbon content, soil/water Eh (redox potential), and
phosphate levels. Lead exhibits a high degree of adsorption on clay-rich soil. Lead compounds can also
be adsorbed onto hydrous oxides of iron and manganese and be immobilized in double and triple salts.
Lead can also be biomethylated, forming tetramethyl and tetraethy! lead. Metalic lead and its compounds
are heavier them water and tend to settle out. Some of the compounds are slightly soluble while others are
insoluble in water. Throughout most of the natural environment, the divalent form, Pb+a, is the most stable
ionized form.
Geophysical surveys can be used to determine the vertical and lateral variations in both subsurface
stratigraphy and subsurface metal contamination. A variety of survey techniques (e.g., ground penetrating
radar, electrical resistivity, electromagnetic induction, rnagnetometry, and seismic profiling) can effectively
detect the locations and extent of buried waste deposits. Borehole geophysics can be conducted at
selected well locations in order to better characterize subsurface stratigraphy. Field screening techniques
such as x-ray fluorescence (XRF) can be used to pinpoint sampling locations at areas of greatest
contamination {"hot spots'). So# samples are typically analyzed In the laboratory for the USEPA Target
Analyte List (TAL) metals, TCLP toxicity, total cyanide, total organic carbon, pH, acidity/alkalinity, and cation
exchange capacity.
Waste piles at LBRS are usually by-products from recycling or smelting operations. These waste
piles can be broken down into several components: battery casings (made of hard rubber, ebonite, or
polypropylene), battery internal components (e.g., polyvinyl chloride, paper), matte (a metallic sulfide waste
containing iron and lead), slag, and contaminated debris. Waste samples are analyzed for the parameters
mentioned above.
Groundwater does not normally create a major pathway for lead migration. However, since lead
compounds are soluble at low pHs, if battery breaking activities have occurred on-site, and the battery add
was disposed on-site, elevated concentrations of lead and other metals may occur in groundwater.
Monitoring wells are installed and sampled upgradient and downgradient from a lead battery recycling site.
Samples from the wells are analyzed for TAL metals, total cyanide, total organic carbon, total suspended
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solids, total dissolved solids, pH, alkalinity/acidity, hardness, sulfate, chloride, specific conductance,
temperature, arid dissolved oxygen. The Office of Emergency and Remedial Response (OERR) has
recommended an interim potable groundwater cleanup level of 15 ppb for lead (USEPA, 1990a).
A variety of contaminated structures, buildings, and equipment may be encountered at IBRS.
Sampling methods to determine the nature and extent of contamination on building, structure, and
equipment surfaces have not yet been standardized. Surface-wipe sampling Is generally used.
Basic Approaches to the Control of Lead Battery Recycling Sites
Remediation strategies for LBRS may incorporate several distinct technology options assembled into
a treatment train to attain specific site goals. These technologies include:
o No action
o Immobilization: preventing contaminant migration through construction of physical barriers
(eg., caps, slurry walls, liner) or utilizing chemical or thermal processes (eg.,
solidification/stabilization and vitrification),
o Separation/concentration: includes technologies utilizing chemically or physically induced
phase separation processes to concentrate lead contamination for further treatment, partial
recycling, or disposal while remediating a major portion of the contaminated material,
o Excavation and off-site disposal.
o Treatment Technologies for Soils, Sediments, and Sludges
No Action
Two out of 10 Record of Decisions (RODs) for LBRS have selected no action as a remedial
alternative, because the results of the Remedial Investigation (Rl) showed that the removal processes
conducted at sites were effective in removing contaminated soil from the site and the concentrations of
contaminants found in the groundwater were below any applicable or relevant and appropriate requirements
(ARARs). No action involves environmental monitoring and institutional restrictions such as site fencing,
deed restrictions, restrictions on groundwater usage, warning against excavation and a public awareness
program.
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Immobilization Options
Capping-
Capping involves the installation of an impermeable barrier over the contaminated soil to restrict
access and reduce infiltration of water into the soil. A variety of cap designs and materials are available.
Most designs are mufti-layered to conform with the performance standards in 40 CFR 264.310 which
addresses RCRA landfill closure requirements. However, single-layered designs are used for special
purposes at LBRS, for example, when treated soil is backfilled into an excavated area. Low permeability
clays and synthetic membranes are commonly used. They can be covered with top soil and vegetated to
protect them from weathering and erosion. Sofl materials are readly available, and synthetic materials are
widely manufactured and distributed.
The cost of a cap depends on the type and amount of materials selected, the thickness of each
layer, and the region. In a recent RCRA Fart S permit application for a 4 acre hazardous waste landfill, the
installed cost of a multi-layered cap was estimated at $5.45/fta. The design for this cap included 3 ft of top
soil, overlying a 1 ft sand layer, overlying 1 ft of compacted clay, overlying a 30 mil High Density
Polyethylene (HOPE) liner, overtying 2 ft of compacted clay (USEPA, 1985).
Table 1 summarizes the capping data needs for soils, sediments, and sludges.
Solidification/Stabilization (S/S)-
Solldrfication processes, either in situ or ex situ, produce monolithic blocks of waste with high
structural integrity. The contaminants do not necessarily interact chemically with the solidification reagents
(typically cement/lime) but are primarily mechanically locked within the solidified matrix. Stabilization
methods usually involve the addition of materials such as fly ash or blast furnace slag which limit the
solubility or mobility of waste constituents - even though the physical handling characteristics of the waste
may not be changed or improved. Ex situ S/S is widely demonstrated and equipment is readily available.
There is however no data cm long-term stability available.
Ex situ S/S involves mixing the excavated contaminated soil with Portland cement and/or lime along
with other binders such as fly ash or silicate reagents to produce a strong, monolithic mass. Cement is
generally suitable for immobilizing metals (such as lead, antimony, and cadmium) which are found at LBRS.
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TABLE 1. DATA NEEDS FOR TREATMENT TECHNOLOGIES FOR
SOILS, SEDIMENTS, AND SLUDGES
Technology
Data requirement
Capping
o Extant of contamination
(USEPA, 1987a)
o Depth to groundwater tabie
o Climate
o Waste volume
Solidification/stabilization
o Metal concentrations
(USEPA, 1986a and Amlella at al.. 1990)
o Moisture content
o Bulk density
o Grain-size distribution
o Waste volume
o Sulfate oontent
o Organic content
o Debris size and type
o TCLP
Soil washing/acid teaching
o Soil type and uniformity
(USEPA, 1969c and USEPA, 1990c)
o Moisture content
o Bulk density
o Grain-size distribution
o Gay content
o Metal concentrations/species
o pH
o Cation exchange capacity
o Organic matter content
o Waste volume
o Mineralogicai characteristics
o Debris size and type
o TCLP
Off-site land disposal
o Soil characterization as dictated by the
(USEPA, 1987b)
landfill operator and the governing
regulatory agency
o Waste voluma
o TCLP
Because the pH of the cement mixture is high (approximately 12), most multivalent cations are converted
into insoluble hydroxides or carbonates. They are then resistant to leaching.
To date, 5 out of 10 RODs for LBRS have selected ex situ S/S as an integral part of a treatment
alternative.
Costs to use S/S technology are expected to be in a range of $27-5164 per cu yd (USEPA, 1989a).
Data needs for S/S are summarized in Table 1.
Three full-scale S/S operations have been implemented at LBRS. Approximately 7,300 tons of soil
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contaminated with lead (EP Tox >400 mg/L) were treated in a mobile plant with portiand cement, fly ash,
and water at a rate of 300 tons/day at Norco Battery Site in California. EP Toxicity of the treated soil after
28 days was less than 5 mg/L (USEPA, 1991 b). Approximately 11,000 tons of soil (TCIP as high as 422
mg/L) were treated by the proprietary MAECTITE™ process developed by Maecorp, Inc. at the Lee's Farm
in Wisconsin. TCLP of the treated soil was less than 1 mg/L About 20,000 cubic yards of lead-
contaminated soil were recently solidified at Cedartown Battery, inc. in Georgia. Analytical data on this site
is currently being processed.
Numerous S/S treatability studies have been completed at LBRS. A pilot-scale treatability test
conducted at the Gould Site in Oregon demonstrated that a mix of approximately 14% portiand cement Type
Ml, 25% cement kiln dust and 35% water successfully stabilized soils and waste products crushed to 1 /8
in. size. Bench-scale treatability studies conducted on soils from three LBRS (C&R Battery Site in Virginia,
Sapp Battery Site in Florida, Gould Site in Oregon) demonstrated that cement-based (i.e., cement or cement
with additives) blends decreased the teachability of lead and met the EP Toxicity criterion of 5 mg/L
In situ treatment of contaminated soils is innovative. Two specific in situ S/S techniques, under the
Superfund innovative Technology Evaluation (SITE) Program, hold promise for LBRS,
International Watte Technologies/Geo-Con, Inc.- This in situ solidification/stabilization
technology immobilizes organic and inorganic compounds in wet or dry soils, using additives to produce
a cement-like mass. The basic components of this technology are: Geo-Con's deep soil mixing system
(DSM) which delivers and mixes the chemicals with the soil in situ; and a batch mixing plant to supply the
International Waste Technologies (IWT) proprietary treatment chemicals. The IWT technology can be applied
to soils, sediments, and sludges contaminated with organic compounds and metals. The SITE Demon-
stration of this technology occurred at a PCB-contaminated site in April, 1988 and the results are
summarized in an Applications Analysis Report (USEPA, 1990b).
S.M.W. Seiko, Inc.- The Soil-Cement Mixing Wall (S.M.W.) technology developed by Seiko, Inc.
involves the in situ stabilization and solidification of contaminated soils. Multi-axis, overlapping, hollow-stem
augers are used to inject solidification/stabilization agents and blend them with contaminated soils in situ.
The product is a monolithic block down to the treatment depth. This technology applies to soils con-
taminated with metals and semi-volatile organic compounds. This project was accepted into the SITE
Demonstration Program in June 1989. Site selection is currently underway.
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Vttrification-
As with solidification, there are both in situ arid ex situ procedures for vitrification, in situ vitrification
converts contaminated soils into chemically inert, stable glass and crystalline materials by a thermal
treatment process. Large electrodes are inserted into soil containing significant levels of silicates. Because
soil typically has low conductivity, flaked graphite and glass frit are placed on the soil surface between the
electrodes to provide a starter path for electric current A high current passes through the electrodes and
graphite. The heat melts contaminants, gradually working downward through the soil. Volatile compounds
are collected at the surface for treatment After the process ends and the soil has cooled, the waste material
remains fused in a chemically inert and crystalline form that has very low leachability rates. This process
can be used to remove organics and/or immobilize inorganics in contaminated soils or sludges. It has not
yet been applied at a Superfund site. However, it has been field demonstrated on radioactive wastes at the
DOE's Hanford Nuclear Reservation by the Geosafe Corporation. Large-scale remediation of this process
has been suspended temporarily because of the loss of off gas confinement and control during the recent
large-scale testing of its equipment that resulted in fire.
Ex situ vitrification involves heating the excavated contaminated soil by a thermal treatment process
to form chemically inert materials. Two specific ex situ vitrification techniques under the SITE program are
potentially applicable to LBRS.
Retech, Inc. Plasma Reactor-Thls thermal treatment technology uses heat from a plasma torch
to create a molten bath that detoxifies contaminants in soil. Organic contaminants vaporize and react at
very high temperatures to form innocuous products. Solids melt into the molten bath. Metals remain in this
phase, which - when cooled - forms a non-leachabie matrix. It is most appropriate for soils and sludges
contaminated with metals and hard-to-destroy organic compounds. A demonstration is planned in late 1990
at a Department of Energy research facility in Butte, Montana.
Babcock and Wilcox Co. Cyclone Furnace Proceas-This cyclone furnace technology is designed
to decontaminate wastes containing both organic and metal contaminants. The cyclone furnace retains
heavy metals in a non-ieachable slag aid vaporizes organic materials prior to incinerating them. The treated
soils resemble natural obsidian (volcanic glass), similar to the final product of vitrification. This technology
is applicable to solids and soil contaminated with organic compounds and metals. Babcock and Wilcox
Co. is developing this process under the SITE Emerging Technologies Program.
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Separation/Concentration Options
Soil Washing and Acid Leaching-
Soil washing is a water-based process for mechanically scrubbing soils ex situ to remove
undesirable contaminants. The process removes contaminants from soils in one of two ways: by dissolving
or suspending them in the wash solution or by concentrating them into a smaller volume of soil through
simple particle size separation techniques. Acid leaching removes lead from soils by first converting the lead
to a soluble salt and then precipitating a lead salt from solution.
Implementation of this technology requires excavating the lead-contaminated soil, washing the lead
on-site with a solution (such as nitric acid or EDTA), and returning the treated soil to the site for disposal
in the excavation area. One of the limitations of soil washing as a viable alternative concerns the physical
nature of the soil. Soils which are high in clay, silt, or fines have proven difficult to treat. Data needs for
soil washing/acid leaching are summarized in Table 1.
Figure 2 Is a process flow diagram of an Acid Leaching Process developed by the U.S. Bureau of
Mines. This process converts lead sulfate and lead dioxide to lead carbonate, which is soluble In nitric acid.
Lead is recovered from the leaching solution by precipitating with sulfuric acid (Schmidt, 1989). There is
a potential market for lead sulfate. The clean soil is stored or returned to the site. Waste streams from the
washing system require further treatment before final discharge.
Actual field experience of cleaning soil at LBRS is limited. Two sites (Lee's Farm in Woodviile,
Wisconsin and ILCO site in Leeds, Alabama) have unsuccessfully attempted soil washing of contaminated
soil. Two RODs (Arcanum Iron and Metal Site and United Scrap Co. Site in Ohio) out of 10 for LBRS have
selected acid leaching as an integral part of the treatment alternative but full-scale treatment has not
occurred. The Bureau of Mines (BOM) conducted bench-scale studies to evaluate the performance of acid
leaching solutions on lead in contaminated soil at battery recycling sites. Table 2 shows some
representative results from the Bureau of Mines tests. The results indicated that nitric acid solutions can
achieve very high removal efficiencies for soil (greater than 99%) and an EP Toxicity level less than 1 mg/L
(Schmidt, 1989). BOM estimates the cost of full-scale operation to be $208 per cu yd of soil.
EPA recently completed a series of laboratory tests on soil and casing samples from metal recycling
sites. The soil samples from these sites were subjected to bench-scale washing cycles using water, EDTA,
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FEED
CASINGS
UME
RINSE
WER
RINSE
GYPSUM
1 REGENERATION 1* NH,
SOU
ACID WASH
FIltER |
SOU
PITER
RINSE
SLUDGE
FILTER
RINSE
¦I EVAPORATION
SCREEN
PRECIPITATION
MAKEUP
HNOj
Figure 2, Bureau of Mines soil washing process,
Source: Schmidt 1989.
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TABLE 2. REPRESENTATIVE RESULTS OF THE BUREAU OF MINES TREATABILITY TESTS
ON SELECTED SAMPLES OF BATTERY BREAKER SOIL WASTES
Site/waste
Common
lead
SfMCkMI
Average*
lead
total
(ppm)
Leaching
!¦ ¦ ill n rl
iiMtiKXl
Total
lead
(PP«n)
EP
Toxicity
("»g/L)
United Scrap Lead soil
Pb, PbS04, PbOx
8.000-18.000
15% HN03, 2-hr wash
and 1% HNOj, 24-hr
soak
200
<1.0
United Scrap Lead toil
Pb, PbS04, PtoO,
8,000-18.000
80 g/L F* 4-hr & 20
g/L F», 4-hr, 2-stage
wash, 1% HN03, 24-hr
soak
203
<1.0
Arcanum soil
Pb (6.6%), PbS04
71,000
80 g/L F*. 4-hr, 50'C
4 20 g/L F*. 4-hr,
S0*C, 2-ttage leach
and 1% HNOj, 24-hr
wash
334
0.26
Arcanum soil
Pb (6.6%), PbS04
71,000
15% HNO,, 2-hr, 50* C
leach and 1% HN03,
50*C, 24-hr wash
<250
<1.0
CAR Battery Soil Sample B
Pb. PbS04,
PbCOj, PbOj
17,000
15% HNOj, 2-hr and
2% HNOj, 24-hr wash
and 1-hr water rinse
29
<0.1
*No initial EP Toxicity data available.
F* Ruosilicic acid
Source: Schmidt, 1989
or a surfactant (Tide detergent), respectively. Soil washing did not remove significant amounts of lead from
any of the soil fractions. The lead was not concentrated in any particular soil fraction but rather was
distributed among all the fractions. A comparison of lead concentrations in the wash waters indicated that
the EDTA wash performed better than the surfactant and water washes (PEl Associates Inc., 1989). While
EDTA was reasonably effective in removing lead. Bureau of Mines researchers observed that its effectiveness
seemed to vary with the species of lead present (Schmidt, 19%). Additional bench-scale studies are
required to verify that site-specific cleanup goals can be achieved employing these techniques. EFA
researchers are also in the early stages of investigating the use of milder acids (e.g., acetic acid) than those
acids used to date (e.g., nitric, fluosilicic) for leaching of lead from soils (USEPA, 1990d).
Soli Excavation and Off-Site Disposal
Excavation and removal of contaminated soil to a RCRA landfill have been performed prior to
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implementation of land disposal restrictions (LDRs) at LBRS. Excavation and removal are applicable to
almost all site conditions, although they may be cost-prohibitive for sites with large volumes, greater depths
or complex hydrogedogic environments. Determining the feasibility of off-site disposal requires knowledge
of LDRs and other regulations developed by state governments. Without treatment, this technology may
not meet RCRA LDRs. The LDRs prohibit the land disposal of certain RCRA hazardous wastes unless they
meet specified treatment standards. If lead-contaminated wastes (i.e., soils and fragments of battery cases)
fail the Toxicity Characteristic Leaching Procedure (TCLP) test with lead levels equal to or greater than 5.0
mg/L, they are a RCRA hazardous waste (D008).
Cost estimates for this technology range from $287-5488 per cu yd of soil,
o Treatment Technologies for Waste Piles
Waste pile removal and off-site disposal have been practiced in the past but probably will not
continue due to LDRs, unless the materials are treated prior to disposal.
Table 3 summarizes the data needs for treatment technologies for waste piles.
TABLE 3. DATA NEEDS FOR TREATMENT TECHNOLOGIES
FOR WASTE PILES
Technology
Data requirement
Off-site landfill
o Wast* pile characterization as dictated
(USEPA, 1987b)
by land disposal restrictions
o Waste volume
o TCLP
Washing of battery casings
o Casing type
o Bulk density
o Grain-size distribution
o Metal concentrations
o TCLP
Separation of battery casings
o Composition of battery casings
o Metal concentrations
o Waste volume
o Other information required by recipient
o TCLP
Recycling
o Potential buyer/user
o Allowable lead content in ebonite/plastic for use
as fuels
o Lead content for acceptance by smelter
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Washing of Battery Casinos
This technology, developed by the Bureau of Mines (BOM), is similar to acid leaching of soil but
somewhat less complicated. Lead contamination is principally in the form of PbS04 in microcracks in the
casing. Casing materials are granulated to less than 3/8 inch to create enough exposed surface areas that
the PbS04 could then be successfully removed by the leaching agent such as nitric acid.
There has been no actual field experience to date in the washing of battery casings at LSRS. BOM-
conducted bench-scale treatability studies that showed good removal efficiencies (Table 4). The residual
battery casing materials have an EP Toxicity lead concentration less than 5 mg/L (Schmidt, 1989).
TABLE 4. REPRESENTATIVE RESULTS OF THE BUREAU OF MINES TREATMENT TESTS ON
SELECTED CHIP SAMPLES OF BROKEN BATTERY CASING WASTES
Site/waste
Common
Inn!
Average*
lead
total
EP
Toxicity
<">g/D
United Scrap laad
granulated chips
PbS04, Pb
3.000
0.5% HN03. 1-hr.
20*C wash
86
<0.2
Arcanum broken
chips
PbS04, Pb
3,000
1% HN03, tap water,
50* C. 24-hr, agitated
210
<3.5
C&R Battery casing
chips
PbS04, Pb
175,000
1% HNOa 4-hr, wash
and water rinse
277
0.15
Gould buried casing
chips
(broken)
PbC03, PbS04
193.000
Ammonium cartoon-
ate carbonation, 1%
HN03, 20*C. 4-hr
wash
145
0.52
Rhone-Poulenc
casing chips (broken)
PbCOa
65,000
Calcium carbonate
carbonation. 0.5%
HN03, 20*C, 1-hr
wash
516
3.68
'No initial EP Toxicity data available.
Source: Schmidt, 1989
Separation and Cleaning of Battery Casinos
This alternative comprises excavation of the waste piles, followed by on-site separation of battery
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casing fragments. Separation is followed by recycling (possibly off-site) of those components that have
recycle value; RCRA off-site disposal of hazardous non-recyclable components; and on-site disposal of
nonhazardous components.
Canonie Environmental Services Corp. under contract to NL Industries, Inc. has developed a
proprietary process for remediating lead battery and smelting wastes at the Gould Site in Portland, Oregon
(Canonie Environmental, undated). The process separates the waste materials into recyclable and
nonrecydable products. The recyclable products consist of:
o Materials with a lead content sufficiently high for recycling, and
o Cleaned materials such as plastic and ebonite that will pass the EP Toxicity test for lead,
o The materials that cannot be cleaned to pass the EP Toxicity test for lead and do not contain
sufficient lead for recycling are considered "nonrecydable".
The process is shown schematically in Figure 3. The battery casing is crushed and washed in the
first stage. The fines are screened from the washed material, the solids are separated from the water in a
settling tank, and the settled pulp Is filtered from the solution. These materials are the filter cake that will
typically contain more than 40% lead and less than 30% moisture. Following the first wash, the screen
oversize is fed to a gravity separation device. This system separates the plastic and ebonite in the waste
from furnace products, rocks, and trash excavated with the waste. The ebonite and plastic material passes
to the second wash stage where the residual amounts of lead contamination are removed.
Performance at the Gould SHe-The Gould site contains approximately 117,500 tons of waste.
Canonie claims that its separation and washing process there could produce approximately 80,500 tons of
recydable materials and 37,000 tons of material for stabilization and subsequent on-site disposal. At other
sites, the amount of recyclable material may vary according to site history and use (Canonie Environmental,
undated).
Canonie Environmental conducted a marketing study to identify the markets for the products from
the above process. The market suggested for the lead fines are primary and secondary lead smelters.
Plastic, if it can be successfully deaned, appears to have numerous potential users. The most likely market
for ebonite appears to be as a fuel supplement for cement kilns or power plants (Canonie Environmental,
1990). Additional market research is planned to assess the effect of the new RCRA boiler and industrial
furnace regulations regarding combustion of hazardous wastes.
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Figure 3, Battery waste treatment process.
Source: Canonie Environmental.
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innovative Processes for Waste Piles Treatment
The Horsehead Resource Development Co., Inc. Flame Reactor Process-It is a patented,
hydrocarbon-fueled, flash smelting system that treats residues and wastes containing metals. The reactor
processes wastes with a very hot reducing gas >2000°C produced from the combustion of solid or gaseous
hydrocarbon fuels in oxygen-enriched air. in a compact, low cost reactor, the feed materials react rapidly,
allowing a high waste throughput The end products are a non-1 eachable slag (glass-like when cooled) and
a recyclable heavy metal-enriched oxide, which may be marketable. A SITE demonstration was performed
at the Monaca facility In Pennsylvania in March 1991. The waste material is a secondary lead smelter blast
furnace slag from the National Smelting and Refining Site in Atlanta, Georgia Lead and other metals were
removed from the raw waste and concentrated in the bag house dust which may be recycled for its lead
content. The process reduced the lead content of the slag from 5.4% to 0.6%. All samples of processed
waste slag passed the TCLP test for metals. For lead, the TCLP values fell from approximately 5 mg/L to
<0.33 mg/L (USEPA, 1991c).
The Risk Reduction Engineering Laboratory (RREL) Debris Washing System (DWS)-Developed
by RREL staff and IT Environmental Programs, Inc., this technology will decontaminate debris found at
Superfund sites throughout the country. The DWS can clean various types of debris (e.g., metallic, masonry,
or other solids) that are contaminated with hazardous chemicals such as pesticides, PCBs, lead, and other
metals. This process is being evaluated by EPA in the SITE Program. Bench-scale studies conducted on
six pieces of debris including plastic spiked with DDT, lindane, PCB and lead sulfate, then washed using
surfactant achieved an overall percentage reduction of lead greater than 98%. This technology has potential
application to battery casings and other metallic and masonry debris found at lead battery recycling sites.
As part of the emerging technology portion of the SITE Program, the Center for Hazardous
Materials Research (CHMR) proposes to research, develop, and evaluate the economics of using
secondary lead smelters for the recovery of lead from rubber battery casings. Secondary lead smelting
technology is a process which may be able to remove the lead from the battery casings and other waste
materials. The net result will be the detoxification of these materials while providing a usable product (i.e.,
reclaimed lead).
o Treatment Technologies for Water
Treatments using precipitation/flocculation/sedimentation and ion exchange are often considered
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for remediation of LBRS. Contaminated water from pits, ponds, and lagoons is typically pumped and treated
together with groundwater.
Table 5 summarizes the data needs for treatment technologies for water.
TABLE 5. DATA NEEDS FOR TREATMENT TECHNOLOGIES
FOR WATER
Data requirement
/mm liiMM ¦ —
(USEPA, 1989b)
o Total suspended solids
o pH
o Matai concentration*
o Oil and grams*
o Specific gravity of suspended solids
Ion exchange
(USEPA. 1989b)
o Total suspended solids
o Total dissolved solids
~ Inorganic cations and anions
o Oil and grease
o pH
Pumping vis wells
o Depth to water table
o Groundwater gradients
O Hydraulic conductivity
o Specific yield estimate
o Porosity
o Thickness of aquifers
o Storativity
Precioitation/Floccuiatlon/Sedlmerrtation
The combination of precipitation/floccuiation/sedimentation is a well-established technology with
specific operating parameters for metals removal from ground and surface waters. Typical removal of metals
employs precipitation with hydroxides, carbonates, or sulfides. Generally lime, soda ash, or sodium sulfide
is added to water In a rapid-mixing tank along with flocculating agents such as alum, lime, and various iron
salts. This mixture then flows to a fiocculation chamber that agglomerates particles, which are then
separated from the liquid phase in a sedimentation chamber. Hydroxide precipitation with lime is the most
common choice. Metal sulfides exhibit significantly lower solubility than their hydroxide counterparts,
achieve more complete precipitation, and provide stability over a broad pH range. At a pH of 4.5, sulfide
precipitation can achieve the EPA-recommended standard for potable water (i.e., 15 »g/L), Sulfide
precipitation - often effective - can be considerably more expensive than hydroxide precipitation, due to
higher chemical costs and increased process complexity. The precipitated solids would then be handled
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in a manner similar to contaminated soils. The supernatant would be discharged to a nearby stream or to
a publicly owned treatment works (POTW).
Ion Exchange
Ion exchange is a process whereby the toxic ions are removed from the aqueous phase in an
exchange with relatively harmless ions held by the ion exchange material. Modern ion exchange resins
consist of synthetic organic materials containing ionic functional groups to which exchangeable ions are
attached. These synthetic resins are structurally stable and exhibit a high exchange capacity. They can be
tailored to show selectivity towards specific ions. The exchange reaction is reversible and concentration-
dependent; the exchange resins are regenerate for reuse. Ail metallic elements - when present as soluble
species, either anionic or cationic - can be removed by ion exchange.
A practical upper concentration limit for ion exchange is about 2,500 to 4,000 mg/L A higher
concentration results in rapid exhaustion of the resin and inordinately high regeneration costs. Suspended
solids in the feed stream should contain less than 50 mg/L to prevent plugging the resins (USEPA, 1986b).
Innovative Processes for Water Treatment
The Bio-Recovery Systems, Inc. Biological Sorption Process-Bio-Recovery Systems, Inc. in Las
Cruces, New Mexico is testing AlgaSORB*, a new technology for the removal and recovery of heavy metal
ions from groundwater. This biological sorption process is based on the affinity of algae ceil walls for heavy
metal ions. This technology is being tested for the removal of metal ions that are "hard" or contain high
leveis of dissolved solids from groundwater or surface leachates. This process is being developed under
the SITE Emerging Technologies Program.
Colorado School of Mines' Wetlands-Based Treatment-This approach uses natural biological and
geochemical processes inherent in man-made wetlands to accumulate and remove metals from
contaminated water. The treatment system incorporates principal ecosystem components from wetlands,
such as organic soils, microbial fauna, algae, and vascular plants. Waters which contain high metal
concentrations and have low pH flow through the aerobic and anaerobic zones of the wetland ecosystem.
The metals can be removed by filtration, ion exchange, adsorption, absorption, and precipitation through
geochemical and microbial oxidation and reduction.
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Conclusion
EPA's recent publication of the document, Selection of Control Technology for the Remediation
of Lead Battery Recycling Site#, EPA/540/2-91/014, enables EPA, State, and private sector remediation
managers to quickly identify past experience and information that can be applied to site characterization and
control technology evaluation activities.
Regarding the remediation of soils, sediments, and sludges, the feasibility of the previously popular
remedy of excavation and off-site disposal has been basically eliminated unless a waiver can be obtained
or the soil is determined to pose a threat to groundwater, but is not considered a RCRA hazardous waste.
Cement-based solidification and stabilization has been implemented at full-scale on at least three sites
(Norco, CA; Lee's Farm.WI; Cedartown Battery, GA) and is scheduled for implementation at several others.
Solidification/stabilization of soils can be expected to remain a popular option for lead and other heavy
metal contaminated soils, sediments, and sludges due to (a) relative simplicity, (b) ready availability of
equipment and vendors, and (c) lew cost Disadvantages include: (a) S/S can cause substantial increases
(e.g. 30%) in the volume of material, (b) long-term immobilization of lead Is not yet demonstrated, and (c)
if organic contaminants are also present in the soil, solidification of organics is not widely demonstrated.
Should solidification of soils, sediments, and sludges fall out of favor due to concern about or
observed leaching failures, then this can be expected to improve the chances of acceptance for the use of
novel in situ and ex situ vitrification technologies, which may provide improved permeation and leaching
resistance, but which tend to be more complicated and expensive than cement-based solidification. Also
benefitting from a decline in the acceptability of solidification would be soil washing and acid leaching
technologies. These technologies are more complicated, costly, and novel than solidification, but they have
the potentially significant advantage of actually removing the lead from the soil, which should minimize the
need for long-term monitoring and would eliminate the potential of any long-term leaching problems. The
success or failure of acid leaching technology at the United Scrap Lead site in Ohio is viewed as critical to
the future acceptability of this technology for lead battery recycling site remediation.
Recycling of waste piles to reduce the volume of hazardous waste, and to recover lead, lead
compounds, plastic, and hard rubber is an enticing challenge that has continued to receive considerable
attention. To date, large-scale recycling of defunct LBRS waste materials is not known to occur. The site
to watch in the next year or so regarding recycling is the Gould site, Portland, OR to see if success is
attained in separating and recycling of lead fines to a secondary smelter, plastic to a plastics recycier, and
20
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hard rubber as a fuel supplement. Also important is the Tonolli site, Nesquehoning, PA where a full-scale
treatability study is examining the feasibility of using hard rubber battery scraps as a fuel supplement In a
nearby secondary lead smelter. Battery scraps from other defunct LBRS may be tested as well. For sites
where lead leaching from slag is posing a health or environmental threat, a process (flame reactor) for
recovering lead from slag and simultaneously converting the slag to a non-hazardous material (i.e., TCLP
leachate < 5 mg/l lead) is undergoing testing in EPA's Superfund Innovative Technology Evaluation
Program (SITE). Within another several years, the use of acid leaching for cleaning and recovery of lead
from battery cases may also be demonstrated at the United Scrap Lead site to be a viable option.
The selection of control technology for LBRS remediation is expected to remain an interesting and
important remediation issue for the next several years.
References
Arnieiia. E. F. and L J. Blythe. 1990. Solidifying Traps. Chemical Engineering, pp. 92-102.
Canonie Environmental. Undated. Information Sheet on Process for Remediating Lead Battery Sites.
Canonie Environmental. 1990. Marketing Studies Report for Gould, Inc., Portland, Oregon.
Federal Register. 1990. 40 CFR Parts 148 et al. Land Disposal Restrictions for Third Third Scheduled
Wastes; Rule. U.S. Environmental Protection Agency, Washington, DC. pp.22567-22660.
PEI Associates, inc. 1989. Lead Battery Site Treatability Studies. Contract No.68-03-3413. Submitted to
Risk Reduction Engineering Laboratory, Edison, New Jersey.
Schmidt, B. William. 1989. Assessment of Treatment Techniques at Superfund Battery Sites. International
Symposium on Hazardous Waste Treatment: Treatment of Contaminated Soils, Cincinnati, Ohio.
USEPA. 1985. Handbook, Remedial Action at Waste Disposal Sites (Revised). EPA/625/6-85/006. U.S.
Environmental Protection Agency Office of Emergency and Emergency Response, Washington, DC.
USEPA. 1986a. Handbook for Stabilization/Solidification of Hazardous Wastes. EPA/540/2-86/001.
Hazardous Waste Engineering Research Laboratory, Cincinnati, Ohio.
USEPA. 1986b. Mobile Treatment Technologies for Superfund Wastes. EPA/540/2-86/003(f). U.S.
Environmental Protection Agency Office of Solid Waste and Emergency Response, Washington, DC.
USEPA. 1987a. A Compendium of Technologies Used in the Treatment of Hazardous Wastes.
EPA/625/8-87/014. Center for Environmental Research Information, Office of Research and
Development, Cincinnati, Ohio.
USEPA. 1987b. Technology Briefs: Data Requirements for Selecting Remedial Action Technology.
EPA/600/2-87/001. Hazardous Waste Engineering Research Laboratory, Cincinnati, Ohio.
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USEPA. 1989a. Stabilization /Solidification of CERCLA and RCRA Wastes: Physical Tests, Chemical
Testing Procedures, Technology Screening, and Field Activities. EPA/625/6-89/022. Center for
Environmental Research Information, Cincinnati, Ohio.
USEPA. 1989b. Guide for Conducting Treatability Studies under CERCLA. Interim Final.
EPA/540/2-89/058. U.S. EPA Office of Solid Waste and Emergency Response, Washington, DC.
USEPA. 1989c. Superfund Treatability Clearinghouse Abstracts. EPA/540/2-89/001. U.S. Environmental
Protection Agency Office of Emergency and Remedial Response, Washington, DC.
USEPA. 1990a. Memorandum from Henry L Longest, Director, Office of Emergency and Remedial
Response to Patrick M. Tobin, Director, Waste Management Division, Region IV, Cleanup Level for Lead
in Groundwater. U.S. Environmental Protection Agency, Office of Emergency and Remedial Response,
Washington, DC.
USEPA. 1990b, International Waste Technoiogies/Geo-Con In Situ Stabilization/Solidification, Applications
Analysis Report EPA/540/A5-89/004. U.S. Environmental Protection Agency, Office of Research and
Development, Cincinnati, Ohio.
USEPA. 1990c. Treatment Technology Bulletin: Soil Washing Treatment EPA/540/2-90/017. U. S.
Environmental Protection Agency Office of Emergency and Remedial Response, Washington, DC.
USEPA. I990d. Workshop on Innovative Technologies for Treatment of Contaminated Sediments.
Summary Report EPA/600/2-90/054. U.S. Environmental Protection Agency Office of Research and
Development, Cincinnati, Ohio.
USEPA. 1991a. Memorandum from Don R. Clay, Assistant Administrator, Office of Solid Waste and
Emergency Response on Update on Soil Lead Cleanup Guidance. U.S. Environmental Protection
Agency, Office of Solid Waste and Emergency Response, Washington, DC.
USEPA. 1991b. Federal On-Scene Coordinators Report on Norco Battery Site Removal Action. U. S.
Environmental Protection Agency, Region IX, California.
USEPA. 1991c. Demonstration Bulletin: Flame Reactor. EPA/540/M5-91 /005. U.S. Environmental
Protection Agency Office of Research and Development, Cincinnati, Ohio.
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TECHNICAL REPORT DATA
(Please read instructions on the reverse before compter
1. REPORT NO.
EPA/600/A-92/Q19
3.
4. TITLE AND SUBTITLE
5. REPORT DATE
Control Technologies for Defunct Lead Battery
Recycling Sites — Overview and Recent Developments
6. PERFORMING ORGANIZATION CODE
l^chaTf^. Royer, RREL, Edison, NJ 08837-3679
Ari Selvakumar & Roger Gaire, FWEI, Edison, NJ 08837
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Technical Assistance Section, TSB, STDD, RREL
US Environmental Protection Agency (MS-104)
2890 Woodbridge Ave., Edison, NJ 08837-3679
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-C9-0033
12. SPONSORING AGENCY NAME AND ADDRESS
13. TYPE OF REPORT AND PERIOD COVERED
Risk Reduction Engineering Laboratory, Cincinnati, OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, OH 45268
Published Paper
14. SPONSORING AGENCY CODE
EPA/600/14
15. SUPPLEMENT**"
Presented in ."Third .International Seminar on "Battery Waste Management Volume 3 11/4-6/91
pp:l-'22 Diinfield •Beachr-FL -' Project 0ffj£)?rr Michael D. Royer FTS -340-6633
16. ABSTRACT
At least 29 lead battery recycling sites are or have been slated
for investigation and possible remediation under the Superfund program. This
paper condenses information regarding the characteristics and remediation of these sites.
The information provided includes: (1) description of operations commonly conducted,
and wastes generated; (2) technologies implemented or selected for site remediation;
(3) case studies of treatability studies on common wastes; (4) past experience regarding
the recyclability of materials found at these sites, and (5) profiles of potentially
applicable innovative treatment technologies.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
COSATI Field/Group
Lead, Lead Smelting, Lead-Acid Battery,
Lead Battery Recycling Sites, Solid-
ification, Soil Washing, Acid Leaching,
Recycling
Control Technology
Remediation
REPRODUCED BY
U.S. DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL INFORMATION SERVICE
SPRINGFIELD. VA. 22161
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURIJpj^p^l {pYfe^ePOr,/
21. NO. OF PAGES
24
20
SECURIT^IIir^
22. PRICE
EPA Form 2220-1 (»-73)
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