180 Second Str eet Chel sea, Massachusetts 02150 Tel : 617-887-2300 Fax: 617-887-0399

Technical Repor t # 31
Char acter ization of Foundr y Sand Waste
Oct ober 2000
CHARACTERIZATION OF FOUNDRY SAND WASTE
Eric S. Winkler, Ph.D. - Principal Investigator
Alexander A. Bol'shakov, Ph.D. - Project Engineer
Center for Energy Efficiency and Renewable Energy
University of Massachusetts at Amherst
CHELSEA CENTER FOR RECYCLING AND ECONOMIC DEVELOPMENT
TECHNICAL RESEARCH PROGRAM
Oct ober 2000
This report has been reviewed by the Chelsea Center for Recycling and Economic Development and approved for publication.
Approval does not signify that the contents necessarily reflect the views and policies of the Chelsea Center, nor does the
mention of trade names or commercial products constitute endorsement or recommendation for use.
All rights to this report belong to the Chelsea Center for Recycling and Economic Development. The material may be duplicated
with permission by contacting the Chelsea Center. This project was funded by EOEA through the Clean Environment Fund,
which is comprised of unredeemed bottle deposits.
The Chelsea Center for Recycling and Economic Development, a part of the University of Massachusetts Center for
Environmentally Appropriate Materials, was created by the Commonwealth of Massachusetts in 1995 to create jobs, support
recycling efforts, and help the economy and the environment by increasing the use of recyclables by manufacturers. The
mission of the Chelsea Center is to develop an infrastructure for a sustainable materials economy in Massachusetts, where
businesses will thrive that rely on locally discarded goods as their feedstock and that minimize pressure on the environment by
reducing waste, pollution, dependence on virgin materials, and dependence on disposal facilities. Further information can be
obtained by writing the Chelsea Center for Recycling and Economic Development, 180 Second Street, Chelsea, MA 02150.
Chelsea Center for Recycling and Economic Development, University of Massachusetts Lowell
Center for Energy Efficiency and Renewable Energy (CEERE)
The Center for Energy Efficiency and Renewable Energy (CEERE) is located at the University
of Massachusetts at Amherst campus and administered within the Department of Mechanical and
Industrial Engineering. The center works with issues of energy and its use, production,
economics and environmental impact. CEERE's primary mission is to promote energy efficient
technologies, practices and the use of renewable energy resources while minimizing negative
impacts on the environment. CEERE's activities are designed to support state, federal and private
stakeholders that deal with issues of energy and its environmental impact.
Acknowledgements
The authors wish to thank all the reviewers of this report, including: the Massachusetts
Department of Environmental Protection; representatives from the foundry industry in
Massachusetts, New Hampshire, Michigan and other states; the FIRST Consortium for Market
Development of Beneficial Use of Foundry By-Products; and the Chelsea Center for Recycling
and Economic Development.

i
TABLE OF CONTENTS
List of Tables................................................................................................................................. ii
List of Figures .............................................................................................................................. iii
EXECUTIVE SUMMARY............................................................................................................... iviv
INTRODUCTION............................................................................................................................... 1
Recycling, reclamation, reuse ........................................................................................... 2
Sand characterization and the BUD process..................................................................... 4
Residual sand applications ................................................................................................ 7
Objectives of the study...................................................................................................... 8
REGULATED AND RECOMMENDED STANDARDS............................................................................ 9
Drinking water standards .................................................................................................. 9
Non-hazardous waste characteristics .............................................................................. 10
ANALYTICAL TECHNIQUES........................................................................................................... 13
Leaching procedures (TCLP and SPLP) ......................................................................... 14
Methods for determination of metals .............................................................................. 16
Methods for organic compound analysis ........................................................................ 17
Statistical treatment ........................................................................................................ 18
CHARACTERIZATION OF VIRGIN AND SPENT FOUNDRY SAND ..................................................... 20
Physical characteristics of spent sand ............................................................................. 20
Characteristics of foundry binders and resins ................................................................. 22
Chemical composition of foundry sand binders....................................................... 23
CONTAMINANTS IN SPENT FOUNDRY SAND ................................................................................. 31
Metallic contaminant s..................................................................................................... 31
Leaching of organics ....................................................................................................... 34
Emissions of hazardous air pollutants............................................................................. 36
IMPLICATIONS AND CONCLUSIONS............................................................................................... 38
Future work..................................................................................................................... 40
TABLES....... ................................................................................................................................. 41
REFERENCES ................................................................................................................................ 69

ii
LIST OF TABLES
Table 1. Regulated and Recommended Maximum Contaminant Levels, mg/l......................... 41
Table 2. Regulatory Limits and Guidelines for Organic Chemicals, g/l................................. 42
Table 3. Allowable Contaminant Levels for Reuse and Disposal of Contaminated Soil at
Massachusetts Landfills .............................................................................................. 44
Table 4. Proposed Illinois tier system for ranking waste.......................................................... 45
Table 5. Indiana tier system for ranking waste ......................................................................... 46
Table 6. Analysis of Semi-Volatile Organic Compounds by TCLP.......................................... 47
Table 7. Analysis of Volatile Organic Compounds by TCLP ................................................... 48
Table 8. Metallic Contaminants Analytical Methods................................................................. 49
Table 9. Detection Limits for Metallic Contaminants (30 CMR 22.06).................................... 50
Table 10. EPA Analytical Methods (SW-846) for Organic Contaminants................................ 51
Table 11. Physical Properties of Foundry Sands........................................................................ 54
Table 12. Geotechnical Characteristics of Foundry Sand Wastes ............................................. 54
Table 13. Chemical Analysis of Typical Foundry Sands............................................................ 55
Table 14. Spent Foundry Sand Chemical Oxide Composition................................................... 55
Table 15. Conventional Sand Binder Systems and Processes..................................................... 56
Table 16. Leachability of Metals from Foundry Sand Waste..................................................... 57
Table 17. Bulk Content of Metals in Foundry Sand Waste, Reference Sands and Soils............ 58
Table 18. Typical TCLP and SPLP Results from Smelting Operation Sludge........................... 59
Table 19. Lead Leachability versus Total Element Analysis of Red Brass Foundry Sand
Samples and Synthesized Mixtures............................................................................. 59
Table 20. Binders and Sources for Organic Analysis ................................................................. 60
Table 21. Leach Test Variability (Leachate Concentrations) ..................................................... 61
Table 22. Core Oil Binder System Sample: Volatile Analyte Concentrations from GC-FID
Analysis....................................................................................................................... 62
Table 23. Core Oil Binder System Sample: Volatile Analyte Concentrations from GC-MS
Analysis....................................................................................................................... 63
Table 24. Summary of Concentrations of Organic Compounds in Laboratory Extracts ........... 63
Table 25. Comparison of Binder System Waste Streams .......................................................... 65
Table 26. Data for Organic Compounds from Two New England Foundries ........................... 66
Table 27. Variability of Organic Content in Sand from a New England Foundry.................... 67
Table 28. Major Volatile Components Emitted from Novolac Resin at 980C ........................ 68

iii
LIST OF FIGURES
Fig. 1. Distribution of metalcasting facilities in the United States, 1998 ..................................... 2
Fig. 2. Locations of Massachusetts foundries (after Winkler et al. [1]) ...................................... 3
Fig. 3. Massachusetts classification of industrial waste................................................................ 5
Fig. 4. Beneficial Use Determination in Massachusetts (MA DEP, 1999)................................... 6
Fig. 5. Illinois tier grading classification system ............................................................... 11
Fig. 6. Grain size distribution of foundry sands.......................................................................... 20
Fig. 7. Thermal degradation products of Novolac resins versus temperature............................. 38

iv
EXECUTIVE SUMMARY
INTRODUCTION
Metal casting foundries in the U.S. dispose of about 9 million tons of spent sand in landfills per
year. A typical foundry can generate from 8 to 40 individual waste products. These wastes can
have significant regulatory implications. Environmental constraints on the foundries operations
and handling of waste products are becoming increasingly more costly to the industry. A
previous study on the use of spent foundry sand in Massachusetts identified several issues
limiting beneficial use of waste sand. Some of those include: a lack of understanding in chemical
characteristics of sands, life cycle issues, waste management practices, and a lack of clear
regulatory guidance, in particular the Beneficial Use Determination (BUD) process. Issues
relative to risk analysis and appropriate methodology for characterizing sands were also
identified.
Molding sand is mixed with binder and additives. The two basic binder systems are clay-bonded
sand (green sand) and chemically-bonded sand. Chemical binders include phenolic, furan
(furfuryl alcohol), and other systems. Additives include a catalyst to promote the binding
process. Foundry waste sand is physically suitable for many applications, although long-term
environmental effects are not well documented. The BUD application process requires specific
physical and chemical characterization of the waste material. Results of waste characterization
should identify hazardous wastes, determine disposal needs, and other issues. Currently, BUD
applied to spent foundry sand includes wide use as intermediate cover in landfills and a limited
use in construction practices. Other uses for spent sand are documented across the literature. A
detailed characterization of the foundry waste materials is needed to facilitate these uses. Risk
assessment, including fate of metal and organic contaminants, is also needed to characterize the
spent sand.
This study focuses on chemical-specific hazards as it relates to the BUD process and reuse
practices. This information will potentially make the process of permitting more cost effective
and timely. The primary objective of this study is to characterize foundry sand waste streams,
process sands and to qualify its impact on human health and the environment.
REGULATED STANDARDS AND ANALYTICAL TECHNIQUES
Regulations concerning the disposal requirements and environmental effects of utilization of the
spent foundry sand are currently being developed in Massachusetts. Waste classification is used
to specify the handling and storage procedures that minimize impact to the environment. The
analysis of wastes for the BUD applications is performed using approved EPA methods for solid
waste analysis. Most regulated metals are measured using inductively coupled plasma atomic
emission - mass spectrometry (ICP-AES, ICP-MS) and regulated organic compounds are
measured using gas chromatography interfaced with a mass spectrometer (GC-MS). The toxicity
characteristic of solid waste leachates is determined using the Toxicity Characteristic Leaching
Procedure (TCLP, Method 1311). Alternative methods for measuring leaching potential include:
Synthetic Precipitation Leaching Procedure (SPLP) and Extraction Procedure (EP) Toxicity test.

v
Currently, EP has been replaced by TCLP. TCLP is now the most commonly used method to
evaluate leachability of wastes and estimate likely risks to ground water. TCLP requires
determination of 25 organic chemicals in addition to eight metals and six pesticides regulated
under the Resource Conservation and Recovery Act (RCRA). The TCLP is designed to model
the leaching behavior of a materials codisposed in a decomposing municipal solid waste landfill.
Based on results of this study, the various methods for analysis offer different scenarios of fate
and risk estimate. For the purpose of evaluating the impact or reuse practices, the method of
extraction may be important in accurately evaluating risk potential.
Massachusettss foundries have not found it economical to provide waste information that would
adequately fulfill the requirements of the BUD process, beyond the current use as daily cover in
lined landfills. Several institutional barriers to broader acceptance of foundry waste sand as a
beneficially usable material still exist.
CHARACTERIZATION OF VIRGIN AND SPENT FOUNDRY SAND
The major components in foundry sand are quartz sand (70-80%), clay (5-15%), additives (2-
5%), and water (up to 4%). Clean, uniformly sized silica sand is bonded via binder(s) to form
molds for ferrous (iron and steel) and non-ferrous (aluminum, copper, zinc, etc.) metal castings.
The largest volumes of foundry sand are used as green sand (clay-bonded). Green sand consists
of high-quality silica sand, approximately 10% bentonite clay, 2 to 5% water and approximately
5% sea-coal (a carbonaceous ingredient used to improve casting finish). Chemically bonded sand
cast systems use one or more organic binders mixed with catalysts and hardeners. Chemically
bonded sand is typically 97% silica sand by weight.
Numerous authorities have investigated suitability of foundry sands for beneficial use practices.
Some of these practices include: asphalt, brick, utility trench backfill, flowable fill, landfill liners
and covers, Portland cement road sub-base and soil amendments. Physical characteristics of
spent foundry sand are similar to that of fine silica sand. Nearly all types of spent casting sands
fall in the particle range between 0.1 and 0.6 mm. The uniformity of these byproducts suggests
their utility in manufacturing. Precise quantification of physical properties of the residual sand is
important for the marketability of the spent foundry sand. Fineness and compactability (grain
size distribution) is considered in construction applications. For most applications, strength
properties and low hydraulic conductivity are essential. The American Society for Testing and
Materials (ASTM) has developed a 1997 national specification for use of by-products in
structural fills, E1861-97. Additional research is being conducted to support specification of
spent sands in construction materials.
Binders are used to bond sand grains in mold castings. Chemically bonded systems fall into two
broad categories: organic and inorganic systems. The majority of them are selfsetting binders.
The most common types of binders include various phenolic urethane resins, furan (furfuryl
alcohol) resin, alkyd urethane, sodium silicate, phosphate. Composition and relative proportions
of materials used in binder systems are often proprietary. Foundry cores and molds are subjected
to intense heat from the molten metal. The temperature of the mold-metal interface approaches
1000C. As a result, all organic materials (binders, additives, coatings) undergo thermal
degradation and oxidation (burning). The nature and distribution of combustion and degradation

vi
products are complex and not entirely predictable. Residual organic compounds in spent foundry
sands are found only in small quantities. Therefore, spent sand, after casting, typically does not
contain organic contaminants above regulatory threshold levels.
CONTAMINANTS IN SPENT FOUNDRY SAND
The environmental stability of spent foundry sand is reported in several investigations. Various
procedures for evaluation of leachability of chemicals to ground water exist. In these studies the
methods of determining is variable and include: TCLP (EPA Method 1311), SPLP (EPA Method
1312), a multiple extraction procedure (EPA Method 1320), or a "total" analysis. While samples
from the same type of foundry often demonstrate a large scatter in chemical parameters, a
definite similarity of characteristics exists across the foundries regardless of the metals cast.
Studies suggest that spent sand disposed of in a monofill or used in highway construction leaches
metallic and organic constituents below the toxicity characteristic levels. This may be due to
insoluble forms or contaminants or materials not exposed to leaching processes. These studies
suggest that while the presence of the constituents in a bulk waste stream exists, it may not be
leachable.
Metallic Contaminants
Several studies have been conducted on metal contaminants in foundry sands. Foundry sand
wastes, in monofills, leach metals one to two orders of magnitude less than typical municipal
mixed-waste municipal landfills. Spent foundry sand segregated from the other waste streams,
disposed of in monofills or used in construction fills leaches regulated metals well below the
toxicity characteristic levels. TCLP and EP Toxicity laboratory tests usually yield significantly
higher leachability results than what may occur under all conditions. This is because the toxicity
tests are designed to simulate the worst-case conditions in a municipal landfill in the presence of
carboxylic acids as the leachate. The Synthetic Precipitation Leaching Procedure (SPLP) may be
more appropriate to simulate conditions other than those observed in a municipal waste landfill.
Under the SPLP test, leachability of lead from smelting sludge was reported to be two orders of
magnitude lower than that under TCLP.
Even under the TCLP test, extracts from spent foundry sand contained metal concentrations
below the regulatory toxicity characteristic levels, provided the sand was not mixed with other
waste streams (e.g., dust, slag, sludge). Only iron and manganese, which are not regulated under
RCRA, were recorded at increased leaching potentials in a number of occasions. Several reports
suggest that mixed foundry wastes leach below the regulatory levels. However, lead, chromium,
copper and zinc are reported to be of a concern for mixed foundry wastes. There is no direct
correlation between the total metal content and the leachability under TCLP. Quantities of total
metal content in spent and virgin sands and in sandy soils are typically of the same order of
magnitude.
Leaching of Organics
Few peer-reviewed studies have been conducted to determine organic residues in spent foundry
sand and leachates from disposal sites. Laboratory studies indicate that several organic

vii
compounds are present in the spent foundry sand but leachable at low concentrations. Studies on
green sands have demonstrated lower organic compound leaching potential compared to
chemically bonded systems.
In several studies on chemically bonded sands, samples typically had concentrations below the
regulated toxicity characteristic limits. However, benzoic acid, naphthalene, methylnaphthalenes,
phenol, methylenebisphenol, diethylphenol, and 3-methylbutanoic acids, were reported at levels
over 300 g/l in one or more samples. Phenolic urethane and core oil binder systems were more
likely to be of environmental concern than other binder systems. The furan hotbox, alkyd
isocyanate, and furan warm box sample leachates contained few compounds and at
concentrations below 100 g/l. Xylenes were among the most common organic compounds
reported using TCLP, although at concentrations 2 to 4 orders of magnitude lower than the
national drinking water limits. Additional compounds present included benzenesulfonate,
benzo(a)anthracene, bi-n-octyl phthalate, crysene, di-n-butylphthalate, fluoranthrene, pyrene,
toluene-2,4-disulfonate, and 3 isomeric forms of toluenesulfonate.
Organic compounds detected in many spent chemically bonded sands, included: acetone,
diethylbenzenes, p-ethyltoluene, isopropylbenzene, 1,2,4-trimethylbenzene, both 1- and 2-
methylnaphthalene, dimethylnaphthalene isomers, naphthalene, and all three isomeric forms of
xylene. Benzene, tetrachloroethene, cresols, acetone, 1,1,1-trichloroethane, and toluene were
detected in the foundry waste leachates at concentrations well below the toxicity characteristic
limits and below the drinking water standards. However, benzene and trichloroethane were
measured at concentrations around the drinking water limits.
Efforts to reduce the organic compound content should likely focus on the phenolic urethane and
the phenolic isocyanate binder systems, since they contribute more organic content than other
binder systems. Unreacted resins and solvents in freshly mixed sand-binder systems not exposed
to the catalyzing agent or high temperature are also likely sources of leachable organics.
Therefore, fresh casting mixtures and core sand that have not been in contact with hot metal
should be separated from the other waste streams.
Emission of Hazardous Air Pollutants
Thermal decomposition of additives in process sand generates permanent gases in the areas
proximal to the mold-metal interface. The principal evolving gases were found to be hydrogen,
carbon monoxide, carbon dioxide, methane, nitrogen, oxygen, and water vapor. Volatile
hydrocarbons, including: ethane, ethylene, propane, propylene, acetylene, furfuryl alcohol,
methanol, and ethanol, constitute up to 5% of the gas volume. Pyrolysis is likely to be nearly
complete at the mold to metal boundary. Inside the mold body farther from the mold/metal
interface, partial decomposition can be expected. At lower temperature and in an oxygen-lean
atmosphere, more complex organic compounds are formed. Benzene, toluene, nitrous oxide, and
hydrogen cyanide were identified in the atmosphere near a pouring line in a foundry using alkyd
isocyanate resin bonded molds. Concentrations detected in the foundry atmosphere were
generally low.

viii
IMPLICATIONS AND CONCLUSIONS
Utilization of foundry waste products in Massachusetts is subject to Beneficial Use
Determinations by the Department of Environmental Protection under current regulations.
Detailed physical and chemical characterization of the foundry waste materials is necessary in
order to obtain permits. Quantities of twelve metals and regulated organic compounds extracted
from foundry sand waste with the Toxicity Characteristic Leaching Procedure suggest that spent
foundry sand can be beneficially used posing no or limited environmental or human health risk.
Limited data on separate waste streams, suggests that spent sand be segregated from other,
potentially hazardous waste streams (unprocessed molding mix, bag house dust, or sludge), until
such time as detailed characterization can be performed. Some of these wastes have highly
variable levels of the toxicity characteristic constituents. Therefore, mixed foundry wastes are
essentially complex and must be evaluated independently. Non-ferrous foundries may produce
spent sands with contaminants such as, lead, chromium, copper and zinc. Inherent variability of
chemicals in wastes ceases to be a cause for concern when their concentrations are significantly
below the regulated standards. No direct correlation between leaching concentrations and bulk
element content was generally found.
The physical and chemical properties of foundry sands make them well suited for several reuse
applications. Detailed information about leaching potential, methods for measuring risk, and
waste management practices are still subject, which require further study. In some cases,
leaching of chemicals from spent foundry sands does not appear to be a limitation for utilization
of foundry sand wastes in Massachusetts. Additional work in support of developing risk
assessment should include more detailed analysis of different waste streams and use of more
appropriate analytical methods. Further work in the market acceptance of spent foundry sands
will also support this process, specifically, product specification and risk reduction measures.
Regulatory practices in other states also suggest that BUD permit issues may allow for sand
utilization under numerous applications and limit potential risks to health and the environment.

1
INTRODUCTION
The purpose of this work is to evaluate spent foundry sand chemical characteristics. It follows a
previous study [1], which surveyed the possibilities for various uses of the spent foundry sand in
Massachusetts. The report [1] identified several issues, including a lack of understanding in
chemical characteristics of spent foundry sands, temporal variations, life cycle analysis, and
methodology for characterizing sands. This study is designed as a foundation to the Beneficial
Use Determinations (BUD) process with the potential to map out practices which have the least
probability to cause environmental consequences. The BUD process is mandated statewide by
the Massachusetts Department of Environmental Protection (MA DEP). Limitations in the BUD
process stem from a lack of understanding of waste characteristics and evaluation of waste
minimization and beneficial use opportunities based on those characteristics.
Metalcasting foundries in the U.S. and Canada dispose of millions of tons of spent sand in
landfills. A typical foundry can generate from 8 to 40 individual waste products, including: spent
molding sand, core sand waste, cupola slag, scrubber sludge, baghouse dusts, shotblast fines,
buffing wastes, and others. Identification of each generation point is important to avoid
overlooking wastes generated infrequently or in small quantities. Small-quantity wastes may not
have a major impact on disposal expenses or handling requirements. But these wastes can have
significant regulatory implications. Environmental constraints on the foundries operations and
handling of pollution control and waste products are increasingly more costly to the industry. In
a 1997 survey of North American foundries, 66% had planned to change one or more processes
in the next three years to ensure environmental compliance [2].
Economic and environmental concerns dominate the issue of recycling foundry sand. The
presently accepted practice of spent sand disposal in landfills is becoming an economic burden
for foundries as landfills close and regulations grow stricter. This economic burden may in turn
encourage foundries to move into states with regulations more favorable to beneficial use or
cheaper costs to dispose of spent sand. There is also concern over the environmental
ramifications of using process wastes that may contain contaminants in applications where it
may be exposed to people or the environment. Furthermore, technical and economic feasibility
issues are raised for foundries that want to beneficially use their spent sands. Institutional
barriers, such as market, business, and regulatory realities and perceptions hinder the transition to
beneficial use of foundry sand.
The significance of beneficial use barriers should be discussed in order to clarify the real and
perceived problems associated with the utilization of foundry residuals and to promote further
discussion among members involved in beneficial use. This process may help eliminate artificial
barriers. Beneficial use practices in other states have demonstrated that spent foundry sand can
be used in manufacturing processes with varying degrees of success in terms of physical,
environmental, and economic feasibility. These projects are reported to illustrate research efforts
in support of advancing foundry sand utilization practices in Massachusetts.

2
Figure 1. Distribution of metalcasting facilities in the United States, 1998
Most of U.S. metalcasting facilities are concentrated in the Midwest, Southwest, and California,
with the majority of capacity (77%) located in ten states: Alabama, Illinois, Indiana, Michigan,
Ohio, Pennsylvania, Tennessee, Texas, Virginia, and Wisconsin. Illinois and Ohio are home to
more than 200 foundries. Foundry locations have traditionally been sited close to raw materials,
energy supplier, water and transportation. More recently, new foundries have been built near
inexpensive supplies of scrap metal and electricity as well as local markets for the cast products.
Figure 1 illustrates the present distribution of foundries in the United States. Figure 2 indicates
the geographic locations of foundries in Massachusetts [1].
RECYCLING, RECLAMATION, REUSE
Currently, there are no universally accepted definitions for the terms related to waste
management such as recycling, reclamation, and reuse. The federal and states regulations define
these terms in a number of somewhat different ways depending on purpose of a specific
document. In this report recycling is defined as a cyclic process of collection of materials from
waste or materials that would otherwise become waste, and their subsequent reprocessing or
remanufacturing to produce useful products and return them to the previous stage of use.
Recycling of materials implies that there exists a commercially demonstrated processing or

3
manufacturing technology which uses the material as a raw material. A common example is
recycling of scrap metals. With this definition, repeated use of spent sand (after reclamation)
within the same foundry is on-site recycling, which is not currently affected by any regulatory
requirement of a recycling plan approval, nor by a BUD application procedure. Reclamation
requires specialized machinery that recovers a quality portion of spent sand applicable to further
use in mold or core making.
Figure 2. Locations of Massachusetts foundries (after Winkler et al. [1])
The term reuse is controversial. In legislative language on solid waste, reuse is reserved for the
highest level in the hierarchy of pollution prevention [3]. An EPA guide Reuse Resources of
New England [4] specifies reuse as the use of a product or material again in its original
unmodified form or with little enhancement or change to be utilized again for the same purpose.
An example is the reuse of soda bottles (reuse = refill). Spent foundry molds and cores can not
be reused in this sense, i.e. without crushing them down to a raw material (sand) and its
reclamation. On the other hand, within the foundry technical terminology, reuse of by-products is
understood as their various uses outside the foundry for non-casting purposes (as opposite to
reclamation for internal use). The industry meaning of reuse sharply contradicts with the
Environmental Protection Agency (EPA) definitions.
In this report, spent sand processing is referred to either reclamation or beneficial use. Both
terms have distinct meaning. Reclamation is a process of restoring the durable condition of a
spent material to be used in its original function (it may be considered as one cycle in the on-site
recycling process). Beneficial use is any further use, other than the original use, of a discarded
material or by-product that would otherwise become waste. Presumably, a material is discarded
once it is fully used up and can not be reclaimed again for the original process, e.g., because it is

4
worn out. A certain portion of spent foundry sand is discarded during the reclamation process
because of the reduction in sand grain sizes that precludes any further use of spent sand fines in
mold or core making.
SAND CHARACTERIZATION AND THE BUD PROCESS
Molding sand is typically mixed in a specific weight proportion with binder and additives. The
amount of binder required is primarily determined by the process and quality of the sand being
used. Foundries using high quality sand typically require less binder to achieve desired shaping
abilities in the mold. Although the production variables of each particular plant result in the use
of many different types of binders, there are two basic binder systems: clay-bonded sand (green
sand) and chemically bonded sand [5]. Green sand is most frequently used in iron foundries
whereas chemically bonded sand is used primarily in non-ferrous casting. Chemically bonded
sands are also used by many green sand foundries in their core making operations. Chemical
binders include phenolic, furfuryl alcohol, and other inorganic binders. Other additives include a
catalyst to promote the binding process. Other casting processes such as die casting and lost
foam process are used in the industry but are beyond the scope of this report.
Often the chemical characteristics of sand used in the casting process are not fully known.
Additionally, the molding sand mixtures may be proprietary information, especially when
chemically bonded sands are bought pre-mixed. The casting process causes pyrolization and
other decomposition reactions that change the chemical form of the binders and additives in the
sand.
Spent sand must receive its own Material Safety Data Sheets (MSDS) if it is to be considered a
raw material for a new market [6]. The BUD application requires specific physical and chemical
characterization of the waste material in order to identify potentially usable waste streams and
separate potentially hazardous those. Results of a full waste characterization study (not required
for the BUD process) should also include biological (microbial) characterization of waste,
estimation of future waste treatment, determination of disposal needs, risk assessment, and waste
minimization opportunities, such as recycling, beneficial use, or altering the production process.
Other important issues are life cycle analysis and cost effectiveness.
Foundry waste sand is physically suitable for many applications, although long term
environmental effects are not as well known or documented. Federal and state waste regulations
are designed to determine how wastes should be handled and disposed of or recycled. Where
beneficial use is allowed, human exposure and environmental quality are important to the
decision making process. The EPA drinking water standards [7] stipulate threshold levels for
numerous metals and organic substances that are common residuals in the waste sand. Therefore,
understanding the characteristics of waste is fundamental to selecting, designing and
implementing waste management solutions in the foundry industry. A clear understanding of the
waste materials will result in defensible engineering and regulatory decisions regarding
beneficial use of spent molding sand while minimizing environmental impact and maximizing
economics.
Environmental concerns, expressed by MA DEP, include a lack of quantitative data supporting
environmental health risk assessment of beneficial use practices for spent sand.

5
The classification of industrial by MA DEP is shown in Fig. 3. Foundry sand classified as non-
hazardous conventional waste is eligible for BUD. Whether wastes are classified as hazardous or
non-hazardous is subject to tests under the Resource Conservation and Recovery Act (RCRA)
for ignitability, corrosivity, reactivity, and toxicity. The Toxicity Characteristic Leaching
Procedure (TCLP) test is used to characterize leachability of solid waste disposed of in an
environment where organic acidic conditions are present, such as in a municipal landfill. The
importance and limitations of this test are discussed in following chapters.
Figure 3. Massachusetts classification of industrial waste
States use different means of classifying a waste's degree of hazard. In general, states with multi-
tiered classification systems, or systems with several "grades" of hazard level, have set standards
by which waste materials can qualify as an acceptable beneficial use material.
While many states have set beneficial use standards [8], Massachusetts, New York, and Georgia
in particular do not stipulate specific test parameters for either metals or organics. In
Massachusetts, the TCLP and total metal content are used to differentiate hazardous from non-
hazardous industrial solid wastes. If total metal content is under a threshold, then there is no need
for the TCLP test. Spent foundry sand generally falls into a conventional waste category, since it
is not defined as special (special wastes such as asbestos are specifically identified because they
require special handling). Specific metal and organic compound test data and other criteria are
used to qualify a material for beneficial use. The distinctive parameters for spent foundry sand
are not yet determined. Measurement of eight TCLP metals specified by RCRA, and EPA
method 8270 for organic analysis may be suitable for input into various risk assessment
scenarios, although risk assessments are not required currently for the BUD applications.
Special waste
(requires special control
of handling and disposal)
Industrial Waste
Hazardous
Non hazardous
Conventional waste

6
The current BUD process in Massachusetts allows producers of conventional solid waste, with
certain exceptions, to apply for a permit to beneficially use their waste. Following application,
MA DEP reviews the case and determines whether the waste is suitable for beneficial use. A
general scheme of steps in this process is depicted in Fig. 4. The specific parameters to be
determined in "typical foundry sand" include at least eight RCRA metals: Arsenic, Barium,
Cadmium, Chromium, Lead, Mercury, Selenium, Silver, and a suite of polyaromatic
hydrocarbons and chlorinated compounds.
Figure 4. Beneficial Use Determination in Massachusetts (MA DEP, 1999)
Health and environmental risks are a function of both the degree of exposure and the nature and
concentration of the regulated chemicals. This report is focused on the first step of risk
assessment, namely substance-specific hazard identification. Once completed, the information
can be used in many assessments of various exposure scenarios (e.g., landfill ground water or
beneficial use new product ground water pathways). Since the regulatory toxicity thresholds
are based on upper estimates of exposures, the conclusions from this report will likely
overestimate risks, until real-life frequency and duration of exposures are determined. On the
other hand, the results of spent sand characterization compiled in this report will help to
eliminate the need for evaluation of those chemical parameters that clearly do not present any
risk because of their minimal leaching potentials. Questions regarding the exposure and risk
assessments, other physical hazards, nuisance conditions, life cycle analysis, and possible risk
Beneficial Use
Recycling

7
management proposals are still unanswered and are in need of further exploration. These are
subjects for further study.
RESIDUAL SAND APPLICATIONS
In typical foundry processes, sand from collapsed molds or cores is reclaimed and reused in the
casting process. Some new sand and binders are usually added to maintain the quality of the
casting and to make up for sand lost during normal operations. However, there is a net loss to the
sand system through a sand fraction that is not reclaimable. This spent fraction can be available
(when properly processed and characterized) for beneficial use outside the foundry, in most cases
replacing other conventional construction sands or granular materials. The national average
percentage of foundry sand being disposed of is about 10-15%, roughly estimated from a
cumulative number of total replacement sand sold per annum. However, some foundries with
good internal reclamation and sand capture systems, that not only reclaim sand but also reduce
its loss through the baghouse dust collection systems, dispose at a ratio of only 1-2%.
Spent foundry sand beneficially used in the U.S.A., notably in Wisconsin, Michigan, Illinois,
Iowa, Indiana, Minnesota, Pennsylvania, Ohio, California, Texas, and Louisiana. Other countries
such as Canada, Spain, Japan, and New Zealand also beneficially use spent foundry sand.
Numerous application projects on foundry by-product utilization grouped by state (country) or
by material type are documented at the Foundry Industry Recycling Starts Today (FIRST) web
site [9]. The FIRST on-line database contains abstracts for each article, and a number of
complete publications held in the FIRST beneficial use library. Some of the current beneficial
use practices are listed below:
Asphalt and Other Pavers Pipe Bedding
Brick Manufacturing Portland Cement
Cemetery Vaults Potting and Specialty Soils
Concrete Backfill Precast Concrete Products
Construction Fill Road Sub-Base
Drainage Layers Rock Wool Fibers
Flowable Fill Smelting Flux
Grouts and Mortars Soil Amendments
Highway Barriers Utility Trench Backfill
Landfill Liners and Covers
The by-product mixture of sand and binder has hydraulic properties similar to those of sand-
bentonite mixtures that are used as barrier layers throughout the USA. Flowable fill (also known
as a controlled low strength material CLSM) is an ideal application for beneficial use of
foundry sand waste because its physical characteristics are similar to those of fine aggregate used
in high quality CLSM. The spent chemically-bonded casting sand is excellent replacement for
portions of the fine aggregate in CLSM. Roadway structural fill applications provide an
opportunity for high volume utilization of excess system sand. Foundry sand can effectively
replace conventional materials in hot mix asphalt mixtures by providing at least the same quality.
These and a few other typical examples of efficient utilization of the spent foundry sand can be
found in Ref. [1,5,6,9-14].

8
One of the most comprehensive listing of beneficial use applications of spent molding sand and
other foundry byproducts has been summarized in a database assembled at the University of
Wisconsin [10]. This database identifies materials and markets where methods and specifications
with acceptable performance exist as well as areas in need of further research. Overall, 90
projects involving beneficial use of foundry by-products were evaluated or referenced, and
technical reviews of most significant projects in the U.S. and Canada were performed. The
database portrays a common problem in beneficial use practices: a lack of field performance data
and documentation for all materials. Furthermore, these reports are focused on physical
properties and not fate of chemical constituents. Hence their applicability to the BUD process is
anecdotal.
Spent foundry sand must possess several qualities to be beneficially used. It must be
environmentally benign, i.e., it should not leach metals, alkalis, or organics in amounts that
would pose a hazard to human health or the environment under its service condition. It must be
economically favorable. And finally, it should be technically equivalent to the material it is
replacing in the application. These three factors require a set of definitions acceptable to the
industry, regulatory and policy stakeholders.
Beneficially used foundry sand is often diluted with other materials in its final use, although
dilution is not always the best approach. In actual end-use scenarios, spent foundry sand may
be coated or embedded in another material (such as asphalt or concrete) making it unavailable to
infiltrating water hence it would not leach. Furthermore, the chemical form of the metal (e.g.,
oxide or silicate) may have limited solubility.
The TCLP test simulates the worst case scenario and is limited to a codisposal situation. TCLP
testing of the end-use compositions would be very helpful. However, the leachability of spent
foundry sand in its end-use structures has not been fully investigated.
OBJECTIVES OF THE STUDY
The main objective of this study is to characterize the chemical contaminants of spent foundry
sand. Detailed characterization of the foundry waste materials is needed to support the BUD
regulatory protocols and to specify the beneficial practices with the least probable environmental
consequences and minimum waste. Chemical characterization must be performed in accordance
with the EPA-recommended procedures using the approved standard methods. Such provisions
necessitate an overview of regulated standards and analytical techniques.
A second objective is to understand the complete extent of regulated elements and compounds
present in spent foundry sand and to qualify their potential or actual impact on human health and
the environment. Furthermore, the detailed BUD regulations are expected to provide waste
generators with a mechanism to divert safely and beneficially as much of their wastes from
landfills as possible. This would provide numerous benefits to the environment, including
conservation of natural resources and less land needed for disposal.

9
REGULATED AND RECOMMENDED STANDARDS
Policies and regulations concerning the disposal requirements and environmental effects of
utilization of the spent foundry sand are currently being developed in Massachusetts. Waste
classifications are used in order to specify the procedures by which wastes should be handled and
stored so as to minimize impact to human health and environmental quality. Development of
beneficial use policies ensures that materials are used in ways that do not cause harm to human
health or degrade environmental quality. Materials are considered to be solid wastes if they are
used in a manner constituting disposal. Once a BUD is granted, the waste material ceases to be
considered a solid waste.
DRINKING WATER STANDARDS
The potential adverse effect of land disposal of solid waste materials is on surface and ground
water quality. Drinking water standards [7] are set by EPA to control the level of contaminants in
the nation's drinking water. These standards are part of the "multiple barrier" approach to
drinking water protection under the Safe Drinking Water Act (SDWA), which includes assessing
and protecting drinking water sources; making sure water is treated by qualified operators; and
ensuring the integrity of distribution systems. In most cases EPA delegates responsibility for
implementing drinking water standards to states. The SDWA, passed in 1974 and amended in
1986 and 1996, gives the EPA the authority to set drinking water standards. There are two
categories of drinking water standards: National Primary Drinking Water Regulation (or primary
standard) and National Secondary Drinking Water Regulation (or secondary standard).
National Primary Standards are legally enforceable standards that apply to public water systems.
They protect drinking water quality by limiting the levels of specific contaminants (in form of
Maximum Contaminant Levels or Treatment Techniques) that can adversely affect public health
and are anticipated to occur in water.
Secondary standards are non-enforceable guidelines regarding contaminants that may cause
cosmetic effects (such as skin or tooth discoloration) or aesthetic effects (such as taste, odor, or
color) in drinking water. EPA recommends secondary standards to water systems but does not
require systems to comply. States may establish higher or lower levels which may be appropriate
dependant upon local conditions. MA DEP encourages the suppliers of water to meet the
secondary drinking water standards. Additionally, MA DEP mandates that all detection of
sodium (Na) be reported. The agency defines 20 mg/l of Na and 0.1 mg/l of nickel (Ni) as the
concentrations in drinking water at or below which adverse, non-cancer health effects are
unlikely to occur after chronic (lifetime) exposure [15]. MA DEP does not regulate levels of
sodium and nickel but only indicates a potential need for further legislative action to be decided
by its Office of Research and Standards.
Drinking water standards apply to public water systems that provide water for human
consumption. The 1996 Amendments to SDWA require EPA to go through several steps to
determine via technological evaluation (analytical methods of detection; technical feasibility;
impacts of regulation on water systems, the economy and public health) whether setting a certain
standard is appropriate for a particular contaminant.

10
In most cases, the enforceable standard is a maximum contaminant level (MCL), the maximum
permissible level of a contaminant in water which is delivered to any user of a public water
system. The SDWA defines MCL as the level that may be achieved with the use of the best
available technology and other means which EPA finds available. When there is no reliable
method that is economically and technically feasible to measure a contaminant at particularly
low concentrations, an action level for a treatment technique is set rather than MCL. A treatment
technique is an enforceable procedure or level of technological performance which public water
systems must follow to ensure control of a contaminant. An example of treatment technique rules
is the lead and copper rule for the optimized corrosion control and prohibition on lead use.
The EPA drinking water standards divides all regulated contaminants that can adversely affect
public health into four groups: inorganic chemicals, organic chemicals, radionuclides, and
microorganisms. The two latter groups of contaminants have little relevance to the foundry sand
waste, but the metals and organics are of a predominate concern. Maximum contaminant levels
of metals that are mandatory for monitoring under primary and secondary drinking water
regulations [7] are listed in the first column of Table 1. Regulatory limits for organic chemicals
are summarized in Table 2.
The drinking water regulations are closely related to the ground water monitoring requirements
as well as to the monitoring, analysis, inspection, quality assurance in implementing the
hazardous waste management and land disposal restrictions. Under the existing regulations an
owner or operator must sample ground water and analyze those samples for the presence and
concentration of constituents that are routinely analyzed for in the Superfund program
(Comprehensive Environmental Response, Compensation, and Liability Act, 1980). Based on
this information, Regional Administrator sets the ground water protection standards, or levels for
the constituents in ground water [16]. If these levels are exceeded in the ground water, corrective
action must be implemented.
NON-HAZARDOUS WASTE CHARACTERISTICS
The hazardous waste characteristics promulgated by EPA designate broad classes of wastes with
inherent properties which would result in harm to health or the environment if mismanaged. Test
methods and regulatory levels for each characteristic property are then established. The EPA
method 1311 (TCLP) is designed to measure the potential for toxic constituents in the waste to
leach out of the solid phase [17] and contaminate ground water. The Toxicity Characteristic is
met when sample leachate exceeds the maximum concentration of any of the specified [16]
contaminants. The maximum metal concentrations for TCLP toxicity and ground water are listed
in Table 1. In Massachusetts, the total metals content and the TCLP test among other criteria are
used to regulate reuse and disposal of contaminated soil at landfills [18]. The allowable
contaminant levels for reuse of soil at Massachusetts landfills are listed in Table 3.
Appropriate sampling procedures are needed to meet state and federal reporting requirements.
Sampling protocols required by MA DEP establish the number and frequency of samples and
should include procedures for sample collection, sample preservation, chemical analysis, quality
control, chain-of-custody, and data management.

11
Often, the characterization reports of spent sand from foundries have been inadequate for
determining the risk of beneficially used materials on public health or the environment. A risk
assessment, including metal and organic contaminants and life cycle effects, is needed to
characterize the material. Changes in use of a building or road structure, for example, may result
in exposures not specified in the original use determination. While leachable metals or organics
may be locked into a solid substance such as concrete, reducing the risk of environmental
contact, a structure that is demolished has a renewed risk potential that may not be expected.
Though long-term behavior of asphalt, brick, concrete and other materials in the environment is
well known, more specific research is necessary on the stability of those materials that have been
made with addition of foundry waste. Generally, long-term behavior evaluation is needed for all
the applications going through the BUD process.
In states, where the foundry industry is large, they have developed multi-tiered schemes for
classifying a degree of hazard for solid wastes. Winkler et al. [1] reviewed the BUD practices in
those cases. In Illinois, a score is given to each constituent of the waste based on TCLP, pH, and
waste stream size. Values are compared to a toxicological database compiled from the Registry
of Toxic Effects of Chemical Substances and other sources to give an equivalent toxicity score.
These scores are then added to give a final ranking, as illustrated in Fig. 5. Materials that score a
low or negligible rank may be considered for beneficial use, after issues of liability and special
waste are addressed.
Figure 5. Illinois tier grading classification system
Constituents measured in the TCLP are often present in various chemical forms in foundry
wastes. Some of these include benzene, phenols, metal oxides and silicates. These species were
considered in the Illinois tests for determining the level of hazard for foundry waste material [5].
The Illinois four-tier grading classification system is similar to Indiana's, with the maximum
allowed concentrations for both systems shown in Tables 4 and 5. Under the Indiana
classification system, wastes qualifying as type III or IV may be approved for certain beneficial
uses. Wisconsin also uses a four tier classification for foundry wastes based on a detailed
characterization of foundry by-products. The Wisconsin preventive action limit standard (PALS)
determines a benchmark, typically 10% or 20% of the drinking water standard, as the "not-to-
exceed" target in ground water [5].
Among the North-East states, New York regulations specify sixteen items with pre-determined
BUDs [19] allowing beneficial use of specific materials for specific purposes without project
review. These include specific application of such materials as compost, wood chips,
Hazard level:
Score:
High Negligible
High Moderate Low Negligible

12
newspaper/newsprint, glass, tire chips, concrete, asphalt, brick, various soils and ashes. In
situations where a particular proposed beneficial use is not specifically identified, generators and
potential users shall petition for a case-specific BUD. Particularly, the New York State
Department of Environmental Conservation has granted a number of BUD permits for the use of
spent foundry sand as an aggregate in the production of concrete, cement, asphalt, and flowable
fill. Foundry slag has been granted BUDs for the use as road base/sub-base, railroad ballast,
backfill and structural fill within building foundations. Both foundry sand and slag may be used
as daily covers and barriers at New York landfills.
New Jersey DEP has also approved several BUD projects for the beneficial uses of various
foundry waste streams: spent foundry sand as a component in cement, asphalt and concrete
products; baghouse dust as an additive in asphalt products and roadbed aggregate; slag as an
aggregate component in asphalt products or as additive in concrete products; and mixed foundry
waste in roadbed fill and asphalt aggregate.
MA DEP has received an application for a BUD proposing the foundry waste use as a base in the
construction of a paved parking lot at a recreational facility in Middleboro. However, a BUD
permit has not been granted because of high concentration of benzo-anthracenes and benzo (a)
pyrene found in a composite foundry waste sample.
In Massachusetts, general policies have not yet been developed for foundry sand as a reusable
material. Moreover, Massachusetts foundries have not found it economical to provide waste
information that would adequately fulfill the requirements of the BUD process. The latter is
because the Massachusetts foundry industry is dominated by small foundries with small
quantities of residual material that are difficult to market, but cost of necessary testing is rather
prohibitive. Several institutional barriers to broader acceptance of foundry waste sand as a
beneficially usable material are cited and explained [1] in terms of Massachusetts goals in the
following:
1) The wide variety of regulatory and test systems employed by states to manage industrial
wastes present many inconsistencies.
a) Threshold levels of leachable metals and organic compounds in industrial wastes can
vary by a factor of 30 or more.
b) Environmental differences between states such as soil type and climate often are reflected
in policy differences. However, similar broad policy goals -- namely, protection of
human health and short- and long-term environmental quality, should promote efforts to
bring some level of uniformity.
2) No universally accepted practice exists to evaluate the hazard posed by beneficially used
foundry waste. Decision science tools, such as total life cycle or risk analysis method, would
make the beneficial use approval process more comprehensive and capable of assessing
overall risks and benefits.
3) State agencies do not have coordinated regulations that achieve both short and long-term
objectives. A good example of a potentially beneficial coordinated policy would be between

13
the MA DEP and Massachusetts Highway Department to address utilization of foundry sand
for transportation material related applications.
4) In some cases the criteria used to determine the health and safety of recycled materials may
be more stringent (or may not exist) than for virgin materials or natural environmental
conditions.
5) Environmental regulations and policies are complex and difficult for the business community
to understand. This deters foundries from seeking beneficial use permits, especially among
small foundries with limited personnel.
Recently, the Commonwealth of Massachusetts has taken several actions to assist parties seeking
regulatory acceptance of innovative technologies. Particularly, MA DEP has re-organized its
management structure. One of the goals of the re-organization is to bring together programs that
work on the same problems or sites into consolidated offices, breaking up the older structure of
organizing by the environmental medium regulated, or by enabling legislation. This might help
beneficial use technologies gain regulatory acceptance more efficiently.

14
ANALYTICAL TECHNIQUES
The chemical analysis for the BUD application procedures is normally performed using the EPA
approved methods for analysis of solid wastes (SW 846). However, the equivalent standard
methods developed and approved by other consensus organizations, such as American Society
for Testing and Materials (ASTM) or American Water Works Association (AWWA), may be
applied in some cases. EPA accepts the performance-based measurement system as a set of
processes wherein the data needs, mandates, or limitations are specified, and serve as criteria for
selecting appropriate methods to meet those needs in a cost-effective manner.
Several analytical techniques and methods may be used to separate, identify and quantify
contaminant species contained in both virgin and spent foundry sands and binders used in the
casting process. Most of metallic components can be quantitatively detected by inductively
coupled plasma (ICP) atomic emission and mass spectrometry. The EPA methods for organic
compound analysis typically involve routine analytical instrumentation which include gas
chromatography (GC) interfaced with either mass spectrometer (MS) or flame ionization
detector (FID). Another common method is pyrolysis interfaced with gas chromatography and
mass spectrometry (Py-GC-MS).
Toxicity characteristic of solid waste leachates is determined by Toxicity Characteristic
Leaching Procedure (TCLP, Method 1311). Leaching potential of spent foundry sand can also be
tested by Synthetic Precipitation Leaching Procedure (SPLP, Method 1312), Multiple Extraction
Procedure (Method 1320), Column Leaching Lysimeter Tests and other sequential tests. Some
older data were accumulated using the Extraction Procedure (EP) Toxicity test (Method 1310A)
that was then replaced by the TCLP (both latter tests are similar but direct comparison of results
from them is not always possible). A few modifications included in TCLP relative to the EP
Toxicity test are the use of 0.7 m filter, the extraction fluid determination step, and the choice
of two fluids depending on pH of the sample. The EP Toxicity and TCLP tests were designed to
approximate one set of disposal conditions that might occur when a material was codisposed
with municipal solid waste.
Currently, TCLP is most commonly used to evaluate the leaching potential of wastes, and to
estimate likely risks to ground water. TCLP requires determination of the 25 organic chemicals
in addition to the eight metals and six pesticides on the existing list of constituents regulated
under RCRA. The TCLP is meant to model the leaching behavior of a material disposed in an
actively decomposing municipal solid waste landfill in which carboxylic acids are formed from
microbial processes. It is not meant to model the leaching behavior of materials disposed in other
scenarios. If disposal conditions are different from the municipal landfill conditions, another test
may better predict the actual leaching of a waste and provide better numerical estimates of
leaching.
Alternative analytical leaching methods, such as the SPLP are becoming increasingly popular
with regulatory agencies. The SPLP, Method 1312, was developed to simulate leaching under
acid rain condition, similar to an industrial waste monofill. The procedure is similar to the TCLP,
however the amount of acidity used in the test is significantly less. Furthermore, an aqueous
solution of nitric/sulfuric acid mixture is used in the SPLP as an extraction fluid, unlike a more
rigorous buffered acetic acid in the TCLP. States have begun to allow the use of the SPLP for

15
characterization of waste in BUD applications. This procedure may soon become the preferred
approach, since it simulates more closely the field conditions for beneficial use.
Besides the acidic toxicity tests, the ASTM D3987-85 shake water leach test is a useful indicator
in considering the potential environmental impact of foundry sand waste and its beneficial use
practices. Moreover, a total analysis may precede the leach/extraction testing. If a total analysis
of the waste demonstrates that individual analytes are present at such low concentrations that the
appropriate toxicity levels could not be exceeded, the leaching tests need not be run. Routine
total analysis at the first instance is the most common current practice in Massachusetts.
LEACHING PROCEDURES (TCLP AND SPLP)
The TCLP is the test required to determine whether a solid or multiphasic waste is a toxicity
characteristic hazardous waste under RCRA regulations. TCLP estimates the leachability of
metals, volatile and semi-volatile organic compounds, and pesticides under a defined set of
laboratory conditions. TCLP was developed to simulate the leaching of constituents into ground
water under conditions found in municipal solid waste (MSW) landfills. The TCLP does not
simulate the release of contaminants to non-ground water pathways or conditions which are not
characteristic of MSW disposal sites.
In the TCLP, solid samples are extracted with an acetate buffer solution. The extraction fluid
employed is a function of the alkalinity of the solid phase of the waste. A liquid-to-solid ratio of
20:1 by weight is used for an extraction period of 18 2 hours. After extraction, the solids are
filtered through a 0.6 to 0.8 m filter from the liquid extract, and analyses are conducted on the
leachate to determine the constituent concentrations. If the extract contains any of the specified
constituents at a concentration equal to or greater than the respective regulatory limit (see Tables
1 and 2, Toxicity Limits), then the waste is considered hazardous under the toxicity
characteristic.
Method performance studies have been performed to determine the effect of various
perturbations on specific elements in the TCLP protocol. Ruggedness testing determines the
sensitivity of small procedural variations which might be expected to occur during routine
laboratory application. None of the parameters had a significant effect on the results of the
ruggedness test.
Many TCLP precision (reproducibility) studies have been performed, and have shown that in
general the precision of the TCLP is comparable to or exceeds that of the EP Toxicity test, and
that method precision is adequate. One of the more significant contributions to poor precision
appears to be related to sample homogeneity, inter-laboratory variation (due to the nature of
waste materials), and the inability of the laboratory to obtain a representative subsample of 100
grams.
The results of a study of semi-volatile organic compounds, in Table 6 [17], showed excellent
precision, with greater than 90 percent of the results exhibiting relative standard deviations
(RSD) less than 25%. Over 85% of all individual compounds in the multi-laboratory study fell in
the RSD range of 20-120%. It was determined that the high acetate content of the extraction fluid
did not present problems (i.e., column degradation of the gas chromatograph) for the analytical

16
conditions used. However, in some instances, the acetate matrix causes the lab to report elevated
results.
A special extractor vessel, the zero-headspace extractor (ZHE) is used when testing for volatile
analytes. The ZHE allows for liquid/solid separation, extraction, and final extract filtration
within the device without opening the vessel and effectively precludes headspace.
Eleven laboratories participated in a collaborative study of the use of the ZHE with two waste
types which were fortified with a mixture of volatile organic compounds (VOC). The results of
the study are shown in Table 7 [17]. Precision results for VOC tend to occur over a considerable
range. However, the range and mean RSD compared very closely to the same collaborative study
done for metals. Blackburn and Show [20] concluded that at the 95% level of significance: 1)
recoveries among laboratories were statistically similar, 2) recoveries did not vary significantly
between the two sample types, and 3) each laboratory showed the same pattern of recovery for
each of the two samples.
EPA Method 1312, the SPLP is an agitated extraction method used to evaluate the potential for
leaching metals into ground and surface waters. This method provides a more realistic
assessment of metal mobility under actual field conditions, and therefore, may be often
preferable in waste characterization for BUD applications. However, the SPLP test may not be
used for discriminating hazardous from non-hazardous waste under RCRA regulations. For the
latter purpose, the TCLP is the only approved method.
The SPLP extraction fluid is intended to simulate precipitation. For the eastern part of the USA
(east of the Mississippi River), the fluid is slightly more acidic at pH 4.20 reflecting the air
pollution impacts of heavy industrialization and coal utilization. A pH of 5.00 is used west of the
Mississippi. When the leachability of VOC or cyanide is being evaluated, reagent water is used
as the extraction fluid. The procedure requires particle size reduction to less than 9.5 mm, and as
with the TCLP, extraction for volatile constituents is performed in a zero-headspace extractor.
The SPLP is a method of choice when evaluating fate and transport of metals in a properly
engineered waste land disposal facility from which municipal solid waste is excluded. Other
situations may dictate the selection of a different leaching procedure.
METHODS FOR DETERMINATION OF METALS
EPA standard methods specify procedures for sample preparation techniques, sampling
approaches, and accurate quantitative analysis within specified concentration ranges. These
procedures are significantly different for organic and inorganic constituents. Table 8 lists the
analytical methods approved by EPA for sample preparation and determination of metallic
contaminants. Included are methods for the analysis of environmental samples (such as drinking
or ground water samples): both the EPA methods [21] and ASTM methods [22], and for the
analysis of solid waste leachate samples [17].
Determining concentrations of most of the metals can be achieved by inductively coupled plasma
atomic emission (EPA 200.7, EPA 6010, ASTM C1111-98 methods) or mass spectrometry (EPA
200.8, EPA 6020, ASTM D5673-96 methods). Also, highly suitable for most of metals but less

17
expensive technique is atomic absorption spectrometry (EPA 200.9, EPA 7000 series, ASTM
3919-99, ASTM4691-96 methods). Table 9 represents the analytical techniques used for the
analysis of metallic contaminants in drinking water and their detection limits as specified by MA
DEP [15].
Inductively coupled plasma atomic emission spectrometry (ICP-AES) determines trace
elements, including metals, in solution. All matrices, including ground water, TCLP and EP
Toxicity extracts, and solid wastes, require digestion prior to analysis. Samples must be
solubilized or totally digested using appropriate sample preparation methods (e.g., EPA 3005-
3060 methods). The ICP-AES is characterized by simultaneous, or rapid sequential,
multielemental determination of elements. Detection limits, sensitivity, and optimum ranges of
the metals vary with the matrices and model of analyzer. Use of this technique should be
restricted to spectroscopists who are knowledgeable in the correction of spectral, chemical, and
physical interferences.
Inductively coupled plasma mass spectrometry (ICP-MS) is applicable to the determination of
sub-g/l concentrations of a large number (over 60) of elements in water samples and in waste
extracts or digests. Acid digestion prior to analysis is required for ground water and solid wastes
as with the ICP-AES technique. Detection limits in simple matrices are generally below 0.1 g/l,
except for the less sensitive elements (e.g., Se and As) that may be 1.0 g/l or higher. The
greatest disadvantage of ICP-MS is isobaric elemental interferences. Mathematical correction for
interfering isotopic ions can minimize these interferences. An appropriate internal standard is
required for each analyte determined by ICP-MS. In general ICP-MS exhibits superior sensitivity
than other techniques for most elements.
Flame atomic absorption spectrometry (Fl-AAS) direct aspiration determinations are normally
completed as single element analyses and are relatively free of interelement spectral
interferences. Either a nitrous-oxide/acetylene or air/acetylene flame is used as an energy source
for dissociating the aspirated sample. In the analysis of some elements, the temperature or type
of flame used is critical. If the proper flame and analytical conditions are not used, chemical and
ionization interferences can occur. Fl-AAS and ICP-AES have comparable detection limits
(within a factor of 4), except that ICP-AES exhibits greater sensitivity for refractories (Al, Ba,
etc.).
Graphite furnace atomic absorption spectrometry (GF-AAS) uses an electrically heated graphite
furnace for sample atomization. In a furnace, the processes of dissolution, drying, decomposition
of sample, and formation of atoms may be allowed to occur over a much longer time period than
in a flame or ICP, and at controlled temperatures. This allows an experienced analyst to remove
unwanted matrix components by using temperature programming and/or matrix modifiers. The
major advantage of this technique is that it affords very low detection limits, in general, lower
than those in ICP-AES or Fl-AAS. Because this technique is so sensitive, interferences can be a
problem for complex matrices.
For arsenic and selenium, the hydride generation atomic absorption technique may be utilized to
reduce and separate these two elements selectively from a sample digestate. Selective reduction
of mercury is used in cold-vapor atomic absorption technique. These procedures are sensitive but
subjected to interferences from oxidizing agents and volatile compounds.

18
METHODS FOR ORGANIC COMPOUND ANALYSIS
The most commonly used technique for determination of organic constituents is the capillary gas
chromatography with mass spectrometric detection (GC-MS). With this technique, EPA
established two different methods for detection of volatile organic compounds (Method 8260)
and for detection of semi- volatile organic compounds (Method 8270). These methods appear to
have the scope of analytes which may be present in residues of spent foundry sand. For some
specific compounds, other methods could be also useful. Method 8151, capillary gas
chromatography with an electron capture detector may be applied for determining certain
chlorinated acidic compounds and pentachlorphenols in aqueous, soil and waste matrices.
Method 8082, capillary gas chromatography with electron capture detectors or electrolytic
conductivity detectors is used to determine the concentrations of polychlorinated biphenyls
(PCB) in extracts from solid and aqueous matrices. All relevant analytical methods for organic
compound detection are summarized in Table 10.
Method 8270 is used to determine the concentration of semi-volatile organic compounds in
extracts prepared from various types of matrices such as solid waste, soils and ground water.
This method can be used to quantitate most neutral, acidic and basic organic compounds that are
soluble in methylene chloride and capable of being eluted without derivatization. The estimated
quantitation limit of the method for determining an individual semi-volatile compound is
approximately 10 g/l for ground water samples. Some of these organic compounds may be
found in spent foundry sand.
Method 8260 is used to determine volatile organic compounds in a variety of solid waste
matrices. This method is applicable to nearly all types of samples, including ground and surface
water, waste solvents, soils, and sediments. Method 8260 can be used to quantitate most volatile
organic compounds that have boiling points below 200C (low molecular weight halogenated
hydrocarbons, aromatics, ketones, nitriles, acetates, acrylates, ethers, and sulfides). The
quantitation limits of Method 8260 for individual compounds are instrument dependent and
dependent on the choice of sample preparation/introduction method. Using standard quadrapole
instrumentation and the purge-and-trap technique, limits should be approximately 0.5 mg/kg
(wet weight) for wastes, and 5 g/l for ground water. Lower limits may be achieved using an ion
trap mass spectrometer or other instrumentation of improved design.
Method 8250 (the packed column version of Method 8270) was tested by 15 laboratories using
organic-free reagent water, drinking water, surface water, and industrial waste water spiked at six
concentrations over the range 5-1300 g/l. Single operator accuracy and precision, and method
accuracy were found to be directly related to the concentration of the analyte and essentially
independent of the sample matrix.
Chromatograms from calibration standards analyzed with Day 0 and Day 7 samples were
compared to detect possible deterioration of GC performance. These recoveries (using Method
3510 extraction) range from 70 to 108%. The method is applicable to concentration techniques
for preparing the extract for the appropriate determinative methods (see Table 10).
Several EPA methods were designed exclusively for analysis of drinking water [23]. These
include Method 524.2 for detection of volatile organics, Method 525 for detection of extractable

19
semi- volatile organics, and Methods 508 and 508A for detection of polychlorinated biphenyls
(PCB). EPA Methods 624, 625, and 608 were correspondingly allocated for determination of
volatile, semi-volatile organic contaminants, and PCBs in surface water and wastewater.
STATISTICAL TREATMENT
To establish and analyze chemical characteristics for a wide spectrum of foundry sand wastes
that shows a high degree of random variation, statistical protocols must be used. The statistical
analysis play a critical role in the interpretation of results and in regulatory determinations made
with regard to beneficial use applications. Statistical inference obtained from an array of data
requires systematic techniques that provide unbiased, accurate, and reproducible results. These
results require interpretation in accordance with the objective for which the raw data was
obtained. Different interpretations may be reached from the same data set if different parameters
are used for evaluation. Consistent techniques of categorizing and testing data can be established
only on the statistical basis. In deciding which statistical test is appropriate, one needs to
consider the theoretical properties of the test and the characteristics of the data.
Statistical tests are used as a means of examining and comparing highly variable values of the
spent sand leaching potential. It is important to be able to determine whether or not there is a
statistically significant difference from an average level for each parameter and constituent. In
making this comparison, the analyst must apply a statistical procedure to make a determination
whether there is statistically significant change. Such a variation can be a result of sampling
error, analysis error, or natural variation. The total expected error is usually considered in the
propagation of errors treatment. It is usually done by determining the summation of the variances
of all the measurements made in the process.
Almost all statistical procedures are based on the assumption that samples are independent and
selected at random, and therefore reflect the true range of natural variability. Replicate samples
are not considered to be statistically independent measurements. Several statistical parameters
such as simple maxima, means, medians, and relative standard deviations can be used to provide
an overview of the randomly scattered data. However in chemical analysis of spent foundry sand,
the data scatter is so large that the relative standard deviations are often greater than the
respective mean values, and therefore, the normality of data sets is violated.
The factors more appropriate for large multivariate data sets are measures of the central tendency
and the variance. These measures include the mean, median and mode; the upper confidence
level for normally distributed data and the use of non-parametric statistics for data that is not
normally distributed (i.e., the Wilcoxon test), and the use of quartiles. For the purpose of
evaluating solid wastes, the confidence interval of 80% on normally-distributed data sets has
been selected. For non-normal data sets, a variety of transformations (e.g., square root,
logarithmic, arcsine square root, and etc.) can be performed to stabilize the variances, improve
the normality of data distribution, and obtain the confidence intervals. If either trans formation is
applied, all subsequent statistical evaluations are performed at the transformed scale. The 80%
upper confidence limit is then compared with the appropriate regulatory threshold. If the upper
limit is less than the regulatory value the chemical contaminant is not considered to be present in
the waste at a hazardous level; otherwise the opposite conclusion is drawn.

20
CHARACTERIZATION OF VIRGIN AND SPENT FOUNDRY SAND
PHYSICAL CHARACTERISTICS OF SPENT SAND
Spent foundry sands have been found suitable for various beneficial use applications. For sand
use in construction applications, its fineness and compactability (grain size distribution) must be
considered. Its physical characteristics have been characterized as having good strength
properties and a relatively low hydraulic conductivity. The latter quality assures that the material
is not freely draining after compaction into highway embankments [11]. Bulk specific gravity,
moisture content, and grain size distribution are the most useful characteristics of beneficially
used sand. Large foreign objects (metallic entrapments, etc.) are typically screened out before
utilizing foundry sand waste.
The grain size distribution of spent casting sands is usually uniform, with all of the particles
passing the 600 m sieve; more than 50 percent of the particles passing the 300 m sieve; and
nearly all of the particles retained at the 150 m sieve. The finest content passing the 200 m
sieve constitutes up to 20% of waste foundry sand. The uniform size of spent casting sand
provides good flowability. The material properties of five samples of foundry sands and a
reference sample of siliceous river-run sand are given in Table 11 and the particle size
distribution is shown in Fig. 6 [12]. Distribution of the grain sizes influences many properties of
the material. Most notable are the effects upon permeability and surface fineness, both associated
with the strength properties.
Figure 6. Grain size distribution of foundry sands
A Siliceous river-run sand
B Thermally reclaimed sand
C Mechanically reclaimed sand
D Spent clay-bonded sand
E Spent clay-bonded sand

21
The material characteristics of spent foundry sand are similar to that of fine silica sand, but differ
in a few aspects. Nearly all types of spent casting sands fall in the particle range between 0.1 and
0.6 mm. Because of a very thin band in grain sizes, waste foundry sands are blended with a
coarse crushed limestone for flowable fill applications. Sand B in Fig. 6 was thermally reclaimed
after casting to burn off the excess polymer bonding agents [12]. Sand C is the same material as
B, except the bonding agents were not removed, but sand was screened to separate any cores.
Sands D and E are spent bentonite-bonded sands with different absorption percent, both screened
of excess residuals. The bentonite was more fully fused in the sample D, and it was coarser than
sand E. The uniformity of these byproducts suggests their utility in manufactured products
processes.
Green (clay-bonded) sand, commonly used in metalcasting, is composed of uniform high-quality
quartz sand (85-95%), cohesive bentonite clay (4-10%) as the binder, a volatile carbonaceous
sea-coal additive (2-10%) to improve casting surface finish, iron oxide (0.5-5%) for strength, and
water (2-5%). Spent chemically bonded casting sand has a very low moisture absorption. Clay-
bonded sands have higher absorption with 5 to 10 percent clay minerals. The clay remaining in
spent sand after the casting cycle is partially sintered and not present as raw bentonite. For green
sand processes, reclaiming the sand may be as simple as capturing it once the metal casting is
removed and returning it directly to the beginning of the process. Other green sand processes
may require mechanical lump reduction to separate the sand into reusable grains.
Precise quantification of physical properties of the residual sand material is important for the
marketability of the spent foundry sand. The sand wastes from the green sand systems are
typically characterized by specific gravity (2.39-2.69 g/cm
3
), permeability (10
-3
- 10
-6
cm/sec),
and moisture content (0.1-10 %). Molding sands are refractory to temperatures approaching
1700C, although phase transformations involving volume changes may occur at lower
temperatures.
The American Society for Testing and Materials (ASTM) has developed a 1997 national
specification for use of by-products in structural fills (E1861-97). A successful use of waste
foundry sand in flowable fill was reported by Tikalsky et al. [12] and Stern [13]. Naik et al. [14]
reported on utilization of used foundry sand in concrete. When foundry sands are used as a
partial replacement for fine aggregates in the production of concrete the combined fine
aggregates should have the gradation recommended by the ASTM C33 standard. Partridge et al.
[11] conducted geotechnical investigations to determine the engineering properties of spent
foundry sand for highway embankment construction. Results from the latter study are
represented in Table 12.
Asphalt production may benefit from the sub-angular shape of foundry waste sand if used as a
mix ingredient. Current regulations in many states are discouraging the use of rounded river
bottom aggregate and are instead using more angular, manufactured aggregates. Foundry sand
could potentially meet the needs of this market. A successful decade-long project using waste
sand in asphalt production has been demonstrated in Canada [6]. Some concern of a possible
negative impact on air emissions resulting from the processing of waste sand containing organics
has been addressed. It has been proven that these materials add very little to the air emission of
an asphalt plant and that these additions may be adequately captured by the facilities existing air
pollution control equipment.

22
In order to establish technical specifications and performance standards for various engineered
beneficial uses of spent foundry sands and slags, an industry-sponsored consortium for market
development, the Foundry Industry Recycling Starts Today (FIRST) has been recently founded.
The FIRST web site [9] compiles a comprehensive list of foundry by-product utilization projects.
The FIRST library contains a large number of technical publications related to beneficial use,
marketability, characterization, and minimization of foundry waste streams. However, additional
testing for materials properties is needed to support development of specifications including
foundry sand.
CHARACTERISTICS OF FOUNDRY BINDERS AND RESINS
The annual generation of foundry waste (including dust and spent foundry sand) in the United
States alone is reported to range from 9 to 13.6 million metric tons [24]. Typically, about 1 ton of
foundry sand is required for each ton of iron or steel casting produced. Massachusetts foundries
use more than 40 thousand tons of sand and spend a total of about $0.6 million on sand disposal
per year [1].
A brief description of the chemical composition of typical foundry sand is useful, particularly as
it relates to the various binder systems employed. The makeup of residual sand material from
iron and non-ferrous foundries in Massachusetts is typical to other states. The major components
are 70-80% quartz sand, 5-15% clay, 2-5% additives, and up to 4% moisture. Foundry sand
consists primarily of clean, uniformly sized silica sand that is bonded via binder(s) to form molds
for ferrous (iron and steel) and non-ferrous (copper, aluminum, brass) metal castings. The
chemical composition of typical foundry sand is given in Table 13.
The most common casting process used in the foundry industry is the sand cast system.
Virtually all sand cast molds for ferrous castings are of the green sand type. In addition to green
sand molds, chemically bonded sand cast systems are also used. The latter systems involve the
use of one or more proprietary organic binders in conjunction with catalysts using different
hardening and setting procedures. In chemically bonded sand cast systems, additions may be as
much as 3% of mixture by weight. Chemically bonded systems are most often used for making
cores (used to produce cavities in molding operations) and molds for non-ferrous castings. The
type of metal being cast determines which additives and what gradation of sand is used.
Spent foundry sand consists primarily of silica sand, coated with a thin film of burnt carbon,
residual binder and dust. Silica sand is hydrophilic and consequently attracts water to its surface.
Table 14 lists the chemical composition of a typical sample of spent foundry sand as determined
by X-ray fluorescence. Depending on the binder and type of metal cast, the pH of spent foundry
sand can vary from approximately 4 to 8. It has been reported that some spent foundry sands
mixed with untreated sludges can be corrosive to metals (due to pH of the sludge).
Virgin foundry sand is a uniformly graded material. However after casting, sand often contains
metal, mold and core materials containing partially degraded binder. Spent foundry sand may
also contain leachable contaminants, including heavy metals and organic compounds such as
phenols that are captured between sand grains or coated on the grain surface during the molding
process and casting operations. Among foundry by-products, baghouse dusts often have the
highest contaminant leaching potential, partially because of the small size of their particles. The

23
dusts vary in their composition and physical makeup. Large quantities of silicon oxide, carbon
silicate, metals (Fe, Zn), and metal oxides have been detected in foundry dusts.
The main volume of all foundry sand is being used as green (clay-bonded) sand. Spent sand from
the green sand process is the major by-product, and it seems to pose the least environmental
concern. A possible reason for this is that the virgin green system is environmentally harmless
and it does not form potentially harmful compounds during an optimized casting process. In
contrast, virgin chemically-bonded systems may contain toxic/irritant constituents (binders,
hardeners) that decompose for the most part when molten metal is poured into molds. Therefore,
fate of binders and resins shall be particularly concerned and be given further consideration.
Chemical Composition of Foundry Sand Binders
All foundries, worldwide, employ the use of binders to hold together individual grains of sand
that are used to form mold castings. A binder is any material, added to virgin sand, which by
means of adhesion and/or cohesion, bonds sand grains to a degree suitable for metal casting
requirements. The two principle types of binders are clay-bonded "green sand" and chemically
bonded sand. This section includes the characterization of foundry sand binders and resins with
respect to their organic compound content.
Due to the proprietary nature of the composition of foundry sand binders, there is little publicly
available information regarding the relative proportions of materials used in common binders and
resins. A qualitative list of the composition of some binders is provided in the American
Foundrymens Society publications [25-27]. A variety of foundry binder systems is categorized
by type of the curing/setting process in Table 15. The most common types of binders currently in
use include the following:
Furan (Furfuryl Alcohol) Resin
Phenolic Urethane
Phenolic Nobake-Acid
Phenolic Resole-Ester
Sodium Silicate
Phosphate
Alkyd (Oil) Urethane
Shell Liquids/Powders and Flake Resins
The majority of binder systems used in modern foundries are selfsetting chemical binders.
Phenolic Urethane and Sodium Silicate binders are most prevalent among Massachusetts
foundries. Oil-based and cement-based systems are old technologies and rarely used today. All
systems fall into two broad categories: organic and inorganic systems. The most common binders
for both types of systems are described below.
Furan Systems
Furan resins are organic systems. They were first introduced to the foundry industry in the late
1950s. In the early 1960s the furan nobake (FNB) process emerged. In the furan process, the
resin converts from liquids to solids at room temperature when exposed to an acid catalyst; a
process termed polymerization. The polymerization reaction is exothermic and produces a small

24
amount of water as a by-product. The system is considered one of the easiest chemical systems
to reclaim.
There are two main chemicals in the furan process: furfuryl alcohol based resin and an acid
catalyst. The term furan is only a generic term that denotes the basic structure of a class of
compounds. There is no dioxin furan used in making furan resins. The main component used in
formulating the resins is furfuryl alcohol, which is a colorless to pale yellow liquid and
polymerizes very readily in the presence of acid.
There are several grades of resins, usually classified under three general categories, depending
on the nitrogen and water content:
Resin Grade Nitrogen (%) Water (%)
Low 0 3 0 5
Medium 2 8 5 15
High 5 11 10 30
All of the furan resins contain furfuryl alcohol either as the monomeric chemical or in a
polymeric form. Other chemicals that may be incorporated in the resin system are urea,
formaldehyde, water, phenol or phenolic derivatives, and other chemicals, depending upon the
proprietary formula. Typically, optimum binder levels may vary from approximately 0.8 to 1.5%
of the sand mixture by weight [25].
The second part of the FNB system is the acid catalyst that causes the furan resin/sand mix to
cure or harden. Catalysts are usually proprietary mixtures of acids and solvents, water and
methanol. The two main classes of catalysts are the phosphoric acid-based (normally 70 85%
phosphoric acid) and the sulfonic acid-based (solutions of benzensulfonic acid (BSA) or
toluenesulfonic acid (TSA), or other sulfonic acids, at times in combination). The solvents are
water or methanol. The concentrations of the acids vary from 50 to 80%.
Phenolic Acid-Cured Systems
The phenolic acid-cured system became popular in the 1970s as an alternative to the furan
system. The system is organic and based on complex polymers that are formed in a condensation
reaction which takes place when phenol and formaldehyde are reacted at elevated temperatures.
The polymerization reaction is exothermic and produces water as a by-product (0.2%). Phenolic
resins do not require the use of additional additives to the sand mixture. Sand reclamation is very
easy due to the brittle nature of the bond at room temperature. The brittleness can cause
veining and some foundries add 1 2% iron oxide to reduce this problem.
The resins are modified with silane, an adhesion promoter. In general, resin contents are in the
range of 1.0 to 1.5% for cores and 0.8 to 1.3% for molds. The acid catalysts most commonly
used in this system are TSA, BSA or blends of the two. Xylenesulfonic acid (XSA) is also used
as a catalyst. Acids are used at between 20 to 40% of the resin weight.

25
Phenolic Ester-Cured Systems
The ester cured phenolic self-setting system has been under development for 30 years in
England. However, only in the past several years have the developments in the chemistries for
foundry applications been available [26].
The chemical components are relatively simple; however, the reaction between the chemicals is
sophisticated. The two components are a phenolic compound and an ester, and by combining the
two, the ester causes the phenolic compound to polymerize into an insoluble gelled binder. The
by-products of the reaction are a polymerized phenol/formaldehyde resin, a metallic salt and an
alcohol. All conventional, commercially available mixing devices work with the ester cured
phenolic system [26].
One of the unique properties of the ester cured phenolic system is that it undergoes a secondary
cure during the casting process. This thermosetting phase allows for some sand expansion, but
also causes the system to increase in hot strength and reduce distortion. The result is a thermally
stable bond during the casting process. All metals can be cast on the system and the system is
readily reclaimable.
Chemicals used in this process are resins and catalysts. The phenolic compound resin is an
alkaline liquid containing:
Less than 0.5% formaldehyde
Less than 2% phenol
A significant portion of an inorganic compound
The reaction between the ester and the resin is a balanced reaction; therefore, the proper ratio
must be maintained as recommended by the manufacturer. The total level of chemicals based on
sand is determined by the strength requirements of the cores/molds. Depending on the sand type,
the levels recommended are 0.75% for zircon sand and up to 3% for olivine sand. The resin is
alkaline in nature and proper care must be taken when handling it.
The catalyst/hardeners are compounds of commercially available esters. There are a large
number of esters that can be used for the polymerization process. The important aspect is that
they are relatively non-toxic. The recommended level of ester is determined by the resin or
binder.
The cure rate is not affected by the acid demand value (ADV) which is a measure of the amount
of basic material present in the sand that is soluble in dilute acidic solution. Since the reaction
which cures many resins systems is acid catalyzed, and since the acid used is typically very mild,
the presence of basic substances which can neutralize the weak acid will retard the curing
reaction. The ADV of the sand should therefore be continually evaluated, since drastic changes
can require a catalyst modification.
The ester cured phenolic system can be reclaimed by attrition or thermal reclaimers. The net
amount of usable sand returned is similar to other systems and is a function of loss on ignition
(LOI) of the sand. Depending on the metal cast, the LOI has to be controlled through loss in the
reclamation unit and new sand additions.

26
Alkyd Urethane Systems
The urethane family of organic binders was developed in the middle 1960s. The alkyd urethane
system was the first developed when it was discovered that an isocyanate reacted with the core
oil, causing the metallic dryer to perform better, thereby creating a urethane bond.
Alkyd urethane systems cure in three stages. The first stage is the urethane reaction and unites
the hydroxyl groups from the resin with the cyano groups in the isocyanate (coreactant). A weak
urethane bond develops which is then strengthened as the unsaturated alkyd resin reacts with
oxygen, i.e., the oxidation of the unsaturated oil bonds (stage two). The third stage occurs during
heating the mold to 350 400F when additional crosslinking develops. This final stage
determines the ultimate strength of the resin.
Chemicals used in the process are resins, catalysts, and coreactants. The resin is a modified
vegetable or natural oil capable of forming a urethane bond when reacted with a polyisocyanate
and catalyst. The catalyst is a combination of amines and metallic drying agents which facilitate
both urethane and oxidization reactions. The coreactant is polyisocyanate (or polymeric
isocyanate) which is the coreactant to resin and contains about 10% by weight nitrogen. It reacts
with water to form a urethane polymer and CO
2
gas as a by-product and should be added at 18
20% of resin. Too much coreactant will increase the possibility of gas defects and should be used
accordingly.
This system is less sensitive to sand chemistry than acid catalyzed systems and is completely
compatible with silica, alumina silicate, zircon, chromite and olivine sands.
Sometimes, the reclaimed sand from the alkyd urethane systems must be bonded with a different
type of chemical system than used originally. Some foundries use a different type of chemical
binder system to make cores, but not molds, and that can cause a problem in reclamation.
Chemical compatibility in a reclaimed sand is dependent upon the sand to metal ratio,
reclamation method, amount of new sand and chemical systems. In general, reclaimed sand
from an alkyd resin system can be rebound with silicates but is not always compatible with
phenolic urethane, furan and phenolic acid systems.
The system may require an iron oxide addition to control lustrous carbon, veining, and /or
nitrogen pinhole defects. Magnetite (black) oxide or Hematite (red) oxide should be added to 2
3% or 1 2% based on silica sand, respectively.
All metals can be poured using this system. Some steels may pick up surface carbon, although
the properties of the castings are generally not affected. With the proper iron oxide addition,
nitrogen pinholing is not a problem.
Phenolic Urethane No-Bake Systems
The phenolic urethane system is an organic system. It was introduced to U.S. foundries in 1970.
This system is cured by the reaction between a polybenzylic-ether-phenolic resin and a
polyphenyl polyisocyanate in the presence of a catalyst, such as a derivative of pyridine.

27
The unique feature of the system is the curing reaction itself. There is a delay in the curing
reaction after the three components are mixed with the sand. This delay is the work life of the
mix and enables the sand mix to remain free flowing until the curing reaction begins.
The resin and coreactant may be modified with solvents. Total binder level is based on the
weight of the sand and is usually in the range of 0.7 2.0%. The normal ratio of resin to catalyst
is 50:50. Catalyst usage is generally 0.4 10% of the weight of resin, depending on the strip time
desired, type of sand, sand temperature and catalyst type. The resin has a polymeric isocyanate
(coreactant) which will react with water to form a urethane polymer and CO
2
gas as a by-
product.
Additives can be used to correct many problems which occur on casting. Iron oxide, either black
(Fe
3
O
4
) or red (Fe
2
O
3
), is the most common and is used to reduce gas defects in steel castings.
Once the reaction starts, it is extremely rapid and thorough. Because this crosslinking reaction
does not evolve side products, the curing rate is constant throughout the entire sand mass.
The bonded sand is readily reusable through reclamation by current methods. However, as with
other chemical binders, care should be exercised to assure efficient binder removal, as measured
by LOI tests. The use of sands having a high LOI (greater than 2%) can result in greater gas
evolution and less than optimum tensile strength development.
Phenolic Urethane Cold Box Systems
The phenolic urethane cold box process uses two resin components, Part I phenolic resin and
Part II polymeric isocyanate, and a gaseous catalyst vapor. Both resin components are mixed
with sand and the catalyst vapor is then passed through the sand mix. Hardening is achieved
almost instantly at room temperature. Catalyst vapor is followed by an air purge, which sweeps
the catalyst from the now hardened core. Water based coatings, alcohol lightoff, or solvent
refractory coatings may be applied to the core surface.
The phenolic resin is a phenol-formaldehyde polymer blended with solvents and additives to
produce a low viscosity resin solution. The polymeric isocyanate is a
methylchloroisothiazolinone (MCI) type blended with solvents and additives. No by-products,
such as water, are formed during curing. The two resin components are mixed in equal parts on
the sand, i.e. 0.75% Part I and Part II.
Two tertiary amine catalysts are commonly used to cure the combined resins. Triethylamine
(TEA) and dimethylethylamine (DMEA) are both volatile, flammable corrosive liquids.
Warming the catalyst gas and the following air purge can reduce cycle times and minimize
catalyst usage. The exhaust gas from the corebox during the gassing and purging cycle will
contain the amine vapor, since it does not react with the core binders. This exhaust gas should be
collected in a wet scrubber with a solution of dilute acid that neutralizes the amine to form to
form non-volatile acid salt.
Clay/sugar blends are proprietary powdered sand mix additives used to suppress veining in
ferrous casting. They are typically used at 1 1.5% based on sand. Iron oxides of various types
are also used as additives. Depending on the need levels, from 0.25 to 3.0% are used.

28
Sodium Silicate Ester-Cured Systems
The sodium silicate/ester cured system is an inorganic system. It was developed in the late 1960s
as an alternative to existing sodium silicate nobake systems using powdered dicalcium silicate,
Portland cements, or ferosilicon as curing agents. The organic ester is hydrolyzed at a controlled
rate by the alkaline sodium silicate. The acid produced reacts with sodium silicate to form a
silica gel, which bonds the mold or core. No heat or gas is generated on curing.
The system provides an inorganic alternative to the organic chemical setting processes. Some
advantages are: low cost, ability to use with impure sands, low gas emission and resistance to
expansion defects in casting. The curing rate is mildly temperature dependent. Curing speed
depends upon the SiO
2
:Na
2
O ratio of the sodium silicate binder and the composition of the ester
hardener. High ratio silicates are needed for fast curing.
Sodium silicate binders consist of solutions of sodium silicate in water. Many proprietary sodium
silicate resins contain additions of sugars, carbohydrates, or polymers, primarily to improve
shakeout. Most suppliers market a range of silicates varying in SiO
2
:Na
2
O ratio, solid content
and additives. Sodium silicates are nonflammable, nonexplosive alkaline liquids of relatively low
toxicity.
The catalysts used are low viscosity liquid aliphatic organic esters with a sweet or acetic acid-
like smell. Typical organic esters are:
Glycerol diacetate (Diacetin) fast cure
Ethylene glycol diacetate (EGDA) medium cure
Glycerol triacetate (Triacetin) slow cure
Some of the esters may be weakly acidic but there are no known specific hazards associated with
the use of these materials. These esters are usually supplied as blends to obtain a desired strip
time. Mixtures generally contain between 2.5-4.0% sodium silicate as a weight/weight addition
to the sand. The ester catalyst (hardener) addition rate is 10-15% calculated by weight of the
sodium silicate (binder). Fine sands generally require more binder.
Additives to the binder system are generally liquid organic polymers that enhance shakeout and
improve humidity resistance. The presence of sugar or polymer breakdown agents increase the
gas evolution during pouring. Since the binders are nitrogen, sulfur and phosphorus free, the
system is suitable for most cast metals.
Sand reclamation is usually by mechanical/attrition methods. The system is reclaimable to a
lesser extent than the organic systems and unless special binders are used, the utilization is
usually less than 50%. Reclaimed sands previously bonded using acid catalyst must not be
included in a mixture. The buildup of alkaline residues in the recycled sand may increase the risk
of sand burn-on.

29
Cement Bonded Sand Systems
Cement has been used as an inorganic binder for foundry mold and core sands since the late
1800s. But it was not until the early 1930s that the use of cement as a foundry binder became
significant. The major drawback of cement sand involves its slow curing rate.
Hydraulic cement is defined as a finely powdered, calcareous material that, when mixed with
water, forms a plastic paste that sets and hardens to rocklike consistency. The formation of a
rigid interlocking matrix of hydration products binds the composite cement mass together.
The hydraulic cement-bonded sands are quite sensitive to temperature variations. Temperatures
below about 68F require the use of additives such as calcium chloride, polyphosphate,
aluminum salts, carbon dioxide and molasses which are added in an effort to increase the cure
rate. The mechanical reclamation of hydraulic cements is a dry process with, reportedly, 80%
reclaimed sand mixtures successfully reused in foundries.
Phosphate Systems
The phosphate self-setting inorganic system was developed as an alternative to sodium silicate
with improved shakeout properties and reclaimability. The chemical process is based on the
reaction of the catalyst/hardener with water. This provides a mildly alkaline reaction and the
catalyst/hardener slowly undergoes hydration which alters its chemical reactivity and physical
state. The reaction between the resin and catalyst is very exothermic.
Chemicals of the process include a resin and a catalyst. Recommended resin levels are 2.5
3.0% for molds and 3.5 4.0% for core production. The catalyst/hardener level varies from 18
35% of the resin depending on the sand temperature, impurities, mixing efficiency, and desired
work life. The system consists of water soluble acidic aluminum phosphate liquid resin and a
powdered magnesium oxide catalyst/hardener. The resin is acidic and all equipment used must
be acid resistant. The phosphate sand system, after pouring and shakeout, can be mechanically
reclaimed and recycled.
Castable/Fluid Sand Systems
This is a novel inorganic system in which chemically bonded sand mixtures are converted into
fluid slurries from which molds or cores are cast and then self hardened. Variations include the
use of sodium silicate, cement, or synthetic organic resins. The system is mainly used in
foundries in Russia and Europe.
The fluid properties result from the addition of foaming agents to a sand mixture and air
entrainment during mixing. Sodium silicate binders are hardened by the addition of dicalcium
silicate, while the Portland cement binders react with water to form a bond. Alternatively, acid
catalyzed phenol furfuryl resins are used for bonding purposes.
In the silicate system, high SiO
2
:Na
2
O ratio binders are used without the addition of sugars or
polymers for breakdown purposes. In the various versions of the fluid sand system the main
binders are:

30
Sodium silicate with a 2.8 3.0 ratio of SiO
2
:Na
2
O
Portland cement (ordinary grade)
Nitrogen free phenol furfuryl alcohol resin catalyzed with TSA acid
The foaming agents employed are usually alkyl benzene sulfonates or alkyl sulfates. The
hardener, dicalcium silicate, is a finely ground powder derived from the basic slag produced in
ferrochrome production or other melting operations. Faster hardening is achieved by increasing
the proportions of dicalcium silicate used with a sodium silicate binder or acid catalyst used with
a furan resin. Additionally water or acid catalyst may be necessary to obtain the necessary
fluidity when using fine sands. Typical mixture formulations are:
Sodium silicate bonded:
100 parts silica sand
5 6 parts sodium silicate (2.8 3.0 ratio)
3 5 parts dicalcium silicate
0.1 part foaming agent
1.5 2.0 parts water
Cement bonded:
100 parts silica sand
8 10 parts Portland cement
6 parts water
0.1 part foaming agent
Resin bonded:
100 silica sand
2.5 parts acid catalyst plus foaming agent
1.7 parts resin
During the casting process, foundry cores and molds are subjected to intense heat from the
molten metal. The temperature of the mold-metal interface approaches that of the molten metal
(about 1000C). Heat transfer causes the temperature of the sand further from the mold-metal
interface to rise as well. As a result, all organic materials (binders, additives, coatings) undergo
thermal degradation and oxidation (burning) at high temperatures. The nature and distribution of
combustion and degradation products are complex and not entirely predictable. Because of the
high temperature involved, all residual relatively complex organic compounds are found in spent
foundry sands at very small concentrations. Therefore, despite the frequent use of toxic, irritant,
and hazardous organic chemicals in molds or cores, spent sand after casting does not typically
contain organic contaminants at hazardous levels. Leachability and total content of toxicity
characteristic constituents in foundry sand waste are discussed in the next section.

31
CONTAMINANTS IN SPENT FOUNDRY SAND
The environmental stability of spent foundry sand (collected with at least a minimum quality
control) has been shown very clearly by a number of investigations [8,11,28-37]. Variations may
be attributed to differences in processes, sand quality control, and testing procedures. Chemical
characteristics are essential to the determination of the sand product as an environmentally
benign material. On the other hand, long term environmental and human health effects from
common beneficial use practices are still being studied and are not well documented in the
technical literature. Results of the chemical analysis obtained for the Toxicity Characteristic
Leaching Procedure and bulk element content of foundry sand waste and other waste
components are discussed below.
METALLIC CONTAMINANTS
Different procedures for evaluation of leachability of chemicals to ground water exist. For many
inorganic compounds, Toxicity Characteristic Leaching Procedure, Synthetic Precipitation
Leaching Procedure ("acid rain" test), sequential aqueous extraction procedure, or "total" bulk
metal laboratory analysis may be used. To properly evaluate the fate of contaminants in wastes,
the pH of the ground water that is expected to migrate through the sand waste must be observed.
The exposure of beneficially used materials to the environment in different practices is variable.
For example, Portland cement in a foundation versus fill material in a bridge abutment have very
different exposures. However, it is useful to analyze for total metals because the soil ingestion
and inhalation remediation objectives are also measured in this way. For metals in ground water,
investigative samples should be unfiltered.
While samples from the same type of foundry often demonstrate a large scatter in chemical
parameters, a definite similarity of the spent sand characteristics exists across the foundries
regardless of the metals cast [28]. This result signifies that the type of molding process,
additives, type of charge (virgin or scrap) and type of metal poured may not be suitable terms for
measuring statistical differences in a degree of hazard. Therefore, specific characterization of
foundry sand waste based on process type or metal poured is not always feasible. However a
broader statistical analysis should be performed instead. Although this variation is present in
many cases, especially in characterizing mixed foundry waste, there are other situations when
individual waste streams and mixed waste alike have quite acceptable (small) coefficients of
variation in chemical characteristics.
Review of Available Data on Metal Leaching
An overview of publicly available results on leachability of metals from foundry sand waste is
represented in Table 16. The Federal primary and secondary drinking water standards as well as
the toxicity characteristic levels are included in the table to facilitate reference to regulatory
standards. Four significantly different methods were used for the characterization of leachability
of metals from foundry waste sands. The first is field leachate measurements obtained with
ground water monitoring lysimeters. The second is TCLP and/or EP Toxicity acetic acid tests.
The third is sequential aqueous extraction tests. Finally, fourth is a rigorous leaching in
concentrated aqua regia (German standard method DIN 38 414 S7).

32
Random scattering around mean values is very large. The standard deviations are usually greater
than the respective mean concentrations. Within this scatter the differences between TCLP and
EP Toxicity test results become statistically insignificant. One of the consequences of the
extensive fluctuations is an inconsistency in data representation by different researchers.
Average, median, or maximum values are occasionally reported. Only a few projects [28, 29]
were completed with comprehensive statistical analys es that included the determination of a
roster of statistical parameters to characterize a vast pool of analytical data. A detailed discussion
of waste stream variability and sampling techniques for leaching from foundry waste was
presented by Krueger et al. [30].
Several conclusions can be drawn from the Table 16. Perhaps the most important is that spent
foundry sand disposed of in a foundry monofill [31] or used in highway construction [8] leaches
regulated metals well below the toxicity characteristic levels. This is usually because the
constituents are either present in forms that are not soluble or are unavailable to the leaching
media. Even when the presence of the constituents in a bulk waste stream can be traced, it does
not always imply that they could readily be leached. A comparison to a mixed-waste municipal
landfill [32] indicates that the foundry sand waste leaches one to two orders of magnitude less
than the typical waste in a municipal landfill. The latter is otherwise known to leach high
concentrations of toxic substances in many instances [33]. Unlike usually neutral foundry
monofills, an actively decomposing municipal landfill is contaminated with organic acids typical
of microbial action.
The Table 16 also shows that the TCLP and EP Toxicity laboratory tests usually yield
significantly higher leachability results than that in real field conditions. This is because the
toxicity characteristic tests are designed to simulate the worst case conditions in a municipal
landfill in the presence of carboxylic acids as the leachate. Such conditions do not necessarily
realize in other disposal scenarios, and never realize in foundry monofills. An "acid rain" test
with a mixture of nitric and sulfuric acids [34] also proved to be less aggressive than the acetic
acid used in the TCLP (see Table 18 for a comparison of metal leachability in TCLP and SPLP).
To accurately simulate real field conditions the sequential aqueous extraction method seems to
be the most appropriate.
Nonetheless, even under the more rigorous TCLP test, extract contained concentrations typically
below the regulatory toxicity characteristic levels if the spent foundry sand was not mixed with
the other foundry waste streams (e.g., dust, slag, or sludge). In most occasions, mixed foundry
waste also leaches below the regulatory levels. For example, a Michigan ferrous foundry mixes
spent sand with several kinds of baghouse dust, after separately analyzing and characterizing
each of them as non-hazardous. The resulting mixture meets all (primary and secondary)
drinking water standards and may thus be allowed for various beneficial uses, including direct
land application. On the other hand, an examination of Table 16 reveals in at least one event
when a mixture of spent green sand and dusts from a brass foundry was reported to leach lead
(Pb) in both TCLP and EP Toxicity tests above the toxicity characteristic threshold. In that case,
spent sand was not analyzed separately from dusts, but some of the dusts leached up to 170 mg/l
of lead [36]. Table 19 demonstrates elevated concentrations of lead (well above the toxicity
characteristic level) leached from spent molds after casting of highly leaded copper-based alloys
(5-25% Pb).

33
Different dusts/fines and slags behave differently. Slags from ferrous and aluminum foundries
are usually non-hazardous and often beneficially used. In other occasions, all foundry waste
streams are mixed for landfill disposal posing no environmental risk. But there is less data on
chemical characterization of foundry waste streams other than spent sand. Some of those streams
are known to be hazardous, especially leaded brass/bronze baghouse and shotblast dusts which
contain elevated levels of lead. Characterization of dusts and fines should be subject to separate
investigation. This report is focused on spent foundry sand, chiefly because it is a major bulk by-
product and enough data on chemical analysis of foundry sands exist to draw some unambiguous
conclusions.
Results of the laboratory analysis depend significantly on type of leaching procedure that is
applied. A rigorous extraction in the German DIN 38 414 S7 test (with aqua regia) causes very
high leaching of chromium and somewhat elevated leaching of lead from foundry waste
compared to TCLP or EP Toxicity tests (see Table 16). Since the DIN 38 414 S7 is notably more
aggressive that TCLP, results from this test are not applicable for a comparison with the toxicity
characteristic levels adopted in the USA. Contrary to the DIN 38 414 S7 test, the SPLP method
displays two orders of magnitude decrease in lead leachability relative to TCLP, while chromium
leachability in latter tests differs only about 5 times (see Table 18). Finally, the results from
sequential aqueous extraction procedure do not raise a concern on metal leachability of foundry
waste (Table 16).
Table 17 summarizes the results of the total metal analysis of the foundry waste sand as well as
unprocessed molding sand and natural sand and sandy soil. It is clear from this table that
quantities of total metal content in spent and virgin sand and in sandy soils are of the same order
of magnitude. Most often, less metals were found in sands than in soils. Taking into
consideration a 20x dilution factor included in the TCLP method, the data in Table 17 may be
divided 20 times in order to estimate the upper limits for leaching concentrations (with an
assumption that 100% of metal content would leach in the TCLP test). From the data in Table
17, such upper estimates for leachate concentrations are below the toxicity characteristic levels
for all regulated metals except chromium. However, actual TCLP leachability of chromium from
foundry sand is rather weak as seen in Table 16. No meaningful correlation between the total
metal content and the leachability of it from foundry waste in the TCLP tests was generally
observed (see Table 19).
The chemical forms of the actual metallic species and compounds (e.g., oxides, silicates) present
in the foundry by-products have not yet been investigated. Each metal compound exhibits unique
fate, transport, and toxicity characteristics. In this sense, elemental metals analysis represents a
worst case scenario, assuming that all metal forms exhibit maximum degree of risk to human
health and the environment. Model experiments with leachability of lead present in several
chemical forms, portray a significant difference between leaching potential of metal
particles/droplets, metal oxides, or metal silicates (Table 19). Moreover, there is an apparent lack
of quantitative data on differences between the results from the TCLP and SPLP, or other
extraction methods, with most of the research concentrated only on the TCLP or EP Toxicity
tests.
Mixed materials add significant complexity to understanding the waste sands. However, as long
as a mixture of spent sands and foundry fines/dusts is categorized as a non-hazardous material, it

34
can find its way into a variety of applications. Although fines can sometimes downgrade the
marketability of a given mix because of size gradation issues (e.g., in asphalt), some applications
require finer material, such as flowable fill (low-strength concrete), where the fines help achieve
the desired maximum compressive strength needed. The testing procedure can identify all
contaminants whether they come from the casting molds, cores , fines or sweepings from the
cleaning room. This suggests further need to assess materials in the content of recycling,
beneficial use and handling practices.
LEACHING OF ORGANICS
A limited number of investigations have been conducted to determine the potential and extent of
organic residues in spent foundry sand and leachates from disposal sites containing spent
foundry sand.
Green sand appears to be of very low organic compound leaching potential compared to the
chemically-bonded sands. This result seems reasonable if one recognizes that mineral green sand
systems would leach little organic matter. Since the major volume of spent foundry sand comes
from the green sand processes, the foundry waste is rarely analyzed for the organic content.
A detailed study by Ham et al. [35] specified organic compounds in ferrous foundry process
waste leachates. The study determined the potential and extent of ground-water contamination by
organic contaminants arising from ferrous solid-waste monofills. TCLP was used on waste
samples representing nine common binder systems to identify organic compounds released from
the spent foundry sand in monofills. No other wastes other than foundry sand were in the
monofill. Leachates were analyzed by GC-MS (mass spectroscopic detection) for qualitative
analysis and by GC-FID (flame ionization detection) for quantitative analysis. Laboratory results
indicate that a wide variety of organic compounds were present in the spent foundry sand
leachates and that most are present at low concentrations. No samples produced concentrations
above the regulatory toxicity limits.
Table 20 provides information on the types of binders evaluated and sample sources for each of
the binders. A core oil binder system sample (#6) resulted in the most leachable organic
compounds of the nine systems tested. Overall error introduced by sample selection, leaching,
and analysis, was evaluated. The entire leaching procedure for volatile compounds was carried
out four times on composites of a core oil binder sample, and then analyzed. The results for all
volatile organic compounds present at quantifiable concentrations are given in Table 21. The
average concentration and the relative standard deviation of the four measurements for each
compound are also given.
Tables 22 25 list the concentrations measured against the calibration standards on the GC-FID
and estimated from GC-MS data for a core oil binder system sample, as an example of the
results. Table 22 gives the average of four leach test results from GC-FID analysis. These
organic leachate concentrations are compared to quantitation limits of the detector and to
Massachusetts Drinking Water Standards and Guidelines [38]. None of the averaged quantity of
the 29 volatile chemicals exceeded the regulatory levels. Table 23 gives results from GC-MS
analysis of volatile organic compounds. Some compounds identified by GC-MS could not be

35
obtained as standards for the GC-FID. Tables 24 and 25 provide a summary of organic
compounds for various binder systems and an overall comparison of binder systems respectively.
Three compounds from the toxicity characteristic list (benzene, tetrachloroethene, and cresols)
and another three from the Massachusetts Standards and Guidelines for Drinking Water (acetone,
1,1,1-trichloroethane, and toluene) were detected in the foundry waste leachates at measurable
concentrations. Maximum concentrations measured in any of the composite waste leachates were
well below the regulatory toxicity characteristic limits (see Table 24). Only benzene and
trichloroethane in three binder system samples were close to the drinking water maximum
concentration limits of 5 and 200 g/l, respectively. Trichloroethane is one of the constituents of
core coating or core pattern spray.
The phenolic urethane and core oil binder systems were more likely to be of environmental
concern than the others, both from the number of compounds leached and concentration of the
compounds (see Table 24). Benzoic acid, naphthalene, methylnaphthalenes, phenol,
methylenebisphenol, diethylphenol, and 3-methylbutanoic acid were at the highest level at over
300 g/l in one or more samples. Foundry waste from a core oil process appeared to leach the
largest quantities of organic compounds relative to the other binder system processes.
Fortunately, only a few modern foundries still use core oil binders.
Table 25 demonstrates that the core room sweepings contribute the most to the organic content in
the samples with the phenolic urethane and the phenolic isocyanate binder systems. For the core
oil systems, the molding sand contributes the most organic compounds in the leachate. The
remaining binder systems leached very little. The furan hot box, alkyd isocyanate, and furan
warm box sample leachates contained only a few compounds at concentrations below 100 g/l.
Xylenes are among the most common organic compounds leached in the TCLP procedure,
although at concentrations 2 to 4 orders of magnitude lower than the drinking water limits. At
least some of the xylene isomeric forms were detected in the leachates from all of the nine binder
systems analyzed (see Tables 24, 25). Toluene was present at levels 20 to 2000 times lower than
the drinking water standards in seven of nine binder systems. Naphthalene was found in six of
nine binder systems sampled.
A detailed report from two New England foundries provided information for total concentrations
of semi-volatile organic compounds in mixed waste (spent sand and baghouse dust). Tables 26
and 27 include the data for the organic compounds listed in the report. Additional compounds
detected, not found in the previous study, include benzo(a)anthracene, bi-n-octyl phthalate,
crysene, di-n-butylphthalate, fluoranthrene, and pyrene. Most of them (benzo(a)anthracene,
crysene, fluoranthrene, and pyrene) would be present only after contact with molten iron. These
data suggest that organic compounds, most notably mono- and polyaromatic hydrocarbons
(PAH), are present at relatively low levels. Taking into consideration a 20x dilution factor
included in the TCLP method, the data in Tables 26 and 27 should be divided 20 times in order
to estimate the upper limits for leaching concentrations (with an assumption that 100% of
organic matter would leach in the TCLP test). Such upper estimates for organic compounds are
well below the drinking water standards.

36
It can reasonably be accepted that several organic compounds are present in most if not all spent
foundry sands. From the detailed study outlined in this report, it appears that acetone,
diethylbenzenes, p-ethyltoluene, isopropylbenzene, 1,2,4-trimethylbenzene, both 1- and 2-
methylnaphthalene, dimethylnaphthalene isomers, naphthalene and all three isomeric forms of
xylene are present at sufficient concentrations to be detected by modern analytical instruments,
but none of these components are specified by the toxicity characteristic regulations.
While not having an exhaustive and comprehensive list of all organic compounds present in
foundry sand and their binders, sufficient data, as given in this report, exist to draw some
conclusions about the nature of and related implications of both virgin and spent foundry sand.
All foundry sands and specifically their binders/resins are composed of materials which include
a large number of organic compounds. Most of the organic constituents are volatilized within
that inner part of the mold starting where the sand kisses the molten metal at about 1000C.
The remainder of the core sand is clearly affected by hot evolving gases. Major decomposition of
binders occurs until temperature drops below 200C. Some heavy compounds, such as phthlates,
could then condense in the peripheral areas.
Unreacted resins and solvents in freshly mixed sand-binder systems not exposed to the
catalyzing gas or high temperature, would be the most likely source of leachable organics.
Therefore, fresh casting mixtures and core sand that have not been in contact with hot metal,
should be excluded or separated from the other foundry waste streams. It may also be concluded
that improper handling of waste streams increases the risk of contamination of spent sand.
EMISSIONS OF HAZARDOUS AIR POLLUTANTS
The reaction of sand binder systems subjected to hot liquid metal is their thermal decomposition.
As a result of this process major permanent gases are produced in the vicinity of the mold-metal
interface. The principal evolving gases are hydrogen, carbon monoxide, carbon dioxide,
methane, nitrogen, oxygen, and water vapor. Total gaseous hydrocarbons, including: ethane,
ethylene, propane, propylene, acetylene, furan, methanol, and ethanol, constitute up to 5% of
methane volume [39].
Every organic binder can be expected to behave similarly at the mold-metal interface. Pyrolysis
is likely to be nearly complete at the mold to metal boundary. Further from the interface, deeper
into the mold body, partial decomposition can be expected. At lower temperatures and in an
oxygen-lean atmosphere, more complex organic compounds are formed. The mixture of paraffin
hydrocarbons should be produced, as well as some of the aromatics, especially during
decomposition of the polymers that are built around phenolic rings. Formaldehyde and ammonia
may also be formed.
Benzene, toluene, nitrous oxide, and hydrogen cyanide were identified [40] in the atmosphere
near a pouring line in a foundry using alkyd isocyanate resin bonded molds. The concentrations
detected in the foundry atmosphere were generally low. Many species evolve as vapor at high
temperature but they may condense in the cooler regions of the mold. For example, methylene
diphenyl isocyanate (used as a reactant in the binder [40]) was found in the effluent in the
shakeout operation.

37
Thermal decomposition of phenol-formaldehyde resins consists of breaking the bonds between
aromatic rings and methylene bridges. Phenol and methylphenols are then created from formed
radicals. Bisphenols, trisphenols, etc., and their methyl derivatives are also produced. The other
volatile products are components with three condensed rings: fluorene, dibenzofuran, xanthene,
anthracene and phenanthrene. Hetper and Sobera [41] recorded twenty major compounds that
volatilize from Novolac resin at 770C within 1 second. High boiling components were benzene,
toluene, o-xylene, p-xylene, phenol, o-cresol, p-cresol, 2,6- and 2,4-dimethylphenol, 2,4,6-
trimethylphenol, diphenylmethane, dibenzofuran, fluorene, 10H-xanthene, 1-methylfluorene,
anthracene and phenanthrene, methyl-2-benzylphenols, hydroxybenzylphenols and their mono-
and dimethyl derivatives, bis(hydroxybenzyl)phenols and their mono- and dimethyl derivatives.
The majority of volatile organics from the Novolac resin containing 15% hexamethylene-
tetramine evolve between 150-195C and 450-650C [42]. The volume of volatilized
components (benzene, toluene and cresols) ranges from 0.3 to 1.5% by weight. The source of
these compounds is suspected to be core washing process before use. Table 28 lists the
concentration of the major volatile components emitted from the Novolac resin at 980C. These
conditions closely resemble the pouring environment. Quantities of emissions of benzene,
toluene, phenol, and naphthalene are displayed as a function of temperature in Fig. 7. These are
all air pollutants and will not be present to a large degree on the waste sand, but rather will be
captured in the core machine emission controls.
The amount of volatiles produced below 500C is rather insignificant compared to the volumes
released at 750 and 980C. Fixed gases are the major resin degradation products at all pyrolysis
temperatures. Except for these permanent gases, phenol is the major pyrolysis product. At 750C
benzene, toluene and naphthalene begin to evolve. At 980C phenol is no longer the major
component. Benzene becomes the major product and the amount of naphthalene increases
approximately by a factor of 20.
Patterson indicated that oxidizing conditions at the mold-metal interface (because of the evolving
gases) can promote penetration of molten metal into the core sand [43]. The latter process may
cause an increase in leachability of metals from the used sand.

38
Figure 7. Thermal degradation products of Novolac resins versus temperature
IMPLICATIONS AND CONCLUSIONS
Possible utilization of foundry waste products in Massachusetts is regulated under Beneficial Use
Determinations by the Department of Environmental Protection (310 CMR 19). The detailed
chemical characterization of foundry waste materials is necessary as part of the application
process. On the other hand, further development of the BUD regulatory protocols can only be
based on collected information regarding typical characteristics of spent foundry sand. With
these objectives, the statistical data collected from foundries in several U.S. states and other
countries has been summarized and analyzed.
Quantities of twelve heavy metals and a number of organic compounds extracted from foundry
sand waste with the Toxicity Characteristic Leaching Procedure (TCLP) suggests that spent
foundry sand can be beneficially used posing no environmental or human health risk. Only iron
and manganese, not regulated under RCRA, showed increased leaching potential in a number of
occasions. This is provided that spent sand is separated from other waste components such as
unprocessed sand, baghouse dust, slag, or sludge, which may be hazardous at some instances.
Some of these waste streams have highly variable levels of toxic constituents. Therefore, mixed
foundry wastes are complex and must be evaluated with a high degree of scrutiny. For mixed
foundry wastes, lead, chromium, copper and zinc could also be of a concern in leaded brass and
bronze foundries. On the other hand, inherent variability of chemicals in wastes ceases to be a
P
e
a
k

a
r
e
a
, C

39
cause for concern when their concentrations are anyway well below drinking water standards. No
meaningful correlation between leaching metal concentrations and bulk element content was
generally observed.
Several organic compounds are present in most spent core sands though at low levels. Acetone,
diethylbenzenes, p-ethyltoluene, isopropylbenzene, 1,2,4-trimethylbenzene, both 1- and 2-
methylnaphthalene, dimethylnaphthalene isomers, naphthalene and all three isomeric forms of
xylene are present at low concentrations. Compounds from the toxicity characteristic list
(benzene, 1,1,1-trichloroethane, phenol, tetrachloroethene, toluene, and cresols) were detected in
the foundry waste leachates at concentrations well below the regulatory toxicity limits, and
generally below the drinking water standards. Benzene and trichloroethane were found at
concentrations around the drinking water limits.
It is reasonable to expect organic compounds to be present in virgin mixtures of foundry sand
and binders, given the initial composition of binders and resins. The presence of phenol,
polybenzylic ether, benzenesulfonic acid and formaldehyde in commonly used binder systems is
of special concern. These compounds possibly give rise to other compounds formed in spent
sand but not initially found in virgin sand. Many of these are aromatic compounds, and should be
evaluated in risk assessment studies to determine if their concentrations pose any impact to
human health and the environment.
Additional efforts should be exercised to fully understand the complete extent of compounds
present in foundry sand and their potential or actual deleterious effects to human health and the
environment.
Despite the fact that a few semi-volatile organic compounds were found in the laboratory sand
leach tests, none of the 45000 compounds in the library were measured above the instrumental
detection limit of 1 g/l in the ground water samples collected around foundry landfills in
Wisconsin. Several volatile compounds were tentatively identified in ground water at trace levels
below the instrumental quantitation limits which are below the maximum concentration limits for
drinking water. Of the compounds measured in ground water, naphthalene, tetrachloroethane,
and 1,1,1-trichloroethane were also detected in laboratory leachate tests, suggesting that they
may originate from foundry sand waste.
The absence of detectable quantities of organic compounds in ground water around foundry
landfills appears to be caused by low levels of organic content leached from most foundry
wastes. Both the mixed waste samples and isolated foundry sand waste streams could not be
considered hazardous by characteristics based on the release of organic contaminants. However,
any effort to reduce the organics should focus on the phenolic urethane and the phenolic
isocyanate binder systems, since they contribute the most to organic compound content.
Leaching of chemicals from spent molding sand and technical requirements for beneficial use
applications do not restrict the utilization of foundry sand wastes. Keeping such utilization
practices in mind, any mixing of spent sand with the other foundry waste streams (baghouse
dust, slag and sludge) or unused virgin sand-binder blends should be avoided. Furthermore,
metal reclaimers can use separated baghouse dusts as feedstocks and recycle them into raw
materials. A better understanding of the chemical reactions at the mold-metal interface may lead

40
to process substitutions, mold additives or binder formulations that can result in environmentally
safer processes and products.
FUTURE WORK
There is a need to study a broader group of foundry sand wastes in order to quantify and
categorize potential risks of spent sand in each. Leachability characterization of the other
foundry waste streams (baghouse and shotblast dusts, fines, slags, and sludges) should be
investigated. Additional attention should be paid to specific molecular forms of metals present in
wastes. Furthermore, a comparative study of sensitivity of foundry waste samples to different
leaching procedures (SPLP versus TCLP) is needed to evaluate dependence of leaching
potential of foundry by-products on different fate scenarios (disposal at foundry monofills,
disposal at municipal landfills, various beneficial uses followed by disposal at municipal
landfills, and etc.). Exposure analysis and risk assessment of specific use practices must be
completed on known contaminants, commonly measured in mixed waste sands.

41
Table 1. REGULATED AND RECOMMENDED MAXIMUM CONTAMINANT LEVELS, mg/l
Standards
Drinking Water
a
Ground Water
b
Toxicity Limits
c
European Landfill
d
Method: Total Analysis (Digestion) TCLP / EPA TCLP / EPA DIN 38414 S4 / TVA
As 0.05 0.05 5.0 0.1
Ba 2.0 1.0 100.0 5.0
Be 0.004
Cd 0.005 0.01 1.0 0.1
Cr 0.1 0.05 5.0 CrIII: 2.0, CrIV: 0.1
Cu 1.3* 0.5
Hg 0.002 0.002 0.2 0.01
Pb 0.015* 0.05 5.0 1.0
Sb 0.006
Se 0.05 0.01 1.0
Tl
U
.
S
.

P
r
i
m
a
r
y

R
e
g
u
l
a
t
i
o
n
s
0.002
Ag 0.1 0.05 5.0
Al 0.05-0.2 10
Cu 1.0 0.5
Fe 0.3
Mn 0.05
Zn
U
.
S
.

S
e
c
o
n
d
a
r
y

R
e
g
.
5 10
Ni ** 2.0
Co 0.5
Sn 2.0
* Action level which triggers treatment of water system if exceeded in more than 10% tap water
samples.
** Ni is mandatory for monitoring along with other contaminants tabulated by the National
Primary Drinking Water Regulations, but no maximum contaminant level is currently specified
by EPA. MA DEP defines 0.1mg/l of Ni as the concentration in drinking water at or below which,
adverse, non-cancer health effects are unlikely to occur after chronic (lifetime) exposure. At this
time MA DEP only indicates a potential need for further action to be decided.
a
Code of Federal Regulations. Title 40. Parts 141, 143. Washington. US Government Printing
Office.
b
Code of Federal Regulations. Title 40. Parts 264. Washington. US Government Printing
Office.
c
Code of Federal Regulations. Title 40. Parts 261. Washington. US Government Printing
Office.
d
Schweizerische Technische Verordnung ber Abflle (TVA). 10.12.1990, SR 814015, Bern
1990.

42
Table 2. REGULATORY LIMITS AND GUIDELINES FOR ORGANIC CHEMICALS, g/l
Standards
Drinking Water
a, aa
Ground Water
b
Toxicity Limits
c
Total Analysis (Digestion) TCLP TCLP Method:
Acrylamide 79-06-1 (0.5)* 5000
Alachlor 15972-60-8 2 100000
Atrazine 1912-24-9 3
Benzene 71-43-2 5 500
Benzo(a)pyrene 50-32-8 0.2
Carbofuran 1563-66-2 40
Carbon tetrachloride 56-23-5 5 500
Chlordane 57-74-9 2 30
Chlorobenzene 108-90-7 100 100000
2,4-D acid 94-75-7 70 100 10000
Dalapon 75-99-0 200
1,2-Dibromo-3-
chloropropane (DBCP)
96-12-8 0.2
o-Dichlorobenzene 95-50-1 600
p-Dichlorobenzene 106-46-7 75 7500
1,2-Dichloroethane 75-34-3 5 500
1,1-Dichloroethylene 75-35-4 7 700
cis-1, 2-Dichloroethylene 156-59-2 70
trans-1,2-
Dichloroethylene
156-60-5 100
Dichloromethane 75-09-2 5
1,2-Dichloropropane 78-87-5 5
Di(2-ethylhexyl)adipate 103-23-3 400
Di(2-ethylhexyl)phthalate 117-81-7 6
Dinoseb 88-85-7 7
Dioxin (2,3,7,8-TCDD) 1746-01-6 0.00003
Diquat 85-00-7 20
Endothall 145-73-3 100
Endrin 72-20-8 2 0.2 20
Epichlorohydrin 106-89-8 (2)*
Ethylbenzene 100-41-4 700
Ethylene dibromide 106-93-4 0.05
Glyphosate 1071-53-6 700
Heptachlor 76-44-8 0.4
Heptachlor epoxide 1024-57-3 0.2
}

8
Hexachlorobenzene 118-74-1 1 130
Hexachloropentadiene 77-47-4 50 500
Lindane 58-89-9 0.2 4 400
Methoxychlor 72-43-5 40 100 10000
Oxamyl (Vydate) 23135-22-0 200
Polychlorinated biphenyls
(PCBs)
1336-36-3 0.5
Pentachlorophenol 87-86-5 1 100000
continued on next page
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Picloram 1918-02-1 500
Simazine 122-34-9 4
Styrene 100-42-5 100
Tetrachloroethylene 127-18-4 5 700
Toluene 108-88-3 1000
Trihalomethanes, total
(TTHMs)
100
Toxaphene 8001-35-2 3 5 500
2,4,5-TP (Silvex) 93-72-1 50 10 1000
1,2,4-Trichlorobenzene 120-82-1 70
1,1,1-Trichloroethane 71-55-6 200
1,1,2-Trichloroethane 79-00-5 5
Trichloroethylene 79-01-6 5 500
Vinyl chloride 75-01-4 2 200
Xylenes, total 1330-20-7 10000
Foaming agents Secondary 500
Acetone 67-64-1 3000
Aldicarb 116-06-3 3
Aldicarb sulfone 1646-88-4 2
Aldicarb sulfoxide 1646-87-3 4
Bromomethane 74-83-9 10
Chloroform 67-66-3 5 6000
o-Cresol 95-48-7 200000
m-Cresol 108-39-4 200000
p-Cresol 106-44-5 200000
Cresols, total 1319-77-3 200000
Dichlorodifluoromethane 75-71-8 1400
1,1-Dichloroethane 75-34-3 70
1,3-Dichloropropene 10061-01-5 0.5
2,4 Dinitrotoluene
(2,4-DNT)
121-14-2 130
1,4-Dioxane 123-91-1 50
Ethylene glycol 107-21-1 1400
Hexachloroethane 67-72-1 3000
Methyl ethyl ketone 78-93-3 350 200000
Methyl isobutyl ketone 108-10-1 350
Methyl tertiary butyl ether 1634-04-4 70
Metolachlor 51218-45-2 100
Nitrobenzene 98-95-3 2000
Pyridine 110-86-1 5000
Tetrahydrofuran 109-99-9 1300
2,4,5-Trichlorophenol 95-95-4 400000
2,4,6-Trichlorophenol 88-06-2 2000
Trichlorotrifluoroethane
(Freon 113)
76-13-1 210000
* Action level which triggers treatment of water system if exceeded in more than 10% tap water samples.
aa
Guide to the Regulation of Toxic Chemicals in Massachusetts Waters. Office of Research and
Standards, MA DEP, Boston, 1990.
See the other references under Table 1.
Table 2. continued
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Table 3. ALLOWABLE CONTAMINANT LEVELS FOR REUSE AND DISPOSAL OF
CONTAMINATED SOIL AT MASSACHUSETTS LANDFILLS
Reuse Levels (mg/kg)
a
CONTAMINANT
Lined Landfills Unlined Landfill
Total Arsenic 40 40
Total Cadmium 80 30
Total Chromium 1000 1000
Total Lead 2000 1000
Total Mercury 10 10
Total Petroleum Hydrocarbons (TPH) 5000 2500
Total Polychlorinated Biphenyls (PCB)
b
< 2 < 2
Total SVOC
c
100 100
Total VOC
d
10 4
Electric Conductivity
e
(mho/cm)
8000 mho/cm 4000 mho/cm
Listed or Characteristic
Hazardous Waste (TCLP)
f
NONE NONE
Notes:
a
The reuse levels are expressed as total levels in mg/kg and apply to reuse of soil as daily cover, intermediate cover,
and pre-capping contour material at lined landfills and unlined landfills.
b
Total concentrations of polychlorinated biphenyls EPA Method 8080.
c
Total concentrations of compounds listed in EPA Method 8270.
d
Total concentration of compounds listed in EPA Method 8260.
e
For soil which may be expected to contain elevated NaCl.
f
TCLP testing shall be performed for metals or organic compounds when the total concentrations in the soil are above
the theoretical levels at which the TCLP criteria may be exceeded. For guidance parties shall consult United States
Environmental Protection Agency, Memorandum #36, "Notes on RCRA Methods and QA Activities", pp. 19-21, Gail
Hanson, January 12, 1993.
[Please note that the methods specified in footnotes d, e, and f indicate the universe of chemicals to be added in
calculating the total concentrations for these classes of contaminants. Section 5.0 of the Policy # COMM-97-001 provides
guidance for determining which specific chemicals must be considered chemicals of concern (e.g., contaminants) within
the soil. The Policy does not specify the analytical test methods to be used to quantify the specific contaminants. Readers
can consult 310 CMR 40.0017 Environmental Sample Collection and Analysis, 310 CMR 30.110 Criteria, Procedures for
Determining Which Wastes are to be Regulated as Hazardous Waste or Non-Hazardous Waste and 310 CMR 30.151
Representative Sampling Methods for additional information which may be applicable to the selection of appropriate
sampling and analytical methods.]

45
Table 4. PROPOSED ILLINOIS TIER SYSTEM FOR RANKING WASTE
Waste type Chemical
Waste
Low Risk Potentially
Usable
Beneficially
Usable
Hazard level Highest Lowest
Parameter, mg/l
Maximum allowed concentrations: Primary standards
Arsenic * 0.25 0.05 0.05
Barium * 5.0 1.0 1.0
Cadmium * 0.05 0.01 0.01
Chromium * 0.25 0.05 0.05
Lead * 0.25 0.05 0.05
Nitrate * 50 10 10
Selenium * 0.05 0.01 0.01
Silver * 20 4 4
Maximum allowed concentrations: Secondary standards
Chloride * 500 250 250
Manganese * 3.75 0.75 0.15
Copper * 10 5 5
Iron * 15 5 5
Sulfates * 800 400 400
Zinc * 50 10 5
Total Dissolved
Solids
* 5000 1200 1200
* Wastes leaching above Low Risk levels would be considered Chemical Wastes and
handled under disposal requirements of a Chemical Waste.

46
Table 5. INDIANA TIER SYSTEM FOR RANKING WASTE
Waste type I II III IV
Hazard level Highest Lowest
Parameter, mg/l Maximum allowed concentrations: EP Toxicity Test
Arsenic 5.0 1.25 0.5 0.05
Barium 100 25 10 1
Cadmium 1.0 0.25 0.1 0.01
Chromium 5.0 1.25 0.5 0.05
Lead 5.0 1.25 0.5 0.05
Mercury 0.2 0.05 0.02 0.002
Selenium 1.0 0.25 0.1 0.01
Silver 5.0 1.25 0.5 0.05
Maximum allowed concentrations: Leaching Method Test
Barium * 25 10 1
Boron * 50 20 2
Chlorides * 6.250 2.500 250
Copper * 6.25 2.5 .25
Cyanide, total * 5 2 .2
Fluoride * 35 14 1.4
Iron * * 15 1.5
Manganese * * .5 .05
Nickel * 5 2 .2
Phenols * 7.5 3 .3
Sodium * 6.250 2.500 250
Sulfate * 6.250 2.500 250
Sulfide, total * 12.5 5 1
Total Dissolved
Solids
* 12.500 5.000 500
Zinc * 62.5 25 2.5
Acceptable range (standard units)
pH * 4-11 5-10 6-9

* Testing is not required for these parameters.

47
Table 6. ANALYSIS OF SEMI-VOLATILE ORGANIC COMPOUNDS BY TCLP

48
Table 7. ANALYSIS OF VOLATILE ORGANIC COMPOUNDS BY TCLP

49
Table 8. METALLIC CONTAMINANTS ANALYTICAL METHODS
Environmental Samples Solid Waste Leachates
Method
Analyte
Sample Preparation
EPA ASTM EPA (SW-846)
As 3005A, 3010A, 3015,
3050A, 3051
200.7,
200.8, 200.9
D2972-93C,
D2972-93B
6010A, 6020, 7060A,
7061A, 7062
Ba 3005A, 3010A, 3015,
3050A, 3051
200.7, 200.8 6010A, 6020, 7080A,
7081
Be 3005A, 3010A, 3015,
3020A, 3040, 3050A,
3051
200.7,
200.8, 200.9
D3645-93B 6010A, 6020, 7090,
7091
Cd 3005A, 3010A, 3015,
3020A, 3040, 3050A,
3051
200.7,
200.8, 200.9
6010A, 6020, 7130,
7131A
Cr 3005A, 3010A, 3015,
3020A, 3040, 3050A,
3051
200.7,
200.8, 200.9
6010A, 6020, 7190,
7191, 7195, 7196A,
7197, 7198
Cu 3005A, 3010A, 3015,
3040, 3050A, 3051
200.7,
200.8, 200.9
D1688-95C,
D1688-95A
6010A, 6020, 7210,
7211
Hg 3051 245.1,
245.2, 200.8
D3223-91 7470A, 7471A
Pb 3005A, 3010A, 3015,
3040, 3050A, 3051
200.8, 200.9 D3559-95D 6010A, 6020, 7420,
7421
Sb 3005A, 3015, 3040,
3051
200.8, 200.9 D3697-92 6010A, 6020, 7040,
7041, 7062
Se 3005A, 3010A, 3015,
3050A, 3051
200.8, 200.9 D3859-93A,
D3859-93B
6010A, 7740, 7741A,
7742
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3005A, 3010A, 3015,
3020A, 3050A, 3051
200.8, 200.9 6010A, 6020, 7840,
7841
Ag 3005A, 3015, 3050A,
3051
200.7,
200.8, 200.9
6010A, 6020, 7760A,
7761
Al 3005A, 3010A, 3015,
3050A, 3051
200.7,
200.8, 200.9
6010A, 6020, 7020
Fe 3005A, 3010A, 3015,
3040, 3050A, 3051
200.7, 200.9 6010A, 7380, 7381
Mn 3005A, 3010A, 3015,
3040, 3050A, 3051
200.7,
200.8, 200.9
6010A, 6020, 7460,
7461
Zn
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3005A, 3010A, 3015,
3050A, 3051
200.7, 200.8 6010A, 6020, 7950,
7951
Na 3005A, 3010A, 3015,
3050A, 3051
200.7 D4191-97,
D6071-96
6010A, 7770
Ni
*
*
3005A, 3010A, 3015,
3040, 3050A, 3051
200.7,
200.8, 200.9
6010A, 6020, 7520
** Mandatory for monitoring, but no maximum contaminant level is currently specified by EPA.

50
Table 9. DETECTION LIMITS FOR METALLIC CONTAMINANTS (30 CMR 22.06)
Contaminant MCL(mg/l) Methodology Detection Limit (mg/l)
Antimony 0.006 Atomic Absorption; furnace
ICP-Mass Spectrometry
Hydride-Atomic absorption
0.003
0.0008
a
0.0004
0.001
Arsenic 0.05 Inductively Coupled Plasma-AES 0.05
Barium 2 Atomic Absorption; furnace technique
Atomic Absorption; direct aspiration
Inductively Coupled Plasma-AES
0.002
0.1
0.002 (0.001)
Beryllium 0.004 Atomic Absorption; furnace
Atomic Absorption; platform
Inductively Coupled Plasma-AES
b
ICP-Mass Spectrometry
0.0002
0.00002
0.0003
0.0003
Cadmium 0.005 Atomic Absorption; furnace technique
Inductively Coupled Plasma-AES
c
0.0001
0.001
Chromium 0.1 Atomic Absorption; furnace technique
Inductively Coupled Plasma-AES
0.001
0.007 (0.001)
c
Mercury 0.002 Manual Cold Vapor Technique
Automated Cold Vapor Technique
0.0002
0.0002
Nickel 0.01
d
Atomic Absorption; furnace
Atomic Absorption: Platform
Inductively Coupled Plasma-AES
b
ICP-Mass Spectrometry
0.001
0.0006
0.005
0.0005
Selenium 0.05 Atomic Absorption; furnace
Atomic Absorption: gaseous hydride
0.002
0.002
Sodium 310 CMR
22.06A
e
Inductively Coupled Plasma-AES
Atomic Absorption; direct aspiration
0.03
Thallium 0.002 Atomic Absorption; furnace
Atomic Absorption; platform
ICP-Mass Spectrometry
0.001
0.0007
c
0.0003
a
Lower MDLs are reported using stabilized temperature graphite furnace atomic absorption.
b
Using a 2x preconcentration step as noted in Method 200.7. Lower MDL may be achieved
when using a 4x preconcentration.
c
Using concentration technique in Appendix A to EPA Method 200.7.
d
Maximum concentration limit for nickel is no longer stipulated.
e
All public water systems shall monitor for the determination of sodium concentration levels. No
maximum contamination level is currently specified, but the guideline of 20 mg/l is issued by
the Office of Research and Standards, MA DEP (1990).

51
Table 10. EPA ANALYTICAL METHODS (SW-846) FOR ORGANIC CONTAMINANTS
Analyte Name CAS No. Prep.M.* Analyte Detection Methods
Acetone 67-64-1 5041 8240B, 8260A, 8315
Acrylamide
(2-Propeneamide)
79-06-1 8032, 8316
Alachlor 15972-60-8 8081, 8082A
Aldicarb sulfone 1646-88-4 8318
Aldicarb (Temik) 116-06-3 8318
Aroclor-1242(PCB-1242) 53469-21-9 8080A, 8081, 8082A, 8250A, 8270B
Aroclor-1248(PCB-1248) 12672-29-6 8080A, 8081, 8082A, 8250A, 8270B
Aroclor-1254(PCB-1254) 11097-69-1 8080A, 8081, 8082A, 8250A, 8270B
Aroclor-1260(PCB-1260) 11096-82-5 8080A, 8081, 8082A, 8250A, 8270B
Atrazine 1912-24-9 8141A
Benz(a)anthracene
(Benzo(a)anthracene)
56-55-3 3640A,
3650A
8100, 8250A, 8270B, 8310, 8410
Benzene 71-43-2 5041 8020A, 8021A, 8240B, 8260A
Benzo(a)pyrene 50-32-8 3640A,
3650A
8100, 8250A, 8270B, 8275, 8310, 8410
Benzoic acid 65-85-0 3640A 8250A, 8270B, 8410
Bis(2-ethylhexyl)
phthalate
(Diethylhexylphthalate)
117-81-7 3640A 8060, 8061, 8250A, 8270B, 8410
Bromomethane
(Methyl bromide)
74-83-9 5041 8010B, 8021A, 8240B, 8260A
2-Butanone (MEK,
Methyl ethyl ketone)
78-93-3 8015A, 8240B, 8260A
sec-Butylbenzene 135-98-8 8021A, 8260A
tert-Butylbenzene 98-06-6 8021A, 8260A
Carbofuran (Furadan) 1563-66-2 8270B, 8318
Carbon tetrachloride
(Tetrachloromethane)
56-23-5 5041 8010B, 8021A, 8240B, 8260A
Chlordane 57-74-9 3650A 8270B
Chlorobenzene 108-90-7 5041 8010B, 8020A, 8021A, 8240B, 8260A
Chloroform
(Trichloromethane)
67-66-3 5041 8010B, 8021A, 8240B, 8260A
Cresols (Methyl phenols) 1319-77-3 3650A 8040A
2,4-D (Dichloro
phenoxyacetic acid)
94-75-7 3640A,
3650A
8150B, 8151, 8321
Dalapon 75-99-0 8150B, 8151, 8321
1,2-Dibromo-3-chloro
propane (DBCP)
96-12-8 3640A 8010B, 8011, 8021A, 8081, 8240B, 8260A, 8270B
1,2-Dibromoethane (EDB,
Ethylene dibromide)
106-93-4 3640A 8010B, 8011, 8021A, 8240B, 8260A
1,2-Dichlorobenzene
(o-Dichlorobenzene)
95-50-1 3640A 8010B,
8270B,
8020A,
8410
8021A, 8120A, 8121, 8250A, 8260A,
1,4-Dichlorobenzene
(p-Dichlorobenzene)
106-46-7 3640A 8010B,
8270B,
8020A,
8410
8021A, 8120A, 8121, 8250A, 8260A,
Dichlorodifluoromethane 75-71-8 8010B, 8021A, 8240B, 8260A
1,1-Dichloroethane 75-34-3 5041 8010B, 8021A, 8240B, 8260A
continued on next page

52
1,2-Dichloroethane 107-06-2 5041 8010B, 8021A, 8240B, 8260A
cis-1,2-Dichloroethene
(cis-1,2-Dichloro
ethylene)
156-59-2 8021A, 8260A
1,1-Dichloroethene
(1,1-Dichloroethylene)
75-35-4 5041 8010B, 8021A, 8240B, 8260A
trans-1,2-Dichloroethene
(trans-1,2-
Dichloroethylene)
156-60-5 5041 8010B, 8021A, 8240B, 8260A
2,4-Dichlorophenol 120-83-2 3640A 8040A, 8250A, 8270B, 8275, 8410
1,2-Dichloropropane 78-87-5 5041 8010B, 8021A, 8240B, 8260A
1,1-Dichloropropene 563-58-6 8021A, 8260A
Dicyclohexyl phthalate 84-61-7 8061
2,4-Dimethylphenol 105-67-9 3640A,
3650A
8040A, 8250A, 8270B
Di-n-butyl phthalate 84-74-2 3640A 8060, 8061, 8250A, 8270B, 8410
2,4-Dinitrotoluene
(2,4-DNT)
121-14-2 3640A,
3650A
8090, 8250A, 8270B, 8275, 8330, 8410
Dinoseb (DNBP, 2-sec-
Butyl-4,6- dinitrophenol)
88-85-7 3640A 8040A, 8150B, 8151, 8270B, 8321
Di-n-octyl phthalate
(Dioctyl ester)
117-84-0 3640A, 8060, 8061, 8250A, 8270B, 8410
1,4-Dioxane 123-91-1 8240B, 8260A
Endrin 72-20-8 3640A 8080A, 8081, 8250A, 8270B
Epichlorohydrin
(Chloromethyl oxirane)
106-89-8 8010B, 8240B, 8260A
Ethyl acetate 141-78-6 8260A
Ethylbenzene 100-41-4 5041 8020A, 8021A, 8240B, 8260A
Fluoranthene 206-44-0 3640A 8100, 8250A, 8270B, 8310, 8410
2-Fluorobiphenyl 321-60-8 3542 8250A, 8270B
2-Fluorophenol 367-12-4 3542 8250A, 8270B
Formaldehyde 50-00-0 8315
Heptachlor 76-44-8 3640A,
3650A
8080A, 8081, 8250A, 8270B
Heptachlor epoxide 1024-57-3 3640A 8080A, 8081, 8250A, 8270B
Hexachlorobenzene 118-74-1 3640A,
3650A
8081, 8120A, 8121, 8250A, 8270B, 8275, 8410
Hexachlorobutadiene (1,3-
Hexachlorobutadiene)
87-68-3 3640A,
3650A
8021A, 8120A, 8121, 8250A, 8260A, 8270B, 8410
-Hexachlorocyclohexane
( -BHC, Lindane)
58-89-9 3640A 8080A, 8081, 8121, 8250A, 8270B
Hexachlorocyclopentadie
ne
77-47-4 3640A,
3650A
8081, 8120A, 8121, 8250A, 8270B, 8410
Hexachloroethane 67-72-1 3640A,
3650A
8120A, 8121, 8250A, 8260A, 8270B, 8410
Isopropylbenzene 98-82-8 8021A, 8260A
4,4'-Methoxychlor
(Methoxychlor)
72-43-5 3640A 8080A, 8081, 8250A, 8270B
Methylene chloride
(DCM, Dichloromethane)
75-09-2 5041 8010B, 8021A, 8240B, 8260A
2-Methylnaphthalene 91-57-6 3640A 8250A, 8270B, 8410
4-Methyl-2-pentanone
(MIBK, Methyl isobutyl
ketone)
108-10-1 8015A, 8240B, 8260A
continued on next page
Table 10. continued

53
2-Methylphenol
(o-Cresol, 2-Cresol)
95-48-7 3640A 8041, 8250A, 8270B, 8410
3-Methylphenol
(m-Cresol, 3-Cresol)
108-39-4 3640A 8041, 8270B
4-Methylphenol
(p-Cresol, 4-Cresol)
106-44-5 3640A 8041, 8250A, 8270B, 8275, 8410
Naphthalene 91-20-3 3640A,
3650A
8021A,
8410
8100, 8250A, 8260A, 8270B, 8275, 8310,
Nitrobenzene (NB) 98-95-3 3640A,
3650A
8090, 8250A, 8260A, 8270B, 8330, 8410
Pentachlorophenol (PCP) 87-86-5 3640A,
3650A
8040A, 8041, 8151, 8250A, 8270B, 8410, 4010
Phenanthrene 85-01-8 3640A 8100, 8250A, 8270B, 8275, 8310, 8410
Phenol 108-95-2 3640A,
3650A
8040A, 8041, 8250A, 8270B, 8410
Phenolics -- 9065, 9066, 9067
Picloram 1918-02-1 8151
Pyrene 129-00-0 3640A,
3650A
8100, 8250A, 8270B, 8275, 8310, 8410
Pyridine 110-86-1 3650A 8240B, 8260A, 8270B
Simazine 122-34-9 8141A
Styrene 100-42-5 5041 8021A, 8240B, 8260A
2,4,5-TP (2,4,5-Trichloro
phenoxy--proprionic
acid, Silvex)
93-72-1 3640A,
3650A
8150B, 8151, 8321
2,3,7,8-Tetrachloro
dibenzo-p-dioxin
(2,3,7,8-TCDD)
1746-01-6 8280, 8290
1,1,1,2-Tetrachloroethane 630-20-6 8010B, 8021A, 8240B, 8260A
Tetrachloroethene
(Tetrachloroethylene)
127-18-4 5041 8010B, 8021A, 8240B, 8260A
Toluene (Methyl benzene) 108-88-3 5041 8020A, 8021A, 8240B, 8260A
Toxaphene 8001-35-2 3650A 8080A, 8081, 8250A, 8270B
2,4,6-Tribromophenol 118-79-6 3542 8250A, 8270B
1,2,4-Trichlorobenzene 120-82-1 3640A 8021A, 8120A, 8121, 8250A, 8260A, 8270B, 8410
1,1,1-Trichloroethane 71-55-6 5041 8010B, 8021A, 8240B, 8260A
1,1,2-Trichloroethane 79-00-5 5041 8010B, 8021A, 8240B, 8260A
Trichloroethene
(Trichloroethylene)
79-01-6 5041 8010B, 8021A, 8240B, 8260A
Trichlorofluoromethane 75-69-4 5041 8010B, 8021A, 8240B, 8260A
2,4,5-Trichlorophenol 95-95-4 3640A 8250A, 8270B, 8410,
2,4,6-Trichlorophenol 88-06-2 3640A 8250A, 8270B, 8410
1,2,4-Trimethylbenzene 95-63-6 8021A, 8260A
1,3,5-Trimethylbenzene 108-67-8 8021A, 8260A
Vinyl chloride
(Chloroethene)
75-01-4 5041 8010B, 8021A, 8240B, 8260A
m-Xylene 108-38-3 8021A, 8260A
o-Xylene 95-47-6 8021A, 8260A
p-Xylene 106-42-3 8021A, 8260A
Xylenes, total 1330-20-7 5041 8020A, 8240B
* Sample Preparation Methods (3542, 5041) and Cleanup Methods (3640A, 3650A).
Table 10. continued

54
Table 11. PHYSICAL PROPERTIES OF FOUNDRY SANDS
Code Description
Bulk specific
gravity (dried)
Absorption
percent
Fineness
modulus
A Siliceous river-run sand (reference) 2.56 0.7 2.62
B
Thermally reclaimed chemically-
bonded sand
2.68 0.2 0.81
C
Mechanically reclaimed chemically-
bonded sand
2.69 0.3 1.10
D Spent clay-bonded sand 2.30 4.2 0.66
E Spent clay-bonded sand 2.50 1.1 1.75
F Spent clay-bonded sand 2.48 2.3 1.05
Table 12. GEOTECHNICAL CHARACTERISTICS OF FOUNDRY SAND WASTES
Weathered waste
foundry sand
Fresh waste foundry
sand
Specific gravity, g/cm
3
2.53 2.46
Percentage of fines passing 200 m sieve, % 22 40
Clay particles with size below 0.005 mm, % 9
Optimum moisture content in a standard
Proctor compaction test, %
27.1 23.1
Cohesion intercept (drained), kN/m
2
6.9 13.1 13.8 15.2
Internal friction angle (drained) 35 38 33 39
Percentage of swelling, % 0 0.9
Hydraulic conductivity, 10
-8
m/sec 1.2

55
Table 13. CHEMICAL ANALYSIS OF TYPICAL FOUNDRY SANDS
Compound Chelford WS (50) Silica Sand (%) Manfield Red Sand (%)
SiO
2
97.91 78.2
Al
2
O
3
1.13
Fe
2
O
3
0.50
10.12
TiO
2
0.04 -
CaO 0.11 2.4
MgO 0.02 1.8
K
2
O 0.65 3.1
Na
2
O 0.07 0.2
LOI* 0.21 4.1
*Loss on Ignition
Table 14. SPENT FOUNDRY SAND CHEMICAL OXIDE COMPOSITION
Constituent Percentage (%)
SiO
2
87.91
Al
2
O
3
4.70
Fe
2
O
3
0.94
CaO 0.14
MgO 0.30
SO
3
0.09
Na
2
O 0.19
K
2
O 0.25
TiO
2
0.15
P
2
O
5
0.00
Mn
2
O
3
0.02
SrO 0.03
LOI* 5.15
*Loss on Ignition

56
Table 15. CONVENTIONAL SAND BINDER SYSTEMS AND PROCESSES
Thermosetting Processes Self-Setting Processes Gas-Cured Processes
1. Shell process:
Novolac ("shell") resin
Phenol Formaldehyde
2. Hot Box processes:
Urea Formaldehyde
Phenol Formaldehyde
a. Novolac
b. Resole
Furan Modified
a. UF + FA
b. PF + FA
c. PF + UF
3. Warm Box process:
Furan (furfuryl alcohol)
a. free formaldehyde
b. UF or PF
4. Core Oil process:
Oils
1. Acid No-Bake processes:
Furan no-bake
a. H
3
PO
4
b. TSA
c. BSA
Phenol Formaldehyde
a. TSA
b. BSA
c. xelenesulfonic acid
2. Ester Cured processes:
Phenolic Resole
a. free phenol
b. free formaldehyde
3. Urethane No-Bake (Amine
Cured) processes:
Alkyd Urethane
a. vegetable oil
b. polyisocyanate
Phenolic Urethane
a. pyridine derivative
b. polyphenyl PIC
Polyol Urethane
1. Free Radical Curing:
Vinyl Urethane Oligomer
a. N
2
+ SO
2
2. Cold Box processes:
Phenolic Urethane
Polymeric Isocyanate
a. TEA vapor + air
b. DMEA vapor + air
Furan + SO
2
a. methyl alcohol
b. organic peroxides
Acrylic/Epoxy + SO
2
a. hydroperoxide
Phenolic Resole + Ester
a. glycol ethers
b. methylformate vapor
1. Clay Based processes:
Bentonites
Fire Clays
Kaolin Clay
1. Ester Cured processes:
Sodium Silicate
a. glycerol diacetate
b. EGDA
c. glycerol triacetate
Ethyl Silicate
2. Cement Bonding process:
Hydraulic Cements
3. Oxide Cured process:
Phosphates
a.aluminum phosphate
b.magnesium oxide
1. CO
2
Silicate process:
Sodium Silicate
(SiO
2
:Na
2
O) + CO
2
Notes: FA = furfuryl alcohol PIC = polyisocyanate
UF = urea formaldehyde TSA = toluenesulfonic acid
PF = phenol formaldehyde BSA = benzenesulfonic acid
TEA = triethylamine EGDA = ethylene glycol diacetate
DMEA = dimethylethylamine
(TSA+BSA)
{
{
I
n
o
r
g
a
n
i
c


B
i
n
d
e
r
s
O
r
g
a
n
i
c


B
i
n
d
e
r
s
57
Table 16. LEACHABILITY OF METALS FROM FOUNDRY SAND WASTE
Primary Contaminants (mg/l) Secondary Contaminants (mg/l)
** Leaching
Method
As Ba Cd Cr Hg Pb Se Ag Cu Fe Mn Zn Ni
R
e
f
.
Drinking Water Maximum Contaminant Level Total Elem 0.05 2.0 0.005 0.01 0.002 0.015* 0.05 0.1 1.0 0.3 0.05 5.0 7
Toxicity Characteristic Level TCLP 5.0 100 1.0 5.0 0.2 5.0 1.0 5.0 16
Highway embankment constructed with Indiana ferrous
foundry waste sand. Maximum measured values.
Field
Leachate
0.054 0.85 0.09 11
Median Wisconsin field leachate values, averaged over
six ferrous foundry mixed waste landfills.
Field
Leachate
<.005 <0.46 <.001 <0.02 <.005 <0.02 <0.13 <.002 0.02 0.54 0.27 0.15 31
Typical Wisconsin mixed municipal solid waste
landfill. Maximum values.
Field
Leachate
0.07 1 1.1 0.3 54 1.7 50
Spent molding sands. Average over 52 Penn foundries. TCLP 0.06 0.4 0.03 0.1 0.005 0.3 0.08 <.049 0.25 70 0.9 2.2 0.2 37
Spent sand waste. Average over a cluster of 28 out of
33 Pennsylvania ferrous and non-ferrous foundries.
TCLP,
ASTM D346
0.006 0.33 0.03 0.1 .0005 0.25 0.03 0.06 0.2 28 0.35 0.4 0.1 29
Mixed molding waste (sand, binder, dust, sludge).
Gostyn foundry, Poland.
TCLP
EP

0.1

0.25

1
0.2
13
31
1.6
2.2
1.4
0.9
7

44
Wisconsin brass foundry sands + dusts. Average value. TCLP+EP 11 36
Wisconsin brass foundry sands + dusts, chemically
treated to convert metals into non-leaching forms.
TCLP+EP 0.018 0.18 36
Wisconsin ferrous foundry waste sand. Average of two. EP 0.04 1.1 31
Wisconsin typical ferrous foundry mixed waste landfill. EP <.005 <0.46 <.001 <.003 <0.01 <0.13 <.002 <.002 66 2.9 0.4 31
Molding sand (6% western bentonite, 7% sea-coal)
subjected to process temperature. Maximum values.
3 Leaching
Cycles, H
2
O
<0.75 <1.1 1.1 15 <0.75 1.2 45
Brown-black furan-bonded sand waste + dust (1:1), air
dried. Dessau foundry, Germany.
DIN 38414 S4
H
2
O pH=7.5
0.01 <0.1 0.07 <.001 0.6 0.25 0.5 0.3 46
Black-brown silicate waterglass-bonded fine sand
waste, air dried. Magdeburg foundry, Germany.
DIN 38414 S4
H
2
O,pH=10.1
0.13 <0.1 0.08 <.001 0.6 0.5 1.1 0.6 46
Brown-black furan-bonded sand waste + dust (1:1), air
dried. Dessau foundry, Germany.
DIN 38414 S7
Aqua Regia
0.45 0.3 69 0.02 11 27 33 6 46
Black-brown silicate waterglass-bonded fine sand
waste, air dried. Magdeburg foundry, Germany.
DIN 38414 S7
Aqua Regia
0.67 0.3 79 <.002 4.6 8.5 17 16 46
Notes: TCLP concentration value exceeding the RCRA regulated level is given in bold. See other notes under Table 17.
58
Table 17. BULK CONTENT OF METALS IN FOUNDRY SAND WASTE, REFERENCE SANDS AND SOILS
Primary Contaminants (mg/kg) Secondary Contaminants (mg/kg)
**

Method
As Ba Cd Cr Hg Pb Se Ag Cu Fe Mn Zn Ni
R
e
f
.
Drinking Water Maximum Contaminant Level Total Elem 0.05 2.0 0.005 0.01 0.002 0.015* 0.05 0.1 1.0 0.3 0.05 5.0 7
Toxicity Characteristic Level, mg/l TCLP 5.0 100 1.0 5.0 0.2 5.0 1.0 5.0 16
Brown-black furan-bonded sand waste + dust (1:1), air
dried. Dessau foundry, Germany.
Total Elem
X-ray fluo
<2 <2 284 <2 14 27 33 5 46
Black-brown silicate waterglass-bonded fine sand
waste, air dried. Magdeburg foundry, Germany.
Total Elem
X-ray fluo
<2 <2 5870 <2 7 7 32 21 46
Spent molding sands. Average over 52 Penn foundries. Total Elem 2.3 24 2.2 29 1.5 49 2.2 <1.9 308 1.5% 108 246 37
Spent sand waste. Average over a cluster of 30 out of
33 Pennsylvania ferrous and non-ferrous foundries.
Total Elem 1.1 13 1.9 8.9 0.06 24 1.2 2.4 117 3.9% 72 26 29 29
Molding waste (sand, binder, dust, sludge). Median
values derived from14 samples. Gostyn foundry,Poland
Total Elem 3 101 45 15 15% 291 112 32 44
Black spent sand piles. Samples averaged over two
New England iron casting foundries.
Total Elem
EPA 6010
2 30 <0.2 2.8 0.02 7.5 <5 <0.5 1
Black spent sand + dust. Massachusetts iron foundry.
Average of 4 samples collected within 6 months.
Total Elem
EPA 6010
4.5 35 0.2 3.4 0.01 9 <5 <0.5 1
Florida natural soil: Candler fine sand (96.7% sand,
2.5% clay, 0.8% silt, 0.8% organics, pH=6.5).
8 Leaching
Cycles, H
2
O
0.23 0.20 0.44 0.08 47
Unprocessed sand for molding. Median values obtained
with 5 samples. Gostyn foundry, Poland.
Total Elem 1 6 0.4 970 21 44
US sandy soils, lithosols on sandstones. Vegetation safe Total Elem 5.1 400 40 0.08 17 0.5 14 1-3% 345 40 175 37
US non-contaminated soils. Maximum values. Total Elem 60 3000 0.7 1000 0.3 200 2 5 100 5% 3000 300 300 48,49
Note: A cell is blank if a parameter was not measured.
< Below detection limit.
Below unspecified detection limit
* Action level which triggers treatment of water system if exceeded in more than 10% tap water samples.
** Ni is mandatory for monitoring along with other contaminants tabulated by the National Primary Drinking Water Regulations, but no maximum
contaminant level is currently specified by EPA. MA DEP defines Ni 0.1mg/l as the concentration in drinking water at or below which, adverse,
non-cancer health effects are unlikely to occur after chronic (lifetime) exposure. MA DEP only indicates a potential need for further legislative
action to be decided.
59
Table 18. TYPICALTCLP AND SPLP RESULTS FROM SMELTING OPERATION SLUDGE
Metal
Leaching
TCLP
(mg/l)
SPLP
(mg/l)
Pb 570 1.5
Cd 1.9 0.13
Cr 5.1 0.9
Table 19. LEAD LEACHABILITY VERSUS TOTAL ELEMENT ANALYSIS OF
RED BRASS FOUNDRY SAND SAMPLES AND SYNTHESIZED MIXTURES
Sample
EP Toxicity
a
Pb, mg/l
Total
b
Pb
mg/kg
Ratio
EP Tox/Total
Ref.
Spent molding sand, Leaded brass foundry A
70 1900 0.04 51
Spent molding sand, Leaded brass foundry B 111 1100 0.10 51
Spent molding sand, Leaded brass foundry C
35 52
Clean virgin sand + Pb fine particles (0.1%)
673 1000 0.67 51
Clean virgin sand + PbO (1%) 6380 10000 0.64 51
Clean virgin sand + PbSiO
3
(0.1%) 318 1000 0.32 51
a
100g sample, 2000 ml acetic acid solution (0.5N), pH=5.0, agitation 24 hours.
b
1g random sub-sample, total acid digestion (HNO
3
+ HCl).
60
Table 20. BINDERS AND SOURCES FOR ORGANIC ANALYSIS
Sample Description and/or Collection Point
Core Binder
System
Sample
Number
System
(Molding)
Sand Type
System Sand Core Butts
Core Room
Wastes
Phenol
formaldehyde
1 Green sand
Spent system
sand
Core butt dump
hopper
Core sand from
floor and
broken cores
Phenolic
urethane
2 Green sand Prior to muller
From scalping
area on return
sand belt
Ungassed sand
from feed after
mixing
Furan hot box 3 Green sand From silo
Separated from
waste sand
Core room
filter
Furan
a
no-bake 4 N.A.
Sand
reclamation
dust
Core butts
from sand
reclamation
Reacted sand
Phenolic
a
ester 5 N.A.
Sand
reclamation
dust
Core butts Reacted sand
Core oil 6 Green sand N.A.
Waste core
butts
N.A.
Phenolic
isocyanate
7 Green sand
Virgin sand
after muller
Open storage
are separated
from system
sand
Core room
sweepings
Alkyd
isocyanate
8 No-bake
Raw sand from
mixer
Spent core
butts
Core sand from
floor and
broken cores
Furan warm
box
9 Green sand N.A. Core butts Off floor
a
Same foundry
N.A. = not available
61
Table 21. LEACH TEST VARIABILITY (LEACHATE CONCENTRATIONS)
Replicate Leachate Samples, g/l Volatile Analytes in a
Core Oil Binder System Sample
1 2 3 4 Mean
% RSD*
Acetone 180 130 180 170 165.0 14
Sec-Butylbenzene 8.9 9.0 9.2 12 9.8 15
Diethylbenzenes 110 100 120 160 122.5 21
1,3-Dimethylnapthalene 61 60 49 44 53.5 16
1,5- & 2,3-Dimethylnapthalene 30 30 24 22 26.5 16
2,6-Dimethylnapthalene 21 21 18 16 19.0 13
Ethylbenzene 25 22 23 22 23.0 6
p-Ethyltoluene 360 330 430 670 447.5 34
Isopropylbenzene 37 35 44 65 45.2 30
1-Methylnapthalene 75 75 68 64 70.5 8
2-Methylnapthalene 86 86 79 74 81.2 7
Naphthalene 360 340 330 370 350.0 5
Toluene 9.9 7.1 8.1 7.2 8.1 16
1,2,4-Trimethylbenzene and
t-Butylbenzene
270 250 300 470 322.5 31
m/p-Xylene 85 77 84 88 83.5 6
o-Xylene 122 120 140 170 138.0 17
*Percent Relative Standard Deviation
62
Table 22. CORE OIL BINDER SYSTEM SAMPLE: VOLATILE ANALYTE CONCENTRATIONS
from GC-FID Analysis
Analyte
Quantitation limit
(g/l)
Composite Leach
Concentration*
(g/l)
MA Standards and
Guidelines for
Drinking Water (g/l)
Acetone 100 160 3000
Benzene 2 <2 5
sec-Butylbenzene 0.4 9.8
Chloroform 2 <2 5
Dichloromethane 3 <3 5
Diethylbenzenes 0.3 120
1,3-Dimethylnaphthalene 1 53
1,5- and 2,3-
Dimethylnaphthalene
2 27
2,6-Dimethylnaphthalene 1 19
Ethyl Acetate 8 <8
Ethylbenzene 0.4 23 700
p-Ethyltoluene 0.4 450
n-Hexane 0.4 <0.4
Isopropylbenzene 0.4 45
Methyl ethyl ketone 0.8 <0.8 350
Methyl isobutyl ketone 20 <20 350
1-Methylnaphthalene 2 70
2-Methylnaphthalene 1 81
Naphthalene 1 350
Tetrachloroethene 2 <2
Toluene 0.5 8.1 1000
1,1,1-Trichloroethane 2 <2 200
1,2,4-Trimethylbenzene
and t-Butylbenzene
0.3 320
1,3,5-Trimethylbenzene 0.4 <0.4
m- & p-Xylene 0.4 84
o-Xylene 0.4 140
} 10000
*Average of four leach tests
63
Table 23. CORE OIL BINDER SYSTEM SAMPLE : VOLATILE ANALYTE CONCENTRATIONS
from GC-MS Analysis
Analyte Number of Isomers
Composite
Concentration*
(g/l)
1,2,3,4-Tetrahydronaphthalene 1 40
C3-benzenes 7 500
C4-benzenes 9 200
C5-benzenes 4 20
Unsaturated C4-benzenes 2 20
*Each concentration is estimate of total concentration of all isomers present
Table 24. SUMMARY OF CONCENTRATIONS OF ORGANIC COMPOUNDS IN LABORATORY EXTRACTS
Binder System Sample Number (from Table 20)
Compound
(1)
LOQ
a
(g/l)
(2)
1A
(3)
1B
(4)
2A
(5)
2B
(6)
3
(7)
4
(8)
5
(9)
6
(10)
7
(11)
8
(12)
9
(13)
Acetone
100 200 160
Benzene 2 2 11 9 11
Benzoic acid N.D. 300
b
200
b
400
b
2,4-Dimethylphenol 20 120 94
Ethylbenzene 0.4 0.6 24
1,1,1-Trichloroethane 2 49 2
Naphthalene 1 6 85 480 130 130 73 1
2-Methylnaphthalene 1 6 25 320 81 77 8
Phenol 30 150 340 210 540
Dimethylphthalate 40 61
Phenanthrene 30 38
Tetrachloroethene 2 7 6
Toluene 0.5 0.5 0.9 4.7 2.4 61 37 45 9.9 2.2
o-Cresol 30 40 110
m/p-Cresol 30 45
o-Xylene 0.4 0.7 1.5 1.7 140 2.3 0.4
m/p-Xylene 0.4 0.5 1.3 2.3 0.4 0.8 1.0 84 0.6 0.6
a
LOQ = limit of quantitation in g/l
b
Concentrations for benzoic acid estimated from GC-MS data
Note: dash represents concentration was below quantitation limit for that compound
N.D. = not determined
65
66
Table 25. COMPARISON OF BINDER SYSTEM WASTE STREAMS
Sample 2B
Phenolic Urethane
Sample 6
Core Oil
Sample 7
Phenolic Isocyanate
Sample 8
Alkyd Isocyanate
Concentration (g/l) Concentration (g/l) Concentration (g/l) Concentration (g/l)
Analyte
(1)
LOQ
*
(g/l)
S.S.
(3)
C.B.
(4)
F.S.
(5)
S.S.
(6)
C.B.
(7)
F.S.
(8)
S.S.
(9)
C.B.
(10)
F.S.
(11)
S.S.
(12)
C.B.
(13)
F.S.
(14)
Benzene 2 8 - - - - - - - - - - -
sec-Butylbenzene 0.4 - - - 5.6 - - - - - - 1.0 1.0
Diethylbenzenes 0.3 - - 42 35 1.7 27 1.5 4.3 8.1 19 23 14
1,3-Dimethylnaphthalene 1 1 6 250 45 - - 1 2 13 8 6 1
1,5- & 2,3-Dimethylnaphthalene 2 - 3 - 22 - - - - - - - -
2,6-Dimethylnaphthalene 1 - 2 110 16 - - - - 6 4 2 -
Ethylbenzene 0.4 0.7 - - 30 - 1.0 - - - - 0.7 1.3
p-Ethyltoluene 0.4 - - 34 36 5.2 143 - 30 0 7.5 - -
n-Hexane 0.4 - - 14 - - - - - - - - 2.2
Isopropylbenzene 0.4 - - 2.7 5.6 - 14 - - 1.8 - 0.7 0.4
1-Methylnaphthalene 2 5 10 1,300 59 - - 3 10 60 19 34 9
2-Methylnaphthalene 1 5 12 2,100 67 - 2 6 16 91 31 44 15
Naphthalene 1 17 14 550 100 6 47 11 37 150 81 250 190
Tetrachloroethene 2 - 7 - - - - - - - - - -
Toluene 0.5 2.1 2.4 58 14 - - - - - - 1.7 1.0
1,1,1-Trichloroethane 2 - 88 - - - - - - 11 - - -
1,2,4-Trimethylbenzene and
t-Butylbenzene
0.3 0.4 - 32 50 2.5 93 0.7 2.2 81 7.3 13 0.9
1,3,5-Trimethylbenzene 0.4 - - - - - - 0.6 - 5.9 - 6.2 4.0
m/p-Xylene 0.4 0.5 0.7 4.1 83 0.5 9.1 - - 0.8 - 1.4 2.6
o-Xylene 0.4 0.5 - 5.7 49 0.7 34 - 0.5 55 - 2.0 2.4
*
LOQ = limit of quantitation in g/l
Note: S.S. = system sand; C.B. = core butts; F.S. = core room floor sweepings
Dash represents concentration was below quantitation limit for that compound
67
Table 26. DATA FOR ORGANIC COMPOUNDS FROM TWO NEW ENGLAND FOUNDRIES
Test Performed Method Units MDL Results
Composite: Black sand pile and bag
house dust
03/19/96
baghouse
03/19/96
N.E. Co #1
03/19/96
N.E. Co #2
B/NA EXTRACTABLES
Phenol EPA 8270 g/kg 700 ND ND ND
2-Chloroethyl ether EPA 8270 g/kg 300 ND ND ND
Chlorophenol EPA 8270 g/kg 500 ND ND ND
1,3 Dichlorobenzene EPA 8270 g/kg 100 ND ND ND
1,4 Dichlorobenzene EPA 8270 g/kg 100 ND ND ND
1,2 Dichlorobenzene EPA 8270 g/kg 100 ND ND ND
2-cholorisopropyl ether EPA 8270 g/kg 200 ND ND ND
Nitroso-di-n-propylamine EPA 8270 g/kg 300 ND ND ND
Hexachloroethane EPA 8270 g/kg 500 ND ND ND
Nitrobenzene EPA 8270 g/kg 200 ND ND ND
Isophorone EPA 8270 g/kg 200 ND ND ND
Nitrophenol EPA 8270 g/kg 200 ND ND ND
2,4-Dimethylphenol EPA 8270 g/kg 300 1180 650 616
2-chloroethoxy EPA 8270 g/kg 200 ND ND ND
2,4-Dichlorophenol EPA 8270 g/kg 200 ND ND ND
1,2,4-Trichlorobenzene EPA 8270 g/kg 200 ND ND ND
Naphthalene EPA 8270 g/kg 200 3000 1930 2150
Hexachlorobutadiene EPA 8270 g/kg 300 ND ND ND
4-Chloro-3-methylphenol EPA 8270 g/kg 200 ND ND ND
Hexachlorophenol EPA 8270 g/kg 100 ND ND ND
2,4,6-Trichlorophenol EPA 8270 g/kg 100 ND ND ND
2,4,5-Trichlorophenol EPA 8270 g/kg 100 ND ND ND
2-Chloronaphthalene EPA 8270 g/kg 200 ND ND ND
Dimethyl Phthalate EPA 8270 g/kg 100 ND ND ND
Acenaphthylene EPA 8270 g/kg 200 ND ND ND
Acenapthene EPA 8270 g/kg 200 ND ND ND
2,4-Acenapthene EPA 8270 g/kg 200 ND ND ND
4-Nicrophenol EPA 8270 g/kg 200 ND ND ND
2,4-Dinitrotoluene EPA 8270 g/kg 100 ND ND ND
Diethyl Phthalate EPA 8270 g/kg 200 ND ND ND
Fluorene EPA 8270 g/kg 300 ND ND ND
4-ChloroPhenyl Phenyl Ether EPA 8270 g/kg 200 ND ND ND
2-Methyl-4,6dinitrophenol EPA 8270 g/kg 200 ND ND ND
N-Nitrosodiphenylamine EPA 8270 g/kg 300 ND ND ND
4-Bromophenyl Phenyl Ether EPA 8270 g/kg 100 ND ND ND
Hexachlorobenzene EPA 8270 g/kg 200 ND ND ND
Pentachlorophenol EPA 8270 g/kg 100 ND ND ND
Phenanthrene EPA 8270 g/kg 100 850 560 745
Anthracene EPA 8270 g/kg 200 ND ND ND
Di-n-butylphthalate EPA 8270 g/kg 100 160 ND 731
Fluoranthene EPA 8270 g/kg 100 162 131 181
Benzidine EPA 8270 g/kg 500 ND ND ND
Pyrene EPA 8270 g/kg 300 ND ND ND
Butyle Benzyl Phthalate EPA 8270 g/kg 100 ND ND ND
Benzo (a) anthracene EPA 8270 g/kg 100 ND ND ND
3,3'-Dichlorbenzidine EPA 8270 g/kg 100 ND ND ND
continued on next page.
68
.continued from previous page
Crysene EPA 8270 g/kg 100 ND ND ND
Bis(2-Ethylexyl)phthalate EPA 8270 g/kg 400 ND ND ND
Bi-n-octyl phthalate EPA 8270 g/kg 1000 ND ND ND
Benzo (b) fluoranthene EPA 8270 g/kg 500 ND ND ND
Benzo (k) fluoranthene EPA 8270 g/kg 500 ND ND ND
Benzo (a) pyrene EPA 8270 g/kg 100 ND ND ND
Indeno (1,2,3-cd)Pyrene EPA 8270 g/kg 100 ND ND ND
Dibenzo (a,h) Anthracena EPA 8270 g/kg 100 ND ND ND
Benzo (g,h,i) perylene EPA 8270 g/kg 100 ND ND ND
2-FLUOROPHENOL (SURR) %
PHENOL-D5 (SURR) %
NITROBENZENE-D5 (SURR) %
2-FLUOROBIPHENYL (SURR) %
2,4,6-Tribromophenol (SURR) %
TERPHENYL-D14 (SURR) %
Formaldehyde MSTH,HACH mg/l 0.1 8.93 5.33 8.26
Table 27. VARIABILITY OF ORGANIC CONTENT IN SAND FROM A NEW ENGLAND FOUNDRY
Test Performed Method Unit MDL Results
Composite: Black sand
pile and bag house dust
12/18/96 01/08/97 02/03/97 04/11/97 06/11/97
B/NA EXTRACTABLES
Phenol EPA 8270 g/kg 700 7200 5700 5510 5840 ND
2,4-Dimethylphenol EPA 8270 g/kg 300 2600 1600 930 1330 ND
Naphthalene EPA 8270 g/kg 200 4600 3500 2360 2870 2140
Phenanthrene EPA 8270 g/kg 100 1800 980 640 790 ND
Di-n-butylphthalate EPA 8270 g/kg 100 360 ND ND ND ND
Fluoranthene EPA 8270 g/kg 100 430 160 ND ND ND
Pyrene EPA 8270 g/kg 300 320 ND ND ND ND
Benzo (a) anthracene EPA 8270 g/kg 100 150 ND ND ND ND
Crysene EPA 8270 g/kg 100 230 140 ND ND ND
Bi-n-octyl phthalate EPA 8270 g/kg 1000 300 ND ND ND ND
2-Fluorophenol (SURR) % 64 67 52 94 108
PHENOL-D5 (SURR) % 77 76 55 99 106
Nitrobenzene-D5 (SURR) % 65 62 43 75 52
2-Fluorobiphenyl (SURR) % 79 66 58 80 63
2,4,6-Tribromophenol
(SURR)
% 74 102 52 86 70
Terphenyl-D14 (SURR) % 82 73 67 75 56
Formaldehyde MSTH,HACH mg/l 0.1 <0.1 <0.1 <0.1 11.9 <.01
69
Table 28. MAJOR VOLATILE COMPONENTS EMITTED FROM NOVOLAC RESIN AT 980C
Components Concentration (g/g)
Carbon monoxide 73000
Methane 47000
Ethene 10400
Propene 2600
HCN small amount
1,3-Butadiene 700
1-Butene 500
1,3-Cyclopentadiene 300
1-Pentene 100
2-Propenenitrile 100
1,3-Pentadiene 63.8
Benzene 23.1
Phenol 13.8
Naphthalene 8.8
Toluene 6.5
2-Methyl phenol 6.0
4- Methyl phenol 4.6
2-Methyl,1-1'-biphenyl 3.3
Biphenyl 2.1
Phenanthrene 2.9
Acenaphthylene 2.1
2,4-Dimethyl phenol 1.8
2,5-Dimethyl phenol 0.9
Indene 1.6
1-Methylnaphthalene 1.2
2-Methylnaphthalene 1.2
Anthracene 1.1
Benzofuran 1.0
Dibenzofuran 0.7
Flourene 0.9
* Only components that are greater than 0.8% of the total emitted volatiles are listed
Average relative standard deviation is equal to 15%.
70
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