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2.0 DESCRIPTION OF CRUMB RUBBER INFILL USED IN SYNTHETIC TURF
Modem synthetic turf Fields are structured in layers: a bottom layer composed of
geotextile, middle drainage layers and padding, and a top layer of synthetic grass. The top layer
contains cushioning infill material of crumb rubber produced from recycled tires. The crumb
rubber material, which has been processed to the size of coarse sand, is spread two to three
inches thick over the base turf material and raked down in between the plastic fibers which
simulate grass. The crumb rubber helps support the blades of fiber, and also provides a surface
with some give, so that it feels more like the soil under a natural grass surface.
The crumb rubber used in many synthetic turf systems is made of styrene butadiene
rubber (SBR) primarily from recycled tires and is used as infill in the top grass layer of the
synthetic turf. Other infill material may be made from ethylene propylene diene monomer
(EPDM) and thermoplastic elastomers (TPEs) which are produced specifically for field turf
applications]SBR crumb rubber is produced through either mechanical grinding or cryogenic
reduction (freezing process to reduce rubber to granules). This report focuses mainly on the
characteristics of SBR crumb rubber.
in general, SBR crumb rubber is manufactured from automotive and/or truck scrap tires.
Tires contain many different substances but approximately 40% is rubber. Rubber consists of
elastic polymers that are obtained directly from plants (natural rubber) or manufactured from
petroleum (synthetic rubber). Natural rubber, obtained from the latex of rubber trees, accounts
for about 23% of all rubber consumed in the United States. The balance is synthetic rubber. Of
the synthetic rubbers, SBR and polybutadiene rubber are most utilized, accounting for 71% of
synthetic rubber production. A variety of specialty synthetic rubbers, such as butyl, EPDM
rubber, polychloroprene, nitrile, and silicone, account for the balance of synthetic rubber
production. A comparison of two tire manufacturers showed similarities in tire components
between the various types of tires produced (Firestone and Dow Chemical Company Technical
Specifications).
Due to the manufacturing processes of crumb rubber, various amounts of the components
used in the original production of the tire, besides rubber, occur in the crumb rubber.
Vulcanizing agents, accelerators, activators, antiozonants, antioxidants, retarders, plasticizers and
extenders are used in the original tire manufacturing process. In addition, studies have shown
that various chemicals such as benzene, phthalates and alkylphenols may become bonded to tires
during use (Willoughby, .2006). However, as seen in Cocheo et. al., (1983), phthalates,
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alkylphenols, and benzene can also off -gas during tire manufacturing. Ali of these chemicals
have been detected in direct.analyses of crumb rubber using vigorous extraction methods (see
Table 2-1). It is difficult to discern the original source of the chemicals found in crumb rubber.
They may be present as a -result of manufacturing, or due to environmental sources present while
the tires are in use. Studies have been conducted to identify chemicals or particulates released by
tires or tire shreds, chips or crumb in the field or laboratory setting. Tables 2-2 and 2-3
summarize the results of these studies and are organized by chemical group.
2.1 Manufacturing Processes of Rubber
Initially, rubber was manufactured from natural plant sources using a vulcanization
process that was discovered in 1893. In 1912, carbon was added .to the process to strengthen .
rubber. Synthetic rubber took over as the major source of rubber in the United States'(US)
during the 1950s, and by the 1990s, natural rubber had only 30% of the US market (SBR Tire
'Facts, 2007).
The process of manufacturing tires begins with the selection of the type of rubber. The
choice of the rubber to be used depends on cost and performance requirements. The specialty.
rubbers often -impart superior performance properties but do so at a higher product cost. Many
rubber products contain less than 50% by weight of rubber. The balance is a selection of fillers,
extenders, and processing or protective coatings. Aromatic process oils are excellent
plasticixers/softeners for tire rubbers. They are created by the extraction of lubricating oils from
highly aromatic (HA) oils to remove the aromatics. As noted in Firestone and Dow Chemical
Company technical specifications, Willoughby (2006), and the material safety data sheets
(MSDSs) for the rubber infll materials from select parks in NYC, these oils are a significant
component of the major type of rubber (SBR) used in the manufacturing of crumb rubber.
Additional studies (KEMi 2006, Crain and Zhang 2006 and 2007, RAMP 2007, N1LU 2006,. and
NBI 2004) show the presence of polycyclic aromatic hydrocarbons (PAHs) in rubber granulates,
ieachate, indoor air and in particulate matter.. The composition of these oils is therefore critical
to understanding COPCs in crumb rubber since the PAHs noted as detected in the listed studies
may very likely be due to these oils. These oils are rich in PAHs (approximately 20-300/6),
including the carcinogenic PAHs. Typically the boiling point range of these oils is 250-680°C.
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process as summarized in Section 1.2, is approximately 1.8-13.9%. A table summarizing the
components of HA oil can be found in Appendix 13-1 (Table B-6),
2.2 Manufacture of Rubber Tires
Rubber tires are manufactured by compounding, mixing and forming the ingredients used
to make the specific rubber, then tire components are formed and the tire is built from those
components. Reinforcing cords, also known as steel belts, are added at this stage. Vulcanization
is the last step that converts the essentially plastic, raw rubber mixture to an elastic state. The
process of manufacturing tires requires the use of many types of chemicals, including
vulcanizing agents, accelerators, activators, antiozonants, antioxidants, retarders, plasticizers and
extenders. These chemicals are therefore potentially found in the tires used to make crumb
rubber (Cocheo et. al., 1983).
Tires contain many different substances but approximately 40% is rubber. Rubber
consists of elastic polymers that are obtained directly from plants (natural rubber) or
manufactured from petroleum (synthetic rubber).
Natural rubber, obtained from the latex of rubber trees, accounts for about 23% of all
rubber consumed in the United States. The balance is synthetic rubber. Of the synthetic rubbers,
SBR and polybutadiene rubber arc most utilized, accounting for 71% of synthetic rubber
production (Mechanical -Engineering -Archives 2006, IISRP 2007). A variety. of specialty
synthetic rubbers, such as butyl, EPDM rubber, polychloroprene, nitrile, and silicone, account for
the balance of synthetic rubber production.
A typical scrapped automobile tire weighs 9.1 kg (20 lb). Roughly 5.4 kg (12 lb) to 5.9
kg (13 lb) consists of recoverable rubber, composed of 35% natural rubber and 65% synthetic
rubber. Steel -belted radial tires are the predominant type of tire currently produced in the United
States. A typical truck tire weighs 18.2 kg (40 lb) and also contains from 60 to 70% recoverable
rubber. Truck tires typically contain 65% natural rubber and 35% synthetic rubber (SBR Tire
Facts, 2007). Although the majority of truck tires are steel -belted radials, there are still a Number
of bias ply truck tires, which contain either nylon or polyester belt material.
The components of Firestone's and Dow Chemical Company's rubber are summarized in
technical specification documents. Although they are only two of many different rubber
manufacturers, .a similarity between the two vendors is readily apparent, even between three
different types of rubber, solution-SBR, cold polymerized emulsion SBR, and high cis-
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polybutadiene rubber. In general, the following similarities were observed between the two
manufacturers for the compounds used to produce the rubber:
• The polymer used to produce solution-SBR contained approximately 1840% bound
styrene.
• The oil content in the polymer ranged from 27.3-32.5% in solution-SBR and cold
polymerized emulsion SBR. Oils used include, aromatic oil, high viscosity
.naphthenic oil, and treated distillate aromatic extract oil.
Besides the polymer used, the other components of the rubber were similar between
manufacturers and the relative proportions (parts by weight) of these other
components ranged as follows:
o Carbon black: 50.00 — 68.75
o Zinc oxide: 3.00
o Stearic acid: 1.00 -- 2.00
o Sulfur: 1.5 — 1.75
o N-tert-butyl benzothiazole sulfonamide (TBBS): 0.9 — 1.50
o Naphthenic or aromatic oil: 5.00 —15.0
The components summarized above are the principal components- of the major type of
rubber (SBR) used for the manufacturing of crumb rubber and therefore have -the potential..to
have.a significant presence in crumb rubber. As discussed in subsequent sections of this report,
some of these components have been. found to be prevalent in crumb rubber, including zinc
(from the zinc oxide), benzothiazole compounds (from TBBS), and PAHs (possibly from the oils
used). These compounds may be attributed to the SBR used in the manufacturing of crumb
rubber. .
Further discussions on the manufacture of tires and their components can be found in
Appendix B-I.- Appendix B- I also contains summaries of pertinent articles reviewed for this
chapter.
2.3 Chemicals Identified in Rqcycled Jire
The 2007 California Environmental Protection Agency (CaIEPA) report provides a
n
Alk
discussion on the chemicals released by recycled tires and where in the tire production process ,
the given substance most likely originated. The discussion focuses on metals (zinc, iron,
manganese, barium, lead, and chromium), volatile organic compounds (VOCs) (methyl isobutyl
ketone [MIBK], .naphthalene, acetone, toluene, total petroleum hydrocarbons [TPH), methyl
ethyl ketone [MEK]), and semi -volatile organic compounds (SVOCs) (benzothiazoles, aniline,
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phenol, diphenylnitrosoamine and dimethyinitrosoamine). The results from the Cal£PA (2007)
report on chemicals found in recycled tires are presented below.
Metals:
• Zinc, iron, and manganese were the metals detected most frequently. Iron and
manganese are components of the steel belts and beads while zinc oxide is used as an
activator in the vulcanization process. Since the production of crumb rubber removes
approximately 99% of the steel belting and bead material, this should reduce the
release of iron and manganese from the recycled tire material.
• Barium was also detected in several instances which could be a result of its use to
catalyze the synthesis of polybutadiene rubber.
• The presence of lead in several instances may be due to its former use as an activator
in the vulcanization process, in the form of lead oxide.
• The presence of chromium in several instances may be due to its use in steel
production; however, removal of the steel wire during the production of crumb rubber
should reduce the release of chromium.
VOCs:
• M1BK and naphthalene were the VOCs detected at the highest concentrations. MIBK
may result from its use in the production of rubber antioxidants and naphthalene can .
originate from carbon black.
• Other VOCs detected may result from the use of petroleum oils and coal tar fractions
in tire production: acetone, toluene, ethyl benzene, TPH, PAHs, and MEK.
• . Conclusions could not be drawn about the release of VOCs from surfaces using .this
crumb rubber due to the lack of data.
SVOCs:
• Five different benzothiazoles were detected; these compounds have been proposed as
environmental markers for tire -derived material. Benzothiazoles are used in tire
production to accelerate the vulcanization process, as antioxidants, and to help bond
the metal wire and metal belts to the tire rubber.
• Aniline was detected and could be due to its addition to tires to inhibit rubber
degradation.
• Phenols detected may be due to use of petroleum oils and/or coal tar fractions as
softeners and extenders in tire production: Also, steel cords and fabrics comprising
the belts were treated with phenol/formaldehyde to improve their adhesion to rubber.
• The detection of two nitrosamines (diphenyl and dimethyl) could be the result of their
use to inhibit both the vulcanization process during tire production and the
decomposition of rubber in the finished product.
2.4 Different Types of Crumb Rubber and Manufacturing Processes
In general, crumb rubber is manufactured from automotive and/or truck scrap tires.
Crumb rubber can be differentiated by the type of raw material used as well as the type of
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processing used. During the manufacturing process, the steel and polyester/nylon fiber is
removed from the tire, leaving the tire rubber with a granular consistency. Continued processing
with mechanical grinding; possibly with the aid of cryogenics, further reduces the size of the
particles. Various size reduction techniques can be used to obtain a wide range of particle sizes.
The particles are sized and classified based on different criteria:
(1) color
(2) magnetically separated
(3) removal of polyester/nylon fiber
(4) mesh size of granulates
There are essentially four types of crumb rubber infill materials as discussed below
(Melos.GmbH, 2004):
SBR Infrll Granules
SBR infill granules are the most cost-effective infill granules since these come from
recycled materials. The material has a high rubber content that gives, it high elasticity, and
carbon black gives it resistance to UV and the weather. Since this product is manufactured from
recycled materials (principally old car tires), some variation in quality is expected. As the supply
of granules may come from different sources, the quality of this material is typically not
traceable. Impurities like stones and metals may be present in the granules.. Depending on the
length of time the original material was used, it may become brittle after a relatively short time.
This.material has high heat absorption, but it cannot be flameproofed. Studies note that the PAH
and zinc content of SBR material is highly variable (Melos GmbH, 2007).
Coated SBR Infill Granules
Coated SBR granules combine the elasticity of SBR materials with a free choice of
colors. The cost is somewhere between SBR and EPDM infill granules, which makes -coated
SBR the logical alternative where colored (green or brown) granules are to be used. It is'not
possible to flameproof this material. When the coating is degraded or destroyed, the material
exhibits similar characteristics of uncoated SBR infill granules.
EPDM Infill Granules
EPDM infill granules are produced especially for playing fields -and so the material can
be tailored to individual requirements so it is possible to supply flame retardants and foamed
granules in any desired color. No impurities like stones or metals will be present. The heat
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cyclohexanone and aldehydes such. as formaldehyde and ethylbenzene aldehyde isomers were
ainong the chemicals detected at the highest concentrations. Leachate samples also had
detectable VOCs.
Metals have also been detected at significant levels, including barium, chromium, copper,
iron, lead, manganese, and zinc. Zinc has been found at concentrations that are orders of
magnitude above other metals in samples from one study. These metals along with aluminum
have also been identified in Leachate from crumb rubber.
All of these chemicals have been detected in direct analyses of crumb rubber if vigorous
extraction methods are used (see Table 2-1). Phthalates, alkylphenols, and benzene have been
found to off -gas during tire manufacturing (Cocheo et. al., 1983). In addition, studies have also
shown that various chemicals such as phthalates, alkylphenols, and benzene may become bonded
to tires during use (Willoughby, 2006). Since these chemicals are used during the tire
manufacturing process, or -are present in the.environment while the tires are in use, their presence
in the crumb rubber.would be expected. It should also be noted that there are a number of
uncertainties associated with using these COPCs to assess potential exposures. These are
discussed at length in Chapter 2.
In addition, crumb rubber includes some amount of dusts and small particles, which may
be further increased by mechanical abrasion and wear that comes with use of the fields. The
Norwegian Institute of Air. Pollution (NILU, 2006) conducted a study to measure indoor air
quality in sports halls that use synthetic turf in order to generate data for use in exposure studies. '
The range of PM 10 detected in the halls was 31 to 40 uglm3, while the measured concentrations
of PM 2.5 were I - 0 to 19 uglm3. In the two halls with SBR rubber. granulate, it was calculated
that 23 to 28% of the PM 10 consisted of rubber, while 35% to 50% of the PM 2.5 was
associated with the rubber particulate. Results of the airborne dust showed the presence of
PAHs, phthalates, other SVOCs, benzothiazoles, and aromatic amines.
Relative concentrations of chemicals detected were noted to be higher in infill material
produced with recycled SBR granulates as opposed to EPDM rubber granulates. :The one
exception to this is that chromium concentrations were significantly higher in infill material
produced with EPDM rubber granulates. Intill materials produced with EPDM rubber granulates
are considerably more expensive than materials produced with recycled SBR granulates. -
Studies have identified concentrations of COPCs in crumb rubber. As discussed in
Chapter 2, little is known about the release and bioavailability of these materials from a crumb
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rubber matrix. Studies have identified concentrations of these chemicals and the maximum
levels identified are shown below:
• Total PAHs: 76 mg/kg
• VOCs: methyl isobutyl ketone: 11.4 mg/kg
• Benzothiazole: 171 mg/kg
• Alkylphenols: 4-t-octy[phenol: 33,700 mg/kg
• Metals: zinc: 17,000 mg/kg, chromium: 5200 mg/kg, depending on source of rubber
granulate
• Bis(2-ethylhexyl)phthalate: 203 mg/kg
Tables 2-1 through 2-3 provide detailed lists of COPCs identified in crumb rubber or in
environmental media impacted by crumb rubber. A table on COPCs identified in the tire
41 manufacturing process can also be found in Appendix B-1 (Table B-7).
2.6 Analytic Methods for Identifying COPCs in Crumb Rubber
Based on the studies reviewed, direct. measurement of crumb rubber for extractable'
organic compounds should be performed using rigorous extraction procedures (Le, soxhlet or
pressurized fluid extraction) followed by gas chromatography -mass spectrometry' (GC/MS) .
analysis. Measurements of crumb rubber for metals should be performed using rigorous acid or
microwave digestion procedures followed by inductively coupled plasma atomic emission
spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (1CP-MS), or cold
vapor atomic absorption (CVAA) analysis, depending on the metal of interest. Further testing
may focus on the major COPCs identified in Table 2-1 and how these COPCs differ in crumb
rubber manufactured using mechanical grinding versus cryogenic processing, and in crumb
rubber produced from different sources (i.e. SBR granules versus EPDM granules versus TPE
granules).
2.7 Material Safe ata 5 eets for Crumb Ru ber
MSDSs for Rubber Infill Materials were provided by the NYC DPR and can be found in
Appendix A. The MSDSs provided were from two different synthetic turf manufacturers (Aturf
and Forever Green Athletic Fields), representing three different manufacturers of the rubber infill
material (Recycling Technologies lnt'l, LLC; Re-Tek, Inc and SJM group of New York). The
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compositions of the different materials were, in general, very similar and are summarized in.
Table 2-4.
In general, the following similarities were observed between the rubber infill materials:
• The three main components of each were the rubber material, carbon black, and the
process oils.
• The carbon black content was similar and ranged from 27-35%.
• zinc oxide or zinc compounds exhibited similar proportions (1-5%).
• Sulfur and stearic acid were noted as being present in two of the three materials
between I and 5%.
As discussed previously and in subsequent sections, the process oils and the zinc oxide
observed in all of these materials can be significant contributors to COPCs in crumb rubber.
2.8 - Impact of Environmental_Factors on Synthetic Turf Material over Time
Environmental factors such as temperature, humidity, rain, air pollution, UV radiation
and usage may all impact synthetic turf material over. time. Studies pertaining to the effect of
temperature, humidity, rain, and air pollution on the synthetic turf material were.not identified
and represent a data gap as to the material's durability. As discussed in Chapter 3, the surface
temperature of synthetic turf systems has been measured as high as 174 degrees Fahrenheit ('F)
(Williams and Pulley, 2002); however, no studies measuring the.effect of temperature on the.turf
material itself have been located.
Verschoor (2007) evaluated the leaching,of zinc from new, I -year old and 3-year old turf,
where two different types of aged samples were evaluated: 1). aged samples that were produced
by laboratory .exposure to' UV equivalent to 1 or 3 years sunlight exposure in accordance with
ISO 4892-3 and 2) aged samples that were taken from synthetic turf fields of different ages (1
.and 3.years of use). The data from the study showed that zinc concentrations in-leachate from
,rubber crumbs of car and truck tires aged in, the laboratory increase with aging; whereas in
samples aged under field conditions, zinc concentration increases with age for the car tire crumbs
but not for truck tire crumbs. The study notes that trends of field emissions are more difficult to
interpret because the variety in field samples is high. Kolitzus (2007) notes that current synthetic ,
turf fields should last for 10 to 15 years and UV radiation is not considered to be an issue as pile
fibers. are being produced by reliable manufacturers. The author notes that a test method to
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determine the resistance of synthetic turf%to UV radiation has not been developed on the
international level.
McNiff and Petrunak (2007) evaluated the effect of high usage on the synthetic turf
fields. Simulated foot traffic was applied to the turf fields using a "Brinkman Traffic Simulator".
The traffic simulator was pulled with a tractor. Two passes of the traffic simulator produces the
equivalent number of cleat dents created between the hash marks at the 40-yard line during one
National Football Game. Thus, 24 passes per week are equivalent to the cleat dents sustained
from 12 games per week. Surface hardness and impact attenuation were conducted in
accordance with American Society for Testing and Materials (ASTM) methods on "no wear" turf
and "wear" turf which simulated turf after having up to 96 games played on it. It is clear from
the results that even after wear simulating 96 games, the hardness index remained well below the
maximum Gmax rating of 200.
2.9 Background Levels of COPCs in the Environment
Most of the chemicals found in crumb rubber are common in an urban environment.
Possible exposure sources for a variety of these chemicals are listed in Table 2-5. A significant
outdoor source for PAHs, for instance, is vehicular exhaust. Worn tires also contribute to a small
percentage of urban respirable dust. Breathing air containing PAHs from cigarette smoke and
eating grilled or charred meats are the major contributors to an individual's PAH exposure.
Table 2-6 lists PAH levels in a variety of foods. Diet is an important source not only of PAHs
but also numerous other chemicals.
In general, there is limited. data on environmental background levels of the various PAHs
that have been found in crumb rubber. The Statewide Rural Surface Soil Survey, a background
study that collected 269 rural soil samples throughout New York State and analyzed 179
analytes, including some PAHs, provides some background soil levels (6NYCRR Part 375
Appendix D). These rural background levels, however, may not be representative of background
levels in an urban setting like NYC. Menzie (1992) estimated that PAH concentrations in rural
soil ranged between 0.01 to 1.01 mg/kg (dry weight) whereas in urban settings the soil might.
contain from 0.06 to 5.8 mg/kg of PAHs. The 'soil' of NYC has been moved, contaminated,
replaced with other soil, and augmented with clean soil multiple times in the past 400 years. As
in most urban areas, there are places where concentrations of any given chemical are much
higher or lower than in others.
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2.10 Potential Data Gans
Potential data gaps include the lack of consistent test methods for determining the
chemicals in crumb rubber made from different source materials and from different processing
techniques. Additional tests could be performed to determine the variability of infill material,
including:
Analyses of crumb rubber that is manufactured using mechanical grinding versus
crumb rubber that is manufactured using cryogenic processing.
• Analyses of crumb rubber produced from different sources (i.e. SBR granules versus
EPDM granules versus thermoplastic elastomer [TPE] granules),
Following these tests, differences in potential leaching and off -gassing associated with these
materials could be determined.
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' TABLE 2,1: CHEMICALS OF POTENTIAL CONCERN
MATRIX: CRUMB RUBBER
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Croup
Individual Analytes.
Maximum or Range of
Detected
Detected
Concentrations Detected
Matrix Analyzed
Reference
Aniline
0.000742 mg/g tire
Tires, tire shreds,
CalEPA,
Amines
chips, or crumb
2007'
n-n itrosodipheny lam ine
7.03 mg/kg
Crumb rubber
RAMP, 2007
benzene
0.000219 mg/g tire
Tires. tire shreds,
CalEPA.
Aromatic
hydrocarbons
toluene
ethylbenxene
0.0168 mg/kg ,
0.337 mg/kg
chips, or crumb .
rubber
2007•,
RAMP. 2007
Xylenes
0.134 mg/kg
Crumb rubber
RAMP, 2007
benzothiazole
171 mg/kg
Crumb rubber
Reddy &
Benzothiazole
2-hydroxybenzothiazole
80.9 mg/kg
Quinn, 1997
compounds
2-(4-morpholino)
3.76 mg/kg
benzathiazole
acetone
1.45 mg/kg
Tires, tire shreds,
CalEPA,
methyl isobutyl ketone
• 11.4 mg/kg
chips, or crumb
20070,
Ketones
rubber
RAMP, 2007
methyl ethyl ketone
0.000017 mg/g tire
Tires, tire shreds,
CalEPA,
chips, or crumb
20070
barium
0.001700 mg/g tire
Tires, tire shreds,
CalEPA,'
chromium
0.000500 mg/g tire
chips, or crumb
20070
iron
lead
1.100000 mg/g tiro
0.000920 mg/g tire
manganese
0.005800 mg/g tire
zinc
2.320000 mg/g tire
cobalt
141 mg/kg
Crumb rubber
RAMP, 2007
Metals
arsenic
lead
1.01 mg/kg
67.2 mg/kg
manganese
zinc
7.5 mg/kg
17.000 mg/kg
cadmium
<0.5 -- 2 mg/kg
Crumb rubber
Plesser, 2004
chromium
<2 — 5200 mg/kg
copper
lead
<3 — 70 mglkg
8-20 mg/kg
zinc
7300-17.000 mg/kg
naphthalene
0.000100 mg/g tire
Tires, tire shreds,
CalEPA,
2-methylnaphthalene
not provided
chips, or crumb
2007•,
PAHs
ehrysene
3.82 mg/kg
RAMP, 2007
tluoranthene
15.9 mg/kg
pyrene
28.3 mg/kg
3-6 carcinogenic PAHs
0.06 — 8.58 mg/kg
Rubber granules
Crain &
from synthetic turf
Zhang. 2006
samples
and 2007
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' TABLE 24: CHEMICALS OF POTENTIAL CONCERN
MATRIX: CRUMB RUBBER
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Group
Individual Anslytes
Maximum or Range of
Detected
Detected
Concentrations Detected
Matrix Analyzed
Reference
Aniline
0.000742 mg/g tire
Tires, tire shreds,
CalEPA,
Amines
chips, or crumb
2007*
n-nitrosodipheny lam ine
7.03 mg/kg
Crumb rubber
RAMP, 2007
benzene
0.000218 mg/g tire
Tires, tire shreds,
CalEPA,
Aromatic
toluene
0.0168 mg/kg.
chips, or crumb
2007*,
hydrocarbons
ethylbenzcne
0.337 mg/kg
rubber
RAMP, 2007
Xylenes
0.134 mg/kg
Crumb rubber
RAMP, 2007
benzothiazole
I71 mg/kg
Crumb rubber
Reddy &'
Benzothiazole
2-hydroxybenzothiazolc
80.9 mg/kg
Quinn, 1997
compounds
2-(4morpholino)
3.76 mg/kg
benzothiazole
acetone
1.45 mg/kg
Tires, tire shreds,
CalEPA,
methyl isobutyl ketone
. 11.4 mg/kg
chips, or crumb
2007*,
Ketones
rubber
RAMP, 2007
methyl ethyl ketone
0.000017 mg/g tire
Tires, tire shreds,
CalEPA,
chips, or crumb
2007*
barium
0.001700 mg/g fire
Tires, tire shreds,
CaIEPA,
chromium
0.000500 mg/g tire
chips, or crumb
2007*
iron
lead
1.100000 mg/g tim
0.000920 mg/g tiro
manganese
0.005800 mg/g tire
zinc
2.320000 mg/g tire
cobalt
141 mg/kg
Crumb rubber
RAMP, 2007 .
Metals
arsenic
lead
1.01 mg/kg
67.2 mg/kg
manganese
7.5 mg/kg
zinc
17,000 mg/kg
cadmium
<0.5 — 2 mg/kg
Crumb rubber
Plesser, 2004
chromium
<2 — 5200 mg/kg
copper
<3 — 70 mg/kg
lead
8-20 mg/kg
zinc
7300-17.000 mg/kg
naphthalene
0.000100 mg/g tire
Tires, tire shreds,
CalEPA.
2-methylnaphthalene
not provided
chips, or crumb
20070,
PAHs
chry'sene
3.82 mg/kg
RAMP, 2007
fluoranthene
15.9 mg/kg
pyrene
28.3 mg/kg
3-6 carcinogenic PAHs
0.06 — 8.58 mg/kg
Rubber granules
Crain &
from synthetic turf
Zhang, 2006
samples
and 2007
2-13

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TABLE 2-1: CHEMICALS OF POTENTIAL CONCERN
' MATRIX: CRUMB RUBBER
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Croup
Individual Anatytes
Maximum or Range of
Detected
Detected
Concentrations Detected
Matrix Analyzed
Reference
naphthalene through
Total PAHs: I — 76 mglkg
Crumb rubber
Messer, 2004
benzo(g,h.l)perylene
Phcnanthrenc: 0.43 — 5.9 mg/kg
Fluoranthene: 0.12 — 11 mg/kg
Pyrene: 0.16 — 37 mg/kg
Benzo(a)pyrene: 0.12 — 3.1 mg/kg
Benzo(b)fluoranthene: <0.08 — 3.9
mg/kg
Phenols
4-'t-octylphenol
49.8 — 33,700 mglkg
Crumb rubber
Messer; 2004
iso-nonyl phenol
1120 — 21.600 mglkg
(recycled rubber)
bis(2-cthy1hexy0phthalatc
203 mglkg
Cnunb rubber
.RAMP, 2007
diethylphthalate
3.1 mglkg
Phthalates
di-n-butylphthalate
1.6 — 3.9 mglkg
Crumb rubber
Plesser. 2004
diisononyiphthalate
57 — 78 mglkg
(recycled rubber)
bis(2-ethylhexyl)phtha1ate
3.9-29mg/kg
carbon disulfide
0.323 mglkg
Crumb rubber
RAMP, 2007
Other
chloroform
0.732 mglkg
methylene chloride
0.286 mg/kg
tetrachloroethcne
0.280 mg/kg
•CaIEPA, 2007: all concentrations reported by this
study based on leachate studies and are in units of ng reteased/g fire
.2-14

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TABLE 2-2: CHEMICALS OF POTENTIAL. CONCERN
MATRIX: AIR
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Group
Detected
Individual Analytes Detected
Matrix Analyzed
Reference
2-butoxyethanol
Indoor air with synthetic turf
NIPH, 2006
Alcohols
1.2-propanediol
including rubber granulates
I-methixy-2-propanot
ethylbenzene aldehyde isomers
Indoor air with synthetic turf
NIPH, 2006
3-phenyl-2-propenal
including rubber granulates
Aldehydes
formaldehyde
acetaldehyde
hexanal
n-C7 through n-C22
indoor air in tire -retreading factory
Cocheo, 1983
Straight -chain
n-C8 through n-C15
Indoor air with synthetic turf
NIPH, 2006
Alkanes
including rubber granulates
n-hexadecane
Crumb rubber headspace
CT Ag Station,
2007
methylcyclohexane
Indoor air in tire -retreading factory
Cocheo. 1983
trans- i -isopropyl-4-methy lcyclohexane
Cycloalkanes
cis-l-isopropyl-4-methyleyclohexane.
1-isopropyl-3-methy Icyclohexane
indane
ethylcyclohexane
Indoor air with synthetic turf
NIPH, 2006
including rubber granulates
styrene
Indoor air in tirc-retreading factory
Cocheo, 1983
1-isopropyl4-methyl-14-cyciohexadiene
I -methyl-3-(I -methy lv my l )cyciohexene
5-methyl-3-(I-methylvinyl)cyclohexene
1-mcthy 1441-methylvinyl)cyclohexene
dimethylstyrene
Cycloalkenes
cyclodccadene
p-ter-buty (styrene
4-vinylcyclohexene
styrene
Indoor air with synthetic turf
NIPH, 2006
alpha-pinene
including rubber granulates
limonene
3-carene
2,34hydro-1,1,3 -tri methyl-3-phenyl- i H-
indene
n-isopropyl-n'-phcnyl-p-
Airborne dust from indoor air with
NILU, 2006
phenylendiamine
synthetic turf and SBR granulates
Aromatic amines
n-ayciohexyl-2-benzothiazole
sulphonamide
n-phenyl-1,4-phenylenediamine
n-cyclohexyl-2-benzothiazolamine
benzene
Indoor air in tire-retreading'factory
Cocheo, 1983
Aromatic
'toluene
Hydrocarbons
ethylbenzene
xy lens
alkylated benzenes
2-15

k.
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TABLE 2-2: CHEMICALS OF POTENTIAL CONCERN
MATRIX: AIR
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Group
Detected
Individual Analytes Detected
Matrix Analyzed
Reference '
benzene
Indoor air with synthetic turf
NIPH, 2006 '
toluene
including rubber granulates
ethylbenzene
xylenes
alkylated benzenes
1.1'-biphenyl
2-methylnaphthalene
toluene
indoor air with synthetic turf and
NILU, 2006
SBR granulates
alkylated benzenes
Crumb rubber headspace
Plesser, 2004
benzothiazole
Indoor air with synthetic turf
NIPH, 2006
including rubber granulates
benzothiazole
Indoor air with synthetic turf and
NILU, 2006
SBR granulates
2-aminobenzothiazole
Airborne dust from indoor air with
NILU, 2006
Senxothiazole
2-methylthiobcnzothiazole
synthetic turf and SBR granulates
compounds
244-morpholinyl)benzothiazole
2-morpholinothiobenzothiazole
2-mercaptobenzothiazole
2-hydroxybenzothiazole
benzothiazole
Crumb rubber headspace
.CT Ag Station,
.2007
Estee
pentanedioic acid dimethyl ester
Indoor air with synthetic turf
NIPH, 2006
including rubber granulates
acetone
Indoor air with synthetic turf
NIPH, 2006
4-methyl-2-pentanone (MISK)
including rubber granulates
Ketones
cyclohexanone
4-methyl-2-pentanone (MIRK)
Indoor air with synthetic turf and
NILU, 2006
SBR granulates
Organic acids
benzoic acid
Indoor air with synthetic turf
NIPH, 2006
acetic acid
including rubber granulates
PAHs
30 PAHs (naphthalene through perylene)
Indoor air with synthetic turf and
NILU, 2006
SBR granulates
2-isopropyl-6-methylphenol
Indoor air in tire -retreading factory
Cocheo, 1983
Phenols
2,6-di-ter-butt' 1-4-ethylphenol
4-t-"Iphenol
Crumb rubber headspace
CT Ag Station,
'
2007
diethylphthalate
Indoor air in tire -retreading factory
Cocheo, 1983
Phthalates
diisobuty1phthalate
di-n-buty 1phthalate
bis(2-ethy lhexyl )phthalate
diethylphthalate
Indoor air with synthetic turf and
NILU, 2006
diisobutylphthalate
SBR granulates
di-n-butylphthalate
2- 16

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TABLE 2-2. CHEMICALS OF POTENTIAL CONCERN
MATRIX: AIR
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Croup
Detected
Individual Analytes Detected
Matrix Analyzed
Reference
dimethylphthalate
Airborne dust from indoor air with
NILU, 2006
diethylphthalate
synthetic turf and SBR granulates
di-n-butylphthalate
bis(2-ethylhexy I )phthalate
butylbenzylphihalate
tri isobuty lent
Cocheo, 1983
tetraisobutylent
Indoor air in tire -retreading factory
2.5-di-ter-butyl-p-qu inane
nitromethane
Indoor air with synthetic turf
NIPH, 2006
Others
junipene
including rubber granulates
butylated hydroxyanisole
Crumb rubber headspace
CT Ag Station,
2007
trichloromethane
Crumb rubber headspace
Piesser, 2004
cis-l.2-dichloroethene
2-17

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TABLE 2-3: CHEMICALS OF PQTENTIAL CONCERN
MATRIX! CRUMB RUBBER LEACHATE
BASED ON ANALYSES PERFORMED IN THE LITERATURE REVIEWED
Analyte Group
Individual Analytes Detected
Matrix Analyzed
Reference
Detected
Straight Chain
n-hexadenne
Crumb rubber leachate
CT Ag Station,
A Ikanes
2007
aniline
Tire shred leachate
CalEPA, 2007
Amines
nitrosodimethylamine
n-n i trosod iphe ny lam i ne
benzothiazole
Crumb rubber leachate
Reddy, 1997
2-hydroxybenzothiazole
2-(4morphol ino)benzothiazole
Benzothiazole
compounds
benzothiazolc
Crumb rubber leachate
CT Ag Station,
2007
morpholino-thin-benzothiazole
Tire shred and whole tire
CaIEPA, 2007
2-(4-morpholinyl)-benzothiazole
Icachatcs
aluminum
Crumb rubber leachate
. Chalker -Scott,
cadmium
2007
chromium
copper
iron
magnesium
Metals
manganese
molybdenum'
selenium
zinc
cadmium
Crumb rubber.leachate
CT Ag Station,
lead
2007
selenium
zinc
butyb ted hydroxyanisole
Crumb rubber leachate
CT Ag Station.
2007
Other
sulfur
Crumb rubber leachate
Chalker -Scott.,
2007
0
J
2-I8

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TABLE 2-4: RUBBER INFILL COMPONENTS FROM SYNTHETIC TURF IN SELECT PARKS IN NYC
TABLE PREPARED USING DATA FROM:
MSDS FOR RUBBER INFILL MATERIALS PROVIDED BV NEW VORK CITY PARKS DEPARTMENT
(NYC Department of Parks and Recreation)
Crumb Rubber
Source of
Constituents Noted on
Manufacturer
Information
MSDS
CAS N
Weight %
MSDS from
Naphthenic/aromatic oil
64742-01=4
<25%
DPR(dated April
-2002)
RTI Ground Rubber
Carbon black
1333-864
C35%
Talc, Respirable Dust
14807-96-6
<5%
Zinc compounds
1314-13-2
<3%
MSDS from DPR
NR (reprocessed rubber)
9003-31-0
44%
(received by NYC
on 4/9/07)
CIS-Polybutadiene
NA
11%
HAF Black (carbon
NA
33%
black)
Rubber (ReTekek, Cured Black
Oil (Softener)
NA
5.5%
Inc,)
Stearic Acid
00057-114
1.1%
Wax
NA
1.1%
Zinc Oxide
01314-13-2
1.7%
Sulfirr
07704-34-9
1.1%
NOBS
NA
0.4%
ANTIOZ
NA
1.1%
MSDS from DPR
Reprocessed rubber
40-55%
(received by NYC in
NR
9003-31-0
July 2006)
SBR
9003-55-8
Carbon black
1333-86-4
27-33%
Reprocessed Ground
Process oil
647424W7
10-20%
Rubber (SJM Group
of New York)
Zinc oxide
01314-13-2
1.5%
Sulfur
07704-34-9
1-5%
Stearic Acid
00057-114
1-5%
RTI = Recycling Technologies Int'I, LLC
NA = Not available
NOBS = n-oxydiethylent-2-benzothiazole sulfonamide
ANTIOZ = antiozonants
2-19

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TABLE 2-5: CHEMICALS OF POTENTIAL CONCERN AND THEIR PRESENCE IN THE ENVIRONNIENT
Chemical or
Wbere found and/or major uses
Principal exposure sources for New Yorkers
chemical class
Henzothiazoles
Used for vulcanization and as preservatives in tires; as starting compounds in:
Food and medications
pharmaceutical manufacture; occur naturally in cocoa, asparagus, whisky and mango;
as a flavoring agent (e.g. in caramel, coffee, garlic, tomato, potato, meat, and other
products)
Polycyclic
Farmed during combustion or burning processes. including fires, burning of fuel, and.
Tobacco smoke, vehicular exhaust, food (especially shelifish, fish,
Aromatic
natural events such as volcano eruptions'. rarely produced intentionally
and charbroiled or grilled meats)
Hydrocarbons
(PA.Hs)
Volatile organic
VOCs are carbon -containing compounds with high vapor pressures and low water
Fuel (including.gasoline and oil) paints, varnishes, waxes, lacquers,
compounds
solubility. They are used in diverse products and may evaporate into the air while you
paint strippers and other solvents, cleaning products, air fresheners,
(VOCs)
are using them or when they are stored. Although many VOCs are now synthetically
pesticides, building materials, copiers. printers, correction Fluids,
produced, many of these chemicals occur in nature.
carbonless copy paper, adhesives, permancnt markers, photographic
solutions dry-cleaned clothing, -trees, etc.
iron*
Essential trace clement that is common in the environment; main component of steel
Ambient air. food and drinking water, and contact with consumer
and other alloys; iron compounds arc used widely as catalysts. pigments,
products containing iron compounds; people who work as
pharmaceuticals, dietary supplements, in agriculture and leather tanning
ironworkers or do demolition and scrap metal recycling generally
have eater exposure
Zinc
Essential trace element that is common in the environment --present in air, water, soil
Meat, poultry, fish, leafy greens; dietary supplements
and food; used widely for commercial and industrial applications, such as pennies, dry
tell batteries, pharmaceuticals, anti-perspirants/deodorants, anti -dandruff shampoos,
sun block aingalvanized metals wood preservatives -etc.
Leads
Construction, storage batteries; ammunition; nuclear and-x=ray shielding devices; cable
Lead paint; herbal remedies and cosmetics containing lead; imported
covering; ceramics; crystallware; solders; noise control materials; bearing and casting
products (including condiments, spices and other foods); people.who
metals-, alloys; piping; petroleum refining; piamintsm plastics and electronic devices
work with lead directly have increased ex sure
Talc
Used in cosmetics (including talcum powder). ceramics, pharmaceuticals, paints.
Use of products containing talc or from food packaging (which may
synthetic rubber. plaster, crayons, and as dusting powder in various industries
contain talc)
Carbon black"
Used in tires and other rubber products; as a pigment for eye cosmetics, inks, dyes. and
Particulate matter from worn tires; contact with products containing
paints; as a UV light absorber, has many industrial applications
carbon; workers in certain industries have increased exposure levels
Sulfur'
Essential clement present in proteins and other foods; utilized in the manufacture of
Protcin-rich foods, ambient air, water
agricultural chemicals and petroleum refining in particular. but has numerous other
uses
Aromatic amines
Used in the manufacture of azo.dyes,. plastics. rubber, isocyanates, inks, rains,
Tobacco smoke, occupational cxposure to these compounds
varnishes, perfumes, artificial sweeteners, leather, biocides, polymers; in research ..
settings and closed processes wlcanizin a ant
2-20
40

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TABLE 2-5; CHEMICALS OF POTENTIAL CONCERN AND THEIR PRESENCE IN THE ENVIRONMENT
Chemical or
Where found and/or major uses
Principal exposure"sources for New Yorkers
chemical class
. .
Barium*
Pigments; in manufacture of rubber, photographic paper, x-ray contrast material,
Ambient air, food, water, contact with barium -containing products;
ceramics/bricks; also used with metals, oil, glass, plastic, pyrotechnics
medical diagnostic procedures involving a barium enema
Chromium'
Used widely in metal alloys and metalplating; as catalysts; in the textile industry; in
Ambient air, food, water, contact with chromium -containing
tanning leather, pigments, varnishes, inks, paints, glazes; chemical synthesis,
products; occupational exposures am likely to be higher
photography.
Stearic acid
Used in soaps, lubricants, baked and confectionary products, vulcanization of tires.
Ambient air, tobacco smoke, food and beverages, use of products
plastics, rubber production, pharmaceuticals, candles, -cosmetics.
containing stearic acid
or ano hilic/antistatic czatings, ointments paper production, paints -
Phthalates
Used to make plastics more flexible; extensive industrial and commercial uses
Ambient air, food and beverages, contact with products containing
phthalates
Alkyl phenols
Used in petroleum refining. as surfactants, antioxidants in plastics and rubber.
Contact with products containing alkyl phenols
biocides, dyes, pharmaceuticals, adhesives,
*Naturally present in the earths crust
Sources: Hazardous Substances Data Bank at hht pJl toxnet.nim.nih.gov/cgi-bin/sis/hbWgm?HSDB and Agency for Toxic Substances and Disease Registry at
btw:,I/www.Ltsdir.cdc.goX/toxpro2.b=llk22Lm-WI05-
2-21

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TABLE 2.6: PAH LEVELS IN FOODS
Food
Concentration of total PAHs
Source
(dry weight unless specified)
Vegetables
4.2 µg/kg (wet weight, ww)
Tateno T. et al. [PAHs] produced from grilled vegetables. J
Food Hy+g Sac Jpn, 1990; 31: 271-76.
Fruit
0.716 µg/kg (ww)
Falc6 G, at al. [PAHs] in foods: human exposure through the
diet in Catalonia, Spain. J Food Prof. 2003; 66: 2325-3 L
Wheat grain
4.0 µg/kg
Jones, at al. Changes in the [PAH] content of wheat grain and
pasture grassland over the last century from one site in the UK.
SO Total Environ, 1989;78: 117-130
Wheat flour
1.5 µg/kg
Dennis, at al. Factors affecting the [PAH] content of cereals,
fats, and other food products. Food Addlt Contam, 1991; 8:
517-30.
Bran
5.5 µgAg
Ibid.
Raw.coffee beans
15.22-20.61 µg/kg
Houessou A. at al. Effect of Roasting Conditions on the [PAH)
Content in Ground Arabica Coffee and Coffee Brew. J. Agric.
Food Chem. 2007, 55: 9719--26
Roasted coffee beans
19.81-117.33 µg/kg
Ibid.
Brewed coffee
0.12-1.74 µg/L
Ibid.
Olive oil
26.3 µg/kg (ww)
Moret S. et al. [PAHs] in edible fats and oils; occurrence and
analytical methods. J Chromatogr A. 2000; 882(1-2): 245-53.
Oysters
1972.0 µg/kg
Sanders M. Distribution of [PAHs] in oyster (Cramostrea
virginica► and surface sediment from two estuaries in South
Carolina.,4rch Environ Contam Toxleol. 1995;28(4):397-405
Smoked fish
784.5 µg/kg
Akpan, at al. [PAHs] in fresh and smoked Fish samples from
three Nigerian cities. Bull Environ Conrom Toxicol, 1994; 53(2):
246-253.
BBQ beef
42.5 µg/kg
Lodovici M, et al. [PAH] contamination in the Italian diet.
Food Addit Contam, 1995; 12(5): 703-713.
Grilled frankfurter:
790.4 µg/kg
Larsson-BK, at al. [PAHs] in grilled food J.4grk Food Chem.
1983;31(4):867-73.
Lamb sausage
45,43 µg/kg
Mottier P, et al. Quantitative determination of [PAHs] in -
barbecued meat sausages by gas chromatography coupled to
mass spectrometry.J.4gric Food Chem, 2000;48(4):1160-6
2-22