(navigation image)
Home American Libraries | Canadian Libraries | Universal Library | Community Texts | Project Gutenberg | Children's Library | Biodiversity Heritage Library | Additional Collections
Search: Advanced Search
Anonymous User (login or join us)
Upload
See other formats

Full text of "The Aquatic toxicity of scrap automobile tires"

FILE COPY 



THE AQUATIC TOXICITY OF 
SCRAP AUTOMOBILE TIRES 



NOVEMBER 1996 




Ontario Environment 



Ministry of 
Environmei 
and Energy 



ISBN 0-7778-4835-X 



THE AQUATIC TOXICITY 

OF 

SCRAP AUTOMOBILE TIRES 



NOVEMBER 1996 
REPRINTED JUNE 1997 



© 



Cette publication technique 
n'est disponible qu'en anglais. 

Copyright: Queen's Printer for Ontario, 1996 

This publication may be reproduced for non-commercial purposes 

with appropriate attribution. 



PIBS 3509E 



THE AQUATIC TOXICITY 

OF 

SCRAP AUTOMOBILE TIRES 



Report prepared by: 

S.G. Abernethy 1 

B.P. Montemayor 

J.W. Penders 2 



'Aquatic Toxicology Section, Standards Development Branch 
Ontario Ministry of Environment and Energy 

environmental Programs, University of Guelph 
Guelph, Ontario 

Report prepared for: 

Waste Reduction Branch 
Ontario Ministry of Environment and Energy 



ACKNOWLEDGEMENTS 

This study was a collaborative project funded by a grant to the University of Guelph through the 
Industrial Waste Diversion Program (Tires) from the Waste Reduction Branch, Conservation and 
Prevention Division, Ontario Ministry of Environment and Energy (MOEE). Mary Pysch 
administered the grant application. Scott Abernethy (MOEE) was the research leader for the 
project. Beta Montemayor and Jason Penders (University of Guelph) conducted the laboratory 
experiments. 

The following MOEE staff are acknowledged: John Lee, Mike Mueller and David Poirier kindly 
provided the services of their toxicity testing laboratories; Gary Westlake helped initiate the 
project; Vince Taguchi, Don Robinson, Peter Jones, Paul Yang, Marg Zeigler, Dan Toner, and 
Otto Meresz conducted chemical analyses or provided data interpretations; Mary Pysch, Neal 
Ahlberg, Irena Pater, Deo Persaud and Don MacGregor (Environment Canada) reviewed the draft 
report and made suggestions for the final report; and Phil Bye collected scrap tires and water 
samples from a tire trench. 

Tom Millar of the Turkey Point Property Owner's Association collected scrap tires and water 
samples from an artificial reef in eastern Lake Erie. 



EXECUTIVE SUMMARY 

The potential for contamination of surface water by automobile scrap tires is a concern because 
tires have been proposed for use as artificial reefs and floating breakwalls in lakes and rivers. 
Several laboratory studies have revealed that whole tires or tire pieces placed in a tank of water 
(static, no flow) release chemical substances lethal to certain aquatic species, especially rainbow 
trout. The lethality was observed for tires that had not been previously placed in water or 
exposed to an aquatic environment. One study tested tires that had been previously exposed to 
an aquatic environment (tires collected from a ten-year-old floating breakwall in Lake Ontario). 
These tires were placed in a tank of static water, but were found to be nonlethal to trout. Field 
studies have noted that fish and other aquatic life are attracted to aquatic tire structures soon 
after construction. Clearly, water flow and other natural processes such as biodégradation must 
be considered when assessing the potential toxicity of tires in an aquatic environment. 

Therefore, the release of chemical substances from tires to water needs to be investigated with 
tests designed to better simulate field conditions. The purpose of this study was to test scrap 
tires placed in flowing water, since water flow and dilution largely determine the occurrence of 
toxicity in natural waters. For the present study, a group of tires was collected from an artificial 
reef in Lake Erie and from a tire trench site in contact with groundwater. Also collected for 
testing were two groups of recently-discarded tires that had not had contact with an aquatic 
environment. 

The first objective was to measure the rate of chemical release in flowing water. Each group 
of tires was placed in a tank of flowing water for several months, and water samples were 
collected periodically for trout lethality tests. The tests showed that the tires were nonlethal to 
trout at a minimum water flow rate of 1.5 litres per minute per 600 litre water volume, a flow 
less than that provided by most Ontario surface waters. Therefore tires in Ontario waters are 
not expected to cause acute lethality because of sufficient natural dilution. Other environmental 
processes such as biodégradation, photolysis and particle-binding may also reduce contaminant 
levels in waters around an aquatic tire structure. 

The rate of chemical release decreased during each tire submersion period in the flow-through 
tests, probably because of a continuous process of leaching. Chemical release also may have 
been blocked by a bacterial growth that formed on the surface of the submersed tires. The 
composition of the rubber at the tire surface also may have changed over time in flowing water, 
possibly affecting chemical release. 

The second objective was to compare the toxicity of groups of tires that had had different 
exposure periods to an aquatic environment. Each group of tires was placed in a tank of static 
water without flow. After several days, a water sample was collected for a trout test and for 
chemical analyses. The trout tests showed that tires collected from the artificial reef in Lake 
Erie were less toxic than scrap tires that had not been previously exposed to an aquatic 
environment. The chemical analyses detected many more contaminants released by the 
previously unsubmersed scrap tires than by the reef tires. Previous exposure to an aquatic 



environment probably depleted the reef tires of leachable chemicals. There may have been other 
environmental processes (for example, a change in the composition of the tire rubber) that were 
responsible for the lower toxicity in static water tanks of the tires collected from the artificial 
reef compared to the previously unsubmersed scrap tires. 

The third objective was to characterize, identify and confirm the toxicant found in static tire 
water. The toxicant could not be identified, but it was characterized as an organic mixture and 
aromatic amines were the suspected principal component. The report provides guidance for a 
limited further investigation to identify some of the principal toxic constituents. 



111 



TABLE OF CONTENTS 

Page 

ACKNOWLEDGEMENTS i 

EXECUTIVE SUMMARY ii 

1.0 INTRODUCTION 1 

2.0 METHODS 1 

2.1 TTRE WATER 2 

2.1.1 FLOW-THROUGH TIRE WATER 2 

2.1.2 STATIC TIRE WATER 3 

2.2 TOXICITY IDENTIFICATION EVALUATION (TIE) 3 

2.3 TOXICITY TESTS 6 

2.4 CHEMICAL ANALYSES 7 

3.0 RESULTS 8 

3.1 FLOW-THROUGH TIRE WATER 8 

3.2 STATIC TIRE WATER 13 

3.3 TOXICITY IDENTIFICATION EVALUATION 13 

3.3.1 STATIC TTRE WATER 13 

3.3.1.1 TROUT LETHALITY 13 

3.3.1.2 CHEMICAL CHARACTERIZATION 14 

3.3.2 TTRE CRUMB WATER 15 

3.3.2.1 D. MAGNA LETHALITY 15 

3.3.2.2 C. DUBIA SURVIVAL AND REPRODUCTION 16 

3.3.2.3 CHEMICAL CHARACTERIZATION 16 

4.0 DISCUSSION 17 

5.0 CONCLUSIONS 22 

REFERENCES 23 



IV 



APPENDICES 

A ANALYSES OF TIRE WATER AND CONTROL WATER 

B ANALYSES OF SURFACE WATERS 

C ANALYSES OF TIRE CRUMB WATER AND CONTROL WATER 

D GC/MS ANALYSES FOR EXTRACT ABLE ORGANIC COMPOUNDS: TTRE WATER 

E GC/MS ANALYSES FOR EXTRACT ABLE ORGANIC COMPOUNDS: SURFACE WATERS 

F GC/MS ANALYSES FOR EXTRACT ABLE ORGANIC COMPOUNDS: TTRE CRUMB WATER 

G GC/MS ANALYSIS FOR VOLATILE ORGANIC COMPOUNDS: TTRE WATER 

H LC/MS ANALYSIS FOR EXTRACT ABLE ORGANIC COMPOUNDS: TIRE WATER 

I SCANNING ELECTRON MICROSCOPY: TTRE CRUMB MATERIAL 

J UV/VIS SPECTROMETRY: TTRE WATER AND TIRE CRUMB WATER 

K FTTR ANALYSIS: TIRE CRUMB MATERIAL 

L CHEMICAL ANALYSES FOR TOTAL UNFILTERED REACTTVE PHENOLS: 

TIRE WATER. SURFACE WATER 

M ACUTE LETHALrrY TO RAINBOW TROUT OF FLOW-THROUGH TTRE WATER: 

TIME TO 50% MORTALITY (LT50) IN THE SINGLE CONCENTRATION TESTS 

N ACUTE LETHALITY TO RAINBOW TROUT OF FLOW-THROUGH TTRE WATER: 

PERCENTAGE MORTALITY IN THE DILUTION SERIES TESTS 

O ACUTE LETHALITY TO RAINBOW TROUT OF STATIC TTRE WATER: 

PERCENTAGE MORTALITY E\ T THE DILUTION SERIES TESTS 

P ACUTE LETHALITY TO RAINBOW TROUT OF STATIC TTRE WATER 

SUBJECTED TO TOXICITY REDUCTION TREATMENTS 

Q ACUTE LETHALITY TO DAPHNIA MAGNA OF ITRE CRUMB WATER 

SUBJECTED TO TOXICITY REDUCTION TREATMENTS 

R ACUTE LETHALITY TO DAPHNIA MAGNA OF TIRE CRUMB WATER 

TREATED WITH EDTA 

S ACUTE LETHALITY TO DAPHNIA MAGNA OF TIRE CRUMB WATER 

SUBJECTED TO SOLID PHASE EXTRACTIONS 

T CHRONIC TOXICITY TO CERIODAPHNIA DUBIA OF TTRE CRUMB WATER 

U ACUTE LETHALrrY TO TROUT OF SOLVENT-EXTRACTS OF TIRE CRUMB 



1.0 INTRODUCTION 

The potential for contamination of surface water by automobile scrap tires is a concern because 
tires have been proposed for use as artificial reefs and floating breakwalls in lakes and rivers. 
Laboratory studies, reviewed in a previous report (Abemethy, 1994) have revealed that whole 
tires or tire pieces placed in a tank of water (static, no flow) release chemical substances lethal 
to certain aquatic species, especially rainbow trout. The lethality was observed for tires that had 
not been previously placed in water or exposed to an aquatic environment. One study (Day et 
al., 1993) tested tires that had been previously exposed to an aquatic environment (tires collected 
from a ten-year-old floating breakwall in Lake Ontario). These tires were placed in a tank of 
static water, but were nonlethal to trout. Field studies have noted that fish and other aquatic life 
are attracted to aquatic tire structures soon after construction (Mueller and Liston, 1994; Nelson 
et al., 1994). 

Clearly, water flow and other natural processes such as biodégradation must be considered when 
assessing the potential toxicity of tires in an aquatic environment. Therefore the release of tire 
chemicals needs to be investigated with tests designed to better simulate field conditions. The 
purpose of the present study was to test scrap tires placed in flowing water, since water flow and 
dilution largely determine the occurrence of toxicity in natural waters. The specific objectives 
were to: 

(1) measure the rate and extent of chemical release from tires placed in flowing water; 

(2) compare the acute lethality of tires that had been previously submersed in an aquatic 
environment for various periods of time; and 

(3) characterize, identify and confirm the toxicant found in static tire water. 



2.0 METHODS 

To investigate the chemical leaching process (objective 1), rainbow trout acute lethality tests were 
conducted on samples of water in contact with whole tires. The tires were placed in flowing 
water or in a fixed- volume of static water for a period of time to prepare flow-through or static 
tire water respectively. Tire water samples were collected and diluted to different ratios, and 
trout were exposed to the dilution series following a standard test procedure. The trout tests were 
conducted on four groups of scrap tires described in section 2.1 (objective 2). To characterize 
and identify the toxicant (objective 3), a Toxicity Identification Evaluation was conducted. 
Samples of static tire water were subjected to bench-top treatments, and trout tests were 
conducted on the treated waters. Similarly, tire crumb was leached with water, and the water 
was treated for toxicity tests of two daphnid (small crustaceans) species. The tire crumb was 30 
to 40 mesh-size particles of granulated scrap tires, devoid of the fine fibre and steel components 
normally found in tires. Extensive chemical analyses were conducted on the static tire water and 
on the tire crumb water. 



2.1 Tire water 

Whole scrap tires, ranging in weight from 7 to 12 kilograms each, were used to prepare flow- 
through and static tire water. The tires were from four sources and were tested as separate 
groups. The tire groups were named and denoted as A, B, C and D: 

Reef tires (A) Five scrap tires were collected in March 1994 from an artificial reef in Lake Erie, 
near Turkey Point. Three tires were smaller than average so the total amount of tire material was 
about equal to four average-sized tires. The reef had been constructed in November, 1992 with 
about two thousand tires sunk in twenty-three feet of water. An ambient water sample for 
chemical analyses was collected at the same time as the tires were removed for testing. 

Trench tires (B) Four tires were collected in July, 1994 from a covered trench just north of 
Mount Forest, Ontario. The trench had been excavated around 1991 for an unauthorized tire site, 
holding about 33,000 tires. The trench was partly-filled with ground water from a fluctuating 
water table. A surface water sample, for a trout test and chemical analyses, was collected from 
a connecting trench, suspected of having contact with the tires. 

Scrap tires (C) Four tires of a set discarded from an automobile. None had been placed in water 
or exposed to an aquatic environment before the present study. 

Scrap tires (D) Three tires of a set discarded from an automobile. One of the tires had been 
placed in water for a previous toxicity study, described in Abernethy (1994). In that study, the 
tire had been placed in a 300-litre water tank on three separate occasions for a total of thirty-six 
days, and in a 600-litre flow-through tank for twelve days. The other two scrap tires of group 
D had not been placed in water or exposed to an aquatic environment before the present study. 

Each of the four groups of scrap tires was tested more than once. A total of three flow-through 
tire waters and fourteen static tire waters were prepared, as specified below. Unless indicated 
otherwise, the tires were not washed or cleaned, but were tested as received. 



2.1.1 Flow-through tire water 

Flow-through tire water was prepared in a polycarbonate tank (177 x 66 x 60 cm). A group of 
four or five tires was submersed in a 600-litre volume of water, and the water flow rate was 
controlled with a head tank. The water inlet and outlet were at opposite ends of the tank so the 
water flowed over the tires. A water sample for a trout test was collected near the outlet at 
various times over the submersion period. The flow rate was adjusted periodically, and the tire 
water from the previous flow rate was flushed out before further water samples were collected. 
A second tank without tires was the experimental control. A flow-through experiment with flow 
rates adjusted over time was conducted for each of three groups of tires (see Table 1). 



Table 1 . Flow-through tire water preparation conditions. 



tire group 1 



submersion range of no. water 
period flow rates samples 

(days) (L/min) collected 



A reef tires 


84 


0.5-2.0 


13 


B trench tires 


78 


0.16-1.0 


18 


C scrap tires 


42 


0.5-1.5 


6 



1 tires described in section 2.1. 

2.1.2 Static tire water 

Static tire water was prepared by placing a number of tires in a fixed volume of water for a 
submersion period, then a water sample was collected for a trout test. Table 2 gives the 
specifications for each of fourteen batches of static tire water, identified as numbers 4 to 17. The 
tires of groups A and D were used to make several consecutive batches of tire water. 
Sometimes, a water sample was collected but the tire submersion was continued at a reduced 
water volume. A batch number followed by a, b or c refers to a tire water volume reduced by 
sampling. During the tire submersion period, the water was aerated using a glass air stone and 
an aquarium air pump. A second water tank without tires was the experimental control. 

Water temperatures ranged from 14 to 18 °C during the submersion periods. The static tire 
waters and control waters were similar in pH (8.0 to 8.4), dissolved oxygen concentration (8 to 
10 mg/L) and specific conductivity (324 to 362 umhos/cm). The water in contact with tires 
became a pale green-yellow colour and had a fishy, ammonia-like odour. The colour may 
indicate oxidation products of aromatic amines and/or phenols, and the odour is a characteristic 
of aliphatic amines. The tire surfaces were coated with a clear slimy material after each 
submersion period, probably due to bacterial growth. The control water was clear and odourless. 



2.2 Toxicity Identification Evaluation (TIE) 

Samples of static tire water were collected for trout tests, chemical analyses and for bench-top 
treatments designed to characterize the physical-chemical properties of the toxicant. The 
effectiveness of each treatment was assessed by comparing the toxicity of a treated sample to the 
toxicity of an unaltered baseline sample. Samples of dilution water were subjected to the same 
treatments and were tested to check for experimental artifacts, such as potential toxicity caused 
by an extraction solvent. All the samples of a tire water were not tested simultaneously. Some 
were stored for further treatments and testing. Stored samples were held as 20-litre aliquots in 
filled, sealed plastic-lined buckets at 15 °C in the dark. Unless indicated, a sample of tire water 
was collected, held, treated and tested all in the same 20-litre bucket. 



Table 2. Static tire water preparation conditions. 



tire 


submersion 


no. 


water 


tire 


water 


period 


tires 


volume 


group 1 


batch 


(days) 




(htres) 




4 


12 


l 2 


300 


D scrap tires 


5a 


16 


3 


300 




5b 


26 


3 


220 




6a 


8 


3 


300 




6b 


13 


3 


280 




7 


13 


l 3 


300 


A reef tires 


8 


13 


1 


300 




9 


13 


3 


300 




10 


15 


3 


300 




11 


12 


3 


300 




12 


11 


3 


300 




13a 


3 


3 


300 




13b 


6 


3 


280 




13c 


13 


3 


260 




14 


11 


3 


300 




15 


3 


5 


600 




16a 


2 


4 


600 


C scrap tires 


16b 


3 


4 


580 




16c 


15 


4 


510 




17a 


1 


4 


600 


B trench tires 


17b 


4 


4 


580 





j 2 

The tires are described in section 2.1; This tire had been used for a previous study, 
described in section 2.1; 3 This tire was washed and scrubbed with water to remove the 
mud and zebra mussels found on all the tires from Lake Erie. All other tires were 
tested as received, without cleaning or washing. 

Samples of static tire water were subjected to the following treatments (the appendices give 
further details of the treatment methods): 

Aeration - Aerated for 24 hours. 

Pre-tested - Ten fish were exposed for a 24-hour test, the fish were removed and ten more fish 
were added for a second test of the same sample. 



Steam distillation - Four litres were boiled to reduce the volume to three litres. Distilled water 
was used to reconstitute the original volume. 



Sulphur binding - A 24-hour nonlethal concentration (560 ug/L) of mercuric chloride was added 
to bind organo-sulphur compounds. 

Carbon sorption - Activated charcoal was added to tire water one day before the test fish. 

Carbon extraction - Activated charcoal was soaked in tire water, then extracted with ethanol. 
The ethanol was dissolved in dilution water for a trout test. 

Solvent extraction - Four litres were extracted by hand-shaking for one minute in a separatory 
funnel with 40 mL dichloromethane. The phases were allowed to separate for one hour, then the 
water was drained off and aerated for 24 hours to purge the dissolved solvent. 

Water quality - Distilled water and dechlorinated tap water were used for dilution series tests. 

Leaching - The number of tires, the volume of water and the contact time were varied. 

Solvent extracts - Dichloromethane and methanol were used to extract compounds from tire 
crumb. The solvent extracts were added to water for trout tests. 

Tire crumb water was made by stirring one hundred grams of tire crumb in four litres of water 
for twenty-four hours. A relatively low weight (tire) to volume (water) ratio was used because, 
compared to a whole tire, tire crumb presents a much larger surface area for toxicant partitioning 
into water. The tire crumb was allowed to settle for twenty-four hours, and the water was 
decanted for toxicity tests, chemical analyses and TEE treatments. Tire crumb or samples of tire 
crumb water were subjected to the following treatments for Daphnia magna acute lethality tests: 

Filtration - A water sample was passed through a 1.2 um glass fibre filter. This also was a pre- 
treatment for solid phase extraction (SPE). 

SPE - A water sample was passed through a 3-mL C, 8 SPE column, and the column was eluted 
with 750 uL methanol. 

Adjustment of pH - Tire crumb was leached with water adjusted to pH 2, 4, 10 and 11. The 
leachates were readjusted to pH 7.5 to 8.1 for testing. IN solutions of hydrochloric acid and 
sodium hydroxide were used. 

Sequential extracts - Tire crumb was leached nine times in succession with separate four litre 
volumes of water. 

Solvent-extracted - Tire crumb was Soxhlet-extracted with dichloromethane and then leached with 
water. 

Metal chelation - A water sample was spiked with EDTA (ethylenediaminetetraacetate), a metal- 
binding agent. 



Samples of tire crumb water also were subjected to filtration and sequential extractions with 
water for Ceriodaphnia dubia 7-day survival and reproduction tests. The water samples were 
stored at 4 °C in the dark until needed to renew the toxicity test solutions during a test. 

Two trout tests were conducted on a commercial automotive product used to clean and protect 
tire surfaces. The product is a proprietary mixture, but it is believed to contain the same 
alkylphenols used as protective agents in tire manufacture. Single concentrations of 1000 and 
2000 parts per million (volume/volume) of the whole product were tested. The product formed 
a milky-white dispersion when added to water, and was found to be nonlethal at both test 
concentrations. 



2.3 Toxicity tests 

The toxicity tests were conducted from September 1993 to October 1994. Canadian national 
procedures were followed for acute lethality testing of rainbow trout and Daphnia magna 
(Environment Canada, 1990a; 1990b). The procedures give specifications for animal cultures, 
dilution water, test conditions, observations, measurements and calculations. The chronic tests 
of Ceriodaphnia dubia also followed a standard procedure (Environment Canada, 1992). 
Dechlorinated municipal tap water was used for animal cultures and to prepare and dilute tire 
water. It was an alkaline hard water that was temperature-adjusted and aerated to oxygen 
saturation before use. The animal cultures and toxicity tests had a daily photoperiod of 16 hours 
of fluorescent light. 

The trout were hatchery fish acclimated in the laboratory for at least two weeks at 13 to 17 °C. 
The daphnids were from reproducing laboratory cultures at 18 to 22 °C (D. magna) and at 23 to 
27 °C (C. dubia). The trout were raised in tanks with aerated flow-through water, and the 
daphnids were raised in static cultures with water replacement two or three times per week. The 
cultures were fed daily. The fish were fed commercial trout chow. D. magna were fed a 
combination of two algae species (Selenastrum capricomutum and Chlorella fusca). C. dubia 
were fed a mixture of yeast, cereal grass and trout chow supplemented twice weekly with the 
two-algae diet. 

A sample of tire water was diluted to different ratios for toxicity testing. The dilutions are 
expressed as a percentage by volume. An undiluted sample of tire water is defined as the 100% 
concentration. 10% tire water would be diluted with 90% dechlorinated municipal tap water. 
The water temperature, pH, dissolved oxygen concentration and specific conductivity of the 
toxicity test dilutions were measured before and after the tests. The test animals were checked 
daily to observe survival or reproduction rates. Table 3 summarizes the test conditions. 

A toxicity test was ended after a fixed exposure time, and the cumulative percent mortality was 
calculated for each tire water dilution. The toxicity test data were used to estimate the median 
lethal concentration (LC50) and 95% confidence limits for each day of exposure. Median lethal 
times (LT50s) and 95% confidence limits were estimated from the cumulative percent mortality 



over time in each tire water dilution. Low values of LC50 or LT50 denote high toxicity. The 
Probit method was used to estimate toxicity values when partial mortalities (16 to 84%) occurred, 
otherwise the Spearman-Karber method was used. The LT50s and LC50s for separate samples 
were considered significantly different if the confidence limits did not overlap. If confidence 
limits are not shown, they could not be calculated from the data. For some samples, the toxicity 
value is reported as LC50 > 100% or LT50 > 96 hours. These samples caused some mortality, 
but it was less than 50%, so the standard estimate of toxicity could not be made. 

Table 3. Toxicity test specifications. 



Test species 


trout 


D. magna 


C. dubia 


Exposure time (days) 


4 


2 


1 


Life stage 


fry 


neonates 


neonates 


Weight or age 


0.7-4.3 g 


< 24 hours 


< 24 hours 


Test vessel 


20-L plastic bucket 


50-mL glass vial 


30-mL plastic cup 


Solution volume 


20 L 


50 mL 


15 mL 


Loading 


10 fish 


3 neonates 


1 neonate 


Replicates 










none 


4 


10 


Temperature (°C) 










13 to 17 


18 to 22 


23 to 27 


Aeration 










yes 


no 


no 


Food 










none 


none 


algae and YCT 1 



YCT is Yeast, Cereal grass and Trout chow in aqueous suspension. 



2.4 Chemical analyses 

At the same time as water samples were collected for toxicity tests and TIE treatments, samples 
also were collected for chemical analyses for: copper, nickel, lead, zinc, iron, cadmium, 
chromium, ammonia, nitrates, nitrite, pH, specific conductivity, dissolved inorganic carbon, 
dissolved organic carbon, chloride, sulphate, hardness, alkalinity, calcium, magnesium, sodium, 
potassium, fluoride and total unfiltered reactive phenols, measured by the 4-anti-aminopyrine test. 



Characterization analyses were conducted to identify nontarget organic compounds using gas 
chromatography/(full scan) mass spectrometry (GC/(FS)MS). The samples were partitioned into 



base-neutral and acid fractions, and extracted with dichloromethane. The reported concentrations 
are approximate, and were calculated relative to the internal standard, d 10 -phenanthrene. One tire 
water sample was analyzed for volatile compounds by a purge-and-trap method followed by 
GC/(FS)MS. One sample was scanned for extractable polar organic compounds using reverse 
phase liquid chromatography/(particle beam) mass spectrometry. 

Ultraviolet (250-400 nm) and visible (400-800 nm) light absorbence spectroscopy was used to 
scan tire water and tire crumb water. Tire crumb was Soxhlet-extracted with dichloromethane, 
and the extract was analyzed for organic functional groups by Fourier Transform Infrared 
Spectroscopy (FTIR). 

Tire crumb was extracted with distilled water at pH 6 following the MOEE leachate procedure 
(as per Schedule 4, Ontario Regulation 347), and the extract was analyzed for inorganic 
contaminants. The tire crumb also was scanned directly for metals by an Inductively Coupled 
Plasma (ICP) technique, and a portion was examined by scanning electron microscopy for 
crystalline structures indicative of certain compounds. 



3.0 RESULTS 

All the data are presented in the appendices. The key data are summarized below to support the 
main findings. 



3.1 Flow-through tire water 

Appendix M lists the LT50 results of the trout tests and Appendix N gives the LC50 test results. 
The figures below are a compilation of the LT50 data for the tire water samples collected over 
time during each of the three sets of flow-through experiments: 

Reef tires (Figure 1) 

At the start (days 7, 11 and 21), the tire water was toxic at 1 L/min flow, but this same flow 
resulted in nontoxic conditions towards the end of the period (days 65, 78 and 84). Flow rates 
of 1.5 and 2.0 L/min produced nontoxic samples (days 30 to 60), and the toxicity was restored 
by lowering the flow to 0.5 L/min. The 4d-LC50 was significantly lower for the day-1 1 sample 
(45%) than for the day-21 sample (71%), although the flow was 1.0 L/min in both cases. In a 
trout test, toxicity was not observed until the second day of exposure, and tended to increase over 
the exposure period. The 30 to 40% concentrations were the highest nonlethal levels. The only 
mortality at 2.0 L/min occurred for the sample at day 29, whereas samples collected at day 31 
and day 36 were nonlethal at this same flow rate. 

No metals, phenols or organic compounds were detected in the water sample collected at the 
Lake Erie tire reef, and other chemical parameters were within normal limits. 

8 



Trench tires (Figure 2) 

Nontoxic tire water was generally produced at flows of 0.5 and 1.0 L/min (days 5 to 16). When 
the flow was lowered to 0.25 L/min (days 21 to 32), lethal conditions occurred initially but the 
water samples tended to be less toxic (LT50 > 96 hours) towards the end of this period. A low 
flow of 0.16 L/min restored the lethality, but flows around 0.36 L/min were nonlethal at the end 
of the flow period (days 68, 69 and 78). 

The sample of water suspected of having contact with the tire trench was nonlethal to trout. The 
chemical data are listed in Appendices B, E and L. GC/MS analysis found only traces of a few 
nitrogen and sulphur compounds that would be associated with tire leachate. No metals or 
phenols were detected, and the other parameters were within normal limits, except the water pH 
(9.2 and 9.4) was relatively high. 

Scrap tires (Figure 3) 

The sample collected on day 15 at 0.5 L/min flow was lethal, but the same flow later produced 
a sample that was nonlethal (day 39) and one that was LT50 > 96 hours (day 42). Higher flow 
rates (1.0 and 1.5 L/min) were nonlethal. 

In summary, the key findings are: 

•• the decrease in toxicity with the increase in water flow rate; the flow rate of 1.5 L/min 

per 600 L water volume produced nonlethal conditions for all tires in all tests; 

• the decrease in toxicity over time in flowing water; 

• the tires from the three-year-old trench were generally less toxic than the tires from the 
1.5-year-old artificial reef in Lake Erie. 

The implications of these findings for tires in the aquatic environment are discussed in section 
4. 



Tires from the Lake Erie artificial reef 



10 



20 



30 40 50 BO 

Flow time (days) 



120 




Figure 1 . Flowthrough tire water toxicity vs flow rate 



Legend for LT50 results: 

• Lethal (greater than 50% mortality in the 96-hour test) 
A LT50 > 96 hours (some mortality, but less than 50%) 
A Nonlethal (no fish died in the test period) 



Tires from the submerged trench 



Ç 

E 

re 
o 




10 20 



30 40 50 60 

Flow time (days) 



70 eo 



Figure 2. Flowthrough tire water toxicity vs flow rate 



Legend for LT50 results: 

• Lethal (greater than 50% mortality in the 96-hour test) 
▲ LT50 > 96 hours (some mortality, but less than 50%) 
A Nonlethal (no fish died in the test period) 



Tires recently discarded from an automobile 



I 

«s 

o 




10 



15 



20 



25 30 

Flow time (days) 



O 

o 

in 



Figure 3. Fbwthrough tire water toxicity vs flow rate 



Legend for LT50 results: 

• Lethal (greater than 50% mortality in the 96-hour test) 
A LT50 > 96 hours (some mortality, but less than 50%) 
A Nonlethal (no fish died in the test period) 



3.2 Static tire water 

Appendix O gives the trout lethality data for the static tire water dilution tests. Surprisingly, tire 
water batch 4 was nonlethal yet the same tire had produced lethality in three previous tire water 
batches (see Abernethy, 1994). Just before making batch 4, the tire had been submersed in a 
flow-through tank containing five trout averaging 170 grams each (a separate sublethal toxicity 
study). During the preparation of tire water batch 4 there was a persistent layer of brown- 
coloured bubbles on the water surface, indicative of natural surfactants probably from organic 
matter and bacterial growth in the water tank. 

Scrap tires leached for the first time (batch 16) were more toxic than the reef tires (batches 7 to 
15). For example, batch 15 (4d-LC50 = 77%) and batch 16b (4d-LC50 = 36%) were both made 
by soaking tires for three days. Batch 16c had the lowest 4d-LC50 (27%) of any of the batches 
tested. Increasing the number of tires per volume of water and/or the submersion time increased 
toxicity using the reef tires (batch 8 vs 9 and batch 14 vs 15) but only slightly increased toxicity 
using scrap tires (batch 16b vs 16c). This suggests the scrap tires not previously submersed may 
have released more toxicant than the reef tires, and the amount released reached the toxicant's 
water solubility limit. 



3.3 Toxicity Identification Evaluation 

3.3.1 Static tire water 

3.3.1.1 Trout lethality 

A comparison of daily LC50s over the course of a trout test (Appendix O) shows that a threshold 
LC50 generally was reached after three days of exposure. Little difference in toxicity was found 
for tire water batches that differed in: makes and models of tires used or the tire surface 
condition (scrubbed tire, batch 7 versus unscrubbed tire, batch 8), the dilution water quality 
(batches 12 and 13c) and the sample age or storage time (batch 14). 

A comparison of the LT50s (Appendix P) shows that baseline tests of fresh unaltered samples 
typically caused 100% mortality within seventeen hours of exposure. No mortality was observed 
in the first six to ten hours of exposure. The toxicant was relatively stable in water: Only a slight 
reduction in toxicity occurred from longer sample storage times. Storage temperature (15 versus 
20 °C), exposure to light and the type of container (plastic versus glass) did not influence the 
toxicity (tests 10, 11, 13 to 16, 19 to 23, 26 and 28). Pre-aeration (tests 12 and 26) slightly 
reduced toxicity. Soaking the same tires for three, six or thirteen days (tests 28, 30 and 31) did 
not influence the LT50. 

Steam distillation (test 28) partially detoxified the tire water, suggesting that a toxic component 
was boiled-off and thus had a boiling point less than that of water (100 °C). This could be 
confirmed by capturing the steam, cooling it to distilled water and conducting a toxicity test on 

13 



the water. Another component of the toxicant was not boiled-off, and is therefore likely to be 
polar. As a class, polar compounds like many amines and phenols have higher water solubilities, 
lower vapour pressures and higher boiling points than nonpolar compounds of the same molecular 
weight. 

Sulphur compounds such as benzothiazoles were prevalent in tire water, and they have been 
found in surface water receiving effluent from a tire manufacturing plant (Jungclaus et al.. 1976). 
However, a tire water sample was not detoxified by adding an organo-sulphur binding agent (test 
25) (Russell, 1975). Tire water was partially detoxified by extraction with methylene chloride 
(test 26, 30 and 33), and completely detoxified by the addition of activated carbon (test 23, 24, 
25 and 27). A portion of the toxicity was recovered from the contaminated carbon by solvent 
extraction with ethanol (test 38). 

As was observed from the LC50 results, the time to mortality' (LT50) was not altered 
significantly by dilution with distilled water compared to well-buffered, hard water (test 29 and 
34). The results were confounded by the 10 to 20% control mortality in distilled water alone. 
Calamari et al. (1980) found that aliphatic amines were more toxic to trout in soft water 
compared to hard water. There was no evidence here implicating these substances as toxicants 
even though the tire water had an odour characteristic of aliphatic amines. Since distilled water 
differs in other water quality parameters (like pH and conductivity), the comparison was not 
conclusive by itself. 

The Soxhlet-extract of the tire crumb was a viscous dark-brown liquid or tire oil. 50 mg/L of 
the tire oil was lethal in two trout tests (Appendix U). Subjectively, the fish responses to tire oil 
differed from those observed during the tire water tests. The toxicant in tire oil is probably 
different than that leached from tires. The methanol extract of tire crumb also was lethal to trout. 



3.3.1.2 Chemical characterization 

The tire and control waters were chemically similar (Appendix A) except low, nontoxic levels 
of zinc were found in the tire waters. Total phenols were measured at slightly higher levels in 
tire water batches 4, 5 and 6 than in batches 7, 10 and 13 (Appendix L). When tire water was 
scanned with ultra-violet and visible tight (Appendix J), no significant light absorbence was 
found. This suggests the major components of the tire water were not aromatic, or at least not 
concentrated enough to be detected by this technique. However ultra-violet fluorescent 
spectroscopy is the preferred technique for confirming the presence of aromatic compounds. 

The organic compounds detected by GC/MS are listed in Appendix D and the numbers detected 
are shown in Table 4. The total number of compounds is comprised of the numbers identified, 
classified and unknown. These three designations were based on the degree of confidence of 
identification. Identified compounds were known specifically (e.g. aniline) and with a high 
degree of confidence. Classified compounds could not be identified, but had specific structural 
features of a compound class (e.g. an aryiamine). Unknown compounds are substances that 

14 



could not be identified, and no known structural features of a compound class were evident. 
Control waters were found to be relatively uncontaminated. As expected, the prevalent 
compounds in tire waters are common rubber-processing chemicals (benzothiazoles, arylamines, 
alkylphenols), their impurities and breakdown products. Tire water batches 4 and 6b (scrap tires, 
group D) had significantly more detectable compounds than batches 7, 10 and 15 (reef tires). 

Table 4. Numbers of extractable organics in static tire water. 

Tire Number of compounds 

water 

batch tota ' identified classified unknown 



4 


35 


17 


6 


12 


6b 


26 


11 


10 


5 


7 


3 





3 





10 


9 


2 


5 


2 


15 


4 


1 


2 


1 



GC/MS for volatile organics (Appendix G) did not reveal any significant contaminants. LC/MS 
analysis for polar organics (Appendix H) did not find any additional chemicals except for an 
alkylphenol. Further LC/MS scans would be desirable because the toxicant has polar properties. 
However the sample preparation for this technique is too labour-intensive for routine applications. 



3.3.2 Tire crumb water 

3.3.2.1 D. magna lethality 

Appendix Q lists the LC50 results for the D. magna tests of tire crumb water. Filtration removed 
a portion of the toxicity, probably associated with fine particles of tire crumb that remained 
suspended in the water. Nine sequential water-extractions of the same tire crumb sample (TCW- 
9 series) did not exhaust the toxicant, so it was probably a major constituent of the rubber. The 
toxicity was removed when tire crumb was first Soxhlet-extracted (TCW-extracted). When tire 
crumb was extracted with water at extreme pH values, then tested at the baseline pH, the toxicity 
was influenced significantly. The 2d-LC50s were < 5%, 24% and 78% for the pH 2, 11 and 
baseline extracts respectively. 

When samples of tire crumb water were treated with the metal-chelating agent EDTA, the 
toxicity was reduced (Appendix R). This suggests a cation metal as the prime cause with an 
additional toxicant present. Acute lethality was reduced by the solid phase extraction (SPE) for 
nonpolar organic compounds. However, some samples of SPE-treated dilution water had slight 
toxicity, indicating a toxic artifact that confounded the results (Appendix S). The toxicant was 



15 



not eluted from the SPE columns by methanol. Nelson et al. (1994) had similar SPE results 
testing water-leachate of plugs cut out of tires, and identified cationic metal (zinc) toxicity. 



3.3.2.2 C. dubia survival and reproduction 

Appendix T lists the results of the C. dubia chronic tests. 7d-LC50s and 7d-EC50s (inhibition 
of reproduction) were similar, ranging from 7 to 19%. The sequential extractions of the same 
tire crumb sample (TCW-9 series) did not exhaust the toxicant material, so it was probably a 
major constituent of the rubber. Water filtration had little effect on the chronic toxicity. 



3.3.2.3 Chemical characterization 

Tire crumb water had high concentrations of zinc and total phenols (Appendices C and L). The 
acidic batch, prepared at pH 2, contained 14 mg/L of zinc and 220 ug/L of total phenols, the 
highest levels found in any of the prepared tire waters. In the standard MOEE leachate test, only 
0.28 mg/L of zinc was extracted from the tire crumb. Other inorganic metals were leached out 
at lower (< 100 ug/L) levels. GC/MS analyses found numerous organic compounds in tire crumb 
water (Table 5). Only 15 to 40% of the detectable compounds could be identified. Many 
benzothiazoles, ary lamines and alkylphenols were present at levels about ten to one hundred 
times higher than in the tire water. The unknown compounds tended to have the longer 
chromatographic retention times that indicate higher molecular weights and lower water 
solubilities. 

Table 5. Numbers of extractable organic compounds in tire crumb water. 





Number of compounds 






Tire crumb 










water batch 


total 


identified 


classified 


unknown 


1 


68 


26 


24 


18 


9a 


111 


31 


31 


49 


pH2 ] 


92 


18 


26 


48 


pH2 


86 


22 


11 


53 


pH 11 


101 


27 


58 


16 


pH8 2 


66 


10 


27 


29 



base/neutral fraction; baseline pH 

More organic compounds were leached out by water at extreme pH than at the baseline pH of 
8. The acid fraction of the pH 2 extract contained cyclic diketones, including p-benzoquinone 
(CAS #106-51-4) at roughly 800 ug/L. The ketones could be rubber additives or the oxidation 
products of aniline- or hydroquinone-type additives. The base-neutral fraction of the pH 2 extract 
contained mg/L levels of aniline and several other cyclic amines. About 3 mg/L total of three 

16 



resin acids was found in the pH 11 extract. As expected, the organic bases (amines) readily 
dissolved in the acidic water, and the organic acids (resin acids) in basic water, because the 
compounds would be in the dissociated (ionized) form and thus polar like water. 

An examination of the white particles of tire crumb by electron microscopy suggested the 
presence of titanium with lesser amounts of silicon and aluminium. This was probably from the 
titanium oxide used for tire whitewall paint. The structures that composed the black particles of 
tire crumb were consistent with silicon, sulphur and zinc, and included an unresolved envelope 
of organic compounds (Appendix I). Waddell and Evans (1994) identified the same inorganic 
constituents using x-ray emission spectroscopy. No significant light absorbence was found when 
the samples of tire crumb water were scanned with ultra-violet and visible light (Appendix J). 

The dichloromethane Soxhlet-extract of tire crumb was a viscous dark-brown liquid, a tire oil. 
FTIR spectra indicated it contained a mixture of paraffinic, naphthenic and aromatic hydrocarbons 
with a minor quantity of carbonyl compounds (esters and possibly acids). The spectra resembled 
those obtained from lubricant oils (Appendix K). The petroleum-derived hydrocarbons 
comprising the tire oil were not found in water extracts of tire material. With respect to the 
inorganic constituents of tire crumb, direct analysis by ICP found 17.6 mg/g of zinc as the 
primary metallic constituent. 



4.0 DISCUSSION 

The key results for discussion are summarized as follows: 

• The samples of flow-through tire water collected at a minimum flow rate of 1.5 IVmin per 
600-litre water volume were nonlethal to trout for all tires in all tests. 

In the flow-through experiments, the minimum flow that produced nonlethal conditions 
corresponds to a tank flushing time of about 15 to 20 hours for 90% replacement of the water 
volume with uncontaminated in-coming water (calculated following Sprague (1969)). Ontario 
surface waters vary in flow characteristics, but most provide enough dilution to prevent lethality 
around tire structures. 

• The samples of flow-through tire water collected at the end of a submersion period were 
less toxic than those collected at the beginning, for the same water flow rate. 

There are several explanations for the decrease in the rate of chemical release during the tire 
submersion periods. Over time, the tires probably were depleted of chemical substances by a 
continuous process of leaching. Chemical release also may have been reduced by a bacterial 
growth that formed on the surface of the tires during the submersion periods. The composition 
of the rubber at the tire surface also may have changed over time in the flowing water, possibly 
affecting chemical release. 

17 



• Under static water conditions, the reef tires were less toxic than the scrap tires that were 
placed in water for the first time. Chemical analyses detected many contaminants 
released from the scrap tires that had not been previously submersed, but few 
contaminants from the reef tires. 

• A tire that had been lethal to trout under static water conditions was placed in a tank of 
flowing water for two weeks. A subsequent batch of static tire water was nonlethal. 

Previous exposure to an aquatic environment probably had depleted the reef tires of potential 
toxicant and other detectable chemicals due to a continuous process of leaching. However, other 
processes (for example, a change in the composition of the tire rubber) may be involved in 
reducing the toxicity of previously submersed tires. Day et al. (1993) found that tires collected 
from a ten-year-old floating breakwall in Lake Ontario were nonlethal to trout in comparable 
static test conditions. 

• The tires from the 3-year-old tire trench site tended to be less toxic inflowing water than 
the tires from the 1.5-year-old Lake Erie artificial reef. 

This point is difficult to explain because the tires in the covered trench were in contact with 
ground water, but were not exposed to an aquatic environment per se. The difference in toxicity 
was slight between these two groups of tires, so the finding may not be significant. 

The results of the toxicity identification evaluation suggest that the tire water toxicant was a 
nonvolatile mixture of polar and nonpolar organic compounds. Latawiec (1994) also concluded 
that the toxicant is a mixture of polar and nonpolar compounds. The higher ratio of polar to 
nonpolar toxicants leached from scrap tires (1:1) compared to new tires (1:4) would explain why 
the leachate from scrap tires is more toxic to trout than leachate from new tires (Day et al., 
1993). As tires age, polar oxygen-containing breakdown products are formed from the parent 
rubber compounds. 

The specific chemical cause of the tire water toxicity remains unknown. Researchers at the 
National Water Research Institute published a series of papers investigating tire water leachate 
(Anthony, 1993; Anthony and Barclay 1993; Anthony and Latawiec 1993; and Latawiec, 1994). 
The leachate was concentrated into solvent extracts for chemical analyses coupled with toxicity 
tests using the luminescence of a marine bacterium. The studies found: the solvent extracts were 
an intense yellow colour; the coloured compounds were high molecular weight, polar and easily 
oxidized suggesting aldehydes, quinones and nitrogen heterocyclic groups; many of the organic 
chemicals can be classified as conjugated heterocyclics; an aliphatic nitro-species attached to a 
5-member ether heterocycle was a main component; and bacterial luminescence was affected 
primarily by the 75 to 80% methanol SPE extracts. 

In the present study, a different mixture of chemicals was detected by GC/MS in every tire water 
sample analyzed. One reason would be the different compounding recipes used to manufacture 
various tires. Also, the compounds in a tire degrade and transform as the tire ages by oxidation 

18 



and other processes (Hofmann, 1989). Nevertheless, a few chemicals and chemical classes were 
predominant in tire water. These are the ones widely used in rubber compounding recipes. 

Likewise, the specific toxicant mixture might vary for different tires and differ for the same tire 
over time, but it is believed that most of the toxicity can be attributed to principal components 
from a few chemical classes widely used in the manufacture of all tires. This is consistent with 
the finding (Day et al., 1993) that toxicant leaching in water has been found for all makes and 
models of new and used tires that have been tested. 

The search for the identity of the toxicant is complicated because about twenty thousand 
chemicals are known in the rubber industry. Hofmann (1989) provides an extensive technical 
review of the industry and the chemical compounds involved. The compounding ingredients used 
to make synthetic rubber occur in proprietary formulations that may lose their identity after they 
are mixed and reacted. The first suspects as toxicants would be the chemicals used in the largest 
amounts, the accelerators, fillers, plasticizers and protective agents. 

The present findings implicate (aromatic) amine compounds as the principal toxicants. The tire 
water colour, odour, chemical composition and the TIE results were all consistent with the 
physical-chemical and toxicological properties of amines. The tire crumb water (pH 2 extract) 
contained aniline at a level almost one hundred times higher than a typical acute LC50 for D. 
magna (0.5 mg/L) reported in the literature. The extract also contained about 26 mg/L total of 
six other amines. As a chemical class, aromatic amines have significant environmental hazards 
(MacLaren, 1980; Fishbein, 1991). Some are easily oxidized to para-benzoquinone, also found 
in the pH 2 extract. Para-quinones and hydroquinone, a prevalent reduced form, are very toxic 
to fish. Verschueren (1983) reported 48-hour approximate fatal concentrations to goldfish 
(Carassius auratus) of 0.28 mg/L for hydroquinone and 6 mg/L for p-phenylenediamine. 
Yoshioka et al. (1986) reported a 48-hour LC50 for red killifish (Orizias latipes) of 20 mg/L for 
p-phenylenediamine and 2 mg/L for dipheny lamine. 

Aromatic amines may comprise up to three percent by weight of an automobile tire. Derivatives 
of p-phenylenediamine are the most common additives used to protect rubber from aging and 
weathering. The protective action (and toxicity) of amines can be altered by changing their 
molecular size using different substituents (attached groups). For example, the largest molecules 
hardly migrate in rubber so they are good anti-oxidants, but their immobility makes them poor 
anti-ozonants. Smaller molecules are effective anti-ozonants because they can continually rise 
to the tire surface where the protective action is required. The smallest-sized phenylenediamines 
are not used in tires because they migrate too fast and are rapidly lost by direct volatilization and 
by a water-leaching effect. They are also known to cause dermatological effects (Hofmann. 
1989). Chemical migration out of a tire implies that the concentrations at the tire surface 
eventually would be depleted and the toxicant release rate would decrease over time, as was 
inferred from the trout test results of tire water. 

The tire crumb material leached zinc at levels above known toxicity values, and thus zinc 
probably was the major toxicant to D. magna and C. dubia in the tire crumb water tests. In the 

19 



literature, 0.8 mg/L zinc is a typical D. magna acute LC50, and 0.1 mg/L is a typical chronic 
toxicity value for C. dubia. Nelson ef al. (1994) identified zinc as the toxicant in plugs cut out 
of whole tires. However whole tires did not leach zinc at toxic levels in the present study. Zinc 
is a key ingredient in rubber-compounding recipes. The high lethality to D. magna and low zinc 
level of the pH 11 extract and the partial removal of toxicity by the EDTA treatment suggest the 
presence of an additional, organic toxicant. 

The resin acid (diterpenoid carboxylic acids) levels found in the pH 11 extract approximate acute 
toxicity values for daphnid species. Large amounts of resin acids (2 to 7% of the rubber) may 
be used as plasticizers and emulsifiers in rubber compounding. They are only partially removed 
during washing, so some of the residues occur in the finished products (Hofmann, 1989). 
Salmonid species are sensitive to the acute effects of both resin acids and tire water. The resin 
acids are nonvolatile like the tire water toxicant, but none were detected in a previous study 
(Abernethy, 1994). Many high molecular weight aromatic and aliphatic carboxylic (fatty) acids 
are known rubber plasticizers that merit further consideration as potential tire water toxicants. 

Alkylphenol compounds are used in large amounts in tire manufacture, many were detected in 
tire water and as a group they are nonvolatile like the toxicant. However, a commercial product 
containing alkylphenols was nonlethal to trout at high concentrations of the product, so there is 
less reason to suspect them as toxicants based on these results. Many phenolic compounds form 
coloured-complexes with ferric chloride. This suggests a simple colorimetric measure of phenols 
and a method to remove them from solution. 

If a further investigation of the toxic constituents is conducted, it should be limited to identify 
a few specific, representative compounds (for example, certain aromatic amines). Then samples 
of ambient water around a tire structure could be collected, and the chemical levels compared 
to surface water quality standards to help make decisions about placing tires in natural water 
bodies. For this, an analytical method is required to separate and identify mixtures of polar and 
water-miscible compounds. Appropriate specialized procedures using liquid chromatography are 
being developed and should be more widely available within a few years. Some of the toxicant 
was extractable in methylene chloride, and the tire crumb water provided an enriched source of 
leachate especially at extreme pH. Toxicity tests conducted on pH-adjusted, solvent-extracted 
tire crumb water might be able to isolate the toxicant in a concentrated form for easier 
identification. Likewise, Soxhlet-extractions with other solvents, such as hot water, might be able 
to generate large amounts of the toxicant. 

Large amounts of carbon black, saturated with polynuclear aromatic hydrocarbons and sulphur 
heterocyclic compounds, are used as filler in rubber tires. Carbon black has a wide 
environmental distribution in automobile tire dust (Lee and Hites, 1976), but only traces of a few 
sulphur heterocyclics were detected in tire water. It is probable that carbon black compounds 
are generally immobile in tires placed in water. The carbon black is not the same as the 
activated carbon that detoxified the static tire water in the trout tests. Activated carbon has a 
very high surface area to volume ratio, many binding sites and thus a large capacity to sorb 
chemicals, removing them from water. 

20 



Lerner et al. (L993) investigated potential chemical contamination from shredded tires used as 
a substitute for gravel aggregate in domestic septic drainage fields. The laboratory study noted 
that microbial activity was eventually induced after a month of soaking shredded tires in water 
(indicating biodégradation). Laboratory leachates were prepared in waters adjusted to various pH 
and ionic strengths, and leachates were collected from a pilot septic drainage field. The typical 
rubber compounds, zinc and benzothiazoles, were leached from tire shreds regardless of the water 
quality of the laboratory leachates. Fewer contaminants were found in the septic samples. The 
authors recommended: (shredded) tires should not be used in ways that offer a clear path to 
groundwater; controlled and monitored demonstration projects would be necessary before 
permitting environmental usage; and storage of tires for six to twelve months in open lagoons 
may render them more acceptable for environmental uses. 

The Minnesota Pollution Control Agency investigated the potential environmental impacts of 
scrap tire pieces used as sub-grade material for roadway support over wetlands. Studies were 
conducted to identify metals and hydrocarbons leached from tires into water and soil under 
laboratory and field conditions (TCTC, 1990). A limited number of soil samples and a terrestrial 
vegetation survey did not show any differences between a tire site and a control site. Elevated 
levels of metals were found in a groundwater sample collected beneath a road section with a tire 
sub-grade compared to a sample beneath another section without a tire sub-grade. The authors 
recommended that tires should be placed only in the unsaturated zone of the road sub-grade, and 
that such roads should be designed to limit infiltration of water through the sub-grade. 



21 



5.0 CONCLUSIONS 

Overall the evidence suggests that tires in Ontario waters are unlikely to cause acute lethality to 
trout and other aquatic life primarily because relatively low rates of water flow can provide 
sufficient dilution to prevent the effect. 

The flow-through tests showed that the scrap tires were nonlethal to trout at a minimum water 
flow rate of 1.5 L/min per 600 L water volume, a flow less than that provided by most Ontario 
surface waters. Other natural processes (for example, biodégradation, photolysis and particle- 
binding) also may reduce the potential for toxicity in waters around a tire structure. Bench-top 
treatments of tire water using coagulants and flocculants, ultra-violet light and biological 
treatment processes would provide more information on these processes and their importance for 
toxicity reduction. 

The decrease in the rate of chemical release during each tire submersion period in the flow- 
through tests was probably due to a continuous process of leaching that depleted the tires of 
chemical substances. The chemical release rate also may have been reduced by a bacterial 
growth that formed on the surface of the submersed tires. The composition of the rubber at the 
tire surface also may have changed over time, possibly affecting chemical release. 

The static tests showed that tires collected from the artificial reef in Lake Erie were less toxic 
than scrap tires that had not been previously exposed to an aquatic environment. Chemical 
analyses of the static tire waters detected many more contaminants released by the scrap tires 
than by the reef tires. Previous exposure to an aquatic environment probably had depleted the 
reef tires of potential toxicant and other detectable chemicals due to a continuous process of 
leaching. Before tires are placed in surface waters, leaching (for example, storage in lagoons for 
six to twelve months) and treatment of the leachate would ensure that potential toxicants and 
other contaminants are not being directly released to the aquatic environment. 

The toxicant in static tire water was characterized as a nonvolatile mixture of polar and nonpolar 
organic compounds, but the specific constituents were not identified. Aromatic amines were 
suspected as the principal component of the toxicant. The complete identification of all the toxic 
constituents released by tires would be practically impossible due to the large numbers of 
compounds used in tire manufacture and the chemical reactions that occur as tires age. 

If a further investigation of the toxic constituents is conducted, it should be limited to identify 
a few specific, representative compounds (for example, certain aromatic amines). Then samples 
of ambient water around a tire structure could be collected, and the chemical levels compared 
to surface water quality standards to help make decisions about placing tires in natural water 
bodies. Although trout lethality tests were appropriate for the present investigation, the use of 
more sensitive chronic sublethal tests would be the next logical step for further studies at lower, 
more realistic levels of exposure. 



22 



REFERENCES 

Abernethy, S. 1994. The Acute Lethality to Rainbow Trout of Water Contaminated by an 
Automobile Tire. ISBN 0-7778-2381-0. Aquatic Toxicology Section, Standards 
Development Branch, Ontario Ministry of the Environment and Energy, Toronto. 

Anthony, D.H.J. 1993. A preliminary chemical examination of hydrophobic tire leachate 
components. Part I: A comprehensive analytical approach to the identification/ 
characterization of tire leachate components. Contribution number 93-76, National Water 
Research Institute (NWRI), Burlington, Ontario. 

Anthony, D.H.J, and D.W. Barclay. 1993. A preliminary chemical examination of hydrophobic 
tire leachate components. Part II: On-site, large-sample preconcentration of tire leachate 
components for chemical characterization. Contribution number 93-25, NWRI, 
Burlington, Ontario. 

Anthony, D.H.J, and A. Latawiec. 1993. A preliminary chemical examination of hydrophobic 
tire leachate components. Part HI: preliminary chromatographic and FTIR/UV/Vis 
spectrometric examination of major tire leachate components. Contribution number 93- 
78, NWRI, Burlington, Ontario. 

Calamari, R., S. Da Gasso, S. Galassi, A. Provini and M. Vighi. 1980. Biodégradation and 
toxicity of selected amines on aquatic organisms. Chemosphere 9: 753-762. 

Day, K.E., K.E. Holtze, J.L. Metcalfe-Smith, C.T. Bishop and B.J. Dutka. 1993. Toxicity of 
leachate from automobile tires to aquatic biota. Chemosphere 27 (4): 665-675. 

Environment Canada. 1990a. Biological Test Method: Reference method for determining acute 
lethality of effluents to rainbow trout. Ottawa, Canada. EPS l/RM/13. 

Environment Canada. 1990b. Biological Test Method: Reference method for determining acute 
lethality of effluents to Daphnia magna. Ottawa, Canada. EPS l/RM/14. 

Environment Canada. 1992. Biological Test Method: test of reproduction and survival using the 
cladoceran Ceriodaphnia dubia. Ottawa, Canada. EPS l/RM/21. 

Fishbein, L. 1991. Chemicals used in the rubber industry. The Science of the Total 
Environment, 101: 33-43. 

Hofmann, W. 1989. Rubber Technology Handbook. Oxford University Press, Canada. 

Jungclaus, G.A., L.M. Games and R.A. Hites. 1976. Identification of trace organic compounds 
in tire manufacturing plant wastewaters. Analytical Chemistry 48 (13): 1894-1896. 



23 



Latawiec, A. L994. Draft report - Spectroscopic investigations related to tire leachates. UV-Vis, 
GC/FT-IR and GC/MS analyses performed as part of Environment Canada NWRI contract 
KW405-3-0094. 

Lee, M.L. and R.A. Hites. 1976. Characterization of sulphur-containing polycyclic aromatic 
compounds in carbon blacks. Analytical Chemistry 48 (13): 1890-1893. 

Lerner, A., A. Naugle, J. LaForest and W. Loomis. 1993. A study of waste tire leachability in 
potential disposal and usage environments. Amended volume 1: final report. Principal 
Investigators: W.L. Miller and P.A. Chadik, The College of Engineering, University of 
Florida Department of Environmental Engineering Sciences. 

MacLaren Limited, 1980. Environmental aspects of selected aromatic amines and azo dyes in 
Ontario. Ontario Ministry of the Environment, Air Resources Branch ARB-TDA-83-79, 
prepared by J.F. MacLaren Limited. 

Mueller, G. and C.R. Liston. 1994. Evaluation of tire reefs for enhancing aquatic communities 
in concrete-lined canals. North American Journal of Fisheries Management 14: 616-625. 

Nelson, S.M., G. Mueller and D.C. Hemphill. 1994. Identification of tire leachate toxicants and 
a risk assessment of water quality effects using tire reefs in canals. Bulletin of 
Environmental Contamination and Toxicology 52: 574-581. 

Russell, E.R. 1975. Removal of mercury from aqueous solution by shredded rubber. E.I. Du 
Pont De Nemours and Company, Savannah River Laboratory report DP- 1395, prepared 
for the United States Energy Research and Development Administration. 

Sprague, J.B. 1969. Measurement of pollutant toxicity to fish. I: Bioassay methods for acute 
toxicity. Water Research 3: 793-821. 

TCTC, 1990. Twin City Testing Corporation. Waste tires in sub-grade road beds. Report 
prepared for the Minnesota Pollution Control Agency, St. Paul, MN. 

Verschueren, K. 1983. Handbook of Environmental Data on Organic Chemicals, 2nd edition. Van 
Nostrand Reinhold, New York. 

Waddell, W.H. and L.R. Evans. 1994. PDΠanalysis provides window into rubber. Rubber and 
Plastics News, May 9, 1994. 

Yoshioka, Y. and T. Mizuno, Y. Ose and T. Sato. 1986. The estimation for toxicity of chemicals 
on fish by physico-chemical properties. Chemosphere 15 (2): 195-203. 



24 



• 0> 

U i-> 

■H 
W U 
(0 U 

•H 

a a 
o 
ja .» 

U in 
iO o 
■ 

Tj° 
ID c 

> 3 

C 

w o 

w g 
TS nj 



r* 


CM ^ CM ^* 






* ? 


iû'J H on O • P~ CM 


T5 TS 


ro 


fH 


nH'ÏHHMHOOHCNn 


G G 


CM CM 


A 








a 








V 


^ rH rH ** 






a s 


■* <*oon O • VO CM 


TS Ti 


"<* 


m u 


nHliHHOlHCOHtNm 


C C 


CM CM 



TS TS T3 T3 TS TS 
^ G a G C G G 



TS TS T5 oo TS r- 

<tf G G C ud G rH 



H 










to 




cri 


CM 


rH 















,"! en 


* 


s 


m 


ro <J\ iH ^û 


• 




U3 CM 


Xi T3 


CM 


TS TS O T3 Xi TS 




O J 




t-i 


n 


H rn CTl H CN ffl 


00 


rH 


cm ro 


G C 


CM CM 


CM G G ro G G G 


a 


■H 


£ 




















H 


. S 


u 




















H 


2 m . 


V 




r- 


CM 


CM 












g 


w -, H 
10 o g 


m s 


m 


m 0~i CM LD 


• 




<D CM 


T3 T! 


<H 


TS TS TS TS TS TS 


S 


n 


u 


00 


Hm a\ h (n ui 


co 


rH 


CM ro 


G G 


CM CM 


ro G G G G G G 


O 


rQ iJ-H 

c u g 
§ 0) 






















Pi 






















O 


o - 1 - 1 ^ 
g Q) .. 






















u 


m 




m 


<H 


oo 














-C (N 


* 


s 


ro 


CO 00 ro CM 


• 




r- cm 


13 Xi 


O 




1 


o> ■ 


.S 


B 


ro 


<H CO CTi <H CM <Tl 


00 


rH 


CM ro 


C G 


ro CM 




<! 


ot) § 


u 






















u v 3 


■p 




ro 


o 


CN 












^-s 


4J AJ -H 
•H U G 

2 <D "D 


n) S 


ro 


ro r- ro i-H 


. 




r- cm 


TS T3 


O 




s 


n 


o 


m 


iH ro CTi <H CM <T\ 


00 


rH 


cm ro 


C G 


CM CM 




Eh 


4J <8 






















■*— ' 


0) 
























■ -a 






















« 


-v. aJ 'S' 






















H 


0) <H 






















Eh 


3 C -, 






















g 


d) Il 


^ 




rH 


LD 


m 














10 73 -H 


* 


s 


ro 


ro <Ti ro •<* 






oo ro 


T! T5 


rH 




S 


C 
W 


A 


^ 


m 


<H ro (Ti rH CM CTi 


00 


rH 


cm ro 


G G 


rH CM 




H 


,h * c- 


u 














ro 






Eh 


u «h ». 

^ (0 ° 


4J 




CM 


<H 


^r 






O 








«uÇ 


«J 3 


ro 


ro 00 ro *3< 


• 




00 ro 


TS • 


rH 




h 


g -H 


m 


u 


ro 


tH ro (Ti iH CM (T\ 


CO 


rH 


CM ro 


G O 


rH CM 




O 


4J N 






















01 


0) " oo 






















ta 


U (H _ 






















r* 


m <D 






















1 


0* ^-< 






B 


o 
o 
















S rH 






U O 
















ai g ai 

(0 






\ 


o o 








En 










h 


O 


(d 








» 








Il £ 




(D 


Xi u 








(Xi 


u 






c * 



-H * CT* 




i> 


e 


et; a; to 








OS 


•H 








(D 


n in 




oi 


CC Pi 


• 


U C 


Eh 






g 




ce ce; ti [ii - 




- 




u • 


•H CCS 


Eh - 




xJ TJ • 




(D 


« 


• geesh 




U-, 


h tu 


(0 u 


G 0) 


Eh Eh -Ci, 




10 <D -H 

5j 5-1 
4J Q) ^ 




>H 


>1 


•* &-) t5 * ,3 




^ 


S S 


^ (0 


03 Sh 


- - lu 2 






«J 


4J 


Eh 2 fc, 




n^ 


D D 


H-l r4 


Cl O 


Pu tu Eh Eh Eh 2 5 




g -U> 0) 




ft 


•H 


5 -2 - >, 








4-1 


5h G 


2 2 - - -D 




(u •-* a 






> 


e 5 g -u 




■. 


^ 


« 


-H 


O 5 tu tu tu 




-H Qi 




rH 


•H 


tn - 3 ^ -h 




Q) 


d) Q) 


g - 




222 -Ê 




c ti o 
o c U 

U 3 




10 


4J 


tn g -h ~-h G 




ti T3 -u 


G (U 


» - 


- .5d5 E 3 






u 


u 


a) G w g in -h 




•H 


■H (tS 


•H a-) 


C c 


SH rH 3 -H 








•H 


G 


C -H Q) G m rH 




M 


M ,G 


C -H 





(D . . --H g 




l-i il in 




g 


T3 TD U G -H nS (0 




o 


o a 


O 5-1 


X! .Q 


ChX TS U G gO 




(D »-H 
iJ fc< o 
(0 2 • 




(D 


G 


^ iH OTO -U rV 




3 rH rH 


g 4-" 


5h 5h 


ÛU u c ofl ^ 






A 


o 


(0 (0 (C O rH 


X 


rH 


X! G 


Ë -H 


(0 ITS 


O -H Q) -H 5h ri X 




S 5 o 




U 


U£UE IDftfl 


ÛW 


u in 


as C 


U U 


U C rH N -H U U 





s 


in 


























u 


H 


r- 


00 








O 










O 




— - 


* ? 


m 


m 


rH 


LO 


o 


• 




r- ci 


T3 TS 


CN 


"0 TS T5 '-D ^ T3 T3 






£-1 


m 


rH 


>* 


CTi <H CN 


o\ 


00 


rH 


CM CM 


G G 


CN CN 


C C C(NH ce 




vu 


J3 


























W 





























Eh 


V 


<tf 


rH 








o 














< 


ta s 


CM 


n 


O^ 


<3< 


rH 


• 




V£> O 


Tl T3 


iH 


T3 13 T! T3 0> TD T3 




S 


m o 


m 


H 


m 


CO tH CN 


c^ 


CO 


rH 


cm m 


G G 


iH CN 


G G CG m G G 




J 




























o 




























« 




























g 




























o 


m 


























U 


H 


<o 


CN 








CN 










o 






* ? 


LT1 


st 1 


CN 


LO 


ce 


• 




(Xi n 


T3 TS 


CN 


T3 T3 œ "^ T3 T3 




Q 


£H 


ro 


«H 


«a< 


CT\ <H CN 


c^ 


ce 


rH 


cn m 


G G 


CN CN 


CN G G m <H G G 


< 


| 





















ro 






X 




4J 


O 


cn 








cn 






o 






H 


*— 


rd 5 


U3 


^r 


H 


m 


c^ 


• 




o es 


TS • 


CN 


T3 T3 T3 T3 P» T3 T3 


G 


? 


m u 


m 


tH 


«s< 


CTi <H (M 


CT> 


CO 


iH 


m m 


G o 


CN CN 


G G G G co G G 


w 


S. 


























eu 
eu 


1 


o 

H 


CM 


m 








CN 
















* g 


^o 


m< 


n 


^ 


C^ 


• 




00 V£> 


TS T3 


CN 


T3 TS Tî [-■ T3 T3 T3 




S 


4Ï 


m 


iH 


"!* 


m H M 


CM 


CO 


H 


cn m 


G G 


CN CN 


G G G cn G G G 




H 





























H 


JJ 


>x> 


C- 








n 
















(d g 


l£> 


■C 


m 


in 


en 


• 




en r- 


T3 TS 


CN 


T3 T3 T3 T3 T3 T3 X3 




h 


» u 


m 


<H 


■«3 


Oï iH CN 


CM 


ce 


rH 


cn m 


G G 


CN CN 


G G G G G G G 




O 




























w 




























H 




























w 



























CN 

< 



U 
<D 



u 
ta 
a 

H 

u 

•H 

a> 

J3 



u o 

\ u 

O rd 

.g a 
e 
3. ia 

rd Ci fa 



>i - fa 
-u H 2 

■H Z3 

> 
•H 

JJ 
U 

G 



T. 
W 
(U 

G 

G H 

o rd rd 



ci ci 



ci 



O 
U 

ta 
u 

rd 



fa 

Ë D 

G 



e -u 

G -H 

H --H G 
m s w -h 

(P 3 01H 

G -H rd rd 
OlTS -U ^ 
rd O O 



Ci Ci Pi 
fa fa fa 



0)0)0) 
T3 T5 -U 
•H -H rd 

o o a 

G i-i iH 

.G G 



Ci 
Ci 

U • 

rd U 

U rd 

4-1 U 



£ - 
G 0) 

•H JJ 
C-H 

O l-i 

•H 



U 
-H 

U C 

•H rd 

G Cn 

rd S-i 

rji o 

U G 

O-H 



G 

O 



U,GUgCflûrdQ,M-iuc/) rdC 



C 
O 

X! Si 

U U 

rd rd 

U U 



H E- 
fa fa" 
D P 



0) Q) 

a u 
o 



Eh Eh Eh 



Eh 

Eh - 

- fa 

fa S 



fa fa 

S 2 

D 5 



fa 



S 

3 



U G rH 



T3 U 
rd C 
0) -h 

N 



GEO 
O "S ^ 
H rd .G 
•H U U 



Xi 

i 

s 
u 

Eh 

•a <D 

a u 

" 'H 
03 



H 

Xi 
v 
U 




S 4J 



cn <y> in cn 

hhhh cl finmc c^j G G 



r- 



CN 
CN 



T3 tJ T3 T! o T5 T3 
G G G C u? G G 



m 

H 



eu 
< 



« 

W 

S 



u 



W 

h 
O 

W 
U 
CO 

3 



Xi 

o 
d 

<D 
M 
•P 

(D 

■H 
Eh 



■H 
W 
<D 
rtJ 





eu 



o 
u 

g 



u 



V 
■H 

o 
>i 



cn in CM <3i 

Ln<3 , coin r O r Cm- r O <h t3 T3 vd 

MHHN C CHC1 Cnn ce CO CN 



TJ T3 T3 T3 o 

G G G G ^h 



T3 T3 
G G 



in ^ 


T3 T3 


<H 


'O T3 Tî T3 es) T3 T3 


<H CN 


G G 


O) CM 


G G G G m G G 



00 



u 

(D 
I 

ft 



id 

u 

■H 



J3 
U 



g 
U 

o 

,G 

g 



O 

u 
m 

u 

w 

(0 Pi 



U (D 



Pi 



>i - II, 
•U B 2 

•H P 

> - 

•H M - 



2 Pi 

-2 

g D 



Pi 
fa 



O 
U 
(0 

u 

w 
<d 



G G 

T5 "O U 

O (d (0 

U ,G U 



W g 
(1) G 
G -H 
OiTJ 
(d O 
g W 



>i 
■H 

G 



3 

■H 

ta 
id 

o 

ft 03 






Pi Pi Pi 

II, II, II, 
2 2 2 



0> d) 

•H -H 
fc >-l 
O O 

G rH 

ftiw U 



d) 
4-> 

(0 
,G 

ft 
i— I 

G 



Pi 

Pi 

U • 






id 



g - 
G d) 
•H JJ 

G-* 
O U 
g J-> 

g -H 

(0 G 



U 

-H 

U G 

•H <d 

G Oi 

(d h 
Si o 
U G 
O-H 



G G 
O O 
-QXI 
U U 

<d (d 
u u 



Eh Eh 

II, II, Eh 

2 2 - 

D D II, 



Eh » 
II, 



Eh Eh 
fa II, 



II, 



d) d) 

ft* T3 
û U (d 



O 
U 



o 

G 

H d) -H 



C 
O 

u 

N -H 



g G 

G -h 

•H g 

g o 

(d ,c 
u o 



g 



es 

a u 



o o 

o o o 

o o o o 
O T3 cn) ^ cn T! T3 

H CHHH C C 



H 
H 

a u 



o o 

CN *0 'O LD ro T3 T3 

H CCntN C C 



U 
X 

H 



W 
Pj 

< 



U 



a s 

au 



(0 

« 

o 
■p 
a! 
n 



u 

Eh 



U 



^ m o r- 
<-o iH ^ cri H 



r- • oo cn 
cn en r^ r-t cn m 



cn m 



o m cn • 

'sf ffl i-l <H CT» 00 



CN CN 



in 



TS o 



CN 

CN 



T3 TS <H 

C CHCN 



o 
o o 

<o T3 TS <— i r^ T3 TJ 

N C CHKl C C 



T3 "O T3 «h T3 T3 



^o 



T3 T3 



o 

O CN 

^H O G G 



TJ 'O T3 T3 T3 13 T3 
C C G C C C G 



U 





o 

g r. U 










U O (C 










^ u u 




Eh 




U 


O ro 




- 




© 


.G U W 




PS u 




•p 


g pi pi m 




PS -H 




© 


i U) 


PS PS PS 


c 


Eh 


g 


(0 PS fa fa - 


» » » 


U • -H (d 


Eh - 


S 


« S PS S Eh 


fa fa ki 


rO U C Oi 


Eh Eh -fa 


^ 


>, -& o -5 


s s s 


J-i cC rd U 


- - fa 2 


R) 


4-) Eh S fa 


D D 5 


4-1 M 01 O 


fa fa Eh Eh Eh S 5 


a 


•h D - 2 - >i 




4-1 ^ a 


2 S - - -D 




> - g D £ -U 


^ 


-H 


p D fa fa fa 


r4 


•H CO - 3 3 -H 


ai ai ai 


g - 


s s s - g 


(0 


JJ tQ g -H --H C 


TJ T3 -U 


3 <D - - 


- - D D D g 3 


U 


U 0) 3 0) g 03 -H 


•H -H CO 


•H 4J C C 


U <-i 3 -H 


•H 


3 C -H 0) 3 01 H 


u u s: 


C -H o 


(D CD > .. --H g 


g 


T3 T3 U C -h jj n) 


û 


O >h .Q ,0 


a,y T30CÊ0 


0) 


C M -H Oi 'O 4J X 


3 iH iH 


g 4J SH i-l 


Qj U ro C O 'D U 


X 


o <c rd m o o i-i 


ffi rH J5 2 


g -h co 03 


-H CD -H U ro 43 


u 


O £ o g w a (0 


Dj4-( U tO 


ucuu 


U C rH. N -H U U 



APPENDIX D 
GC/MS ANALYSES FOR EXTRACTABLE ORGANIC COMPOUNDS: TIRE WATER 

Notes: samples were partitioned into base-neutral and acid fractions and extracted 
with dichloromethane; A- = approximate concentration relative to the internal 
standard d 10 -phenanthrene; (A-) = approximate concentration in control sample; R.T. 
= chromatographic retention time. Some of the chemicals and chemical classes found 
are laboratory artifacts unrelated to tire leachate. Trace contaminants known from 
routine laboratory operations (surfactants and plasticizers) and from the outdoor 
air supply were found in all water samples. Tire rubber does contain some soaps and 
plasticizers, but the following compound classes are believed to be extraneous: the 
carboxylic acids with short retention times; linear alcohol ethoxylates; and 
hydrocarbons including the alkanes . 

TIRE WATER BATCH 4 

(one tire submersed for 12 days in 300 L static aerated water) 

Entry R.T. Cone. CAS No. 

Identity 

1 11.67 A-0.3 000062-53-3 

Aniline 

2 13.48 A-l 

A methyl benzenamine 

3 13.95 A-0.4 ' 42966-64-3 

2-Pentanamine, N-ethyl-4-methyl- 

4 14.36 A-0.5 

A nitrogen compound 

5 14.80 A-0.2 000144-19-4 

1, 3-Pentanediol, 2,2, 4-trimethyl- 

6 15.13 A-0.2 

Unidentified 

7 15.56 A-0.2 001696-20-4 

Morpholine, 4-acetyl- 

8 16.26 A-2 (A-0.3) 000095-16-9 

Benzothiazole (8CI9CI) 

9 16.63 A-0.4 (A-0.4) 000766-93-8 

Formamide, N-cyclohexyl- 

10 19.80 A-7 

1, 5-Ditertbutyl-3, 3-dimethylbicyclo [3 . 1.0]Hexan- 
2 -one 

11 20.39 A-0.4 

Unidentified 

12 20.90 A-0.3 001696-20-4 

Morpholine, 4-acetyl- 

13 20.99 A-2 

A dibutylthiophene 

14 21.42 A-0.3 000084-66-2 

Diethyl phthalate 

15 21.82 A-0.3 000615-22-5 

Benzothiazole, 2- (methyl thio) - 

16 21.90 A-0.3 000122-39-4 

Benzenamine, N-phenyl- 

Dl 



TIRE WATER BATCH 4 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

17 22.43 A-l 000552-82-9 

Benzenamine, N-methyl-N-phenyl- 

18 22.51 A-2 000934-34-9 

2 (3H) -Benzothiazolone 

19 22.62 A-0.6 

A chlorine compound 

20 23.06 A-0.6 

A phenyl -propyl phenol 

21 23.46 A-0.6 (A-0.4) 

A chlorophosphate 

22 23.56 A-0.3 

Unidentified 

23 23.65 A-0.8 004130-42-1 

A C10-alkyl phenol 

24 23.86 A-0.3 010425-87-3 

Benzyl alcohol, cc-isobutyl-2 , 4 , 5-trimethyl- 

25 23.93 A-0.3 

Unidentified 

26 24.73 A-0.7 000599-64-4 

Phenol, 4- (1 -methyl -1-phenylethyl) - 

27 25.18 A-0.3 

Unidentified 

28 25.47 A-0.4 

Unidentified 

29 25.54 A-0.4 

Unidentified 

30 25.82 A-0.3 

Unidentified 

31 26.05 A-0.3 

Unidentified 

32 26.66 A-2 000102-77-2 

Morpholine, 4- (2-benzothiazolylthio) - 

33 28.33 A-0.8 

Unidentified 

34 29.85 A-0.5 

Unidentified 

35 31.54 A-0.3 

Unidentified 



D2 



TIRE WATER BATCH 6b 

(three tires submersed for 13 days in 280 L static aerated water) 

Entry R.T. Cone. /ID CAS No. 

1 6.083 A-2 000108-10-1 

2-Pentanone, 4 -methyl - 

2 9.619 A-3 (A-3) 000111-76-2 

Ethanol, 2-butoxy- 

3 11.51 A-0.7 (A-l) 

An alcohol/ether 

4 11.57 A-l (A-2) 

An alcohol/ether 

5 12.05 A-0.8 

Unidentified 

6 12.94 A- 6 

A methyl benzenamine 

7 13.06 A-0.6 000765-87-7 

1 , 2 -Cyclohexanedione 

8 13.40 A-0.6 

An amine 

9 13.81 A-0.9 

Unidentified 

10 15.68 A-30 000095-16-9 

Benzothiazole 

11 17.96 A-l 000088-04-0 

Phenol, 4-chloro-3 , 5-dimethyl- 

12 19.20 A-30 

A phenol 

13 19.78 A-0.9 

Unidentified 

14 20.37 A- 8 

A C8-alkyl thiophene 

15 20.81 A-l 000084-66-2 

Diethyl phthalate 

16 21.18 A-0.6 000615-22-5 

Benzothiazole, 2- (methylthio) - 

17 21.28 A-2 000122-39-4 

Benzenamine, N-phenyl- 

18 21.79 A-2 001205-39-6 

Benzenamine, 2 -methyl -N-phenyl- 

19 21.85 A-3 000934-34-9 

2 (3H) -Benzothiazolone 

20 22.40 A-0.7 

A phenol 

21 23.03 A-2 

A phenol 

22 24.10 A-0.6 

Unidentified 



D3 



TIRE WATER BATCH 6b - continued. 

Entry R.T. Cone. /ID CAS No. 

23 25.98 A-4 000102-77-2 

Morpholine, 4- (2-benzothiazolylthio! 

24 27.67 A-l 

Unidentified 

25 29.91 A-l 

A silicon compound 

26 30.94 A-l 

A silicon compound 



TIRE WATER BATCH 7 

(one tire submersed for 13 days in 300 L static aerated water) 

Entry R.T. Cone . ID CAS No. 

1 17.85 A-0.4 

A carboxylic acid ester 

2 19.20 A-0.6 

A phenol 

3 21.03 A-0.4 

A tetramethylbutyl phenol 



TIRE WATER BATCH 10 

(three tires submersed for 15 days in 300 L static aerated water) 

Entry R.T. Cone . CAS No . 

1 15.58 A-0.8 (A-0.7) 000095-16-9 

Benzothiazole 

2 16.73 A-0.5 (A-0.3) 

A phenol 

3 17.18 A-0.1 (A-0.1) 

Unidentified 

4 19.09 A-l 

A phenol 

5 19.81 A-0.5 

A nitrogen compound 

6 20.76 A-0.5 

A nitrogen compound 

7 20.93 A-0.3 

A tetramethylbutyl -phenol 

8 21.09 A-0.2 000615-22-5 

Benzothiazole, 2- (methylthio) - 

9 24.74 A-0.6 

Unidentified 



D4 



TIRE WATER BATCH 15 

(five tires submersed for 3 days in 600 L static aerated water) 

Entry R.T. Cone. CAS No. 

Identity 

1 15.19 A-0.4 000095-16-9 

Benzothiazole 

2 17.10 A-0.6 

An ester 

3 17.36 A-0.5 

An ester 

4 31.77 A-0.3 

Unidentified 



D5 



APPENDIX E 
GC/MS ANALYSES FOR EXTRACTABLE ORGANIC COMPOUNDS: SURFACE WATERS 

LAKE ERIE, TURKEY POINT TIRE REEF 

No extractable organic compounds were detected in the water sample 
collected from the tire reef. 

NORTH END TIRE TRENCH 

Entry R . T . Cone . CAS No . 

Identity 

1 8.578 A-0.6 

A nitrogen compound 

2 12.71 A-0.4 

A nitrogen compound 

3 13.10 A-l 

A nitrogen compound 

4 14.30 A-0.8 

Unidentified 

5 .14.40 A-0.4 

A nitrogen compound 

6 14.92 A-3 000095-16-9 

Benzothiazole 

7 15.43 A-2 

Unidentified 

8 15.52 A-0.9 

Unidentified 

9 16.29 A-0.4 

A nitrogen compound 

10 19.16 A-0.5 

Unidentified 

11 19.60 A-l 

A C8-alkyl-thiophene 

12 19.69 A-0.5 

Unidentified 

13 19.93 A-0.5 000134-62-3 

Benzamide, N, N-diethyl-3 -methyl - 

14 20.40 A-0.3 

Unidentified 

15 20.75 A-0.6 

An unsaturated hydrocarbon 

16 20.95 A-0.8 

Unidentified 

17 21.13 A-0.9 

Unidentified 

18 21.28 A-2 

An alkane 



El 



NORTH END TIRE TRENCH - continued. 

Entry R.T. Cone. CAS No. 

Identity 

19 25.16 A- 2 Provisional ID 1 

1, 2-Benzisothiazole, 3- ( 4 -morpho liny 1) 

20 26.92 A-4 

A silicon compound 

21 29.14 A-8 

A silicon compound 

22 30.17 A-l 

A silicon compound 

23 32.10 A-0.3 

Unidentified 



1 A check of other mass spectral databases, and further mass spectrum determinations 
showed that 4- (2-benzothiazolythio) -morpholine was mis-identified in the reference 
database, and thus in two previous analyses (tire water batch 4 and 6) and in the 
analyses reported previously in Abernethy (1994). This compound, eluting at about 
25.16 minutes, is now identified provisionally as 3- (4-morpholinyl) -1, 2- 
benzisothiazole . 



E2 



APPENDIX F 

GC/MS ANALYSES FOR EXTRACTABLE ORGANIC COMPOUNDS: 

TIRE CRUMB WATER 



TIRE CRUMB WATER BATCH 1 

(4-L aqueous extract of 100 grams of 30 to 40 mesh size tire granules) 

Entry R.T. Cone. CAS No. 

Identity 

1 5.997 A-20 000108-10-1 

2-Pentanone, 4-methyl- 

2 6.040 A-30 

Unidentified 

3 6.592 A-l 

Unidentified 

4 8.503 A-20 000110-12-3 

2-Hexanone, 5 -me thy 1- 

5 8.708 A-40 

Unidentified 

6 9.293 A-10 000108-94-1 

Cyc 1 ohexanone 

7 9.542 A-50 000111-76-2 

Ethanol, 2-butoxy- 

8 10.38 A-9 028292-43-5 

2 -Hexanamine , 5 -methyl - 

9 10.66 A-30 

Unidentified 

10 11.02 A-30 000062-53-3 

Aniline 

11 11.96 A-10 

A hydrocarbon 

12 12.73 A-5 

A hydrocarbon 

13 12.85 A-10 

A methyl-benzeneamine 

14 13.08 A-6 

Unidentified 

15 13.34 A-8 

A nitrogen compound 

16 13.72 A-30 

Unidentified 

17 14.03 A-200 000149-57-5 

Hexanoic acid, 2-ethyl- 

18 14.14 A-40 

Unidentified 

19 14.76 A-20 

A methyl ester of an ethyl hexanoic acid 

20 14.86 A-50 

A tetramethyl thiopyran + an acid 

Fl 



TIRE CRUMB WATER BATCH 1 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

21 14.99 A-40 

A methyl ester 

22 15.17 A-9 

A methyl ester 

23 15.30 A-10 000065-85-0 

Benzoic acid 

24 15.65 A-400 000095-16-9 

Benzothiazole 

25 15.96 A-300 

A carboxylic acid 

26 16.07 A-200 000766-93-8 

Formamide, N-cyclohexyl- 

27 16.15 A-60 

A methyl ester 

28 16.22 A-100 ' 

A methyl ester 

29 16.58 A-600 

A methyl ester 

30 16.73 A-200 ' 

An alkane 

31 16.80 A-10 

A methyl ester 

32 16.84 A-10 

Unidentified 

33 16.96 A-20 000103-70-8 

Formamide, N-phenyl- 

34 17.23 A-30 

A hydrocarbon 

35 17.38 A-20 

A dimethoxyphenol 

36 17.51 A-10 

An ester 

37 17.66 A-5 

Unidentified 

38 17.78 A-10 

An ester 

39 18.37 A-5 

A hydrocarbon 

40 18.41 A-10 

A hydrocarbon 

41 18.66 A-600 000101-83-7 

Cyclohexanamine, N-cyclohexyl- 

42 18.88 A-80 000118-12-7 

lH-Indole, 2 , 3-dihydro-l , 3 , 3-trimethyl-2- 
methylene 



F2 



TIRE CRUMB WATER BATCH 1 - continued. 

Entry R . T . Cone . CAS No . 

Identity 

43 19.14 A-200 000085-41-6 

lH-Isoindole-1,3 (2H) -diohe 

44 19.27 A-10 

A hydrocarbon 

45 19.39 A-10 

Unidentified 

46 19.77 A-20 007560-83-0 

Cyclohexanamine, N-cyclohexyl-N-methyl- 

47 19.86 A-20 007507-89-3 

Ethanone, 1- (2, 6-dihydroxy-4-methoxyphenyl) 

48 20.24 A-5 

Unidentified 

49 20.31 A-40 054845-33-9 

Thiophene, 2 , 5-bis (2-methylpropyl) - 

50 20.75 A-10 000084-66-2 

Diethyl phthalate 

51 20.83 A-5 

A hydrocarbon 

52 20.98 A- 8 

A C8-alkylphenol 

53 21.02 A-4 

Unidentified 

54 21.11 A- 8 000615-22-5 

Benzothiazole, 2- (methyl thio) - 

55 21.21 A-10 000122-39-4 

Benzenamine, N-phenyl 

56 21.48 A-9 

Unidentified 

57 21.67 A-8 

Unidentified 

58 21.71 A-2 000552-82-9 

Benzenamine, N-phenyl -N-me thy 1 

59 21.95 A-200 000934-34-9 

2 (3H) -Benzothiazolone 

60 22.45 A-3 000483-78-3 

Naphthalene, 1 , 6-dimethyl-4- ( 1-methylethyl) 

61 22.53 A-4 

A linear alcohol ethoxylate 

62 22.86 A-20 

Unidentified 

63 23.23 A-3 

Unidentified 

64 24.63 A-3 

Unidentified 



F3 



TIRE CRUMB WATER BATCH 1 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

65 24.75 A-2 018781-72-1 

lH-Carbazole, 2,3,4, 4a-tetrahydro-4a-methyl- 

66 25.89 A-20 000102-77-2 

Morpholine, 4- (2-benzothiazolylthio) - 

67 26.12 A-2 002387-23-7 

Urea, N,N' -dicyclohexyl- 

68 29.84 A-10 

Unidentified 



TIRE CRUMB WATER BATCH 9A 

(4-L aqueous extract of 100 grams of 30 to 40 mesh size tire granules) 

Entry R.T. Cone. CAS No. 

Identity 

1 5.43 A-70 000108-10-1 

2-Pentanone, 4 -methyl - 

2 5.57 A-10 

Unidentified 

3 5.82 A-3 000626-93-7 

2-Hexanol 

4 6.06 A-4 010342-97-9 

2-Propanamine, N-methyl-N- ( 1-methylethyi; 

5 7.91 A-10 000110-12-3 

2-Hexanone, 5 -methyl - 

6 8.20 A-7 

Unidentified 

7 8.56 A-10 002425-74-3 

Formamide, N (1 , 1-dimethylethyl) - 

8 8.66 A-20 001757-42-2 

Cyclopentanone, 3 -methyl - 

9 8.94 A-10 000111-76-2 

Ethanol, 2-butoxy- 

10 10.16 A-30 000108-91-8 

Cyclohexy lamine 

11 10.43 A-40 000062-53-3 

Aniline 

12 10.49 A-10 000108-95-2 

Phenol 

13 11.39 A-10 

Hydrocarbon 

14 11.62 A-2 

Hydrocarbon 

15 12.16 A-3 000098-68-2 

Ethanone, 1 -phenyl - 

F4 






TIRE CRUMB WATER BATCH 9A - continued. 

Entry R.T. Cone. CAS No. 

Identity 

16 12.27 A-10 

A methyl aniline 

17 12.50 A-7 000617-94-7 

Benzenemethanol, a,a-dimethyl 

18 12.78 A-10 

A nitrogen compound 

19 13.03 A- 5 

A carboxylic acid 

20 13.15 A-30 

Unidentified 

21 13.48 A-200 

A carboxylic acid 

22 13.59 A-40 

Unidentified 

23 13.69 A- 8 003302-10-1 

Hexanoic acid, 3 , 5 , 5-trimethyl- 

24 13.86 A-3 

A methyl ester of an ethyl hexanoic acid 

25 14.20 A-20 

A methyl ester of an ethyl hexanoic acid 

26 14.30 A-40 

Unidentified 

27 14.45 A-10 

A methyl ester of a carboxylic acid 

28 15.05 A-300 000095-16-9 

Benzothiazole 

29 15.32 A-100 

An ester 

30 15.45 A-90 

An ester 

31 15.51 A-40 000766-93-8 

N-Cyclohexyl formamide 

32 15.60 A-90 

An ester 

33 15.92 A-200 

An ester 

34 15.98 A-40 

An ester 

35 16.04 A-80 

An ester 

36 16.26 A-5 

Hydrocarbon 

37 16.38 A-10 

A methyl pyridine 

38 16.47 A-5 

Unidentified 



F5 



TIRE CRUMB WATER BATCH 9A - continued. 

Entry R.T. Cone. CAS No. 

Identity 

39 16.51 A- 5 

An ester 

40 16.57 A- 8 

An ester 

41 16.78 A- 9 

Unidentified 

42 16.95 A-6 000054-11-5 

Pyridine, 3- (1 -methyl -2 -pyrrolydinyl) - , (S) 

43 17.16 A-2 

Unidentified 

44 17.20 A-5 

A methyl ester of a hydroxy acid 

45 17.88 A-2 

Unidentified 

46 18.02 A-200 003570-07-8 

Bicyclo [2.2. l]heptan-2 -amine, N,N, 2 , 3 , 3- 
pentamethyl 

47 18.28 A-20 000147-47-7 

Quinoline, 1 , 2-dihydro-2 , 2 , 5-trimethyl- 

48 18.45 A-40 

A linear alcohol ethoxylate 
■49 18.55 A-50 025013-16-5 

Phenol, (1, 1-dimethylethyl) -4-methoxy- 

50 18.81 A-3 

A hydroxymethoxyphenyl ethanone 

51 19.13 A-7 

Unidentified 

52 19.17 A-9 007560-83-0 

Cyclohexanamine, N-cyclohexyl-N-methyl- 

53 19.28 A-7 

Unidentified 

54 19.45 A-5 

Unidentified 

55 19.65 A-2 

Unidentified 

56 19.71 A-10 054845-35-1 

Thiophene, 2-butyl-5- (2-methylpropyl) - 

57 20.36 A-6 

A C8 alkyl phenol 

58 20.49 A-3 000615-22-5 

Benzothiazole, 2- (methyl thio) - 

59 20.62 A-6 000122-39-4 

Benzenamine, N-phenyl- 

60 20.92 A-10 

Unidentified 



F6 



TIRE CRUMB WATER BATCH 9A - continued. 

Entry R.T. Cone. CAS No. 

Identity 

61 21.07 A-7 

Unidentified 

62 21.13 A-3 

Unidentified 

63 21.39 A-300 000934-34-9 

2 (3H) -Benzothiazolone 

64 21.84 A-6 

An alkylated aromatic hydrocarbon 

65 21.97 A-10 

A linear alcohol ethoxylate 

66 22.25 A-10 

Unidentified 

67 22.50 A-5 

Unidentified 

68 22.57 A-4 003622-84-2 

Benzenesulfonamide, N-butyl- 

69 22.63 A-5 

Unidentified 

70 22.80 A-7 

An alkylated aromatic hydrocarbon 

71 23.34 A-10 

A biphenyl diol 

72 23.61 A-3 

Unidentified 

73 23.84 A-4 000611-64-3 

Acridine, 9-methyl- plus unidentified 

74 23.91 A-4 

Unidentified 

75 24.04 A-10 

Unidentified 

76 24.16 A-10 

Unidentified 

77 24.25 A-9 006267-02-3 

Acridine, 9 , 10-dihydro-9 , 9-dimethyl- (9C 

78 24.67 A-4 

Unidentified 

79 24.74 A-4 

Unidentified 

80 24.96 A-40 

A phenol 

81 25.28 A-40 000102-77-2 

Morpholine, 4- (2-benzothiazolylthio) - 

82 25.43 A-4 

Unidentified 

83 25.54 A-20 002387-23-7 

Urea, N, N' -dicyclohexyl- 



F7 



TIRE CRUMB WATER BATCH 9 A - continued. 

Entry R.T. Cone. CAS No. 

Identity 

84 25.63 A-30 

A phenol 

85 26.03 A-6 

Unidentified 

86 26.23 A-4 

Unidentified 

87 26.31 A-4 

Unidentified 

88 26.59 A-10 

A phenol 

89 26.92 A-6 

Unidentified 

90 27.05 A-50 

Unidentified 

91 27.16 A-8 

Unidentified 

92 27.23 A-20 000097-39-2 

Guanidine, N, N' -bis (2-methylphenyl) - (9C 

93 27.45 A-5 

Unidentified 

94 28.42 A-90 

A methyl naphthofurandione 

95 28.49 A-30 

Unidentified 

96 28.76 A-4 

Unidentified 

97 28.87 A-20 

Unidentified 

98 29.03 A-10 

Unidentified 

99 29.30 A-300 

Unidentified 

100 29.46 A-6 

Unidentified 

101 29.80 A-20 000117-81-7 

Bis (2-ethylhexyl) phthalate 

102 30.14 A-8 

Unidentified 

103 30.18 A-7 

Unidentified 

104 30.32 A-60 

Unidentified 

105 30.63 A-10 

Unidentified 

106 31.08 A-6 

Unidentified 



F8 



TIRE CRUMB WATER BATCH 9A - continued. 

Entry R.T. Cone. CAS No 

Identity 

107 31.27 A-5 

Unidentified 

108 31.41 A-7 

Unidentified 

109 31.54 A-2 

Unidentified 

110 31.61 A-3 

Unidentified 

111 34.05 A-4 

Unidentified 



TIRE CRUMB WATER PH 2 - ACID FRACTION 

(4-L aqueous extract at pH 2 of 100 grams of 30 to 40 mesh size tire granules) 

Entry R.T. Cone. CAS No. 

Identity 

1 5.355 A-10 000108-10-1 

2-Pentanone, 4 -me thy 1- 

2 7.909 A-8 

An alcohol or ether 

3 8.547 A- 6 

Unidentified 

4 8.623 A-30 000108-94-1 

Cyc lohexanone 

5 8.899 A-10 000111-76-2 

Ethanol, 2-butoxy- 

6 9.201 A-800 000106-51-4 

2 , 5-Cyclohexadiene-l , 4-dione 

7 10.37 A-40 ' 000062-53-3 

Aniline 

8 10.45 A-30 000108-95-2 

Phenol 

9 11.30 A-10 

Unidentified 

10 11.56 A-5 

Unidentified 

11 12.11 A-10 

A hydrocarbon 

12 12.19 A-40 

A methyl -benzenamine 

13 12.41 A-9 000617-94-7 

Benzyl alcohol, a, a-dimethyl- 

14 12.68 A-20 004458-32-6 

1-Propanamine, N-ethyl-N-methyl- 



F9 



TIRE CRUMB WATER PH 2 - ACID FRACTION - continued. 

Entry R . T . Cone . CAS No . 

Identity 

15 13.08 A-80 000149-57-5 

Hexanoic acid, 2 -ethyl - 

16 13.14 A-20 

Unidentified 

17 13.94 A-20 

Unidentified 

18 13.98 A-8 

Unidentified 

19 14.28 A-10 000098-55-5 

3-cyclohexene-l-methanol, a, a, 4-trimethyl- 

20 14.61 A-3 

A nitrogen compound 

21 14.91 A-600 000095-16-9 

Benzothiazole 

22 15.00 A-20 

Unidentified 

23 15.14 A-20 

A tetrahydromethyl-thiophene 

24 15.30 A-40 000765-93-8 

Formamide, N-cyclohexyl- 

25 15.41 A-20 001551-32-2 

Thiophene, 2-ethyltetrahydro- 

26 15.49 A-30 

Unidentified 

27 15.84 A-20 

A butylphenol 

28 16.55 A-7 

Unidentified 

29 16.67 A-7 

Unidentified 

30 16.82 A-20 074367-33-2 

Propanoic acid, 2 -methyl-, 2 , 2-dimethyl- 

31 16.97 A-9 

Unidentified 

32 17.08 A-10 074367-34-3 

Propanoic acid, 2-methyl-3-hydroxy-2 , 4 , 4- 
trimethyl pentyl ester- 

33 17.20 A-50 053927-61-0 

Benzenamine, N- (2, 2-dimethylpropyl) -N-methyl- 

34 17.26 A-6 

Unidentified 

35 17.47 A-6 

A dihydroxy-methyl-benzaldehyde 

36 17.57 A-6 

Unidentified 



F10 



TIRE CRUMB WATER PH 2 - ACID FRACTION - continued. 

Entry R . T . Cone . CAS No . 

Identity 

37 17.87 A-4 

Unidentified 

38 18.16 A-90 

An aromatic nitrogen compound 

39 18.43 A-500 85-41-6/19377-95-8 

lH-Isoindole-1, 3 (2H) -dione + Bicyclo [3.1. OJhexan- 
2 -one, 1 , 5-bis (butyl) -3 , 3 -dimethyl - 

40 18.69 A-20 

Unidentified 

41 19.00 A-10 

Unidentified 

• 42 19.14 A-10 

Unidentified 

43 19.51 A-3 

Unidentified 

44 19.59 A-30 

A dibutylthiophene 

45 20.04 A-10 000084-66-2 

Diethyl phthalate 

46 20.24 A-4 

A phenol 

■ 47 20.50 A-9 000122-39-4 

Benzenamine, N-phenyl- 

48 20.83 A-9 

Unidentified 

49 20.93 A-10 

Unidentified 

50 20.99 A-3 

Unidentified 

51 21.11 A-200 000934-34-9 

2 (3H) -Benzothiazolone 

52 21.72 A-8 

Unidentified 

53 22.11 A-10 

A butyl -Indole 

54 25.14 A-60 ' 

1, 2-Benzisothiazole, 3- (4-morpholinyl) - 

55 25.30 A-10 

Unidentified 

56 25.37 A-10 002387-23-7 

Urea, N, N' -dicyclohexyl- 

57 25.47 A-10 

Unidentified 

58 25.89 A-4 

Unidentified 



Fll 



TIRE CRUMB WATER PH 2 - ACID FRACTION - continued. 

Entry R.T. Cone. CAS No. 

Identity 

59 26.74 A-9 

Unidentified 

60 28.32 A-10 

Unidentified 

61 28.61 A-50 

Unidentified 

62 30.03 A-50 

Unidentified 

63 30.23 A-20 

Unidentified 

64 30.46 A- 6 

Unidentified 

65 30.64 A-9 

Unidentified 

66 30.72 A-7 

Unidentified 

67 30.93 A-700 

Unidentified 

68 31.17 A-20 

Unidentified 

69 31.23 A-40 

Unidentified 

70 31.36 A-9 

Unidentified 

71 31.48 A-20 

Unidentified 

72 31.59 A-60 

Unidentified 

73 31.81 A-6 

Unidentified 

74 32.39 A-5 

Unidentified 

75 32.58 A-10 

Unidentified 

76 32.72 A-10 

Unidentified 

77 32.88 A-20 

Unidentified 

78 33.00 A-10 

Unidentified 

79 33.22 A-30 

Unidentified 

80 33.33 A-10 

Unidentified 

81 34.14 A-40 

Unidentified 



F12 



TIRE CRUMB WATER PH 2 - ACID FRACTION - continued. 

Entry R . T . Cone . CAS No . 

Identity 

82 35.38 A-5 

Unidentified 

83 38.80 A-20 

Unidentified 

84 39.13 A-10 

Unidentified 

85 45.52 A-200 

Unidentified 

86 47.99 A-40 

Unidentified 



TIRE CRUMB WATER PH 2 - BASE-NEUTRAL FRACTION 

(4-L aqueous extract at pH 2 of 100 grams of 30 to 40 mesh size tire granules) 

Entry R.T. Cone. CAS No. 

Identity 

1 5.26 A-3 

Unidentified 

2 5.50 A-10000 

An amine 

3 5.94 A-200 000108-88-3 

Benzene, methyl - 

4 5.99 A-200 000109-01-3 

Piperazine, 1-methyl- 

5 6.34 A-200 000109-02-4 

Morpholine, 4 -methyl - 

6 6.55 A-70 

Unidentified 

7 6.76 A-200 

A nitrogen compound 

8 7.70 A-200Û 028292-43-5 

2 -Hexanamine , 5 -methyl - 

9 7.90 A-4000 000108-91-8 

Cyclohexanamine 

10 8.40 A-30 

A nitrogen compound 

11 8.46 A-50 

Unidentified 

12 8.63 A-40 

Unidentified 

13 8.91 A-200 

A Hexanol 

14 9.46 A-50 

Unidentified 



F13 



TIRE CRUMB WATER PH 2 - BASE-NEUTRAL FRACTION - continued. 

Entry R . T . Cone . CAS No . 

Identity 

15 9.64 A-90 

Unidentified 

16 10.08 A-60 

A C-6 alkyl amine 

17 10.66 A-40000 000062-53-3 

Aniline 

18 10.82 A-100 

Unidentified 

19 10.92 A-100 

Unidentified 

20 12.10 A-400 

A methyl benzenamine 

21 12.29 A-10000 

A methyl benzenamine 

22 12.70 A-100 ' 

An amine 

23 12.99 A-70 

A nitrogen compound 

24 13.07 A-400 

A nitrogen compound 

25 13.19 A-90 

A nitrogen compound 

26 13.60 A-100 000768-52-5 

Benzenamine, N- ( 1-methylethyl) - 

27 13.89 A-100 

A dimethyl aniline and unidentified 

28 14.15 A-80 000112-34-5 

Ethanol, 2- (2-butoxyethoxy) - 

29 14.24 A-300 

Unidentified 

30 14.48 A-200 

A chloro methyl pyridine 

31 14.91 A-80 000095-16-9 

Benzothiazole 

32 14.95 A-200 

A diethyl aniline 

33 15.13 A-50 

A nitrogen compound 

34 15.22 A-80 000105-60-2 

Caprolactam 

35 15.30 A-300 000766-93-8 

Formamide, N-cyclohexyl- 

36 15.48 A-100 000119-65-3 

Isoguinoline 

37 15.83 A-100 001124-53-4 

Acetamide, N-cyclohexyl- 



F14 



TIRE CRUMB WATER PH 2 - BASE-NEUTRAL FRACTION - continued. 

Entry R . T . Cone . CAS No . 

Identity 

38 16.12 A-100 

An amine 

39 16.28 A-200 

An amine 

40 16.77 A-90 000054-11-5 

Pyridine, 3- (l-methyl-2-pyrrolidinyl) - 

41 16.89 A-20 

A nitrogen compound 

42 16.95 A-70 

A nitrogen compound 

43 17.21 A-100 

A C-6 alkyl aniline 

44 17.28 A-40 

A methyl quinoline 

45 17.85 A-10000 000101-83-7 

Cyclohexanamine, N-cyclohexyl- 

46 18.02 A-90 

Unidentified 

47 18.18 A-500 

A dimethyl quinoline 

48 18.41 A-10000 ' 

A nitrogen compound 

49 18.73 A-50 

A nitrogen compound 

50 18.77 A-60 

A nitrogen compound 

51 18.85 A-100 

Unidentified 

52 19.01 A-1000 007560-83-0 

Cyclohexanamine, N-cyclohexyl-N-methyl- 

53 19.33 A-300 

Unidentified 

54 19.78 A-30 

Unidentified 

55 20.27 A-200 

Unidentified 

56 20.58 A-90 

Unidentified 

57 20.64 A-50 

Unidentified 

58 20.84 A-1000 

Unidentified 

59 20.93 A-200 

A nitrogen compound 

60 21.02 A-100 016954-69-1 

2-Benzothiazolamine, N-methyl- 



F15 



TIRE CRUMB WATER PH 2 - BASE-NEUTRAL FRACTION - continued. 

Entry R.T. Cone. CAS No. 

Identity 

61 21.14 A-90 

Unidentified 

62 21.46 A-60 

Unidentified 

63 21.85 A-50 

Unidentified 

64 21.97 A-40 

Unidentified 

65 22.11 A-600 

Unidentified 

66 23.70 A-70 

Unidentified 

67 24.32 A-20 002622-63-1 

1 -methyl -2 -Phenylbenz imidazole 

68 25.46 A-800 ' 

Unidentified 

69 25.85 A-50 

Unidentified 

70 26.25 A-100 

Unidentified 

71 26.42 A-100 

Unidentified 

72 26.54 A-20 

Unidentified 

73 26.83 A-500 

Unidentified 

74 28.05 A-200 

Unidentified 

75 28.61 A-90 

Unidentified 

76 28.82 A-10 

Unidentified 

77 30.58 A-60 

Unidentified 

78 30.65 A-20 

Unidentified 

79 30.91 A-200 

Unidentified 

80 31.08 A-20 

Unidentified 

81 31.24 A-100 

Unidentified 

82 31.60 A-3000 

Unidentified 

83 31.75 A-10 

Unidentified 



F16 



TIRE CRUMB WATER PH 2 - BASE-NEUTRAL FRACTION - continued. 

Entry R.T. Cone. CAS No. 

Identity 

84 31.89 A-30 

Unidentified 

85 32.61 A-60 

Unidentified 

86 32.88 A-100 

Unidentified 

87 33.30 A-100 

Unidentified 

88 34.12 A-60 

Unidentified 

89 34.94 A-100 

Unidentified 

90 35.04 A-30 

Unidentified 

91 38.60 A-30 

Unidentified 

92 48.00 A-200 

Unidentified 



TIRE CRUMB WATER PH 11 

(4-L aqueous extract at pH 11 of 100 grams of 30 to 40 mesh size tire granules) 

Entry R.T. Cone . CAS No . 

Identity 

1 6.144 A-l 000595-46-0 

Propanedioic acid, dimethyl- 

2 6.447 A-5 000109-02-4 

Morpholine, 4 -methyl - 

3 6.644 A-2 

A carboxylic acid 

4 7.419 A-0.6 

Unidentified 

5 7.566 A-0.4 

Unidentified 

6 7.746 A-2 000111-45-5 

Ethanol, 2- (2-propenyloxy) - 

7 7.953 A-7 

An alcohol 

8 8.043 A-3 000503-74-2 

Butanoic acid, 3-methyl- 

9 8.191 A-2 

An ester 



F17 



TIRE CRUMB. WATER PH 11 - continued. 

Entry R . T . Cone . CAS No . 

Identity 

10 8.356 A-2 

An amine 

11 8.488 A-4 

A hexylamine 

12 8.666 A-20 ' 000108-94-1 

Cyclohexanone 

13 8.727 A-20 

A hexylamine 

14 8.967 A-40 000111-76-2 

Ethanol, 2-butoxy- 

15 9.079 A- 5 

A hexylamine 

16 9.241 A- 5 

Unidentified 

17 9.462 A-2 

An unsaturated hydrocarbon 

18 9.672 A-6 

An amine 

19 9.908 A-0.7 

Unidentified 

20 10.01 A-l 

A hydrocarbon + a C4-alkylbenzene 

21 10.37 A-20 000062-53-3 

Aniline 

22 10.46 A-30 000108-95-2 

Phenol 

23 10.71 A-6 000632-22-4 

Urea, tetramethyl- 

24 10.83 A-30 

A carboxylic acid 

25 11.12 A-2 

Unidentified 

26 11.22 A-2 

A carboxylic acid 

27 11.37 A-7 000104-76-7 

Hexanol, 2 -ethyl 

28 11.53 A-3 000766-39-2 

2 , 5-Furandione, 3 4-dimethyl- 

29 11.68 A-5 

A hydroxy-benzaldehyde, 

30 11.84 A-4 

A methylphenol 

31 12.09 A-4 000098-86-2 

Ethanone, 1 -phenyl - 

32 12.20 A-8 

A methyl -benzenamine 



F18 



TIRE CRUMB WATER PH 11 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

33 12.37 A-3 

A methylphenol 

34 12.45 A-9 000617-94-7 

Benzenemethanol, a, a-dimethyl 

35 12.62 A-10 

A carboxylic acid 

36 12.76 A-3 

A carboxylic acid 

37 12.86 A-10 

An amine 

38 13.03 A-2 

A carboxylic acid 

39 13.15 A-20 000100-74-3 

Morpholine, 4-ethyl- 

40 13.24 A-5 

An amine 

41 13.84 A-300 

A carboxylic acid 

42 13.95 A-50 

A linear alcohol ethoxylate 

43 14.02 A-20 

A linear alcohol ethoxylate 

44 14.12 A-4 

A methyl ester 

45 14.19 A-l 

Unidentified 

46 14.27 A-20 000112-34-5 

Ethanol, 2- (2-butoxyethoxy) - 

47 14.42 A-200 

A carboxylic acid + unidentified 

48 14.72 A-20 

A methyl ester 

49 15.05 A-300 ' 000095-16-9 

Benzothiazole 

50 15.24 A-400 

A methyl ester 

51 15.78 A-70 

A methyl ester 

52 15.89 A-70 

A butyl -phenol 

53 16.15 A-500 

A methyl ester + unidentified 

54 16.46 A-10 000103-70-8 

Formamide, N-phenyl- 

55 16.63 A-20 

A methyl ester 



F19 



TIRE CRUMB WATER PH 11 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

56 16.68 A-40 

A methyl ester 

57 16.83 A-20 

Unidentified 

58 16.89 A-10 

A methyl ester 

59 16.98 A-10 

A methyl ester 

60 17.24 A-100 ' 000334-48-5 

Decanoic acid 

61 17.52 A-4 000621-59-0 

A hydroxy-methoxy-benzaldehyde 

62 17.91 A-20 

A methyl ester 

63 18.19 A-20 

A methyoxy-naphthalene 

64 18.43 A-60 

A linear alcohol ethoxylate 

65 18.49 A-70 

A C10-alkylphenol 

66 19.62 A-50 

A dibutyl-thiophene 

67 19.82 A-200 

A C12-carboxylic acid 

68 20.08 A-10 000084-66-2 

Diethyl phthalate 

69 20.28 A-6 

A dibutyl -phenol 

70 20.39 A-8 000615-22-5 

Benzothiazole, 2- (methyl thio) - 

71 20.52 A-10 000122-39-4 

Dipheny lamine 

72 20.91 A-10 

A carboxylic acid 

73 21.02 A-3 001205-39-6 

Benzenamine, 2 -methyl -N-phenyl- 

74 21.51 A-300 000934-34-9 

2 (3H) -Benzothiazolone 

75 21.75 A-9 

A C5-alkyl -naphthalene 

76 21.93 A-30 

A linear alcohol ethoxylate 

77 22.06 A-40 

A C14-carboxylic acid 

78 22.17 A-10 

Unidentified 



F20 



TIRE CRUMB WATER PH 11 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

79 22.26 A-20 

A C10-alkyl -phenol 

80 22.51 A-7 003622-84-2 

Benzenesulfonamide, N-butyl- 

81 22.71 A-9 

A C5-alkyl -naphthalene 

82 23.08 A-9 

Unidentified 

83 23.26 A-20 

A biphenyl-diol 

84 23.84 A-5 

Unidentified 

85 23.93 A-20 

Unidentified 

86 24.02 A-10 

Unidentified 

87 24.15 A-4 

A dimethyl-dihydroacridine 

88 24.20 A-6 

A C16-carboxylic acid 

89 24.59 A-90 000149-30-4 

2 -Mercaptobenzothiazole 

90 24.86 A-50 

A methylenebis-phenol 

91 25.18 A-40 

1, 2-Benzisothiazole, 3- (4-morpholinyl) - 

92 25.54 A-20 

A methylenebis-phenol 

93 26.52 A-7 

Unidentified 

94 27.12 A-70 

An octahydrodimethyl-phenanthrenecarboxylic acid 

95 27.73 A-300 

A methyl ester of a C20-carboxylic acid 

96 28.18 A-200 

A resin acid 

97 28.39 A-300 

A resin acid 

98 29.55 A-2000 

A resin acid 

99 30.61 A-100 

Unidentified 

100 31.33 A-10 

Unidentified 



F21 



TIRE CRUMB WATER PH 11 - continued. 

Entry R.T. Cone. CAS No 

Identity 

101 31.52 A-7 

Unidentified 



TIRE CRUMB WATER PH 8 

(4-L aqueous extract at pH 8 of 100 grams o£ 30 to 40 mesh size tire granules) 

Entry R.T. Cone . CAS No . 

Identity 

1 5.587 A-3 

An amine 

2 6.605 A-0.3 

A halogenated compound 

3 8.669 A-0.4 000108-94-1 

Cyclohexanone 

4 10.38 A-0.9 000062-53-3 

Aniline 

5 12.35 A-0.8 000637-88-7 

1, 4-Cyclohexanedione 

6 13.12 A-l 

A carboxylic acid 

7 13.26 A-0.3 

A terpene 

8 14.24 A-0.5 000091-20-3 

Naphthalene 

9 14.33 A-0.5 

A cyclic ketone 

10 14.91 A-20 000095-16-9 

Benzothiazole 

11 15.41 A-l 

A carboxylic acid 

12 15.85 A-l 

A butyl -phenol 

13 16.29 A-0.3 

A dimethyl -naphthalene 

14 16.68 A-2 

Unidentified 

15 16.82 A-2 

A carboxylic acid ester 

16 17.09 A-0.7 

A carboxylic acid ester 

17 17.21 A-0.2 

Unidentified 

18 17.59 A-l 

Unidentified 



F22 



TIRE CRUMB WATER PH 8 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

19 18.18 A-l 

A methoxy-naphthalene 

20 18.45 A-20 

A C10-alkylphenol 

21 19.03 A-6 

Unidentified 

22 19.15 A-l 

Unidentified 

23 19.30 A-3 

Unidentified 

24 19.34 A-2 

Unidentified 

25 19.45 A-4 

Unidentified 

26 19.59 A-2 

A dibutyl-thiophene 

27 20.09 A-0.8 

A carboxylic acid ester 

28 20.25 A-2 

A C8-alkylphenol 

29 20.40 A-20 000615-22-5 

Benzothiazole, 2- (methyl thio) - 

30 20.73 A-0.6 

Unidentified 

31 21.00 A-0.9 001205-39-6 

Benzenamine, 2 -methyl -N-phenyl- 

32 21.10 A-4 000934-34-9 

2 (3H) -Benzothiazolone 

33 21.46 A-0.4 

Unidentified 

34 21.56 A-0.7 

Unidentified 

35 21.72 A-3 

A C5-alkyl -naphthalene 

36 22.09 A-0.8 

Unidentified 

37 22.24 A-l 

Unidentified 

38 22.67 A-2 

A C5-alkyl -naphthalene 

39 24.05 A-2 

Unidentified 

40 24.13 A-2 

A dihydro-dimethyl-acridine 

41 25.14 A-l 

1, 2-Benzisothiazole, 3- ( 4 -morpho liny 1) 



F23 



TIRE CRUMB WATER PH 8 - continued. 

Entry R.T. Cone. CAS No. 

Identity 

42 25.31 A-0.6 

Unidentified 

43 25.47 A-0.7 

Unidentified 

44 25.90 A-0.6 

Unidentified 

45 26.32 A-l 

Unidentified 

46 26.84 A-5 

Unidentified 

47 27.08 A-l 

Unidentified 

48 27.24 A-0.4 000090-30-2 

1-Naphthalenamine, N-phenyl- 

49 28.16 A- 3 

Unidentified 

50 28.63 A-l 

Unidentified 

51 28.69 A-5 

Unidentified 

52 30.04 A-0.9 

Unidentified 

53 30.49 A-l 

Unidentified 

54 30.94 A-2 

A methyl ester of a resin acid 

55 31.24 A-2 

Unidentified 

56 31.46 A-2 

Unidentified 

57 31.59 A-l 

Unidentified 

58 32.24 A-0.8 

An alkane 

59 33.05 A-2 

An alkane 

60 33.90 A-2 

An alkane 

61 34.85 A-l 

An alkane 

62 35.94 A-l 

An alkane 

63 36.52 A-0.9 

Unidentified 

64-66 37-40 A-l 

three alkanes 



F24 



APPENDIX G 

GC/MS ANALYSIS FOR VOLATILE ORGANIC COMPOUNDS: TIRE WATER 

Volatile organic compounds were analyzed by a purge-and-trap system 
followed by gas chromatography/ (full scan) mass spectrometry 
(GC/(FS)MS). The concentrations are approximate and were 
calculated relative to the internal standard d 10 -ethylbenzene . No 
volatile organic compounds were detected in tire water batch 4. 



Gl 



APPENDIX H 

LC/MS ANALYSIS FOR EXTRACTABLE ORGANIC COMPOUNDS: TIRE WATER 

Extractable organic compounds were determined in the following 
manner: The extracts were divided into base, neutral and acid 
fractions and were analyzed by reverse phase liquid chromatography/ 
(particle beam) mass spectrometry. Most of the compounds detected 
in tire water batch 5 were also detected in the GC/MS scans except 
for an alkylated phenol that was probably from an antioxidant 
mixture from the tire. 



HI 



APPENDIX I 

SCANNING ELECTRON MICROSCOPY: TIRE CRUMB MATERIAL 

A sample of tire crumb material was fractionated by separating the 
white and black particles found in the mixture. Examination of the 
particles by scanning electron microscopy indicated that the white 
material was primarily titanium with lesser amounts of silicon and 
aluminium. This was probably titanium oxide whitewall paint. 
Examination of samples of the black particles showed that it was a 
heterogeneous mixture composed primarily of silicon, sulphur and 
zinc with lesser amounts of calcium and iron. An "unresolved 
envelope" of organic compounds was noted in all samples. 



II 



APPENDIX J 

UV/VIS SPECTROMETRY: TIRE WATER AND TIRE CRUMB WATER 

A sample of tire water (batch 10) was scanned in the ultraviolet 
(UV) and visible (VIS) light ranges. No significant light 
absorbance was found. Four samples of tire crumb water (batch 5) 
were scanned in the UV range. No significant light absorbance was 
found in the following samples: baseline, pH 3, pH 11 or spiked 
with a 1% (wt/vol) phenol solution 



Jl 



APPENDIX K 

FTIR ANALYSIS: TIRE CRUMB MATERIAL 

A sample of tire crumb material was Soxhlet-extracted with 
dichloromethane. This gave a significant quantity (96,450 ppm) of 
extract, a viscous dark-brown liquid. Fourier Transform Infrared 
(FTIR) spectra on this liquid indicated it contained a mixture of 
paraf finie, naphthenic and aromatic hydrocarbons with a minor 
quantity of carbonyl compounds (esters and possibly acids) . The 
spectra resembled those obtained from lubricant oils. 



Kl 



APPENDIX L 

CHEMICAL ANALYSES FOR TOTAL UNFILTERED REACTIVE PHENOLS 1 : 
TIRE WATER, SURFACE WATER AND TIRE CRUMB WATER 



Phenols 


Tire 


Tire 


(ug\L) 


water 


submersion 




batch 


time (days) 


0.6 


4 


5 


2.6 


4 


8 


2.2 


4 


12 


3.6 


5a 


7 


2.6 


5a 


9 


2.8 


5a 


12 


2.8 


5a 


15 


2.2 


5a 


16 1 


2.0 


5a 


16 2 


2.0 


5a 


16 3 


4.4 


5b 


26 


2.4 


6 


8 


3.0 


6 


13 


nd 


7 


1 


nd 


7 


6 


1.8 


7 


13 


nd 


10 


15 


1.6 


13c 


13 


Ambient tire water (f. 


ield samples) 


nd 


Lake 


approx . 




Erie 


1 year 




reef 




nd 


trench 


approx . 




site 


3 years 



Tire crumb water 

13 na pH 8 

65 na pH 11 

220 na pH 2 

1 Phenols with alkyl, aryl , nitro, benzoyl, nitroso or aldehyde 
para-substituents are not well-measured by this test, so the 
reported concentrations are minima. Phenols were generally 
nondetectable (<0.2 ug/L) or very low in the control water samples, 
nd = not detected; 2 sample stored 10 days at 2 0°C in the dark; 
sample stored 10 days at 2 0°C under light; 4 sample stored 10 days 
at 15°C under light 



LI 



APPENDIX M 

ACUTE LETHALITY TO RAINBOW TROUT OF FLOW- THROUGH TIRE WATER: 
TIME TO 50% MORTALITY (LT50) IN THE SINGLE CONCENTRATION TESTS 1 



Lake 
reef 


Erie 
tires 




trench site 
tires 




scrap 
group 


tires 
C 




Flow 
time 


Flow 
rate 


LT50 


Flow 
time 


Flow 
rate 


LT50 


Flow 
time 


Flow 
rate 


LT50 


7 


1 


30.9 


5 


0.5 


NL 


15 


0.5 


42.5 


11 


1 


32.2 


7 


0.5 


NL 


21 


1 


NL 


21 


1 


36.1 


8 


1 


NL 


22 


1.5 


NL 


29 


2 


>96 


9 


1 


NL 


36 


1 


NL 


31 


2 


NL 


12 


1 


NL 


39 


0.5 


NL 


36 


2 


NL 


14 


0.5 


NL 


42 


0.5 


>96 


43 


1.5 


NL 


16 


0.5 


NL 








58 


1.5 


NL 


20 


0.5 


95 








65 


1 


NL 


21 


0.25 


73 








71 


0.5 


47.8 


22 


0.25 


79.5 








74 


0.5 


50 


23 


0.25 


>96 








78 


1 


NL 


26 


0.25 


53.8 








84 


1 


NL 


28 
32 
39 
68 
69 
78 


0.25 
0.25 
0.16 
0.38 
0.36 
0.34 


>96 

>96 

34 

NL 

NL 

NL 









95 % confidence limits could not be calculated because partial 
mortality (> to < 100 %) was not observed. 

Table legend 

Flow time cumulative days 

Flow rate L/min 

LT50 hours 

NL nonlethal, no fish died 

>96 % mortality >0 and <50 



Ml 



APPENDIX N 

ACUTE LETHALITY TO RAINBOW TROUT OF FLOW-THROUGH TIRE WATER: 
PERCENTAGE MORTALITY IN THE DILUTION SERIES TESTS 



The tires were collected from the artifical reef in Lake Erie 
Test 38: 1.0 L/min flow for 11 days 



Concentration 


Expoi 


sure 


time 










% vol /vol 




24 


hours 


48 


hour s 


72 hours 


96 hours 


100 













10C 


) 




100 


100 


80 













80 






100 


100 


65 













40 






70 


80 


40 




















30 


50 


30 





















































LC50 






NL 






68 






50 


45 


95 % 


C.L.s 










56- 


-76 




43-59 


38-53 


Test 


40: 1, 


.0 


L/min 


flow 


' for 


21 


days 






Concentration 


Exposure 


time 










% voi 


L/vol 




24 


hours 


48 


hours 


72 hours 


96 hours 


100 













80 






90 


90 


80 













60 






70 


80 


65 




















30 


30 


40 


























30 


























20 





















































LC50 






NL 






83 






73 


71 


95 % 


C.L.s 










75- 


-93 




61-82 


60-80 



Nl 



Test 41: 2.0 L/min flow for 29 days 



Concentration Exposure time 

% vol /vol 24 hours 48 hours 



72 hours 



100 

80 

65 

40 



LC50 









30 








10 





























NL 


NL 


>100 



Test 42: 2.0 L/min flow for 31 days 



Concentration Exposure time 

% vol /vol 24 hours 48 hours 



72 hours 96 hours 



100 

80 

65 



LC50 



















































NL 


NL 


NL 


NL 



Test 43: 2.0 L/min flow for 36 days 



Concentration Exposure time 

% vol/vol 24 hours 48 hours 72 hours 



96 hours 



100 

80 

65 



LC50 



















































NL 


NL 


NL 


NL 



N2 



APPENDIX O 

ACUTE LETHALITY TO RAINBOW TROUT OF STATIC TIRE WATER: 
PERCENTAGE MORTALITY IN THE DILUTION SERIES TESTS 

Test 17 : batch 7 



Concentration 


Exposure 


time 










% vol /vol 


24 


hours 


48 


hours 


72 


hour s 


96 hours 


100 


IOC 


i 


IOC 


i 


10C 


I 


100 


65 


17 




83 




83 




83 


40 







33 




33 




33 


30 









































LC50 


75 




48 




48 




48 


95 % C.L.S 


65- 


86 


40- 


59 


40- 


59 


40-59 



Test 18: batch 7 (6d-old) 



Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 hours 


96 hours 


100 




100 


100 


100 


100 


65 




20 


90 


100 


100 


40 







20 


60 


60 



















LC50 
95 % 


C.L.S 


75 
68-82 


53 
45-61 


43 
N.C. 


43 
N.C. 


Test 


19: batch 8 








Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 hours 




100 




100 


100 


100 




65 




80 


100 


100 




40 




10 


10 


20 




















LC50 
95 % 


C.L.S 


56 
68-70 


47 
N.C. 


47 
N.C. 





Ol 



Test 


21: 


batch 9 










Concentrât 
% vol /vol 


ion 


Exposure 
24 hours 


time 

48 hours 


72 hours 


9 6 hours 


100 






90 




100 


100 


100 


65 






50 




100 


100 


100 


40 











50 


80 


80 


30 














10 


10 























LC50 
95 % 


C.L.S 




68 
56- 


•82 


42 
37-48 


36 
32-40 


36 
32-40 


Test 


29: 


batch 12 


(8d-c 


>ld) 






Concentrât 
% vol /vol 


ion 


Exposure 
24 hours 


time 

48 hours 


72 hours 


96 hours 


100 






90 




100 


100 


100 


65 






20 




80 


100 


100 


40 











80 


100 


100 


30 











60 


90 


90 























LC50 
95 % 


C.L.s 




77 
65- 


92 


25 
N.C. 


<30 
N.C. 


<30 
N.C. 


Test 


29: 


bate 


h 12 


(8d-c 


dd) , distilled dilution 


water 


Concentrât 
% vol /vol 


ion 


Exposure 
24 hours 


time 

48 hours 


72 hours 


9 6 hours 


100 






90 




100 


100 


100 


65 






30 




90 


90 


90 


40 











30 


50 


80 


30 






































20 


LC50 
95 % 


C.L.s 




74 
61- 


89 


51 
42-63 


44 
37-53 


44 
36-51 



02 



Test 


32: 


batch 13c 












Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 


hour s 


96 hours 


100 






100 




100 


100 




100 


80 






80 




100 


100 




100 


65 






50 




100 


100 




100 


40 











10 


60 




80 


30 














30 




30 


20 














10 




10 

























LC50 
95 % 


C.L.! 


3 


66 
53-74 




51 
N.C. 


35 
28- 


43 


32 
27-39 


Test 


34: 


batch 13c 


(14d 


-old) 








Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 


hours 


96 hours 


80 











70 


100 




100 


65 











50 


80 




90 


40 













































LC50 
95 % 


C.L.: 


3 


>80 
N.A. 




65 
55-81 


52 

47- 


57 


51 
N.A. 


Test 


34: 


batch 13c 


(14d 


-old) , distilled 


dilution water 


Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 


hours 


96 hours 


80 











70 


100 




100 


65 











60 


90 




90 


40 














10 




20 


20 










































10 


LC50 
95 % 


C.L. 


s 


> 80 

N.A. 




63 
53-78 


49 
42- 


56 


47 

40-54 



03 



Test 35: batch 14 



Cone ent r a t i on 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 hours 


96 hours 


100 




100 


100 


100 


100 


80 




100 


100 


100 


100 


65 




60 


100 


100 


100 


40 










50 


60 


30 

































LC50 
95 % 


C . L . s 


59 
53-65 


51 
40-65 


42 
37-48 


40 
36-46 


Test 


36: bate 


h 14 (20d- 


old) 






Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 hours 


96 hours 


100 




50 


100 


100 


100 


80 




30 


100 


100 


100 


65 







100 


100 


100 


40 







30 


50 


50 


30 










30 


30 


20 

































LC50 
95 % 


C.L.S 


> 96 
N.A. 


45 
41-51 


37 
32-44 


37 

32-44 



04 



Test 46: batch 15 (3d-soak of tires) 



Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 


hours 


96 hours 


100 









100 


100 




100 


80 









30 


60 




60 


65 









10 


10 




10 


40 









































LC50 

95 % 


C.L.s 


NL 




81 

74-89 


77 

70- 


84 


77 

70-84 


Test 


66: Tire 


water 


batch 16b (3 -day so 


ak) 




Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 


hours 


96 hours 


100 




100 




100 


100 




100 


80 




70 




100 


100 




100 


65 




60 




100 


100 




100 


40 




10 




30 


30 




40 


30 









10 


10 




50 


20 









































LC50 
95 % 


C.L.s 


62 
52-72 




42 
37-51 


42 
37- 


51 


36 

30-44 


Test 


67: Tire 


water 


batch 16c (fre 


sh sample) 




Concentration 
% vol /vol 


Exposure 
24 hours 


time 

48 hours 


72 


hours 


96 hours 


65 




100 




100 


100 




100 


40 









100 


100 




100 


30 









80 


100 




100 


20 









20 


40 




40 


10 









































LC50 
95 % 


C.L.s 


51 

N.C. 




24 
20-28 


27 
22- 


34 


27 

22-34 



05 



APPENDIX P 

ACUTE LETHALITY TO RAINBOW TROUT OF STATIC TIRE WATER 
SUBJECTED TO TOXICITY REDUCTION TREATMENTS 

Percentages listed under sample treatment refer to tire water 
samples diluted to different volumetric ratios with dechlorinated 
municipal tap water. Distilled water was used as the diluent in 
some tests as indicated by distilled diluent. Baseline means the 
undiluted and untreated sample of tire water (TW) tested for 
toxicity in comparison to the corresponding treated samples. When 
toxicity testing occurred immediately after collecting the sample, 
the sample age {age) is given as 1 day. Where samples were stored 
for later treatment and testing, age refers to the storage time. 
Samples were stored in filled and sealed plastic-lined 20-L buckets 
at 15 °C in the dark unless indicated. 



TW# 


Tst 
# 


Sample 
treatment 








age 
(d) 


LT50 
(h) 


95% 
CL. 's 


4 


8 


baseline 








1 


NL 


N.A. 


5a 


9 


baseline 








1 


4-20 


N.A. 






pre-tested 


for 24h 




1 


23 


N.A. 




10 


stored @ 2 


°C 






10 


26.7 


23.4-31.6 






stored @ 20 


°C 


under 


light 


10 


31.9 


28.8-35.9 






stored @ 20 
in a glass 


°C under light 
container 


10 


33.2 


28.6-42.9 






stored 








10 


24.6 


21.6-34.2 




11 


stored 








26 


18.7 


7.7-21.2 


5b 


10 


baseline 








1 


20.1 


12.0-24.6 


6a 


11 


baseline 








1 


2-18 


N.A. 


6b 


12 


baseline 








1 


2-17 


N.A. 






pre-tested 


for 24h 




1 


15.1 


N.A. 






pre-aerated 


f 


or 24h 




1 


15.9 


14.2-17.8 




13 


stored 








8 


21.9 


19.7-25.0 




14 


stored 








14 


19.0 


13.9-21.2 




15 


stored 








28 


25.5 


23.2-29.7 




16 


stored 








35 


27.5 


25.2-32.0 


7 


16 


baseline 








1 


2-18 


N.A. 




17 


baseline 








1 


16.3 


13.3-20.1 



PI 



TW# 


Tst 
# 


Sample 
treatment 








age 
(d) 


LT50 
(h) 


95% 
CL. 's 






65 % 








1 


30.8 


25.1-56.3 






40 % 








1 


>96 


N.A. 






30 % 








1 


NL 


N.A. 




18 


baseline 
65 % 








6 
6 


5-22 
32.7 


N.A. 
29.0-37.1 






46 % 








6 


71.6 


59.2-100 




19 


stored 








13 


20.5 


13.5-24.6 






stored @ 2C 


)°C 


under 


light 


13 


20.8 


12.7-24.0 


8 


19 


baseline 
65 % 
40 % 








1 
1 
1 


6-19 
17.9 
>72 


N.A. 

8.7-21.4 

N.A. 




20 


stored 








7 


16.9 


13 .6-21.0 




21 


stored 








14 


22.4 


18.9-23.9 




22 


stored 








30 


25.9 


23.2-84.6 


9 


21 


baseline 








1 


6-21 


N.A. 






65 % 








1 


23.9 


19.7-27.0 






40 % 








1 


51.7 


41.3-62.4 






30 % 








1 


>96 


N.A. 




22 


stored 








16 


36.6 


28.5-46.9 




23 


stored 








22 


18.1 


15.0-22.0 


10 


22 


baseline 








1 


21.1 


19.6-26.0 




23 


stored, 100 


g 


carbon 


added 


6 


NL 


N.A. 






stored, 200 


g 


carbon 


added 


6 


NL 


N.A. 






stored 








6 


16.2 


12.8-20.6 




24 


stored, 50 


g 


carbon 


added 


12 


NL 


N.A. 




26 


stored 








20 


26.1 


23.2-28.4 




26 


pre-aerated for 24h 




20 


30.1 


27.9-39.3 


11 


24 


baseline 








1 


1-17 


N.A. 




25 


baseline 
65 % 








1 
1 


1-17 
28.1 


N.A. 
25.6-30.9 



P2 



TW# Tst Sample 

# treatment 



age 
(d) 



LT50 
(h) 



95% 
CL. 'S 



560 ppb HgCl 2 added to 
100 % tire water 

560 ppb HgCl 2 added to 65 
% tire water 

stored, 25 g carbon added 

26 stored 

pre-extracted with CH 2 C1 2 
in separatory funnel 

tire water in separatory 
funnel without CH 2 C1 2 

28 stored 
steam-distilled 

29 stored 

12 27 baseline replicate A 
baseline replicate B 
65 % 

65 % - distilled diluent 
stored, 50 g carbon added 

29 baseline 
65 % 

65 % - distilled diluent 

40 % 

40 % - distilled diluent 

30 % 

30 % - distilled diluent 

30 baseline 

tire water in separatory 
funnel without CH 2 C1 2 

pre-extracted with CH 2 C1 2 
in separatory funnel 

13a 28 baseline 

13b 30 baseline 



1 
1 



1-17 



1-17 



N.A. 



N.A. 



1 


96 


N.A 


7 


2-18 


N.A 


7 


NL 


N.A 



>96 



N.A. 



16 


17.8 




11.6-27.2 


16 


39.7 




N.A. 


20 


14.9 




9.2-24.1 


1 


4.5-21, 


.5 


N.A. 


1 


4.5-21. 


.5 


N.A. 


1 


31.9 




26.9-40.8 


1 


4.5-21. 


.5 


N.A. 


1 


NL 




N.A. 


8 


2.5-22 




N.A. 


8 


26.1 




18.4-32.2 


8 


26.8 




17.5-34.2 


8 


42.6 




34.9-46.7 


8 


68.9 




56.7-93.6 


8 


47.5 




40.4-53.7 


8 


NL 




N.A. 


8 


11.9 




5.8-24.3 


8 


29.2 




N.A. 



26-46 



N.A. 



20.7 13.4-32.1 
0.5-17.5 N.A. 



P3 



TW# 


Tst 
# 


Sample 
treatment 


13c 


31 


baseline 




32 


baseline 
80 % 
65 % 
40 % 
30 % 
20 % 




33 


stored 



age LT50 95% 
(d) (h) C.L.'s 



1 


19.50 


13.5-28.2 


1 


0.5-17 


N.A. 


1 


17.9 


9.3-20.8 


1 


22.4 


20.0-26.7 


1 


68.3 


60.0-77.4 


1 


> 96 


N.A. 


1 


> 96 


N.A. 


7 


> 96 


N.A. 


7 


NL 


N.A. 



tire water in separatory 
funnel without CH 2 C1 2 

pre-extracted with CH 2 C1 2 7 NL N.A. 
in separatory funnel 

34 80 % 14 38.7 31.4-44.0 

80 % - distilled diluent 14 38.7 31.4-44.0 

65 % 14 47.8 39.2-57.3 

65 % - distilled diluent 14 43.0 35.5-50.1 

40 % 14 NL N.A. 

40 % - distilled diluent 14 > 96 N.A. 

20 % 14 NL N.A. 

20 % - distilled diluent 14 NL N.A. 

14 35 baseline 1 < 16.5 N.A. 

80 % 1 < 16.5 N.A. 

65 % 1 21.6 17.3-27.9 

40 % 1 67.0 N.A. 

30 % 1 NL N.A. 

20 % 1 NL N.A. 

10 % 1 NL N.A. 

39 baseline 20 22.96 16.5-25.4 

80 % 20 30.35 26.6-37.3 

65 % 20 35.79 31.9-40.3 

40 % 20 93.85 N.A. 



P4 



TW# Tst Sample 

# treatment 



age 
(d) 



LT50 
(h) 



95% 
CL. 's 



30 % 

20 % 

3 8 ethanol extract 

of carbon used to 
detoxify tire water 

ethanol extract of carbon 
used in control water 



15 


46 


baseline 
80 % 
65 % 
40 % 
30 % 
20 % 


16a 


65 


baseline 


16b 


66 


baseline 
80 % 
65 % 
40 % 
30 % 
20 % 
10 % 


16c 


67 


baseline 
80 % 
65 % 
40 % 
30 % 
20 % 
10 % 


17a 


68 


baseline 


17b 


69 


baseline 



20 


>96 


N.A. 


20 


NL 


N.A. 


1 


>100 


N.A. 



NL 



N.A. 



1 


21-49 


N.A. 


1 


67.8 


52.8-100 


1 


>96 


N.A. 


1 


>96 


N.A. 


1 


>96 


N.A. 


1 


>96 


N.A. 


1 


5-22 


N.A. 


1 


2-27 


N.A. 


1 


13.8 


7.7-24.7 


1 


16.8 


8.9-31.6 


1 


> 96 


N.A. 


1 


96 


N.A. 


1 


> 96 


N.A. 


1 


> 96 


N.A. 


1 


7-24 


N.A. 


1 


7-24 


N.A. 


1 


7-24 


N.A. 


1 


24-48 


N.A. 


1 


24-48 


N.A. 


1 


> 96 


N.A. 


1 


> 96 


N.A. 


1 


53 


45.5-61.8 


1 


14.8 


8.1-26.9 



P5 



APPENDIX Q 

ACUTE LETHALITY TO DAPHNIA MAGNA OF TIRE CRUMB WATER 
SUBJECTED TO TOXICITY REDUCTION TREATMENTS 



Tire crumb water 


24h-LC50 


95 % 


48h 


-LC50 


95 % 


bat ch# /description 


(% v/v) 


C.L.s 


{% 


v/v) 


C.L.S 


3 


89 


61-100 


19 




13-26 


6 


79 


48-100 


23 




18-28 


7 


> 100 




50 




35-73 


8 filtered 


> 100 




100 






8 unfiltered 


50-100 




50 




35-70 


9A 


> 100 




56 




39-88 


9C 


> 100 




46 




34-61 


9D 


> 100 




35 




27-46 


9E filtered 


> 100 




50- 


100 




9E unfiltered 


> 100 




54 




41-73 


9F 


> 100 




74 




59-92 


9G 


> 100 




> 100 




9H 


21 


12-32 


15 




11-20 


91 


81 


66-100 


77 




64-93 


9J 


> 100 




88 




68-10 


solvent-extracted crumb 


> 100 




> 100 




"fresh" tire crumb 


91 


72-100 


85 




69-100 


pH 2 


5 


1-11 


< 5 






pH 11 


34 


26-43 


24 




21-28 


pH baseline 


100 


na 


78 




62-100 


pH 2 


9 


4-13 


< 5 






pH 11 


24 


18-32 


15- 


30 




pH baseline 


74 


61-89 


74 




61-89 


pH 4 


> 100 




60- 


100 




pH 10 


49 


na 


42 




na 


filtered 


> 100 




59 




46-73 


unfiltered 


> 100 




45 




32-61 



Ql 



H 



H 

(h 
< 



W 
H 

S 

Q 
H 



eu E-< 
> Q 
•h W 



U 

CD 



.g 
u 



01 0) 
G .G 

•M Eh 
M 
CD 

co 
^ si 



o 
> 



4J 

w 

<D X 
4J -H 



c 
o 

u 

eu 

3 



10 

g 
.G 

O 4-> 



R) 



X 
U 
O 

-U 

w 

M-l 

o 



jj 
id 

c 
o 

-H 
4J 

3 



TS 



« O 

■Su 

CO 'J 

(U CO 
4J (0 

Q O 
(U M 
CO 4J 



o 



eu 

eu -*- 1 

•U 
(0 T3 

S C 

(d 



J eu 3 
"^,-G ^ 



e'- 
er) 






ai 

W 






co -u 

CO 4-1 

tO o o 

3 LT) 

6 coJg 



w 
0) 



o 
u 



m 



(0 

«SO 

i— i 

<C J eu 

Q Di 
W G 
r- ? 

eu cm o 
xi ■ xi 

Eh O CO 



01 
<D 
U 



G T) 
O 

(0 G 

3 O 

ej 



co 

(13 

:•: 



w 4-) 

«, G 

eu eu 



eu 
co a 
(0 x 
3 eu 



























£ 






















w 






















e 


co 


CM 


CM 


CM 


O 






CM 






^ 


iH 


H 


-H 


-H 


00 


r- 


-H 


r-i 




U -H 






















4J 






















<D 






















4J 0) 






















id U 






















O G 






















•h m 






















H O 






















& & 


■<* 


H 


<H 


O 








CM 






ta w 


CN 


iH 


<H 


r-i 


Oï 


ce 


r> 


^H 


rH 


G 


























a> 






















g 






















•u 






















id 


^^ 




















Q) 


.G 




















h 






















V 



























00 


CM 


CM 


<-4 








CM 




U 


g 


^1 


<H 


H 


<H 


r- 


eo 


m 


<H 


>H 


a> 


n -h 




















P< 


a> 




















n 


v © 




















H 


id M 




















n) 


o G 




















€ 


•h a 




















■H 


H O 




















G 

Id 


& & 


** 


CM 


CM 










CN 






t£ H 


(N 


H 


H 


^ 


CM 


CM 


o 


H 


O 


H 


























<M 






















O 


2 




















V 


*— * 




















G 






















O 


0) 


00 


CN 


CM 


o 






CM 


CM 






6 


** 


,H 


<H 


<H 


(Ti 


co 


<H 


iH 


<H 


-O 


< -H 




















id 


43 




















0) 


ID 




















"0 


4-> a) 
id U 




















M 


O G 























epli 
xpos 


** 


CN 


CM 










CM 




S 


« u 


es 


rH 


i-i 


VD 


r^ 


LT) 


■>h/ 


<H 


O 




o 






















pH 
















eu 























G 


rH 




> 










o 


m 


CM 


-H 

.-H 


o 




< -» 










in 


CM 


iH 


(U 


i-> 




%i 




■«* 


CM 


H 


o 


o 


O 


co 

Rj 


c 
o 




w ~ 




O 


O 


O 


o 


o 


O 


X! 


u 



APPENDIX S 

ACUTE LETHALITY TO DAPHNIA MAGNA OF TIRE CRUMB WATER 
SUBJECTED TO SOLID PHASE EXTRACTIONS 

Water samples were passed through a 3-mL C 18 column and tested for 
toxicity before and after the column treatment. The columns were 
eluted (solvent-washed) with methanol, and the eluate was added to 
dilution water for toxicity testing. Four replicate experiments 
were conducted. 



Repl. 



Sample 



Treatment 



Mortality 



B 



tire crumb water 



dilution water 



tire crumb water 



dilution water 



tire crumb water 



dilution water 



tire crumb water 



dilution water 



before SPE 
after SPE 
methanol 
before SPE 
after SPE 
methanol 
before SPE 
after SPE 
methanol 
before SPE 
after SPE 
methanol 
before SPE 
after SPE 
methanol 
before SPE 
after SPE 
methanol 
before SPE 
after SPE 
before SPE 
after SPE 



94 % 

92 % 

nonlethal 

6 % 

17 % 

nonlethal 

92 % 

100 % 

nonlethal 

nonlethal 

nonlethal 

nonlethal 

83 % 

67 % 

nonlethal 

nonlethal 

17 % 

nonlethal 

92 % 

17 % 

nonlethal 

nonlethal 



SI 



APPENDIX T 
CHRONIC TOXICITY TO CERIODAPHNIA DUBIA OF TIRE CRUMB WATER 

Tire crumb water batch 9b 



Cone ent rat i on 


% mortality 


% inhibition of 


{% vol /vol) 








reproduction 


25 


100 






100 


15 


10 






83 


10 









25 


5 






















n = 20.75 1 


LC50 or EC50 


19 


(17- 


-20) 


12 (9-14) 


(95% C.L.s) 











Tire crumb water batch 9c 



Concentration 


% mortality 


% inhibition of 


(% vol /vol) 








reproduction 


25 


90 






100 


15 


100 






68 


10 


40 









5 


10 



















n = 27.85 


LC50 or EC50 


9 (7- 


-12) 




14 (12-16) 


(95 % C.L.s) 











Tire crumb water batch 9h 



Concentration 


% mortal i 


ty 


% inhibition of 


(% vol /vol) 










r eproduc t i on 


25 


100 








100 


15 


60 








95 


10 


30 








67 


5 


20 








26 





10 








n = 19.3 


LC50 or EC50 


11 


(8- 


-15) 




7 (5-10) 


(95 % C.L.s) 













Tl 



Tire crumb water batch 9m 



Concentration 


% mortality 


% inhibition of 


{% vol /vol) 








r epr oduc t i on 


25 


90 






100 


15 


40 






49 


10 


20 






22 


5 


40 






13 












n = 12.4 


LC50 or EC50 


15 


(12- 


-21) 


13 (9-17) 


(95 % C.L.s) 











Tire crumb water batch 7 - unfiltered 



concentration 


% mortality 


% inhibition of 


(% vol /vol) 








reproduction 


25 


100 






100 


15 


100 






100 


10 


50 






44 


5 


30 












5 






n = 31.0 


LC50 or EC50 


8 (5- 


■10) 




12 (10-15) 


(95 % C.L.s) 











Tire crumb water batch 7 - filtered 

concentration % mortality % inhibition of 
(% vol /vol) reproduction 

25 100 100 

15 40 86 

10 30 39 

5 15 

20 n = 20.75 

LC50 or EC50 13 (11-17) 10 (7-12) 

(95 % C.L.s) 

1 The average number of young per female control animal is shown as 
" (n = ) " . The inhibition of reproduction was a percentage of this. 

T2 



APPENDIX U 

ACUTE LETHALITY TO TROUT 
OF SOLVENT-EXTRACTS OF TIRE CRUMB 



extract and 
concentration 



LT50 (95% CL. 's) 
(h) 



"tire oil" 1 (mq/L! 

43 

solvent control 

50 

25 

12.5 

6 

solvent control 



4-24 

nonlethal 

7-24 

21 

nonlethal 

nonlethal 

nonlethal 



methanol extract 2 (mL/L) 

5 35 (13-50) 

solvent control nonlethal 

5 7-24 

solvent control nonlethal 

1 A dark brown viscous liquid ("tire oil") was soxhlet-extracted 
from tire crumb with dichloromethane . It was a mixture of 
paraf finie, naphthenic and aromatic hydrocarbons resembling 
lubricant oils. Dichloromethane was used to dissolve the tire oil 
in water. The solutions were pre-aerated for 2 4 hours to purge the 
solvent before adding the fish. The solvent controls had the same 
amount of carrier solvent as used for the highest test 
concentrations. Reported concentrations are nominal. 

2 10 grams of tire crumb were stirred for 24 hours in 150 mL of 
methanol. The mixture was left quiescent for 24 hours so the 
rubber particles could "settle out", then 100 mL of the methanol 
was added to 2 0L of water for a trout test. The solvent controls 
had the same amount of carrier solvent as used for the highest test 
concentrations. Reported concentrations are nominal. 



Ul