RECONNAISANCE STUDY OF COAL TAR SEALCOAT APPLICATION IN TORONTO AND AN ESTIMATE OF RELATED PAH EMISSIONS

DIAMOND ENVIRONMENTAL GROUP, UNIVERSITY OF TORONTO

August 2011

RECONNAISANCE STUDY OF COAL TAR SEALCOAT APPLICATION IN TORONTO AND AN ESTIMATE OF RELATED PAH EMISSIONS

Prepared by Diamond Environmental Group, Department of Geography and Department of Chemical Engineering 45 St George Street, Physical Geography Building University of Toronto M5S 3G3 Phone: (+1) 416-978-1749 http://faculty.geog.utoronto.ca/mdiamond/index.html

Project Leader Prof. Miriam Diamond, PhD. Project Team Emma Goosey, PhD - postdoctoral researcher Susan Csiszar, MSc - PhD candidate (modelling applications) Stefanie Verkoeyon, MSc, research assistant Clayton Catching- research assistant Prepared For Environment Canada, Ontario, Environmental Protection Operations Division

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CONTENTS EXECUTIVE SUMMARY BACKGROUND METHODS SURFACE SAMPLING METHOD SEALANT EMULSIONS EXTRACTION METHOD GC-MS ANALYSIS QA/QC RESULTS CATEGORIZING CTS SAMPLES COMMERCIAL SEALCOAT EMULSIONS QUINOLINE COAL TAR SEALANT ACROSS TORONTO ESTIMATING WASH-OFF CONCLUSION REFERENCES APPENDIX 5 6 7 7 9 9 10 10 11 11 17 19 20 23 25 26 28

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Abbreviations
<DL Ace Acy Antr AS B[a]A B[a]P B[b]F&B[j]F B[ghi]P Chry CTS DBA DCM Fla Flu GC-MS GTA HMW Ip LMW MSDS Naph NIST OS PAH Phe Py QA/QC Quin RDS RSD SD SRM UAS USGS < Detection Limit Acenaphthene Acennaphthylene Anthracene Asphalt sealcoat Benz[a]anthracene Benzo[a]pyrene Benzo[b]fluoranthene & Benzo[j]fluoranthene Benzo[ghi]perylene Chrysene Coal Tar Sealcoat Dibenz[a,h]anthracene Dichloromethane Fluoranthene Fluorene Gas chromatography- mass spectrometry Greater Toronto Area High molecular weight Indeno[1,2,3-cd]pyrene Low molecular weight Material safety data sheet Naphthalene National Institute of Standards and Technology Other surfaces Polyacyclic aromatic hydrocarbons Phenanthrene Pyrene Quality assurance /quality control Quinoline Recovery determination standard Relative Standard Deviation Standard Deviation Standard Reference Material Uncoated asphalt United States Geological Survey

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Executive Summary
Coal tar sealcoats have been found to be a source of polycyclic aromatic hydrocarbons (PAH) to urban surface water and sediments in several US cities (e.g., Van Metre et al. 2000, Mahler et al. 2005). The goal of this study was to establish the frequency and spatial extent of paved surface coverage with coal tar sealcoats (CTS) in the City of Toronto, and to estimate CTS as a source of PAH to storm water. This was accomplished by (1) collecting surface samples from commercial parking lots and private driveways across Toronto, (2) analyzing the PAH and quinoline concentrations of all samples, (3) estimating the area of paved surfaces across Toronto using data from the field study combined with GIS land coverage data, and (4) using the data collected to estimate PAH releases from CTS to Toronto. Surface samples (n = 92) were taken across Toronto. All samples were analyzed for 16 PAH and quinoline by GC-MS. Twenty-one samples or 23 % of total samples were identified as CTS based on total PAH content and compound profiles, as well as isomer ratios. About 90 % of CTS use was in private residential areas (n = 20) with about 10 % use in commercial parking lots (n = 1). PAH concentrations (n = 21 samples) of 54 24 000 mg kg-1 in samples containing CTS were an order of magnitude greater than asphalt sealcoat but considerably lower than those reported by Mahler et al. (2005). Quinoline concentrations varied from <detection limit (<DL) to 2400 mg kg-1, and were significantly higher (p<0.05) in CTS than asphalt sealcoat and non-sealcoat surfaces. The area of driveways and parking lots covered with CTS was approximated at 24 km2 of the Toronto area (630 km2) by means of analysis of high resolution GIS imagery. The estimated contribution of 17PAH from CTS entering Torontos storm water runoff ranged from 8 22000 kg y-1 with a median and mean of 96 and 1400 kg y-1, respectively. The wide range estimated resulted from the wide range of PAH concentrations measured in CTS samples. To put this estimated runoff contribution into perspective, the measured mean value of 18PAH discharged from Torontos tributaries to Lake Ontario is 2200 kg y-1 (Helm et al. 2011).

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Background
Several years ago Barbara Mahler and Peter Van Metre of the United States Geological Survey (USGS) found that coal tar sealcoat (CTS) could be adding as much as 50 % of PAH in urban runoff and urban surface waters and sediments (Mahler et al. 2005, Yang et al. 2010). They discovered this when studying the dramatic rise in PAH concentrations in urban lake sediments, that they first correlated with the rise in vehicle miles travelled (Van Metre et al. 2000). They found that CTS was mainly used to coat urban residential driveways and small commercial and residential parking lots (EHS 2010). Additionally, they found that CTS was the main sealcoat used in US cities east of the continental divide due to the availability of coal tar residues from coking sources (Van Metre et al. 2009). Cities west of the divide tended to use asphalt-based seal coats where the asphalt originates as an end-product from oil production.

Sealcoats are marketed to provide protection and aesthetic appeal to older asphalt and concrete driveways and parking lots. The sealcoat emulsions are purported to prevent damage to the original material, reduce surface erosion, and prevent surfaces from cracking which in turn would prevent water infiltration and exposure to ultra-violet rays. The low cost and availability of CTS through major retail outlets has made this product an easy choice for consumers. Manufacturers and companies that apply sealcoats recommend resurfacing about every 5 years. Currently there are four main categories for sealcoats based on the primary material: coal tar, asphalt emulsion, acrylic and asphalt cutbacks (Environment Canada, 2010). The PAH content of these materials ranges between 2700 ppm in asphalt to a percentage of the solid weight in CTS (>26 000 ppm).

CTS wears off through abrasion and wash off, where it could add significantly to PAH loadings in storm water (Mahler et al. 2005, Van Metre et al. 2010a). Coal tar can add to runoff 65 times the PAH concentration of uncoated driveway; asphalt based sealcoats can add 10 times the total PAHs (Minnesota Pollution Control Agency, 2009). Abrasion also allows CTS to enter the indoor environment as it is tracked in from coated surfaces (Mahler et al. 2010, Van Metre et al. 2010b SETAC presentation). Recent work by Diamond, Helm and co-workers has yielded loading estimates of roughly 2200 kg y-1

(Figure 1) of total PAH (sum of 18 compounds) to nearshore Lake Ontario from Toronto tributaries
(Helm et al. 2011, Diamond et al. 2010). Tributaries were estimated to be the largest contribution to the total of 3640 kg y-1 originating also from atmospheric deposition and waste water treatment plant discharges. Sealcoat material would be a logical contributor to these tributary loadings.
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The aim of this reconnaissance study was to identify the use of CTS in Toronto and to assess whether CTS could be contributing significantly to PAH loadings from Toronto to the surrounding environment.

Kg y-1
40 4000

30

3000

20

2000

10

1000

PBDEs
Wet Dep Rivers Dry Dep WWTP

PCBs
Gas Absorp

PAHs

PCMs

Figure 1: Summary of chemical loadings to near shore Lake Ontario (Diamond et al. 2010).

Methods
Surface Sampling Method
Samples were collected from parking lots and driveways across Toronto at locations chosen according to 25 km2 grids. The locations were selected according to ease of access, as well as their position relative to past PAH passive air sampling locations (Melymuk et al. in prep). The locality of the samples in relation to Toronto and the model grids are displayed in Figure 2.

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Figure 2: Sampling locations within Toronto (grey highlighted area); red dots are sampling locations, blue dots are passive air sampling locations.

Pavement surface samples were collected in February and March 2011. Samples were obtained by scraping an area of 0.25 m2 using a stainless steel blade (mounted in a holder) from driveways and parking lots (Figure 3). The scrapings were transferred a glass jar, sealed and returned to the laboratory, where they were placed in a -18C freezer, until extraction (Figure 4).

Figure 3: Sample Collection.

Figure 4: Example of collected scrapings.

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Sealant Emulsions
Fresh commercial sealant emulsions were also sampled for the presence of PAHs and quinoline. These commercial samples were purchased from public stores. Unfortunately only two sealants were available as purchasing was done during winter (these sealants are denoted as Emulsion 1 and Emulsion 2). The sealants were analysed for PAH content in the fresh emulsion (~20 g) and then dried under vacuum conditions in a desiccator at room temperature.

Extraction Method
Scrapings

Samples were weighed and extracted in dichloromethane (DCM) (15 mL) via shaking (10 sec), and followed by ultra-sonication (20 min). The eluent was removed to a DCM cleaned (200 mL) bottle. This process was repeated until the eluent remained clear (a sign of the removal of all binder present). The samples were then stored at -18C until analysis. The residual sample contents were allowed to air dry and were re-weighed. This was done to establish the actual weight of the extracted binder, and to allow for later comparison of binder vs. total sample concentration and the presence of PAH. The extract was applied to preconditioned columns containing alumina (8 g), anhydrous silica gel (4 g), and sodium sulphate (1 g). An aliquot (1 mL) of the extract was eluted with DCM (30 mL) into a round bottom flask. Samples were then solvent exchanged into hexane via rotary evaporator, reduced under a stream of nitrogen (99.99 %) to near dryness and re-eluted with nonane (200 L). At this time 5 L of the recovery determination standard (RDS) was added.

Emulsions

Samples taken from the raw commercial emulsion were analysed for the content of PAHs in the wet emulsion and after it had been allowed to dry. The wet emulsion (~1.5 g) was dissolved in acetone (140 mL), after which an aliquot (1 mL) was removed and diluted with DCM (9 mL). An aliquot (1 mL) of the DCM:acetone solution was taken and applied to conditioning columns, continuing with the same method as the scraped samples. Dried emulsion (~0.2 g) was extracted using the same method as for the scrapings; DCM extracted until eluent remained clear. The pre (wet emulsion) and post (dried material) weight measurements were acquired and indicated that emulsion contained ~53 % solid materials, whilst the second emulsion contained ~50 % solid materials.

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GC-MS Analysis
Sample analysis was conducted on a 158 Agilent 6890N gas chromatograph coupled to an Agilent 5975 Inert Mass Selective Detector, using a 60 m HP-5 MS column for the detection of the PAH and quinoline compounds (the method is described in the Appendix).

Quality Assurance/Quality Control

Three procedures were used to continuously monitor for quality assurance and quality control (QA/QC) throughout the analysis: (1) monitoring of recoveries via deuterated internal standards (recoveries were 56-120 %), (2) monitoring attribution of the source of analyte via laboratory and field blanks (blanks contributed < 5 %), and (3) monitoring precision by analysis of a coal tar standard reference material (SRM) (NIST SRM 1597A) (reproducibility test results are reported in Table 1). The SRM is a complex mixture of PAH from coal tar that was isolated from coal tar and dissolved in toluene (NIST 2006). The recovery of the SRM throughout the analysis did not deviate more than 20 % from the certified values (certified values are available from the National Institute of Standards and Technology (NIST)). Recovery determination standard (RDS), para-terphenyl, was measured within the QA/QC protocol of 70 100 %. Table 1: NIST SRM 1597a reproducibility results (mg kg-1), *standard deviation (SD), + relative standard deviation (RSD).
Sample Naph Acy Ace Flu Phe Ant Fla Py B[a]A Chry B[b]F&B[j]F B[k]F B[a]P Ip B[ghi]P DBA 1 1041 270 8.9 111 468 101 312 213 99 62 89 46 95 46 59 6.2 2 1024 254 6.6 141 410 107 321 230 91 69 92 42 82 44 46 6.0 3 1023 260 7.1 124 430 103 310 2335 95 58 102 30 92 51 44 6.7 4 1017 233 7.5 132 447 110 331 246 94 62 109 37 90 37 43 6.3 5 1034 261 7.1 148 449 102 324 243 90 55 104 33 89 43 41 5.7 Mean 1028 256 7.4 131 441 105 320 233 94 61 99 38 89 44 47 6.1 Certified Results 1030 263 7.63 145 454 107 327 240 98.1 66.2 107.3 41.2 93.5 50.5 55.5 6.93 SD 9.6 14 0.9 14 22 4 9 13 4 5 8 7 5 5 7 0.4 RSD (%) 0.9 5 12 11 5 4 3 6 4 9 8 17 5 11 15 6

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Results
Concentrations of total PAH and individual compounds varied over six orders of magnitude (PAH 0.02 24 000 mg kg-1, Table 2). The most abundant compounds according to mean values were benzo[b]fluroanthene and benzo[j]fluroanthene, pyrene, benzo[a]pyrene, chrysene and

benz[k]fluoranthene. In contrast, the most abundant PAH in urban air (gas and particle phases) are phenanthrene and fluorine in the gas phase, and fluoranthene, pyrene and benzo[b]fluroanthene and benzo[j]fluroanthene in the particulate phase, (Melymuk et al. in prep). Observations made during sampling suggested that the variability in surface samples was primarily due to differencing in surfacing materials, as well as the age of material, intensity of area use, wear rate, etc.

Table 2: Summarized PAH compound concentrations (mg kg-1) from 92 sampling locations in Toronto, *standard deviation (SD), + relative standard deviation (RSD).
PAH Naphthalene Quinoline Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz[a]anthracene Chrysene Benzo[b]fluroanthene & benzo[j]fluroanthene Benz[k]-fluoranthene Benzo[a]pyrene Indeno(1,2,3-cd)pyrene Benzo[ghi]perylene Dibenz[a,h]anthracene Minimum N.D. 0.0002 N.D. N.D. N.D. 0.0007 0.0035 0.0028 0.0047 0.0013 0.0026 0.0022 0.0027 0.0024 N.D. N.D. N.D. 5th Percentile 0.0003 0.0035 0.0002 0.0005 0.0007 0.006 0.0081 0.015 0.023 0.005 0.007 0.01 0.013 0.01 0.0053 0.0042 0.0017 Median 0.029 0.063 0.006 0.006 0.011 0.059 0.14 0.16 0.65 0.24 0.38 0.72 0.41 0.35 0.33 0.25 0.047 Mean 0.13 0.13 0.70 2.4 2.4 26 30 87 710 270 430 790 410 570 83 200 5.9 95th Percentile 0.55 0.41 3.6 12 8.7 190 170 440 1400 720 880 4100 1200 760 260 320 4.7 Maximum 2.4 1.7 28 78 101 630 1300 2300 35 000 11 000 20 000 29 000 13 000 21 000 2700 8000 190 SD 0.33 0.21 3.1 11 11 83 150 300 4000 1400 2400 3700 2000 2800 370 1000 29 RSD (%) 250 170 450 450 470 310 490 340 570 540 560 470 500 490 450 510 490

Categorizing CTS samples

Each sample from the 92 taken from driveways and parking lots was placed into one of four categories of surface types CTS, asphalt sealcoat (AS), uncoated asphalt (UAS), and other impervious surfaces (OS). This assignment was based on three criteria: (1) the PAH concentration of samples, (2) PAH compound profiles, and (3) isomer ratios calculated for various molecular weight compounds (Mahler et al. 2005, Austin Report 2005, Ahrens and Depree 2010). The result of the categorization processes was the assignment of 21 of 92 samples as CTS, 35 samples were AS, 28 were UAS samples, and 8 samples were

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other materials. This translated into CTS coverage of ~23 % of parking lots and drive ways sampled, and 38, 30, and 9 % coverage of AS, UAS and other.

Sample Concentrations
Total PAH concentrations in those samples identified as CTS had PAH concentrations up to three orders of magnitude higher than other samples (Table 3). Such high concentrations are indicative of coal tar as no other materials have been noted to be so enriched in PAH (Ahrens and Depree 2010). The PAH content of other source materials such as rubber tire particles, diesel, and used engine oil are in the range of 10 - 2000 mg kg-1 (Takada et al. 1991, Wang et al. 1999, Intron 2007). Several samples categorized as CTS had PAH concentrations that overlap with this lower range, and hence identification of those samples as CTS was based on the two other criteria listed. For example, one ambiguous sample had a low total PAH concentration but high concentrations of benz[a]anthracene and chrysene. In this case, the categorization of CTS was aided by the analysis of isomer ratios 228 and 278 as discussed below. Samples in the other three categories had much lower PAH concentrations and inconsistent presence of all compounds. Table 3: Sample categorisation Material (Scraping) CTS AS UAS Other 53 - 24,000 1 14 0.1 0.9 0.02 0.15 This Study Mahler et al. (2005) 9,500 83,000 340 2000 7.1 - 20

It is interesting to note that the PAH content reported in this study were considerably lower and span a broader range in comparison to those listed by Mahler et al. (2005), the reason for which is unclear. Precipitation rates of ~850 mm are similar in Toronto and Austin Texas where Mahler and co-workers sampled. Austin has a humid subtropical climate with an annual mean temperature of 20.3oC which suggests greater likelihood of losses of PAH due to volatilization. In comparison, Toronto has a humid continental climate with an annual mean temperature of 7.8oC which offers less opportunity for PAH volatilization. However, Toronto winter conditions of freeze-thaw cycles and especially prolonged periods when pavement is partially thawed, lead to pavement wear which could explain greater losses of PAH from all categories of surface types in Toronto versus Austin. Watts et al. (2010) commented that
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wind abrasion and removal when snow ploughing were other mechanisms leading to the wear of CTS. Mahler et al. (2005) suggested that abrasion by vehicle travel alone was a key factor in increasing the removal of CTS from used versus test plots of CTS in Austin. In Toronto we suggest that the freezethaw cycles plus extra abrasion caused by snow ploughing etc., accelerate CTS loss beyond that from vehicle abrasion. If the commercial CTS products that are applied in Toronto have similar PAH concentrations as those measured by Mahler et al. but pavement wear and abrasion is greater, then the corollary is greater PAH removal from Toronto than Austin surfaces.

Sample Profiles
CTS samples had a distinct profile with significantly higher (t= 2.01 2.47, p< 0.05) concentrations of the low molecular weight compounds (LMW), as well as phenanthrene, benz[a]anthracene and chrysene, as illustrated in Figures 5 and 6. Concentrations of the lowest molecular weight compounds naphthalene and quinoline varied ~10-fold amongst the four categories of surface covers. In contrast, concentrations of phenanthrene, benz[a]anthracene and chrysene varied ~five orders of magnitude.

Figure 5: PAH profiles for median concentrations of the 4 sample subcategories

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Figure 6: PAH concentrations (mg kg-1) of 21 surface samples identified as CTS (21 lines represent concentration profiles of individual samples).

Isomer Ratios
Isomer ratios have been used as a diagnostic tool in CTS studies by Mahler et al. (2005), Van Metre et al. (2009) and Ahrens and Depree (2010). The isomer pairs used for diagnosis have been benz[a]anthracene and chrysene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene, benzo[a]pyrene and benzo[e]pyrene, fluoranthene and phenanthrene. The latter was not possible in this study as we did not quantify benzo[e]pyrene. Ahrens and Depree (2010) found that samples of pavement sampled in Auckland New Zealand fell along a straight line in a plot of isomer ratios of benz[a]athracene:(benz[a]athracene + chrysene) vs. indeno[1,2,3-cd]pyrene:(indeno[1,2,3-cd]pyrene + benzo[ghi]perylene). The end members along this line were coal tar (pyrogenic hydrocarbons) in the upper right quadrant of the graph, and in the lower left, were asphalt and bitumen which have a petrogenic source. As seen in Figure 7, samples from this study
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also were spread between these two end members, but with considerably more scatter than that found by Ahrens and Depree. The second isomer ratio investigated was the sum of concentrations of isomer pairs of (benz[a]anthracene + chrysene) concentrations versus (fluoranthene + phenanthrene) concentrations (Figure 8). Samples with elevated concentrations of fluoranthene and phenanthrene (within the circled) were identified as CTS. These samples also displayed PAH concentrations on orders of magnitude higher than other samples. The third and final isomer ratio explored was that of the (benz[a]anthracene + chrysene) concentrations vs the respective isomer ratio of benz[a]anthracene:chrysene. All categories were separated by their concentrations of benz[a]anthracene + chrysene with CTS samples having the highest values (Figure 9).

Figure 7: Ratio profiles of benz[a]athracene: (benz[a]athracene + chrysene) vs. indeno[1,2,3cd]pyrene: (indeno[1,2,3-cd]pyrene + benzo[ghi]perylene).

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Figure 8: Sum of (benz[a]anthracene + chrysene) concentrations vs. sum of (fluoranthene + phenanthrene) concentrations. Circled area indicates samples with profiles indicative of CTS.

Figure 9: Sum of (benz[a]anthracene + chrysene) concentrations vs the respective isomer ratio of benz[a]anthracene:chrysene.
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Commercial Sealcoat Emulsions

Concentrations of total PAH in the wet samples of commercial seal coat ranged from 90 000 to 120 000 mg kg-1 (see Table 4). The range of total PAH in the dried commercial samples fell to ~32 000 mg kg-1, a loss of ~70 % of the PAH mass during the 48-hour drying process. Concentrations of the emulsions were two and one orders of magnitude higher for the wet and dry samples, respectively, than the CTS samples collected across Toronto.
Table 4 Commercial sealcoat PAH concentrations (mg kg-1) PAH Napthalene Quinoline Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz[a]anthracene Chrysene Benzo[b]fluroanthene & benzo[j]fluroanthene Benz[k]fluoranthene Benzo[a]pyrene Indeno(1,2,3-cd)pyrene Benzo[ghi]perylene Dibenz[a,h]anthracene PAH Emulsion 1 Wet 6500 1400 4800 6700 5800 22 800 12 400 22 600 19 000 2000 1000 1900 3200 4300 2900 2900 400 120 000 Emulsion 2 Wet 4800 800 1900 1800 3500 15 300 21 500 15 900 10 200 600 300 400 1700 1100 700 700 90 89 000 Emulsion 1 Dry 1900 200 1200 1700 1600 6400 3400 9100 5000 1500 700 2200 2800 2800 1700 1500 300 36 000 Emulsion 2 Dry 1000 90 1200 1200 1900 7000 5000 900 5200 700 300 500 1100 1100 800 600 90 28 000

The profiles of compounds varied between the two commercial mixtures, the wet and dried mixtures and the weathered CTS samples Toronto (Figure 10). The wet commercial emulsions had the highest concentrations of phenanthrene, anthracene, fluoranthene as well as pyrene. The dried commercial emulsions were also high in phenanthrene, fluoranthene and pyrene, but not anthracene. In contrast, the CTS samples collected across Toronto had the highest concentrations of the higher molecular weight, less volatile compounds benzo[b]fluroanthene, benzo[j]fluroanthene, pyrene, benzo[a]pyrene, chrysene and benz[k]fluoranthene. Thus, mostly the lower molecular weight PAHs were lost quickly as the wet commercial mixture dried. Then subsequent weathering by wash-off results in the loss of a fraction of all PAH compounds in CTS regardless of molecular weight (in contrast to volatilization losses that depend on molecular weight).
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Figure 10: Emulsion 1 and 2 commercial sealcoats PAH concentrations from the original solution and the resultant dried material, (mg kg-1).

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Quinoline

Quinoline concentrations in wet sealcoat were in the order of 1000 mg kg-1 or 0.1 % w/w. Environment Canada (2010) reported concentrations of quinoline of <0.01 % (w/w) in wet sealcoat. This concentration decreased to, on average, 170 mg kg-1 in the dried commercial emulsions, 51 mg kg-1 in CTS samples, and 50, 34 and 11 in asphalt sealcoat, uncoated asphalt and other(Figure 11). The volatility of quinoline allowed for an 80-90 % loss of mass during the 48-hour drying process of the commercial sealcoat samples and a further 30 % loss relative to CTS samples.

Figure 11: A, commercial sealcoat quinoline concentrations, and B, mean quinoline sample concentrations in coal tar sealcoats (CTS), asphalt sealcoats (AS), uncoated asphalt (UAS), and other samples (other) (mg kg-1).

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Coal Tar Sealant Coverage across Toronto

Results of the sampling campaign and subsequent chemical analysis suggested that ~23 % of parking lots and driveways sampled were covered by CTS. As can been seen in Figure 12, the CTS sites are located mainly in the suburbs Etobicoke and Scarborough and less so in the centre of Toronto and North York. The absence of CTS from the inner city is not surprising since there are fewer driveways and parking lots than in the suburbs. Even so, anecdotal evidence suggests that driveway sealants tend to be more popular outside of the central part of the city.

Figure 12: Map of the City of Toronto indicating all sampling locations and those identified as CTS.

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Figure 13 Flow chart summarizing method followed to estimate land use cover and CTS coverage in Toronto.

We next extrapolated this percentage coverage of CTS to Toronto in order to arrive at the total area that could be coated in CTS. The extrapolation procedure is illustrated in Figure 13. First, land cover across for the City of Toronto (as of 2007) was estimated using high resolution GIS available from www.toronto.ca/open (Figures 14 and 15). The high resolution data were discriminated into eight land coverage categories of which we selected the land coverage category parking lots and driveways which excluded roadways and buildings. Of a total area of 630 km2 in Toronto, the land coverage category parking lots and driveways covered 112 km2 or 18 % of Toronto (Figure 15). The data set was then further manipulated to eliminate small areas of imperviously covered land such as side walks, which were less than the required space for an average vehicle parking space (15 m2). This reduced total area most likely to be parking lots and driveways to 106 km2. The final stage of the analysis was to estimate the area likely to have CTS. We did this by multiplying the frequency of CTS occurrence of 23 % (21 out of 92 samples identified as CTS) by the area of parking lots and driveways of 106 km2 to yield a value of 24 km2 or 4 % of the total Toronto area. This extrapolated area of 24 km2 is not location-specific, but rather is an estimate of the aggregate area within Toronto likely to be coated with CTS.

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Figure 14: High resolution GIS land cover dataset for the City of Toronto, with 8 different classes, representing 630 km2 (www.toronto.ca/open, City of Toronto 2007).

Figure 15: GIS map of the City of Toronto showing other paved surface in red. Inset is a magnified version of a 1 km by 0.7 km grid. Diamond Environmental Group 22 | P a g e

Estimating Wash-Off
Finally, CTS-derived PAH mobilized via storm water wash-off was estimated from the data reported herein. Mahler and co-workers (e.g., Mahler et al. 2005, Van Metre et al. 2009, 2010) and Watts et al. (2010) found that wash-off is a major removal mechanism of CTS. Because of high wash-off rates, CTS requires re-application every 3 to 5 years following application. Several studies have reported that particle and chemical wash-off follows a so-called first flush effect where most wash-off occurs during the initial rain event (Vaze and Chiew 2003, Egodawatta et al. 2009). Using this information, Csiszar et al. inter alia (Submitted 2011) reported that ~60 % of atmospherically derived surface films that coat all impervious surfaces are washed-off during a given rain event. In the absence of a specific wash-off rate for CTS, we used this information to estimate the amount of PAH that is washed-off CTS surfaces in the City of Toronto. The mass of PAH washed-off a surface into storm water, MSW (g) can be calculated using equation 1 where R is the run-off ratio (defined as volume fraction of rain water that is converted to storm water), WE is the wash-off efficiency (60 % as described above), and mPAH is the mass of PAH associated with the surface dust. The run-off ratio can be related to the fraction impervious area surface and was assumed to be 60 % for Toronto (Csiszar et al. submitted). The remaining 40 % of run-off was assumed to remain as surface storage on impervious surfaces, infiltrate the impervious surface through cracks, or be transferred to soil. The mass of PAH associated with the surface dust can be calculated using equation 2 where CPAH (g m-2) is the measured PAH concentration, and AS (m2) is the estimated CTS surface area in Toronto (24106 m2) as described above. We applied the above formulation using the median of measured PAH concentrations in CTS samples.

m sw = RWE m PAH
m PAH = C PAH AS

(1) (2)

Using this simple calculation, we estimated that a median of ~2 kg (range of 0.2 to 500 kg) of 17PAH would be washed-off from CTS-coated surfaces during one rain event. Another 1.5 kg of 17PAH would be subject to surface storage, infiltration or transfer to soil, as mentioned above, although this division between runoff and other is highly uncertain. Table 5 lists the medians, means, and ranges of transfer to
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storm water from eight selected compounds resulting from one rain event. Pyrene accounted for the largest contribution (30 %) to the median wash-off loadings out of the 17 congeners and quinoline accounted for the smallest percentage (0.01 %). Table 5: Estimated CTS wash-off per rain event for 8 PAH compounds per event and per year for 17PAH. PAH Quin Flu Phe Py B[a]A Chry Ip B[ghi]P 17PAH per event 17PAH per year Median (kg) 310-4 0.008 0.1 0.7 0.08 0.2 0.07 0.07 2 96 Mean (kg) 610-4 0.01 0.3 3 1 1 1 3 33 1400 Range (kg) 210-5 - 0.006 110-4 - 0.04 0.001 - 2 0.1 - 15 0.02 - 7 0.03 - 9 510-5 - 24 0.002 - 44 0.2 - 500 8 - 22000

In order to estimate yearly transfers, we assumed that this calculated amount would be transferred during each rain event and multiplied by the number of rain events over 5mm per year. With 44 rain events exceeding 5 mm in one year (Environment Canada, 2002), we estimated a median transfer of ~96 kg yr-1. We also calculated a high and low estimate of PAH removed by wash-off using the high and low measured CTS concentrations. The results span a very wide range of 8 to 22 000 kg yr-1 (Table 5) transferred to storm water. The modeled range is so broad due to the large range in measured concentrations; these calculations do not account for uncertainty in the coefficients used to parameterize the wash-off process. Uncertainty in the wash-off efficiency WE would likely be subsumed within this wide range of estimated values. These estimates of 8 to 22 000 kg yr-1 compare to 2200 kg yr-1 of 17 PAH tributary loadings to Lake Ontario from Toronto (Diamond et al. 2010). Over the 24 km2 area coated in CTS, the wash-off rates equate to 0.04, 0.6, 0.003 and 9.2 kg yr-1 ha-1 (median, mean, low and high values, respectively). In comparison, Watts et al. (2010) reported wash-off rates of 16 PAH measured from two parking lots freshly coated with CTS of 9.8-10.8 kg ha-1 over a 2 year period. Whereas the range reported by Watts et al. was determined from two freshly coated parking lots, our lower rates come from samples that were all aged a minimum of several months to years. Thus, our calculated wash-off rates appear to be reasonable.
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A next step would be measuring actual wash-off rates to better quantify the contribution of CTS to PAH loadings in Torontos storm water.

Conclusion
From the 92 samples of surface pavement collected from driveways and parking lots throughout Toronto, 21 were identified to be derived from CTS. This frequency represents approximately 23 % of the area of land coverage classified as parking lots and driveways using high resolution GIS imagery of the City of Toronto. These values translated into 24 km2 or 4 % estimated to be coated in CTS relative to the total land area of 630 km2 of Toronto. The concentration of total PAH in samples containing CTS ranged from 54 to 24 000 mg kg-1, which was an order of magnitude higher than that in other surface samples, but lower than the range reported by Mahler and co-workers in the U.S. PAH were also measured, but at lower concentrations, in the three other categories of surface types asphalt sealcoat (AS), uncoated asphalt (UAS) and other materials (Other) which comprised 38, 30 and 9 % of all samples. CTS samples were enriched in low molecular weight PAH as well as phenanthrene, benz[a]anthracene, and chrysene. Concentrations of quinoline in CTS varied from 0.0014 to 0.29 mg kg-1, and were only marginally elevated relative to its concentration in other surface samples. The low content of quinoline is presumed to be partly present due to its low concentration in coal tar (natural product), as well as its volatility and the loss of the compound during the drying of the material (recorded >80 % loss from the tested commercial emulsions). PAH wash-off from CTS was estimated to contribute 96 and 1400, 8 and 22 000 kg y-1 to storm water (calculated from median, mean, low and high 17PAH concentrations measured in this study). The very wide range was due to the wide range in concentrations measured in CTS samples. These values compare with 2200 kg y-1 17PAH that are discharged from Torontos streams (extrapolated from measured concentrations). We suggest that CTS is worn off at greater rates in Toronto than in warmer climates due to freeze-thaw cycles and abrasion by snow plowing (in addition to vehicle wear), which could explain why we find relatively low concentrations of PAH in surface samples identified as CTS in Toronto relative to Austin Texas. Further, we suggest that contributions of CTS to total PAH in storm water are likely due to the low spatial frequency of 4 % CTS coverage of the total Toronto land area.

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References
Ahrens, M. J., Depree, C. V., 2010. A source mixing model to apportion PAHs from coal tar and asphalt binders in street pavements and urban aquatic sediments. Chemosphere 81: 1526-1535. Austin Report, 2005. PAHs in Austin, Texas sediments and coal-tar based pavement sealants polycyclic aromatic hydrocarbons. City of Austin watershed protection and development review department, environmental resources management division. May 2005. Csiszar, S. A., Diamond, M. L., Thibodeaux, L. J., Submitted 2011. Modeling Urban Films Using a Dynamic Multimedia Fugacity Model. Submitted to Chemosphere. Diamond, M.L., Helm, P. Robson, M. Csiszar, S. A., Melymuk, M., 2010. Urban sources and loadings of toxics to Lake Ontario from integrated measurements and modeling. Great Lakes Commission, http://www.glc.org/ Egodawatta, P., Thomas, E., Goonetilleke, A., 2009. Understanding the physical processes of pollutant build-up and wash-off on roof surfaces. Sci. Total Environ. 407, 1834-1841. EHS (Environmental Health Strategies), 2010. Final report: Technical and economic study of VOC emissions from coal-tar based pavement sealants. Prepared for Products Division, Chemical Sectors Environmental Stewardship Branch, Environment Canada. January 2010. Ennis, T. E., 2011. Austins Experience in Implementing a Coal Tar Sealant Ban. Green CiTTS Webinar. Environment Canada, 2002. Canadian Climate Normals 1971 2001: Toronto in: Environment Canada (Ed.). Government of Canada, Ottawa, Ontario. Environment Canada, 2010. Final report technical and economic study of VOC emissions from coal tarbased pavement sealants. Environmental Stewardship Branch, prepared by Environmental Health Strategies Inc. Helm, P., Robson, M., Kaltenecker, G., Gilbert, B., Diamond, M. L. Melymuk, L., Brimacombe, C., Chen, T., Kolic, T., Reiner, E.J., 2011. Urban tributaries as a pathway of PCBs, PBDEs, PAHs, and polycyclic musks to adjacent Lake Ontario, Canada. SETAC Europe, Milan, May 2011. Poster presentation. Intron, 2007. Environmental and health risks of rubber infill: rubber crumb from car tyres as infill on artificial turf. KNVB/ NOC*NSF/ WG materialen/ VACO/ DSM/ RecyBEM/ TenCate. A833860/R20060318. Mahler, B. J., Van Metre, P. C., Bashara, T. J., Wilson, J. T., Johns, D. A., 2005. Parking lot sealcoat: An unrecognized source of urban PAHs. Environ. Sci. Technol., 39, 55605566. Mahler, B. J., Van Metre, P. C., Wilson, J.T., Musgrove, M., 2010. Coal-tar-based parking lot sealcoat: an unrecognized source of PAH to settled house dust. Environ. Sci. Technol., 44, 894-900.
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Minnesota Polution Control Agency, 2009. Coal Tar-based Sealcoat, Environmental concerns. WQSTRM4-12, www.pca.state.mn.us NIST (National Institute of Standards & Technology), 2006. Certificate of Anaylsis, standard reference material 1597a. Analytical Chemistry Division, Gaithersburg, MD 20899. Onishi, A., Cao, X., Ito, T., Shi, F., Imura, H., 2010. Evaluating the potential for urban heat-island mitigation by greening parking lots. Urban For. Urban Green, 9, 323-332. Takada, H.; Onda, T.; Harada, M.; Ogura, N., 1991. Distribution and sources of polycyclic aromatic hydrocarbons (PAHs) in street dust from the Tokyo Metropolitan area. Sci. Total Environ., 107, 4569. Van Metre, P. C.; Mahler, B. J.; Furlong, E. T., 2000. Urban sprawl leaves its PAH signature. Environ. Sci. Technol., 34, 4064-4070. Van Metre, P. C., Mahler, B.J., Wilson, J.T., 2009. PAHs underfoot: Contaminated dust from coal-tar sealcoated pavement is widespread in the United States. Environ. Sci. Technol., 43, 20-25. Van Metre, P. C., Mahler, B. J., 2010. Contribution of PAHs from coal-tar pavement sealcoat and other sources to 40 U.S. lakes. Sci. Total Environ., 409, 334-344. Van Metre et al. 2010b Presentation at 2010 SETAC North America Conference, Portland, Oregon. Vaze, J., Chiew, F. H. S., 2003. Study of pollutant wash-off from small impervious experimental plots. Water Resources Research 39, 10. Wang, Z., Fingas, M., Shu, Y. Y., Sigouin, L., Landriault, M., Lambert, P., Turpin, R.,Campagna, P., Mullin, J., 1999. Quantitative characterization of PAHs in burn residue and soot samples and differentiation of pyrogenic PAHs from petrogenic PAHs the 1994 mobile burn study. Environ. Sci. Technol., 33, 31003109. Watts, A. W., Ballestero, T. P., Roseen, R. M., Houle, J. P., 2010. Polycyclic Aromatic Hydrocarbons in stormwater runoff from sealcoated pavements. Environ. Sci. Technol., 44, 8849-8854. Yang, Y., Mahler, B. J., Van Metre, P. C., Ligouis, B., Werth, C. J., 2010. Potential contributions of asphalt and coal tar to black carbon quantification in urban dust, soils, and sediments. Geochemica et Cosmochemica Acta, 74, 6830-6840. Yang, Y. N., Van Metre, P. C., Mahler, B. J., Wilson, J. T., Ligouis, B., Razzaque, M. M., Schaeffer, D. J., Werth, C. J., 2010. Influence of coal-tar sealcoat and other carbonaceous materials on Polycyclic Aromatic Hydrocarbon loading in an urban watershed. Environ. Sci. Technol. 44, 1217-1223.

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Appendix
GC-MS Method and Parameters
Column Injector Sample Volume Solvent A and B Syringe wash Purge Pulse Pressure Inlet Temperature GC Oven Temperature DB-5MS, J&W Pulsed splitless 1 L isooctane 3 times both solvents 1 minute 35 psi at 1.05 minutes 280C 0 min 100C 3 min 100C 44 min 320C 54 min - 320C Constant Helium 1.2 mL min-1 300C EI 70 eV SIM m/z = 66, 82, 128, 136, 149, 152, 153, 162, 164, 166, 178, 188, 191, 202, 212, 217, 218, 228, 240, 252, 264, 276, 278, 418 10 Absolute value

Column Mode Carrier Gas Interface Temperature MS Ion source MS Mode

Dwell EM

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Sample PAH Concentrations (ng g-1)

Site 1 1.D 2 2.D 3 3.D 4 4.D 5 5.D 6 6.D 7 7.D 10 10.D 12 12.D 13 13.D 14 14.D 15 16 16.D 17 17.D Napth 193 547 21 119 963 311 3 272 42 26 200 39 77 710 8 74 14 1618 51 45 134 92 10 45 33 3 40 Quin 176 313 26 175 454 75 29 101 334 23 280 80 116 79 1744 41 8 249 63 25 86 32 44 65 106 31 380 Acy 4 3473 8 2 10 9 7 1000 8 5 15 2 2 2462 8 8 832 795 3 2 5 6 6 3 2 0 6 Ace 33 6279 3 3 8 4 12 1296 27 2 6 3 2 4237 17 6 1822 78236 9 5 12 13 6 3 4 3 31 Flu 9 11114 10 8 52 36 7 4473 14 6 22 3 15 9021 16 21 3188 101872 5 5 11 12 5 4 2 0 0 Phe 43 191922 45 163 355 415 20 16559 142 118 374 34 325 164621 43 413 18374 199712 65 70 114 101 82 14 18 9 80 Antr 12 17385 499 30 174 19 1573 955 9362 14 242 4 57 27847 2908 225 31639 198552 95 91 159 138 553 16 18 32 6593 Fla 320 1118531 189 809 4187 2508 39 149497 674 136 774 34 929 177938 704 250 140876 2277187 132 156 112 34 281 15 78 38 147 Py 330 921568 2755 674 2906 2129 744 45866 9252 89 507 29 722 122312 10797 111 2139782 35040304 65 73 52 19 4346 17 75 688 2740 B[a]A 9 34441 1607 16 48 87 237 9636 2115 37 128 8 177 37762 5925 65 998852 11365514 36 33 21 4 3084 3 14 649 3018 Chry 15 60059 1810 34 93 143 865 51942 1966 28 111 5 121 27232 8031 27 1199653 20092711 22 25 9 3 2769 3 24 590 2642 B[b]F&B [j]F 20 58195 2763 24 35 91 482 188857 943 73 288 114 266 60740 9122 55 4248731 28996618 65 70 11 6 4736 2 17 3277 6612 B[k]F 17 23899 1699 18 15 48 493 72484 3601 56 183 103 267 18684 10465 102 350817 12937014 58 196 32 20 2739 5 97 733 3113 B[a]P 19 33176 2504 16 16 71 862 37382 2484 51 220 13 280 69504 8898 28 1555831 21381627 20 21 5 2 3428 10 29 783 2941 Ip 85 58427 841 32 26 114 324 13065 2152 29 110 22 251 30366 5192 42 152608 2635562 76 4 9 7 2048 189 22 550 5442 B[ghi]P 175 28955 567 40 34 97 481 23258 1948 26 112 26 169 27185 3013 24 457228 8042352 28 27 28 10 1222 560 22 298 5098 DBA 8 1988 53 4 11 4 428 257 1770 8 18 23 4 634 1170 2 6301 58729 3 2 6 3 300 2 3 139 2432

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Site 18 18.D 19 19.D 23 25 25.D 26 26.D 27 27.D 28 28.D 29 29.D 30 30.D 31 31.D 32 32.D 33 33.D 34 34.D 36 36.D 37 37.D 38

Napth 7 1 96 149 0 1 0 0 2 39 69 0 6 239 320 13 204 13 137 1 12 5 3 6 3 8 12 18 14 21

Quin 11 5 239 120 3 23 1 0 9 52 108 0 57 417 101 54 471 51 218 188 56 268 120 19 23 149 12 96 90 64

Acy 0 14 0 6 2 2 6 1 6 8 6036 0 1 20 643 1 1025 55 1422 2 76 24 1 3 1 4 0 2 1 2

Ace 2 12 37 7 1 14 1 3 14 3 11321 1 1 14 1227 4 1908 16 3890 3 204 16 2 1 1 4 0 4 4 4

Flu 2 3 14 11 16 4 1 3 19 10 6995 1 1 11 1083 8 1991 36 7189 16 493 15 4 7 2 5 1 1 1 1

Phe 7 36 50 41 1 19 7 12 62 60 31878 9 10 132 31398 21 50755 213 101852 134 14270 29 23 29 17 28 5 23 20 27

Antr 411 405 23 26 19 1379 32 53 208 12 23522 15 29 30 2815 207 11032 236 148314 406 2122 125 139 8 4 260 3 10 8 12

Fla 19 164 115 40 4 37 30 42 197 112 129631 45 44 428 92263 27 172978 356 314033 490 43554 68 93 40 42 112 14 62 57 55

Py 415 2545 107 35 95 602 460 618 2679 94 113201 679 609 384 85637 580 148089 483 451311 7263 67471 1411 1645 60 60 1990 5 60 56 54

B[a]A 246 2113 297 2 48 209 262 293 690 16 14409 230 98 54 8894 4267 20809 45 38454 3381 9714 374 671 15 7 864 1 12 9 9

Chry 183 1172 62 7 23 379 259 339 1672 21 16043 445 466 71 17488 2291 28210 79 70966 3829 12201 526 1201 29 13 956 4 25 11 10

B[b]F&B [j]F 530 5256 65 6 2925 380 1214 858 1741 44 12644 1162 1539 75 29161 2202 51522 109 53444 7032 17842 1635 2610 109 18 2592 4 49 16 16

B[k]F 177 2239 81 11 36039 282 2584 377 4956 46 15938 376 129 188 8043 658 34053 118 156396 5795 12569 436 837 43 10 1311 4 55 23 28

B[a]P 212 2144 129 16 894 243 326 350 1653 12 10177 423 434 40 10837 784 19222 92 112537 4330 16665 64 1047 25 14 1229 3 21 13 11

Ip 2049 1598 0 7 3902 227 1152 337 1048 50 9651 407 443 96 14794 898 42683 40 8233 2629 6907 469 759 33 7 995 2 20 6 6

B[ghi]P 364 539 0 8 502 151 115 145 919 21 11877 207 418 0 13058 754 20906 39 30565 1715 5961 361 631 18 7 833 3 12 7 5

DBA 128 124 8 4 21 155 49 27 62 2 761 52 23 0 809 74 1003 20 589 562 245 139 65 24 4 150 1 14 3 3

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Site 38.D 39 39.D 40 40.D 41 41.D 42 42.D 43 43.D 44 44.D 45 45.D 46 46.D 47 47.D 48 48.D 49 49.D 50 50.D 51 51.D 52 52.D 53

Napth 32 22 36 57 15 24 2414 0 0 0 10 2 8 1 545 0 299 1 468 2 37 1 79 58 60 5 79 1 58 39

Quin 55 403 345 177 38 96 298 6 5 2 19 6 14 12 627 6 309 4 165 8 353 12 47 63 84 41 65 26 32 31

Acy 33 1581 35 11 216 27 28293 0 21 0 2 0 2 0 18 5 4704 0 6129 0 3767 0 6 1 14 1 3 1 7 1

Ace 153 990 56 29 705 5 63924 0 13 0 2 1 1 1 21 12 13701 0 15384 1 12791 1 14 1 57 19 1 1 5 0

Flu 29 2398 137 82 1799 4 8400 0 31 1 1 3 4 2 39 3 24198 1 2728 2 23393 1 4 4 36 32 13 4 12 4

Phe 6120 91802 1069 228 23871 39 236895 1 1192 8 39 7 21 5 163 9 164104 4 189534 7 213372 7 646 22 535 179 54 24 58 8

Antr 1066 209346 6425 2049 211289 43 48648 5 2715 40 33 47 249 33 52 43 473062 25 14705 45 1301834 22 111 40 165 820 86 1006 62 15

Fla 23656 57563 6386 573 98471 104 734726 3 7476 45 250 17 130 14 622 53 424047 14 466208 16 1016557 29 4322 88 2532 559 141 163 245 17

Py 21868 958299 100069 8878 1928179 95 299357 50 124454 705 103 268 2065 236 328 824 6440374 217 227695 252 16067166 442 1732 26 633 7987 40 2421 67 6

B[a]A 3571 492658 44135 2034 1058772 19 69867 15 63982 312 23 63 1158 111 233 485 2904089 99 56490 102 7033414 199 630 6 276 3388 9 1071 49 2

Chry 4247 612684 59396 895 1248989 19 122295 24 79569 419 44 27 1720 152 382 604 4372524 131 93031 150 10898853 294 822 26 1096 4318 38 1493 98 7

B[b]F&B [j]F 5536 12230777 236347 3423 4012094 22 92886 59 158869 1708 37 23 2839 207 270 1111 5505147 211 78692 406 16663792 528 587 16 1306 8047 30 3719 88 9

B[k]F 2359 5545207 88382 5631 2298984 22 31218 37 72023 634 29 205 2217 109 105 1590 2410355 94 45188 103 13436510 494 1599 14 1985 3737 31 2935 78 3

B[a]P 6038 8249799 70097 4989 1540 10 86662 22 107140 494 30 152 1598 151 184 651 7707677 144 70155 158 12980948 307 661 14 340 5005 22 1721 36 4

Ip 1867 1589093 40990 3971 701549 6 50361 19 20638 289 20 84 1160 64 160 561 392185 81 47017 196 1798604 247 507 12 360 3202 12 1421 156 2

B[ghi]P 1925 2926222 28131 3788 203025 3 45899 17 38003 198 18 115 613 62 185 296 1633585 74 37384 78 4427164 138 388 20 336 1630 15 606 95 6

DBA 145 178953 3429 535 289 26 868 5 2324 24 15 16 45 66 154 36 89452 5 622 9 186359 12 245 4 147 57 2 23 57 1

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Site 53.D 54 54.D 55 55.D

Napth 305 288 41 26 83

Quin 115 121 55 11 85

Acy 452 6 714 0 2

Ace 543 3 763 3 2

Flu 2435 39 4310 7 13

Phe 51836 726 628321 9 25

Antr 12743 1496 11019 10 41

Fla 236612 491 255923 39 142

Py 73144 122 73000 11 46

B[a]A 25671 109 59835 15 8

Chry 107853 256 96433 23 30

B[b]F&B [j]F 104501 151 5451 22 30

B[k]F 20492 30 1644 16 82

B[a]P 33019 364 938 62 25

Ip 1354 30 14 0 18

B[ghi]P 7840 18 489 0 25

DBA 144 6 211 0 3

Minimum

5th Percentile

15

23

10

12

10

Median Mean

29 132

63 129

6 697

6 2391

11 2370

59 26482

138 30331

159 86630

654 712378

241 265140

381 427379

723 792369

406 409618

345 571906

330 83297

252 196103

47 5910

95th Percentile

546

409

3605

11982

8679

190609

170921

443019

1394745

720445

876820

4118580

1227492

762019

260418

317417

4721

Maximum SD RSD (%)

2414 331 250

1744 214 166

28293 3133 450

78236 10733 449

101872 11215 473

628321 82946 313

1301834 147866 488

2277187 298005 344

35040304 4048167 568

11365514 1418074 535

20092711 2409367 564

28996618 3743020 472

13436510 2028607 495

21381627 2823619 494

2635562 374328 449

8042352 1006750 513

186359 28721 486

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