Evaluation of Hydrogenated Resin Acids as Molecular Markers for Tire

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Evaluation of Hydrogenated Resin Acids as Molecular Markers for Tire-wear Debris in Urban Environments Hidetoshi Kumata,*,† Mika Mori,‡,§ Sho Takahashi,† Shohei Takamiya,† Mikio Tsuzuki,† Tatsuya Uchida,† and Kitao Fujiwara† † ‡

Faculty of Life Sciences, Tokyo University of Pharmacy and Life Sciences, Hachioji, Tokyo 192-0392, Japan, Graduate School of Life Sciences, Tokyo University of Pharmacy and Life Sciences, Hachioji, Tokyo 192-0392, Japan

bS Supporting Information ABSTRACT: To propose new molecular markers for tire-wear emissions, four dihydroresin acids, that is, 8-isopimaren-18-oic acid (I), 8-pimaren-18-oic acid (II), 13β(H)-abieten-18-oic acid (III), and 13α(H)-abiet-8-en-18-oic acid (IV), were identified and investigated for source specificities, distributions, and environmental stabilities. The absence of I
IV in natural sources and the linear correlations between dihydroresin acids with different skeletons in tires and in environmental samples demonstrated that I
IV are specific markers for synthetic rubbers. The ratio of III + IV to the sum of III + IV plus abietic acid showed the resin acids distribution between different environmental compartments receiving contributions from traffic and natural sources. The physicochemical properties and results of photolysis experiments suggested that I
IV can set lower limits for tire-wear contributions to environmental loads of particulate matter (PM) and polycyclic aromatic hydrocarbons with molecular weight g202. By comparing III + IV concentrations or (III+IV)/pyrene or (III+IV)/benzo[a]pyrene ratios in tires and those in environmental matrices, the contributions of tire-wear emissions to PM, pyrene, and benzo[a]pyrene were estimated to be 0.68 ( 0.54%, 6.9 ( 4.8%, and 0.37 ( 0.18% in roadside PM and 0.83 ( 0.21%, 0.88 ( 0.52%, and 0.08 ( 0.06% in rooftop PM.

’ INTRODUCTION Automobile and truck tire-treads wear on roads and generate tire-wear debris of various size ranges. Although most of the mass of tire-wear particles is from particles much larger than 10 μm, minor airborne and inhalable fractions are also generated.1,2 Various studies have reported the direct and indirect adverse health effects of the chemical components of tire-tread rubbers.3,4 Tire treads are commonly composed of natural and/or synthetic rubbers, carbon black, and extender oils, respectively, accounting for 40
60%, ∼30%, and 10
20% by mass.5,6 Small amounts (less than ∼2% each) of vulcanization accelerators, retarders, softeners, and antioxidants are also added during manufacture to obtain the desired properties.5,7,8 Carbon black and extender oils can be a source of high concentrations of polycyclic aromatic hydrocarbons (PAHs), including carcinogenic benzo[a]pyrene.5,9,10 Dehydroabietic acid (DHA), a major component of emulsifiers, as well as some benzothiazole-type vulcanization accelerators has been reported to cause contact dermatitis.11 Another more subtle effect of tire wear on human health may be the presence of latex allergens.12 A recent epidemiological study revealed contemporaneous linear correlations between asthma mortality rates and radial-tire use, rather than with other traffic-related factors.13 More recently, evidence that organic extracts from tire rubber can cause localized damage to the plasma membrane of human lung epithelial cells has been r 2011 American Chemical Society

reported.14 These findings stress the necessity of wide-scale monitoring to assess the relative importance of tire wear to urban air quality. Attempts to estimate the concentrations of tire particles in environmental samples have been made using molecular marker(s), for example, benzothiazole (BT), 2-hydroxybenzothiazole (HOBT), 2-(4-morpholinyl)benzothiazole (24MoBT), and N-cyclohexyl-2-benzothiazolamine (NCBA), which are breakdown products (BT, HOBT) or impurities (24MoBT, NCBA) in vulcanization accelerators added to rubber during manufacture.5,8,15
20 The development of other molecular marker(s) that have different structures and different physicochemical properties from those of benzothiazole-type markers would aid in assessing and understanding the impact of traffic-derived emissions on the environment. The present study focused on a group of resin acids contained in commercially used disproportionated rosins used in the tiremanufacturing process as an emulsifying agent. Disproportionated rosins are produced by transforming natural resin acids in pine-tree gum-rosin to more stable DHA; hydrogenated resin Received: June 24, 2011 Accepted: October 18, 2011 Revised: September 19, 2011 Published: October 18, 2011 9990

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Environmental Science & Technology acids are produced as byproducts. Previous studies reported the occurrence of such hydrogenated resin acids in tire-tread rubbers and proposed them as potential tire-wear markers.5,21 However, this was only for a single brand of tire manufactured at least 18 years ago and their reports did not provide enough information to assign the peaks of the hydrogenated acids on the chromatograms. More importantly, the environmental distributions of hydrogenated resin acids have not been well described, and hence their utilities as molecular markers for tire wear have never been evaluated. The objectives of this study were (1) to identify hydrogenated resin acids in tires from a wide range of tire manufactures to reflect the mean concentration/composition of tire-wear emissions, (2) to elucidate the environmental distribution of hydrogenated resin acids in a Tokyo suburb, and (3) to determine the fates of the target resin acids in atmospheric and terrestrial environments by examining their physicochemical properties and by conducting laboratory experiments. Through the course of this study, special emphasis was made on evaluating utilities of the target resin acids as molecular markers for tire wear.

’ MATERIALS AND METHODS Sample Collection. The study was conducted in the city of Hachioji, which has an area of 186 km2 and ca. 540 000 residents. The city is part of metropolitan Tokyo, located ca. 30 km from the downtown area. More details about the study area, for example, traffic intensity and air quality, are available in the Supporting Information. We analyzed gum rosin, disproportionated rosin, tire treads, and smoke from pine-trees as source materials, and road dusts and airborne particulate matter as environmental matrices. The gum rosin and disproportionated rosin were kindly provided by Harima Chemicals, Inc. (Tokyo, Japan). Gum rosin can be regarded as a raw material from pine-trees as it is prepared by removing volatile turpentine from the resin obtained from pinetrees. Disproportionated rosin consists mostly of DHA, and gum rosin consists of DHA plus pimaric, palustric, abietic, and neoabietic acids. Automobile tires from five different manufacturers, representative of the market share in Japan, were purchased in 2006. The tire-tread surfaces were manually rasped using a solvent-rinsed metal rasp and the resultant particles were saved for analysis. The pine-smoke samples were obtained as follows: an appropriate amount of lyophilized and ground needles and branches of Pinus thunbergii was burnt on an aluminum tray and the resultant smoke was absorbed onto a glass-fiber thimble held above the fire. Road dust was collected from road surfaces near each of seven air-pollution-monitoring stations in Hachioji. Three of the stations are located close to, but not facing, main roads with heavy traffic, and are referred to as “traffic-pollution-monitoring sites (TPMS)”. The other stations are in residential areas and are referred to as “residential-air-monitoring sites (RAMS)”. Road dusts were also collected at the middle of three different tunnels to examine the contributions from atmospheric fallout and soil. Two of the tunnels are located in Hachioji, and the third, the Yaesu Tunnel (length: 1400 m, part of the Tokyo Metropolitan Expressway), is in downtown Tokyo. Dusts were collected by brushing them onto a solvent-rinsed stainless-steel plate and then transferring them to a plastic bottle. Five road dust samples collected by municipal road sweepers in December 2006 were also analyzed. One sample was collected on

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residential semirural streets in Hachioji and the others were collected on heavily trafficked trunk routes in downtown Tokyo. These dusts can be regarded as averages for a wide range of residential and urban areas. The collected dust samples were sieved, and the 0.99; Figure 3), suggesting that all the tire manufacturers, except for that of tire no. 5, use the same type of disproportionated rosin. Considering that tire materials are the only materials widely used and continuously emitted to the environment as abrasions, the observed linearity demonstrates the source specificity of I
IV as molecular markers for tire wear. To investigate the resin acids distribution between different environmental compartments that receive various contributions from traffic and natural sources, the ratios of III + IV to the sum of III + IV plus Ab [H2Ab/(H2Ab+Ab) ratios] are compared (Figure 4). Ab was chosen as it was the resin acid present in tire rubber in the lowest amount on average (Figure 1), but it is abundant in natural rosins and in wood smoke (Supporting Information Figure S1). Consequently, higher H2Ab/ (H2Ab+Ab) ratios, that is, approaching unity, indicate that relative contributions from synthetic rubbers predominate over those from natural sources, and vice versa. It is reasonable that the 9993

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Figure 5. Decay of resin acids (upper) and compositional changes (lower) over 24 h of photoirradiation with a solar simulator (upper). I + II, III + IV are defined in the caption to Figure 3. (III + IV)/DHA, (III + IV)/Pyr, and (III + IV)/BaP are ratios of III + IV to DHA, pyrene, and benzo[a]pyrene, respectively. Sweeper dusts, TPMS, and RAMS are defined in the footnotes to Table 1. Abbreviations of compound names (I, II, III, IV, and DHA) are defined in the caption to Figure 1.

ratios observed in tunnel dusts (0.93 ( 0.03) are almost the same as the market-share mean ratio for tire rubbers (0.93) because exclusive contributions from vehicle tires can be expected in such locations. Rooftop SPM and sweeper dusts from trunk routes showed quite high ratios (0.89 ( 0.15 and 0.84 ( 0.04, respectively), indicating strong contributions from synthetic rubbers. Low values in road dusts from residential areas (i.e., RAMS: 0.44 ( 0.13 and sweeper dusts from Hachioji: 0.39) indicate that residential areas in Hachioji city are more affected by rosins from natural sources than is downtown Tokyo. A similar relation was also observed in Hachioji. Ratios in TPMS (0.67 ( 0.19) were significantly higher than those in residential road dusts (p < 0.01). This is consistent with the relative proximity of the sampling locations to traffic sources (TPMS > RAMS) and/ or distance from natural sources (TPMS > RAMS). The differences between roadside and rooftop SPM (0.77 ( 0.13 versus 0.89 ( 0.15; p < 0.02) can be explained if Ab is mostly associated with soil particles or plant residues, which are less available for atmospheric transport than are tire-wear materials. Environmental Distributions of PAHs. As reported previously,5,10 tires contain PAHs at significant concentrations (Supporting Information Table S3). Among PAHs, pyrene is the most abundant species, accounting for 41
52% of ∑PAH. It should be noted that four of the tire brands contained retene, known to be a useful tracer for pine-combustion products, at the same magnitude as most of the parental species. Selected environmental samples were also analyzed for PAHs, as shown in Supporting Information Table S4. The concentrations of PAHs observed in road dusts as well as in SPM were of the same

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magnitudes as those reported in previous studies.5,10,22 The source diagnostic isomer pair ratios, Flu/(Flu+Pyr) and IP/ (IP+BgP), were within the ranges for petroleum combustions (i.e., 0.4
0.5 for Flu/(Flu+Pyr) and 0.2
0.5 for IP/(IP+BgP) or coal and vegetative combustions (i.e., > 0.5 for Flu/(Flu+Pyr) and >0.5 for IP/(IP+BgP).28 Application of Dihydroresin Acids as Tire-wear Markers. The organic configuration in particles emitted from a source will be altered by environmental processes such as vaporization, leaching, and photolysis; this should be taken into account when discussing the utilities/limitations of molecular markers. For example, the Henry’s law constants (KH0 ) estimated for resin acids (I and II: 2.9  10
4; III and IV: 3.9  10
4; DHA: 7.3  10
4, Supporting Information Table S5) suggest that vaporization can alter their concentrations in tire-wear materials during retention in the atmosphere and on road surfaces. The solubilities of 1.7  10
5 mol/L assumed for I
IV, because of their structural resemblances to DHA (Supporting Information Table S5), indicate that resin acids will leach out tire-wear materials during washout and runoff events. Also, laboratory experiments revealed the susceptibility of the target resin acids to photochemical reactions (Figure 5). Although none of the analytes decreased in concentration until an hour from the beginning of the experiments, the concentrations of all the target resin acids decreased significantly after that, and at 24 h from the beginning of irradiation with a solar simulator, the concentrations of I + II, III + IV, and DHA decreased to 21%, 24%, and 14%, respectively, of the initial levels. The energy from an hour of irradiation (i.e., 9 MJ/m2) is approximately the same as the average daily global solar radiation in the winter months in Tokyo. Presumably, the residence times of tire-wear materials in the atmospheric/terrestrial environments is in the same range as the dry periods between rain events (i.e., 3.9 days on average in Hachioji in 2006).29 Consequently, resin acids emitted into the environment as tire-wear particles could have experienced photodecomposition to some extent. Caution should be exercised in handling the results shown in Figure 5. First, there is a possibility that tire-wear particles in the road dust used for the experiment had already been aged, which could partly mask the degradability of the resin acids. Selecting tunnel dust (collected in the middle of a tunnel of length 1400 m) as a test matrix could have minimized the uncertainty caused by direct photolysis. However, the possibility of reactions with ozone or other oxidants derived from outside air should still be taken into account. The latter scenario may also enhance the degradability of resin acids in the “real” environment. Second, because of the difference in the size cut for road dusts and airborne SPM (63 μm versus 10 μm), the photodegradabilities of resin acids in the latter medium is considered to be faster than that shown in Figure 5. All these factors will lower resin acid concentrations in tire-wear particles existing in ambient matrices than the source end-members that can be deduced from their concentrations in tire treads (Supporting Information Table S3). All the above-mentioned factors indicate that the use of dihydroresin acids as tire-wear markers leads to set lower limits for tire-wear contributions to the load of ambient particulate matter. Compared with 24MoBT and NCBA (BTs), resin acids will provide lower estimates for particle loads because their KH0 values are higher than those of BTs (24MoBT: 2.3  10
11, NCBA: 2.3  10
8, Supporting Information Table S5). On the other hand, the similar solubilities of resin acids and NCBA (4  10
5 mol/L, Supporting Information Table S5) 9994

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Table 1. Relative Contributions from Tire-wear Debris to Selected Substances of Environmental Concerna sweeper dustsb

road dusts tunnel

TPMSc

RAMSd

downtown (trunk routes) 0.70 ( 0.30

particulate matter

2.0 ( 0.5

0.14 ( 0.11

0.07 ( 0.04

POC

7.6 ( 2.3

2.2 ( 1.7

1.3 ( 1.0

na

DHA

49 ( 11

98 ( 47

47 ( 36

pyrene

8.9 ( 2.1

4.7 ( 1.0

benzo[a]pyrene

4.8 ( 2.0

0.95 ( 0.56

airborne SPMe

Hachioji (residential)

road side

rooftop

0.05

0.68 ( 0.54

0.83 ( 0.21

0.94

5.7 ( 4.1

4.0 ( 1.6

178 ( 58

43

90 ( 33

51 ( 24

6.1
9.4

na

na

6.9 ( 4.8

0.88 ( 0.52

0.84
0.85

na

na

0.37 ( 0.18

0.08 ( 0.06

a

na: data for calculations are not available. b Sweeper dusts: road dusts collected by municipal road sweepers. c TPMS: collected around traffic pollution monitoring sites in Hachioji-city. d RAMS: collected around residential area monitoring sites in Hachioji-city, e SPM: airborne particulate matter with diameter 2.6% and >0.5% in road dusts from inside and outside tunnels, respectively).8 This is in part a result of the differences among the volatilities of 24MoBT and resin acids, as discussed above. It is also partly a result of differences in the sizes of the particles analyzed, that is, 63 μm.16 Hence, 24MoBT-based estimates in previous reports could have been significantly affected by the inclusion of larger particles. Similar calculations using the ratios of III + IV to DHA, pyrene, or benzo[a]pyrene provided relative contributions from tirewear to the corresponding pollutants in environmental matrices (Table 1). However, caution should be exercised in interpreting these estimates. As can be deduced from Figure 5, photolysis will lead to discrimination among dihydroresin acids and other tirederived pollutants (i.e., DHA and PAHs). For example, the (III +IV)/pyrene and (III+IV)/benzo[a]pyrene ratios decreased significantly after 8 h of irradiation. Considering this with their similar (pyrene) or less (benzo[a]pyrene) volatile, and more hydrophobic natures compared with dihydroresin acids (Supporting Information Table S5), the estimates listed in Table 1 can be regarded as lower limits for tire-wear contributions to ambient pyrene and benzo[a]pyrene. The situation could be more complicated for DHA. The photolysis experiments revealed that DHA is more susceptible to photochemical reactions than are I
IV, which leads to overestimation, but the lower volatility of DHA compared to I
IV can lead to underestimation. As can be

seen in Table 1, the relative contributions of tire wear to DHA exceeded 100% in many of the samples analyzed, indicating photolysis to be an important process in environmental alteration of dihydroresin acids. Consideration of Particulate Emissions from Road Traffic. Exposure to inhalable atmospheric particulate matter is now increasingly being recognized as a potent health risk in many cities around the world (e.g., refs 30
33 and references therein). Since no definitive threshold for adverse health effects induced by inhalable particulate matter has yet been established,34 there is a general consensus that levels of ambient particulate matter should be reduced as much as possible. Road traffic and biomassburning are the most important sources of airborne particulate matter in urban environments. Fine particulate emissions in vehicle exhausts have already been subjected to regulations, but nontailpipe emissions are totally uncontrolled. Recent studies have indicated that a large part of total PM10 emissions originates from nontailpipe emissions.35,36 Nontailpipe emissions mostly arise from vehicle-induced resuspension of dust deposited on the road, and in part from direct emissions from vehicle wear (brakes, tires, discs, road materials, etc.). Our results show that dihydroresin acids I
IV have the potential to complement other existing marker compounds and broaden the application of chemical marker techniques in the assessment of the relative importance of tire-wear to nontailpipe emissions. Zn and S are important components in rubber vulcanizing processes and are typically regarded as elemental identifiers for tire-rubber materials. For example, in road simulator studies, tire-wear emissions were successfully distinguished by a chemical mass balance (CMB) approach using elemental compositions.1,2 However, neither Zn nor S can be specific to tire wear in the real environment,35 which might limit the utility of this approach. The source specificities of I
IV enable semiquantitative source apportionment, setting a lower limit to tire-wear contributions, as discussed above. Although the relative contribution of tire wear is not very high (e.g., 0.8% in rooftop SPM, Table 1), unambiguous detection of dihydroreisn acids clearly indicates the existence of tire-wear particles in ambient matrices at significant levels. These features of dihydroresin acids are suitable for monitoring spatial and temporal variations of direct emissions from vehicle wear, which would be a great help in conducting efficient traffic and air-quality management. However, further studies are necessary to increase the utility of dihydroresin acids as tire-wear markers. For example, the reactions of resin acids with ozone or other oxidants, and biodegradability in soil should be investigated to better understand their fates in atmospheric/terrestrial environments. Also, investigation 9995

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particle distributions of dihydroresin acids will be necessary to expand the use of these markers to aquatic environments.

’ ASSOCIATED CONTENT

bS

Supporting Information. Descriptions of the study area, and detailed conditions for instrumental analyses of resin acids and identification of target analytes. Five figures demonstrating the extracted ion chromatograms of resin acids from gum rosin, disproportionated rosin, pine-wood smoke, and tire-tread rubber (Figure S1), the EI mass spectra of methyl esters of selected resin acids (I
VI: Figures S2
S4), and the EI mass spectra of TMS esters of dihydroresin acids II and IV (Figure S5) are provided. Five additional tables listing the air pollution parameters monitored in downtown and suburban areas in Tokyo (Table S1), a listing of the relative retention times, quantification and confirmation ions for GC/MS (SIM) analyses (Table S2), the concentrations of resin acids and PAHs in tire-rubber samples (Table S3), the environmental distributions of resin acids and PAHs (Table S4), and the physicochemical properties of resin acids, benzothiazolamines, and selected PAHs (Table S5). This material is available free of charge via the Internet at http://pubs.acs.org.

’ AUTHOR INFORMATION Corresponding Author

*Phone: +81-42-676-6793; fax: +81-42-676-5354; e-mail: kumata@ ls.toyaku.ac.jp. Present Addresses §

Japan Food Research Laboratories, Tama, Tokyo 206-0025, Japan.

’ ACKNOWLEDGMENT We thank laboratory members for their help in collecting environmental samples, Mr. Suganuma of the Ministry of Land, Infrastructure, Transport and Tourism, and Mr. Morita of Nippon Highway Service Co. Ltd. for arranging sweeper dust collections. Mr. Shiratori of Harima Chemicals Inc. provided rosin samples and helpful documents on pine chemistry. Financial support was provided by the Japanese Ministry of Education, Culture, Sports, Science and Technology, Grant-in Aid for Scientific Research (KAKENHI) (C), 23510034. ’ REFERENCES (1) Gustafsson, M.; Blomqvist, G.; Gudmundsson, A.; Dahl, A.; Swietlicki, E.; Bohgard, M.; Lindbom, J.; Ljungman, A., Properties and toxicological effects of particles from the interaction between tyres, road pavement and winter traction material. Sci. Total Environ. 2008, 393, 226
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