Abstract
Urban particulate matter (PM), asphalt, and tire samples were investigated for their content of benzothiazole and benzothiazole derivates. The purpose of this study was to examine whether wear particles, i.e., tire tread wear or road surface wear, could contribute to atmospheric concentrations of benzothiazole derivatives. Airborne particulate matter (PM10) sampled at a busy street in Stockholm, Sweden, contained on average 17 pg/m3 benzothiazole and 64 pg/m3 2-mercaptobenzothiazole, and the total suspended particulate-associated benzothiazole and 2-mercaptobenzothiazole concentrations were 199 and 591 pg/m3, respectively. This indicates that tire tread wear may be a major source of these benzothiazoles to urban air PM in Stockholm. Furthermore, 2-mercaptobenzothiazole was determined in urban air particulates for the first time in this study, and its presence in inhalable PM10 implies that the human exposure to this biocide is underestimated. This calls for a revision of the risk assessments of 2-mercaptobenzothiazole exposure to humans which currently is limited to occupational exposure.
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References
Ahlbom J, Duus U (2003) HA oils in automotive tyres—prospects of a national ban. http://www.kemi.se/upload/Trycksaker/Pdf/Rapporter/Rapport5_03.pdf
Avagyan R, Sadiktsis I, Thorsén G, Östman C, Westerholm R (2013) Determination of benzothiazole and benzotriazole derivates in tire and clothing textile samples by high performance liquid chromatography–electrospray ionization tandem mass spectrometry. J Chromatogr A 1307:119–125. doi:10.1016/j.chroma.2013.07.087
Bergvall C, Westerholm R (2007) Identification and determination of highly carcinogenic dibenzopyrene isomers in air particulate samples from a street canyon, a rooftop, and a subway station in Stockholm. Environ Sci Technol 41:731–737. doi:10.1021/es062232p
Cadle SH, Williams RL (1978) Gas and particle emissions from automobile tires in laboratory and field studies. J Air Pollut Control Assoc 28:502–507. doi:10.1080/00022470.1978.10470623
Cadle SH, Williams RL (1980) Environmental degradation of tire-wear particles. Rubber Chem Technol 53:903–914. doi:10.5254/1.3535066
EPA (1994) Reregistration eligibility decision fact sheet: sodium and zinc salts of 2-mercaptobenzothiazole. http://www.epa.gov/oppsrrd1/REDs/factsheets/2380fact.pdf
EPA (2002) Child-specific exposure factors handbook. http://ofmpub.epa.gov/eims/eimscomm.getfile?p_download_id=36528
Evans JJ, Shoemaker CA, Klesius PH (2000) In vivo and in vitro effects of benzothiazole on sheepshead minnow (Cyprinodon variegatus). Mar Environ Res 50:257–261. doi:10.1016/s0141-1136(00)00090-8
Fauser P, Tjell JC, Mosbaek H, Pilegaard K (1999) Quantification of tire-tread particles using extractable organic zinc as tracer. Rubber Chem Technol 72:969–977. doi:10.5254/1.3538846
Fauser P, Tjell JC, Mosbaek H, Pilegaard K (2002) Tire-tread and bitumen particle concentrations in aerosol and soil samples. Pet Sci Technol 20:127–141. doi:10.1081/LFT-120002092
Fishbein L (1991a) Chemicals used in the rubber industry. Sci Total Environ 101:33–43. doi:10.1016/0048-9697(91)90100-s
Fishbein L (1991b) Municipal and industrial hazardous-waste management—an overview. Toxicol Ind Health 7:209–220. doi:10.1177/074823379100700524
Fishman RL, Turner JR (1999) Tire wear contributions to ambient particulate matter. Air & Waste Management Association, pp 1081–1095
Gidhagen L, Johansson C, Langner J, Olivares G (2004) Simulation of NOx and ultrafine particles in a street canyon in Stockholm, Sweden. Atmos Environ 38:2029–2044. doi:10.1016/j.atmosenv.2004.02.014
Haroune N, Combourieu B, Besse P, Sancelme M, Kloepfer A, Reemtsma T, De Wever H, Delort AM (2004) Metabolism of 2-mercaptobenzothiazole by Rhodococcus rhodochrous. Appl Environ Microbiol 70:6315–6319. doi:10.1128/aem.70.10.6315-6319.2004
Heldstab J, de Haan van der Weg P, Künzle T, Keller M, Zbinden R (2003) Modelling of PM10 and PM2.5 ambient concentrations in Switzerland 2000 and 2010. http://www.dehaan.ch/pubs/EnvDoc169.pdf. Accessed: ENVIRONMENTAL DOCUMENTATION No. 169
Jung JH, McLaughlin JL, Stannard J, Guin JD (1988) Isolation, via activity-directed fractionation, of mercaptobenzothiazole and dibenzothiazyl disulfide as 2 allergens responsible for tennis shoe dermatitis. Contact Dermatitis 19:254–259. doi:10.1111/j.1600-0536.1988.tb02922.x
Kim MG, Yagawa K, Inoue H, Lee YK, Shirai T (1990) Measurement of tire tread in urban air by pyrolysis-gas chromatography with flame photometric detection. Atmos Environ A Gen Top 24:1417–1422. doi:10.1016/0960-1686(90)90049-s
Kloepfer A, Jekel M, Reemtsma T (2004) Determination of benzothiazoles from complex aqueous samples by liquid chromatography-mass spectrometry following solid-phase extraction. J Chromatogr A 1058:81–88. doi:10.1016/j.chroma.2004.08.081
Kloepfer A, Jekel M, Reemtsma T (2005) Occurrence, sources, and fate of benzothiazoles in municipal wastewater treatment plants. Environ Sci Technol 39:3792–3798. doi:10.1021/es048141e
Kumata H, Takada H, Ogura N (1996) Determination of 2-(4-morpholinyl)benzothiazole in environmental samples by a gas chromatograph equipped with a flame photometric detector. Anal Chem 68:1976–1981. doi:10.1021/ac9511556
Kumata H, Sanada Y, Takada H, Ueno T (2000) Historical trends of N-cyclohexyl-2-benzothiazolamine, 2-(4-morpholinyl)benzothiazole, and other anthropogenic contaminants in the urban reservoir sediment core. Environ Sci Technol 34:246–253. doi:10.1021/es990738k
Kumata H, Mori M, Takahashi S, Takamiya S, Tsuzuki M, Uchida T, Fujiwara K (2011) Evaluation of hydrogenated resin acids as molecular markers for tire-wear debris in urban environments. Environ Sci Technol 45:9990–9997. doi:10.1021/es202156f
Lee YK, Kim MG, Whang KJ (1989) Simultaneous determination of natural and styrene butadiene rubber tire tread particles in atmospheric dusts by pyrolysis-gas chromatography. J Anal Appl Pyrolysis 16:49–55. doi:10.1016/0165-2370(89)80035-x
Ni HG, Lu FH, Luo XL, Tian HY, Zeng EY (2008) Occurrence, phase distribution, and mass loadings of benzothiazoles in riverine runoff of the Pearl River Delta, China. Environ Sci Technol 42:1892–1897. doi:10.1021/es071871c
Omstedt G, Bringfelt B, Johansson C (2005) A model for vehicle-induced non-tailpipe emissions of particles along Swedish roads. Atmos Environ 39:6088–6097. doi:10.1016/j.atmosenv.2005.06.037
Pierson WR, Brachaczek WW (1974) Airborne particulate debris from rubber tires. Rubber Chem Technol 47:1275–1299. doi:10.5254/1.3540499
Reddy CM, Quinn JG (1997) Environmental chemistry of benzothiazoles derived from rubber. Environ Sci Technol 31:2847–2853. doi:10.1021/es970078o
Reemtsma T, Fiehn O, Kalnowski G, Jekel M (1995) Microbial transformations and biological effects of fungicide-derived benzothiazoles determined in industrial waste-water. Environ Sci Technol 29:478–485. doi:10.1021/es00002a025
Remberger M, Woldegiorgis A, Kaj L, Andersson J, Palm CA, Dusan B, Ekheden Y, Brorstroem-Lunden E (2006) Results from the Swedish screening 2005: subreport 2. Biocides. http://www3.ivl.se/rapporter/pdf/B1700.pdf
Sadiktsis I, Bergvall C, Johansson C, Westerholm R (2012) Automobile tires—a potential source of highly carcinogenic dibenzopyrenes to the environment. Environ Sci Technol 46:3326–3334. doi:10.1021/es204257d
Saito T (1989) Determination of styrene butadiene and isoprene tire tread rubbers in piled particulate matter. J Anal Appl Pyrolysis 15:227–235. doi:10.1016/0165-2370(89)85036-3
Sorahan T (2009) Cancer risks in chemical production workers exposed to 2-mercaptobenzothiazole. Occup Environ Med 66:269–273. doi:10.1136/oem.2008.041400
The Commission of the European Communities (2003) Commission regulation (EC) No 2032/2003 of 4 November 2003 on the second phase of the 10-year work programme referred to in Article 16(2) of Directive 98/8/EC of the European Parliament and of the Council concerning the placing of biocidal products on the market, and amending Regulation (EC) No 1896/2000. http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=CONSLEG:2003R2032:20070104:EN:PDF
Thorpe A, Harrison R (2008) Sources and properties of non-exhaust particulate matter from road traffic: a review. Sci Total Environ 400:270–282. doi:10.1016/j.scitotenv.2008.06.007
Wik A, Dave G (2009) Occurrence and effects of tire wear particles in the environment—a critical review and an initial risk assessment. Environ Pollut 157:1–11. doi:10.1016/j.envpol.2008.09.028
Zeng EY, Tran K, Young D (2004) Evaluation of potential molecular markers for urban stormwater runoff. Environ Monit Assess 90:23–43. doi:10.1023/b:emas.0000003564.24169.86
Acknowledgments
Christer Johansson at Department of Applied Environmental Science at Stockholm University is acknowledged for providing the PM10 filter samples. Jan Gustavsson and Mikael Eriksson at Camfil AB are acknowledged for providing the high-volume sampler for TSP sampling. Mats Gustafsson and Tomas Halldin at VTI are acknowledged for supplying tire samples and information regarding the tires included in this study. Billy Sjövall at SLB is acknowledged for helping with the sampling at Hornsgatan. This study has been financed by Stockholm University.
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Responsible editor: Constantini Samara
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Six tables with detailed information on the analyzed tires, detailed description of air particulate samples, MS/MS parameters, and detailed information on method validation and determined mass fractions of benzothiazoles in stored and re-analyzed tire particles. One figure showing LC-MS/MS chromatograms of a tire sample.
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Avagyan, R., Sadiktsis, I., Bergvall, C. et al. Tire tread wear particles in ambient air—a previously unknown source of human exposure to the biocide 2-mercaptobenzothiazole. Environ Sci Pollut Res 21, 11580–11586 (2014). https://doi.org/10.1007/s11356-014-3131-1
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DOI: https://doi.org/10.1007/s11356-014-3131-1