Journal of Toxicology and Environmental Health, Part A, 77:1502–1521, 2014 Copyright © Taylor & Francis Group, LLC ISSN: 1528-7394 print / 1087-2620 online DOI: 10.1080/15287394.2014.955905
RISK ASSESSMENT OF VOLATILE ORGANIC COMPOUNDS BENZENE, TOLUENE, ETHYLBENZENE, AND XYLENE (BTEX) IN CONSUMER PRODUCTS Seong Kwang Lim1, Han Seung Shin2, Kyung Sil Yoon3, Seung Jun Kwack4, Yoon Mi Um1, Ji Hyeon Hyeon1, Hyo Min Kwak1, Ji Yun Kim1, Tae Hyung Kim1, Yeon Joo Kim1, Tae Hyun Roh1, Duck Soo Lim1, Min Kyung Shin1, Seul Min Choi1, Hyung Sik Kim1, Byung-Mu Lee1 1 Division of Toxicology, College of Pharmacy, Sungkyunkwan University, Suwon, Gyeonggi-do, South Korea 2 Department of Food Science and Biotechnology and Institute of Lotus Functional Foods Ingredients, Dongguk University–Seoul, Seoul, South Korea 3 Lung Cancer Branch, Research Institute, National Cancer Center, Goyang, Gyeonggi-do, South Korea 4 Department of Biochemistry and Health Science, College of Natural Sciences, Changwon National University, Changwon, Gyeongnam, South Korea
Exposure and risk assessment was performed by evaluating levels of volatile organic compounds (VOC) benzene, toluene, ethylbenzene, and xylene (BTEX) in 207 consumer products. The products were categorized into 30 different items, consisting of products of different brands. Samples were analyzed for BTEX by headspace-gas chromatography/mass spectrometry (headspace-GC/MS) with limit of detection (LOD) of 1 ppm. BTEX were detected in 59 consumer products from 18 item types. Benzene was detected in whiteout (ranging from not detected [ND] to 3170 ppm), glue (1486 ppm), oil-based ballpoint pens (47 ppm), and permanent (marking) pens (2 ppm). Toluene was detected in a leather cleaning product (6071 ppm), glue (5078 ppm), whiteout (1130 ppm), self-adhesive wallpaper (15–1012 ppm), shoe polish (806 ppm), permanent pen (609 ppm), wig adhesive (372 ppm), tapes (2–360 ppm), oil-based ballpoint pen (201 ppm), duplex wallpaper (12–52 ppm), shoes (27 ppm), and air freshener (13 ppm). High levels of ethylbenzene were detected in permanent pen (ND–345,065 ppm), shoe polish (ND–277,928 ppm), leather cleaner (42,223 ppm), whiteout (ND–2,770 ppm), and glue (ND–792 ppm). Xylene was detected in permanent pen (ND–285,132 ppm), shoe polish (ND–87,298 ppm), leather cleaner (12,266 ppm), glue (ND–3,124 ppm), and whiteout (ND–1,400 ppm). Exposure assessment showed that the exposure to ethylbenzene from permanent pens ranged from 0 to 3.11 mg/kg/d (men) and 0 to 3.75 mg/kg/d (women), while for xylene, the exposure ranges were 0–2.57 mg/kg/d and 0–3.1 mg/kg/d in men and women, respectively. The exposure of women to benzene from whiteout ranged from 0 to 0.00059 mg/kg/d. Hazard index (HI), defined as a ratio of exposure to reference dose (RfD), for ethylbenzene was 31.1 (3.11 mg/kg/d/0.1 mg/kg/d) and for xylene (2.57 mg/kg/d/0.2 mg/kg/d) was 12.85, exceeding 1 for both compounds. Cancer risk for benzene was calculated to be 3.2 × 10−5 based on (0.00059 mg/kg/d × 0.055 mg/kg-d−1 , cancer potency factor), assuming that 100% of detected levels in some products such as permanent pens and whiteouts were exposed in a worst-case scenario. These data suggest that exposure to VOC via some consumer products exceeded the safe limits and needs to be reduced.
the major volatile organic compounds (VOC), and a number of investigators have raised the
Benzene, toluene, ethylbenzene, and xylene (BTEX) are considered to be among
Address correspondence to Dr. Byung-Mu Lee, Division of Toxicology, College of Pharmacy, Sungkyunkwan University, Seobu-ro 2066, Suwon, Gyeonggi-do, 440-746, South Korea. E-mail: [email protected] 1502
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issue of potential human hazard and risk of BTEX exposure (Kumar et al., 2014; Saxena and Ghosh, 2012; Schnatter et al., 2012; Tunsaringkarn et al., 2012) (Figure 1). The International Agency for Research on Cancer (IARC, 2014) categorized benzene as Group 1 (“Carcinogenic to humans”), ethylbenzene as Group 2B (“Possibly carcinogenic to humans”), and toluene and xylene as Group 3 (“Not classifiable as to its carcinogenicity to humans”). Exposure to benzene is widely recognized to increase the risk of cancers such as leukemia and hematopoietic cancers (Bond et al., 1986; Schnatter et al., 2012). BTEX induce irritation of the skin, eyes, and respiratory tract (Midzenski et al., 1992; Murata et al., 1993; Cometto-Muniz and Cain, 1995; Ahaghotu et al., 2005). The common adverse effect of BTEX is reported to be neurotoxicity, including drowsiness, headache, tremor, coma, and dizziness (Tunsaringkarn et al., 2012; Garte et al., 2008; Abbate et al., 1993; Ernstgard et al., 2002). Some studies also showed that the adverse effects of toluene include reproductive toxicity (Ono et al., 1996; Korbo et al., 1996). VOC are released from a number of sources in varying locales, and were detected at high levels in workplaces such as photocopy centers, petroleum depot stations, steel plants, sewage-processing plants, and automotive paint shops (Al Zabadi et al., 2008; Chang et al., 2010; Lee et al., 2006; Rezazadeh Azari et al., 2012; Rumchev et al., 2007; Vitali et al., 2006). Tobacco smoke is another key source of VOC exposure, with higher levels detected in sidestream than in mainstream smoke (Darrall et al., 1998; Fowles and Bates, 2000). Individuals spend most of their time indoors (Bruinen de Bruin et al., 2008) and a significant portion of human exposure to air pollutants, including VOC, occurs through indoor air (Rumchev et al., 2007; Katsoyiannis et al., 2008; Annesi-Maesano et al, 2013). In many cases, the levels of VOC indoors were higher than those outdoors because of low ventilation rates (Edward et al., 2001). Indoor air of elementary schools, stores, and restaurants has been reported to contain higher levels of
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Benzene
Toluene
Ethylbenzene
ortho-xylene
meta-xylene
para-xylene
FIGURE 1. Chemical structures ethylbenzene and xylene.
of
benzene,
toluene,
VOC than the outdoor air (Lof et al., 2009; Pegas et al., 2011; Annesi-Maesano et al 2013). The concentration of BTX was found to be higher indoors than outdoors (Schneider et al., 2001). VOC are used in a wide range of products, including building materials, paints, furniture, and personal products, which are major sources of VOC found indoors (Haghighat et al., 2002; Katsoyiannis et al., 2008; 2012; Nazaroffa and Weschler, 2004; Wang et al., 2007). Sack and Steele (1992) reported that sources of VOC among household products include automotive products, household cleaners/polishes, paint-related products, fabric and leather treatments, cleaners for electronic equipment, oils, greases, and lubricants, glue-related products, and miscellaneous other products. Toluene and xylene in particular were frequently found in household products. The Danish Environmental Protection Agency (DEPA) investigated the indoor concentrations of VOC, including BTX, released from consumer products, including carpets, textile fabrics, glues, electric products, toys, paints, and air fresheners (Jensen and Knudsen, 2006). The U.S. Consumer Product Safety Commission (CPSC) withdrew a regulation
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banning the use of benzene as an intentional ingredient in consumer products since it is not commonly used (Voluntary Children’s Chemical Evaluation Program [VCCEP], 2006a). The National Toxicology Program (NTP, 1994) reported that benzene remaining in consumer products did not lead to significant exposure. However, a precautionary statement was mandatorily placed on labels of products containing high BTEX levels (U.S. Environmental Protection Agency [EPA], 2013a, 2013b; Korean Agency for Technology and Standards [KATS], 2008a). Nonetheless, regulations exist regarding a number of products, including cosmetics, wet tissues, toy, and marking pens (European Commission [EC], 2006, 2011; Health Canada, 2011; Ministry of Food and Drug Safety [MFDS], 2013; KATS, 2008b, 2009a, 2012). While there are regulations proscribing BTEX in consumer products, few reports are available on exposure and risk associated with these items, with the exception of a recent demonstration of risk of benzene exposure from candles (Petry et al., 2013, 2014). The aim of this study was to therefore determine the concentrations of BTEX in various consumer products, including toys, shoes, air fresheners, glues, stationery, detergents, and wallpaper. In addition, an exposure and risk assessment for BTEX was performed.
METHODS Sampling In this study, 207 consumer products were obtained from the local market. Selected items included toys, shoes, shoe polish, leather cleaner, pencils, whiteout, marking pens, glues, tapes, air fresheners, insecticides, detergents, linoleums, and wallpapers. All of the products were categorized into 30 item types, and each item type comprised different brands of products. To prevent the loss of BTEX from the products owing to evaporation, all items were opened just prior to the gas chromatography/mass spectrometry (GC/MS) analysis.
Analysis of Benzene, Toluene, Ethylbenzene, and Xylene (BTEX) Levels Samples were analyzed in accordance with the analytical guidelines of Korea Standard (KS) M 1993:2009 (KATS, 2009b) and U.S. Environmental Protection Agency (EPA) Method 5021 (U.S. EPA, 1996). First, 0.1–1 g of each product was transferred into a headspace-sampling vial. An identical headspace vial was left empty as a gas blank. A headspace gas chromatograph/mass spectrometer (HS-GC/MS) instrument (Shimadzu GCMS-QP2010, Shimadzu, Japan) was used for the analysis of VOC levels in the headspace of the consumer products. A DB-624B column (60 m, 0.32 mm ID, 1.8 µm film thickness) supplied by J & W Scientific (Folsom, CA) was used for the separation of sample compounds. The headspace autosampler was used at an oven temperature of 150◦ C and sample equilibration time of 30 min. Following sample injection, the column oven was maintained at 50◦ C for 3min. After the initial isothermal step, the temperature was first increased to 250◦ C at 15◦ C/min increments. The mass spectrometer detector was operated in electron impact mode with ionization energy of 70eV and source temperature of 230◦ C, and in scan mode. Risk Calculation On the basis of published findings, benzene was classified as a human carcinogen (Group 1) and shown to produce chronic eosinophilic leukemia (Rinsky et al., 1981) and hepatocarcinoma (Maltoni et al., 1985). Ethylbenzene was classified as a possible carcinogenic agent (Group 2B), while toluene and xylene were not classified as human carcinogens (Group 3; IARC, 2014). Cancer risk for benzene was calculated using the following equation (U.S. EPA, 1995): Cancer risk = CDI × CPF
(1)
where CDI is the chronic daily intake (mg/kg/d), and CPF is the cancer potency factor (kg-d/mg).
RISK ASSESSMENT OF VOCs IN CONSUMER PRODUCTS
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Noncarcinogen risk is characterized in terms of a hazard index (HI). HI for toluene, ethylbenzene, and xylene is calculated using the following equation: HI =
CDI RfD
(2)
where RfD is the reference dose for the specific substance. Inhalation CDI (CDIi ) can be computed based on the following equation (U.S. EPA, 1995): CDIi =
C × CF × IR × EF × ED BW × AT (or LT)
where C is the contaminant concentration (µg/m3 ), CF is the conversion factor (mg/µg), IR is the inhalation rate (m3 /d), EF is the exposure frequency (d/yr), ED is the exposure duration (yr), BW is the body weight (kg), and AT or LT is the average time or the lifetime (d). Exposure via dermal absorption occurs when gas and liquid come into contact with the skin. Dermal CDI (CDIdl ) for liquid products used directly on the skin can be computed using the following equation (U.S. EPA, 1997): CDId =
C × CF × AF × SA × ABSs × EF × ED BW × AT (orLT)
where C is the contaminant concentration (mg/kg), CF is the conversion factor (mg/µg), AF is the skin adherence factor (mg/cm2 ), SA is the surface area (cm2 ), ABSs is skin absorption rate (%), EF is the exposure frequency (d/yr), ED is the exposure duration (yr), BW is the body weight (kg), and AT or LT is the average time or the lifetime (d). Dermal CDI (CDIdg ) via skin absorption of evaporation from products directly used on the skin can be computed using the following equation (U.S. EPA, 1997): CDIdg =
C × SA × CF × PC × ET × EF × ED BW × AT (or LT)
where C is the contaminant concentration (mg/kg), SA is the surface area (cm2 ), CFis the
conversion factor (10−6 m3 /cm3 ), SA is surface area (cm2 ), PC is the permeability constant (cm/h), ET is the exposure time (h/d), EF is the exposure frequency (d/yr), ED is the exposure duration (yr), BW is the body weight (kg), and AT or LT is the average time or the lifetime (d). Scenarios for Exposure by Inhalation BTEX Concentrations A number of assumptions were made for deriving the indoors air exposure by adjusting the BTEX concentrations detected in consumer products: (1) BTEX concentrations in some items such as pencil, shoes, linoleums, and wallpapers were assumed to be released steadily over 4 mo; (2) during use, some products like whiteouts, ballpoint pens, and marking pens were assumed to release BTEX, which are absorbed into the body via inhalation; (3) consumer products were assumed to be used in a room with a volume of 20 m3 ; (4) BTEX released from products such as linoleums, wallpapers, air fresheners, and insecticides were assumed to spread immediately throughout the room; and (5) total BTEX levels released from some products (including pencils and whiteout) were assumed to be inhaled under the worst-case scenario. Inhalation Rate and Absorption Rate Information on inhalation rates of adult Koreans were obtained from a Ministry of the Environment study (MOE, 2007), and inhalation rates of children are based on data from Layton (1993) and U.S. EPA (1997). The age categories used in this study (Table 1) were based on data from KATS (2004). Respiratory absorption rates of BTEX were assumed to be 50% for benzene, 50% for toluene, 60% for ethylbenzene, and 60% for xylene, respectively (U.S. EPA, 1999; Sabourin et al., 1987; Lof et al., 1993; Sedivec and Flek, 1976) (Table 2). Exposure Time, Duration, and Frequency Exposure duration and frequency were estimated on the basis of the use of products. Since BTEX is released constantly into the room over 4 mo from items such
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TABLE 1. Inhalation Rate, Body Weight, and the Average Time Spent at Home by Age for Koreans
Age (yr) 65 Ref.
∗ Value
Inhalation rate (m3 /h)
Body weight (kg)
Time spent at home (min)
Surface area of feet (cm2 )
Surface area of body (cm2 )
Men
Men
Men
Men
Men
Women
0.19 0.19 0.28 0.28 0.35 0.35 0.42 0.42 0.58 0.53 0.63 0.53 0.65 0.53 0.66 0.52 0.65 0.53 0.65 0.54 0.65 0.54 0.66 0.54 0.66 0.53 KATS, 2004; MOE, 2007; Layton, 1993; U.S. EPA, 1997
Women
8.2 7.4 — 12.06 11.3 — 16.9 16.3 — 24.9 23.6 891 36.4 34.1 891 51.1 47.5 815 63.4 53.5 706 68.5 53.98 827.6 70.82 54.97 674.9 71.84 57.05 659.9 69.6 59.21 686.9 67.56 59.64 762.6 64.3 57.15 987.9 Kostat, 2005; MOE, 2007
Women — — — 891 891 815 706 861.7 866.3 939.9 951.9 997.4 1,114
Women
392∗ 376∗ 6,030∗ 473 462 7,280 605 597 9,310 754 754 10,160 969 962 14,900 1137.5 1040 17,500 1,260 966 18,523 1,270 965 18,677 1,268 972 18,644 1,235 981 18,156 1,209 974 17,785 1,177∗∗ 944∗∗ 17,305∗∗ U.S. EPA, 1997; MOE, 2007
Women 57,90∗ 7,110 9,190 11,600 14,800 16,000 15,829 15,822 15,938 16,084 15,971 15,480∗∗
was determined for 2-year-old infants. was determined for people aged >65 and 1.0 × 10−6 ). For noncancer risk, toluene, ethylbenzene, and xylene were detected in 50, 22, and 20 of the studied consumer products, respectively. One of the products (oil-based marking pens) was found to impart increased risk (HI > 1). In our current study, BTEX were not detected in toys and detergents. Further, BTEX were not detected in all products within the same item type, suggesting that removing BTEX from consumer products is feasible. Despite the fact that BTEX were prohibited for use in marking pens in Korea (KATS, 2008a), BTEX were detected in some of the marking pens studied. Other products did not exceed the regulation limits of BTEX. Noncancer risk (HI) from ethylbenzene and xylene exposure resulting from the use of one permanent pen was associated with HI > 1. Cancer risk from benzene resulting from the use of whiteout also exceeded 1 × 10−6 . Some products analyzed in this study contained excessively high levels of BTEX. These values were calculated based on a worst-case scenario as a conservative method of estimating risk. Models for exposure and risk assessment indoors are needed (Kephalopoulos et al., 2007), and a number of models have been developed to estimate consumer exposure, including ConsExpo (Consumer Exposure Model: RIVM, 2013), E-FAST (Exposure and Fate Assessment), and MCCEM (Multi-Chamber Concentration and Exposure Model; U.S. EPA, 2013c). However, a comprehensive model of consumer exposure is yet to be generalized. In this study, equations described in U.S. EPA guidance were applied for exposure assessment (U.S. EPA, 1995, 1997). Exposure and risk assessment was calculated using exposure data available for Korean population. However, there is limited information of the exposure parameters specific for the Korean setting, and individual differences are present in the patterns of product use. A number of assumptions were used in our exposure assessment. Indoor
RISK ASSESSMENT OF VOCs IN CONSUMER PRODUCTS
exposure may occur through inhalation, ingestion, or absorption across the skin. A number of studies showed that VOC exposure occurs predominantly via inhalation. VOC exposure via the skin is relatively low compared to inhalation (Safe Work Australia [SWA], 2012). In agreement with these past findings, our study found that skin exposure is less than 1% of inhalation. Total exposure from the use of consumer products is therefore almost similar to inhalation. In cases of exposure by inhalation from nonsealed products, total BTEX concentrations of products were adjusted to represent their concentrations in air, which were subsequently used for calculating exposure. This approach assumes that BTEX released from the consumer product promptly diffuse throughout the total room air volume. In addition, this analysis assumes that nonsealed products constantly release BTEX into the air for 4 mo. BTEX emission patterns differ between different products (Ho et al., 2011), which may alter the exposure level per hour. However, if people regularly spend time indoors, levels of human exposure to BTEX would correspond to the amount of BTEX that is constantly released from the products. The emission pattern of VOC over time was studied from interior finishing materials, including furniture and building materials (Haghighat et al., 2002; Kim and Yoo, 2009; Ho et al., 2011). Ventilation rate affects indoor air quality, with reduced ventilation rate during winter possibly increasing indoor VOC levels (Edwards et al., 2001). Room ventilation rates were reported to vary between 0.5 and 2.5 ACH (Bremmer and van Veen, 2000; EC, 2003). The ventilation rate used in this study was 1.34 ACH, based on the findings of a study conducted in Korean homes (Bae et al., 2004). A number of other factors affect indoor air quality, including temperature, humidity, number of sources of VOC, rate of VOC release, surface area of the source material, and many others (Maroni et al., 1995; Spengler, 1995). Increasing effort was recently directed toward reducing exposure to VOC by adjusting these factors (Leung et al., 2005). The release rate of VOC may be elevated at air temperatures
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above the 23–26◦ C range (American Society of Heating, Refrigerating and Air-conditioning Engineers [ASHRAE], 2004). In this study, the effect of these factors on levels of BTEX was not considered. A number of studies examined the risk of VOC, including BTEX, present in the indoor air of different environments (Chang et al., 2010; Kumar et al., 2014; Guo et al., 2004; Kim et al., 2011; Colman Lerner et al., 2012). Lee et al. (2006) investigated the concentration of benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS) in seven photocopy centers in Taiwan and performed a risk assessment in workers. Data showed that HI of BTEXS ranged from 1.8 to 26.2, while the lifetime cancer risk from benzene exposure ranged from 2.5 × 10−3 to 8.5 × 10−5 . Levels of benzene and toluene in the air of gas stations were found to be in the 0.16–1.63 and 0.2–2.72 ppm ranges, respectively (Rezazadeh Azari et al., 2012). BTEX concentrations in automotive paint shops ranged from 0.4 to 53.1 ppb for benzene, 1.9 to 93.8 ppb for toluene, 0.4 to 23.8 ppb for ethylbenzene, and 1.2 to 75.0 ppb for xylene (Vitali et al., 2006). The Voluntary Children’s Chemical Evaluation Program (VCCEP, 2005, 2006b) predicted the concentrations of toluene and xylene resulting from residential use of metal parts degreasers, spray paint, and spray polish products. In cases that involve amounts typically used and open windows, 8-h timeweighted average (TWA) levels of toluene were 0.4 ppm for the degreasing metal parts scenario, 4.7 ppm (1 h usage time) for spray painting scenario, and 0.41 ppm for shoe polish spray scenario. The authors determined the 8-h TWA levels of xylene to be 0.42 ppm for a metal parts degreasing scenario, and 0.91 ppm (1 h usage time) for a spray painting scenario. In our current study, there is limited information available for assessing exposure to VOC from consumer products, especially in the Korean setting. Therefore, standardized guidelines on parameters for exposure assessment are needed to provide better exposure and risk assessment. It should be noted that
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exposure in indoors air usually occurs with a mixture of chemicals, but risk assessment carried out in this study was for individual chemicals, necessitating a further assessment of risk associated with combined and mixture exposure (Jensen and Knudsen, 2006; Scientific Committee on Health and Environmental Risks [SCHER], 2007). In the future, more data on the interactions between chemicals and toxicities of mixtures of compounds may be needed for a comprehensive risk assessment of consumer products (Meek et al., 2011; Billionnet et al., 2012). FUNDING This research was supported by a grant (10043831) from the Korean Agency for Technology and Standards (KATS) in 2011. REFERENCES Abbate, C., Giorgianni, C., Munaò, F., and Brecciaroli, R. 1993. Neurotoxicity induced by exposure to toluene. An electrophysiologic study. Int. Arch. Occup. Environ. Health 64: 389–392. Ahaghotu, E., Babu, R. J., Chaterjee, A., and Singh, M. 2005. Effect of methyl substitution of benzene in the percutaneous absorption and skin irritation in hairless rats. Toxicol. Lett. 159: 261–271. Al Zabadi, H., Ferrari, L., Laurent, A. M., Tiberguent, A., Paris, C., and Zmirou-Navier, D. 2008. Biomonitoring of complex occupational exposures to carcinogens: The case of sewage workers in Paris. BMC Cancer 8: 67. American Society of Heating, Refrigerating and Air-conditioning Engineers, Inc. 2004. Thermal environmental conditions of human occupancy. http://www.almasesepahan.com/ fh/download/ASHRAE_Thermal_Comfort_ Standard.pdf Annesi-Maesano, I., Baiz, N., Banerjee, S., Rudnai, P., and Rive, S. 2013. Indoor air quality and sources in schools and related health effects. J. Toxicol. Environ. Health B 16: 491–550.
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Lisbon in spring. Environ. Geochem. Health 33: 455–468. Petry, T., Cazelle, E., Lloyd, P., Mascarenhas, R., and Stijntjes, G. 2013. A standard method for measuring benzene and formaldehyde emissions from candles in emission test chambers for human health risk assessment purposes. Environ. Sci. Process Impacts 15: 1369–1382. Petry, T., Vitale, D., Joachim, F.J., Smith, B., Cruse, L., Mascarenhas, R., Schneider, S., and Singal, M. 2014. Human health risk evaluation of selected VOC, SVOC and particulate emissions from scented candles. Regul. Toxicol. Pharmacol. 69: 55–70. Rezazadeh Azari, M., Naghavi Konjin, Z., Zayeri, F., Salehpour, S., and Seyedi, M. D. 2012. Occupational exposure of petroleum depot workers to BTEX compounds. Int. J. Occup. Environ. Med. 3: 39–44. Rinsky, R. A., Young, R. J., and Smith, A. B. 1981. Leukemia in benzene workers. Am. J. Ind. Med. 2: 217–245. RIVM (National Institute for Public Health and the Environment). 2013. ConsExpo. http:// www.rivm.nl/en/Topics/Topics/C/ConsExpo Rumchev, K., Brown, H., and Spickett, J. 2007. Volatile organic compounds: Do they present a risk to our health? Rev. Environ. Health 22: 39–55. Sabourin, P. J., Chen, B. T., Lucier, G., Birnbaum, L. S., Fisher, E., and Henderson, R. F. 1987. Effect of dose on the absorption and excretion of [C14]benzene administered orally or by inhalation in rats and mice. Toxicol. Appl. Pharmacol. 87: 325–336. Sack, T. M., and Steele, D. H. 1992. A survey of household products for volatile organic compounds. Atmos. Environ. 26A: 1063–1070. Safe Work Australia. 2012. Guidance on the interpretation of workplace exposure standards for airborne contaminants. http://www. safeworkaustralia.gov.au/sites/SWA/about/ Publications/Documents/680/Guidance_ Interpretation_Workplace_Exposure_ Standards_Airborne_Contaminants%20. pdf Saxena, P., and Ghosh, C. 2012. A review of assessment of benzene, toluene,
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ethylbenzene and xylene (BTEX) concentration in urban atmosphere of Delhi. Int. J. Phys. Sci. 7: 850–860. Schnatter, A. R., Glass, D. C., Tang, G., Irons, R. D., and Rushton, L. 2012. Myelodysplastic syndrome and benzene exposure among petroleum workers: an international pooled analysis. J. Natl. Cancer Inst. 104: 1724–1737. Schneider, P., Gebefügi, I., Richter, K., Wölke, G. W., Schnelle, J., Wichmann, H. E., and Heinrich, J.: INGA Study Group. 2001. Indoor and outdoor BTX levels in German cities. Sci. Total Environ. 267: 41–51. Scientific Committee on Health and Environmental Risks. 2007. Opinion on risk assessment on indoor air quality. http:// ec.europa.eu/health/ph_risk/committees/ 04_scher/docs/scher_o_055.pdf Sedivec, V., and Flek, J. 1976. The absorption, metabolism, and excretion of xylenes in man. Int. Arch. Occup. Environ. Health 37: 205–217. Spengler, J. D. 1995. Indoor air quality— Innovation and technology. In Indoor air: An integrated approach, ed. L. Morawska, N. D. Bofinger, and M. Maroni, 1–33. Oxford, UK: Elsevier Science Ltd. Tunsaringkarn, T., Siriwong, W., Rungsiyothin, A., and Nopparatbundit, S. 2012. Occupational exposure of gasoline station workers to BTEX compounds in Bangkok, Thailand. Int. J. Occup. Environ. Med. 3: 117–125. U.S. Environmental Protection Agency. 1991. Indoor air facts no. 4, Sick building syndrome (EPA/402-F-94-004). Indoor Air Group, Research Triangle Park, NC. http://nepis.epa.gov/Exe/ZyNET.exe/000 002JA.TXT?ZyActionD=ZyDocument& Client=EPA&Index=1991+Thru+1994& Docs=&Query=&Time=&EndTime=& SearchMethod=1&TocRestrict=n&Toc= &TocEntry=&QField=&QFieldYear=& QFieldMonth=&QFieldDay=&IntQField Op=0&ExtQFieldOp=0&XmlQuery=& File=D%3A%5Czyfiles%5CIndex%20Data %5C91thru94%5CTxt%5C00000009%5 C000002JA.txt&User=ANONYMOUS
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RISK ASSESSMENT OF VOLATILE ORGANIC COMPOUNDS BENZENE, TOLUENE, ETHYLBENZENE, AND XYLENE (BTEX) IN CONSUMER PRODUCTS Seong Kwang Lim1, Han Seung Shin2, Kyung Sil Yoon3, Seung Jun Kwack4, Yoon Mi Um1, Ji Hyeon Hyeon1, Hyo Min Kwak1, Ji Yun Kim1, Tae Hyung Kim1, Yeon Joo Kim1, Tae Hyun Roh1, Duck Soo Lim1, Min Kyung Shin1, Seul Min Choi1, Hyung Sik Kim1, Byung-Mu Lee1 1 Division of Toxicology, College of Pharmacy, Sungkyunkwan University, Suwon, Gyeonggi-do, South Korea 2 Department of Food Science and Biotechnology and Institute of Lotus Functional Foods Ingredients, Dongguk University–Seoul, Seoul, South Korea 3 Lung Cancer Branch, Research Institute, National Cancer Center, Goyang, Gyeonggi-do, South Korea 4 Department of Biochemistry and Health Science, College of Natural Sciences, Changwon National University, Changwon, Gyeongnam, South Korea
Exposure and risk assessment was performed by evaluating levels of volatile organic compounds (VOC) benzene, toluene, ethylbenzene, and xylene (BTEX) in 207 consumer products. The products were categorized into 30 different items, consisting of products of different brands. Samples were analyzed for BTEX by headspace-gas chromatography/mass spectrometry (headspace-GC/MS) with limit of detection (LOD) of 1 ppm. BTEX were detected in 59 consumer products from 18 item types. Benzene was detected in whiteout (ranging from not detected [ND] to 3170 ppm), glue (1486 ppm), oil-based ballpoint pens (47 ppm), and permanent (marking) pens (2 ppm). Toluene was detected in a leather cleaning product (6071 ppm), glue (5078 ppm), whiteout (1130 ppm), self-adhesive wallpaper (15–1012 ppm), shoe polish (806 ppm), permanent pen (609 ppm), wig adhesive (372 ppm), tapes (2–360 ppm), oil-based ballpoint pen (201 ppm), duplex wallpaper (12–52 ppm), shoes (27 ppm), and air freshener (13 ppm). High levels of ethylbenzene were detected in permanent pen (ND–345,065 ppm), shoe polish (ND–277,928 ppm), leather cleaner (42,223 ppm), whiteout (ND–2,770 ppm), and glue (ND–792 ppm). Xylene was detected in permanent pen (ND–285,132 ppm), shoe polish (ND–87,298 ppm), leather cleaner (12,266 ppm), glue (ND–3,124 ppm), and whiteout (ND–1,400 ppm). Exposure assessment showed that the exposure to ethylbenzene from permanent pens ranged from 0 to 3.11 mg/kg/d (men) and 0 to 3.75 mg/kg/d (women), while for xylene, the exposure ranges were 0–2.57 mg/kg/d and 0–3.1 mg/kg/d in men and women, respectively. The exposure of women to benzene from whiteout ranged from 0 to 0.00059 mg/kg/d. Hazard index (HI), defined as a ratio of exposure to reference dose (RfD), for ethylbenzene was 31.1 (3.11 mg/kg/d/0.1 mg/kg/d) and for xylene (2.57 mg/kg/d/0.2 mg/kg/d) was 12.85, exceeding 1 for both compounds. Cancer risk for benzene was calculated to be 3.2 × 10−5 based on (0.00059 mg/kg/d × 0.055 mg/kg-d−1 , cancer potency factor), assuming that 100% of detected levels in some products such as permanent pens and whiteouts were exposed in a worst-case scenario. These data suggest that exposure to VOC via some consumer products exceeded the safe limits and needs to be reduced.
the major volatile organic compounds (VOC), and a number of investigators have raised the
Benzene, toluene, ethylbenzene, and xylene (BTEX) are considered to be among
Address correspondence to Dr. Byung-Mu Lee, Division of Toxicology, College of Pharmacy, Sungkyunkwan University, Seobu-ro 2066, Suwon, Gyeonggi-do, 440-746, South Korea. E-mail: [email protected] 1502
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issue of potential human hazard and risk of BTEX exposure (Kumar et al., 2014; Saxena and Ghosh, 2012; Schnatter et al., 2012; Tunsaringkarn et al., 2012) (Figure 1). The International Agency for Research on Cancer (IARC, 2014) categorized benzene as Group 1 (“Carcinogenic to humans”), ethylbenzene as Group 2B (“Possibly carcinogenic to humans”), and toluene and xylene as Group 3 (“Not classifiable as to its carcinogenicity to humans”). Exposure to benzene is widely recognized to increase the risk of cancers such as leukemia and hematopoietic cancers (Bond et al., 1986; Schnatter et al., 2012). BTEX induce irritation of the skin, eyes, and respiratory tract (Midzenski et al., 1992; Murata et al., 1993; Cometto-Muniz and Cain, 1995; Ahaghotu et al., 2005). The common adverse effect of BTEX is reported to be neurotoxicity, including drowsiness, headache, tremor, coma, and dizziness (Tunsaringkarn et al., 2012; Garte et al., 2008; Abbate et al., 1993; Ernstgard et al., 2002). Some studies also showed that the adverse effects of toluene include reproductive toxicity (Ono et al., 1996; Korbo et al., 1996). VOC are released from a number of sources in varying locales, and were detected at high levels in workplaces such as photocopy centers, petroleum depot stations, steel plants, sewage-processing plants, and automotive paint shops (Al Zabadi et al., 2008; Chang et al., 2010; Lee et al., 2006; Rezazadeh Azari et al., 2012; Rumchev et al., 2007; Vitali et al., 2006). Tobacco smoke is another key source of VOC exposure, with higher levels detected in sidestream than in mainstream smoke (Darrall et al., 1998; Fowles and Bates, 2000). Individuals spend most of their time indoors (Bruinen de Bruin et al., 2008) and a significant portion of human exposure to air pollutants, including VOC, occurs through indoor air (Rumchev et al., 2007; Katsoyiannis et al., 2008; Annesi-Maesano et al, 2013). In many cases, the levels of VOC indoors were higher than those outdoors because of low ventilation rates (Edward et al., 2001). Indoor air of elementary schools, stores, and restaurants has been reported to contain higher levels of
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Benzene
Toluene
Ethylbenzene
ortho-xylene
meta-xylene
para-xylene
FIGURE 1. Chemical structures ethylbenzene and xylene.
of
benzene,
toluene,
VOC than the outdoor air (Lof et al., 2009; Pegas et al., 2011; Annesi-Maesano et al 2013). The concentration of BTX was found to be higher indoors than outdoors (Schneider et al., 2001). VOC are used in a wide range of products, including building materials, paints, furniture, and personal products, which are major sources of VOC found indoors (Haghighat et al., 2002; Katsoyiannis et al., 2008; 2012; Nazaroffa and Weschler, 2004; Wang et al., 2007). Sack and Steele (1992) reported that sources of VOC among household products include automotive products, household cleaners/polishes, paint-related products, fabric and leather treatments, cleaners for electronic equipment, oils, greases, and lubricants, glue-related products, and miscellaneous other products. Toluene and xylene in particular were frequently found in household products. The Danish Environmental Protection Agency (DEPA) investigated the indoor concentrations of VOC, including BTX, released from consumer products, including carpets, textile fabrics, glues, electric products, toys, paints, and air fresheners (Jensen and Knudsen, 2006). The U.S. Consumer Product Safety Commission (CPSC) withdrew a regulation
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banning the use of benzene as an intentional ingredient in consumer products since it is not commonly used (Voluntary Children’s Chemical Evaluation Program [VCCEP], 2006a). The National Toxicology Program (NTP, 1994) reported that benzene remaining in consumer products did not lead to significant exposure. However, a precautionary statement was mandatorily placed on labels of products containing high BTEX levels (U.S. Environmental Protection Agency [EPA], 2013a, 2013b; Korean Agency for Technology and Standards [KATS], 2008a). Nonetheless, regulations exist regarding a number of products, including cosmetics, wet tissues, toy, and marking pens (European Commission [EC], 2006, 2011; Health Canada, 2011; Ministry of Food and Drug Safety [MFDS], 2013; KATS, 2008b, 2009a, 2012). While there are regulations proscribing BTEX in consumer products, few reports are available on exposure and risk associated with these items, with the exception of a recent demonstration of risk of benzene exposure from candles (Petry et al., 2013, 2014). The aim of this study was to therefore determine the concentrations of BTEX in various consumer products, including toys, shoes, air fresheners, glues, stationery, detergents, and wallpaper. In addition, an exposure and risk assessment for BTEX was performed.
METHODS Sampling In this study, 207 consumer products were obtained from the local market. Selected items included toys, shoes, shoe polish, leather cleaner, pencils, whiteout, marking pens, glues, tapes, air fresheners, insecticides, detergents, linoleums, and wallpapers. All of the products were categorized into 30 item types, and each item type comprised different brands of products. To prevent the loss of BTEX from the products owing to evaporation, all items were opened just prior to the gas chromatography/mass spectrometry (GC/MS) analysis.
Analysis of Benzene, Toluene, Ethylbenzene, and Xylene (BTEX) Levels Samples were analyzed in accordance with the analytical guidelines of Korea Standard (KS) M 1993:2009 (KATS, 2009b) and U.S. Environmental Protection Agency (EPA) Method 5021 (U.S. EPA, 1996). First, 0.1–1 g of each product was transferred into a headspace-sampling vial. An identical headspace vial was left empty as a gas blank. A headspace gas chromatograph/mass spectrometer (HS-GC/MS) instrument (Shimadzu GCMS-QP2010, Shimadzu, Japan) was used for the analysis of VOC levels in the headspace of the consumer products. A DB-624B column (60 m, 0.32 mm ID, 1.8 µm film thickness) supplied by J & W Scientific (Folsom, CA) was used for the separation of sample compounds. The headspace autosampler was used at an oven temperature of 150◦ C and sample equilibration time of 30 min. Following sample injection, the column oven was maintained at 50◦ C for 3min. After the initial isothermal step, the temperature was first increased to 250◦ C at 15◦ C/min increments. The mass spectrometer detector was operated in electron impact mode with ionization energy of 70eV and source temperature of 230◦ C, and in scan mode. Risk Calculation On the basis of published findings, benzene was classified as a human carcinogen (Group 1) and shown to produce chronic eosinophilic leukemia (Rinsky et al., 1981) and hepatocarcinoma (Maltoni et al., 1985). Ethylbenzene was classified as a possible carcinogenic agent (Group 2B), while toluene and xylene were not classified as human carcinogens (Group 3; IARC, 2014). Cancer risk for benzene was calculated using the following equation (U.S. EPA, 1995): Cancer risk = CDI × CPF
(1)
where CDI is the chronic daily intake (mg/kg/d), and CPF is the cancer potency factor (kg-d/mg).
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Noncarcinogen risk is characterized in terms of a hazard index (HI). HI for toluene, ethylbenzene, and xylene is calculated using the following equation: HI =
CDI RfD
(2)
where RfD is the reference dose for the specific substance. Inhalation CDI (CDIi ) can be computed based on the following equation (U.S. EPA, 1995): CDIi =
C × CF × IR × EF × ED BW × AT (or LT)
where C is the contaminant concentration (µg/m3 ), CF is the conversion factor (mg/µg), IR is the inhalation rate (m3 /d), EF is the exposure frequency (d/yr), ED is the exposure duration (yr), BW is the body weight (kg), and AT or LT is the average time or the lifetime (d). Exposure via dermal absorption occurs when gas and liquid come into contact with the skin. Dermal CDI (CDIdl ) for liquid products used directly on the skin can be computed using the following equation (U.S. EPA, 1997): CDId =
C × CF × AF × SA × ABSs × EF × ED BW × AT (orLT)
where C is the contaminant concentration (mg/kg), CF is the conversion factor (mg/µg), AF is the skin adherence factor (mg/cm2 ), SA is the surface area (cm2 ), ABSs is skin absorption rate (%), EF is the exposure frequency (d/yr), ED is the exposure duration (yr), BW is the body weight (kg), and AT or LT is the average time or the lifetime (d). Dermal CDI (CDIdg ) via skin absorption of evaporation from products directly used on the skin can be computed using the following equation (U.S. EPA, 1997): CDIdg =
C × SA × CF × PC × ET × EF × ED BW × AT (or LT)
where C is the contaminant concentration (mg/kg), SA is the surface area (cm2 ), CFis the
conversion factor (10−6 m3 /cm3 ), SA is surface area (cm2 ), PC is the permeability constant (cm/h), ET is the exposure time (h/d), EF is the exposure frequency (d/yr), ED is the exposure duration (yr), BW is the body weight (kg), and AT or LT is the average time or the lifetime (d). Scenarios for Exposure by Inhalation BTEX Concentrations A number of assumptions were made for deriving the indoors air exposure by adjusting the BTEX concentrations detected in consumer products: (1) BTEX concentrations in some items such as pencil, shoes, linoleums, and wallpapers were assumed to be released steadily over 4 mo; (2) during use, some products like whiteouts, ballpoint pens, and marking pens were assumed to release BTEX, which are absorbed into the body via inhalation; (3) consumer products were assumed to be used in a room with a volume of 20 m3 ; (4) BTEX released from products such as linoleums, wallpapers, air fresheners, and insecticides were assumed to spread immediately throughout the room; and (5) total BTEX levels released from some products (including pencils and whiteout) were assumed to be inhaled under the worst-case scenario. Inhalation Rate and Absorption Rate Information on inhalation rates of adult Koreans were obtained from a Ministry of the Environment study (MOE, 2007), and inhalation rates of children are based on data from Layton (1993) and U.S. EPA (1997). The age categories used in this study (Table 1) were based on data from KATS (2004). Respiratory absorption rates of BTEX were assumed to be 50% for benzene, 50% for toluene, 60% for ethylbenzene, and 60% for xylene, respectively (U.S. EPA, 1999; Sabourin et al., 1987; Lof et al., 1993; Sedivec and Flek, 1976) (Table 2). Exposure Time, Duration, and Frequency Exposure duration and frequency were estimated on the basis of the use of products. Since BTEX is released constantly into the room over 4 mo from items such
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TABLE 1. Inhalation Rate, Body Weight, and the Average Time Spent at Home by Age for Koreans
Age (yr) 65 Ref.
∗ Value
Inhalation rate (m3 /h)
Body weight (kg)
Time spent at home (min)
Surface area of feet (cm2 )
Surface area of body (cm2 )
Men
Men
Men
Men
Men
Women
0.19 0.19 0.28 0.28 0.35 0.35 0.42 0.42 0.58 0.53 0.63 0.53 0.65 0.53 0.66 0.52 0.65 0.53 0.65 0.54 0.65 0.54 0.66 0.54 0.66 0.53 KATS, 2004; MOE, 2007; Layton, 1993; U.S. EPA, 1997
Women
8.2 7.4 — 12.06 11.3 — 16.9 16.3 — 24.9 23.6 891 36.4 34.1 891 51.1 47.5 815 63.4 53.5 706 68.5 53.98 827.6 70.82 54.97 674.9 71.84 57.05 659.9 69.6 59.21 686.9 67.56 59.64 762.6 64.3 57.15 987.9 Kostat, 2005; MOE, 2007
Women — — — 891 891 815 706 861.7 866.3 939.9 951.9 997.4 1,114
Women
392∗ 376∗ 6,030∗ 473 462 7,280 605 597 9,310 754 754 10,160 969 962 14,900 1137.5 1040 17,500 1,260 966 18,523 1,270 965 18,677 1,268 972 18,644 1,235 981 18,156 1,209 974 17,785 1,177∗∗ 944∗∗ 17,305∗∗ U.S. EPA, 1997; MOE, 2007
Women 57,90∗ 7,110 9,190 11,600 14,800 16,000 15,829 15,822 15,938 16,084 15,971 15,480∗∗
was determined for 2-year-old infants. was determined for people aged >65 and 1.0 × 10−6 ). For noncancer risk, toluene, ethylbenzene, and xylene were detected in 50, 22, and 20 of the studied consumer products, respectively. One of the products (oil-based marking pens) was found to impart increased risk (HI > 1). In our current study, BTEX were not detected in toys and detergents. Further, BTEX were not detected in all products within the same item type, suggesting that removing BTEX from consumer products is feasible. Despite the fact that BTEX were prohibited for use in marking pens in Korea (KATS, 2008a), BTEX were detected in some of the marking pens studied. Other products did not exceed the regulation limits of BTEX. Noncancer risk (HI) from ethylbenzene and xylene exposure resulting from the use of one permanent pen was associated with HI > 1. Cancer risk from benzene resulting from the use of whiteout also exceeded 1 × 10−6 . Some products analyzed in this study contained excessively high levels of BTEX. These values were calculated based on a worst-case scenario as a conservative method of estimating risk. Models for exposure and risk assessment indoors are needed (Kephalopoulos et al., 2007), and a number of models have been developed to estimate consumer exposure, including ConsExpo (Consumer Exposure Model: RIVM, 2013), E-FAST (Exposure and Fate Assessment), and MCCEM (Multi-Chamber Concentration and Exposure Model; U.S. EPA, 2013c). However, a comprehensive model of consumer exposure is yet to be generalized. In this study, equations described in U.S. EPA guidance were applied for exposure assessment (U.S. EPA, 1995, 1997). Exposure and risk assessment was calculated using exposure data available for Korean population. However, there is limited information of the exposure parameters specific for the Korean setting, and individual differences are present in the patterns of product use. A number of assumptions were used in our exposure assessment. Indoor
RISK ASSESSMENT OF VOCs IN CONSUMER PRODUCTS
exposure may occur through inhalation, ingestion, or absorption across the skin. A number of studies showed that VOC exposure occurs predominantly via inhalation. VOC exposure via the skin is relatively low compared to inhalation (Safe Work Australia [SWA], 2012). In agreement with these past findings, our study found that skin exposure is less than 1% of inhalation. Total exposure from the use of consumer products is therefore almost similar to inhalation. In cases of exposure by inhalation from nonsealed products, total BTEX concentrations of products were adjusted to represent their concentrations in air, which were subsequently used for calculating exposure. This approach assumes that BTEX released from the consumer product promptly diffuse throughout the total room air volume. In addition, this analysis assumes that nonsealed products constantly release BTEX into the air for 4 mo. BTEX emission patterns differ between different products (Ho et al., 2011), which may alter the exposure level per hour. However, if people regularly spend time indoors, levels of human exposure to BTEX would correspond to the amount of BTEX that is constantly released from the products. The emission pattern of VOC over time was studied from interior finishing materials, including furniture and building materials (Haghighat et al., 2002; Kim and Yoo, 2009; Ho et al., 2011). Ventilation rate affects indoor air quality, with reduced ventilation rate during winter possibly increasing indoor VOC levels (Edwards et al., 2001). Room ventilation rates were reported to vary between 0.5 and 2.5 ACH (Bremmer and van Veen, 2000; EC, 2003). The ventilation rate used in this study was 1.34 ACH, based on the findings of a study conducted in Korean homes (Bae et al., 2004). A number of other factors affect indoor air quality, including temperature, humidity, number of sources of VOC, rate of VOC release, surface area of the source material, and many others (Maroni et al., 1995; Spengler, 1995). Increasing effort was recently directed toward reducing exposure to VOC by adjusting these factors (Leung et al., 2005). The release rate of VOC may be elevated at air temperatures
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above the 23–26◦ C range (American Society of Heating, Refrigerating and Air-conditioning Engineers [ASHRAE], 2004). In this study, the effect of these factors on levels of BTEX was not considered. A number of studies examined the risk of VOC, including BTEX, present in the indoor air of different environments (Chang et al., 2010; Kumar et al., 2014; Guo et al., 2004; Kim et al., 2011; Colman Lerner et al., 2012). Lee et al. (2006) investigated the concentration of benzene, toluene, ethylbenzene, xylene, and styrene (BTEXS) in seven photocopy centers in Taiwan and performed a risk assessment in workers. Data showed that HI of BTEXS ranged from 1.8 to 26.2, while the lifetime cancer risk from benzene exposure ranged from 2.5 × 10−3 to 8.5 × 10−5 . Levels of benzene and toluene in the air of gas stations were found to be in the 0.16–1.63 and 0.2–2.72 ppm ranges, respectively (Rezazadeh Azari et al., 2012). BTEX concentrations in automotive paint shops ranged from 0.4 to 53.1 ppb for benzene, 1.9 to 93.8 ppb for toluene, 0.4 to 23.8 ppb for ethylbenzene, and 1.2 to 75.0 ppb for xylene (Vitali et al., 2006). The Voluntary Children’s Chemical Evaluation Program (VCCEP, 2005, 2006b) predicted the concentrations of toluene and xylene resulting from residential use of metal parts degreasers, spray paint, and spray polish products. In cases that involve amounts typically used and open windows, 8-h timeweighted average (TWA) levels of toluene were 0.4 ppm for the degreasing metal parts scenario, 4.7 ppm (1 h usage time) for spray painting scenario, and 0.41 ppm for shoe polish spray scenario. The authors determined the 8-h TWA levels of xylene to be 0.42 ppm for a metal parts degreasing scenario, and 0.91 ppm (1 h usage time) for a spray painting scenario. In our current study, there is limited information available for assessing exposure to VOC from consumer products, especially in the Korean setting. Therefore, standardized guidelines on parameters for exposure assessment are needed to provide better exposure and risk assessment. It should be noted that
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exposure in indoors air usually occurs with a mixture of chemicals, but risk assessment carried out in this study was for individual chemicals, necessitating a further assessment of risk associated with combined and mixture exposure (Jensen and Knudsen, 2006; Scientific Committee on Health and Environmental Risks [SCHER], 2007). In the future, more data on the interactions between chemicals and toxicities of mixtures of compounds may be needed for a comprehensive risk assessment of consumer products (Meek et al., 2011; Billionnet et al., 2012). FUNDING This research was supported by a grant (10043831) from the Korean Agency for Technology and Standards (KATS) in 2011. REFERENCES Abbate, C., Giorgianni, C., Munaò, F., and Brecciaroli, R. 1993. Neurotoxicity induced by exposure to toluene. An electrophysiologic study. Int. Arch. Occup. Environ. Health 64: 389–392. Ahaghotu, E., Babu, R. J., Chaterjee, A., and Singh, M. 2005. Effect of methyl substitution of benzene in the percutaneous absorption and skin irritation in hairless rats. Toxicol. Lett. 159: 261–271. Al Zabadi, H., Ferrari, L., Laurent, A. M., Tiberguent, A., Paris, C., and Zmirou-Navier, D. 2008. Biomonitoring of complex occupational exposures to carcinogens: The case of sewage workers in Paris. BMC Cancer 8: 67. American Society of Heating, Refrigerating and Air-conditioning Engineers, Inc. 2004. Thermal environmental conditions of human occupancy. http://www.almasesepahan.com/ fh/download/ASHRAE_Thermal_Comfort_ Standard.pdf Annesi-Maesano, I., Baiz, N., Banerjee, S., Rudnai, P., and Rive, S. 2013. Indoor air quality and sources in schools and related health effects. J. Toxicol. Environ. Health B 16: 491–550.
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