Occurrence and human exposure assessment of short- and medium

Publication Date (Web): December 6, 2018 ... paraffins (SCCPs and MCCPs) in 159 dust samples from plastic sports courts and synthetic turf in Beijing,...
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Ecotoxicology and Human Environmental Health

Occurrence and human exposure assessment of shortand medium-chain chlorinated paraffins in dusts from plastic sports courts and synthetic turf in Beijing, China Dandan Cao, Wei Gao, Jing Wu, Kun Lv, shanzhi xin, Yawei Wang, and Guibin Jiang Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b04323 • Publication Date (Web): 06 Dec 2018 Downloaded from http://pubs.acs.org on December 7, 2018

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Environmental Science & Technology

Occurrence and human exposure assessment of short- and medium-chain chlorinated paraffins in dusts from plastic sports courts and synthetic turf in Beijing, China

Dandan Cao,† Wei Gao,† Jing Wu,† Kun Lv,

†,‡

Shanzhi Xin,† Yawei Wang,*,†,

§, 

Guibin Jiang†

†State

Key Laboratory of Environmental Chemistry and Ecotoxicology, Research

Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China ‡Shandong §Institute 

University, Jinan, 250100, China

of Environment and Health, Jianghan University, Wuhan 430056, China

University of Chinese Academy of Sciences, Beijing 100049, China

*Corresponding authors Yawei Wang: Tel: +86-10-62840620; e-mail: [email protected].

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ABSTRACT

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This study presents the first investigation of concentrations and congener group

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patterns of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) in

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159 dust samples from plastic sports courts and synthetic turf in Beijing, China. The

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geometric mean concentration of SCCPs and MCCPs in dusts from plastic tracks

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(5429 and 15157 μg g–1) and basketball courts (5139 and 11878 μg g–1) were

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significantly higher than those from plastic tennis courts, badminton courts, and

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synthetic turf, meanwhile they were 1–3 orders of magnitude higher than those in

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dusts from other indoor environments. The friction between sneaker soles and plastic

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track materials may lead to the wear and decomposition of rubber, which may be an

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important source of chlorinated paraffins (CPs) in the dust from plastic tracks. The

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mean estimated daily intakes of CPs from plastic tracks and basketball courts are

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generally higher than those estimated from dietary, breast milk, or other indoor dust

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sources. The margin of exposure for adults and children was greater than 1000 both at

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mean and high exposure scenarios, indicating that no significant health risks were

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posed by CPs in the dust from plastic sports courts and synthetic turf.

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■ INTRODUCTION

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Over the past decades, plastic sports courts and synthetic turf have been increasingly

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used in sports facilities.1, 2 Plastic sports courts and synthetic turf offer the advantages

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of shock absorption, energy restitution, vertical deformation, slide and slip resistance,

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and wear resistance, as well as significantly reducing the likelihood of athletic

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injuries.1 The use of recycled scrap tire rubber crumbs in plastic sports courts and

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synthetic turf leads to a range of organic contaminants (e.g., polycyclic aromatic

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hydrocarbons,3–6 benzothiazole7) and heavy metals (e.g., Pb8, 9) being present in these

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materials. Furthermore, due to flame- and aging-resistant requirements as well as for

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performance enhancement, plasticizers, flame retardants, anti-oxidants, and UV-filters

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are intentionally added during the production of plastic sports court and synthetic turf

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materials. Given the specific weather conditions that plastic sports courts and

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synthetic turf materials face, including abrasion, high temperatures (up to 60 C at

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noon10), sunlight irradiation, freezing and thawing cycles, and wetting and drying

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cycles,1 the environmental release of these contaminants is inevitable.

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Chlorinated paraffins (CPs), a group of synthetic organic chemicals consisting of

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n-alkanes with varying degrees of chlorination, are used worldwide as

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high-temperature lubricants, sealants, flame retardants, plasticizers, and metal cutting

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fluids.11 Comparably, short- (C10–C13), or medium-chain (C14–C17) CPs (SCCPs or

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MCCPs, respectively) are believed to be more toxic to organisms than long-chain

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CPs.12 SCCPs are particularly persistent in the environment,13 subject to long-range

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transport,14 and have the potential for bioaccumulation and biomagnification in food

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webs.15, 16 Therefore, the production and use of SCCPs have been severely restricted

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or banned by the US Environmental Protection Agency and the European Union.17

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SCCPs have been listed as a new persistent organic pollutant under the Stockholm

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Convention in May 2017.18 SCCPs entered into the priority control list of chemicals

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in China since December 2017.19 China is currently the largest producer of CP

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products worldwide,20 and therefore assessments on the occurrence and health risks of

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CPs are receiving increased attention.

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To date, no report is available on the occurrence and human exposure assessment

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of SCCPs and MCCPs in the environment surrounding plastic sports courts and

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synthetic turf despite knowledge of intentional CP addition into polyurethane sports

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court materials as flame retardants and plasticizers.21 Herein, we analyzed 159 dust

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samples from outdoor and indoor plastic sports courts and synthetic turf from 17

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locations in Beijing to evaluate the occurrence, congener group profile, and human

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exposure level of SCCPs and MCCPs in these sampling matrices. Further, we

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assessed the possible risk of exposure of SCCPs and MCCPs for the general

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population.

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■EXPERIMENTAL SECTION

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Sample collection. A total of 148 settled dust samples from outdoor plastic sports

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courts (plastic track, plastic basketball court, and plastic tennis court) and synthetic

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turf from 17 universities in Beijing were collected in February (winter) and August

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(summer) 2015. Additionally, 11 dust samples were collected from indoor plastic

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badminton courts randomly selected from the 17 universities during the winter. To

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explore the source of CPs in the dust from the plastic tracks, five plastic track material

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samples and five pairs of sneaker soles were also collected. To probe the release of

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CPs from plastic tracks to the surrounding environment, three plastic tracks were

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randomly selected and road dust samples from the area surrounding each of the three

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plastic tracks, at distances of ~3 m and ~50 m, were collected. A vacuum cleaner (see

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Supplemental Information) was used to sample the settled dust on the surface of

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plastic sports courts, synthetic turf, and roads. Plant material and other debris were

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removed and the dust samples were then passed through a 0.45 mm stainless steel

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screen, packed in aluminum foil, and stored in the refrigerator at –20 °C before

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sample pretreatment and analysis.

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Instrumental and quantitative analysis. The instrumental analysis and quantitative

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method used herein have been described in previous work.22, 23 Briefly, identification

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and quantification of the target analytes were performed on an Agilent gas

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chromatograph tandem quadrupole time of flight mass spectrometer (Agilent

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Technologies, Santa Clara, USA) operating in negative chemical ionization mode and

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controlled by Mass Hunter Acquisition B.07.1. The accurate mass information of

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[M-Cl]– ions of SCCPs and MCCPs were summarized in Table S1. The standard

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curves for quantification of SCCPs and MCCPs were provided in Figure S1.

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Quality assurance and quality control. Three procedural blanks (consisting of only

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diatomaceous earth) were run for every batch of 7–9 samples. Field blanks were

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processed in the same way as dust sample collection using a vacuum cleaner to suck

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baked anhydrous sodium sulfate. CP concentrations in both the procedural blanks and

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field blanks comprised less than 5% of those concentrations in dust samples.

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13C

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to each sample pretreatment. ε-HCH was added to each vial prior to instrumental

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analysis to assess the stability of the response of the instrument and the recoveries of

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the surrogate. The recoveries of surrogate standards in all of samples ranged from

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78% to 133%. The background concentrations of CPs measured in the procedural and

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field blanks were not subtracted from the levels measured in all the samples nor were

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they adjusted by the surrogate recoveries. Method detection limits of SCCPs were

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calculated as three times the standard deviation of the procedural blanks plus the

10-1,5,5,6,6,10-hexachlorodecane

was used as a surrogate standard and added prior

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procedural blanks. The MCCPs in the procedural blanks were lower than the

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instrument detection limits, and therefore the method detection limits of MCCPs were

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replaced by the instrument detection limits. Method detection limits for samples with

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varying SCCP and MCCP concentrations are summarized in Table S2.

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Assessment of estimated daily intake (EDI) and margin of exposure. The EDI of

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CPs for children and adults in plastic sports courts and synthetic turf through dust

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ingestion, dermal absorption, and inhalation was calculated using the following

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equations:

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EDIingestion = Cdust × IRdust ingestion × T/BW

(1)

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EDIdermal absorption = Cdust × BSA × AS × AF × T/BW

(2)

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EDIinhalation = Cair × IRinhalation × T/BW

(3)

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Where Cdust is the concentration of CPs in the dust samples; IRdust

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ingestion rate of dust from plastic sports courts and synthetic turf in outdoor and

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indoor environments; IRinhalation is the inhalation rate; T is the average daily time spent

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in outdoor or indoor plastic sports court or synthetic turf environments; AS is the

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amount of skin-adhered dust; AF is the dermal absorption factor of CPs. Herein the

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value of 0.14 was used as AF to estimate the dermal absorption of CPs according to

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the previous studies22, 24, 25; BSA is the body surface area; and BW is the body weight.

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Reference values for exposure factors in equations (1), (2), and (3) were summarized

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in Table S3.

ingestion

is the

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The margin of exposure (MOE)26 was used to assess the severity of possible

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health risks posed by CPs in the dust from plastic sports courts and synthetic turf.

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MOE was defined as follows:

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MOE = NOAEL/EDI

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Where the NOAEL (no observed adverse effect level) values of SCCPs and MCCPs

(4)

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are 100 mg kg–1 day–1 and 23 mg kg–1 day–1, respectively, as stated in the European

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Union Risk Assessment Report.27, 28

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Statistical analysis. SPSS version 18.0 (SPSS Inc.) and Microsoft Excel (2010) were

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used for statistical analysis. Statistical significance and seasonal difference were

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tested by one-way analysis of variance and t-test, respectively, and the difference was

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considered statistically significant at the level of p < 0.05. The logarithm

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concentrations of SCCPs and MCCPs followed a normal distribution and were used

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for one-way analysis of variance and t-test. To compare and distinguish the

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distribution of congener group profiles of SCCPs and MCCPs in sample groups of

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different origin, a principal component analysis was conducted to project the

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percentage of SCCP and MCCP congener groups in two dimensions.

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■RESULTS AND DISCUSSION

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SCCPs and MCCPs in dusts from plastic sports court and synthetic turf. The

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SCCP and MCCP concentrations in the 148 outdoor dust samples from plastic sports

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courts and synthetic turf as well as in the 11 indoor dust samples from a plastic

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badminton court are shown in Table S4 and Figure 1. The geometric mean (GM)

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SCCP concentration in dusts retrieved from plastic track, basketball court, tennis

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court, and synthetic turf were 5429, 5139, 298, and 101 μg g–1, respectively, and the

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GM MCCP concentrations were 15157, 11878, 529, and 241 μg g–1, respectively. The

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one-way analysis of variance for the concentration of CPs in the collected dust

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samples suggested that the SCCP and MCCP concentrations in dusts retrieved from

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plastic tracks and basketball courts were significantly higher than those in tennis court

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and synthetic turf samples (p < 0.05). In addition, the difference between the

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concentration in plastic tennis courts and synthetic turf was also significant (p < 0.05).

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The GM SCCP and MCCP concentrations in the dusts from indoor badminton courts

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were 1467 and 1836 μg g–1, respectively, which were significantly higher than those

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in plastic tennis court and synthetic turf samples, but significantly lower than those in

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plastic track and basketball court samples (p < 0.05) (Figure 1). Thus, the highest CP

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concentrations were found in dusts retrieved from plastic tracks, followed by those

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from basketball courts, indoor plastic badminton courts, tennis courts, and finally

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synthetic turf. Generally, the main materials used in plastic track, basketball court,

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tennis court, and indoor badminton court manufacturing are polyurethane,

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polyurethane and ethylene propylene diene monomer, acrylic coating, and polyvinyl

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chloride,

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polyethylene/nylon, and the filling materials are mainly rubber particles and sand.1, 29

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Additionally, CP-52 is widely used as a flame retardant and plasticizer in the sports

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material such as paving materials of polyurethane plastic tracks.21 CP concentrations

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in the materials of plastic track and synthetic turf blades were herein measured as well

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as sneaker soles (Table S5). The GM SCCP and MCCP concentrations in the

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materials of plastic track were up to 35536 and 161859 μg g–1. High-leveled CPs were

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also found in the synthetic turf blades and sneaker soles with the GM concentrations

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of 260 and 3057 μg g–1 for SCCP, and 632 and 4840 μg g–1 for MCCP, respectively.

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These results indicate that the observed CP concentration differences may be due to

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variations in the CP additive quantities in different materials. The widely use of

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CP-52 in polyurethane plastic tracks and basketball courts than that in plastic tennis

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court, badminton court, and synthetic turf may result in the higher CP concentrations

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observed in dusts from plastic track and basketball court.

respectively.

Synthetic

turf

blades

are

composed

of

nylon

or

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The SCCP and MCCP concentrations in dusts from plastic sports court and

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synthetic turf is higher in summer than that in winter. Seasonal variations were

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observed through a significant increase in SCCP and MCCP concentrations in plastic

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track and basketball court samples collected in the summer compared to those

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collected in winter (p < 0.05), whereas seasonal differences were not significant for

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tennis court and synthetic turf samples (p > 0.05) (Table S4 and Figure S2). Human

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and environmental factors (e.g. friction between plastic surface and sneaker sole, high

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air temperature and stronger light in the summer) may accelerate the release of CPs

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from the plastic sports court and synthetic turf. Generally, the MCCP concentrations

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in all indoor and outdoor dust samples were higher than those of SCCPs (Table S4).

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The GM concentration ratio of MCCPs to SCCPs in plastic track, basketball court,

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tennis court, and synthetic turf samples were 2.8, 2.3, 1.8, and 2.4, respectively, all

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higher than the MCCP:SCCP ratio in indoor plastic badminton court samples (1.3).

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Further, the MCCP:SCCP ratios in dusts from outdoor courts was closer to those in

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commercial CP-52 (Table S6), implying that CPs in dust samples from outdoor plastic

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sports courts and synthetic turf may be more affected by the CP-52 additives. The

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higher fraction of SCCPs in indoor dust can likely be attributed to the volatilization of

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lighter congeners of CPs from the constituent materials.25

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A comparison of dust CP concentrations between the values obtained herein and

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those reported in previous studies of indoor dust of varying origins (Table S7) clearly

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showed that the SCCP and MCCP concentrations in plastic track and basketball court

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dusts were 1–3 orders of magnitude higher than in dusts from other indoor

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environments.22, 25, 30-32 Further, the SCCP and MCCP concentrations in dusts from

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plastic tennis courts and synthetic turf were comparable25,

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magnitude higher32 herein and those in indoor plastic badminton court samples were

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1–2 orders of magnitude higher herein.22, 25, 30-32

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or 1–2 orders of

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In general, congener group profiles based on the carbon chain length and chlorine

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atom substitution in the dusts were similar among the different types of plastic sports

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courts and synthetic turf, seasons, and indoor/outdoor use. Table S8 and Figure S3

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show the GM concentration and percentage-based homologue patterns of SCCPs and

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MCCPs in the dusts. The most abundant (C13-CPs) and second highest (C11- and

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C12-CPs) carbon chain length group accounted for 41–54%, 7.5–24%, and 12–18% of

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the total SCCPs, respectively. The most abundant (C14-CPs) and second highest (C15-

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and C16-CPs) carbon chain length group accounted for 47–59%, 20–24% and 9.5–12%

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of the total MCCPs content, respectively. Finally, Cl7- and Cl8-CPs species were the

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most abundant species, accounting for 27–38% and 29–34% of SCCPs, and 22–28%

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and 37–42% of MCCPs, respectively. The congener group profiles in these dust

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samples were similar to those in commercial CP-52. In addition, the congener group

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profiles of SCCPs in the dust samples obtained herein were considerably different

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from those in the atmosphere of an urban setting in Beijing (which tend to have a

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shorter carbon chain length (C10–11) and lower chlorine atom substitution (Cl5–7)).33

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These results indicate that the CPs in the dusts from plastic sports courts and synthetic

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turf may be derived from commercial CP-52, and not from atmospheric deposition.

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The source of CPs in plastic track dusts. In order to have a complete assessment of

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the dust samples retrieved from plastic track, plastic track material and sneaker soles

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were investigated as potential sources of CPs in the plastic track dust. High CP

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concentrations were found in both the plastic track material and the sneaker soles. The

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SCCP and MCCP concentrations in plastic track material were 6.5 and 11 times as

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high as those in the plastic track dust, whereas they were relatively lower in sneaker

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soles (0.56 and 0.32 times, respectively) (Table S5 and Figure S4). High CP

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concentrations in the plastic track material and the sneaker soles may imply that they

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are important sources of CPs in the plastic track dust compared to atmospheric

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deposition. The friction between sneaker soles and plastic track material will lead to

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wear and decomposition of rubber in both materials, accelerating the release of CPs

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and allowing their adsorption onto the plastic track dust particles. In order to further

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assess the possible relationship between plastic track material, sneaker soles, and the

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dust samples were collected from three different function areas (plastic tracks, road

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and indoors22), principal component analysis was conducted to investigate the main

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characteristics of their SCCP and MCCP congener group profiles (Figure 2). The first

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two principal components accounted for 52% and 69 % of variances for SCCPs and

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MCCPs, respectively. For SCCPs, C10- and C12-CPs, as well as C13- and C11-CPs were

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the most highly contributing congener groups in components 1 and 2, respectively.

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For MCCPs, C14- and C15-CPs, as well as C14-, C16-, and C17-CPs were the most

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highly contributing congener group to components 1 and 2, respectively (Figure 2a, c).

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As shown in the score plot, all data clustered into three groups according to their

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characteristics (Figure 2b, d). For SCCPs, most of the plastic track material and

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sneaker sole were clustered and overlapped in the third and fourth quadrants with

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plastic track dust, while these three sample groups were clustered and overlapped in

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the first and second quadrants for MCCPs. These results indicate that the congener

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group profiles of SCCPs and MCCPs for these three sample groups were similar, and

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imply that plastic track material and sneaker sole are the most important sources of

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CPs in plastic track dust. For SCCPs, most of the road dust (far) and indoor dust

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samples were distributed in the first and second quadrants, while these two groups of

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samples were distributed in the third and fourth quadrants for MCCPs, indicating that

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CPs in the road dust (far) and indoor dust samples were derived from different sources

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compared to the plastic track dust. The overlapping areas between the sample groups

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in the score plot indicate the similar congener group profiles for SCCPs and MCCPs,

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implying that they might have the same CP source.

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Since the CP concentrations in the plastic track material and dust were so high, it

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is likely that they might be the CP source to the surrounding environment. In order to

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assess this, road dust samples were collected from the areas surrounding the plastic

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track at varying distances. The SCCP and MCCP concentration in dust retrieved from

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the plastic track was approximately 50 times higher than that in the surrounding road

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dust (~3 m). The SCCP and MCCP concentration in road dust from a farther sampling

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site (~50 m) was one order of magnitude lower than that in surrounding road dust, and

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were 2–3 orders of magnitude lower than that in plastic track dust. Further, the

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concentration was lower22, 25, 30, 31 or comparable32 to that from indoor dust. With the

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increase in distance from the plastic track, the SCCP and MCCP concentration

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significantly decreased (Figure 3), indicating that the plastic track is an important

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source of CPs to the surrounding environment. For SCCPs, the congener group

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profiles of road dust (far) were different to those of indoor dust and plastic track dust;

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however, they were similar to those of indoor dust for MCCPs (Figure 2b, d). Thus,

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CPs in road dust (far) were likely derived from composite sources including plastic

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track dust, atmospheric deposition, and other potential sources, which is consistent

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with the result of principal component analysis.

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Human exposure assessment. The general population can undergo three main routes

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of exposure to CPs when using plastic sports courts or synthetic turf, including dust

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ingestion, dermal absorption, and inhalation. As there is still no data of atmospheric

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CP concentration above plastic sports courts or synthetic turf, inhalation exposure

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assessments used reported SCCPs and MCCPs concentrations in indoor22 and outdoor

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atmosphere33 in Beijing. It should be noted that this treatment may underestimate the

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exposure contribution through inhalation. Since people that exercise breathe at a faster

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rate than people resting, therefore estimated daily intakes through inhalation was

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calculated using short-term inhalation rates during moderate intensity activity.34 The

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exposure time used was taken from average time spent on the outdoor turf over

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seasons.34 The GM concentration of CPs in dust as well as the mean and 95th

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percentile (hereafter referred to as high) exposure factors were used to calculate the

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mean and high estimated daily intakes. The estimated daily intake of CPs from dust

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via ingestion, dermal absorption, and inhalation for adults and children on plastic

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sport courts and synthetic turf was calculated using equations (1), (2), and (3), and the

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results are summarized in Table 1 and Table S9.

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There were differences in human intake through dust ingestion, dermal

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absorption, and inhalation between adults and children. For ingestion, children’s

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frequent hand-to-mouth contact resulted in a significantly higher dust intake rate

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(IRingestion) than that of adults, and therefore a higher CP intake from dust ingestion

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than that for adults. For dermal absorption, the body surface area of children and the

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amount of dust adhered to skin (mg cm–2) were lower than for adults, resulting in

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children’s lower intake through dermal absorption than for adults. For inhalation, the

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higher inhalation rate (IRInhalation) per children’s unit of weight leads to a higher

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inhalation intake than for adults. In outdoor plastic sport courts and synthetic turf, the

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sum of the three exposure routes for children and adults were very similar. In indoor

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badminton courts, the sum of the three exposure routes of children was approximately

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twice than that for adults. This is in agreement with previous reports indicating that

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CP intake through indoor dust is significantly higher for children than for adults.22, 25,

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31, 32

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The human exposure level of CPs from different environmental media in this

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work and previous studies are summarized in Table 1 and Table S10, respectively.

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The mean SCCP intake from plastic tracks and basketball courts during winter (635

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and 561 ng kg–1 day–1 for adults; 524 and 464 ng kg–1 day–1 for children) were

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comparable or slightly lower than dietary intake (620 ng kg–1 day–1). However, SCCP

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intake from plastic tracks and basketball courts during the summer (1457 and 1476 ng

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kg–1 day–1 for adults; 1209 and 1225 ng kg–1 day–1 for children) were approximately

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twice as high as dietary intake.35 For adults, the mean intake of ∑SCCPs + MCCPs

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(sum-CPs) from plastic tracks (2555 ng kg–1 day–1 in winter; 5193 ng kg–1 day–1 in

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summer)and basketball courts (1949 ng kg–1 day–1 in winter; 4651 ng kg–1 day–1 in

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summer) in our study were 6.6–18 times and 1.6–4.1 times as high as indoor

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environment and dietary intake, respectively.22 For children, the mean intake of

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sum-CPs from plastic tracks (2109 ng kg–1 day–1 in winter; 4286 ng kg–1 day–1 in

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summer) and basketball courts (1609 ng kg–1 day–1 in winter; 3839 ng kg–1 day–1 in

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summer) in our study were 0.74–2.0, 1.1–3.0, and 0.93–2.5 times as high as those

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from indoor environment,22 dietary,22 and breast milk intake,36 respectively. In general,

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the mean intake of sum-CPs from plastic tracks and basketball courts for adults and

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children in this study were both 1–2 orders of magnitude higher than those from

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indoor dust, both in China and in other countries (in Sweden (16.7 and 110 ng kg–1

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day–1),32 Northeast China (45 and 83 ng kg–1 day–1),31 building material mall in China

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(150 and 427 ng kg–1 day–1)25). While the exposure time to sports courts is obviously

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less than that to indoor environments, the intake of CPs from plastic tracks and

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basketball courts was, in general, higher than that from indoor environmental or

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dietary intake, indicating that the estimated daily intake of CPs would be significantly

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underestimated if the CP intake from plastic tracks and basketball courts was ignored

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for regular exercisers or players. In general, the intake of sum-CPs from plastic tennis

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courts and synthetic turf for adults (96 and 46 ng kg–1 day–1 in winter; 224 and 79 ng

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kg–1 day–1 in summer) and children (80 and 38 ng kg–1 day–1 in winter; 185 and 65 ng

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kg–1 day–1 in summer) were lower than dietary22, 35 or breast milk36 intake, and lower

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than or comparable to other indoor environmental intake.22,

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sum-CPs from indoor badminton courts for adults (105 ng kg–1 day–1) and children

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(339 ng kg–1 day–1) were generally lower than dietary22, 35 and breast milk36 intake, but

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higher or comparable to plastic tennis court and synthetic turf intake as well as from

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other indoor environments.31, 32

25, 31, 32

The intake of

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The percentile contribution of SCCP and MCCP intake from ingestion, dermal

329

absorption, and inhalation in plastic sport courts and synthetic turf are summarized in

330

Table S11. The percentage of inhalation in plastic sports courts and synthetic surf

331

accounted for less than 4.0%, except for the inhalation in plastic tennis courts and

332

synthetic turf during the summer (4.8–37%). Regardless of the indoor or outdoor

333

nature of the sports court or synthetic turf, inhalation accounted for a relatively small

334

contribution of the total intake, as also found in the human exposure to SCCPs and

335

MCCPs from indoor dust.22 There are differences in the main exposure route of adults

336

and children for outdoor sports courts and synthetic turf. In plastic tracks, basketball

337

courts, tennis courts, and synthetic turf, the main exposure route for adults is dermal

338

absorption, accounting for 77–93% in average exposure (mean EDI) scenarios for

339

SCCPs and MCCPs. However, the main exposure route for children was dust

340

ingestion, accounting for 35–55% in average exposure scenarios, even accounting for

341

78% in high exposure scenario for SCCPs and MCCPs. In indoor badminton courts,

342

the main exposure route for both adults and children was dust ingestion, accounting

343

for more than 56% and 92%, respectively. It is reported that ingestion of settled

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indoor dust is a significant contribution to human exposure of phthalates,

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polybromodiphenyl ethers, pesticides, organophosphate esters, and CPs, 22, 25, 31, 37, 38

346

showing that dust ingestion is an important route for human exposure to pollutants in

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the dust, especially for children.

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We used the uncertainty factor 1000 (three factors of 10 represent the research

349

period less than one year, interspecies differences, and individual differences,

350

respectively) to evaluate the health risks of CP intake and considered that there is no

351

significant risk for human health if the MOE was greater than 1000.39 The MOE of

352

exposure from CPs in the dust of indoor and outdoor sports courts in summer and

353

winter was summarized in Table 2. In both indoor and outdoor plastic sports courts

354

and synthetic turf, the MOE of SCCPs and MCCPs for both adults and children were

355

all above 1000, regardless of the average or high exposure scenario. This suggests that,

356

although the concentrations and estimated daily intakes of SCCPs and MCCPs in dust

357

from plastic sports courts and synthetic turf are relatively high, the resulting human

358

health risks were still below the margin of exposure, and there was no obvious human

359

health risk for CP exposure for people exercising or playing on plastic sports courts

360

and synthetic turf. It should be noted that this calculation only provided a rough

361

estimation of CPs exposure, and different populations with varying exercise duration

362

should have different exposure risks. Professional athletes may have longer exercise

363

duration than the reference values used in this study, and may be associated with more

364

hand-to-mouth contact, which may lead to higher exposure risk of CPs. In contrast,

365

population with less exercise time should have a lower exposure risk of CPs from

366

plastic sports courts and synthetic turf.

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Implications. CPs is widely used in plastic sports court and synthetic turf materials.

368

This study shows that the concentration of CPs in the dust from plastic tracks and

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basketball courts is 1–3 orders of magnitude higher than that of indoor dust, which

370

can help us to better understand the occurrence and human exposure level of CPs in

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the environment of plastic sports courts and synthetic turf.

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More importantly, other chemicals could also be intentionally added to improve

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the performance of plastic sports courts and synthetic turf, including inorganic and

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organic plasticizers (e.g., antimony, phthalate esters), antioxidants (e.g., phenols), and

375

UV-filters (e.g., benzophenone, benzotriazole). These chemicals could also pose

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potential threats to human health through their environmental release. Considering the

377

relatively higher exposure level via ingestion, dermal absorption, and inhalation,

378

health risk assessments should be performed carefully for users of plastic sports courts

379

and synthetic turf, especially for children and professional athletes.

380

As SCCPs have been listed in the Stockholm Convention, the production and use

381

of SCCPs will be gradually phased out, therefore likely reducing the use and the

382

human exposure risks of CPs. It is worth mentioning that the CP concentration in one

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plastic track dust sample was 2–3 orders of magnitude lower than that in the

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remaining 19 plastic track dust samples. This sample was not included in the above

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statistical analysis, yet it indicates that it is possible to use alternative raw materials

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and technologies in the manufacturing of plastic track materials to decrease CP

387

concentration and human exposure risks.

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■ ASSOCIATED CONTENT

390

Supporting Information

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Additional results are provided in Supporting Information. This material is available

392

free of charge via the Internet at http://pubs.acs.org.

393

■ AUTHOR INFORMATION

394

Corresponding Author

395

*Yawei

396

[email protected].

397

Notes

398

The authors declare no competing financial interest.

399

■ ACKNOWLEDGMENTS

400

We thank the National Basic Research Program of China (2015CB453102), the

401

National Natural Science Foundation of China (21625702, 21337002, 21621064, and

402

21407157), the Strategic Priority Research Program of the Chinese Academy of

403

Science (XDB14010400) and Sanming Project of Medicine in Shenzhen

404

(SZSM201811070) for financial support.

Wang:

Tel:

+86-10-62840620;

fax:

405

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+86-10-62849124;

e-mail:

Environmental Science & Technology

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■ REFERENCES

407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461

(1) Cheng, H. F.; Hu, Y. N.; Reinhard, M. Environmental and health impacts of artificial turf: A Review. Environ. Sci. Technol. 2014, 48(4), 2114-2129. (2) Fleming, P. R.; Anderson, L. J.; Ansarifar, M. A. The behaviour of recycled rubber shockpads for synthetic sports pitches (P150). ISEA 2008 Conference on Engineering of Sport 7, Vol 2 2008, 77-87. (3) Ruffino, B.; Fiore, S.; Zanetti, M. C. Environmental-sanitary risk analysis procedure applied to artificial turf sports fields. Environ. Sci. Pollut. Res. 2013, 20(7), 4980-4992. (4) Gomes, J.; Mota, H.; Bordado, J.; Cadete, M.; Sarmento, G.; Ribeiro, A.; Baiao, M.; Fernandes, J.; Pampulim, V.; Custodio, M.; Veloso, I. Toxicological assessment of coated versus uncoated rubber granulates obtained from used tires for use in sport facilities. J. Air Waste Manage. 2010, 60(6), 741-746. (5) van Rooij, J. G. M.; Jongeneelen, F. J. Hydroxypyrene in urine of football players after playing on artificial sports field with tire crumb infill. Int. Arch. Occup. Environ. Health 2010, 83 (1), 105-110. (6) Ginsberg, G.; Toal, B.; Simcox, N.; Bracker, A.; Golembiewski, B.; Kurland, T.; Hedman, C. Human health risk assessment of synthetic turf fields based upon investigation of five fields in Connecticut. J. Toxicol. Environ. Health A 2011, 74(17), 1150-1174. (7) Li, X. L.; Berger, W.; Musante, C.; Mattina, M. I. Characterization of substances released from crumb rubber material used on artificial turf fields. Chemosphere 2010, 80(3), 279-285. (8) Van Ulirsch, G.; Gleason, K.; Gerstenberger, S.; Moffett, D. B.; Pulliam, G.; Ahmed, T.; Fagliano, J. Evaluating and regulating lead in synthetic turf. Environ. Health Persp. 2010, 118 (10), 1345-1349. (9) Kim, S.; Yang, J. Y., Kim, H. H.; Yeo, I. Y.; Shin, D. C.; Lim, Y. W. Health risk assessment of lead ingestion exposure by particle sizes in crumb rubber on artificial turf considering bioavailability. Environ. Health Toxicol. 2012, 27, e2012005. (10) Serensits, T. J.; McNitt, A. S.; Petrunak, D. M. Human health issues on synthetic turf in the USA. Proc. Inst. Mech. Eng. Part P 2011, 225(P3), 139-146. (11) Fiedler, H. Short-Chain Chlorinated Paraffins: Production, Use and International Regulations. In Chlorinated Paraffins, Boer, J., Ed. Springer Berlin Heidelberg: Berlin, 2010; pp 1-40. (12) El-Sayed Ali, T.; Legler, J. Overview of the Mammalian and Environmental Toxicity of Chlorinated Paraffins. In Chlorinated Paraffins Boer, J., Ed. Springer Berlin Heidelberg: Berlin 2010; pp 135-154. (13) Reth, M.; Zencak, Z.; Oehme, M. First study of congener group patterns and concentrations of short- and medium-chain chlorinated paraffins in fish from the North and Baltic Sea. Chemosphere 2005, 58(7), 847-854. (14) Ma, X. D.; Zhang, H. J.; Zhou, H. Q.; Na, G. S.; Wang, Z.; Chen, C.; Chen, J. W.; Chen, J. P. Occurrence and gas/particle partitioning of short- and medium-chain chlorinated paraffins in the atmosphere of Fildes Peninsula of Antarctica. Atmos. Environ. 2014, 90, 10-15. (15) Zeng, L. X.; Wang, T.; Wang, P.; Liu, Q.; Han, S. L.; Yuan, B.; Zhu, N. L.; Wang, Y. W.; Jiang, G. B. Distribution and trophic transfer of short-chain chlorinated paraffins in an aquatic ecosystem receiving effluents from a sewage treatment plant. Environ. Sci. Technol. 2011, 45(13), 5529-5535. (16) Ma, X. D.; Zhang, H. J.; Wang, Z.; Yao, Z. W.; Chen, J. W.; Chen, J. P. Bioaccumulation and trophic transfer of short chain chlorinated paraffins in a marine food web from Liaodong Bay, North China. Environ. Sci. Technol. 2014, 48(10), 5964-5971. (17) EC Directive 2000/60/EC of the European Parliament and of the Council of October 23, 2000 establishing a framework for community action in the field of water policy (L 327 of 22-12-2000). (18) UNEP/POPS/COP.8/14 Recommendation by the Persistent Organic Pollutants Review Committee to list short-chain chlorinated paraffins in Annex A to the Convention and draft text of the proposed amendment; 2017. (19) Ministry of Ecological Environment of People’s Republic of China. List of priority control chemicals (first batch). 2017, http://www.mee.gov.cn/gkml/hbb/bgg/201712/t20171229_428832.htm. (20) Tang, E. T.; Yao, L. Q. Industry status of chlorinated paraffin and its development trend. China Chlor-Alkali 2005, 2, 1-3. 20

ACS Paragon Plus Environment

Page 20 of 27

Page 21 of 27

462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483 484 485 486 487 488 489 490 491 492 493 494 495 496 497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513

Environmental Science & Technology

(21) Chen, Q., Zhao, R. J. The application of chlorinated paraffins-52 in polyurethane paving materials. Guangdong Rubber 2005, 1, 9-11. (22) Gao, W., Cao, D. D.; Wang, Y. J.; Wu, J.; Wang, Y.; Wang, Y. W.; Jiang, G. B. External exposure to short- and medium-chain chlorinated paraffins for the general population in Beijing, China. Environ. Sci. Technol. 2018, 52(1), 32-39. (23) Reth, M.; Zencak, Z.; Oehme, M. New quantification procedure for the analysis of chlorinated paraffins using electron capture negative ionization mass spectrometry. J. Chromatogr. A. 2005, 1081, 225-231. (24) Wang, Y. L.; Hu, J. X.; Lin, W.; Wang, N.; Li, C.; Luo, P.; Hashmi, M. Z.; Wang, W. B.; Su, X. M.; Chen, C.; Liu, Y. D.; Huang, R. L.; Shen, C. F. Health risk assessment of migrant workers' exposure to polychlorinated biphenyls in air and dust in an e-waste recycling area in China: Indication for a new wealth gap in environmental rights. Environ. Int. 2016, 87, 33-41. (25) Shi, L. M.; Gao, Y.; Zhang, H. J.; Geng, N. B.; Xu, J. Z.; Zhan, F. Q.; Ni, Y. W.; Hou, X. H.; Chen, J. P. Concentrations of short- and medium-chain chlorinated paraffins in indoor dusts from malls in China: Implications for human exposure. Chemosphere 2017, 172, 103-110. (26) Iino, F.; Takasuga, T.; Senthilkumar, K.; Nakamura, N.; Nakanishi, J. Risk assessment of short-chain chlorinated paraffins in Japan based on the first market basket study and species sensitivity distributions. Environ. Sci. Technol. 2005, 39(3), 859-866. (27) ECB European Union Risk Assessment Report, Vol 4: Alkanes, C10–13, Chloro; European Chemicals Bureau, European Commission, 2000. (28) ECB European Union Risk Assessment Report, Vol 4: Alkanes, C14–17, Chloro; European Chemicals Bureau: European Commission, 2007. (29) Dai, Y. In Development and Application of New Stadium Material-Silicon PU in Sports Field Surface Layer, Proceedings of the 1st Symposium on research, production and technology exchange of polyurethane pavement materials, 2011; 48-57. (30) Hilger, B.; Fromme, H.; Volkel, W.; Coelhan, M. Occurrence of chlorinated paraffins in house dust samples from Bavaria, Germany. Environ. Pollut. 2013, 175, 16-21. (31) Liu, L. H.; Ma, W. L.; Liu, L. Y.; Huo, C. Y.; Li, W. L.; Gao, C. J.; Li, H. L.; Li, Y. F.; Chan, H. M. Occurrence, sources and human exposure assessment of SCCPs in indoor dust of northeast China. Environ. Pollut. 2017, 225, 232-243. (32) Friden, U. E.; McLachlan, M. S.; Berger, U. Chlorinated paraffins in indoor air and dust: Concentrations, congener patterns, and human exposure. Environ. Int. 2011, 37(7), 1169-1174. (33) Wang, T.; Han, S. L.; Yuan, B.; Zeng, L. X.; Li, Y. M.; Wang, Y. W.; Jiang, G. B. Summer-winter concentrations and gas-particle partitioning of short chain chlorinated paraffins in the atmosphere of an urban setting. Environ. Pollut. 2012, 171, 38-45. (34) EPA. Exposure factors handbook (EPA/600/R-09/052 F); Washington, DC, USA, 2011. (35) Harada, K. H.; Takasuga, T.; Hitomi, T.; Wang, P. Y.; Matsukami, H.; Koizumi, A. Dietary exposure to short-chain chlorinated paraffins has increased in Beijing, China. Environ. Sci. Technol. 2011, 45(16), 7019-7027. (36) Xia, D.; Gao, L. R.; Zheng, M. H.; Li, J. G.; Zhang, L.; Wu, Y. N.; Qiao, L.; Tian, Q. C.; Huang, H. T.; Liu, W. B.; Su, G. J.; Liu, G. R. Health risks posed to infants in rural China by exposure to short- and medium-chain chlorinated paraffins in breast milk. Environ. Int. 2017, 103, 1-7. (37) Mercier, F.; Glorennec, P.; Thomas, O.; Le Bot, B. Organic contamination of settled house dust, A review for exposure assessment purposes. Environ. Sci. Technol. 2011, 45(16), 6716-6727. (38) van den Eede, N.; Dirtu, A. C.; Neels, H.; Covaci, A. Analytical developments and preliminary assessment of human exposure to organophosphate flame retardants from indoor dust. Environ. Int. 2011, 37(2), 454-461. (39) Pieters, M. N.; Kramer, H. J.; Slob, W. Evaluation of the uncertainty factor for subchronic-to-chronic extrapolation: Statistical analysis of toxicity data. Regul. Toxicol. Pharm. 1998, 27(2), 108-111.

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Table 1. Estimated Daily Intake (Value of Mean) of CPs from Dust via Ingestion, Dermal Absorption, and Inhalation for Adults and Children on

515

Plastic Sport Courts and Synthetic Turf. Mean Adults (21 to