HBCDs AND TBBP-A IN INDOOR AIR AND DUST IN BIRMINGHAM, UK: IMPLICATIONS FOR HUMAN EXPOSURE

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1 SUPPORTING INFORMATION FOR ABDALLAH ET AL, 2008 HBCDs AND TBBP-A IN INDOOR AIR AND DUST IN BIRMINGHAM, UK: IMPLICATIONS FOR HUMAN EXPOSURE Mohamed Abou-Elwafa Abdallah, Stuart Harrad, Adrian Covaci 13 pages-7 tables Abdallah et al 2008 SI Page 1 of 13

2 Table SI-1: Vehicle-specific variables of the studied cars. no. Brand Model Age Seats Seat cover 1 Fiat Punto 8 years 5 Fabric 2 Fiat Punto 3 years 5 Fabric 3 Vauxhall Astra 6 years 5 Fabric 4 Vauxhall Corsa 2 years 5 Fabric 5 Fiat Punto 6 years 5 Fabric 6 Vauxhall Corsa 4 years 5 Fabric 7 Ford Van 10 years 7 Plastic + fabric 8 Ford Mondeo 10 years 5 Fabric 9 Ford Focus 6 years 5 Fabric 10 Vauxhall Astra 3 years 4 Fabric 11 Volvo V70 6 years 5 Leather 12 Hyundai Coupe 4 years 4 Leather 13 Ford Fiesta 12 years 5 Fabric 14 Ford Focus 8 years 4 Fabric 15 Ford Fiesta 4 years 5 Fabric 16 Ford Mondeo 3 years 5 Fabric 17 Ford Escort 9 years 5 Fabric 18 Ford Fiesta 4 years 5 Fabric 19 Ford Focus 1 week 5 Fabric 20 Jaguar XJR 2 years 5 Leather Abdallah et al 2008 SI Page 2 of 13

3 Passive air sampling protocols Passive air samplers, each comprising one PUF disk (140 mm diameter, 12 mm thickness, cm 2 surface area, and g cm -3 density) sheltered by either one or two different size stainless steel housings (18 cm, one L bottom housing - not used in part-sheltered configuration - and 23 cm, two L top housing respectively) were deployed in homes, offices, and public microenvironments at a height of approximately 1 m above the floor. PUF disks were washed in tap water, dried at room temperature and pre-extracted with hexane:dichloromethane (1:1) for 8 h in a Soxhlet apparatus to remove target or interfering compounds prior to field deployment. Before sampling, PUF disks were treated with 10 ng of d 18 --HBCD as a sampling efficiency standard (SES) designed to provide a quantitative measure of analyte losses during the sampling process. Shelters were cleaned carefully and solvent rinsed to remove potential contamination. Conversion of contaminant masses per sample into concentrations in air requires knowledge of the air sampling rate of the specific PUF disk sampler configuration used and their deployment time. We used HBCD diastereomer-specific sampling rates derived from a specific calibration exercise conducted by our research group using both our sampler configurations (i.e. fully- and part-sheltered) in an office microenvironment (0.87, 0.89, and 0.91 m 3 d -1 (fully-sheltered) and 1.38, 1.54, and 1.55 m 3 d -1 (part-sheltered) for -, -, and -HBCD respectively)[16]. Further details of the calibration exercise, vapour:particle phase distribution of HBCDs and validation of passive air sampling of HBCDs in indoor air are described elsewhere [16]. Abdallah et al 2008 SI Page 3 of 13

4 Active air sampling protocols A low volume, double inlet pump (Capex L20X) was operated for 24 h at a flow rate of 39 L min -1 to yield a single sample comprising approximately 56 m 3 air. The particulate phase was collected by employing a 47 mm membrane filter (1.0 µm pore size, Whatman) housed in a standard open face 47 mm filter holder airside of the PUF plug sorbent. Two PUF plugs (4 cm diameter 8 cm length) housed by a glass holder (3 cm diameter 25 cm length), were used as a gas phase sorbent. Filters and PUF plugs were each treated with 10 ng of SES (d 18 --HBCD) prior to each active sampling session. The designated flow rate of 39 L min -1 was achieved and maintained by using a flow meter (Platon 50 L min -1 ) connected to an adjustable valve. The flow meter was calibrated using a Gilibrator air flow calibrator (Gilian) which is classified as a primary standard device. The PUF plug holders were covered with aluminium foil throughout sampling to minimize photodegradation. Following sample collection, the particulate and vapour phases were analysed separately. On average, 69% of HBCDs were present in the vapour phase which is in agreement with our previous findings [16] suggesting PUF disk passive samplers are suitable for monitoring HBCDs in indoor air. [16] Harrad, S.; Abdallah, M. Calibration of two passive air sampler configurations for monitoring concentrations of hexabromocyclododecanes in indoor air. J. Environ. Monit. 2008, 10, Abdallah et al 2008 SI Page 4 of 13

5 Table SI-2: Optimized MS/MS parameters* for the analysis of HBCDs and TBBP-A. Parameter Curtain gas Turbo gas temperature Ion spray voltage Declustering potential Focusing potential Collision gas Collision energy Cell entrance potential Collision cell exit potential a.u. arbitrary units Value (units) 35 (a.u.) 500 ( C) (V) -5 (V) -365 (V) 5 (a.u.) 40 (ev) -6 (V) -10(V) * These parameters were obtained using direct infusion experiments of the target compounds (TBBP-A, -, - and - HBCDs, native and 13 C- labelled isomers, 2 ng µl -1 each in MeOH) into the MS/MS system via a built-in Harvard syringe pump at a flow rate of 10 µl min -1. Abdallah et al 2008 SI Page 5 of 13

6 Table SI-3: Summary of recoveries (expressed as %) of 13 C-labelled internal standards added to the studied air and dust samples and d 18 --HBCD employed as SES* for the studied air samples. Compound Air samples Dust samples Average SD Average SD 13 C--HBCD C--HBCD C--HBCD C-TBBP-A d 18 --HBCD a d 18 --HBCD b d 18 --HBCD c * Sampling Efficiency Standard designed to provide a quantitative measure of analyte losses during the sampling process a Applied to filters; b applied to PUFs used in active air sampling; c applied to PUFs used in passive air sampling. Abdallah et al 2008 SI Page 6 of 13

7 Table SI-4a: Concentrations of HBCD isomers in SRM2585 compared to the indicative values [23]. Average concentration (ng g -1 ) ± standard deviation (n=10) Measured Indicative -HBCD 20 ± ± 3.7 -HBCD 4.3 ± ± 1.1 -HBCD 121 ± ± 22 Table SI-4b: Summary of standard addition method results for TBBP-A in SRM 2585*. Mass added (ng) Mass recovered Recovery (%) RSD (%) (n=5) (ng) *Estimated TBBP-A concentration in SRM2585 = 245 ng g -1 ± 7.4 (this study). Abdallah et al 2008 SI Page 7 of 13

8 Table SI-5: Concentrations of HBCDs in matched air and dust samples from the same microenvironment. Sample Air samples Dust samples no. concentration (pg m -3 ) concentration (ng g -1 ) -HBCD -HBCD -HBCD -HBCD -HBCD -HBCD Average SD Median Minimum Maximum Abdallah et al 2008 SI Page 8 of 13

9 Table SI-6: Concentrations (ng g -1 ) of HBCD Diastereomers and TBBP-A in Indoor Dust Samples. Sample Code Floor type -HBCD -HBCD -HBCD HBCD TBBP-A House 1 carpet House 2 carpet House 3 carpet House 4 carpet House 5 carpet House 6 carpet House 7 carpet House 8 carpet House 9 carpet House 10 carpet House 11 carpet House 12 carpet House 13 carpet House 14 carpet House 15 carpet <MQL a House 16 carpet House 17 bare floor House 18 carpet House 19 carpet House 20 carpet House 21 carpet House 22 rug House 23 carpet House 24 carpet House 25 carpet House 26 carpet House 27 linoleum House 28 carpet House 29 carpet House 30 rug House 31 carpet House 32 carpet House 33 carpet House 34 linoleum House 35 carpet House 36 carpet b House 37 Bare floor Abdallah et al 2008 SI Page 9 of 13

10 House 38 rug House 39 carpet House 40 carpet House 41 carpet House 42 carpet House 43 rug House 44 rug House 45 carpet Office 1 carpet Office 2 Bare floor Office 3 carpet Office 4 carpet Office 5 carpet Office 6 carpet Office 7 carpet Office 8 carpet <MQL Office 9 carpet Office 10 carpet Office 11 carpet Office 12 carpet Office 13 carpet Office 14 carpet Office 15 carpet <MQL Office 16 carpet Office 17 carpet Office 18 carpet Office 19 carpet Office 20 carpet Office 21 carpet Office 22 carpet Office 23 carpet Office 24 carpet Office 25 carpet <MQL Office 26 carpet Office 27 carpet Office 28 carpet <MQL Car <MQL Car Car Car Car Abdallah et al 2008 SI Page 10 of 13

11 Car Car <MQL Car Car Car Car <MQL Car <MQL Car <MQL Car <MQL Car Car <MQL Car <MQL Car <MQL Car Car <MQL PUB 1 carpet PUB 2 carpet PUB 3 carpet Restaurant 1 carpet a Method quantitation limit; b Not measured. Abdallah et al 2008 SI Page 11 of 13

12 Table SI-7: Concentrations (pg m -3 ) of HBCD Diastereomers and TBBP-A in Indoor Air Samples. Sample Code/Diastereomer -HBCD -HBCD -HBCD HBCD TBBP-A House House House House House House a House House House House House House House House House House House House House House House House House House House House House House House House House House House Office Office Office Office Office Office Office Office Office Office Office Office Office Office Abdallah et al 2008 SI Page 12 of 13

13 Office Office Office Office Office Office Office Office Office Office Office PUB PUB PUB Restaurant a Not measured. Abdallah et al 2008 SI Page 13 of 13