标题：Urinary biomonitoring of occupational exposures to Bisphenol A Diglycidyl Ether (BADGE) – based epoxy resins among construction painters in metal structure coating
摘要：Epoxy resin systems based on Bisphenol A Diglycidyl Ether (BADGE) monomer and its higher oligomers are important commercial formulations used widely in construction for protective coating of steel structures, such as bridges. The literature on occupational exposures and biomonitoring of BADGE-based epoxies among construction painters is remarkably limited. In this first occupational biomonitoring study of epoxies, 44 construction painters performing mid- and top-coating were recruited from 12 metal structure coating sites in New England. Cross-shift changes in the urinary levels of total BADGE and its three major hydrolysis derivatives - BADGE·2H 2 O, BADGE·H 2 O, BADGE·HCl·H 2 O – were assessed. Results for 81 urine samples collected from coating workers were compared with 28 urine samples of a reference group of 14 spray polyurethane foam (SPF) insulation workers. The highest concentrations of all biomarkers were found in the urine samples of mid-coat applicators. The major urinary biomarker of BADGE in this cohort of workers, BADGE·2H 2 O, was detected in 100% of urine samples. The post-shift BADGE·2H 2 O (specific gravity normalized data) in mid-coat applicators had a geometric mean (GM) of 1.46 ng/mL and a geometric standard deviation (GSD) of 3.6 (range, 0.2–18.7 ng/mL). The second most abundant biomarker in urine, BADGE·HCl·H 2 O, was measured in 84% of samples, and had a post-shift GM(GSD) of 0.17 (2.3) ng/mL (range, <0.025–0.59 ng/mL). BADGE·2H 2 O was 8.6 times more abundant than BADGE·HCl·H 2 O. BADGE·H 2 O was quantified only in 10% of the samples (range, 0.11–0.41 ng/mL). Free BADGE in post-shift urine, corrected for background, had GM (GSD) of 0.04 (2.5) ng/mL (range, <0.025–0.16 ng/mL). Urinary BADGE·2H 2 O were significantly higher (p = 0.01) in mid-coat applicators compared to top-coat and SPF workers. Post-shift urinary BADGE·2H 2 O in mid-coat applicators increased by ~2.9× (p = 0.02) and 1.36× in top-coat applicators (p = 0.18) compared to pre-shift values, but not in SPF workers (0.95×; p = 0.40). In conclusion, we demonstrate that (i) significant BADGE uptake occurs via inhalation and skin exposures during application of epoxy-containing paintings (mid-coat), suggesting the need for improvements in hygiene practices and personal protective measures; (ii) BADGE·2H 2 O is a robust and sensitive biomarker for biomonitoring of exposures to BADGE-based epoxies in occupational settings; and (iii) widespread occurrence of BADGE and BADGE·2H 2 O in the urine of all workers, including SPF workers, suggest common exposures from non-occupational sources, such as ingestion or do-it-yourself consumer applications of epoxy resins. In light of this observation, establishing a reliable biological monitoring guidance value (BMGV) for BADGE·2H 2 O will require more background biomonitoring and health effect data. An initial reference value for BADGE·2H 2 O of 0.5 ng/mL (SG-normalized) or 180 nmol/mol creatinine is being proposed as the threshold to discriminate occupational from non-occupational exposures based on the maximum values observed in the reference SPF group.
关键词：Urinary biomonitoring ; bisphenol A diglycidyl ether (BADGE) ; Epoxy resins ; Construction painters ; Epoxy mid-coats ; Isocyanates
