Organophosphate esters in Great Lakes fish: An improved analysis to assess concentrations and human exposure via...

Organophosphate esters (OPEs) are flame retardant and plasticizer chemicals added to electronics, furniture, textiles, and other building materials and consumer products. In this study, fillets of fish often caught by anglers in the North American Great Lakes, Lake Trout (Salvelinus namaycush) across four Great Lakes and nearshore fish species near the large urban and industrial centers of Toronto and Hamilton, Canada, were analyzed for 22 OPEs. A rapid microextraction of homogenized tissues with methanol dramatically reduced preparation and sample handling time while achieving recoveries of 69-141%, and the optimized liquid chromatographic separation improved isomeric separations, including aryl-OPEs. Twelve of the 22 OPEs were detected, with frequencies of detection ranging from 8.3% to 98%, and five compounds were detected in >50% of the fish. The average ± standard deviation for the sum of 12 OPEs (ΣOPE₁₂) ranged from 9.6 ± 0.9 (L. Erie 2017) to 74 ± 44 (L. Superior 2001) ng/g wet weight in Lake Trout, and 12 ± 2.7 to 35 ± 30 ng/g wet weight in nearshore fish species from the Toronto and Hamilton areas. The aryl-OPEs were dominant in Lake Trout, comprising 32-77% of total ΣOPE₁₂ concentrations. In nearshore fish, the OPE patterns reflected the relative degree of exposure to run-off and wastewater inputs in the sampled receiving environments. The intake of OPEs via human consumption of Great Lakes Lake Trout and nearshore fish was estimated to range 6.5-31 ng/kg body weight/day, which is approximately 1-2 orders of magnitude lower than exposures via indoor air and ingestion/inhalation of dusts, and 3 orders of magnitude lower than estimated reference doses. The inclusion of additional OPE analytes enabled patterns of exposure and accumulation to be distinguished in fish of different species and location, and were related to source and food web influences.