title: A mass spectrometry-based method to measure dialkylphosphate degradation products of organophosphorous insecticides in dust and orange juice.
abstract: Dialkylphosphates (DAPs) are urinary metabolites and breakdown products of organophosphorous (OP) pesticides. Urinary DAPs are widely used to assess exposure to OP pesticides in epidemiologic studies. Recent evidence suggests that preformed DAPs are present in food and that they may also be present in other parts of the environment. Thus, DAP concentrations observed in urine may reflect a person's exposure to both parent OP pesticides and preformed DAPs in food and other environmental media. The presence of preformed DAPs in multiple media may indicate that previous studies have overestimated exposure to OP pesticides and that the use of urinary DAPs as biomarkers of exposure for OP pesticides may not accurately characterize exposure in non-acute settings. To establish the presence of DAPs in environmental and food media, we developed analytical methods to measure six DAPs in dust and orange juice. The limits of detection (LOD) for the dimethyl phosphates (dimethylphosphate (DMP), dimethylthiophosphate, and dimethyldithiophosphate) ranged from 2.8-9.9 ng g(-1) and 0.2-0.4 ng mL(-1) in dust and juice, respectively. The LODs for the diethyl phosphates (diethylphosphate (DEP), diethylthiophosphate, diethyldithiophosphate) ranged from 5.2-10.4 ng g(-1) and 0.5-3.0 ng mL(-1) in dust and juice, respectively. The extraction efficiencies for the analytes ranged from 23% to 91% and from 41% to 85% in dust and orange juice, respectively. DMP was detected in about half of the dust samples whereas DEP was detected in 80% of the dust samples tested. Other DAPs were less frequently detected in dust. Less than 3% of intact pesticide present in the matrices was converted to their respective DAPs during the pre-analytic and analytic process. Evaluation of the conversion of intact pesticides in the samples to DAPs will help us to better understand the contribution of preformed DAPs to urinary DAP concentrations.
authors.affiliation: National Center for Environmental Health, Centers for Disease Control and Prevention, 4770 Buford Highway NE, Mailstop F-17, Atlanta, Georgia, USA. dbarr@cdc.gov
authors.forename: Gayanga
authors.initials: G
authors.lastname: Weerasekera
authors.forename: Kimberly D
authors.initials: KD
authors.lastname: Smith
authors.forename: Lesliam
authors.initials: L
authors.lastname: Quirós-Alcalá
authors.forename: Carolina
authors.initials: C
authors.lastname: Fernandez
authors.forename: Asa
authors.initials: A
authors.lastname: Bradman
authors.forename: Brenda
authors.initials: B
authors.lastname: Eskenazi
authors.forename: Larry L
authors.initials: LL
authors.lastname: Needham
authors.forename: Dana B
authors.initials: DB
authors.lastname: Barr
mesh_terms: D001628:Beverages / Q000032:analysis*; D015415:Biomarkers / Q000032:analysis / Q000378:metabolism / Q000652:urine; D032084:Citrus sinensis / Q000737:chemistry*; D004391:Dust / Q000032:analysis*; D004784:Environmental Monitoring / Q000379:methods*; D006801:Humans; D007306:Insecticides / Q000032:analysis* / Q000378:metabolism / Q000652:urine; D057230:Limit of Detection; D013058:Mass Spectrometry / Q000379:methods*; D010755:Organophosphates / Q000032:analysis / Q000378:metabolism / Q000652:urine; D009943:Organophosphorus Compounds / Q000032:analysis* / Q000378:metabolism / Q000652:urine
chemical_list: D015415:Biomarkers; D004391:Dust; D007306:Insecticides; D010755:Organophosphates; D009943:Organophosphorus Compounds; C034789:diethyl phosphate; C007477:dimethyl phosphate