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Alkyl- and aryl-esters of phosphoric acid (both halogenated and non-halogenated) are mainly used as flame retardants (FRs), among other applications, in furniture and consumer products and they are collectively known as organophosphate flame retardants (OPFRs). The absorption, biotransformation or elimination of many of these chemicals in humans and their possible health effects are not yet well known. A major reason for the limited information is the nature of these compounds, which causes several technical difficulties in their isolation and sensitive determination. A novel analytical liquid chromatography tandem mass spectrometry (LC–MS/MS) method for the accurate and sensitive determination of four urinary OPFR metabolites: bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), bis(2-chloroethyl) phosphate (BCEP), bis(1-chloro-2-propyl) phosphate (BCIPP), and diphenyl phosphate (DPhP), using mixed-mode solid phase extraction and isotope. For the first time all four analytes can be identified in one chromatographic run. An extensive investigation of method development parameters (enzymatic hydrolysis, matrix effects, process efficiency, sources of background interferences, linearity, accuracy, precision, stabilities and limits of detection and quantification) was performed in order to address previously reported method inconsistencies and select a process with the highest accuracy and sensitivity. Chromatographic separation was achieved on a Luna C 18 (2) (2.00 mm × 150 mm, 3 μm) with mobile phase 80:20 v/v water: MeOH and MeOH: water 95:5 v/v, both containing 1 mM tributylamine and 1 mM acetic acid. Limits of detection were 0.025 ng mL −1 for BDCIPP and BCIPP and 0.1 ng mL −1 for DPhP and BCEP. Absolute recoveries of all four analytes and their labeled compounds were in the range of 88–107%. The method was tested on 13 adult California urine samples. BCEP was detected at 0.4–15 ng mL −1 with a geometric mean (GM): 1.9 ng mL −1 ; BDCIPP at 0.5–7.3 ng mL −1 , (GM: 2.5 ng mL −1 ) and DPhP at

Benzophenone (BP)-type UV filters are widely used in a variety of personal care products for the protection of skin and hair from UV irradiation. Despite the estrogenic potencies of BP derivatives, few studies have examined the occurrence of these compounds in human matrices. Furthermore, associations among exposure to these compounds and estrogen-dependent diseases (such as endometriosis) have not been examined previously. In this study, we determined the concentrations of five BP derivatives, 2-hydroxy-4-methoxybenzophenone (2OH-4MeO-BP), 2,4-dihydroxybenzophenone (2,4OH-BP), 2,2'-dihydroxy-4-methoxybenzophenone (2,2'OH-4MeO-BP), 2,2',4,4'-tetrahydroxybenzophenone (2,2',4,4'OH-BP), and 4-hydroxybenzophenone (4OH-BP), in urine collected from 625 women in Utah and California, using liquid chromatography (LC)-tandem mass spectrometry (MS/MS). The association of urinary concentrations of BP derivatives with an increase in the odds of a diagnosis of endometriosis was examined in 600 women who underwent laparoscopy/laparotomy (n = 473: operative cohort) or pelvic magnetic resonance imaging (n = 127: population cohort), during 2007-2009. 2OH-4MeO-BP, 2,4OH-BP, and 4OH-BP respectively were detected in 99.0%, 93.3%, and 83.8% of the urine samples analyzed, whereas the detection rates for 2,2',4,4'OH-BP and 2,2'OH-4MeO-BP were below 6.0%. Significant regional differences (higher concentrations in California) and monthly variations (higher concentrations in July and August) were found for urinary concentrations of 2OH-4MeO-BP and 2,4OH-BP. In addition, urinary concentrations of 2OH-4MeO-BP and 2,4OH-BP tended to be higher in more affluent, older, and leaner women. Adjusted odds ratios (ORs) and 95% confidence intervals (CIs) were estimated for the urinary concentrations of BP derivatives and the odds of an endometriosis diagnosis; ORs increased across quartiles of 2OH-4MeO-BP and 2,4OH-BP concentrations, but a significant trend was observed only between 2,4OH-BP and the odds of an endometriosis diagnosis in the operative cohort (OR = 1.19; 95% CI = 1.01, 1.41). When women in the highest quartile of 2,4OH-BP concentrations were compared with women in the first three quartiles, the OR increased considerably (OR = 1.65; 95% CI = 1.07, 2.53). Given that 2,4OH-BP possesses an estrogenic activity higher than that of 2OH-4MeO-BP, our results invite the speculation that exposure to elevated 2,4OH-BP levels may be associated with endometriosis. [ABSTRACT FROM AUTHOR]