Exposure Classification and Temporal Variability in Urinary Bisphenol A Concentrations among Couples in Utah--The HOPE Study.

BACKGROUND: Bisphenol A (BPA) is an endocrine disruptor and potential reproductive toxicant, but results of epidemiologic studies have been mixed and have been criticized for inadequate exposure assessment that often relies on a single measurement. OBJECTIVE: Our goal was to describe the distribution of BPA concentrations in serial urinary specimens, assess temporal variability, and provide estimates of exposure classification when randomly selected samples are used to predict average exposure. METHODS: We collected and analyzed 2,614 urine specimens from 83 Utah couples beginning in 2012. Female participants collected daily first-morning urine specimens during one to two menstrual cycles and male partners collected specimens during the woman's fertile window for each cycle. We measured urinary BPA concentrations and calculated geometric means (GM) for each cycle, characterized the distribution of observed values and temporal variability using intraclass correlation coefficients, and performed surrogate category analyses to determine how well repeat samples could classify exposure. RESULTS: The GM urine BPA concentration was 2.78 ng/mL among males and 2.44 ng/mL among females. BPA had a high degree of variability among both males (ICC = 0.18; 95% CI: 0.11, 0.26) and females (ICC = 0.11; 95% CI: 0.08, 0.16). Based on our more stringent surrogate category analysis, to reach proportions ≥ 0.80 for sensitivity, specificity, and positive predictive value (PPV) among females, 6 and 10 repeat samples for the high and low tertiles, respectively, were required. For the medium tertile, specificity reached 0.87 with 10 repeat samples, but even with 11 samples, sensitivity and PPV did not exceed 0.36. Five repeat samples, among males, yielded sensitivity and PPV values ≥ 0.75 for the high and low tertiles, but, similar to females, classification for the medium tertile was less accurate. CONCLUSION: Repeated urinary specimens are required to characterize typical BPA exposure. CITATION: Cox KJ, Porucznik CA, Anderson DJ, Brozek EM, Szczotka KM, Bailey NM, Wilkins DG, Stanford JB. 2016. Exposure classification and temporal variability in urinary bisphenol A concentrations among couples in Utah-the HOPE study. Environ Health Perspect 124:498-506; http://dx.doi.org/10.1289/ehp.1509752.

Biomonitoring method for bisphenol A in human urine by ultra-high-performance liquid chromatography-tandem mass spectrometry.

An ultra-high-performance liquid chromatography-tandem mass spectrometry method for the measurement of total bisphenol A in human urine was developed and validated. The method utilized liquid/liquid extraction with 1-chlorobutane and a human urine aliquot size of 800µL. Chromatography was performed on an Acquity UPLC(®) system with a Kinetex(®) Phenyl-Hexyl column. Mass spectrometric analysis was with negative electrospray ionization on a Quattro Premier XE™. The surrogate matrix method was used for the preparation of calibration standards in synthetic urine due to the presence of BPA in control human urine. The validated calibration range was 0.75-20ng/mL with a limit of detection of 0.1ng/mL. The internal standard was d16-bisphenol A. Method validation utilized quality control samples at three concentrations in both synthetic urine and human urine. Bisphenol A mono-glucuronide was fortified in synthetic urine in each analytical run to monitor the enzymatic conversion of the glucuronide conjugate to BPA by ß-glucuronidase. Validated method parameters included linearity, accuracy, precision, integrity of dilution, selectivity, re-injection reproducibility, recovery/matrix effect, solution stability, and matrix stability in human urine. Acceptance criteria for analytical standards and QCs were ±20% of nominal concentration. Matrix stability in human urine was validated after 24h at ambient temperature, after three freeze/thaw cycles, and after frozen storage at -20°C and -80°C for up to 218 days. The method has been applied to the analysis of over 1750 human urine samples from a biomonitoring study. The median and mean urine BPA concentrations were 2.71ng/mL and 4.75ng/mL, respectively.

Internal Functionalization and Surface Modification of Vinylsilsesquioxane Nanoparticles.

The interior of 237 nm spherical vinylsilsesquioxane nanoparticles has been covalently modified and their surface functionalized under mild conditions to yield a novel type of hybrid silsesquioxane nanoparticles. Data obtained from thermogravimetric and elemental analysis show that the vinyl groups inside the nanoparticles can be easily brominated or hydroborated, leading to the nanoparticles containing 59.9 wt% of bromine or 3.6 wt% of boron, respectively. Our results demonstrate that the vinyl groups inside the nanoparticles are highly accessible, which may lead to the preparation of a host of hybrid organosilica nanoparticles with complex structures. We also show that the surface of the brominated and boronated nanoparticles is unhindered for further amination.