Lewisite Metabolites in Urine by Solid Phase Extraction-Dual Column Reversed-Phase Liquid Chromatography-Isotope Dilution Tandem Mass Spectrometry.

Lewisite (2-chlorovinyldichloroarsine) is a chemical warfare agent developed during World War I. A quantitative method using solid phase extraction (SPE) followed by dual column liquid chromatography (LC)-isotope dilution tandem mass spectrometry (MS-MS) was developed for the determination of (2-chlorovinyl)arsonic acid (CVAOA), a metabolite of Lewisite, in human urine. The sample was treated with hydrogen peroxide to oxidize any (2-chlorovinyl)arsonous acid (CVAA) that remained in the trivalent arsenic oxidation state. There was 1.19% (arsenic purity) of bis-(2-chlorovinyl)arsinic acid (BCVAOA), a minor Lewisite metabolite, in the stock CVAA material. The high-throughput method qualitatively assessed BCVAOA simultaneously utilizing normal-phase silica SPE followed by reversed-phase C18 LC for an orthogonal separation. The chromatographic method results in a 5.8-min cycle time with adequate retention (k' = 2.4) of CVAOA. The mass spectrometer was operated in positive electrospray ionization mode with quantitative m/z 186.9→61.0 and confirmation 186.9→91.0 mass transitions. This selective method demonstrated linearity, accuracy and reproducibility for the clinically relevant calibration range (25-3,200 µg/L as CVAA). The method detection limit was 3.3 µg/L as CVAA from a 10 µL injection. This LC-MS-MS emergency response method has a throughput of >240 samples (2.5 extracted 96-well plates) per day.

Fish consumption and hair mercury levels in women of childbearing age, Martin County, Florida.

The health effects of mercury in humans are mostly on the developing nervous system. Pregnant women and women who are breastfeeding must be targeted in order to decrease mercury exposure to the populations at highest risk-infants, unborn fetuses, and young children. This purpose of this study is to understand the demographics of fish-consumption patterns among women of childbearing age (including pregnant women) in Martin County, Florida, and to analyze the associations of mercury levels in participants' hair with socio-demographic variables in order to better design prevention messages and campaigns. Mercury concentrations in hair samples of 408 women ages 18-49 were assessed. Data on demographic factors, pregnancy status, fish consumption, and awareness of fish advisories were collected during personal interviews. Data were analyzed using descriptive statistics and multivariate logistic regression. The geometric and arithmetic means of hair mercury concentration were 0.371 and 0.676 µg/g of hair. One-fourth of the respondents had a concentration ≥1 µg/g of hair. Consuming a higher number of fish meals per month, consumption of commercially purchased or locally caught fish higher in mercury, White race and income ≥$75,000 were positively associated with the likelihood of having higher hair mercury levels. This study confirms the existence of a higher overall mean hair mercury level and a higher percentage of women with ≥1 µg/g hair mercury level than those reported at the national level and in other regional studies. This suggests the need for region-specific fish consumption advisories to minimize mercury exposure in humans.

Fish consumption patterns and mercury exposure levels among women of childbearing age in Duval County, Florida.

Consumption of fish containing methylmercury can pose serious health concerns including neurotoxic effects in adults and toxicity to the fetuses of mothers exposed during pregnancy. In the study described in this article, the authors examined fish consumption patterns and measured hair mercury levels of women of childbearing age in a coastal county in Florida. Women from the community participated in a risk factor assessment survey (N = 703). Hair samples (n = 698) were collected and analyzed for mercury. The authors identified 74.8% below detection limit; 25.2% had detectable limits of mercury, while 7% exceeded 1 pg/g. Hair mercury levels increased with fish consumption and age. Race, income, and education levels were also associated with increased hair mercury levels. Women of Asian/Pacific Islander origin had the highest levels. Although reported fish consumption exceeded the recommendations for women of childbearing age, the study population had lower mercury levels than other comparative studies in Florida and at national levels.

Perfluoroalkylphosphine coordination chemistry of platinum: synthesis of (C2F5)2PPh and (C2F5)PPh2 complexes of platinum(II).

A 1:1 addition of Ph2PCl to an ethereal solution of C2F5Li (formed from the reaction of BuLi with C2F5Cl) yields Ph2P(C2F5)(abbreviated pfepp) (1). The introduction of a fluoroethyl group results in a phosphine with electronic characteristics that approximate phosphites, bridging the electronic gap between traditional donor phosphine ligands and more electrophilic phosphine ligands like PhP(C2F5)2 (2). The pfepp ligand 1 is isolated as a high boiling liquid, which crystallizes upon standing at room temperature in an inert atmosphere. A series of Pt(II) complexes of the type trans-L2PtCl2 (L = pfepp 3; PhP(C2F5)2 4) have been prepared and structurally characterized by multinuclear NMR, IR and X-ray crystallography. The crystal structure of is the first example of a structurally characterized monodentate phosphine with a pentafluoroethyl pendant group.