The transformation of the sulfonamide antimicrobial sulfamethazine (SMZ) by a synthetic analogue of the birnessite-family mineral vernadite (δ-MnO(2)) was studied. The observed pseudo-first-order reaction constants (k(obs)) decreased as the pH increased from 4.0 to 5.6, consistent with the decline in δ-MnO(2) reduction potential with increasing pH. Molecular oxygen accelerated SMZ transformation by δ-MnO(2) and influenced the transformation product distribution. Increases in the Na(+) concentration produced declines in k(obs). Transformation products identified by tandem mass spectrometry and the use of (13)C-labeled SMZ included an azo dimer self-coupling product and SO(2) extrusion products. Product analysis and density functional theory calculations are consistent with surface precursor complex formation followed by single-electron transfer from SMZ to δ-MnO(2) to produce SMZ radical species. Sulfamethazine radicals undergo further transformation by at least two pathways: radical-radical self-coupling or a Smiles-type rearrangement with O addition and then extrusion of SO(3). Experiments conducted in H(2)(18)O or in the presence of (18)O(2)(aq) demonstrated that oxygen both from the lattice of as-synthesized δ-MnO(2) and initially present as dissolved oxygen reacted with SMZ. The study results suggest that the oxic state and pH of soil and sediment environments can be expected to influence manganese oxide-mediated transformation of sulfonamide antimicrobials.

Prenatal exposures to polybrominated diphenyl ethers (PBDEs) can harm neurodevelopment in humans and animals. In 2003–2004, PentaBDE and OctaBDE were banned in California and phased-out of US production; resulting impacts on human exposures are unknown. We previously reported that median serum concentrations of PBDEs and their metabolites (OH-PBDEs) among second trimester pregnant women recruited from San Francisco General Hospital (2008–2009; n=25) were the highest among pregnant women worldwide. We recruited another cohort from the same clinic in 2011–2012 (n=36) and now compare serum concentrations of PBDEs, OH-PBDEs, polychlorinated biphenyl ethers (PCBs) (structurally similar compounds banned in 1979), and OH-PCBs between two demographically similar cohorts. Between 2008–2009 and 2011–2012, adjusted least square geometric mean (LSGM) concentrations of ΣPBDEs decreased 65% (95% CI: 18, 130) from 90.0 ng/g lipid (95% CI: 64.7,125.2) to 54.6 ng/g lipid (95% CI: 39.2, 76.2) (p=0.004); Σ OH-PBDEs decreased six-fold (p<0.0001); and BDE-47, -99, and -100 declined more than BDE-153. There was a modest, non-significant (p=0.13) decline in LSGM concentrations of ΣPCBs and minimal differences in ΣOH-PCBs between 2008–2009 and 2011–2012. PBDE exposures are likely declining due to regulatory action, but the relative stability in PCB exposures suggests PBDE exposures may eventually plateau and persist for decades.

Exposures to environmental pollutants in utero may increase the risk of adverse health effects. We measured the concentrations of 59 potentially harmful chemicals in 77 maternal and 65 paired umbilical cord blood samples collected in San Francisco during 2010-11, including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hydroxylated PBDEs (OH-PBDEs), and perfluorinated compounds (PFCs) in serum, and metals in whole blood. Consistent with previous studies, we found evidence that concentrations of mercury (Hg) and lower-brominated PBDEs were often higher in umbilical cord blood or serum than in maternal samples (median cord:maternal ratio > 1), while for most PFCs and lead (Pb), concentrations in cord blood or serum were generally equal to or lower than their maternal pair (median cord:maternal ratio ≤ 1). In contrast to the conclusions of a recent review, we found evidence that several PCBs and OCPs were also often higher in cord than maternal serum (median cord:maternal ratio > 1) when concentrations are assessed on a lipid-adjusted basis. Our findings suggest that for many chemicals, fetuses may experience higher exposures than their mothers, and highlight the need to characterize potential health risks and inform policies aimed at reducing sources of exposure.

Concern about persistent organic pollutants (POPs) in Californians prompted the state's biomonitoring program to conduct a study in firefighters, who are occupationally exposed to high levels of POPs. In this work we present serum concentrations of several classes of POPs (polybrominated diphenyl ethers [PBDEs], polychlorinated biphenyls [PCBs], and organochlorine pesticides [OCPs]) in 101 Southern California firefighters. Despite recently reported declining trends of PBDEs in Californians, high levels were measured in firefighters' serum (Σ5PBDEs: median = 59.1 ng/(g of lipid); range = 18.8-714 ng/(g of lipid)) in comparison to other populations in California during the same period. In addition, nearly one-third of subjects had particularly high serum levels of decabromodiphenyl ether (BDE-209), consistent with other recent results in firefighters; this pattern may be a marker of recent firefighting activity. In contrast, serum levels of PCBs and OCPs measured in firefighters' sera were not elevated compared to U.S. levels. Multivariable analysis indicated that lower levels of serum PBDEs were associated with turnout gear cleaning and storage practices after fires. Our study supports the hypothesis that firefighting activities are likely to increase exposure to PBDEs and that good housekeeping and personal hygiene practices may reduce exposure to these compounds.