In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy.

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Hurricane Sandy caused extensive physical and economic damage; the long-term mental health consequences are unknown. Flooding is a central component of hurricane exposure, influencing mental health through multiple pathways that unfold over months after flooding recedes. Here we assess the concordance in self-reported and Federal Emergency Management (FEMA) flood exposure after Hurricane Sandy and determine the associations between flooding and anxiety, depression, and post-traumatic stress disorder (PTSD). Self-reported flood data and mental health symptoms were obtained through validated questionnaires from New York City and Long Island residents (N = 1231) following Sandy. Self-reported flood data was compared to FEMA data obtained from the FEMA Modeling Task Force Hurricane Sandy Impact Analysis. Multivariable logistic regressions were performed to determine the relationship between flooding exposure and mental health outcomes. There were significant discrepancies between self-reported and FEMA flood exposure data. Self-reported dichotomous flooding was positively associated with anxiety (ORadj: 1.5 [95% CI: 1.1–1.9]), depression (ORadj: 1.7 [1.3–2.2]), and PTSD (ORadj: 2.5 [1.8–3.4]), while self-reported continuous flooding was associated with depression (ORadj: 1.1 [1.01–1.12]) and PTSD (ORadj: 1.2 [1.1–1.2]). Models with FEMA dichotomous flooding (ORadj: 2.1 [1.5–2.8]) or FEMA continuous flooding (ORadj: 1.1 [1.1–1.2]) were only significantly associated with PTSD. Associations between mental health and flooding vary according to type of flood exposure measure utilized. Future hurricane preparedness and recovery efforts must integrate micro and macro-level flood exposures in order to accurately determine flood exposure risk during storms and realize the long-term importance of flooding on these three mental health symptoms.

Road dust resuspension is a major source of particulate matter in many urban centers, especially those in which traction materials are applied to roadways in winter. Although many studies have investigated the composition and toxicity of road dust, nothing is currently known regarding its photochemical reactivity. Here, we show for the first time that road dust is photochemically active: in particular, we use a molecular probe technique to show that the illumination of aqueous road dust suspensions leads to the production of singlet oxygen (1O2), an important environmental oxidant. In experiments conducted using size-fractionated road dust, we found that the surface area-normalized steady-state 1O2 concentration ([1O2]ss) increased with decreasing particle size. We also observed correlations between [1O2]ss and the dissolved organic carbon content and ultraviolet absorbance properties of dust extracts, which suggests the involvement of chromophoric water-soluble organic carbon in the observed photochemistry. Interestingly, [1O2]ss in aqueous road dust extracts was lower than in the corresponding particle-containing samples, which implies that the particle surface itself also participated in 1O2 production. This work provides evidence that road dust photochemistry may influence the lifetime of urban pollutants that react via 1O2-mediated pathways.

Results suggest that participants with higher PTSD symptoms were more likely to grow from the impact of the storm, indicating resilience. Highly exposed participants were more likely to experience PTG. A decrease in PTG was found among those with both PTSD and depression symptoms. The development and implementation of interventions fostering PTG could be beneficial in clinical disaster response work. (PsycINFO Database Record

The sea surface microlayer (SSML) is often present at the ocean interface and provides a unique environment for chemical reactions to occur. One such reaction is the heterogeneous oxidation of the SSML components with ozone, which is hypothesized to be an important source of volatile compounds that may participate in marine aerosol formation and growth. To better understand this source, a biologically relevant model SSML is constructed using axenic Thalassiosira pseudonana cultures. This model SSML is shown to be reasonably reproducible for repeated experiments with a biological system and offers considerably more chemical and morphological complexities than single-molecule SSML representations for trying to understand the impact of marine biological processes on the atmosphere. Using proton transfer reaction mass spectrometry, this study demonstrates that C7–C10 gas-phase carbonyls arise from the oxidation of the model SSML with ozone. The ability of gas-phase products of ozone oxidation at the SSML to form aerosol particles was investigated with a scanning mobility particle sizer analyzer to determine the particle size and concentration of newly formed ultrafine aerosol particles. These particles are confirmed to be secondary organic aerosol (SOA) by analyzing their composition with an aerosol mass spectrometer, indicating that the source of the aerosol precursors is the organic material generated by the T. pseudonana cultures. The rates of SOA and carbonyl production are larger for 21 day-old cultures than for 7 day-old cultures, likely due to the release of the organic material from cell lysis in the older cultures. By demonstrating that the heterogeneous oxidation of the SSML forms SOA precursors that contribute to aerosol growth, this study emphasizes the importance of biological processes on the chemical reactions that can occur within the SSML.

Hurricane exposure can have a profound impact on mental health, leading to increased symptoms of stress, anxiety, depression and post-traumatic stress disorder that are still present years after the storm. Those displaced following a hurricane are particularly vulnerable to adverse mental health outcomes, especially if displaced to temporary shelters. The current work highlights the experiences and mental health challenges of displaced populations following Hurricane Sandy and Hurricane Harvey, as well as describing barriers to conducting research in the immediate aftermath of Hurricane Harvey and the need for more comprehensive interventions in these vulnerable populations.

The reaction of ozone with iodide in the ocean is a major ozone dry deposition pathway, as well as an important source of reactive iodine to the marine troposphere. Few prior laboratory experiments have been conducted with environmentally relevant ozone mixing ratios and iodide concentrations, leading to uncertainties in the rate of the reaction under marine boundary layer conditions. As well, there remains disagreement in the literature assessment of the relative contributions of an interfacial reaction via ozone adsorbed to the ocean surface versus a bulk reaction with dissolved ozone. In this study, we measure the uptake coefficient of ozone over a buffered, pH 8 salt solution replicating the concentrations of iodide, bromide, and chloride in the ocean over an ozone mixing ratio of 60−500 ppb. Due to iodide depletion in the solution, the measured ozone uptake coefficient is dependent on the exposure time of the solution to ozone and its mixing ratio. A kinetic multilayer model confirms that iodide depletion is occurring not only within ozone's reactodiffusive depth, which is on the order of microns for environmental conditions, but also deeper into the solution as well. Best model-measurement agreement arises when some degree of nondiffusive mixing is occurring in the solution, transporting iodide from deeper in the solution to a thin, diffusively mixed upper layer. If such mixing occurs rapidly in the environment, iodide depletion is unlikely to reduce ozone dry deposition rates. Unrealistically high bulk-to-interface partitioning of iodide is required for the model to predict a substantial interfacial component to the reaction, indicating that the Langmuir−Hinshelwood mechanism is not dominant under environmental conditions.Article pubs.acs.org/JPCA