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Marginal seas are directly subjected to anthropogenic and natural influences from land in addition to receiving inputs from the atmosphere and open ocean. Together these lead to pronounced gradients and strong dynamic changes. However, in the case of mercury emissions from these seas, estimates often fail to adequately account for the spatial and temporal variability of the elemental mercury concentration in surface water (Hg0wat). In this study, a method to measure Hg0wat at high resolution was devised and subsequently validated. The better-resolved Hg0wat dataset, consisting of about one measurement per nautical mile, yielded insight into the sea's small-scale variability and thus improved the quantification of the sea's Hg0 emission. This is important because global marine Hg0 emissions constitute a major source of atmospheric mercury. Research campaigns in the Baltic Sea were carried out between 2011 and 2015 during which Hg0 both in surface water and in ambient air were measured. For the former, two types of equilibrators were used. A membrane equilibrator enabled continuous equilibration and a bottle equilibrator assured that equilibrium was reached for validation. The measurements were combined with data obtained in the Baltic Sea in 2006 from a bottle equilibrator only. The Hg0 sea–air flux was newly calculated with the combined dataset based on current knowledge of the Hg0 Schmidt number, Henry's law constant, and a widely used gas exchange transfer velocity parameterization. By using a newly developed pump–CTD with increased pumping capability in the Hg0 equilibrator measurements, Hg0wat could also be characterized in deeper water layers. A process study carried out near the Swedish island Øland in August 2015 showed that the upwelling of Hg0-depleted water contributed to Hg0 emissions of the Baltic Sea. However, a delay of a few days after contact between the upwelled water and light was apparently necessary before the biotic and abiotic transformations of ionic to volatile Hg0 produced a distinct sea–air Hg0 concentration gradient. This study clearly showed spatial, seasonal, and interannual variability in the Hg0 sea–air flux of the Baltic Sea. The average annual Hg0 emission was 0.90 ± 0.18 Mg for the Baltic proper and extrapolated to 1.73 ± 0.32 Mg for the entire Baltic Sea, which is about half the amount entrained by atmospheric deposition. A comparison of our results with the Hg0 sea–air fluxes determined in the Mediterranean Sea and in marginal seas in East Asia were to some extent similar but they partly differed in terms of the deviations in the amount and seasonality of the flux.

The bifunctional CO-dehydrogenase/acetyl-CoA synthase (CODH/ACS) complex couples the reduction of CO 2 to the condensation of CO with a methyl moiety and CoA to acetyl-CoA. Catalysis occurs at two sites connected by a tunnel transporting the CO. In this study, we investigated how the bifunctional complex and its tunnel support catalysis using the CODH/ACS from Carboxydothermus hydrogenoformans as a model. Although CODH/ACS adapted to form a stable bifunctional complex with a secluded substrate tunnel, catalysis and CO transport is even more efficient when two monofunctional enzymes are coupled. Efficient CO channeling appears to be ensured by hydrophobic binding sites for CO, which act in a bucket-brigade fashion rather than as a simple tube. Tunnel remodeling showed that opening the tunnel increased activity but impaired directed transport of CO. Constricting the tunnel impaired activity and CO transport, suggesting that the tunnel evolved to sequester CO rather than to maximize turnover., (© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The structure of the TriABC inner membrane component of the triclosan/SDS-specific efflux pump from Pseudomonas aeruginosa was determined by cryoelectron microscopy to 4.5 Å resolution. The complete structure of the inner membrane transporter TriC of the resistance-nodulation-division (RND) superfamily was solved, including a partial structure of the fused periplasmic membrane fusion subunits, TriA and TriB. The substrate-free conformation of TriABC represents an intermediate step in efflux complex assembly before the engagement of the outer membrane channel. Structural analysis identified a tunnel network whose constriction impedes substrate efflux, indicating inhibition of TriABC in the unengaged state. Blind docking studies revealed binding to TriC at the same loci by substrates and bulkier non-substrates. Together with functional analyses, we propose that selective substrate translocation involves conformational gating at the tunnel narrowing that, together with conformational ordering of TriA and TriB, creates an engaged state capable of mediating substrate efflux., Competing Interests: Declaration of Interest The authors declare that they have no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)