This study conducted the first comprehensive investigation of sedimentary black carbon (BC) concentration, flux, and budget in the continental shelves of "Bohai Sea (BS) and Yellow Sea (YS)," based on measurements of BC in 191 surface sediments, 36 riverine water, and 2 seawater samples, as well as the reported data set of the atmospheric samples from seven coastal cities in the Bohai Rim. BC concentrations in these matrices were measured using the method of thermal/optical reflectance. The spatial distribution of the BC concentration in surface sediments was largely influenced by the regional hydrodynamic conditions, with high values mainly occurring in the central mud areas where fine-grained particles (median diameters > 6 Φ (i.e., <0.0156 mm)) were deposited. The BC burial flux in the BS and YS ranged from 4 to 1100 μg/cm 2 yr, and averaged 166 ± 200 μg/cm 2 yr, which was within the range of burial fluxes reported in other continental shelf regimes. The area-integrated sedimentary BC sink flux in the entire BS and YS was~325 Gg/yr, and the BS alone contributed~50% (~157 Gg/yr). The BC budget calculated in the BS showed that atmospheric deposition, riverine discharge, and import from the Northern Yellow Sea (NYS) each contributed~51%, 47%, and~2%. Therefore, atmospheric deposition and riverine discharge dominated the total BC influx (~98%). Sequestration to bottom sediments was the major BC output pattern, accounting for~88% of the input BC. Water exchange between the BS and the NYS was also an important BC transport route, with net BC transport from the BS to the NYS.

Dye-decolorizing peroxidases (DyPs) are a family of H2O2-dependent heme peroxidases, which have shown potential applications in lignin degradation and valorization. However, the DyP kinetic mechanism remains underexplored. Using structural biology and solvent isotope (sKIE) and viscosity effects, many mechanistic characteristics have been uncovered for the B-class ElDyP from Enterobacter lignolyticus. Its structure revealed that a water molecule acts as the sixth axial ligand with two channels at diameters of ~3.0 and 8.0 Å leading to the heme center. A conformational change of ERS* to ERS, which have identical spectral characteristics, was proposed as the final step in DyPs’ bisubstrate Ping-Pong mechanism. This step is also the rate-determining step in ABTS oxidation. The normal KIE of wild-type ElDyP with D2O2 at pH 3.5 suggested that cmpd 0 deprotonation by the distal aspartate is rate-limiting in the formation of cmpd I, which is more reactive under acidic pH than under neutral or alkaline pH. The viscosity effects and other biochemical methods implied that the reducing substrate binds with cmpd I instead of the free enzyme. The significant inverse sKIEs of kcat/KM and kERS* suggested that the aquo release in DyPs is mechanistically important and may explain the enzyme’s adoption of two-electron reduction for cmpd I. The distal aspartate is catalytically more important than the distal arginine and plays key roles in determining DyPs’ acidic pH optimum. The kinetic mechanism of D143H-ElDyP was also briefly studied. The results obtained will pave the way for future protein engineering to improve DyPs’ lignolytic activity.

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The Cambridge Crystallographic Data Centre has recently brought to our attention that the CCDC numbers reported for compounds 5 j, 6 j, 7 a, and 9 were incorrect. The data sets corresponding to these compounds are CCDC-934284 (5 j), CCDC-934285 (6 j), CCDC-934286 (7 a) and CCDC-934286 (9) which contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. The editorial office apologizes for the oversight .

a b s t r a c tThe distribution characteristics and potential sources of polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) were investigated in 54 surface sediment samples from four bays (Taozi Bay, Sishili Bay, Dalian Bay, and Jiaozhou Bay) of North China's Yellow Sea. Of the 54 samples studied, 51 were collected from within the four bays and 3 were from rivers emptying into Jiaozhou Bay. Decabromodiphenylethane (DBDPE) was the predominant flame retardant found, and concentration ranged from 0.16 to 39.7 ng g À1 dw and 1.13e49.9 ng g À1 dw in coastal and riverine sediments, respectively; these levels were followed by those of BDE 209, and its concentrations ranged from n.d. to 10.2 ng g À1 dw and 0.05e7.82 ng g À1 dw in coastal and riverine sediments, respectively. The levels of DBDPE exceeded those of decabromodiphenyl ether (BDE 209) in most of the samples in the study region, whereas the ratio of DBDPE/BDE 209 varied among the four bays. This is indicative of different usage patterns of brominated flame retardants (BFRs) and also different hydrodynamic conditions among these bay areas. The spatial distribution and composition profile analysis indicated that BFRs in Jiaozhou Bay and Dalian Bay were mainly from local sources, whereas transport from Laizhou Bay by coastal currents was the major source of BFRs in Taozi Bay and Sishili Bay. Both the P PBDEs and P aBFRs (sum of pentabromotoluene (PBT), 2,3-diphenylpropyl-2,4,6-tribromophenyl ether (DPTE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB)) were at low concentrations in all the sediments. This is probably attributable to a combination of factors such as low regional usage of these products, atmospheric deposition patterns, coastal currents transportation patterns, and degradation processes for higher BDE congeners. This paper is the first study that has investigated the levels of DBDPE in the coastal sediments of China's Yellow Sea.

Elaborating the spatiotemporal variations and dynamic mechanisms of black carbon (BC) in coastal seas, the geographically pivotal intermediate zones that link the terrestrial and open oceanic ecosystems, will contribute significantly to refine the regional and global BC geochemistry. In this study, we implemented a large spatial-scale and multiseason and -layer seawater sampling campaign in high BC emission influenced coastal China seas (Bohai Sea and Northern Yellow Sea) and quantified the thermal/optical reflectance-based particulate BC (PBC) and benzene polycarboxylic acids-based dissolved BC (DBC). We found that the climate and its associated hydrological effects (including the intensive resuspension and coastal current transport) largely regulate both PBC and DBC spatiotemporal variations and dynamics. In combination with previous work on upstream rivers and downstream open ocean, a significant and continuous decrease in the DBC aromatic condensation was observed along the river-to-ocean continuum, probably due to the increment of the photochemical degradation during the waterborne transport. Based on our DBC methodological development, i.e., the determination and subsequent inclusion of the nitrated BC molecular markers, the magnitudes of the current global DBC fluxes and pools were updated. After the update, the DBC fluxes from atmospheric deposition and riverine delivery were estimated at rates of 4.3 and 66.3 Tg yr −1 , respectively, and the global oceanic DBC pool was approximately 36 Gt. This update will greatly assist in constructing a more robust regional and global DBC and BC cycling and budgets.