Factors influencing the oxidation,reduction, methylation and demethylation of mercury species in coastal waters

The objective of this study was to examine the redox reactions and other transformations of mercury (Hg) species in surface waters, and the factors determining the rates of these reactions. For the redox studies completed at the Chesapeake Biological Laboratory (CBL), two isotopes (¹⁹⁹Hg^II and ²⁰²Hg⁰) were added into different types of filtered water (fresh to seawater) to examine the oxidation and reduction reactions. Further studies of both the redox reactions and methylation/demethylation reactions of Hg were conducted with unfiltered water on board research vessels during cruises in May and July 2005 on the Chesapeake Bay and shelf. While CH₃¹⁹⁹Hg^II was added to allow the examination of demethylation, ²⁰¹Hg^II was used to examine both reduction and methylation, and ²⁰²Hg⁰ was used to examine oxidation. Overall, the results showed that both Hg oxidation and reduction were simultaneously occurring and were photochemically mediated in the waters investigated. In contrast to the previously assumed “unreactive” nature of Hg⁰, the studies found that the magnitude of the rate constant for Hg⁰ oxidation was greater than that for reduction, indicating its importance in estuarine and coastal waters. In addition, both experiments at CBL and on board ship showed that Hg^II reduction was similar in magnitude, suggesting that biotic processes were relatively unimportant. While no measurable methylation occurred during the incubation period during the on board studies, concentration of CH₃¹⁹⁹Hg^II decreased over the time during the experiments. It appeared that the demethylation processes were not dominantly photochemically driven, but could be microbially mediated. Further studies are needed in order to help better understand Hg redox and transformations in natural water systems.     

Methylmercury production in sediments of Chesapeake Bay and the mid-Atlantic continental margin

Methylmercury (MeHg) concentration and production rates were studied in bottom sediments along the mainstem of Chesapeake Bay and on the adjoining continental shelf and slope. Our objectives were to 1) observe spatial and temporal changes in total mercury (HgT) and MeHg concentrations in the mid-Atlantic coastal region, 2) investigate biogeochemical factors that affect MeHg production, and 3) examine the potential of these sediments as sources of MeHg to coastal and open waters. Estuarine, shelf and slope sediments contained on average 0.5 to 1.5% Hg as MeHg (% MeHg), which increased significantly with salinity across our study site, with weak seasonal trends. Methylation rate constants (k_meth), estimated using enriched stable mercury isotope spikes to intact cores, showed a similar, but weaker, salinity trend, but strong seasonality, and was highly correlated with % MeHg. Together, these patterns suggest that some fraction of MeHg is preserved thru seasons, as found by others [Orihel, D.M., Paterson, M.J., Blanchfield, P.J., Bodaly, R.A., Gilmour, C.C., Hintelmann, H., 2008. Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem. Environmental Pollution 154, 77] Similar to other ecosystems, methylation was most favored in sediment depth horizons where sulfate was available, but sulfide concentrations were low (between 0.1 and 10 μM). MeHg production was maximal at the sediment surface in the organic sediments of the upper and mid Bay where oxygen penetration was small, but was found at increasingly deeper depths, and across a wider vertical range, as salinity increased, where oxygen penetration was deeper. Vertical trends in MeHg production mirrored the deeper, vertically expanded redox boundary layers in these offshore sediments. The organic content of the sediments had a strong impact on the sediment:water partitioning of Hg, and therefore, on methylation rates. However, the HgT distribution coefficient (K_D) normalized to organic matter varied by more than an order of magnitude across the study area, suggesting an important role of organic matter quality in Hg sequestration. We hypothesize that the lower sulfur content organic matter of shelf and slope sediments has a lower binding capacity for Hg resulting in higher MeHg production, relative to sediments in the estuary. Substantially higher MeHg concentrations in pore water relative to the water column indicate all sites are sources of MeHg to the water column throughout the seasons studied. Calculated diffusional fluxes for MeHg averaged  1 pmol m^− 2 day^− 1. It is likely that the total MeHg flux in sediments of the lower Bay and continental margin are significantly higher than their estimated diffusive fluxes due to enhanced MeHg mobilization by biological and/or physical processes. Our flux estimates across the full salinity gradient of Chesapeake Bay and its adjacent slope and shelf strongly suggest that the flux from coastal sediments is of the same order as other sources and contributes substantially to the coastal MeHg budget.     

Sulfide and iron control on mercury speciation in anoxic estuarine sediment slurries

In order to understand the role of sulfate and Fe(III) reduction processes in the net production of monomethylmercury (MMHg), we amended anoxic sediment slurries collected from the Venice Lagoon, Italy, with inorganic Hg and either potential electron acceptors or metabolic byproducts of sulfate and Fe(III) reduction processes, gradually changing their concentrations. Addition of sulfide (final concentration: 0.2–6.3 mM) resulted in an exponential decrease in the sulfate reduction rate and MMHg concentration with increasing concentrations of sulfide. Based on this result, we argue that the concentration of dissolved sulfide is a critical factor controlling the sulfate reduction rate, and in turn, the net MMHg production at steady state. Addition of either Fe(II) (added concentration: 0–6.1 mM) or Fe(III) (added concentration: 0–3.5 mM) resulted in similar trends in the MMHg concentration, an increase with low levels of Fe additions and a subsequent decrease with high levels of Fe additions. The limited availability of dissolved Hg, associated with sulfide removal by precipitation of FeS, appears to inhibit the net MMHg production in high levels of Fe additions. There was a noticeable reduction in the net MMHg production in Fe(III)-amended slurries as compared to Fe(II)-amended ones, which could be caused by a decrease in the sulfate reduction rate. This agrees with the results of Hg methylation assays using the enrichment cultures of anaerobic bacteria: whereas the enrichment cultures of sulfate reducers showed significant production of MMHg (4.6% of amended Hg), those of Fe(III), Mn(IV), and nitrate reducers showed no production of MMHg. It appears that enhanced Fe(III)-reduction activities suppress the formation of MMHg in high sulfate estuarine sediments.     

Enhanced concentrations of dissolved gaseous mercury in the surface waters of the Arctic Ocean

During an almost three months long expedition in the Arctic Ocean, the Beringia 2005, dissolved gaseous mercury (DGM) was measured continuously in the surface water. The DGM concentration was measured using an equilibrium system, i.e. the DGM in the water phase equilibrated with a stream of gas and the gas was thereafter analysed with respect to its mercury content. The DGM concentrations were calculated using the following equation, DGM = Hg_eq / k_H' where Hg_eq is the equilibrated concentration of elemental mercury in the gas phase and k_H' is the dimensionless Henry's law constant at desired temperature and salinity. During the expedition several features were observed. For example, enhanced DGM concentration was measured underneath the ice which may indicate that the sea ice acted as a barrier for evasion of mercury from the Arctic Ocean to the atmosphere. Furthermore, elevated DGM concentrations were observed in water that might have originated from river discharge. The gas-exchange of mercury between the ocean and the atmosphere was calculated in the open water and both deposition and evasion were observed. The measurements showed significantly enhanced DGM concentrations, compared to more southern latitudes.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

镉和汞胁迫对四角蛤蜊（Mactra veneriformis）血细胞的毒性损伤研究

采用透射电镜观察、溶酶体膜稳定性衡量和微核生成率检测的方法,系统研究了室内模拟Cd和Hg污染胁迫对四角蛤蜊血细胞的毒性损伤。结果表明,Cd对四角蛤蜊血细胞超微结构的损伤表现出明显的浓度依赖效应,125μg/L Cd胁迫下血细胞结构损伤程度高于25μg/L Cd胁迫;不同浓度Cd和Hg暴露14天后,各处理组（2μg/L ...     

云南水汞在打破M≥5级地震平静后强震前的异常分析

通过普洱6．3、宁蒗6．2级和姚安6．5级3个在省内M≥5级地震平静了10余个月,打破5级平静后发生的M≥6级强震前水汞的异常分析,并着重短临异常研究,结果表明这3次地震前水汞均有中期和短、临异常,中、短、临异常台站数为两头少,中间多。中期异常表现为11％。22％的水汞观测台站震前出现2—10个月的中期异常;短期异常表现为震前2—3个月,平均44％的台站观测到短期异常,最大异常幅度与异常判定线比值在1．3—3．2倍之间：强震前都只有1个台站出现临震异常。短期异常有差异,宁蒗6．2级主震前,短期异常在2次前震前出现,普洱6．3、姚安6．5级地震前,水汞短期异常在打破5级平静的地震前出现,水汞短期异常有活跃、平静的现象。最早出现中期异常的台站相对靠近震中。     

水（金）星凌日的程序化预报方法

本文介绍了预报水(金)星凌日的计算方法和凌日图的绘制方法,建立了一套完整的预报程序。作为该程序的一个简单应用,我们结合DE200历表及美国海军天文台提供的岁差章动程序,给出了1999年水星凌日的预报结果。     

The variability of Mercury's exosphere by particle and radiation induced surface release processes

Mercury's close orbit around the Sun, its weak intrinsic magnetic field and the absence of an atmosphere (P_surface<1×10⁻⁸ Pa) results in a strong direct exposure of the surface to energetic ions, electrons and UV radiation. Thermal processes and particle-surface-collisions dominate the surface interaction processes leading to surface chemistry and physics, including the formation of an exosphere (N?10¹⁴ cm⁻²) in which gravity is the dominant force affecting the trajectories of exospheric atoms. NASA's Mariner 10 spacecraft observed the existence of H, He, and O in Mercury's exosphere. In addition, the volatile components Na, K, and Ca have been observed by ground based instrumentation in the exosphere. We study the efficiency of several particle surface release processes by calculating stopping cross-sections, sputter yields and exospheric source rates. Our study indicates surface sputter yields for Na between values of about 0.27 and 0.35 in an energy range from 500 eV up to 2 keV if Na⁺ ions are the sputter agents, and about 0.037 and 0.082 at an energy range between 500 eV up to 2 keV when H⁺ are the sputter agents and a surface binding energy of about 2 eV to 2.65 eV. The sputter yields for Ca are about 0.032 to 0.06 and for K atoms between 0.054 to 0.1 in the same energy range. We found a sputter yield for O atoms between 0.025 and 0.04 for a particle energy range between 500 eV up to 2 keV protons. By taking the average solar wind proton surface flux at the open magnetic field line area of about 4×10⁸ cm⁻² s⁻¹ calculated by Massetti et al. (2003, Icarus, in press) the resulting average sputtering flux for O is about 0.8-1.0×10⁷ cm⁻² s⁻¹ and for Na approximately 1.3-1.6×10⁵ cm⁻² s⁻¹ depending on the assumed Na binding energies, regolith content, sputtering agents and solar activity. By using lunar regolith values for K we obtain a sputtering flux of about 1.0-1.4×10⁴ cm⁻² s⁻¹. By taking an average open magnetic field line area of about 2.8×10¹⁶ cm² modelled by Massetti et al. (2003, Icarus, in press) we derive an average surface sputter rate for Na of about 4.2×10²¹ s⁻¹ and for O of about 2.5×10²³ s⁻¹. The particle sputter rate for K atoms is about 3.0×10²⁰ s⁻¹ assuming lunar regolith composition for K. The sputter rates depend on the particle content in the regolith and the open magnetic field line area on Mercury's surface. Further, the surface layer could be depleted in alkali. A UV model has been developed to yield the surface UV irradiance at any time and latitude over a Mercury year. Seasonal and diurnal variations are calculated, and Photon Stimulated Desorption (PSD) fluxes along Mercury's orbit are evaluated. A solar UV hotspot is created towards perihelion, with significant average PSD particle release rates and Na fluxes of about 3.0×10⁶ cm⁻² s⁻¹. The average source rates for Na particles released by PSD are about 1×10²⁴ s⁻¹. By using the laboratory obtained data of Madey et al. (1998, J. Geophys. Res. 103, 5873-5887) for the calculation of the PSD flux of K atoms we get fluxes in the order of about 10⁴ cm⁻² s⁻¹ along Mercury's orbit. However, these values may be to high since they are based on idealized smooth surface conditions in the laboratory and do not include the roughness and porosity of Mercury's regolith. Further, the lack of an ionosphere and Mercury's small, temporally and spatially highly variable magnetosphere can result in a large and rapid increase of exospheric particles, especially Na in Mercury's exosphere. Our study suggests that the average total source rates for the exosphere from solar particle and radiation induced surface processes during quiet solar conditions may be of the same order as particles produced by micrometeoroid vaporization. We also discuss the capability of in situ measurements of Mercury's highly variable particle environment by the proposed NPA-SERENA instrument package on board ESA's BepiColombo Mercury Planetary Orbiter (MPO).