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

Lindsay Whalin  Eun-Hee Kim  Robert Mason 《Marine Chemistry》2007

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.  相似文献   

Methylmercury production in sediments of Chesapeake Bay and the mid-Atlantic continental margin   总被引：3，自引：0，他引：3  

T.A. Hollweg  C.C. Gilmour  R.P. Mason 《Marine Chemistry》2009,114(3-4):86-101

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.  相似文献   

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas   总被引：3，自引：0，他引：3  

Seunghee Han  Gary A. Gill  Ronald D. Lehman  Key-Young Choe 《Marine Chemistry》2006,98(2-4):156-166

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.  相似文献   

Mercury speciation in surface and deep waters of the Mediterranean Sea     

Jože Kotnik  Milena Horvat  Emmanuel Tessier  Nives Ogrinc  Mathilde Monperrus  David Amouroux  Vesna Fajon  Darija Gibičar  Suzana Žižek  Francesca Sprovieri  Nicola Pirrone 《Marine Chemistry》2007

Mercury speciation and its distribution in surface and deep waters of the Mediterranean Sea were studied during two oceanographic cruises on board the Italian research vessel URANIA in summer 2003 and spring 2004 as part of the Med Oceaneor and MERCYMS projects. The study included deep water profiles of dissolved gaseous Hg (DGM), reactive Hg (RHg), total Hg (THg), monomethyl Hg (MeHg) and dimethyl Hg (DMeHg) in open ocean waters. Average concentrations of measured Hg species were characterized by seasonal and spatial variations. Overall average THg concentrations ranged between 0.41 and 2.65 pM (1.32 ± 0.48 pM) and were comparable to those obtained in previous studies of the Mediterranean Sea. A significant fraction of Hg was present as “reactive” Hg (average 0.33 ± 0.32 pM). Dissolved gaseous Hg (DGM), which consists mainly of Hg⁰, represents a considerable proportion of THg (average 20%, 0.23 ± 0.11 pM). The portion of DGM typically increased towards the bottom, especially in areas with strong tectonic activity (Alboran Sea, Strait of Sicily, Tyrrhenian Sea), indicating its geotectonic origin. No dimethyl Hg was found in surface waters down to the depth of 40 m. Below this depth, its average concentration was 2.67 ± 2.9 fM. Dissolved fractions of total Hg and MeHg were measured in filtered water samples and were 0.68 ± 0.43 pM and 0.29 ± 0.17 pM for THg and MeHg respectively. The fraction of Hg as MeHg was in average 43%, which is relatively high compared to other ocean environments. The concentrations reported in this study are among the lowest found in marine environments and the quality of analytical methods are of key importance. Speciation of Hg in sea water is of crucial importance as THg concentrations alone do not give adequate data for understanding Hg sources and cycling in marine environments. For example, photoinduced transformations are important for the presence of reactive and elemental mercury in the surface layers, biologically mediated reactions are important for the production/degradation of MeHg and DGM in the photic zones of the water column, and the data for DGM in deep sea indicate the natural sources of Hg in geotectonicaly active areas of the Mediterranean Sea.  相似文献   

An Evaluation of Phase Behaviors of the Oil-Gas-Water System in the Displacement of Crude Oil with CO₂          下载免费PDF全文

ZHANG Angang  FAN Zifei  HE Jun 《《地质学报》英文版》2023,97(2):573-580

CO₂ dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO₂ injection into an oil reservoir. This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO₂. The composition of the JL oilfield in the northeast of China is taken as an example. The flash calculation of the oil-gas-water system was performed, based on the method presented by Li and Nghiem. The research re...  相似文献   

云南两次局地暴雨过程水汽输送特征分析     

马志敏  朱莉  连钰  牛法宝  王将 《中低纬山地气象》2021,45(6):50-58

采用常规观测资料、NCEP再分析资料,结合数值试验,对2012年5月24日和2015年9月27日云南两次局地暴雨过程水汽输送特征进行分析。结果表明：（1）两次过程主要受副热带高压影响,强降雨及其水汽输送伴随副热带高压西伸而中断,“5.24”过程动力条件主要由天气尺度系统提供,“9.27”过程动力条件主要为地形抬升作用;（2）两次过程水汽源地均为孟加拉湾、南海、西太平洋,“5.24”过程以西南路径水汽输送为主,输送距离较远,“9.27”过程以东南路径水汽输送为主,输送距离较短,局地特征更显著;（3）“9.27”过程水汽通量及最大雨量值均高于“5.24”过程,水汽通量与强降雨相关性较好,对强降雨具有一定指示意义;（4）两次过程水汽输送均集中在600hPa以下层,以经向偏南水汽输送为主,水汽输送增强时间较强降雨开始时间提前48～72h;（5）数值模拟结果与常规分析一致,同时可显示水汽垂直输送特征,低层以偏南路径为主,中层西南路径增多,中层以上出现偏西路径,存在沿西风带来自印度半岛及青藏高原的水汽贡献。  相似文献   

新疆天山北坡一次区域性暴雪形成机制及水汽输送特征分析     

万瑜 《沙漠与绿洲气象(新疆气象)》2024,18(4):9-16

利用高空、地面常规观测资料、NCEP/NCAR再分析资料，诊断分析了2017年2月新疆天山北坡一次区域性暴雪过程的特征及成因，结合GDAS再分析资料并采用HYSPLIT模式，模拟追踪水汽源地、主要水汽输送通道及其对水汽输送的贡献。结果表明：此次天山北坡暴雪是在典型后倾结构的高低空系统配置下产生的，中、高纬地区短波槽在东移过程中同位相叠加，为暴雪长时间维持提供了稳定的天气尺度背景；暴雪发生时位势不稳定性加强，中低层持续冷垫抬升是主要的动力机制，较强垂直风切变是降雪强度较大的重要原因，高低空急流耦合激发中尺度垂直上升支和次级环流圈，地形作用对暴雪有增幅作用；暴雪主要水汽源地位于阿拉伯半岛西侧的红海和伊朗高原西南侧的波斯湾至阿拉伯海北部一带，水汽通道主要集中在500～850 hPa，水汽辐合区位于700～850 hPa，中高层有偏西气流、中层有西南气流、低层有西北急流将水汽接力输送至暴雪区；利用HYSPLIT模式模拟发现，暴雪期间，西、东、南边界水汽输入均起重要作用，主要水汽输送通道分别为偏西路径、偏西南路径、局地水汽路径，1500 m高度的追踪，三者贡献率大致相当，3000 m高度，局地水汽和偏西路径水汽贡献率更大。  相似文献   

顾及双差残差反演GPS信号方向的斜路径水汽含量   总被引：1，自引：1，他引：0  

张双成  刘经南  叶世榕  陈波 《武汉大学学报(信息科学版)》2009,34(1)

给出了顾及GPS双差残差反演斜路径水汽SWV的解算流程;然后详细给出了双差残差到非差残差的转化算法,并对算法进行了改进;最后利用并址的GPS和WVR实测数据对反演SWV算法进行了验证,结果证实改进的反演算法能以优于4 mm精度近实时估算SWV值,与目前国际研究精度在同一量级。  相似文献   

Sulfide and iron control on mercury speciation in anoxic estuarine sediment slurries   总被引：2，自引：0，他引：2  

Seunghee Han  Anna Obraztsova  Patrizia Pretto  Dimitri D. Deheyn  Joris Gieskes  Bradley M. Tebo   《Marine Chemistry》2008,111(3-4):214-220

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.  相似文献   

ISA accelerometer onboard the Mercury Planetary Orbiter: error budget     

Valerio Iafolla  David M. Lucchesi  Sergio Nozzoli  Francesco Santoli 《Celestial Mechanics and Dynamical Astronomy》2007,97(3):165-187

We have estimated a preliminary error budget for the Italian Spring Accelerometer (ISA) that will be allocated onboard the Mercury Planetary Orbiter (MPO) of the European Space Agency (ESA) space mission to Mercury named BepiColombo. The role of the accelerometer is to remove from the list of unknowns the non-gravitational accelerations that perturb the gravitational trajectory followed by the MPO in the strong radiation environment that characterises the orbit of Mercury around the Sun. Such a role is of fundamental importance in the context of the very ambitious goals of the Radio Science Experiments (RSE) of the BepiColombo mission. We have subdivided the errors on the accelerometer measurements into two main families: (i) the pseudo-sinusoidal errors and (ii) the random errors. The former are characterised by a periodic behaviour with the frequency of the satellite mean anomaly and its higher order harmonic components, i.e., they are deterministic errors. The latter are characterised by an unknown frequency distribution and we assumed for them a noise-like spectrum, i.e., they are stochastic errors. Among the pseudo-sinusoidal errors, the main contribution is due to the effects of the gravity gradients and the inertial forces, while among the random-like errors the main disturbing effect is due to the MPO centre-of-mass displacements produced by the onboard High Gain Antenna (HGA) movements and by the fuel consumption and sloshing. Very subtle to be considered are also the random errors produced by the MPO attitude corrections necessary to guarantee the nadir pointing of the spacecraft. We have therefore formulated the ISA error budget and the requirements for the satellite in order to guarantee an orbit reconstruction for the MPO spacecraft with an along-track accuracy of about 1 m over the orbital period of the satellite around Mercury in such a way to satisfy the RSE requirements.  相似文献