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.     

Air-sea exchange of mercury in Tokyo Bay

In Tokyo Bay the concentrations of dissolved gaseous mercury (DGM) in the surface seawater and total gaseous mercury (TGM) over the sea were measured during December 2003, October 2004 and January 2005. Based on these data, the evasional fluxes of mercury from the sea surface were estimated using a gas exchange model. In addition, an automatic wet and dry deposition sampler was used to measure the wet and dry depositional fluxes of mercury from December 2003 to November 2004 at three locations in and near Tokyo Bay. The results indicate that the average DGM and TGM levels of seven locations are 52 ± 26 ng m⁻³ and 1.9 ± 0.6 ng m⁻³, respectively, which shows that the surface seawater in Tokyo Bay is supersaturated with gaseous mercury, leading to an average mercury evasional flux of 140 ± 120 ng m⁻²d⁻¹. On the other hand, the annual average wet and dry depositional fluxes of mercury at three locations were 19 ± 3 μg m⁻²yr⁻¹ and 20 ± 9 μg m⁻²yr⁻¹, respectively. These depositional fluxes correspond to the daily average total depositional flux of 110 ± 20 ng m⁻²d⁻¹. Thus, it is suggested that in Tokyo Bay, the evasional fluxes of mercury are comparable to the depositional fluxes.     

Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.     

Mercury speciation in surface and deep waters of the Mediterranean Sea

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.     

Vertical export flux of metals in the Mediterranean Sea

We examined metal (Al, V, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb) and particulate organic carbon (OC) concentrations of the marine vertical export flux at the DYFAMED time-series station in the Northwestern Mediterranean Sea. We present here the first data set of natural and anthropogenic metals from sediment trap moorings deployed at 1000 m-depth between 2003 and 2007 at the DYFAMED site. A highly significant correlation was observed between most metal concentrations, whatever the nature and emission source of the metal. Cu, Zn and Cd exhibit different behaviors, presumably due to their high solubility and complexation with organic ligands. The observed difference of atmospheric and marine fluxes in terms of temporal variability and elemental concentration suggests that dense water convection and primary production and not atmospheric deposition control the marine vertical export flux. This argument is strengthened by the fact that significant Saharan dust events did not result in concomitant marine vertical export fluxes nor did they generate significant changes in metal concentrations of trapped particles.     

Seasonal dynamics in colored dissolved organic matter in the Mediterranean Sea: Patterns and drivers

Two autonomous profiling “Bio-Argo” floats were deployed in the northwestern and eastern sub-basins of the Mediterranean Sea in 2008. They recorded at high vertical (1 m) and temporal (5 day) resolution, the vertical distribution and seasonal variation of colored dissolved organic matter (CDOM), as well as of chlorophyll-a concentration and hydrological variables. The CDOM standing stock presented a clear seasonal dynamics with the progressive summer formation and winter destruction of subsurface CDOM maxima (YSM, for Yellow Substance Maximum). It was argued that subsurface CDOM is a by-product of phytoplankton, based on two main characteristics, (1) the YSM was located at the same depth than the deep chlorophyll maximum (DCM) and (2) the CDOM increased in summer parallels the decline in chlorophyll-a. These observations suggested an indirect but tight coupling between subsurface CDOM and phytoplankton via microbial activity or planktonic foodweb interactions. Moreover, the surface CDOM variations observed both by floats and MODIS displayed different seasonal dynamics from what recorded at subsurface one. This implies that CDOM standing stock can be hardly detected by satellite. It is worthnoting that surface CDOM was found to be more related to the sea surface temperature (SST) than chlorophyll-a concentration, suggesting its physical origin, in contrast to the biological origin of YSM and subsurface standing stocks.     

Reprint of “Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea”

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.     

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.     

Particulate barium fluxes on the continental margin: a study from the Alboran Sea (Western Mediterranean)

Particulate biogenic barium (bio-Ba) fluxes obtained from three instrumented arrays moored in the Alboran Sea, the westernmost basin in the Mediterranean Sea, are presented in this study. The mooring lines were deployed over almost 1 year, from July 1997 to May 1998, and were equipped with sediment traps at 500–700 m depth, 1000–1200 m depth and 30 m above the seafloor (1000–2200 m). The results obtained support the growing body of evidence that the relationship between particulate bio-Ba and Corg throughout the water column in margin systems is clearly different from this relation in the open ocean. In the Alboran Sea, the annual averaged bio-Ba fluxes range from 0.39 to 1.07 μmol m⁻² day⁻¹, with mean concentrations of 1.31–1.69 μmol g⁻¹ and bio-Ba/Corg ratios lower than in the open ocean. The low bio-Ba values obtained also indicate that calculating bio-Ba is extremely sensitive to the detrital Ba/Al ratio of each sample. The lithogenic Ba fraction in the Alboran Sea continental margin area contributes between 24% and 85% of the total Ba. Increased bio-Ba export efficiency was observed after periods of high primary productivity and suggests that the processes limiting the bio-Ba formation in the study area relate to settling dynamics of organic matter aggregates. Furthermore, the ballasting effect of the abundant lithogenic and carbonate particles may limit decomposition of organic matter aggregates and enhance the transfer of particles rich in Corg and relatively poor in bio-Ba to the deep seafloor. Lateral input of freshly sedimented biogenic material, including particulate bio-Ba, has been observed on the lower continental slope in the western Alboran Sea. These observations emphasize that the use of the bio-Ba as a proxy of export productivity from the surface ocean must be used cautiously in highly dynamic environments such as those in the Alboran Sea.     

Processes influencing dissolved iron distributions below the surface at the Atlantic Ocean–Celtic Sea shelf edge

Shelf break systems are highly dynamic environments. However little is known about the influence that benthic interactions and water mass mixing may have on vertical distributions of iron in these systems. Dissolved Fe (< 0.4 μm) concentrations were measured in samples from nine vertical profiles across the upper slope (150–2950 m water depth) at the Atlantic Ocean–Celtic Sea shelf break. Dissolved iron concentrations varied between less than 0.2 and 5.4 nM, and the resulting detailed section showed evidence of a range of processes influencing the Fe distributions. The near sea floor data were interpreted in terms of release and removal processes. The concentrations of dissolved Fe present in near seabed waters were consistent with release of Fe from in situ remineralisation of particulate organic matter at two upper slope stations, and possibly release from pore water upon resuspension on shelf. Lateral transport of dissolved iron was evident from elevated Fe concentrations in an intermediate nepheloid layer and its advection along isopycnals. Surface waters at the shelf break also showed evidence of vertical mixing of deeper iron-rich waters. These waters contained macronutrients that sustained primary productivity in these otherwise nutrient-depleted surface waters. The data also suggest some degree of stabilisation of relatively high concentrations of iron, presumably through ligand association or as colloids. This study supports the view that lateral export of dissolved iron to the interior of the ocean from shelf and coastal zones and may have important implications for the global budget of oceanic iron.     

Mercury methylation,demethylation and reduction rates in coastal and marine surface waters of the Mediterranean Sea

In situ experiments using isotopically labeled mercury species (¹⁹⁹Hg(II) and Me²⁰¹Hg) are used to investigate mercury transformation mechanisms, such as methylation, demethylation and reduction, in coastal and marine surface waters of the Mediterranean Sea. The aim of this work is to assess the relative contribution of photochemical versus biological processes to Hg transformation mechanisms. For this purpose, potential transformation rates measured under diurnal and dark incubation conditions are compared with major biogeochemical parameters (i.e. hydrological and biological data) in order to obtain the relative contribution of various biotic and abiotic mechanisms in both surface (high light) and bottom (low light) waters of the euphotic zone. The results demonstrate that coastal and marine euphotic zones are significant reactors for all Hg transformations investigated (i.e. methylation, demethylation, reduction). A major outcome demonstrates that Hg methylation is taking place in oxic surface seawater (0.3–6.3% day^− 1) and is mainly influenced by pelagic microorganism abundance and activities (phyto- and bacterioplankton). This evidences a new potential MeHg source in the marine water column, especially in oligotrophic deep-sea basins in which biogeochemistry is mostly governed by heterotrophic activity. For coastal and marine surface waters, although MeHg is mainly photochemically degraded (6.4–24.5% day^− 1), demethylation yields observed under dark condition may be attributed to microbial or chemical pathways (2.8–10.9% day^− 1). Photoreduction and photochemical reactions are the major mechanisms involved in DGM production for surface waters (3.2–16.9% day^− 1) but bacterial or phytoplanktonic reduction of Hg(II) cannot be excluded deeper in the euphotic zone (2.2–12.3% day^− 1). At the bottom of the euphotic zone, photochemical processes are thus avoided due to the attenuation of UV-visible sunlight radiation allowing biotic processes to be the most significant. These results suggest a new potential route for Hg species cycling in surface seawater and especially at the maximum biomass depth located at the bottom of the euphotic zone (i.e. maximum chlorophyll fluorescence). In this environment, DGM production and demethylation mechanisms are thus probably reduced whereas Hg methylation is enhanced by autotrophic and heterotrophic processes. Experimental results on mercury species uptake during these investigations further evidenced the strong affinity of MeHg for biogenic particles (i.e. microorganisms) that correspond to the first trophic level of the pelagic food web.     

西地中海的弧后盆地

地中海是太平洋之外弧后盆地较为发育的海区。巴利阿里海盆和第勒尼安海盆是西地中海两个位置相邻、互有成因联系的弧后盆地。海盆莫霍面埋深分别为 1 2～ 1 5km和 1 0 km,热流密度分别为 1 0 0 m W/m2和 2 0 0 m W/m2 ,发育有大洋型磁条带异常 ,大洋钻探和拖网取样均采到了拉斑玄武岩。较之巴利阿里海盆 ,第勒尼安海盆更富年青性。两弧后盆地的成生演化是与欧洲板块与非洲 -阿普利亚板块的相互作用息息相关的。中新世 ,随着非洲 -阿普利亚板块向西、西北俯冲 ,科西嘉、撒丁裂离欧洲大陆 ,巴利阿里海盆被打开 ;上新世 ,阿普利亚微板块进一步俯冲 ,导致亚平宁与科西嘉、撒丁之间的裂离 ,形成第勒尼安海盆。     

Particulate organic matter and ballast fluxes measured using time-series and settling velocity sediment traps in the northwestern Mediterranean Sea

Prompted by recent data analyses suggesting that the flux of particulate organic carbon sinking into deep waters is determined by fluxes of mineral ballasts, we undertook a study of the relationships among organic matter (OM), calcium carbonate, opal, lithogenic material, and excess aluminum fluxes as part of the MedFlux project. We measured fluxes of particulate components during Spring and Summer of 2003, and Spring of 2005, using a swimmer-excluding sediment trap design capable of measuring fluxes both in a time-series (TS) mode and in a configuration for obtaining particle settling velocity (SV) profiles. On the basis of these studies, we suggest that distinct OM–ballast associations observed in particles sinking at a depth of 200 m imply that the mechanistic basis of the organic matter–ballast association is set in the upper water column above the Twilight Zone, and that the importance of different ballast types follows the seasonal succession of phytoplankton. As in other studies, carbonate appears to enhance the flux of organic matter over opal. Particles must be at least half organic matter before their settling velocity is affected by ballast concentration. This lack of change in ballast composition with SV in particles with <40% OM content suggests that particle SV reaches a maximum because of the increasing importance of inertial drag. Relative amounts of OM and opal decrease with depth due to decomposition and dissolution; carbonates and lithogenic material contribute about the same amount to total mass, or increase slightly, throughout the water column. The high proportion of excess Al cannot be explained by its incorporation into diatom opal or reverse weathering, so Al is most likely adsorbed to particulate oxides. On shorter time scales, dust appears to increase particle flux through its role in aggregation rather than by nutrient inputs enhancing productivity. We suggest that the role of dust as a catalyst in particle formation may be a central mechanism in flux formation in this region, particularly when zooplankton fecal pellet production is low.     

Vertical distribution of dissolved organic carbon (DOC) in the Western Mediterranean Sea in relation to the hydrological characteristics

Vertical profiles of dissolved organic carbon (DOC) from eight hydrological stations in the Tyrrhenian Sea, Sardinia Channel and Algerian Sea, are reported. DOC exhibits concentrations ranging from 58 to 88 μM in surface water, 43–57 μM in the intermediate layer and 49–63 μM in deep waters. The assessment of the hydrological characteristics allows different water masses in the study area to be identified; moreover, different hydrological processes are observed in the Tyrrhenian and Algerian basins. DOC exhibits different values in the different water masses. The lowest DOC concentrations (43–46 μM) were found in the Tyrrhenian Levantine Intermediate Water (LIW). Correlations between DOC and apparent oxygen utilization (AOU), investigated within each water mass, exhibit different behaviors in the intermediate and deep waters, suggesting the occurrence of different processes of oxygen consumption in the different water masses.     

Factors influencing the abundance of deep pelagic bioluminescent zooplankton in the Mediterranean Sea

Measurements of the density of deep pelagic bioluminescent zooplankton (BL) were made with the Intensified Silicon Intensifier Target (ISIT) profiler in the Ligurian, Tyrrhenian, Adriatic, Ionian Seas and the Strait of Sicily from ～300 m to near seafloor. Mean BL densities ranged from 2.61 m^?3 at 500–1000 m depth in the Adriatic Sea to 0.01 m^?3 at 4000–5000 m depth in the E Ionian Sea. We investigated drivers of spatial variation of deep pelagic BL density. Linear regression was applied between surface chlorophyll a (Chl a) concentration and underlying BL density. Chl a values were determined from satellite derived 100 km radius composites (six 10-day means per ISIT deployment, over preceding 60 days). At 500–1000 m depth we found a significant positive relationship between mean BL density and mean Chl a in the period prior to 0–10 days (at 1% level) and prior to 10–40 days (at 5% level). Beyond 40 days no relationship between BL density and Chl a was found at this depth. At depths 1000–1500 m BL density values were low and no significant relationship with Chl a was detected. Generalised additive modelling (GAM) was used to assess the influence of benthic hotspots (seamount; cold water coral mound; mud volcano) on overlying BL density. A reduction in BL density was found downstream of the Palinuro seamount from 300 to 600 m. No effect on BL density in the overlying water column was detected from the presence of cold water corals. Higher BL densities were detected over the W Madonna dello Ionio mud volcano than at other sites sampled in the NW Ionian Sea. We find surface Chl a to be a good predictor of BL density in the mesopelagic zone; below this depth we hypothesise that processes affecting the efficiency of particle export to deep water may exert greater influence on BL density.     

Mass balance of mercury in the Mediterranean Sea

The Mediterranean Basin is rich in mercury from natural and anthropogenic sources. During an extensive research from 2002–2005, measurements of different mercury forms were carried out in the Mediterranean Sea by the Italian research vessel Urania as a part of the Med Oceanor and MERCYMS projects funded by the EU Framework programme. Further on, transport and fate of mercury forms was simulated in water and air compartments by two different models, and an approximate coupling of both models was performed. The new 3-dimensional model PCFLOW3D was completed with the first version of a biogeochemical module which deals with various mercury species in dissolved and particulate forms. Exchange with the bottom and the atmosphere, methylation, demethylation, reduction and oxidation were taken into account. Based on the integrated hydrodynamic-atmospheric model and results of field measurements the mass balance of total mercury in the Mediterranean Sea was determined in order to estimate main sources and sinks and simulate future trends of mercury contamination in the Mediterranean. The following terms were taken into account: sources of mercury from major rivers and from point sources, exchange with the Atlantic Ocean and the Black Sea, estimated natural sources from geotectonic active areas in the sea, exchange with bottom sediments, and evasion to and deposition from the atmosphere.     

南黄海溶解氧的垂直分布特性

根据中韩黄海水循环动力学合作研究项目1996～1998年对南黄海全海域6个航次的现场调查资料,对南黄海溶解氧的断面分布和垂直分布特征及其季节变化规律进行了系统、全面地研究,并对更半年溶解氧垂直分布最大值的地理分布、强度及与温跃层和生物活动的关系等进行了进一步的探讨.     

地中海黄色物质次表层极大值的季节变化观测

首次通过2008-2009年在西北地中海和东地中海海域投放的两台Bio-Argo浮标的观测数据,分析与研究了该海区黄色物质次表层极大值的季节变化规律.研究表明次表层黄色物质在夏季开始爆发,伴随着叶绿素a浓度的逐渐降低;到冬季在强烈的垂向混合作用下结束.且黄色物质极大值的深度与叶绿素a浓度极大值(DCM)的深度基本一致,说明虽然黄色物质与浮游植物之间并不存在直接联系,但浮游植物的降解是黄色物质的主要来源.文中推测,可能由于该海区浮游植物与微生物的强耦合,导致了黄色物质与叶绿素a之间存在明显的反变关系.     

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.     

Isolation of colloidal monomethyl mercury in natural waters using cross-flow ultrafiltration techniques

A series of experiments was conducted to evaluate the appropriateness of cross-flow ultrafiltration (CFUF) techniques for the determination of the phase speciation of monomethyl mercury (MeHg) in natural waters. Spiral-wound cartridge (Amicon S1Y1) and Miniplate (Amicon) were evaluated for their nominal molecular weight cut-offs of 1 and 10 kDa, respectively. The ultrafiltration behavior of standard macromolecules showed that the permeation of high molecular weight (HMW) organic macromolecules was not significant when a concentration factor (CF)>15 was used. The retention of low molecular weight (LMW) molecules was significant, especially at a low CF<5, suggesting that the use of a high CF (15) will minimize the retention of LMW molecules. Sorptive losses of MeHg in the solution phase to the 1 kDa membrane were negligible, but MeHg bound to HMW macromolecules was still retained (20%), even with a preconditioned membrane. The mass balance recovery of MeHg during ultrafiltration averaged 101±15% (n=7) and 105±14% (n=5) for the 1 and 10 kDa membranes, respectively. Sample storage over 24 h caused significant coagulation (47%) of the <10 kDa MeHg into the 10 kDa–0.45 μm colloidal or the particulate MeHg pool. The 1 kDa–0.45 μm colloidal MeHg in Galveston Bay and the Trinity River water samples accounted for 40–48% of the filter-passing MeHg, although the most abundant fraction (52–60%) of MeHg was the truly dissolved fraction (<1 kDa). The partition coefficient between the colloidal (1 kDa–0.45 μm) and truly dissolved MeHg (average log K_C=5.2) was higher than the partition coefficient based on particle/filter-passing (average log K_D=4.6) or particle/truly dissolved MeHg (average log K_P=4.8), suggesting that MeHg has stronger affinity for natural colloids than macroparticulate materials (>0.45 μm).