Mercury concentration in the ocean

Seventy percent of 342 seawater samples collected in the Bering Sea, North and South Pacific, Japan Sea, East and South China Seas, and Indian Ocean had concentrations of “total” mercury ranging from 3 to 6 ng Hg l^?1 with an arithmetic mean of 5.3 ng l^?1 and a geometric mean of 5.0 ng l^?1. In some cases, a higher concentration was observed at the surface, at the halocline or thermocline, or in the bottom water. But in general, there was no consistent correlation between mercury concentration and depth, except for a statistical tendency for mercury concentration to be slightly higher in the surface water. This tendency suggests that mercury in the ocean is supplied from the atmosphere by rain washout. The latitudinal variation of surface mercury concentrations showed that the maximum concentration at each latitude decreased from 40°N to 30°S. This variation provides evidence that atmospheric mercury is emitted mainly from continental areas naturally or anthropogenically.     

The atmospheric cycling and air–sea exchange of mercury species in the South and equatorial Atlantic Ocean

Measurements of gas-, particle- and precipitation-phases of atmospheric mercury (Hg) were made in the South and equatorial Atlantic Ocean as part of the 1996 IOC Trace Metal Baseline Study (Montevideo, Uruguay to Barbados). Total gaseous mercury (TGM) ranged from 1.17 to 1.99 ng m⁻³, with a weighted mean of 1.61±0.09 ng m⁻³. These values compare well with Pacific Ocean data and earlier results from the Atlantic. The open-ocean samples recorded a distinctive inter-hemispheric gradient, which is consistent with a long-lived trace gas emitted to a greater extent from the Northern than from the Southern Hemisphere. Correlations with surface ²²²Rn measurements indicate an influence of regional terrestrial sources on open-ocean TGM concentrations. Total Hg in precipitation ranged from 10 to 99 pM (volume-weighted average: 17.8±2.9 pM). On average, about 72% of the total Hg was “reactive” (i.e., reducible by SnCl₂). The data showed an apparent rapid nonlinear decrease in concentration with event size (“washout curve”). The wet depositional flux was estimated at 18–36 nmol m⁻² yr⁻¹ (4–7 μg m⁻² yr⁻¹), which is slightly lower than that found in mid-continental locations of North America (6–12 μg m⁻² yr⁻¹). ²¹⁰Pb analyses indicate a strong impact of particles on rain Hg concentrations. Particle-phase Hg (range 5–25 fmol m⁻³; mean 12±1 fmol m⁻³; 66% “reactive”) was comparable to values over the equatorial Pacific. The dry depositional flux is ca. 0.4 nmol m⁻² yr⁻¹, or 0.4–1.0% of the wet flux. Particle-phase Hg concentrations did not change significantly when African dust was present during sampling. However, the Hg/Al ratios were consistent with crustal values during the dust periods. The residence time of TGM was calculated to be 1.3–3.4 yr in this region, based on standing stock estimates. Incubation of rainwater added to surface seawater gave reduction rates [i.e., production of elemental Hg (Hg°); 1.6–4.3% d of total Hg added] comparable to additions of inorganic ionic standards, indicating that Hg⁺² from precipitation is reduced in a similar manner in surface waters. Thus, precipitation-phase Hg is generally available for evasion to the atmosphere following deposition to the surface ocean, effectively enhancing the mobility and residence time of Hg at the Earth's surface.     

Polarographic determination of orthophosphate in seawater

-In the system HCl-Sb (Ⅲ)-ammonium molybdatc-acetone-butanone, PO43-, Sb (Ⅲ) and Mo (VI) form ternary heteropoly acid. This ternary heteropoly acid anion is adsorbed on the dropping mercury electrode and reduced quickly into heteropoly blue. The process of electrochemical reaction will produce a sensitive polarographic wave with peak potential -0.42V (vs S.C.E.). The detection limit is 6×10-8 mol/1. Variable coefficients are 10% and 3% for 0.1 μmol/l and 1 μmol/1 respectively.This method is sensitive, accurate and extremely rapid for analysis of seawater.     

A comparative study of mercury contamination in the Tagus estuary (Portugal) and major French estuaries (Gironde,Loire, Rhône)

Concentrations of mercury were determined for the waters, suspended matter and sediments of the Tagus and of major French estuaries.The Tagus estuary is one of the most contaminated by mercury derived from the outfalls of a chloralkali plant and from other industrial sources. In deposited sediments the median level, 1·0 μg Hg g^?1, is twenty times higher than the natural background and Hg contents depend on the sediment grain-size, age and the distance from waste-outfalls. Suspended matter is more regularly and highly contaminated (median value: 4·5 μg Hg g^?1). In the French estuaries Hg levels in the suspended material decrease with salinity due to dilution and/or remobilization processes. In June 1982, in the Loire estuary, high values of Hg are observed in the middle estuary and attributed to urban and industrial sources.In the Tagus estuary, the general distribution of total dissolved Hg confirms the contamination: it increases seaward from 10 ng 1^?1 in the river to 80 ng 1^?1 in the estuary outlet. The dissolved Hg is almost totally organic in the river, inorganic in the middle estuary due to inorganic Hg effluents and again organic in the lower estuary. This variation is related to the dissolved organic carbon values. The dissolved Hg levels in the Loire Estuary (5–300 ng 1^?1) are much higher than in the Gironde estuary (3–6 ng 1^?1) and of the same order as those observed in the Tagus estuary.     

Mercury speciation in sediments at a municipal sewage sludge marine disposal site

Mercury speciation was performed in excess activated sewage sludge (ASS) and in marine sediments collected at the AAS disposal site off the Mediterranean coast of Israel in order to characterize the spatial and vertical distribution of different mercury species and assess their environmental impact. Total Hg (HgT) concentrations ranged between 0.19 and 1003ng/g at the polluted stations and 5.7 and 72.8ng/g at the background station, while the average concentration in ASS was 1181+/-273ng/g. Only at the polluted stations did HgT concentrations decrease exponentially with sediment depth, reaching background values at 16-20cm, the vertical distribution resulting from mixing of natural sediment with ASS solids and bioturbation by large populations of polycheates. Average Methyl Hg (MeHg) concentration in ASS was 39.7+/-7.1ng/g, ca. 3% of the HgT concentration, while the background concentrations ranged between 0.1 and 0.61ng/g. MeHg concentrations in surficial polluted sediments were 0.7-5.9ng/g (ca. 0.5% of the HgT) and decreased vertically, similar to HgT. A positive correlation between MeHg and Hg only at the polluted stations, higher MeHg concentrations at the surface of the sediment and not below the redoxline, and no seasonality in the concentrations suggest that the MeHg originated from the ASS and not from in situ methylation. By doing selective extractions, we found that ca. 80% of the total Hg in ASS and polluted sediments was strongly bound to amorphous organo-sulfur and to inorganic sulfide species that are not bioavailable. The fractions with potential bioaccessible Hg had maximal concentrations in the range in which biotic effects should be expected. Therefore, although no bioaccumulation was found in the biota in the area, the concentration in the polluted sediments are not negligible and should be carefully monitored.     

ACCUMULATION OF MERCURY IN BLOOD CLAM FROM BOWAI GULF

Accumulation rules of mercury by blood clam (Arca subcrenata Lishke) from Bohai Gulf have been studied. Mercury concentration in soft parts have been related to those in the environment level on the shore and size of animals have also been considered. Uptake ability of mercury in blood clams is high, with the concentration coefficient 1.8 ×103 Hg contents In its soft part are related to those in seawater and in sediment, the relationship- may be expressed by a dual linear regression equation. The total HE content in blood clam individual is power function of its body weight,Arca subcrenata appears to have potential as an indicator of mercury contamination In BohaiGulf.     

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.     

Mercury in the South Polar Seas and in the northeast Pacific Ocean

Seventy-nine total-mercury analyses of seawater samples, collected from the surface down to 5,700 m depth in the northeastern Pacific Ocean and in the South Polar seas, showed a homogeneous distribution of mercury with depth at all stations, although its absolute concentration in the northeastern Pacific (12–30 ng/kg) was 3 to 5 times less than that in the polar waters (50–150 ng/kg). The high concentrations are ascribed to an input of mercury resulting from submarine volcanism.The mercury content was also determined in 8 surface-film samples, 3 sediment cores (0–30 cm), 2 pack-ice samples and 1 sample each of snow and sea smoke.     

Factors influencing the daily behaviour of dissolved gaseous mercury concentration in the Mediterranean Sea

Mercury evasional fluxes from the sea surface into the atmosphere play an important role in the Hg biogeochemical cycle, especially in the Mediterranean basin, which is characterized by the presence of large cinnabar deposits, intense solar radiation and high temperatures for many months of the year. Since the available experimental methodologies to measure mercury flux can be used only in good weather conditions, at present it is necessary to make use of exchange models that require the knowledge of the dissolved gaseous mercury (DGM) concentration in seawater. In this paper, the main factors affecting DGM levels are discussed considering the determination of the DGM daily behaviour in different meteo-marine and weather conditions at coastal and offshore locations of the Mediterranean basin. A fully automatic device for continuous analyses of DGM concentration with a high time resolution was used. Results show that the daily trend of DGM concentration tracks that of the solar radiation intensity, often mapping the movement of the clouds. DGM levels can be decreased by the presence of high winds that increase mercury evasion from the water surface, as well as by the mixing of the surface water layer. The presence of high levels of dissolved organic matter favours the photo-induced reduction of mercury as observed by the measurements performed in a lagoon water.     

Contrasting mercury and manganese deposition in a mangrove-dominated estuary (Guaratuba Bay, Brazil)

Sediment cores were taken at seven sites along the mangrove-bound Guaratuba Bay estuary (southern Brazil), with the purpose of assessing conditions controlling Hg deposition along a horizontal estuarine sediment gradient. The data suggest contrasting depositional patterns for Hg and Mn in this relatively pristine setting. Total Hg contents of bulk sediments ranged from 12 to 36 ng/g along the estuary, the highest values being found in muddier organic-rich sediments of the upper estuary (the corresponding mud gradient is 12 to 42 wt.%, and the organic matter gradient 4 to 10 wt.%). Thus, the deposition of fine sediments relatively enriched in mercury occurs primarily in closer proximity to the freshwater source. The data also indicate a reverse gradient in reactive Mn contents, ranging from 29 to 81 μg/g, and increasing seaward. This implies that reactive Mn is mobilized from fine-grained reducing mangrove forest sediments in the upper estuary, and deposited downstream in sandier, oxygen-rich nearshore sediments. These results suggest that mangrove-surrounded estuaries may act as barriers to mercury transport to coastal waters, but as a source of manganese. The present findings also imply that reactive Mn may be used as an indication of Hg depositional patterns in other similar coastal sedimentary settings.     

Determination and ecological risk assessment of arsenic and mercury in sediments from the Changjiang River Estuary and adjacent East China Sea

Arsenic(As) and mercury(Hg) are pollutants presented in marine environment. A process of atomic fluorescence spectrometry was proposed for the simultaneous determination of As and Hg in marine sediment samples(n =38) collected from the Changjiang River Estuary and adjacent East China Sea. The proposed method used an optimized pretreatment procedure in an aqua regia–H_2 O digestion system. Recoveries of As and Hg increased to97% and 98%, respectively, with suitable precisions(2.7%–4.1%) under optimized process conditions. As and Hg were widely presented in these samples, with the ranges of content values were 2.39–8.77 μg/g for As and48.03–410.8 ng/g for Hg. Results indicate that anthropogenic factors strongly influence the abundances of As and Hg in investigated samples. The preliminary environmental risk assessment was investigated using the I_(geo)accumulation index(I_(geo)) and anthropogenic contribution rate(M). Findings reveal that Hg demonstrates a strong ecological risk(with average values of 1.3 and 72% for I_(geo) and M, respectively) in the sediments from the Changjiang River Estuary and adjacent East China Sea. Therefore, Hg should be considered in future investigations.     

胶州湾近岸沉积物-海水汞的释放研究

本文通过模拟实验研究了胶州湾海泊河口和李村河口沉积物中的汞在不同环境条件下向海水的释放,并对汞的释放动力学数据进行了拟合。总体上两种沉积物汞的释放浓度分别为1.41~5.99μg/L和1.06~3.62μg/L,最大释放率分别为2.7%和3.4%,对胶州湾潮间带水质产生较大的影响。海水的pH值、温度和沉积物厚度都会影响汞的释放。pH<7时,汞的释放作用随pH值的升高而降低,pH>7时,汞的释放作用随pH值的升高而增大;海水温度越高,汞的释放作用越强;随沉积物厚度的增加,汞的释放量增加,释放率降低,海泊河口和李村河口沉积物的有效厚度分别为3.5cm和2.5cm。汞的释放动力学拟合结果表明多个方程都能较好的描述汞的释放动力学过程,其中以Ho的二级动力学方程拟合结果最好。     

Mercury distribution in seawater in Minamata Bay and the origin of particulate mercury

Horizontal and vertical distributions of mercury were determined in seawater in Minamata Bay and Yatsushiro Sea. The concentrations of total and particulate mercury respectively ranged from 56–285 ng l^–1 and 2.1–506 ng l^–1. They were both highest in the inner most part of Minamata Bay where the sediment was most heavily polluted, and decreased with increasing distance from there. Vertically, an evident increase in concentration was observed near the bottom. A good agreement was found between the mercury content in suspended matter and that in fine sediment particles.These facts show that the particulate mercury is supplied mostly from the bottom sediment, and that it is spreading offshore with dispersing in seawater. This process would eventually result in the pollution of sediment in Yatsushiro Sea.     

Spatial distributions of dimethylsulfide in the South China Sea

The concentration of dimethylsulfide (DMS) and supporting parameters were determined in surface seawater and vertical profiles at 26 stations in the South China Sea. The concentrations of DMS in surface seawater ranged from 61 to 148 ng S/l, with a mean of 82 ng S/l. High concentrations of DMS were found in the productive regions. The vertical profiles of DMS were characterized by a maximum at depths typically between 20 and 75 m. The concentrations of DMS were correlated with the levels of chlorophyll a both in the surface seawater and in the vertical distribution. The concentrations of DMS were higher than expected for this chlorophyll-poor tropical sea, as indicated by markedly high DMS (ng S/l)/chlorophyll a (μg/l) ratios ranging from 315 to 3524 with a mean of 1768 for all the surface seawater samples. DMS concentration was significantly correlated with seawater temperature and dissolved oxygen, but it showed an inverse relationship to nutrients (including nitrate, phosphate and silicate). On the basis of sea surface concentrations of DMS and gas exchange calculations, the mean flux of DMS from the South China Sea to the atmosphere was estimated to be 5.5 μmol m⁻² d⁻¹.     

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.     

Environmental impact factors and mercury speciation in the sediment along Fujian and eastern Guangdong coasts

Concentrations of total mercury (THg) and methyl mercury (MeHg) were determined for 32 surface sediments collected along the coastal line of Fujian Province and eastern Guangdong Province. The spatial distributions of THg and MeHg and their environmental impact factors were investigated. The average concentrations of THg and MeHg in the sediments were 31.5 ng/g and 0.096 ng/g, respectively. Both sediment THg and MeHg concentrations showed relatively high value in the Minjiang Estuary and the coastal areas of Quanzhou and Putian. The concentrations overall decreased as the distance to the shoreline increased. The correlations among environmental impact factors and THg, MeHg were analyzed. The sediment THg concentration was highly correlated to the concentrations of organic matter, copper, total nitrogen (TN) and total phosphorus (TP), and significantly correlated to pH value of the bottom seawater and concentration of sediment sulfide. The sediment MeHg concentration was highly correlated to the concentrations of organic matter and copper, and significant correlated to the concentrations of sulfide, TN, TP and pH value of the bottom seawater.     

Chemical leaching and specific surface area measurements of marine sediments in the evaluation of mercury contamination near cinnabar deposits

This paper investigates mercury contamination in recent marine sediment of the Tyrrhenian continental shelf near the mouths of three rivers draining an area with cinnabar deposits (M. Amiata, Italy). By means of chemical leaching, two fractions of the total mercury were distinguished: a ‘non-leachable’ fraction, consisting of mercury held in relatively stable forms and a ‘leachable’ fraction, composed of forms that are more weakly bound to the sediments. The two Hg fractions are correlated to the organic matter content, the distribution of which is strictly dependent on the sediment surface area.In order to eliminate the effects of grain size variations among the samples, the Hg concentrations were normalized to the unit of surface area (ng/m²). Following this procedure, the ‘non-leachable’ Hg was found to be concentrated mostly in a belt along the coast, while the ‘leachable’ Hg fraction was shown to accumulate largely in the zones with high depositional dynamics near the mouths of the rivers.Hypotheses to account for the discrepancy between the low concentrations of ‘leachable’ Hg in the sediment of the outer continental shelf and the high concentrations in the fauna of the same area, reported in previous papers, are presented.     

广东红海湾表层海水重金属含量的时空变化特征与污染水平评价

2007年6月(夏季)和2008年1月(冬季)分别对广东红海湾的汕尾港周边海域35个站位进行了表层海水的采样,在实验室内使用XGY-1011A型原子荧光光度计和HY-1F型多功能极谱仪获得了海水中重金属Hg、Cu、Pb、Zn、Cd的含量,研究了其时空变化特征,并采用综合指数法(WQI)评价其污染程度.结果显示:Hg、Cu、Pb、Zn、Cd的含量范围分别为0.009～0.050、0.9～4.3、0.4～1.4、1.6～19.0、0.1～0.7μg/dm3,平均含量分别为0.025、2.4、0.8、9.4、0.2μg/dm3.该海域表层海水各重金属含量的平面分布总体上呈现以品清湖向汕尾港递减的变化趋势.各站位重金属元素的单项污染指数和综合污染指数(WQI)均小于1,海水受重金属的污染程度较轻微,符合国家二类海水水质标准值的要求.2008年1月(冬季)重金属综合污染指数的平均值(0.17)略大于2007年6月(夏季)的平均值(0.14),海水中重金属污染程度略有加重的趋势.采用多元线性回归方法分析重金属元素含量与环境要素测值的相关程度,相关系数按从大到小的排列顺序大致为:Zn>Cd>Cu>Hg>Pb.     

Marine sampling by scuba diving. 3. Sampling procedures for measurement of mercury concentrations in estuarine waters and seawater

A method for sampling estuarine waters and seawater by scuba diving is described. Samples taken from the Krka River Estuary on the eastern Adriatic coast were analysed for mercury content using cold vapour atomic absorption spectrometry (CVAAS). Mercury levels as low as 1 ng dm⁻³ were determined and these are among the lowest values reported to date. A simple contamination free procedure for the preconditioning of sample containers in the sea was applied. Sampling of water by divers is particularly useful when the intermediate layer in an estuary has to be identified and sampled, as well as for obtaining detailed vertical concentration profiles for mercury and other trace elements.     

广西廉州湾贝类养殖区重金属的含量变化及潜在生态风险评价

根据2012—2017年每年8月廉州湾贝类养殖区现场监测资料,探讨了重金属(Hg、Cu、Pb、Cd)在其海水和表层沉积物中的含量变化,评价了2种介质中重金属的污染状况和沉积物重金属的潜在危害状况.结果表明:海水中重金属平均含量为Cu Pb Cd Hg,除Cu外,Hg、Pb、Cd的年际变化均呈明显上升趋势,其污染程度顺序为Cu Hg Pb Cd,整体水质状况基本属于本底水平;表层沉积物中重金属平均含量为Pb Cu Cd Hg,除Hg外,Cu、Pb、Cd的年际变化趋势和水相中的变化基本一致,其污染程度排序为Cu Pb Hg Cd,整体处于中等污染水平;表层沉积物中重金属的潜在生态风险程度顺序依次为Hg Cd Cu Pb,6次调查结果的综合潜在生态风险指数RI值均低于140,平均值为76. 98,表明该海域属于低潜在生态风险水平.