错流超滤技术在海水胶体态铀、钍、镭同位素和有机碳研究中的应用

建立了由预过滤装置、蠕动泵、中空纤维超滤膜(AmiconH10P10-20,标称截留分子量10KDa)和连接管组成的错流超滤系统,利用荧光标记的40KDa葡聚糖和已知放射性活度的234Th示踪剂评估了超滤膜的截留和吸附性质,探讨了234Th在超滤过程中的渗透行为,考查了该系统用于实际海水样品时铀、钍、镭同位素和有机碳的质量平衡状况.结果表明,10Kda中空纤维超滤膜对40Kda葡聚糖具有良好的截留效率(85%),而吸附损失率为18%.铀、钍、镭同位素和有机碳在超滤过程中均达到极佳的质量平衡,回收率R=95%～98%,优于大多数文献报道的值.234Th在超滤过程中的渗透行为可以很好地用渗透模型加以描述.研究组分胶体态含量占“溶解”态含量的份额大小顺序如下:钍同位素、有机碳、镭同位素约等于铀同位素,这与钍为强颗粒活性元素、铀和镭为水溶性元素的地球化学性质相吻合.     

Optical properties of estuarine dissolved organic matter isolated using cross-flow ultrafiltration

Dissolved organic matter(DOM) from freshwater, mid-salinity, and seawater endmember samples in the Jiulong River Estuary, China were fractionated using cross-flow ultrafiltration with a 10-kDa membrane. The colloidal organic matter(COM; 10 kDa–0.22 μm) retentate, low molecular weight(LMW) DOM(10 kDa) permeate, and bulk samples were analyzed using absorption spectroscopy and three-dimensional fluorescence excitation-emission-matrix spectroscopy. The UV-visible spectra of COM were very similar to those obtained for permeate and bulk samples, decreasing monotonically with increasing wavelength. Most of the chromophoric DOM(CDOM, expressed as the absorption coefficient a355) occurred in the LMW fraction, while the percentage of CDOM in the colloidal fraction was substantially higher in the freshwater endmember(13.4% of the total) than in the seawater endmember(6.8%). The bulk CDOM showed a conservative mixing behavior in the estuary, while there was removal of the COM fraction and a concurrent addition of the permeate fraction in the mid-salinity sample, implying that part of the colloidal CDOM was transformed into LMW CDOM. Two humic-like components(C1: 250, 325/402 nm; and C2: 265, 360/458 nm) and one protein-like component(C3: 275/334 nm) were identified using parallel factor analysis. The contributions of the C1, C2, and C3 components of the COM fraction to the bulk sample were 2.5%–8.7%, 4.8%–12.6%, and 7.4%–14.7%, respectively, revealing that fluorescent DOM occurred mainly in the LMW fraction in the Jiulong River Estuary. The C1 and C2 components in the retentate and permeate samples showed conservative mixing behavior, but the intensity ratio of C2/C1 was higher in the retentate than in the permeate fractions for all salinity samples, showing that the humic component was more enriched in the COM than the fulvic component. The intensity ratio of C3/(C1+C2) was much higher in the retentate than in the permeate fraction for mid-salinity and seawater samples, revealing that the protein-like component was relatively more enriched in COM than the humic-like component. The contribution of the protein-like component(C3) to the total fluorescence in the retentate increased from 14% in the freshwater endmember to 72% for the seawater endmember samples, clearly indicating the variation of dominance by the humic-like component compared to the protein-like component during the estuarine mixing process of COM.     

近岸海水中络合态铁的离心超滤粒径分级方法研究

建立了基于离心超滤技术的近岸海水中络合态铁(Fe)粒径分级方法。经0.45μm滤膜过滤的海水样品,分别用不同孔径(3 k Da、10 k Da、30 k Da、100 k Da)的超滤膜离心超滤并脱盐。不同分子量范围的化合物富集于相应孔径的超滤膜上,以酸溶液提取出Fe,用原子吸收光谱法(GFAAS)测定。在优化的条件下,方法检测限为0.10μg·L-1,线性范围0.25~10μg·L-1,4组不同孔径超滤膜测定同一份样品的相对标准偏差(RSD)为6.4%~10.3%。本方法成功应用于福建九龙江口至厦门西海域水样的测定,结果显示各分子量范围内的络合态Fe含量随盐度增高而降低,且呈非保守分布的变化趋势。     

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.     

基于切向超滤技术的胶体有机碳和无机氮分离及物源初探

利用切向超滤技术对九龙江口天然水体中胶体相(1 kDa～0. 45μm)、真溶解相(1 kDa)和"溶解相"(0. 45μm)的溶解有机碳和无机氮进行了分离与提取,初步探讨了水环境因子对其理化特性的影响机制,进而探讨了它们的来源和转化.结果表明,切向超滤过程的膜空白和质量平衡符合技术要求;溶解有机碳、亚硝酸盐氮、氨氮、硝酸盐氮和无机氮存在形式以真溶液相(1 kDa)为主,其在胶体相中的质量浓度分别为0. 207～0. 810 mg/dm3、0. 001～1. 870μg/dm3、ND～2. 08μg/dm3、0. 62～79. 30μg/dm3和1. 07～81. 10μg/dm3;胶体态溶解有机碳(COC)含量主要受陆源输入控制.     

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.     

Behaviour of colloidal trace metals (Cu, Pb and Cd) in estuarine waters: An approach using frontal ultrafiltration (UF) and stripping chronopotentiometric methods (SCP)

The frontal cascade ultrafiltration (UF) technique in conjunction with stripping chronopotentiometry (SCP) has been evaluated for determining the colloidal distribution of Cu, Pb and Cd in estuarine waters. Metallic concentrations in seven size fractions (0.45 μm–0.22 μm; 0.22 μm–300 kDa; 300–50 kDa; 50–30 kDa; 30–10 kDa; 10–5 kDa; <5 kDa) were determined with the aim to investigate their changes along the salinity gradient of the Penzé system (NW France). These data, completed by analysis of the total dissolved metals at 10 stations over the whole freshwater–seawater mixing zone, provided some insights in the removal and addition processes that affect Cu, Pb and Cd in estuaries.     

海水中胶体有机碳的测定──高温燃烧法和紫外/过硫酸钾法的比较

利用切向超滤(cross-flow ultrafiltration)技术对海水中胶体有机碳(COC)和真溶解有机碳(UOC)进行了分离,并分别用高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳进行了测定。测定结果表明,切向超滤能定量分离海水中的胶体有机碳,高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳的测定结果没有明显的系统误差,表明这两种方法的氧化效率基本相同,胶体粒子的存在,对紫外/过硫酸钾法的氧化效率没有显着影响。     

The effect of resuspension on the fate of total mercury and methyl mercury in a shallow estuarine ecosystem: a mesocosm study

Sediments are the major repository of mercury in estuaries and could be a significant source of Hg to the overlying water column via release from the solid phase during resuspension. There is, however, little information on the effect of resuspension on Hg partitioning and release to the water column. The objective of this study was to determine the effect of resuspension on the cycling of THg and MeHg between the water column and the sediment. Tidal resuspension was simulated using the MEERC STORM facility. The facility can mimic both realistic bottom shear stress and water column turbulence simultaneously. There were three replicates of each resuspension (R) and no resuspension (NR) mesocosms. Two 4-week experiments were conducted in July and October of 2001: experiment 1 without clams and experiment 2 with clams. Both experiments showed that resuspension of muddy sediment introduced significantly higher particulate THg to the water column as TSS increased. The results suggest that THg was mostly bound to sediment particles with very little release during the resuspension events. In contrast, particulate MeHg was significantly lower in the R tanks where sediment particles with poor MeHg were dominant in the water column during the resuspension events. Dissolved THg and MeHg did not change in concert with changes in particulate load, suggesting that the dynamics between dissolved and particulate phases for both THg and MeHg cannot be explained by an equilibrium partitioning.     

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.     

商业平板式超滤膜包完整性检验：对海洋胶体生物地球化学研究的启示

The performance and integrity of a cassette cross-flow ultrafilter(Pellicon 2, Millipore) are examined with a suite of macromolecules of different molecular masses. The retention coefficient during the cross-flow ultrafiltration experiments increases with increasing molecular mass and reaches 90% with 10 kDa dextran in both milli-Q water and ultrafiltered seawater media. Based on a 90% retention coefficient, the molecular mass cut-off for the ultrafiltration membrane is defined at 10 kDa, which is ten times(1 kDa) that rated by the manufacturer. To further validate the accuracy of the laboratory calibration, the samples from the lower Zhujiang River and the Jiulong River Estuary are ultrafiltered with the cassette ultrafiltration membrane and the colloidal organic carbon abundances in these samples are quantified with the ultrafiltration permeation model based on time series permeation subsamples. The colloidal organic carbon abundances are 5.8%–21.1% in the Jiulong River Estuary and 5.6%–11.0% in the lower Zhujiang River. These are consistent with the reported values for both estuaries as well as with the colloidal organic carbon abundances in marine environments over the coastal and open oceans with 10 kDa cut-off membranes. Therefore, these field data support the laboratory calibration result and indicate the validity of the experimental and quantification procedure adopted. The discrepancy between the nominal molecular mass cut-off and the actual pore size of the ultrafiltration membrane should be of great concern for research in colloidal and nanoparticle biogeochemistry. Careful examination of the membrane integrity should be taken during ultrafiltration experiments in order to avoid misleading molecular mass cut-off information.     

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.     

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.     

Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.     

Size fractionation and optical properties of colloids in an organic-rich estuary (Thurso, UK)

The optical characteristics of a black water river estuary from the north coast of Scotland were examined in the filtered (0.4 µm), ultrafiltered (5 kDa) and colloid-enriched fractions of estuarine samples. The samples were collected over the full salinity range during a period when the pH was relatively constant (8.2–8.5) throughout the estuary, allowing the influence of salinity on estuarine colloidal processes to be distinguished. The properties examined in the bulk, the low molecular weight (LMW) and the colloidal fraction (HMW) were UV–visible absorption, 3-D fluorescence excitation–emission matrix (EEM) spectrum, inorganic and organic carbon, mean size (by dynamic light scattering), and size distribution by flow field-flow fractionation analysis (FlFFF). The combined results of these analyses support the view that river-borne, humic-rich colloids underwent two types of transformation upon mixing with the seawater end member. The first one resulted in an apparent increase in the abundance of LMW constituents and may be explained by coiling of the individual humic macromolecules. The second one resulted in an increase in the mean size measured in both the lower and higher colloidal size ranges, and may be explained by aggregation of colloids to form entities that were still mostly colloidal i.e., smaller than 0.4 µm. The LMW contribution to the bulk optical properties increased with increasing salinity. Very similar findings were obtained from simulated mixing experiments using a Nordic Reference NOM extract as a source of freshwater colloids. This indicates that changes in the molecular architecture and molar mass of river-borne colloids—not changes in their chemical nature—were responsible for the observed variations in the spectral characteristics of CDOM in this estuary.     

汞同位素环境样品前处理方法的研究进展

汞同位素技术是汞的生物地球化学循环和污染防治研究的重要手段,在汞的源解析和过程示踪等方面具有广泛应用。由于自然环境中汞含量极低,所以环境样品需先经过一系列严苛的预处理才能开展汞同位素分析。目前,用于同位素分析的固态样品前处理方法主要有湿法消解和燃烧捕集法,液态样品的前处理方法以色谱分离、共沉淀和吹扫捕集为主,气态样品则收集至不同的固态吸附剂后,通过燃烧捕集法富集样品中的汞。相比湿法消解,燃烧捕集法具有富集倍数高、干扰元素少、适用范围广、操作简便等优点,广泛应用于土壤、岩石和大气等样品的前处理中。海水样品的前处理以共沉淀的效率最高,而吹扫捕集能富集海水中不同形态的汞。为拓展汞同位素技术在汞的生物地球化学循环研究中的应用,亟需建立更加快捷、高效的前处理技术。     

福建深沪湾不同环境样品中总汞和甲基汞含量的分布

测定了福建省泉州深沪湾海水、沉积物和生物体中的总汞含量,测定了沉积物、生物体中的甲基汞含量.海水总汞含量范围是1.16 ～7.29 ng/dm3,平均值为3.32 ng/dm3.沉积物中总汞含量为0.006～0.066 μg/g,甲基汞占总汞的比例为4.7％ ～38.6％,该比例与总汞含量呈负相关关系(r=-0.840,p＜0.05),这可能是因为总汞含量的升高使甲基汞合成反应受到抑制,导致反应速率降低甚至为负,即甲基汞的分解.生物体中总汞含量为0.037 ～0.353 μg/g(干重),甲基汞含量为1.01 ～42.50 ng/g(干重),甲基汞占总汞的比例为1.5％ ～40.4％.甲基汞含量与总汞含量显著相关(r =0.484,p＜0.10);总汞含量与甲基汞占总汞比例略有相关(r=-0.293,p＜0.10);甲基汞含量与其占总汞比例无相关性(r=0.061,p＞0.05).可以推测,生物体中的总汞和甲基汞都是外源性的,不同生物体甲基汞占总汞的比例变化很大.对深沪湾居民进行海产品摄入量评估,以美国EPA规定的甲基汞参考计量0.1 μg/(kg·d)为标准,计算得深沪湾周边居民每周食用3次(600g)湾内的海产品是安全的,不会产生汞中毒.未来还需要测定海水中甲基汞的含量,用以计算生物富集因子,表征不同生物对甲基汞的富集程度;通过测定鱼体中的δ13C、δ15N比值来确定不同鱼类的营养级,进而研究甲基汞的生物累积效应与营养级的关系.     

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.     

冷原子荧光法测定近海沉积物中汞含量的不确定度探讨

采用直观的因果图,分析冷原子荧光法测定近海沉积物中汞含量的不确定度影响因素。建立有效的数学模型,对测试过程中不确定度的各个分量进行了分步计算及整体合成,并对评定结果进行了讨论。结果表明,校准曲线、测量标准及仪器性能是冷原子荧光法测定近海沉积物中汞含量不确定度的主要影响因素.     

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.