The impact of resuspension on sediment mercury dynamics, and methylmercury production and fate: A mesocosm study

The objective of this study was to investigate the effects of resuspension on the fate and bioaccumulation of mercury (THg) and methylmercury (MeHg) in shallow estuarine environments, using mesocosms. Two 4-week experiments were conducted in July (Experiment 1) and October (Experiment 2) of 2001 with Baltimore Harbor sediments. Hard clams, Mercenaria mercenaria, were introduced into sediments for Experiment 2. Tidal resuspension (4 h on and 2 h off cycles) was simulated, with 3 replicate tanks for each treatment—resuspension (R) and non-resuspension (NR). Sediment cores were collected during the experiments for THg, MeHg, organic content and AVS analyses, and for the determination of methylation/demethylation using Hg stable isotopes (¹⁹⁹Hg(II) and CH₃¹⁹⁹Hg(II)). Zooplankton samples were collected once a week while clams were taken before and after Experiment 2 for THg and MeHg analyses. Our results suggest that the interplay between Hg methylation and MeHg degradation determines the overall MeHg pool in sediments. Sediment resuspension does not appear to directly impact the Hg transformations but can lead to changes in the association to Hg binding phases, influencing Hg methylation. The bioaccumulation results indicate that sediment resuspension can play an important role in transferring sediment MeHg into organisms.     

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.     

An experimental approach to investigate mercury species transformations under redox oscillations in coastal sediments

This work describes a laboratory experiment designed to unravel mercury species reactivity in superficial coastal sediments oscillating between oxic and anoxic conditions. The experimental set-up has been applied to a sediment slurry from the Arcachon Bay (France) to follow the evolution of both naturally occurring (i.e. endogenous) and isotopically enriched added mercury species (i.e. exogenous, 1??IHg and 2?1MMHg) at environmental levels. The transformation and partition between the different phases (aqueous, solid and gaseous) of the endogenous and exogenous mercury species (inorganic Hg (IHg), monomethyl Hg (MMHg), elemental Hg (Hg?) and dimethyl Hg (DMHg)) have been investigated by isotopic speciation methods throughout the experiment. The results demonstrate that the experimental approach is able to promote sediment redox oscillations and to simultaneously follow the biogeochemical fate of naturally occurring or added mercury species. Experimentally driven redox transition events were found to significantly enhance the aqueous Hg species concentrations, while the MMHg burden is not greatly affected. Indeed, during the anoxic-oxic transition, while aqueous endogenous IHg and MMHg exhibited a two-fold increase, aqueous exogenous IHg and MMHg increased 7 and 4 times, respectively. Transient increases of the net IHg methylation were recorded during the redox transitions with the largest increase of the MMHg contents (factor 1.8) observed during the oxic-anoxic transition. High resolution in situ redox experiments have not been performed up to now, therefore the developed experimental set-up provides novel insights in both the influence of redox conditions on Hg methylation/demethylation and adsorption/desorption processes and kinetics in superficial sediments.     

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.     

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone

The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgT_D) in the groundwater springs were 0.99 ± 0.15 ng l^− 1 (n = 18) and 0.44 ± 0.17 ng l^− 1 (n = 17) at Etretat and Yport respectively. High HgT_D concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg^− 1 (n = 16) and 0.16 ± 0.10 ng mg^− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l^− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l^− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels.     

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

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

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.     

The role of two sediment-dwelling invertebrates on the mercury transfer from sediments to the estuarine trophic web

The annual total and organic mercury bioaccumulation pattern of Scrobicularia plana and Hediste diversicolor was assessed to evaluate the potential mercury transfer from contaminated sediments to estuarine food webs. S. plana was found to accumulate more total and organic mercury than H. diversicolor, up to 0.79 mg kg⁻¹ and 0.15 mg kg⁻¹ (wet weight) respectively, with a maximum annual uptake of 0.21 mg kg⁻¹ y⁻¹, while for methylmercury the annual accumulation was similar between species and never exceeded 0.045 mg kg⁻¹ y⁻¹. The higher organic mercury fraction in H. diversicolor is related to the omnivorous diet of this species. Both species increase methylmercury exposure by burrowing activities and uptake in anoxic, methylmercury rich sediment layers. Integration with the annual biological production of each species revealed mercury incorporation rates that reached 28 μg m⁻² y⁻¹, and to extract as much as 11.5 g Hg y⁻¹ (of which 95% associated with S. plana) in the 0.4 km² of the most contaminated area, that can be transferred to higher trophic levels. S. plana is therefore an essential vector in the mercury biomagnification processes, through uptake from contaminated sediments and, by predation, to transfer it to economically important and exploited estuarine species.     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

The biogeochemistry of mercury at the sediment–water interface in the Thau lagoon. 1. Partition and speciation

Solid sediment, pore and epibenthic waters were collected from the Thau lagoon (France) in order to study the post-depositional partition and mobility of mercury in organic rich sediment. Total Hg (HgT) and monomethylmercury (MMHg) profiles were produced in both dissolved and solid phases. The distribution of HgT in the solid phase appeared to be related to the historical changes in the Hg inputs into the lagoon. HgT was in equilibrium between solid and solution phases in the sulfidic part of the cores, with a mean log K_d of 4.9 ± 0.2. The solid phase appeared to be a source of HgT for pore water in the upper oxic to suboxic parts of the cores. The MMHg represented a small fraction of HgT: 3–15% and 0.02–0.80% in the dissolved and solid phases, respectively. Its distribution was characterized by a main peak in the superficial sediments, and another deeper in the core within the sulfide-accumulating zone. In addition, high dissolved MMHg concentrations and methylated percentage were found in the epibenthic water. Ascorbate (pH 8) dissolution of the sediments and analyses of the soluble fraction suggest that the amorphous oxyhydroxides played a major role in controlling total and methylmercury mobility throughout the sediment–water interface. These features are discussed in terms of sources, transfer and transformations. Diffusive fluxes of HgT and MMHg from sediment to the water column for the warm period were estimated to be 40 ± 15 and 4 ± 2 pmol m⁻² d⁻¹, respectively.     

Geochemical cycling in the Hooghly estuary, India

U–Th decay series isotopes, δ¹⁸O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ¹⁸O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. ²³⁴Th and ²¹⁰Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l⁻¹). ²²⁸Ra and ²²⁶Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, ²¹⁰Pb and ²¹⁰Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. ²³²Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.     

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.     

Mercury in the Southern North Sea and Scheldt estuary

Dissolved and particulate mercury and methylmercury concentrations were determined in the Southern Bight of the North Sea and the Scheldt estuary in the period 1991–1999. Mercury and methylmercury concentrations are higher before 1995 than after 1995, especially in the fluvial part.The North Sea: In the offshore stations, dissolved Hg concentrations are generally higher in winter than in summer while the reverse is true for particulate Hg K_D values (K_D=the concentration of particulate Hg (Hg_P in pmol kg⁻¹) divided by the concentration of dissolved Hg (Hg_D in pmol l⁻¹)) range from 100,000 to 1000,000 l kg⁻¹. Dissolved methylmercury concentrations vary from 0.05 to 0.25 pmol l⁻¹ in summer and from d.l. to 0.23 pmol l⁻¹ in winter and particulate methylmercury concentrations from 1.8 to 36 pmol g⁻¹ in summer and from 0.9 to 21 pmol g⁻¹ in winter. The K_D ranges from 9,000 to 219,000 l kg⁻¹.The Scheldt estuary: In winter, dissolved Hg concentrations are elevated in the upper estuary, decrease exponentially in the low salinity range followed by a very slow decrease towards the mouth. In summer, they are low in the fluvial part, increase in the low salinity range or in the mid-estuary and sometimes show an increase in the lower estuary. Particulate Hg concentrations do not show any seasonal trend.Dissolved MMHg concentrations are much lower in winter, when maximum concentrations are found in the upper estuary, than in summer. In summer, the MMHg concentrations are low at low salinity, they show a first increase in the salinity range from 3 to 12, a decrease in the mid-estuary and a second increase in the lower estuary.The highest particulate MMHg concentrations are found in the upper estuary, while in the lower estuary generally lower and more constant values are observed. The ratio of dissolved MMHg to dissolved Hg (cruise averages between 1.3% and 20%), is higher than the ratio of particulate MMHg to particulate Hg (cruise averages of 0.27–0.90%). The K_D values for MMHg are lower in the summer (30,000–65,000) than in autumn and winter (77,000–114,000).The Scheldt river: In the fluvial part of the Scheldt, dissolved increases in the most upstream stations, while particulate Hg shows no particular pattern. Dissolved MMHg ranges from 0.1 to 0.39 pmol l⁻¹ and particulate MMHg from 3.1 to 43.5 pmol g⁻¹. The MMHg concentrations are comparable to those found in the estuary and no seasonal variations could be observed.     

Investigation of the morphology of pore space in mudstones—first results

A suite of selected Tertiary mudstones was studied to improve the knowledge about microstructure and related transport processes in mudstones. Samples were investigated by mercury- and Wood's metal injection, SEM, XRD, and grain size analysis. Wood's metal injection has the advantage of visualising the ‘frozen’ injection process. The smallest pore casts observed were down to 40 nm in diameter, while the largest, bottle-shaped pores were up to 5 μm in diameter. Bottle-shaped pores occurred in all the samples, usually around silt or sand grains. One sample, which had a porosity of 28.5% according to mercury injection data, had not been impregnated by the molten alloy. We suggest this to reflect a strong deformation of the clay fabric by the high pressure without intrusion into the matrix. This raises questions about the reliability of mercury injection data for very fine-grained, highly porous sediments.After excluding these very fine-grained samples and one very calcareous sample regressions were found which relate porosity (φ), clay content (C), and sand content (S) to capillary displacement pressure (P_d(Hg)): P_d(Hg)=−25.05+0.63 C+0.29S (R²=0.92), and P_d(Hg)=−10.24+0.47 C−0.15φ (R²=0.88).     

长江河口湿地互花米草入侵对沉积物中汞形态特征的影响研究

通过分析长江河口湿地典型植物根际沉积物柱样(0～40 cm)中总汞(THg)、甲基汞(MeHg)及其与粒度、总有机碳(TOC)、还原态硫等环境因子之间的关系,探讨了互花米草(Spartina alterniflora)入侵对沉积物中汞形态特征的影响及主控因子。结果表明:(1)不同植物(互花米草、芦苇(Phragmites communis)、海三棱藨草(Scirpus mariqueter)和水葱(Scirpus tabernaemontani))根际沉积物中THg均值为49.9～100.9 μg/kg,其与粒径小于16 μm颗粒物组分体积百分比及TOC含量之间存在显著正相关关系(r2=0.85,p<0.01;r2=0.58,p<0.01),这意味着沉积物中矿物?有机物复合体细颗粒物的空间分异决定着总汞的空间分异。互花米草入侵促进了细颗粒的沉积,进而间接促进了沉积物中总汞含量的增加。(2)不同植物根际沉积物中MeHg均值为0.3～1.4 μg/kg,MeHg/THg均值为0.4%～1.4%,互花米草、芦苇及海三棱藨草根际沉积物中MeHg含量及MeHg/THg值随深度增加不断减小,但无显著差异,表明了互花米草入侵对沉积物中汞甲基化过程的影响可能有限。Pearson相关分析表明,MeHg/THg与THg、TOC、酸挥发性硫之间不存在显著的正相关关系。硫的K边同步辐射结果进一步表明了硫形态(如有机硫和S2?)变化与MeHg变化关系不大。MeHg/THg值呈表层(0～8 cm)高,底层低的分布规律,表明了表层沉积物中汞的甲基化潜势较大,这可能与表层新鲜有机质(如藻类和植物凋落物)的不断供给及其降解过程密切相关,还需深入研究。     

Carbon stable isotopes in estuarine sediments and their utility as migration markers for nursery studies in the Firth of Forth and Forth Estuary, Scotland

The stable carbon isotope ratios (δ¹³C) of the organic fraction of intertidal sediments in the Forth Estuary and the Firth of Forth, Scotland, were measured to determine if terrestrially derived carbon was present in the estuarine sediments. It was hypothesised that differences in the inputs from marine vs. terrestrial sources to the organic carbon of estuarine and marine sediments, as well as differences in ambient seawater stable oxygen isotope (δ¹⁸O) ratios between the estuary and the Outer Firth, would allow the use of these two stable isotopes as habitat markers for juvenile plaice (Pleuronectes platessa), to allow determination of nursery habitats. Muddy and sandy sediments from the estuary and sandy sediments from the Outer Firth were sampled and δ¹³C measured. Juvenile plaice were caught at two estuarine sites and at two Outer Firth sites and otoliths were removed for δ¹³C and δ¹⁸O analysis. The sandy sediments in the estuary showed a strong gradient of δ¹³C enrichment with distance down the estuary, while the muddy sediments showed a much shallower gradient. δ¹³C and δ¹⁸O measured in the carbonate of juvenile plaice otoliths showed no clear difference between otoliths of fish caught at one of the estuarine sites and at the two Outer Firth sites. However, the isotope ratios of both carbon and oxygen in plaice otoliths from the other estuarine site showed the expected trend of depletion in the heavier isotopes. While the measurements recorded here did not conclusively distinguish between otoliths from juveniles caught in the estuarine site and those caught in the other three sites, they show that stable isotopes have potential to distinguish between estuarine habitats with terrestrial carbon inputs, and coastal marine habitats with predominantly marine carbon inputs.     

An investigation into the effects of silver nanoparticles on antibiotic resistance of naturally occurring bacteria in an estuarine sediment

The aim of this study was to test whether silver nanoparticles (Ag-NPs) released into estuarine environments result in increased antibiotic resistance amongst the natural bacterial population in estuarine sediments. A 50-day microcosm exposure experiment was carried out to investigate the effects of Ag-NPs (50 nm average diameter) on the antibiotic resistance of bacteria in sediments from an estuary in southwest England. Experimental microcosms were constructed using 3.5 kg sediment cores with 20 l of overlaying seawater treated with (final) Ag-NPs concentrations of 0, 50 or 2000 μg l⁻¹ (n = 3). Sediment samples were screened at the end of the exposure period for the presence of bacteria resistant to eight different antibiotics. Multivariate statistical analyses showed that there was no increase in antibiotic resistance amongst the bacterial population in the sediment due to the dosing of the microcosms with Ag-NPs. This study indicates that, under the tested conditions, Ag-NPs released into the coastal marine environment do not increase antibiotic resistance among naturally occurring bacteria in estuarine sediments. These results contrast previous findings where antimicrobial effects of Ag-NPs on key bacterial species in laboratory experiments have been demonstrated, and reasons for this are discussed. The negligible effects demonstrated on bacterial populations under the selected estuarine conditions, provide important information on no observed effect concentrations (NOECs) for environmental regulation.     

环雷州半岛海域表层沉积物与鲬鱼汞污染研究

对2018年1月在广东环雷州半岛近海海域采集的海底表层沉积物、鲬鱼(Platycephalus indicus)进行汞含量的测定,分析比较了鲬鱼不同部位汞含量的差异,并采用单因子污染指数法对沉积物和鲬鱼的汞污染状况进行了风险评价。结果表明,环雷州半岛海域表层沉积物中汞含量范围为0.005×10^-6～0.359×10^-6,平均值为0.081×10^-6,雷州半岛东部海域表层沉积物汞含量高于南部和西部海域。鲬鱼的鳃中汞含量范围为0.032×10^-6～0.034×10^-6,平均值为0.033×10^-6;肌肉中的汞含量范围为0.065×10^-6～0.080×10^-6,平均值为0.073×10^-6;肝脏中的汞含量范围为0.228×10^-6～0.270×10^-6,平均值为0.249×10^-6。鲬鱼样品的汞含量都呈现出肝脏＞肌肉＞鳃。单因子污染指数评价结果显示,雷州半岛海域鲬鱼受到汞的轻微污染,雷州半岛东部海域表层沉积物存在汞污染生态风险,而其南部、西部海域尚未受到汞污染的威胁。     

Mercury pollution in sediments,benthic organisms and inshore fishes of Haifa Bay,Israel

Total mercury concentrations were determined in surficial sediments, eleven species of benthic organisms and six species of fish from Haifa Bay, Israel. The results show that essentially all of the shallow water zone of the Bay receives anthropogenic mercury. A mercury-cell chlor-alkali plant was identified as the source of pollution. Surficial sediments in the vicinity of the plant, containing up to 0·99 μg Hg/g dry weight, were up to 157 times enriched in mercury relative to an unpolluted area. Mercury levels in the benthic organisms reflected the levels in the sediments. Maximal concentrations reaching 38·7 and 18·2 μg Hg/g dry weight were found in the carnivorous gastropod molluscs Arcularia circumcinta and Arcularia gibbosula, respectively. In all fish species, specimens caught in Haifa Bay had higher mercury concentrations in the muscle tissue than specimens caught south of the Bay. A maximal value of 1·66 μg Hg/g wet weight was recorded in Diplodus sargus.     

基于河口潮间带底栖微藻群落水平的环境质量状态评价

The feasibility of community-based bioassessment of environmental quality status was studied using microphytobenthos(MPB) in estuarine intertidal ecosystems.The sediment samples of MPB were collected monthly during a 1-year cycle(September 2006–August 2007) at four sampling stations in the Nakdong River Estuary,Korea.Environmental variables,such as salinity,radiation,grain size of sediment,Si(OH)_4(Si),nitrate(NO_3~–),nitrite(NO_2~–),ammonium(NH_4~+) and phosphates(PO_4~(3–)),were measured synchronously for comparison with biotic parameters.The statistical analyses were carried out for assessment the relationship between biotic and environmental parameters.The results showed that:(1) the MPB community structures were significant differences among four sampling stations;(2) spatial variation in the MPB communities were significantly correlated with environmental variables,especially the nutrient NH_4+ in combination with salinity and grain size;(3) three species(Navicula lacustris,Pleurosigma anglulatum and Fragilaria sp.1) were significantly correlated with nutrients and/or Si;and(4) the species richness and diversity were significantly correlated with the grain size.It is suggested that MPB communities may be used as a potentially robust bioindicator for assessing environmental quality status in estuarine intertidal ecosystems.