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.     

Modelling the equilibrium speciation of nickel in the Tweed Estuary, UK: Voltammetric determinations and simulations using WHAM

The complexation of dissolved Ni has been evaluated in a rapidly-flushed, rural estuary (Tweed, UK) by ligand exchange-adsorptive cathodic stripping voltammetry. Results suggest the presence of strongly binding ligands, L, throughout, with average stability constants of about 10¹⁹ and which are saturated by ambient Ni concentrations. Equilibrium speciation calculations incorporating these constants in WHAM, version 6, predict an increase in Ni complexation (as NiL) from about 50% of total dissolved Ni in fresh water to over 90% in sea water. Equivalent calculations using the default-mode fulvic and humic substances (FS and HS, respectively) encoded in the WHAM database predict a reduction in complexation (as NiFS + NiHS) from about 20% in fresh water to less than 1% in sea water. Discrepancies arising from the two approaches are largely attributed to the different analytical detection windows employed. Thus, a better representation of Ni complexation is derived from including both types of complexant in the speciation calculations, resulting in estimates of net complexation in excess of 60% of total dissolved Ni throughout the estuary. The uncertainties and assumptions inherent in all computations illustrate the difficulty in measuring or predicting metal complexation in estuaries.     

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.     

Radium tracing of submarine groundwater discharge (SGD) and associated nutrient fluxes in a highly-permeable bed coastal zone, Korea

In order to estimate submarine groundwater discharge (SGD) and SGD-driven nutrient fluxes, we measured the concentrations of nutrients, ²²⁴Ra, and ²²⁶Ra in seawater, river water, and coastal groundwater of Yeongil Bay (in the southeastern coast of Korea) in August 2004 and February 2005. The bottom sediments over the shallow areas of this bay are composed mainly of coarse sands. Large excess concentrations of ²²⁴Ra, ²²⁶Ra, and Si supplied from SGD were observed in August 2004, while these excess concentrations were not apparent in February 2005. Based on the mass balance for ²²⁴Ra, ²²⁶Ra, and Si, which showed conservative mixing behavior in seawater, SGD was estimated to be approximately 6 × 10⁶ m³ day^− 1 (seepage rate = 0.2 m day^− 1) in shallow areas (< 9 m water depth) in August 2004, which is much higher than the SGD level typically found in other coastal regions worldwide. During the summer period, SGD-driven nutrients in this bay contributed approximately 98%, 12%, and 76% of the total inputs for dissolved inorganic nitrogen (DIN), phosphorus (DIP), and silicate (DSi), respectively. Our study implies that the ecosystem in this highly permeable bed coastal zone is influenced strongly by SGD during summer, while such influences are negligible in winter.     

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.     

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.     

三门湾海岸带第四系地下水资源

利用三门湾海岸带最近施工完成的水文地质孔、工程地质孔和地下水碳（¹⁴C）测年以及前人的分析研究资料,对三门湾海岸带第四系分布、第四系承压含水层富水性和咸淡水资源分布、承压水年龄和可更新能力进行了深入研究。三门湾海岸带蛇盘滩涂围垦区第一承压含水层（组）富水性较好,绝大部分地区为淡水;宁海县长街镇区域承压水淡水资源总体呈“人”字型分布,北部的大湖−车岙港区域淡水主要分布在第一承压含水层（组）中,在大湖−下洋涂区域淡水主要分布在第二承压含水层（组）中。三门湾海岸带第四系承压水年龄普遍较老。蛇盘滩涂围垦区第一承压含水层地下水年龄为21 642～22 012 cal a BP,未受到后期海侵作用影响;长街下洋涂滩涂围垦区第二承压含水层地下水的年龄为35 052～45 439 cal a BP,部分地段受到后期海侵影响。在目前未开采利用条件下,承压水补给条件差、水资源更新性差。对于拟作为应急供水水源地靶区,应加强地下水资源管理。     

Submarine groundwater discharge of nutrients to the ocean along a coastal lagoon barrier, Southern Brazil

The Patos–Mirim Lagoon system along the southern coast of Brazil is linked to the coastal ocean by a narrow mouth and by groundwater transport through a Holocene barrier. Although other groundwater systems are apparently active in this region, the hydraulic head of the lagoon, the largest in South America, drives groundwater transport to the coast. Water levels in wells placed in the barrier respond to changing water level in the lagoon. The wells also provide a measure of the nutrient concentrations of groundwater flowing toward the ocean. Additionally, temporary well points were used to obtain nutrient samples in groundwater on the beach face of the barrier. These samples revealed a subterranean freshwater–seawater mixing zone over a ca. 240 km shoreline. Previously published results of radium isotopic analyses of groundwater and of surface water from cross-shelf transects were used to estimate a water flux of submarine groundwater discharge (SGD) to nearshore surface waters of 8.5 × 10⁷ m³/day. Using this SGD and the nutrient concentrations in different compartments, nutrient fluxes between groundwater and surface water were estimated. Fluxes were computed using both average and median reservoir (i.e. groundwater and surface water) nutrient concentrations. The SGD total dissolved inorganic nitrogen, phosphate and silicate fluxes (2.42, 0.52, 5.92 × 10⁶ mol day^− 1, respectively) may represent as much as 55% (total N) to 10% (Si) of the nutrient fluxes to the adjacent shelf environment. Assuming nitrogen limitation, SGD may be capable of supporting a production rate of ca. 3000 g C m² year^− 1in the nearshore surf zone in this region.     

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.     

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.     

Nutrient water quality in a tropical coastal zone with groundwater discharge, northwest Yucatán, Mexico

This work is the beginning of a coastal water quality monitoring program to establish the baseline for the implementation of an integrated coastal management of the Yucatán Peninsula tropical ecosystem. Coastal water quality is affected by the increasing economic development. This area has no rivers because of its karst geomorphology, and the coastal freshwater comes from springs or seeps. Coastal water quality was studied in four towns from January to December 2000. Statistically significant differences among water quality variables and processes are discussed. Along with groundwater discharge, domestic and shrimp farming sewage are the main sources of nutrients, predominantly of nitrogen and silica. Salinity dilution is used to estimate the groundwater fraction that influences each area in northwestern Yucatán.     

The effect of groundwater on topographic changes in a gravel beach

In recent years, several attempts to stabilize the beach by control of the percolation of water have been proposed. However, morphodynamics in the surf zone is still not clear because of the complexity of wave actions and sediment transport. Especially, there is a little research on gravel beach morphodynamics including wave breaking in the surf zone. The present study investigates experimentally how groundwater level influences topographic changes in a gravel beach and simulates numerically the wave fields and flow patterns in the surf zone, considering the porosity of the media and the presence of groundwater. In experiments, water-level control tank was designed to control the simulated groundwater elevation and the wave flume was divided into two parts to maintain a constant mean water level. The experimental results show that the berm formed in the upper portion of the shoreline moves up the beach as the groundwater level falls and the lower the groundwater level, the steeper the beach surface. The numerical model was developed to clarify these features capable of simulating the difference of groundwater and mean water level. Numerical results showed different flow patterns due to the groundwater elevation; wave run-up weakens and wave run-down strengthens by the seaward currents caused by elevated groundwater. These deformations of the flow pattern explain well how the beach profile is affected by the groundwater elevation.     

Detection of DNA damage in mussels and sea urchins exposed to crude oil using comet assay

The single-cell microgel electrophoresis assay or the comet assay was used to evaluate DNA damage of dispersed crude oil on sea urchins (Strongylocentrotus droebachiensis) and mussels (Mytilus edulis L.). Sea urchins were exposed to 0.06 and 0.25 mg/L dispersed crude oil in a continuous flow system, while the mussels were exposed to 0.015, 0.06 and 0.25 mg/L dispersed crude oil. Sea urchin coelomocytes and mussel haemocytes were sampled after 4 and 5 weeks exposure, respectively. In the sea urchin coelomocytes, there was a significant concentration-related increase in the percentage of DNA in comet tail. In mussel haemocytes, there was a significantly higher percentage of DNA in comet tail for all treatments compared to the control. The responses were concentration-related up to 0.06 mg/L oil. The two highest exposure concentrations of mussels were not significantly different from each other. These results indicate that the comet assay can be used for biomonitoring of DNA damage in marine invertebrates following oil contamination.     

Submarine groundwater discharge and nutrient addition to the coastal zone and coral reefs of leeward Hawai'i

Multiple tracers of groundwater input (salinity, Si, ²²³Ra, ²²⁴Ra, and ²²⁶Ra) were used together to determine the magnitude, character (meteoric versus seawater), and nutrient contribution associated with submarine groundwater discharge across the leeward shores of the Hawai'ian Islands Maui, Moloka'i, and Hawai'i. Tracer abundances were elevated in the unconfined coastal aquifer and the nearshore zone, decreasing to low levels offshore, indicative of groundwater discharge (near-fresh, brackish, or saline) at all locations. At several sites, we detected evidence of fresh and saline SGD occurring simultaneously. Conservative estimates of SGD fluxes ranged widely, from 0.02–0.65 m³ m^− 2 d^− 1at the various sites. Groundwater nutrient fluxes of 0.04–40 mmol N m^− 2 d^− 1 and 0.01–1.6 mmol P m^− 2 d^− 1 represent a major source of new nutrients to coastal ecosystems along these coasts. Nutrient additions were typically greatest at locations with a substantial meteoric component in groundwater, but the recirculation of seawater through the aquifer may provide a means of transferring terrestrially-derived nutrients to the coastal zone at several sites.     

Distribution of PACs in surficial sediments and bioavailability to mussels, Mytilus edulis of Halifax Harbour

Surficial sediments and blue mussels were collected around the perimeter of Halifax Harbour. Samples were analysed for the levels and fingerprint of polycyclic aromatic compounds (PACs). The objective was to explore the relationship between contaminant profiles in sediments and in mussels and to explore the possibility of deducing their sources, pattern of deposition and circulation in the harbour. Combustion derived compounds predominated in both sets of samples, with more variability observed in the level of petroleum derived hydrocarbons in mussel samples. Biota-sediment accumulation factors (BSAF, dry/dry wt.) varied throughout the harbour, ranging from means of 0.006 to 1.26, where generally fluoranthene displayed the highest BSAF. Sediments and mussels give complementary views of the geographical distribution of contaminants, they reflect the state of benthic and pelagic habitats. Results observed for Halifax Harbour are discussed from the perspective of published data.     

山东北部泥质海岸带白浪河地区地下水水化学演化过程

莱州湾沿岸是中国海(咸)水入侵典型区域之一,受多次海侵海退事件影响,形成了复杂的地下含水系统。为探究其地下水系统水化学特征及演化规律,对比分析白浪河地区内地下水的水化学特征及主要离子的变化规律,研究了不同分区的水化学演化过程。结果表明,内陆的咸水主要由淡水/卤水混合形成,滨海的咸水主要由淡水/海水混合形成。现存卤水在形成过程中发生了淡水的混入,水岩相互作用和阳离子交换在一定程度上改变了卤水的水化学组成。矿物饱和指数结果表明,不同分区的地下水体中,方解石和白云石基本处于饱和状态,岩盐均未达到饱和状态,石膏仅在卤水中达到饱和状态。从陆到海,地下水系统中发生的阳离子交换过程不同,淡水区和微咸水区浅层的地下水主要是水中的Ca2+与含水介质吸附的Na+交换,而其他分区的阳离子交换过程与之相反。     

烟台近岸典型生态区沉积物重金属形态分布及其污染状况

运用Tessier连续提取法,对烟台海岸带3个典型生态敏感区表层沉积物重金属Cr、Cu、Cd、Pb、Zn、Ni的形态分布和污染状况进行了分析研究。结果表明,研究区域中河口区与排污口区重金属Cr、Cu、Cd、Zn和Ni的含量较高,尤其是Cd污染严重。养殖区基本符合海洋沉积物质量第1类标准;重金属Cr、Cu、Pb、Zn和N...     

The effect of submarine groundwater discharge on nutrient and salinity regimes in a coastal lagoon off Perth, Western Australia

Submarine groundwater discharge (SGD) into a coastal lagoon off Perth, Western Australia, contains nitrate and silicate in concentrations two orders of magnitude higher than those of the receiving waters. This discharge delivers enough nitrate to replace that dissolved in the lagoon water mass about every eight days and enough silicate to replace the lagoon silicate in about 48 days. The delivery rate of nitrate nitrogen by SGD is equal to about 48% of that required for observed growth rates of lagoon macrophytes. Surface salinity is lower close to the shore as a result of SGD. During calm conditions a salinity front was observed in the lagoon, with a nearshore pool of nutrient-enriched water floating above the more saline ocean water.     

海岸带经济韧性评估及其对涉海企业TFP的影响研究

研究海岸带经济韧性与涉海企业全要素生产率（Total Factor Productivity, TFP）对推动海洋经济高质量发展具有重要意义。囿于涉海微观企业层面数据的缺乏,这一问题一直未得到定量化的探讨。为此,本文创新性地基于行业分类代码,在全国税收调查数据库中筛选出涉海企业并测算其TFP。同时,在定量评估沿海地区海岸带经济韧性的基础上,将两组数据进行匹配,实证考察了海岸带经济韧性对涉海企业TFP的影响效应和内在机理,得出以下结论：第一,2006-2021年,中国海岸带经济韧性总体呈现上升趋势,其中南部（福建、广东、广西和海南）海岸带经济韧性最强,东部（江苏、上海和浙江）其次,北部（辽宁、河北、天津和山东）最弱。在金融危机冲击时,南部海岸带经济韧性表现最好。在新冠疫情时期,东部海岸带经济则显现出更强的韧性。第二,地区海岸带经济韧性的增强,会促进涉海企业TFP的提高,其中的关键影响机制在于企业创新投入的增加。第三,市场化和数字化程度越高的地区,海岸带经济韧性对涉海企业TFP促进作用更加显著。