Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region.     

Distribution of total mercury and methylmercury in lake sediments in Arctic Ny-Ålesund

The toxicities and bioavailabilities of total mercury (THg) and methylmercury (MeHg) in aquatic systems have made them the subjects of recent research. In this study, we collected a lake sediment core from Ny-Ålesund in Svalbard and analyzed the distributions of THg and MeHg in the sediments. The increased trend of THg was caused by anthropogenic contamination since the 14th century through long-range transportation, especially after the industrial era. However, the peak values of Hg in surface sediment samples could be explained by the increased algal scavenging process in recent decades. All the biogeochemical proxies (e.g., pigments and diatom biomass) revealed recent sharp increases in aquatic primary production due to the current climate warming. Rock-Eval analyses indicated that algal-derived organic matter took up a large portion, and quantitative calculation showed that 89.6-95.8% of the Hg in post-1950 could be explained by scavenging. The distribution of MeHg has a close relationship with total Hg and organic matter. The oxidation-reduction condition is one of the possible factors affecting the methylation rates in H2 lake sediments. Higher algal productivity and organic matter actually led to the increased trend of methylation in the uppermost sediment. This study supports some new key hypotheses on climate-driven factors affecting Hg and MeHg cycling in High Arctic lake sediments.     

Characteristics of mercury speciation in Minnesota rivers and streams

Patterns of mercury (Hg) speciation were examined in four Minnesota streams ranging from the main-stem Mississippi River to small tributaries in the basin. Filtered phase concentrations of methylmercury (MeHg), inorganic Hg (IHg), and dissolved organic carbon (DOC) were higher in all streams during a major summertime runoff event, and DOC was enriched with MeHg but not with IHg. Particulate-phase MeHg and IHg concentrations generally increased with total suspended solids (TSS) concentrations but the event data did not diverge greatly from the non-event data, suggesting that sources of suspended sediments in these streams did not vary significantly between event and non-event samplings. The dissolved fractions (filtered concentration/unfiltered concentration) of both MeHg and IHg increased with increasing DOC concentrations, but varied inversely with TSS concentrations. While MeHg typically constitutes only a minor portion of the total Hg (THg) in these streams, this contribution is not constant and can vary greatly over time in response to watershed inputs.     

Sorption of mercury (II) in Amazon soils from column studies

The sorption of Hg (II) onto four different types of Amazon soils from the A-horizon was investigated by means of column experiments under saturation conditions and controlled metal load. Higher organic matter contents in the soil resulted in higher Hg (II) adsorptions, reaching values as high as 3.8 mg Hg g⁻¹ soil. The amount of mercury adsorbed on a soil column (Q) shows a very poor correlation with soil clay content (r² = 0.2527), indicating that Hg sorption in these topsoil samples is chiefly governed by the organic matter content. Desorption experiments using Negro River (Amazon) waters were conducted using soil saturated with Hg (II) in order to better understand the metal leaching mechanism. The amount of Hg (II) released from soils was around 30% of the total sorbed mercury upon saturation, suggesting that mercury sorption in the soils present in the catchment area of the Negro River basin is not a reversible process.     

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.     

The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Patterns of mercury and methylmercury bioaccumulation in fish species downstream of a long-term mercury-contaminated site in the lower Ebro River (NE Spain)

Since the 19th century, large amounts of industrial waste were dumped in a reservoir adjacent to a chlor-alkali plant in the lower Ebro River (NE Spain). Previous toxicological analysis of carp populations inhabiting the surveyed area have shown that the highest biological impact attributable to mercury pollution occurred downstream of the discharge site. However, mercury speciation in fish from this polluted area has not been addressed yet. Thus, in the present study, piscivorous European catfish (Silurus glanis) and non-piscivorous common carp (Cyprinus carpio) were selected, to investigate the bioavailability and bioaccumulation capacities of both total mercury (THg) and methylmercury (MeHg) at the discharge site and downstream points. Multiple Correspondence Analysis (MCA) was applied to reduce the dimensionality of the data set, and Multiple Linear Regression (MLR) models were fitted in order to assess the relationship between both Hg species in fish and different variables of interest. Mercury levels in fish inhabiting the dam at the discharge site were found to be approximately 2-fold higher than those from an upstream site; while mercury pollution progressively increased downstream of the hot spot. In fact, both THg and MeHg levels at the farthest downstream point were 3 times greater than those close to the waste dump. This result clearly indicates downstream transport and increased mercury bioavailability as a function of distance downstream from the contamination source. A number of factors may affect both the downstream transport and increased Hg bioavailability associated with suspended particulate matter (SPM) and dissolved organic carbon (DOC).     

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.     

Hydroxypropyl-β-cyclodextrin extractability and bioavailability of phenanthrene in humin and humic acid fractions from different soils and sediments

Organic matter (OM) plays a vital role in controlling polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. In this study, both a hydroxypropyl-β-cyclodextrin (HPCD) extraction test and a biodegradation test were performed to evaluate the bioavailability of phenanthrene in seven different bulk soil/sediment samples and two OM components (humin fractions and humic acid (HA) fractions) separated from these soils/sediments. Results showed that both the extent of HPCD-extractable phenanthrene and the extent of biodegradable phenanthrene in humin fraction were lower than those in the respective HA fraction and source soil/sediment, demonstrating the limited bioavailability of phenanthrene in the humin fraction. For the source soils/sediments and the humin fractions, significant inverse relationships were observed between the sorption capacities for phenanthrene and the amounts of HPCD-extractable or biodegradable phenanthrene (p?<?0.05), suggesting the importance of the sorption capacity in affecting desorption and biodegradation of phenanthrene. Strong linear relationships were observed between the amount of HPCD-extractable phenanthrene and the amount degraded in both the bulk soils/sediments and the humin fractions, with both slopes close to 1. On the other hand, in the case of phenanthrene contained in HA, a poor relationship was observed between the amount of phenanthrene extracted by HPCD and the amount degraded, with the former being much less than the latter. The results revealed the importance of humin fraction in affecting the bioavailability of phenanthrene in the bulk soils/sediments, which would deepen our understanding of the organic matter fractions in affecting desorption and biodegradation of organic pollutants and provide theoretical support for remediation and risk assessment of contaminated soils and sediments.     

Mercury exposure in the freshwater tilapia Oreochromis niloticus

Mercury (Hg) can be strongly accumulated and biomagnified along aquatic food chain, but the exposure pathway remains little studied. In this study, we quantified the uptake and elimination of both inorganic mercury [as Hg(II)] and methylmercury (as MeHg) in an important farmed freshwater fish, the tilapia Oreochromis niloticus, using ²⁰³Hg radiotracer technique. The dissolved uptake rates of both mercury species increased linearly with Hg concentration (tested at ng/L levels), and the uptake rate constant of MeHg was 4 times higher than that of Hg(II). Dissolved uptake of mercury was highly dependent on the water pH and dissolved organic carbon concentration. The dietborne assimilation efficiency of MeHg was 3.7-7.2 times higher than that of Hg(II), while the efflux rate constant of MeHg was 7.1 times lower. The biokinetic modeling results showed that MeHg was the greater contributor to the overall mercury bioaccumulation and dietary exposure was the predominant pathway.     

Methylmercury speciation in the dissolved phase of a stratified lake using the diffusive gradient in thin film technique

The diffusive gradient in thin film (DGT) technique was successfully used to monitor methylmercury (MeHg) speciation in the dissolved phase of a stratified boreal lake, Lake 658 of the Experimental Lakes Area (ELA) in Ontario, Canada. Water samples were conventionally analysed for MeHg, sulfides, and dissolved organic matter (DOM). MeHg accumulated by DGT devices was compared to MeHg concentration measured conventionally in water samples to establish MeHg speciation. In the epilimnion, MeHg was almost entirely bound to DOM. In the top of the hypolimnion an additional labile fraction was identified, and at the bottom of the lake a significant fraction of MeHg was potentially associated to colloidal material. As part of the METAALICUS project, isotope enriched inorganic mercury was applied to Lake 658 and its watershed for several years to establish the relationship between atmospheric Hg deposition and Hg in fish. Little or no difference in MeHg speciation in the dissolved phase was detected between ambient and spike MeHg.     

Wetland influence on mercury fate and transport in a temperate forested watershed

The transport and fate of mercury (Hg) was studied in two forest wetlands; a riparian peatland and an abandoned beaver meadow. The proportion of total mercury (THg) that was methyl mercury (% MeHg) increased from 2% to 6% from the upland inlets to the outlet of the wetlands. During the growing season, MeHg concentrations were approximately three times higher (0.27ng/L) than values during the non-growing season (0.10ng/L). Transport of Hg species was facilitated by DOC production as indicated by significant positive relations with THg and MeHg. Elevated concentrations of MeHg and % MeHg (as high as 70%) were found in pore waters of the riparian and beaver meadow wetlands. Groundwater interaction with the stream was limited at the riparian peatland due to the low hydraulic conductivity of the peat. The annual fluxes of THg and MeHg at the outlet of the watershed were 2.3 and 0.092microg/m2-year respectively.     

Levels of methylmercury and controlling factors in surface sediments of the Carson River system, Nevada

Spatial and temporal distribution of methylmercury (MeHg) was determined in surficial sediments collected from a river-reservoir system impacted by Hg-contaminated mine wastes. Despite the fact that total mercury concentrations (HgT) in surface sediments of the Carson River system were in the microg.g(-1) range, levels of MeHg varied from about 2 to 28 ngHg.g(-1) dry weight, representing less than 3% of Hg(T). Concentrations of MeHg were well correlated with both the biotic (r=0.95) and abiotic activity (r=0.85) of the sediment, determined as the ability of each compartment to specifically reduce an alternative electron acceptor. However, the positive relationship between the two measured activities suggests that the abiotic activity may be due to reductant substances produced by micro-organisms. When sediments collected from the Carson River were used in laboratory assays for the determination of potential rates of MeHg production, the addition of inorganic Hg (added as HgCl2) resulted in increased rates of methylation when the spike concentration was lower or equal to 15.3 microg.g(-1) dry weight. This trend was reversed for spike concentration of inorganic Hg above 15.3 microg.g(-1). The reduction of methylation rate was associated with an inhibition of microbial activity. These observations suggest that seasonal inputs into the river of significant amounts of inorganic Hg eroded from mill tailings during winter and spring flooding events could have an inhibiting effect on Hg-methylating micro-organisms. This observation could explain the low [MeHg]/[HgT] ratios previously documented in waters of the Carson River system.     

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).     

Role of extractable and residual organic matter fractions on sorption of phenanthrene in sediments

Two sediments were demineralized and sequentially fractionated into extracted fractions [free lipid (FL), bound lipid (BL) and lignin (LG)] and residual fractions [free lipid free (FLF), bound lipid free (BLF) and lignin free (LGF)]. The sorption isotherms of phenanthrene (Phen) were examined to evaluate the importance of various fractions on sorption. A lignin extraction procedure was for the first time applied to separate the lignin or degraded lignin fraction from sediment organic matter (SOM). The extracted LG was similar to model lignin in terms of elemental ratios and sorption behavior. FL and LG fractions were quite important, as their contents were much higher than reported values. Phen sorption for the extracted fractions was almost linear, whereas that for the residual fractions was nonlinear, especially for LGF with n 0.56–0.63. As the different organic fractions were removed sequentially, sorption energy distribution on the residual sediment organic matter (SOM) became more heterogeneous. In addition, increasing sorption capacity for the residual fractions, except for BLF with its high polarity, suggested that more sorption sites on the SOM matrix became accessible to Phen. The sorption capacity for LGF was comparable to that of condensed SOM. The residual fraction LGF generally controlled the overall sorption at low Phen concentration, but the extractable fraction FL surpassed the former fraction at high Phen concentration, demonstrating the importance of condensed SOM in the sorption of hydrophobic organic compounds (HOCs) in sediments.     

Linking Cellulose Fiber Sediment Methyl Mercury Levels to Organic Matter Decay and Major Element Composition

Methylation of mercury (Hg) to highly toxic methyl Hg (MeHg), a process known to occur when organic matter (OM) decomposition leads to anoxia, is considered a worldwide threat to aquatic ecosystems and human health. We measured temporal and spatial variations in sediment MeHg, total Hg (THg), and major elements in a freshwater lagoon in Sweden polluted with Hg-laden cellulose fibers. Fiber decomposition, confined to a narrow surface layer, resulted in loss of carbon (C), uptake of nitrogen (N), phosphorus (P), and sulfur (S), and increased MeHg levels. Notably, fiber decomposition and subsequent erosion of fiber residues will cause buried contaminants to gradually come closer to the sediment–water interface. At an adjacent site where decomposed fiber accumulated, there was a gain in C and a loss of S when MeHg increased. As evidenced by correlation patterns and vertical chemical profiles, reduced S may have fueled C-fixation and Hg methylation at this site.     

Methylmercury and total mercury in estuarine organisms from Rio de Janeiro, Brazil

Guanabara Bay (GB), located in the Rio de Janeiro State, is still a productive estuary on the south-eastern Brazilian coast. It is an ecosystem heavily impacted by organic matter, oil and a number of other toxic compounds, including Hg. The present study aimed to comparatively evaluate the aquatic total mercury (THg) and MeHg contamination, and the ratios of MeHg to THg (% MeHg), in 3 species of marine organisms, Micropogonias furnieri-carnivorous fish (N = 81), Mugil spp.--detritivorous fish (N = 20) and Perna perna--filter-feeding bivalves (N = 190), which are widely consumed by the population. A total of 291 specimens were collected at the bay in different periods between 1988 and 1998. THg concentrations were determined by cold vapour AAS with stannous chloride as a reducing agent. MeHg was extracted by dithizone-benzene and measured by GC-ECD. Analytical quality was checked through certified standards. All organisms presented both low THg and MeHg concentrations and they were below the maximum limit of 1,000 micrograms Hg.kg-1 wet wt. as established for human intake of predatory fish by the new Brazilian legislation. Carnivorous fish showed higher THg and MeHg concentrations, and also % MeHg in muscle tissues, than organisms with other feeding habits and lower trophic levels. The average of THg concentrations in carnivorous fish was 108.9 +/- 58.6 micrograms.kg-1 wet wt. (N = 61) in 1990 and 199.5 +/- 116.2 micrograms.kg-1 wet wt. (N = 20) in 1998, but they presented different total length and body weights. The average THg content in detritivorous fish was 15.4 +/- 5.8 micrograms.kg-1 wet wt., whereas THg concentrations ranged from 4.1 to 53.5 micrograms.kg-1 wet wt. for the molluscs. The THg and MeHg contents of mussel varied according to the sampling point and water quality. MeHg concentration in detritivorous fish was similar to MeHg concentration in molluscs, but there was a significant difference in the MeHg/THg ratio: the carnivorous fish presented higher MeHg percentages (98%) than the detritivorous fish (54%) and the molluscs (33%). Weight-normalised average concentration of THg in carnivorous fish collected in 1990 (0.18 +/- 0.08 microgram.g-1/0.7 kg wet wt.) and in 1998 (0.16 +/- 0.09 microgram.g-1/0.7 kg wet wt.) presented no significant difference (t = 1.34; P < 0.5). In conclusion, the low THg and MeHg concentrations in the organisms from the GB ecosystem, are related to its eutrophic conditions and elevated amounts of suspended matter. In this situation, Hg could be strongly complexed or adsorbed by the particulate, which would dilute the Hg inputs and reduce its residence time in the water column, with a consequent decrease in its availability to organisms.     

Factors controlling the bioaccumulation of mercury and methylmercury by the estuarine amphipod Leptocheirus plumulosus

The bioaccumulation of inorganic mercury (HgI) and monomethylmercury (MMHg) by benthic organisms and subsequent trophic transfer couples the benthic and pelagic realms of aquatic systems and provides a mechanism for transfer of sedimentary contaminants to aquatic food chains. Experiments were performed to investigate the bioavailability and bioaccumulation of particle-associated HgI and MMHg by the estuarine amphipod Leptocheirus plumulosus to further understand the controls on bioaccumulation by benthic organisms. HgI and MMHg are particle reactive and have a strong affinity for organic matter, a potential food source for amphipods. Microcosm laboratory experiments were performed to determine the effects of organic matter on Hg bioaccumulation and to determine the major route of Hg uptake (i.e. sediment ingestion, uptake from water/porewater, or uptake from 'food'). Amphipods living in organic-rich sediment spiked with Hg accumulated less Hg than those living in sediments with a lower organic matter content. Feeding had a significant impact on the amount of HgI and MMHg accumulated. Similarly, amphipods living in water with little organic matter accumulated more Hg than those living in water with a greater percentage of organic matter. MMHg was more readily available for uptake than HgI. Experimental results, coupled with results from a bioaccumulation model, suggest that accumulation of HgI and MMHg from sediment cannot be accurately predicted based solely on the total Hg, or even the MMHg, concentration of the sediment, and sediment-based bioaccumulation factors. All routes of exposure need to be considered in determining the accumulation of HgI and MMHg from sediment to benthic invertebrates.