Evidence of methylmercury production and modification of the microbial community structure in estuary sediments contaminated with wastewater treatment plant effluents

The Seine’s estuary (France) waters are the receptacle of effluents originating from wastewater treatment plants (WWTP). In this estuary, mudflats are deposition zones for sediments and their associated contaminants, and play an essential role in the mercury (Hg) biogeochemical cycle mainly due to indigenous microorganisms. Microcosms were used to assess the impact of WWTP-effluents on mercury methylation by monitoring Hg species (total dissolved Hg in porewater, methylmercury and total mercury) and on microbial communities in sediments. After effluent amendment, methylmercury (MeHg) concentrations increased in relation with the total Hg and organic matter content of the WWTP-effluents. A correlation was observed between MeHg and acid-volatile-sulfides concentrations. Quantification of sulfate-reducing microorganisms involved in Hg methylation showed no increase of their abundance but their activity was probably enhanced by the organic matter supplied with the effluents. WWTP-effluent spiking modified the bacterial community fingerprint, mainly influenced by Hg contamination and the organic matter amendment.     

Influence of bioturbation by Hediste diversicolor on mercury fluxes from estuarine sediments: a mesocosms laboratory experiment

Mercury, with its reactive forms being the most deleterious for the trophic chains, has been identified as a major pollutant in a few confined bodies of the coastal zone. Due to feeding, burrowing, and bioirrigation activities, infauna are known to play a crucial role in the biogeochemical processes of contaminants. The main goal of the present study is to evaluate the effects of Hediste diversicolor bioturbation on mercury fluxes from estuarine sediments in a mesocosms laboratory experiment. Additionally, an attempt was made to establish a relationship between the amount of remobilised mercury to the water column and the degree of contamination of the sediments using a mercury contamination gradient. The present experiment demonstrated that the bioturbation activity caused by the gallery-diffuser H. diversicolor did not influence the remobilisation of mercury (in dissolved reactive forms) from the sediment to the water column. The concentration of dissolved reactive mercury in the water column also did not reflect the degree of contamination in the sediments. The results obtained were in accordance with the sediment characteristics of the Mondego Estuary and Ria de Aveiro (Portugal), since they are very rich in organic matter content, iron/manganese total and hydrous oxides. These physicochemical characteristics of the sediments may partially justify the retention of mercury by these systems, even when they are subjected to bioturbation. In conclusion, sediments with high organic matter content and a high concentration of iron/manganese hydrous oxides allowed for efficient retention of mercury, and the bioturbation process did not seem to affect the system. Another conclusion from this study is that the remobilisation of mercury by bioturbation to the water column is not a fast process, requiring more than 24h. This study constitutes an important work in the area of the effects of bioturbation on mercury remobilisation. Considering the toxicity of mercury for the biota, it is essential to evaluate the real magnitude of mercury processes occurring in estuarine systems in order to obtain essential information on metal behaviour.     

Total mercury in sediments and in Brazilian Ariidae catfish from two estuaries under different anthropogenic influence

Santos-São Vicente estuary, located in São Paulo State, Brazil, has a history of contamination by inorganic chemicals such as mercury (Hg). In the 1980s the Cubatão was considered one of the most polluted sites in the world as a consequence of the intense industrial activities located in the city close to the estuary. To provide data and evaluate the local biota, total mercury (THg) contents were determined in sediments and in fish, Cathorops spixii, from different areas of the Santos-São Vicente estuary. For comparison, samples were also collected in a non-polluted system with similar hydrochemistry characteristics, the Cananeia estuary. The water characteristics and THg levels in sediment and fish samples confirmed a high human influence in the Santos-São Vicente estuary. The lowest THg values, observed in Cananeia, were evidence of low anthropogenic influence. High values observed in Santos-São Vicente show the necessity for a monitoring program.     

Depth profiles of lithogenic and anthropogenic mercury in the sediments from Thane Creek,Mumbai, India

Mercury（Hg） is well known as one of the most toxic elements to man.The coastal environments adjacent to industrial areas are reported to often be contaminated with mercury.Mercury becomes more toxic in the form of methylmercury（Me-Hg） which is converted from inorganic mercury in aqueous systems by microbial activity and can bio-magnify through the food chain.A simple method for the determination of total mercury and methylmercury in sediments was optimized by slightly modifying an old method using the direct mercury analyzer technique.Core sediment samples from Thane Creek,Mumbai,India were collected and analysed for total mercury and methylmercury.The Hg concentration in the creek varied between 0.54 to 16.03 μg g~（-1） while Me-Hg concentrations ranged between0.04 to 1.07 μg g~（-1）.In surface sediment,mercury concentrations ranged from 4.33 μg g~（-1） to 12.16μg g~（-1）.Total organic carbon content was found to be around 2 percent in different layers of the sediments.The enrichment factors,which indicate the extent of pollution in sediments,were estimated to range from 26 to 50 at different locations in the creek.Lithogenic and anthropogenic concentrations of mercury in the creek were also determined to compare the impact of anthropogenic and natural sources.Anthropogenic inventories were about 5-70 times more in concentration than the lithogenic in the different core sediments.     

富营养化对贵州红枫湖水库汞形态和分布特征的影响

通过对贵州省红枫湖水库中各种汞形态的空间分布及季节变化的研究,探讨了富营养化对各种汞形态分布特征的影响.红枫湖湖水总汞浓度在2.5-13.9ng/L之间,平均值为6.9ng/L.红枫湖水库中汞浓度的空间分布和季节变化均严重受到人为汞污染源的干扰.水体中汞在颗粒态和溶解态之间的分配,主要受内源有机质以及氧化还原条件的影响.由于水华现象,春季后五采样点大量繁殖的藻类吸附了大量的汞,从而改变了汞在水库中的分配和迁移.藻类的生长对水体中溶解气态汞浓度分布也有显著的影响.在夏季,总甲基汞和溶解态甲基汞在水体中的垂直分布表明:在富营养化较严重的后五采样点,水体中升高的甲基汞主要是由于水体中汞的甲基化过程;而在富营养化特征不明显的大坝,水体中升高的甲基汞主要来自沉积物甲基汞的释放.红枫湖水体中各种汞形态的分布特征表明,富营养化对汞的迁移转化影响显著,尤其是汞的甲基化过程.水体富营养化为汞的甲基化提供了有利条件,给水生生态环境及人体健康带来了潜在的威胁.     

A risk assessment approach to contaminants in Port Curtis, Queensland, Australia

Port Curtis is one of Australia's leading ports for which substantial industrial expansion is proposed over the next decade. However, there has been little attempt to date to assess the extent of contamination in waters, sediments and biota or to characterize the potential impacts of contaminants on aquatic biota. Contaminants of potential concern to biota and human health were investigated in the Port Curtis estuary using a screening-level risk assessment approach. Dissolved metal concentrations in waters were below [ANZECC/ARMCANZ, 2000. Australian and New Zealand Guidelines for Fresh and Marine Water Quality, Vol. 1. The Guidelines, Australian and New Zealand Environment and Conservation Council and Agriculture and Resource Management Council of Australia and New Zealand] trigger values, suggesting low risk of these contaminants. In sediments, arsenic, nickel and chromium concentrations exceeded interim sediment quality guidelines-low (ISQG-low), but were also high in the reference zone suggesting a natural origin. Historical data on naphthalene in Harbour sediments showed that it was also of potential concern. Bioaccumulation of contaminants in a range of biota was also used as an indicator of contaminant exposure. Biota were generally enriched in metals and tributyltin, which was also elevated in water and sediments. Although not unique to Port Curtis, mercury in barramundi was identified as a potential risk to human health.     

Mercury distribution, speciation and bioavailability in sediments from the Pearl River Estuary, Southern China

Surface sediments and sediment cores collected from the Pearl River Estuary (PRE) were analyzed for total mercury (THg) concentrations and speciation using a sequential extraction method. The mobility of Hg in sediments was also assessed using a series of single extraction methods. The surface sediments from the PRE showed slightly elevated levels of Hg, with concentrations ranging from 109 to 453 ng/g. The vertical profile of THg in sediment cores indicated an accelerated input of Hg over the past decades. The organo-chelated and strong-complexed Hg species were the dominant Hg species in the sediments, while the more mobile phases of Hg made up less than 0.5% of THg. Less than 10% of the Hg in the sediments was extracted by single extraction, depending on the extractant employed. Significant relationships were found between the total organic carbon and THg, geochemical speciation, and extractability, indicating the important role of organic matter in controlling the distribution, mobility, and bioavailability of Hg in sediments.     

A comparison of anthropogenic mercury pollution in Kastela Bay (Croatia) with pristine estuaries in Ore (Sweden) and Krka (Croatia)

Anthropogenic mercury pollution was studied in Kastela Bay (Croatia), 10 years after chloralkaline plant (PVC) stopped production. The concentration of total mercury determined in sediments which are composed mainly of calcite and quartz, are in the range 14,280-30,400 ng/g. The values are higher than reported in the literature for Elbe and Seine estuaries and also above 25,000 ng/g used for criterion in remediation project in Minamata Bay. The concentration of methylmercury 6.05-36.74 ng/g are typical for slightly to highly contaminated estuarine sediments. The low ratio of methylmercury to total mercury found in sediments of Kastela Bay is in the range 0.04-0.18%. It can be explained that in this region predominate conditions which do not promote in-situ methylation. Sediments were found to be highly anoxic. Concentrations of total mercury in unfiltered surface waters are in the range 69-145 ng/l and in unfiltered bottom waters in the range 230-1,418 ngl(-1). High concentrations found in bottom waters suggest that either resuspension or partial dissolution of sediments takes place. An experiment performed on filtered and unfiltered waters showed that about 85% of total mercury in surface water and almost 100% in bottom water was retained on 45 microm filters. To demonstrate contrasts, two pristine estuaries from norths and south Europe were studied. Silicious sediments of Ore estuary (Sweden) and calcareous sediments of Krka estuary (Croatia) have total mercury concentrations close to accepted background level. The ratio of methylmercury to total mercury is < or = 1% in all samples with one exception. The highest observed ratio (2.70%) was in the surface sediment from E2 station in Krka estuary measured in March 2000. This location is suitable for studying methylmercury formation in pristine environment.     

Sediment pollution and its effect on fish through food chain in the Yangtze River

Suspended sediment adsorbs pollutants from flowing water in rivers and deposits onto the bed. However, the pollutants accumulated in the river bed sediment may affect the bio-community through food chain for a long period of time. To study the problem the concentration of heavy metals （Cr, Cd, Hg, Cu, Fe, Zn, Pb and As） in water, sediment, and fish/invertebrate were investigated in the middle and lower reaches of the Yangtze River during 2006-2007. The concentrations of heavy metals were 100-10,000 times higher in the sediment than in the water. Benthic invertebrates had relatively high concentrations of heavy metals in their tissues due to their proximity to contaminated sediments. Benthic invertivore fish had moderately high concentrations of heavy metals whereas phytoplanktivore fish, such as the silver carp, accumulated the lowest concentration of heavy metals. The concentrations of Cu, Zn, and Fe were higher than Hg, Pb, Cd, Cr, and As in the tissue samples. The concentration of heavy metals was lower in the river sediments than in the lake sediments. Conversely, the concentration of heavy metals was higher in river water than in lake water. While a pollution event into a water body is often transitory, the effects of the pollutants may be long-lived due to their tendency to be absorbed in the sediments and then released into the food chain. The heavy metals were concentrated in the following order： bottom material 〉 demersal fish and benthic fauna 〉 middle-lower layer fish 〉 upper-middle layer fish 〉 water.     

Occurrence of DDA in DDT-contaminated sediments of the Southern California Bight

DDT, DDE and some additional lipophilic derivatives are recognized contaminants in sediments of Southern California Bight (SCB). Only about 10% of total DDTs discharged into the SCB are accounted for using available monitoring data (sediment, water, and biota). DDA represented up to 0.03% DDTs (DDT/DDE/DDD) in SCB surface sediments (top 2 cm) in amounts up to 76 μg DDA/kg dry weight. Highest DDA levels were found where DDT and DDD levels were maximal at the primary wastewater outfall indicating a natural precursor-product relationship for DDT and DDA. Still culture of SCB sediment revealed limited DDA formation following DDT fortification. DDA residues have also been found in contaminated Long Island, NY sediments provided by USGS. The formation of DDA and its potential release from sediments may be significant in resolution of uncertainties concerning the natural recovery of sediments in DDT-contaminated environments.     

Can Nassarius reticulatus be used as a bioindicator for Hg contamination? Results from a longitudinal study of the Portuguese coastline

The focus of this work is to explore the use of the netted whelk, Nassarius reticulatus (L.), as an indicator of mercury (Hg) contamination, by assessing the concentration of Hg in the sediments and in the whelk along the entire Portuguese coast. Total Hg concentrations ranged from below the detection limit (0.01 ng absolute mercury) up to 0.87 mg kg(-1) dry weight (dwt) in sediments and between 0.06 and 1.02 mg kg(-1) (dwt) for organisms, with no significant differences between males and females. Although organic mercury was not detected in the sediments, it represented, on average, 52% of the total Hg in the whelk tissues, and as high as 88% in some cases, suggesting mercury accumulation from dietary intake. Significant negative correlations were found between the total Hg concentrations in the sediments and the log(10) of Hg concentrations in whelk tissues males (r=-0.64; P<0.01) and females (r=-0.52; P<0.01) indicating that the species is a poor indicator of Hg contamination. Nevertheless, since the highest concentrations of organic mercury in the whelk tissues were found in the least contaminated areas, this species must be highly relevant in the trophic web, namely on the possible biomagnification of mercury. The high dietary mercury accumulation from feeding on carrion and the low bioavailability of mercury to whelks in estuarine sediments may be the basis of the mercury accumulation pattern in N. reticulatus.     

Total and organic mercury in the Black Sea harbour porpoise Phocoena phocoena relicta.

This paper reports on mercury (Hg) concentrations in different tissues (liver, muscle, kidney, blubber and brain) of harbour porpoises Phocoena phocoena found dead in the Black Sea between 1997 and 1999, mainly bycaught in fishing nets (n = 79). Total Hg and organic Hg (MeHg) were determined. The main factor affecting Hg accumulation was, as expected, age, with MeHg concentration increasing with age. Accumulation of high concentrations of inorganic Hg in the liver was probably due to a slow demethylation process implying the formation of tiemannite (HgSe). In older adults, liver concentrations reached 35 microg g(-1) dry weight ('ppm') total Hg and 3 microg g(-1) dw MeHg. A geographical comparison with existing data from other regions showed a generally low Hg contamination of Black Sea porpoises, one order of magnitude lower than, e.g. in the North Sea.     

Historical fluxes of metal and metalloids in an aquatic ecosystem affected by land-use change and mining activities in northwestern Mexico

Freshwater reservoirs are essential owing because of their ecological, economic, and social importance. They are particularly vulnerable to contamination, as of metal and metalloids, derived from anthropogenic activities like mining. The temporal variations in trace element concentrations (arsenic (As), mercury (Hg), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn)), enrichment, fluxes, and possible sources were evaluated by studying two sediment cores from the La Angostura (ANG) Reservoir (northwest Mexico), using ²¹⁰Pb geochronology. The enrichment factors showed from null to minor enrichment for most elements, but moderate to severe enrichment of mercury (Hg). Most trace element concentrations had a detrital origin, and notable Hg concentration increases since the past decade were associated with severe drought periods, likely resulting from wildfires. The observed sediment concentrations of As and Hg can cause adverse effects on biota in the ecosystem since they are above the probable effect level (PEL). Development of strategies for metal attenuation in this reservoir is recommended and metals should be controlled until specific ecotoxicological studies are performed.     

Mercury and methylmercury biogeochemistry in a thawing permafrost wetland complex,Northwest Territories,Canada

In arctic and sub‐arctic environments, mercury (Hg), more specifically toxic methylmercury (MeHg), is of growing concern to local communities because of its accumulation in fish. In these regions, there is particular interest in the potential mobilization of atmospherically deposited Hg sequestered in permafrost that is thawing at unprecedented rates. Permafrost thaw and the resulting ground surface subsidence transforms forested peat plateaus into treeless and permafrost‐free thermokarst wetlands where inorganic Hg released from the thawed permafrost and draining from the surrounding peat plateaus may be transformed to MeHg. This study begins to characterize the spatial distribution of MeHg in a peat plateau–thermokarst wetland complex, a feature that prevails throughout the wetland‐dominated southern margin of thawing discontinuous permafrost in Canada's Northwest Territories. We measured pore water total Hg, MeHg, dissolved organic matter characteristics and general water chemistry parameters to evaluate the role of permafrost thaw on the pattern of water chemistry. A gradient in vegetation composition, water chemistry and dissolved organic matter characteristics followed a toposequence from the ombrotrophic bogs near the crest of the complex to poor fens at its downslope margins. We found that pore waters in poor fens contained elevated levels of MeHg, and the water draining from these features had dissolved MeHg concentrations 4.5 to 14.5 times higher than the water draining from the bogs. It was determined through analysis of historical aerial images that the poor fens in the toposequence had formed relatively recently (early 1970s) as a result of permafrost thaw. Differences between the fens and bogs are likely to be a result of their differences in groundwater function, and this suggests that permafrost thaw in this landscape can result in hotspots for Hg methylation that are hydrologically connected to downstream ecosystems. Copyright © 2016 John Wiley & Sons, Ltd.     

Spatial variability in selenium and mercury interactions in a key recreational fish species: Implications for human health and environmental monitoring

Selenium’s (Se) protective effects against mercury (Hg) toxicity have been demonstrated; however, this is seldom considered in health assessments, where dietary exposure is still evaluated by Hg concentration alone. Se:Hg ratios and selenium health benefit values (Se HBVs) offer a more comprehensive seafood safety model. Here we describe total mercury (THg), methylmercury (MeHg) and Se concentrations in fish from a Hg-polluted estuary. Spatial variation in THg, MeHg and Se was evident, though all regions maintained Se:Hg ratio values >1. Se HBV varied between regions and in one region mean negative values (−5.17) were evident. This study provides the first evidence that quoting a single all-encompassing Se HBV is not appropriate when species demonstrate strong site fidelity. It highlights the need for research into Se–Hg relationships in environments with established Hg pollution and reinforces the assertion that Se concentration be considered in assessments of human health risk to Hg exposure.     

The effects of Hurricane Irene and Tropical Storm Lee on the bed sediment geochemistry of U.S. Atlantic coastal rivers

Hurricane Irene and Tropical Storm Lee, both of which made landfall in the U.S. between late August and early September 2011, generated record or near record water discharges in 41 coastal rivers between the North Carolina/South Carolina border and the U.S./Canadian border. Despite the discharge of substantial amounts of suspended sediment from many of these rivers, as well as the probable influx of substantial amounts of eroded material from the surrounding basins, the geochemical effects on the <63‐µm fractions of the bed sediments appear relatively limited [<20% of the constituents determined (256 out of 1394)]. Based on surface area measurements, this lack of change occurred despite substantial alterations in both the grain size distribution and the composition of the bed sediments. The sediment‐associated constituents which display both concentration increases and decreases include: total sulfur (TS), Hg, Ag, total organic carbon (TOC), total nitrogen (TN), Zn, Se, Co, Cu, Pb, As, Cr, and total carbon (TC). As a group, these constituents tend to be associated either with urbanization/elevated population densities and/or wastewater/solid sludge. The limited number of significant sediment‐associated chemical changes that were detected probably resulted from two potential processes: (1) the flushing of in‐stream land‐use affected sediments that were replaced by baseline material more representative of local geology and/or soils (declining concentrations), and/or (2) the inclusion of more heavily affected material as a result of urban nonpoint‐source runoff and/or releases from flooded treatment facilities (increasing concentrations). Published 2013. This article is a U.S. Government work and is in the public domain in the USA.     

The enrichment characteristics of mercury in the sediments of Dongjiu and Xijiu, Taihu lake catchment, in the past century

The concentration and the enrichment factors of mercury (Hg) in the sediment cores of Dongjiu and Xijiu, Taihu Lake catchment, were studied. The accumulation fluxes, anthropogenic input concentration and anthropogenic accumulation fluxes of Hg in recent 100 years were also analyzed based on the 210Pb dating. The results indicate that the increasing concentrations of Hg in the sediments are influ-enced by natural factors and anthropogenic input simultaneously. Generally, about 2/3 of the Hg in the sediment was from anthropogenic sources. In the early 20th century, the anthropogenic input was owing to the urban development and fossil fuel consumptions surrounding the Taihu Lake and the worldwide atmospheric deposition of Hg since the industrial revolution. The concentration and an-thropogenic fluxes of Hg increased with the industrial development in the catchment since the 1930s. It reached the maximum during the middle 1970s and middle 1990s, and decreased since the middle 1990s with constraints on high pollution industries.     

Mercury speciation,bioavailability and risk assessment on soil–rice systems from a watershed impacted by abandoned Hg mine-waste tailings

Mercury(Hg) is a global pollutant and can be accumulated in the food chain, posing exposure risks to humans. In this study, rice plants and corresponding rhizosphere soil samples were collected from a watershed of the Wawu River Basin that is heavily impacted by historic Hg mining and retorting activities. Total mercury(THg)and methylmercury(MeHg) in rice grains, as well as other tissues and soil samples, were measured. Five soil Hg fractions, as well as soil parameters, were also determined.The results show that the average concentrations of THg and MeHg in rice grains were 14 ± 7.0 lg kg^-1 and7.2 ± 4.0 lg kg^-1. Soil organic-bound(Hg-o) and strong complex-bound(Hg-s) were the main Hg fractions,accounting for 44% of the total. To estimate the Hg–ligand interaction in the soils, soil-N/Hg(R = 0.451, p \ 0.05),-S/Hg(R = 0.372, p \ 0.1), and-OM/Hg ratio(R = 0.320,p \ 0.5) with MeHg_soil were observed with significant positive correlations, indicating that the formation of Hg–OM, Hg–N–OM or Hg–S–OM complexes could prevent Hg(II) from methylation in soils. The significant positive correlations of the-N/Hg ratio,-S/Hg ratio and-OM/Hg ratio with MeHg in rice tissues suggested that Hg methylation and MeHg demethylation occurred throughout the rice paddy ecosystem. The estimated MeHg daily intake(EDI) was 0.075 ± 0.041 lg kg^-1 bw d^-1 and was lower than the RfD level of 0.1 lg kg^-1 bw d^-1 recommended by the US EPA. However, approximately 29% of the hazardous index(HI) of MeHg in grain exceeded 1, posing a potential threat to local populations, particularly pregnant women and children.     

The effects of mariculture activities on the adsorption/desorption and chemical fractionations of mercury on sediments

The aims of the present study were to investigate the effects of mariculture activities on inorganic mercury (Hg(2+)) adsorption/desorption on sediments and the distributions of newly adsorbed Hg(2+) on different chemical fractionations. The adsorption amount and binding energy of Hg(2+) on mariculture sediment (MS) were significantly higher (p<0.05) than reference sediment (RS). This may be explained by the strong complexation role that exists between Hg(2+) and organic matter (OM), which derived from unconsumed fish feed and fish metabolites. The reducible Hg(2+) in MS was significantly lower (p<0.01) than RS, which may have been caused by the decreasing amount of iron and manganese hydroxide in MS, lead to the decrease of Hg(2+) bound to them. On the contrary, the residual Hg(2+) was significantly higher (p<0.01) in MS than RS, which suggests that newly adsorbed Hg(2+) was more stable in MS than RS.     

Mercury contamination history of an estuarine floodplain reconstructed from a Pb-dated sediment core (Berg River, South Africa)

Mercury deposition histories have been scarcely documented in the southern hemisphere. A sediment core was collected from the ecologically important estuarine floodplain of the Berg River (South Africa). We establish the concentration of Hg in this ²¹⁰Pb-dated sediment core at <50 ng g⁻¹ Hg_T throughout the core, but with 1.3 ng g⁻¹ methylmercury in surface sediments. The ²¹⁰Pb dating of the core provides a first record of mercury deposition to the site and reveals the onset of enhanced mercury deposition in 1970. The ratio of methylmercury to total mercury is relatively high in these sediments when compared to other wetlands.