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.     

Total and methylmercury in a Brazilian estuary,Rio de Janeiro

Guanabara Bay, in Rio de Janeiro state, is impacted by organic matter, oil and heavy metals. The present study evaluated the total mercury (THg) and methylmercury (MeHg) concentrations and the MeHg to THg ratio (%MeHg) in water samples from different points of the bay and in 245 organisms of three different trophic levels sampled between 1990 and 2000. Dissolved mercury concentration in estuarine water samples ranged from 0.72 to 5.23 ngl(-1). THg and MeHg in mussel, ranging from 11.6 to 53.5 microg THg kg(-1) wet wt. and 4.5-21.0 microg MeHg kg(-1) wet wt., varied according to sampling point and water quality. Planktivorous fish and mussel presented similar MeHg concentrations, meanwhile THg in planktivorous fish were lower than in mussel. Carnivorous fish showed higher THg and MeHg concentrations (199.5 +/- 119.3, 194.7 +/- 112.7 microg kg(-1) wet wt. respectively) than organisms from other feeding habits and lower trophic levels. There was a significant difference in the %MeHg among trophic levels: mussel presented lower MeHg percentage (33%) than planktivorous fish (54%) and carnivorous fish (98%).     

洪泽湖鱼类群落结构及其资源变化

根据2017-2018年在洪泽湖湖心、成子湖湾、保护区湖湾和淮河入湖口进行的鱼类资源调查,结合历年渔业捕捞统计数据,分析了该水域的鱼类群落结构及资源变化趋势.调查共采获鱼类51种,隶属10目16科41属,其中鲤形目种类最多,占总数的62.7%;群落优势种为鳙（Aristichthys nobilis）、（Hemiculter leucisculus）、鲫（Carassius auratus）、刀鲚（Coilia nasus）等7种,鱼类群落的丰富度指数、多样性指数和均匀度指数处于一般至较丰富水平.不同类型湖区间鱼类种类及优势种组成存在一定差异,其中湖心、淮河入湖口的生物多样性指数整体高于成子湖湾、保护区湖湾.与历史资料相比,洪泽湖鱼类的物种数量下降,鱼类资源组成结构发生较大变化,鱼类个体小型化趋势明显,捕捞强度过大、水位波动和水质污染是洪泽湖渔业资源衰退的主要因素.     

Variation Characteristics of Mercury in Speciation during Road Runoff for Different Rainfall Patterns

Mercury (Hg) concentration was investigated during 2010 based on road runoff from Nanjing Ring Highway, China. The emphasis was placed on impact of rainfall characteristics on Hg speciation concentration, and on variation characteristics of Hg speciation during road runoff for different rainfall patterns. Results indicated that average concentration of total mercury (THg) was in the range from 0.472 to 1.304 µg/L, and steady Hg (SHg) was the dominant form of Hg. Rainfall and average rainfall intensity were two important factors of determining Hg speciation concentrations during road runoff for different rainfall patterns. Rainfall pattern had significantly influence on variation of available Hg and dissolved Hg during road runoff, and on their proportions in THg. However, the proportion of SHg in THg was not obviously affected by rainfall pattern. On the other hand, toxic degree of Hg to soil environment is various for different rainfall patterns, based on Hg speciation variation.     

Total mercury body burden in Pacific harbor seal, Phoca vitulina richardii, pups from central California

To determine body and tissue compartment-specific burdens (mg) of total mercury (THg), tissues were weighed and analyzed for THg concentration (microg/g fw) in Pacific harbor seal (Phoca vitulina richardii) pups from central California in 2006. THg concentrations were related as follows: hair > liver = kidney = pelt > muscle > other = heart > brain > blubber > bone. THg burden, however, was related as: pelt = muscle > liver = other > kidney = blubber > brain = heart > bone. THg concentration and burden in muscle were strongly associated with delta(15)N. delta(13)C and delta(15)N values were significantly greater in muscle than liver, and delta(13)C was significantly lesser the longer animals were in rehabilitation. Because THg concentration and burden in muscle correlated most significantly with other tissue compartments, we recommend that muscle from the specific sites we sampled be used instead of liver or hair for biomonitoring THg in harbor seals. Assessment of proportional THg burdens within each tissue compartment for harbor seals pups included use of a conceptual model, allowing for more complete visual characterization of THg body burden.     

溯河洄游长江刀鲚(Coilia nasus)摄食虾类的调查

刀鲚(Coilia nasus)是长江的名贵经济鱼类.虽然传统上认为其溯河生殖洄游全过程不会摄食,但该问题一直尚未完全弄清.作为有效解明这一问题的第一步,本研究在前期长江流域干流和湖泊刀鲚资源调查的基础上,先利用耳石微化学技术筛选出长江河口区、江苏江段、安徽江段和鄱阳湖水域溯河洄游型的刀鲚个体,再对其胃、肠容物的大型游泳动物(鱼、虾类)进行调查分析.结果发现,在河口区、江苏和安徽江段所有刀鲚个体胃充塞度为0级,均未发现摄食有游泳动物;而鄱阳湖水域刀鲚个体的胃充塞度达4~5级,均发现有摄食淡水虾类的日本沼虾(Macrobrachium nipponense)和秀丽白虾(Exopalaemon modestus)的情况.其中29%和71%的刀鲚胃中分别含有1只和2只虾.所有刀鲚个体肠内均未发现有内容物.鉴于鄱阳湖已被确定为溯河洄游型刀鲚的产卵场之一,结果表明长江刀鲚在经河口,通过长江江苏和安徽江段干流到达鄱阳湖产卵场的过程中应该不会摄食大型游泳动物;而进入鄱阳湖产卵场后会开始摄食日本沼虾和秀丽白虾.这种两阶段的现象可能反映出了刀鲚的一种在洄游通道上节约能量,以利长距离溯河;而在产卵场补充能量,以利于性腺最终成熟的生存策略.     

Evaluation of solid residues removed from a mangrove swamp in the São Vicente Estuary, SP, Brazil

Mangrove swamps are found in estuaries along the coastal plains of tropical regions and have be subjected to heavy occupation and use pressure due to their privileged locations and abundance of biological resources. The present work evaluated the ecological characteristics and solid wastes accumulated in eight areas along the Santos - São Vicente Estuary Complex. The superficially deposited residues at each sampling site were collected and subsequently washed, drained, counted, weighed and separated into classes according to their composition and predominant use. The predominant litter type in terms of density was plastic (62.81%) and, by weight, wood (55.53%). The greatest deposition of residues was associated with areas that were less inclined and that had low plant density levels, indicating that the presence of obstacles was not critical for retaining floating residues in mangrove areas. The presence of the most frequently encountered types of solid waste residues could be explained by local activities.     

Bioaccumulation of polychlorinated biphenyls in mullet fish in a former ship dismantling harbour, a contaminated estuary, and nearby coastal fish farms

This study investigated the bioaccumulation of polychlorinated biphenyls (PCBs) toward mullet fish (Liza macrolepis) living in former PCB contaminated areas, the Ann-Ping harbour and the Er-Jen estuary, and fish farms located near the above two areas in 2003. The PCB body burdens of collected fish samples are proportional to the contamination level of their locations with the following rank order (greatest to least) from the Er-Jen estuary, the Ann-Ping harbour to the fish farms. Concentration of PCBs of the estuarine mullet has been approximately decreased to one-half of the peak concentration of the 1990s. Although the concentration of PCBs in farmed fish inhabiting near the two contaminated areas was greater than the average of those of fish from local fish markets in Taiwan, no particularly great contamination level was observed in their bodies. Using the less chlorinated PCB fraction (triCB + tetraCB)/total PCBs as the indicator of the origins of PCBs, fish near former contaminated areas had greater body burdens of the more chlorinated PCB congeners, while the farmed fish exhibited a PCB pattern more like that known to originate from air–water exchange with less chlorinated PCBs predominating. Although the PCB contamination has been stopped for a decade, the residual contaminants, supposedly existing in soil and sediments, still contribute to the body burden of fish residing in the estuary and the harbour.     

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.     

贵州高原水库冬季浮游植物中汞及甲基汞分布特征

为了解贵州高原水库浮游植物中汞和甲基汞的分布特征及浮游植物对汞及甲基汞的富集特点,于2012年12月对贵州省的5座高原水库中浮游植物和汞形态进行采样调查.研究结果表明:冬季贵州高原水库浮游植物群落主要是由硅藻组成,5座水库浮游植物丰度有明显差异.百花湖大坝处浮游植物丰度最高,为29.05×104cells/L;三板溪水库浮游植物丰度最低,仅为0.49×104cells/L.浮游植物中总汞和甲基汞的浓度分别在29.29~277.07 ng/g和1.12~10.93 ng/g之间,总汞含量以百花湖岩脚寨最高,甲基汞含量以百花湖大坝最高.总汞和甲基汞在浮游植物中的生物富集系数分别在1.42×104~9.78×104和3.10×104~4.43×105之间.在浮游植物富集无机汞及甲基汞的系数中,百花湖中浮游植物对无机汞生物富集系数最高,而红枫湖中浮游植物对甲基汞的生物富集系数最高.浮游植物种类组成不同对汞及甲基汞的生物富集有影响.浮游植物中的总汞与水体中的总汞、甲基汞和溶解态甲基汞都存在显著的相关关系,浮游植物中的甲基汞与水体中的总汞及甲基汞不存在显著相关性.甲基汞在浮游植物中富集不是简单的吸收,存在着影响甲基汞在浮游植物中富集的其它因素.浮游植物中的甲基汞与水体富营养化环境因子(透明度、总氮、硝氮)均呈负相关关系,表明水体富营养化的程度不同对浮游植物中的甲基汞浓度有影响.     

Levels and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from Lenga Estuary, central Chile

The Lenga Estuary is a small brackish wetland located southwest of San Vicente Bay, Region VIII, Chile. Surface sediment from nine sites in the estuary were analysed for PAHs and compared to Sediment Quality Guidelines (SQG). Sediment samples were freeze dried and soxhlet extracted for 16 h using DCM. Identification and quantification was carried out by HPLC. Organic carbon was also determined. Results showed total PAH concentrations ranged from 290 to 6118 (2025 ± 1975) ng g⁻¹ d.w. (2025 ± 1975). Results for organic carbon percentages ranged from 1% to 7%. Statistical analysis showed a significant positive correlation (Pearson test) between organic carbon percentage PAHs. Comparison of contaminant levels and international Sediment Quality Guidelines (SQG) (ERL and ER) suggested that sediment of the Lenga estuary did not show any ecotoxicologial risk for benthic organisms where high levels of PAHs were detected. Monitoring of this and other contaminants is recommended in Chile.     

Selenium and mercury concentrations in harbor seals (Phoca vitulina) from central California: Health implications in an urbanized estuary

We measured total selenium and total mercury concentrations ([TSe] and [THg]) in hair (n = 138) and blood (n = 73) of harbor seals (Phoca vitulina) from California to assess variation by geography and sex, and inferred feeding relationships based on carbon, nitrogen, and sulfur stable isotopes. Harbor seals from Hg-contaminated sites had significantly greater [THg], and lesser [TSe] and TSe:THg molar ratios than seals from a relatively uncontaminated site. Males had significantly greater [THg] than females at all locations. Sulfur stable isotope values explained approximately 25% of the variability in [THg], indicating increased Hg exposure for seals with a greater use of estuarine prey species. Decreased [TSe] in harbor seals from Hg-contaminated regions may indicate a relative Se deficiency to mitigate the toxic effects of Hg. Further investigation into the Se status and the potential negative impact of Hg on harbor seals from Hg-contaminated sites is warranted.     

Mercury biomagnification in a contaminated estuary food web: Effects of age and trophic position using stable isotope analyses

The main aim of this study was to ascertain the biomagnification processes in a mercury-contaminated estuary, by clarifying the trophic web structure through stable isotope ratios. For this purpose, primary producers (seagrasses and macroalgae), invertebrates (detritivores and benthic predators) and fish were analysed for total and organic mercury and for stable carbon and nitrogen isotopic signatures. Trophic structure was accurately described by δ¹⁵N, while δ¹³C reflected the carbon source for each species. An increase of mercury levels was observed with trophic level, particularly for organic mercury. Results confirm mercury biomagnification to occur in this estuarine food web, especially in the organic form, both in absolute concentrations and fraction of total mercury load. Age can be considered an important variable in mercury biomagnification studies, and data adjustments to account for the different exposure periods may be necessary for a correct assessment of trophic magnification rates and ecological risk.     

Mercury concentration,speciation and budget in volcanic aquifers: Italy and Guadeloupe (Lesser Antilles)

Quantifying the contribution of volcanism to global mercury (Hg) emissions is important to understand the pathways and the mechanisms of Hg cycling through the Earth's geochemical reservoirs and to assess its environmental impacts. While previous studies have suggested that degassing volcanoes might contribute importantly to the atmospheric budget of mercury, little is known about the amount and behaviour of Hg in volcanic aquifers. Here we report on detailed investigations of both the content and the speciation of mercury in aquifers of active volcanoes in Italy and Guadeloupe Island (Lesser Antilles). In the studied groundwaters, total Hg (THg) concentrations range from 10 to 500 ng/l and are lower than the 1000 ng/l threshold value for human health protection fixed by the World Health Organization [WHO (1993): WHO Guidelines for Drinking Water Quality- http://www.who.int/water_sanitation_health/GDWQ/index.htlm]. Positive co-variations of (THg) with sulphate indicate that Hg-SO₄-rich acid groundwaters receive a direct input of magmatic/hydrothermal gases carrying mercury as Hg⁰_(gas). Increasing THg in a volcanic aquifer could thus be a sensitive tracer of magmatic gas input prior to an eruption. Since the complex behaviour and toxicity of mercury in waters depend on its chemical speciation, we carefully determined the different aqueous forms of this element in our samples. We find that dissolved elemental Hg⁰_(aq) and particulate-bound Hg (Hg_P) widely prevail in volcanic aquifers, in proportions that highlight the efficiency of Hg adsorption onto colloidal particles. Moreover, we observe that dissolved Hg⁰_aq and Hg(II) forms coexist in comparable amount in most of the waters, in stark contrast to the results of thermodynamic equilibrium modelling. Therefore, chemical equilibrium between dissolved mercury species in volcanic waters is either prevented by natural kinetic effects or not preserved in collected waters due to sampling/storage artefacts. Finally, we provide a first quantitative comparison of the relative intensity of aqueous transport and atmospheric emissions of mercury at Mount Etna, a very active basaltic volcano.     

Mercury content of mussels from the St. Lawrence Estuary and northwestern Gulf of St. Lawrence, Canada

A first survey of the mercury content of intertidal mussels in the St. Lawrence Estuary and part of the Gulf of St. Lawrence shows means values ranging from 0.160 to 0.629 ppm (dry weight). Highest values (grand mean 0.430 ppm) were found in the upper part of the lower estuary, lowest values (grand mean 0.172 ppm) on the north shore of the estuary and Gulf, and intermediate values along the Gaspé Peninsula. The results indicate a decreasing gradient in mercury levels from the mouth of the Saguenay Fjord seaward.     

Sediment quality in the Guadalquivir estuary: sublethal effects associated with the Aznalcóllar mining spill

As a complementary assessment of the impact of the Aznalcóllar mining spill on the Guadalquivir estuary two different sediment toxicity tests using fish (Solea senegalensis) and clams (Scrobicularia plana) were performed. The histopathological alterations by recording lesions at 15 and 30 days in fish to the gills, liver, gut and kidney and at 14 days in clams to the gills and gut were used to determine the adverse effects associated with the contaminants bound to sediments. The lesions measured at different tissues in both organisms show that the enrichment of heavy metals from the mining spill stressed some areas in the ecosystem of the estuary. The comparison of these effects with those lethal effects detected in the same samples using a multivariate analysis approach permits to identify the adverse effects associated with the accidental spill on the estuary. The incidence of the impact, located in specific areas of the estuary show an acute effect related to the spill.     

Estuarine ecological risk based on hepatic histopathological indices from laboratory and in situ tested fish

Juvenile Senegalese soles were exposed through 28-day laboratory and field (in situ) bioassays to sediments from three sites of the Sado estuary (W Portugal): a reference and two contaminated by metallic and organic contaminants. Fish were surveyed for ten hepatic histopathological alterations divided by four distinct reaction patterns and integrated through the estimation of individual histopathological condition indices. Fish exposed to contaminated sediments sustained more damage, with especial respect to regressive changes like necrosis. However, differences were observed between laboratory- and field-exposed animals, with the latest, for instance, exhibiting more pronounced fatty degeneration and hepatocellular eosinophilic alteration. Also, some lesions in fish exposed to the reference sediment indicate that in both assays unaccounted variables produced experimental background noise, such as hyaline degeneration in laboratory-exposed fish. Still, the field assays yielded results that were found to better reflect the overall levels of contaminants and physico-chemical characteristics of the tested sediments.     

Levels of Organochlorine Pesticide Residues in Some Organs of the Ganges Perch, Lates calcarifer, from the Ganges–Brahmaputra–Meghna Estuary, Bangladesh

Levels of organochlorine pesticide residues (p,p′ DDT, DDD, DDE, Aldrin, Dieldrin, Lindane, Heptachlor and BHC) were analysed in the dry and wet seasons in four organs (muscle, liver, gut and egg samples) of Ganges Perch, Lates calcarifer, collected during October–November–December, 1996 and May–June–July, 1997 from the Ganges–Brahmaputtra–Meghna estuary. The residues were analysed by using gas-chromatography (GC) in electron capture detector (ECD) mode and were verified by thin layer chromatography (TLC). Among the four organs analysed, the residues were found in the order egg > gut > muscle > liver. The pesticide residues were found in the order ∑DDT > Heptachlor >Dieldrin > Aldrin. Higher levels of residues were found during the dry season due to high lipid content in fishes. A positive correlation was observed between the pesticide residues (∑DDT and ∑OCs) and lipid contents of fish, and the correlation was found to be linear. The concentrations of pesticide residues in muscle, liver and gut were below the FAO/WHO (1993) recommended permissible limit except in eggs.     

Hepatic 7-ethoxyresorufin O-deethylase Activity in eel (Anguilla Anguilla) from The Thames Estuary and Comparisons with other United Kingdom Estuaries

Hepatic microsomal 7-ethoxyresorufin O-deethylase (EROD) activities (indicative of exposure to polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls (PCBs)) were measured in eel Anguilla anguilla from the Thames Estuary. Fish were collected from up to 13 sites during November 1997, May and August 1998 and October 1999. Throughout this period no clear seasonal variation could be identified at every site along the Thames. However, during the summer months, fish sampled from sites in the middle to the upper estuary (Woolwich, Greenhithe and West Thurrock) reported up to 3-fold higher EROD activities compared to sites either at the upper reaches (Richmond and Brentford) at the same time of the year, or fish sampled in winter, along the entire length of the estuary. A laboratory exposure experiment demonstrated a 3-fold elevation of EROD activity 2 days after injection with β-naphthoflavone (β-NF). However, higher levels of activity could be determined in fish sampled from the Weston canal near the Merseyside. The lowest levels of A. anguilla EROD activity were observed in fish sampled from the upper reaches of the River Tamar, Devon, and were comparable to activities determined in fish from the Wear and Humber estuaries. A. anguilla sampled along the Thames, Tyne and Tees estuaries reported between 2.5- and 7-fold higher EROD activities compared to fish collected from the Tamar. These results indicate that a low to moderate induction of A. anguilla CYP1A had occurred (indicative of low to moderate exposure to PAHs and planar PCBs) in fish collected from the Thames, Tyne, Wear, Tees, Humber and Tamar estuaries. However, the highest level of EROD activity was observed in fish from the Weston Canal (Merseyside).     

Fate and tidal transport of butyltin and mercury compounds in the waters of the tropical Bach Dang Estuary (Haiphong, Vietnam)

In this work, two field campaigns were performed in July 2008 (wet season) and March 2009 (dry season) to produce original data on the concentration, partition and distribution of mercury and butyltin compounds along the tropical Bach Dang Estuary located in North Vietnam (Haiphong, Red River Delta). The results demonstrate that mercury and butyltin speciation in the surface waters of this type of tropical estuary is greatly affected by the drastic changes in the seasonal conditions. During high river discharge in the wet season, there was a large estuarine input of total Hg and tributyltin, while the longer residence time of the waters during the dry season promotes increasing MMHg formation and TBT degradation. Although most of the Hg and TBT is transported into the estuary from upstream sources, tidal cycle measurements demonstrate that this estuary is a significant source of TBT and MMHg during the wet (～3kgTBT/day) and dry (～3gMMHg/day) seasons.