Mercury in Florida Bay fish: spatial distribution of elevated concentrations and possible linkages to Everglades restoration

Health advisories are now posted in northern Florida Bay, adjacent to the Everglades, warning of high mercury concentrations in some species of gamefish. Highest concentrations of mercury in both forage fish and gamefish have been measured in the northeastern corner of Florida Bay, adjacent to the dominant freshwater inflows from the Everglades. Thirty percent of spotted seatrout (Cynoscion nebulosus Cuvier, 1830) analyzed exceeded Florida’s no consumption level of 1.5 μg g−1 mercury in this area. We hypothesized that freshwater draining the Everglades served as the major source of methylmercury entering the food web supporting gamefish. A lack of correlation between mercury concentrations and salinity did not support this hypothesis, although enhanced bioavailability of methylmercury is possible as freshwater is diluted with estuarine water. Stable isotopes of carbon, nitrogen, and sulfur were measured in fish to elucidate the shared pathways of methylmercury and nutrient elements through the food web. These data support a benthic source of both methylmercury and nutrient elements to gamefish within the eastern bay, as opposed to a dominant watershed source. Ecological characteristics of the eastern bay, including active redox cycling in near-surface sediments without excessive sulfide production are hypothesized to promote methylmercury formation and bioaccumulation in the benthos. Methylmercury may then accumulate in gamefish through a food web supported by benthic microalgae, detritus, pink shrimp (Farfantepenaeus duorarum Burkenroad, 1939), and other epibenthic feeders. Uncertainty remains as to the relative importance of watershed imports of methylmercury from the Everglades and in situ production in the bay, an uncertainty that needs resolution if the effects of Everglades restoration on mercury levels in fish are to be modeled and managed.

Trace Metal Sensors for Coastal Monitoring, Seaside, California, April 11-13, 2005: workshop proceedings

The Alliance for Coastal Technologies (ACT) Workshop on Trace Metal Sensors for Coastal Monitoring was convened April 11-13, 2005 at the Embassy Suites in Seaside, California with partnership from Moss Landing Marine Laboratories (MLML) and the Monterey Bay Aquarium Research Institute (MBARI). Trace metals play many important roles in marine ecosystems. Due to their extreme toxicity, the effects of copper, cadmium and certain organo-metallinc compounds (such as tributyltin and methylmercury) have received much attention. Lately, the sublethal effects of metals on phytoplankton biochemistry, and in some cases the expression of neurotoxins (Domoic acid), have been shown to be important environmental forcing functions determining the composition and gene expression in some groups. More recently the role of iron in controlling phytoplankton growth has led to an understanding of trace metal limitation in coastal systems. Although metals play an important role at many different levels, few technologies exist to provide rapid assessment of metal concentrations or metal speciation in the coastal zone where metal-induced toxicity or potential stimulation of harmful algal blooms, can have major economic impacts. This workshop focused on the state of on-site and in situ trace element detection technologies, in terms of what is currently working well and what is needed to effectively inform coastal zone managers, as well as guide adaptive scientific sampling of the coastal zone. Specifically the goals of this workshop were to: 1) summarize current regional requirements and future targets for metal monitoring in freshwater, estuarine and coastal environments; 2) evaluate the current status of metal sensors and possibilities for leveraging emerging technologies for expanding detection limits and target elements; and 3) help identify critical steps needed for and limits to operational deployment of metal sensors as part of routine water quality monitoring efforts. Following a series of breakout group discussions and overview talks on metal monitoring regulatory issues, analytical techniques and market requirements, workshop participants made several recommendations for steps needed to foster development of in situ metal monitoring capacities: 1. Increase scientific and public awareness of metals of environmental and biological concern and their impacts in aquatic environments. Inform scientific and public communities regarding actual levels of trace metals in natural and perturbed systems. 2. Identify multiple use applications (e.g., industrial waste steam and drinking water quality monitoring) to support investments in metal sensor development. (pdf contains 27 pages)

Avaliação da exposição ao metil-mercúrio na população ribeirinha da baixada cuiabana, no Pantanal Mato-Grossense, Brasil

Os efeitos tóxicos do metil-mercúrio (MeHg) em seres humanos vêm sendo amplamente discutidos, a partir de episódios de contaminação devida a ingestão frequente de peixe contaminado, em Minamata, no Japão, ou ao consumo de pão preparado com cereais tratados com fungicidas a base de metil-mercúrio, no Iraque, indicando que o metil mercúrio pode afetar o sistema nervoso central. A população ribeirinha na região do Pantanal, Brasil, é dependente do peixe, como principal fonte de alimentos e proteínas. Naquela região, o resultado de décadas de mineração de ouro, em pequena escala, foi a contaminação de muitos sistemas aquáticos com mercúrio. Consequentemente, muitas espécies de peixes possuem níveis de MeHg relativamente altos. O objetivo deste trabalho foi avaliar o nível de exposição ao MeHg entre a população ribeirinha do Pantanal. No primeiro artigo, apresentam-se os resultados da validação do método recordatório de 24 horas auto-referido, utilizando-se, como padrão-ouro, o método da pesagem, tendo-se verificado que há aproximadamente um erro de 30% ao estimar a quantidade de peixe consumido por aquela população. Um erro deste pode ser importante em se tratando do consumo de peixes carnívoros, os quais apresentam altos teores de mercúrio. No segundo artigo, ao analisar a associação entre o status neurocognitivo e a concentração de mercúrio no cabelo da população acima, os resultados indicaram que adultos expostos ao metil-mercúrio, através do consumo de peixe, podem ter déficits importantes nas medidas do desempenho neurocomportamental, sem alterações detectáveis no humor ou afetividade. Os efeitos mais importantes do mercúrio, entre os indivíduos analisados, foram detectados nos testes de velocidade e destreza da coordenação motora fina, na inibição da resposta na busca visual, e em tarefas de atenção. No terceiro artigo, considerando-se as associações observadas na concentração de mercúrio no cabelo com alguns desfechos dos testes neuro-psicológicos aplicados, calculou-se a dose-marcadora (BMD) e o limite inferior do intervalo de confiança do BMD (BMDL). Os resultados da dose marcadora e da dose de referência provisória são concordantes com os resultados estimados pelas agências de saúde internacionais.

Application of Entropy and Fractal Dimension Analyses to the Pattern Recognition of Contaminated Fish Responses in Aquaculture

The objective of the work was to develop a non-invasive methodology for image acquisition, processing and nonlinear trajectory analysis of the collective fish response to a stochastic event. Object detection and motion estimation were performed by an optical flow algorithm in order to detect moving fish and simultaneously eliminate background, noise and artifacts. The Entropy and the Fractal Dimension (FD) of the trajectory followed by the centroids of the groups of fish were calculated using Shannon and permutation Entropy and the Katz, Higuchi and Katz-Castiglioni's FD algorithms respectively. The methodology was tested on three case groups of European sea bass (Dicentrarchus labrax), two of which were similar (C1 control and C2 tagged fish) and very different from the third (C3, tagged fish submerged in methylmercury contaminated water). The results indicate that Shannon entropy and Katz-Castiglioni were the most sensitive algorithms and proved to be promising tools for the non-invasive identification and quantification of differences in fish responses. In conclusion, we believe that this methodology has the potential to be embedded in online/real time architecture for contaminant monitoring programs in the aquaculture industry.

Concentrations of Polychlorinated Biphenyls (PCB’s), Chlorinated Pesticides, and Heavy Metals and Other Elements in Tissues of Belugas, Delphinapterus leucas, from Cook Inlet

Tissues from Cook Inlet beluga whales, Delphinapterus leucas, that were collected as part of the Alaska Marine Mammal Tissue Archival Project were analyzed for polychlorinated biphenyls (PCB’s), chlorinated pesticides, and heavy metals and other elements. Concentrations of total PCB’s (ΣPCB’s), total DDT (ΣDDT), chlordane compounds, hexachlorobenzene (HCB), dieldrin, mirex, toxaphene, and hexachlorocyclohexane (HCH) measured in Cook Inlet beluga blubber were compared with those reported for belugas from two Arctic Alaska locations (Point Hope and Point Lay), Greenland, Arctic Canada, and the highly contaminated stock from the St. Lawrence estuary in eastern Canada. The Arctic and Cook Inlet belugas had much lower concentrations (ΣPCB’s and ΣDDT were an order of magnitude lower) than those found in animals from the St. Lawrence estuary. The Cook Inlet belugas had the lowest concentrations of all (ΣPCB’s aver-aged 1.49 ± 0.70 and 0.79 ± 0.56 mg/kg wet mass, and ΣDDT averaged 1.35 ± 0.73 and 0.59 ± 0.45 mg/kg in males and females, respectively). Concentrations in the blubber of the Cook Inlet males were significantly lower than those found in the males of the Arctic Alaska belugas (ΣPCB’s and ΣDDT were about half). The lower levels in the Cook Inlet animals might be due to differences in contaminant sources, food web differences, or different age distributions among the animals sampled. Cook Inlet males had higher mean and median concentrations than did females, a result attributable to the transfer of these compounds from mother to calf during pregnancy and during lactation. Liver concentrations of cadmium and mercury were lower in the Cook Inlet belugas (most cadmium values were <1 mg/kg and mercury values were 0.704–11.42 mg/kg wet mass), but copper levels were significantly higher in the Cook Inlet animals (3.97–123.8 mg/kg wet mass) than in Arctic Alaska animals and similar to those reported for belugas from Hudson Bay. Although total mercury levels were the lowest in the Cook Inlet population, methylmercury concentrations were similar among all three groups of the Alaska animals examined (0.34–2.11 mg/kg wet mass). As has been reported for the Point Hope and Point Lay belugas, hepatic concentrations of silver were re

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent - Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (11) was then eluted with 10% HNO3 and subsequently reduced by NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min(-1) sample loading rate. The detection limit was 0.2 ng L-1 and much lower than that of conventional method (around 15.8 ng L-1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L-1 of Hg and the linear working curve is from 20 to 2000 ng L-1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.

气候变化对高纬度流域中汞和甲基汞迁移转化的影响——以降水量增加为例

全球变化的研究发现：19世纪以来全球平均气温大约上升了0.6℃，并预计在21世纪会升高更多。温室效应的直接结果是导致全球地面增温，温度的升高会增加下垫面的蒸发量。根据全球水平衡原理，蒸发量应该与降水量相等，因而降水量也会相应增加。气候变化的情景模式研究表明，世界各地雨量变异大，在高纬度地区，包括北欧地区，降水会增加。 流域是水生系统的一个重要的汞和甲基汞的输入源。欧洲淡水系统中，鱼体汞含量过高的湖泊主要局限于北方的高纬度森林地区。在斯堪的纳维亚半岛，就有上万湖泊中的鱼体汞含量超过了健康食用标准0.5 mg/kg。水生系统甲基汞输入源包括：水体或沉积物通过甲基化形成甲基汞，通过大气干、湿沉降输入的甲基汞和陆地生态系统的地表径流输入的甲基汞。 本研究的主要目标是搞清楚未来气候变化引起的大气降水量的增加对北方高纬度森林流域土壤中汞的迁移和形态转化有何影响。未来大气降水量的增加可能会增强森林地区流域土壤中汞的迁移，进而对水生系统的汞循环产生影响。一方面，如果地下水水位上涨，当水流过富含有机质结合含汞土壤层时，将会增加土壤中汞和甲基汞的迁移性，由此而导致流域向河流、湖泊等水生系统中汞输出通量的增加。另一方面，氧化还原电位改变、DOC和营养物质的释放会加剧汞在土壤中的释放过程，并且可能会促进汞的形态转化，可能增加毒性较强的甲基汞的产量，最终导致甲基汞从土壤向水生系统的输出通量的增加。 本研究选择瑞典西海岸花园湖（Gårdsjön）的G1流域作为研究对象，在流域内进行人工模拟增加降雨试验，模拟未来气候变化降水量增加的情景，观测流域地表径流中汞和甲基汞的变化。并在流域内选择四个点（1×1m²），进行汞同位素加入示踪试验。测定土壤剖面甲基汞和总汞及其同位素组成，来分析汞的迁移和形态转化。主要研究结果如下： 1. 通过对G1流域土壤中甲基汞分布的调查，发现甲基汞含量范围为0.020-3.1ng/g，甲基汞含量与TOC含量具有正相关的关系，表明土壤甲基汞的迁移受TOC迁移的影响。估算G1流域的甲基汞储库通量为123g/km2，G1流域甲基汞储库容为0.65g。 2. 通过甲基汞含量和甲基汞储库在土壤剖面的分布，可以看出表层腐殖质层甲基汞浓度最高，甲基汞最富集，而在较深的土壤层位甲基汞储库容量最大，表明甲基汞具有向下迁移的趋势。 3. 根据总汞同位素组成结果，汞同位素（198Hg(NO3)2）加入土壤中后，202Hg/198Hg比值迅速下降，然后随时间推移而上升，表明加入土壤中的汞与土壤中原始汞形态不同，具有不同的迁移方式，且加入土壤中二价汞的迁移性比土壤中的原始汞更强。计算表明，外界加入的汞，将有50-60%长期滞留在土壤中。 4. 根据甲基汞的同位素组成结果，Wet点的新加入的198Hg甲基汞分数要大于其它三点，表明湿润土壤中汞甲基化速率要快于较干燥的土壤中。另外，Wet点的甲基汞分数比以前无人工模拟增加降雨的同位素示踪结果高很多，表明降水量增加会导致汞的甲基化作用在土壤中的形态转化过程中占主导地位，最终导致甲基汞产率的提高。 5. 人工模拟增加降雨试验进行后，地表径流中总汞的浓度没有发生变化，而甲基汞的浓度增大了很多，从0.03ng/L增大到了1ng/L以上，表明降水的增加可以促进土壤中汞的甲基化作用。 6. 地表径流向流域外总汞和甲基汞的输出量的计算显示，受人工模拟增加降雨的影响，流域地表径流量也会增加，最终年地表径流中总汞和甲基汞的输出通量都变大。

Survey of the potential environmental and health impacts in the immediate aftermath of the coal ash spill in Kingston, Tennessee.

An investigation of the potential environmental and health impacts in the immediate aftermath of one of the largest coal ash spills in U.S. history at the Tennessee Valley Authority (TVA) Kingston coal-burning power plant has revealed three major findings. First the surface release of coal ash with high levels of toxic elements (As = 75 mg/kg; Hg = 150 microg/kg) and radioactivity (226Ra + 228Ra = 8 pCi/g) to the environment has the potential to generate resuspended ambient fine particles (< 10 microm) containing these toxics into the atmosphere that may pose a health risk to local communities. Second, leaching of contaminants from the coal ash caused contamination of surface waters in areas of restricted water exchange, but only trace levels were found in the downstream Emory and Clinch Rivers due to river dilution. Third, the accumulation of Hg- and As-rich coal ash in river sediments has the potential to have an impact on the ecological system in the downstream rivers by fish poisoning and methylmercury formation in anaerobic river sediments.

Investigation into mercury bound to biothiols:structural identification using ESI-ion-trap MS and introduction of a method for their HPLC separation with simultaneous detection by ICP-MS and ESI-MS

Mercury in plants or animal tissue is supposed to occur in the form of complexes formed with biologically relevant thiols (biothiols), rather than as free cation. We describe a technique for the separation and molecular identification of mercury and methylmercury complexes derived from their reactions with cysteine (Cys) and glutathione (GS): Hg(Cys)(2), Hg(GS)(2), MeHgCys, MeHgGS. Complexes were characterised by electrospray mass spectrometry (MS) equipped with an ion trap and the fragmentation pattern of MeHgCys was explained by using MP2 and B3LYP calculations, showing the importance of mercury-amine interactions in the gas phase. Chromatographic baseline separation was performed within 10 min with formic acid as the mobile phase on a reversed-phase column. Detection was done by online simultaneous coupling of ES-MS and inductively coupled plasma MS. When the mercury complexes were spiked in real samples (plant extracts), no perturbation of the separation and detection conditions was observed, suggesting that this method is capable of detecting mercury biothiol complexes in plants.

Biology, ecology, population dynamics and distribution of metals in Sepia officinalis on a typical estuarine coastal lagoon - Ria de Aveiro

The common cuttlefish, Sepia officinalis, is a necto-benthic cephalopod that can live in coastal ecosystems, with high influence of anthropogenic pressures and thus be vulnerable to exposure to various types of contaminants. The cuttlefish is a species of great importance to the local economy of Aveiro, considering the global data of catches of this species in the Ria de Aveiro. However, studies on this species in Ria de Aveiro are scarce, so the present study aims to fill this information gap about the cuttlefish in the Ria de Aveiro. The cuttlefish enters Ria de Aveiro in the spring and summer to reproduce, returning to deeper waters in the winter. In terms of abundance, the eastern and center regions of the lagoon, closer to the sea, showed the highest values of abundance, while the northern and southern regions of the main channel had the lowest abundance. This fact may be related to abiotic factors, as well as depth, salinity and temperature. In the most southern point of the Ria de Aveiro (Areão) no cuttlefish was caught. This site had the lowest values of salinity and depth. The cuttlefish has an allometric the females being heavier than males to mantle lengths greater than 82.4 mm. Males reach sexual maturity first than females. In Ria de Aveiro in a generation of parents was found. The cuttlefish, presents itself as opportunistic predators, consuming a wide variety of prey from different taxa. The diet was similar in different sampling locations observing significant differences for the seasons. S. officinalis was captured at 10 sites in the Ria de Aveiro with different anthropogenic sources of contamination. Thus, levels of metals analyzed were similar at all sampling sites, with the exception of a restricted area, Laranjo, which showed higher values. The cuttlefish has the ability to accumulate metals in your body. The levels of Fe, Zn, Cu, Cd, Pb and Hg found in the digestive gland and mantle reflect a differential accumulation of metals in the tissues. This accumulation is related to the type and function of tissue analyzed and the type of metal analysis (essential and non-essential). The metal concentrations in the digestive gland are higher than in the mantle, with the exception of mercury. This may be due to the high affinity of the mantle for the incorporation of methylmercury (MeHg), the most abundant form of mercury. The accumulation of metals can vary over a lifetime, depending on the metal. The concentrations of Zn, Cd and Hg increases throughout life, while Pb decreases and essential metals such as Fe and Cu remain constant. The data collected suggest that the cuttlefish (Sepia officinalis) can be used as a bioindicator of environmental contamination for some metals.

Microbial community composition and mercury cycling in sediments of tagus estuary

Tese de doutoramento, Farmácia (Toxicologia), Universidade de Lisboa, Faculdade de Farmácia, 2016

Bioaccumulation du méthylmercure chez les invertébrés aquatiques aux latitudes tempérées et polaires : rôle des facteurs écologiques, biologiques et géochimiques

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal