Evaluation of mercury speciation and removal through air pollution control devices of a 190 MW boiler.

PubMed

Wu, Chengli; Cao, Yan; Dong, Zhongbing; Cheng, Chinmin; Li, Hanxu; Pan, Weiping

2010-01-01

Air pollution control devices (APCDs) are installed at coal-fired power plants for air pollutant regulation. Selective catalytic reduction (SCR) and wet flue gas desulfurization (FGD) systems have the co-benefits of air pollutant and mercury removal. Configuration and operational conditions of APCDs and mercury speciation affect mercury removal efficiently at coal-fired utilities. The Ontario Hydro Method (OHM) recommended by the U.S. Environmental Protection Agency (EPA) was used to determine mercury speciation simultaneously at five sampling locations through SCR-ESP-FGD at a 190 MW unit. Chlorine in coal had been suggested as a factor affecting the mercury speciation in flue gas; and low-chlorine coal was purported to produce less oxidized mercury (Hg2+) and more elemental mercury (Hg0) at the SCR inlet compared to higher chlorine coal. SCR could oxidize elemental mercury into oxidized mercury when SCR was in service, and oxidation efficiency reached 71.0%. Therefore, oxidized mercury removal efficiency was enhanced through a wet FGD system. In the non-ozone season, about 89.5%-96.8% of oxidized mercury was controlled, but only 54.9%-68.8% of the total mercury was captured through wet FGD. Oxidized mercury removal efficiency was 95.9%-98.0%, and there was a big difference in the total mercury removal efficiencies from 78.0% to 90.2% in the ozone season. Mercury mass balance was evaluated to validate reliability of OHM testing data, and the ratio of mercury input in the coal to mercury output at the stack was from 0.84 to 1.08.

PRELIMINARY RESULTS FROM THE USEPA MERCURY SPECIATION NETWORK AND AIRCRAFT MEASUREMENT CAMPAIGNS

EPA Science Inventory

Since EPA measured high concentrations of reactive gaseous mercury (RGM) in emissions from municipal and hospital waste incinerators in 1995, we have been working to elucidate the role of RGM on atmospheric mercury deposition. EPA has recently established automated speciated me...

Knowledge gained from analyzing mercury speciation data monitored in North America

NASA Astrophysics Data System (ADS)

Zhang, L.; Cheng, I.; Gay, D. A.; Xu, X.; Wu, Z.

2017-12-01

This presentation summarizes knowledge gained in several recent studies through analysis and application of mercury (Hg) speciation data monitored in North America. Annual Hg dry deposition to vegetated surfaces in the rural or remote environment in North America was dominated by leaf uptake of gaseous elemental mercury (GEM), contrary to what was commonly assumed in earlier studies which frequently omitted GEM dry deposition as an important process (Zhang et al., EST, 2016). Dry deposition exceeded wet deposition by a large margin in all of the seasons except in the summer at the majority of the sites. Based on the gaseous oxidized mercury (GOM) concentrations predicted from measured Hg wet deposition using a scavenging ratio method, multi-year average GOM concentrations collected using Tekran speciation instrument were likely biased low by a factor of 2 at about half of the studied sites (Cheng and Zhang, EST, 2017). A decline in the number of source regions impacting ambient GEM and GOM was found from 2005-2014 at an eastern U.S. site through concentration-weighted trajectory (CWT) analysis (Cheng et al., JAS, 2017). Source contributions decreased by up to 20% for GEM, greater than 60% for GOM, and 20-60% for PBM in 2011-2014 than in 2006-2008, largely due to power plant Hg emission reductions since 2009. A study comparing Positive Matrix Factorization (PMF) and Principal Components Analysis (PCA) receptor methods identified similar sources impacting Kejimkujik National Park, Canada, including combustion, industrial sulfur, photochemistry and re-emissions, and oceanic sea-salt emissions. Improving the quality of the Hg data used in receptor methods by imputation did not improve the PMF results, but reducing the fraction of below detection limit data was effective (Xu et al., ACP, 2017). PCA results using reactive mercury (RM=GOM+PBM) or excluding low GOM values were similar to those using the original data. Source contributions from CWT analysis were more sensitive to the use of RM than excluding low GOM values (Cheng et al., ACP, 2016). Future research needs are recommended for improving the understanding of speciated atmospheric mercury based on a series of recently published review papers (Zhang et al., ACP, 2017).

Accumulation route and chemical form of mercury in mushroom species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minagawa, K.; Sasaki, T.; Takizawa, Y.

1980-09-01

Some papers were published on several species of fungi having more accumulating abilities of mercury than other land plants and a relatively small part of mercury being present as methylmercury in most species (Stegnar et al. 1973, Stijve and Roschnik 1974). But, little information is available regarding the routes of mercury in fungi, and also no report on mercury speciation (chemical form and complexation) in them have been published, apart from methylmercury. In order to evaluate accurately their biological characteristics such as absorption, excretion, accumulation and toxicity (The Task Group on Metal Interaction 1978), the mercury speciation present in mushrooms,more » regardless of edible or nonedible, should be identified. In this report, we present (1) contents of total and methylmercury in mushrooms near the acetaldehyde factory which had the mounds of sludge containing mercury, (2) data or exposure experiment of mercury vapor to raw mushrooms (Shiitake) on the market, and (3) data on mercury speciation of mercury other than methylmercury.« less

Speciation of mercury compounds by differential atomization - atomic absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, J.W.; Skelly, E.M.

This paper describes the dual stage atomization technique which allows speciation of several mercury-containing compounds in aqueous solution and in biological fluids. The technique holds great promise for further speciation studies. Accurate temperature control, expecially at temperatures less than 200/sup 0/C, is needed to separate the extremely volatile mercury halides and simple organomercurials from each other. Studies with mercury salts and EDTA, L-cysteine and dithioxamide demonstrate that this technique may be used to study the extent of complex formation. Investigations of biological fluids indicate that there is a single predominant form of mercury in sweat and a single predominant formmore » of mercury in urine. The mercury compound in urine is more volatile than that in sweat. Both quantitative and qualitative analyses are possible with this technique.« less

Mercury speciation comparison. BrooksApplied Laboratories and Eurofins Frontier Global Sciences

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.; Wilmarth, W. R.

2016-12-16

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences (FGS), Inc. in Bothell, WA on behalf of the Savannah River Remediation (SRR) Mercury Program Team. These samples were analyzed for seven species including: total mercury, dissolved mercury, inorganic mercury ((Hg(I) and Hg(II)), elemental mercury, methylmercury, ethylmercury, and dimethylmercury, with an eighth species, particulate mercury, calculated from the difference between total and dissolved mercury after subtracting the elemental mercury. The species fraction of total mercury measured has ranged broadly from a low of 32% to a high of 146%,more » though the vast majority of samples have been <100%. This can be expected since one is summing multiple values that each have at least a ± 20% measurement uncertainty. Two liquid waste tanks particularly important to understanding the distribution of mercury species in the Savannah River Site (SRS) Tank Farm were selected for a round robin analysis by Eurofins FGS and BrooksApplied Laboratories (BAL). The analyses conducted by BAL on the Tank 22 and 38 samples and their agreement with those obtained from Eurofins FGS for total mercury, dissolved mercury, methylmercury, ethylmercury, and dimethylmercury provide a strong degree of confidence in these species measurements« less

A robust framework to predict mercury speciation in combustion flue gases.

PubMed

Ticknor, Jonathan L; Hsu-Kim, Heileen; Deshusses, Marc A

2014-01-15

Mercury emissions from coal combustion have become a global concern as growing energy demands have increased the consumption of coal. The effective implementation of treatment technologies requires knowledge of mercury speciation in the flue gas, namely concentrations of elemental, oxidized and particulate mercury at the exit of the boiler. A model that can accurately predict mercury species in flue gas would be very useful in that context. Here, a Bayesian regularized artificial neural network (BRANN) that uses five coal properties and combustion temperature was developed to predict mercury speciation in flue gases before treatment technology implementation. The results of the model show that up to 97 percent of the variation in mercury species concentration is captured through the use of BRANNs. The BRANN model was used to conduct a parametric sensitivity which revealed that the coal chlorine content and coal calorific value were the most sensitive parameters, followed by the combustion temperature. The coal sulfur content was the least important parameter. The results demonstrate the applicability of BRANNs for predicting mercury concentration and speciation in combustion flue gas and provide a more efficient and effective technique when compared to other advanced non-mechanistic modeling strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

FUNDAMENTALS OF MERCURY SPECIATION AND CONTROL IN COAL-FIRED BOILERS

EPA Science Inventory

The report describes the progress of an experimental investigation of the speciation of mercury in simulated coal combustion flue gasses. The effects of flue gas parameters and coal fly ash on the oxidation of elemental mercury (Hgo) in the presence of hydrogen chloride (HCl) in ...

PRELIMINARY RESULTS FROM THE US EPA MERCURY SPECIATION NETWORK AND AIRCRAFT MEASUREMENT CAMPAIGNS

EPA Science Inventory

Since EPA measured high concentrations of reactive gaseous mercury (RGM) in emissions from municipal and hospital waste incinerators in 1995, we have been working to elucidate the role of RGM on atmospheric mercury deposition. EPA has recently established automated speciat...

Formation of nanocolloidal metacinnabar in mercury-DOM-sulfide systems

USGS Publications Warehouse

Gerbig, Chase A.; Kim, Christopher S.; Stegemeier, John P.; Ryan, Joseph N.; Aiken, George R.

2011-01-01

Direct determination of mercury (Hg) speciation in sulfide-containing environments is confounded by low mercury concentrations and poor analytical sensitivity. Here we report the results of experiments designed to assess mercury speciation at environmentally relevant ratios of mercury to dissolved organic matter (DOM) (i.e., <4 nmol Hg (mg DOM)−1) by combining solid phase extraction using C18 resin with extended X-ray absorption fine structure (EXAFS) spectroscopy. Aqueous Hg(II) and a DOM isolate were equilibrated in the presence and absence of 100 μM total sulfide. In the absence of sulfide, mercury adsorption to the resin increased as the Hg:DOM ratio decreased and as the strength of Hg-DOM binding increased. EXAFS analysis indicated that in the absence of sulfide, mercury bonds with an average of 2.4 ± 0.2 sulfur atoms with a bond length typical of mercury-organic thiol ligands (2.35 Å). In the presence of sulfide, mercury showed greater affinity for the C18 resin, and its chromatographic behavior was independent of Hg:DOM ratio. EXAFS analysis showed mercury–sulfur bonds with a longer interatomic distance (2.51–2.53 Å) similar to the mercury–sulfur bond distance in metacinnabar (2.53 Å) regardless of the Hg:DOM ratio. For all samples containing sulfide, the sulfur coordination number was below the ideal four-coordinate structure of metacinnabar. At a low Hg:DOM ratio where strong binding DOM sites may control mercury speciation (1.9 nmol mg–1) mercury was coordinated by 2.3 ± 0.2 sulfur atoms, and the coordination number rose with increasing Hg:DOM ratio. The less-than-ideal coordination numbers indicate metacinnabar-like species on the nanometer scale, and the positive correlation between Hg:DOM ratio and sulfur coordination number suggests progressively increasing particle size or crystalline order with increasing abundance of mercury with respect to DOM. In DOM-containing sulfidic systems nanocolloidal metacinnabar-like species may form, and these species need to be considered when addressing mercury biogeochemistry.

A COMPUTATIONAL AND EXPERIMENTAL STUDY OF MERCURY SPECIATION AS FACILITATED BY THE DEACON PROCESS

EPA Science Inventory

The paper gives results of a computational and experimental study of mercury (Hg) speciation as facilitated by the Deacon process. Fly ashes that contain trace cupric or ferric oxide are effective catalysts for elemental mercury (Hg) conversion to mercuric chloride in the presenc...

Implications of mercury speciation in thiosulfate treated plants.

PubMed

Wang, Jianxu; Feng, Xinbin; Anderson, Christopher W N; Wang, Heng; Zheng, Lirong; Hu, Tiandou

2012-05-15

Mercury uptake was induced in two cultivars of Brassica juncea under field conditions using thiosulfate. Analysis was conducted to better understand the mechanism of uptake, speciation of mercury in plants, and redistribution of mercury in the soil. Plant mercury and sulfur concentrations were increased after thiosulfate treatment, and a linear correlation between mercury and sulfur was observed. Mercury may be absorbed and transported in plants as the Hg-thiosulfate complex. The majority of mercury in treated plant tissues (two cultivars) was bound to sulfur in a form similar to β-HgS (66-94%). Remaining mercury was present in forms similar to Hg-cysteine (1-10%) and Hg-dicysteine (8-28%). The formation of β-HgS may relate to the transport and assimilation of sulfate in plant tissues. Mercury-thiosulfate complex could decompose to mercuric and sulfate ions in the presence of free protons inside the plasma membrane, while sulfide ions would be produced by the assimilation of sulfate. The concomitant presence of mercuric ions and S(2-) would precipitate β-HgS. The mercury concentration in the rhizosphere decreased in the treated relative to the nontreated soil. The iron/manganese oxide and organic-bound fractions of soil mercury were transformed to more bioavailable forms (soluble and exchangeable and specifically sorbed) and taken up by plants.

ISSUES RELATED TO SOLUTION CHEMISTRY IN MERCURY SAMPLING IMPINGERS

EPA Science Inventory

Analysis of mercury (Hg) speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hgo). Such methods incl...

Bioaccumulation of mercury in benthic communities of a river ecosystem affected by mercury mining.

PubMed

Zizek, Suzana; Horvat, Milena; Gibicar, Darija; Fajon, Vesna; Toman, Mihael J

2007-05-15

The presence of mercury in the river Idrijca (Slovenia) is mainly due to 500 years of mercury mining in this region. In order to understand the cycling of mercury in the Idrijca ecosystem it is crucial to investigate the role of biota. This study is part of an ongoing investigation of mercury biogeochemistry in the river Idrijca, focusing on the accumulation and speciation of mercury in the lower levels of the food chain, namely filamentous algae, periphyton and macroinvertebrates. Mercury analysis and speciation in the biota and in water were performed during the spring, summer and autumn seasons at four locations on the river, representing different degrees of mercury contamination. Total (THg) and methyl mercury (MeHg) were measured. The results showed that the highest THg concentrations in biota correlate well with THg levels in sediments and water. The level of MeHg is spatially and seasonally variable, showing higher values at the most contaminated sites during the summer and autumn periods. The percentage of Hg as MeHg increases with the trophic level from water (0.1-0.8%), algae (0.5-1.3%), periphyton (1.6-8.8%) to macroinvertebrates (0.1-100%), which indicates active transformation, accumulation and magnification of mercury in the benthic organism of this heavily contaminated torrential river.

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, L.; Wang, S. X.; Wu, Q. R.; Wang, F. Y.; Lin, C.-J.; Zhang, L. M.; Hui, M. L.; Hao, J. M.

2015-11-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, municipal solid waste incinerators, and biomass burning. Mercury in coal, ores and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of gaseous elemental mercury (Hg0) to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g.,TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron/steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Atmospheric speciation of mercury in two contrasting Southeastern US airsheds

NASA Astrophysics Data System (ADS)

Gabriel, Mark C.; Williamson, Derek G.; Brooks, Steve; Lindberg, Steve

Simultaneous measurement of gaseous elemental, reactive gaseous, and fine particulate mercury took place in Tuscaloosa AL, (urban airshed) and Cove Mountain, TN (non-urban airshed) during the summers of 2002 and 2003. The objective of this research was to (1) summarize the temporal distribution of each mercury specie at each site and compare to other speciation data sets developed by other researchers and (2) provide insight into urban and non-urban mercury speciation effects using various statistical methods. Average specie concentrations were as follows: 4.05 ng m -3 (GEM), 13.6 pg m -3 (RGM), 16.4 pg m -3 (Hg-p) for Tuscaloosa; 3.20 ng m -3 (GEM), 13.6 pg m -3 (RGM), 9.73 pg m -3 (Hg-p) for Cove Mountain. As a result of urban airshed impacts, short periods of high concentration for all mercury species was common in Tuscaloosa. At Cove Mountain a consistent mid-day rise and evening drop for mercury species was found. This pattern was primarily the result of un-impacted physical boundary layer movement, although, other potential impacts were ambient photochemistry and air-surface exchange of mercury. Meteorological parameters that are known to heavily impact mercury speciation were similar for the study period for Tuscaloosa and Cove Mountain except for wind speed (m s -1), which was higher at Cove Mountain. For both sites statistically significant ( p<0.0001), inverse relationships existed between wind speed and Hg 0 concentration. A weaker windspeed-Hg 0 correlation existed for Tuscaloosa. By analyzing Hg concentration—wind speed magnitude change at both sites it was found that wind speed at Cove Mountain had a greater influence on Hg 0 concentration variability than Tuscaloosa by a factor of 3. Using various statistical tests, we concluded that the nature of Tuscaloosa's atmospheric mercury speciation was the result of typical urban airshed impacts. Cove Mountain showed atmospheric mercury speciation characteristics indicative of a non-urban area along with potential influence from steady regional input of mercury pollution from larger sources.

Formation of soluble mercury oxide coatings: Transformation of elemental mercury in soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Carrie L.; Watson, David B.; Lester, Brian P.

2015-09-21

In this study, the impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reactingmore » with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.« less

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, Lei; Wang, Shuxiao; Wu, Qingru; Wang, Fengyang; Lin, Che-Jen; Zhang, Leiming; Hui, Mulin; Yang, Mei; Su, Haitao; Hao, Jiming

2016-02-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, waste incinerators, biomass burning and so on. Mercury in coal, ores, and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of Hg0 to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g., TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher Hg0 fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron and/or steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

STUDY OF THE FUNDAMENTALS OF MERCURY SPECIATION IN COAL-FIRED BOILERS UNDER SIMULATED POST-COMBUSTION CONDITIONS

EPA Science Inventory

The report discusses a continuation of the study on mercury speciation initiated in the fiscal year 1997 (FY97). The previous study found that cupric oxide (CuO) and ferric oxide (Fe2O3) in the presence of hydrogen chloride (HCl) promote elemental mercury oxidation in simulated f...

Evaluating EDGARv4.tox2 speciated mercury emissions ex-post scenarios and their impacts on modelled global and regional wet deposition patterns

NASA Astrophysics Data System (ADS)

Muntean, Marilena; Janssens-Maenhout, Greet; Song, Shaojie; Giang, Amanda; Selin, Noelle E.; Zhong, Hui; Zhao, Yu; Olivier, Jos G. J.; Guizzardi, Diego; Crippa, Monica; Schaaf, Edwin; Dentener, Frank

2018-07-01

Speciated mercury gridded emissions inventories together with chemical transport models and concentration measurements are essential when investigating both the effectiveness of mitigation measures and the mercury cycle in the environment. Since different mercury species have contrasting behaviour in the atmosphere, their proportion in anthropogenic emissions could determine the spatial impacts. In this study, the time series from 1970 to 2012 of the EDGARv4.tox2 global mercury emissions inventory are described; the total global mercury emission in 2010 is 1772 tonnes. Global grid-maps with geospatial distribution of mercury emissions at a 0.1° × 0.1° resolution are provided for each year. Compared to the previous tox1 version, tox2 provides updates for more recent years and improved emissions in particular for agricultural waste burning, power generation and artisanal and small-scale gold mining (ASGM) sectors. We have also developed three retrospective emissions scenarios based on different hypotheses related to the proportion of mercury species in the total mercury emissions for each activity sector; improvements in emissions speciation are seen when using information primarily from field measurements. We evaluated them using the GEOS-Chem 3-D mercury model in order to explore the influence of speciation shifts, to reactive mercury forms in particular, on regional wet deposition patterns. The reference scenario S1 (EDGARv4.tox2_S1) uses speciation factors from the Arctic Monitoring and Assessment Programme (AMAP); scenario S2 ("EPA_power") uses factors from EPA's Information Collection Request (ICR); and scenario S3 ("Asia_filedM") factors from recent scientific publications. In the reference scenario, the sum of reactive mercury emissions (Hg-P and Hg2+) accounted for 25.3% of the total global emissions; the regions/countries that have shares of reactive mercury emissions higher than 6% in total global reactive mercury are China+ (30.9%), India+ (12.5%) and the United States (9.9%). In 2010, the variations of reactive mercury emissions amongst the different scenarios are in the range of -19.3 t/yr (China+) to 4.4 t/yr (OECD_Europe). However, at the sector level, the variation could be different, e.g., for the iron and steel industry in China reaches 15.4 t/yr. Model evaluation at the global level shows a variation of approximately ±10% in wet deposition for the three emissions scenarios. An evaluation of the impact of mercury speciation within nested grid sensitivity simulations is performed for the United States and modelled wet deposition fluxes are compared with measurements. These studies show that using the S2 and S3 emissions of reactive mercury, can improve wet deposition estimates near sources.

Mercury Methylation by Desulfovibrio desulfuricans ND132 in the Presence of Polysulfides

PubMed Central

Jay, Jenny Ayla; Murray, Karen J.; Gilmour, Cynthia C.; Mason, Robert P.; Morel, François M. M.; Roberts, A. Lynn; Hemond, Harold F.

2002-01-01

The extracellular speciation of mercury may control bacterial uptake and methylation. Mercury-polysulfide complexes have recently been shown to be prevalent in sulfidic waters containing zero-valent sulfur. Despite substantial increases in total dissolved mercury concentration, methylation rates in cultures of Desulfovibrio desulfuricans ND132 equilibrated with cinnabar did not increase in the presence of polysulfides, as expected due to the large size and charged nature of most of the complexes. In natural waters not at saturation with cinnabar, mercury-polysulfide complexes would be expected to shift the speciation of mercury from HgS0(aq) toward charged complexes, thereby decreasing methylation rates. PMID:12406773

Utility of EXAFS in characterization and speciation of mercury-bearing mine wastes

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

1999-01-01

Extensive mining of large mercury deposits located in the California Coast Range has resulted in mercury contamination of both the local environment and water supplies. The solubility, dispersal, and ultimate fate of mercury are all affected by its chemical speciation, which can be most readily determined in a direct fashion using EXAFS spectroscopy. EXAFS spectra of mine wastes collected from several mercury mines in the California Coast Range with mercury concentrations ranging from 230 to 1060 mg/kg (ppm) have been analyzed using a spectral database of mercury minerals and sorbed mercury complexes. While some calcines have been found to consist almost exclusively of mercuric sulfide, HgS, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. This experimental approach can provide a quantitative measurement of the mercury compounds present and may serve as an indicator of the bioavailability and toxicity levels of mercury mine wastes.

Distribution and speciation of mercury affected by humic acid in mariculture sites at the Pearl River estuary.

PubMed

Ding, Lingyun; Zhao, Kaiyun; Zhang, Lijuan; Liang, Peng; Wu, Shengchun; Wong, Ming Hung; Tao, Huchun

2018-05-14

At the Pearl River Estuary of southern China, mercury and its environmental problems have long been a great concern. This study investigated the distribution and speciation of mercury compounds that are significantly influenced by the increasing content of humic acid (HA, a model natural organic matter) in this region. The inorganic mercury and methyl mercury, being adsorbed and converted at different HA levels, were studied in sediments and surface water at both mariculture and their reference sites. In mariculture sediments with higher HA content (up to 4.5%), more mercury were adsorbed at different compound levels, promoting the methylation and accumulation of mercury (P < 0.05) at the sediment-water interface. Seasonal shift in environmental temperature might control the HA content, subsequently favouring mercury methylation (maximum 1.75 ± 0.08 mg L -1 d -1 ) under warm weather conditions. In reference sites received less HA wastes, lower adsorption capacity and methylation rate were observed for mercury in sediments and surface water. Our work points to the significant roles of HA on mercury distribution and speciation both spatially and seasonally, thus addressing the impacts of mariculture activities on estuary eco-system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Recent Advances in the Measurement of Arsenic, Cadmium, and Mercury in Rice and Other Foods

PubMed Central

Punshon, Tracy

2015-01-01

Trace element analysis of foods is of increasing importance because of raised consumer awareness and the need to evaluate and establish regulatory guidelines for toxic trace metals and metalloids. This paper reviews recent advances in the analysis of trace elements in food, including challenges, state-of-the art methods, and use of spatially resolved techniques for localizing the distribution of As and Hg within rice grains. Total elemental analysis of foods is relatively well-established but the push for ever lower detection limits requires that methods be robust from potential matrix interferences which can be particularly severe for food. Inductively coupled plasma mass spectrometry (ICP-MS) is the method of choice, allowing for multi-element and highly sensitive analyses. For arsenic, speciation analysis is necessary because the inorganic forms are more likely to be subject to regulatory limits. Chromatographic techniques coupled to ICP-MS are most often used for arsenic speciation and a range of methods now exist for a variety of different arsenic species in different food matrices. Speciation and spatial analysis of foods, especially rice, can also be achieved with synchrotron techniques. Sensitive analytical techniques and methodological advances provide robust methods for the assessment of several metals in animal and plant-based foods, in particular for arsenic, cadmium and mercury in rice and arsenic speciation in foodstuffs. PMID:25938012

EVALUATION OF THE EFFECT OF SCR ON MERCURY SPECIATION AND EMISSIONS

EPA Science Inventory

The paper presents the results of an investigation on the impact that selective catalytic reduction (SCR) has on both the total emissions and the speciation of mercury (Hg). SCR systems can be used as multipollutant technologies if they enhance Hg conversion/capture. Previous pil...

Speciation analysis of mercury by solid-phase microextraction and multicapillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight-mass spectrometry.

PubMed

Jitaru, Petru; Adams, Freddy C

2004-11-05

This paper reports the development of an analytical approach for speciation analysis of mercury at ultra-trace levels on the basis of solid-phase microextraction and multicapillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight mass spectrometry. Headspace solid-phase microextraction with a carboxen/polydimethylsyloxane fiber is used for extraction/preconcentration of mercury species after derivatization with sodium tetraethylborate and subsequent volatilization. Isothermal separation of methylmercury (MeHg), inorganic mercury (Hg2+) and propylmercury (PrHg) used as internal standard is achieved within a chromatographic run below 45 s without the introduction of spectral skew. Method detection limits (3 x standard deviation criteria) calculated for 10 successive injections of the analytical reagent blank are 0.027 pg g(-1) (as metal) for MeHg and 0.27 pg g(-1) for Hg2+. The repeatability (R.S.D., %) is 3.3% for MeHg and 3.8% for Hg2+ for 10 successive injections of a standard mixture of 10pg. The method accuracy for MeHg and total mercury is validated through the analysis of marine and estuarine sediment reference materials. A comparison of the sediment data with those obtained by a purge-and-trap injection (PTI) method is also addressed. The analytical procedure is illustrated with some results for the ultra-trace level analysis of ice from Antarctica for which the accuracy is assessed by spike recovery experiments.

Estimation of speciated and total mercury dry deposition at monitoring locations in eastern and central North America

USGS Publications Warehouse

Zhang, L.; Blanchard, P.; Gay, D.A.; Prestbo, E.M.; Risch, M.R.; Johnson, D.; Narayan, J.; Zsolway, R.; Holsen, T.M.; Miller, E.K.; Castro, M.S.; Graydon, J.A.; St. Louis, V.L.; Dalziel, J.

2012-01-01

Dry deposition of speciated mercury, i.e., gaseous oxidized mercury (GOM), particulate-bound mercury (PBM), and gaseous elemental mercury (GEM), was estimated for the year 2008–2009 at 19 monitoring locations in eastern and central North America. Dry deposition estimates were obtained by combining monitored two- to four-hourly speciated ambient concentrations with modeled hourly dry deposition velocities (Vd) calculated using forecasted meteorology. Annual dry deposition of GOM+PBM was estimated to be in the range of 0.4 to 8.1 μg m−2 at these locations with GOM deposition being mostly five to ten times higher than PBM deposition, due to their different modeled Vd values. Net annual GEM dry deposition was estimated to be in the range of 5 to 26 μg m−2 at 18 sites and 33 μg m−2 at one site. The estimated dry deposition agrees very well with limited surrogate-surface dry deposition measurements of GOM and PBM, and also agrees with litterfall mercury measurements conducted at multiple locations in eastern and central North America. This study suggests that GEM contributes much more than GOM+PBM to the total dry deposition at the majority of the sites considered here; the only exception is at locations close to significant point sources where GEM and GOM+PBM contribute equally to the total dry deposition. The relative magnitude of the speciated dry deposition and their good comparisons with litterfall deposition suggest that mercury in litterfall originates primarily from GEM, which is consistent with the limited number of previous field studies. The study also supports previous analyses suggesting that total dry deposition of mercury is equal to, if not more important than, wet deposition of mercury on a regional scale in eastern North America.

Characteristics and distributions of atmospheric mercury emitted from anthropogenic sources in Guiyang, southwestern China

EPA Science Inventory

Continuous measurements of speciated atmospheric mercury (Hg), including gaseous elemental mercury (GEM), particulate mercury (PHg), and reactive gaseous mercury (RGM) were conducted in Guizhou Province, southwestern China. Guiyang Power Plant (GPP), Guiyang Wujiang Cement Plant,...

A simple and low cost dual-wavelength β-correction spectrophotometric determination and speciation of mercury(II) in water using chromogenic reagent 4-(2-thiazolylazo) resorcinol

NASA Astrophysics Data System (ADS)

Al-Bagawi, A. H.; Ahmad, W.; Saigl, Z. M.; Alwael, H.; Al-Harbi, E. A.; El-Shahawi, M. S.

2017-12-01

The most common problems in spectrophotometric determination of various complex species originate from the background spectral interference. Thus, the present study aimed to overcome the spectral matrix interference for the precise analysis and speciation of mercury(II) in water by dual-wavelength β-correction spectrophotometry using 4-(2-thiazolylazo) resorcinol (TAR) as chromogenic reagent. The principle was based on measuring the correct absorbance for the formed complex of mercury(II) ions with TAR reagent at 547 nm (lambda max). Under optimized conditions, a linear dynamic range of 0.1-2.0 μg mL- 1 with correlation coefficient (R2) of 0.997 were obtained with lower limits of detection (LOD) of 0.024 μg mL- 1 and limit of quantification (LOQ) of 0.081 μg mL- 1. The values of RSD and relative error (RE) obtained for β-correction method and single wavelength spectrophotometry were 1.3, 1.32% and 4.7, 5.9%, respectively. The method was validated in tap and sea water in terms of the data obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) using student's t and F tests. The developed methodology satisfactorily overcomes the spectral interference in trace determination and speciation of mercury(II) ions in water.

AN ENVIRONMENTAL TECHNOLOGY VERIFICATION (ETV) TESTING OF FOUR MERCURY EMISSION SAMPLING SYSTEMS

EPA Science Inventory

CEMs - Tekran Instrument Corp. Series 3300 and Thermo Electron's Mercury Freedom System Continuous Emission Monitors (CEMs) for mercury are designed to determine total and/or chemically speciated vapor-phase mercury in combustion emissions. Performance for mercury CEMs are cont...

Microbial mercury methylation in Antarctic sea ice.

PubMed

Gionfriddo, Caitlin M; Tate, Michael T; Wick, Ryan R; Schultz, Mark B; Zemla, Adam; Thelen, Michael P; Schofield, Robyn; Krabbenhoft, David P; Holt, Kathryn E; Moreau, John W

2016-08-01

Atmospheric deposition of mercury onto sea ice and circumpolar sea water provides mercury for microbial methylation, and contributes to the bioaccumulation of the potent neurotoxin methylmercury in the marine food web. Little is known about the abiotic and biotic controls on microbial mercury methylation in polar marine systems. However, mercury methylation is known to occur alongside photochemical and microbial mercury reduction and subsequent volatilization. Here, we combine mercury speciation measurements of total and methylated mercury with metagenomic analysis of whole-community microbial DNA from Antarctic snow, brine, sea ice and sea water to elucidate potential microbially mediated mercury methylation and volatilization pathways in polar marine environments. Our results identify the marine microaerophilic bacterium Nitrospina as a potential mercury methylator within sea ice. Anaerobic bacteria known to methylate mercury were notably absent from sea-ice metagenomes. We propose that Antarctic sea ice can harbour a microbial source of methylmercury in the Southern Ocean.

Atmospheric speciated mercury concentrations on an island between China and Korea: sources and transport pathways

NASA Astrophysics Data System (ADS)

Lee, G.-S.; Kim, P.-R.; Han, Y.-J.; Holsen, T. M.; Seo, Y.-S.; Yi, S.-M.

2015-11-01

As a global pollutant, mercury (Hg) is of particular concern in East Asia where anthropogenic emissions are the largest. In this study, speciated Hg concentrations were measured in the western most island in Korea, located between China and the Korean mainland to identify the importance of local, regional and distant Hg sources. Various tools including correlations with other pollutants, conditional probability function, and back-trajectory based analysis consistently indicated that Korean sources were important for gaseous oxidized mercury (GOM) whereas, for total gaseous mercury (TGM) and particulate bound mercury (PBM), long-range and regional transport were also important. A trajectory cluster based approach considering both Hg concentration and the fraction of time each cluster was impacting the site was developed to quantify the effect of Korean sources and out-of-Korean source. This analysis suggests that Korean sources contributed approximately 55 % of the GOM and PBM while there were approximately equal contributions from Korean and out-of-Korean sources for the TGM measured at the site. The ratio of GOM / PBM decreased when the site was impacted by long-range transport, suggesting that this ratio may be a useful tool for identifying the relative significance of local sources vs. long-range transport. The secondary formation of PBM through gas-particle partitioning with GOM was found to be important at low temperatures and high relative humidity.

Atmospheric speciated mercury concentrations on an island between China and Korea: sources and transport pathways

NASA Astrophysics Data System (ADS)

Lee, Gang-San; Kim, Pyung-Rae; Han, Young-Ji; Holsen, Thomas M.; Seo, Yong-Seok; Yi, Seung-Muk

2016-03-01

As a global pollutant, mercury (Hg) is of particular concern in East Asia, where anthropogenic emissions are the largest. In this study, speciated Hg concentrations were measured on Yongheung Island, the westernmost island in Korea, located between China and the Korean mainland to identify the importance of local and regional Hg sources. Various tools including correlations with other pollutants, conditional probability function, and back-trajectory-based analysis consistently indicated that Korean sources were important for gaseous oxidized mercury (GOM) whereas, for total gaseous mercury (TGM) and particulate bound mercury (PBM), regional transport was also important. A trajectory cluster based approach, considering both Hg concentration and the fraction of time each cluster was impacting the site, was developed to quantify the effect of Korean sources and out-of-Korean sources. This analysis suggests that contributions from out-of-Korean sources were similar to Korean sources for TGM whereas Korean sources contributed slightly more to the concentration variations of GOM and PBM compared to out-of-Korean sources. The ratio of GOM/PBM decreased when the site was impacted by regional transport, suggesting that this ratio may be a useful tool for identifying the relative significance of local sources vs. regional transport. The secondary formation of PBM through gas-particle partitioning with GOM was found to be important at low temperatures and high relative humidity.

PILOT-SCALE STUDY OF THE EFFECT OF SELECTIVE CATALYTIC REDUCTION CATALYST ON MERCURY SPECIATION IN ILLINOIS AND POWDER RIVER BASIN COAL COMBUSTION FLUE GASES

EPA Science Inventory

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur and chlorine) and one Po...

Application of thermal desorption for the identification of mercury species in solids derived from coal utilization.

PubMed

Rumayor, M; Diaz-Somoano, M; Lopez-Anton, M A; Martinez-Tarazona, M R

2015-01-01

The speciation of mercury is currently attracting widespread interest because the emission, transport, deposition and behaviour of toxic mercury species depend on its chemical form. The identification of these species in low concentrations is no easy task and it is even more complex in coal combustion products due to the fact that these products contain organic and mineral matter that give rise to broad peaks and make it difficult to carry out qualitative and quantitative analysis. In this work, a solution to this problem is proposed using a method based on thermal desorption. A sequential extraction procedure was employed for the comparison and validation of the method developed. Samples of fly ashes and soils were analyzed by both of these methods, and thermal desorption was found to be an appropriate technique for mercury speciation. Even in the case of low mercury contents, recovery percentages were close to 100%. The main mercury species identified in the samples studied were HgS and, to a lesser extent, HgO and HgSO4. In addition, although the presence of mercury complexes cannot be demonstrated, the desorption behaviour and sequential extraction results suggest that this element might be associated with the mineral matrix or with carbon particles in some of the solids. Copyright © 2014 Elsevier Ltd. All rights reserved.

Transformation of mercury speciation through the SCR system in power plants.

PubMed

Yang, Hong-min; Pan, Wei-ping

2007-01-01

Coal-fired utility boilers are now identified as the largest source of mercury in the United States. There is speculation that the installation of selective catalytic reduction (SCR) system for reduction of NOx can also prompt the oxidation and removal of mercury. In this paper, tests at six full-scale power plants with similar type of the SCR systems are conducted to investigate the effect of the SCR on the transformation of mercury speciation. The results show that the SCR system can achieve more than 70%-80% oxidation of elemental mercury and enhance the mercury removal ability in these units. The oxidation of elemental mercury in the SCR system strongly depends on the coal properties and the operation conditions of the SCR systems. The content of chloride in the coal is the key factor for the oxidization process and the maximum oxidation of elemental mercury is found when chloride content changes from 400 to 600 ppm. The sulfur content is no significant impact on oxidation of elemental mercury.

Ultra-sensitive speciation analysis of mercury by CE-ICP-MS together with field-amplified sample stacking injection and dispersive solid-phase extraction.

PubMed

Chen, YiQuan; Cheng, Xian; Mo, Fan; Huang, LiMei; Wu, Zujian; Wu, Yongning; Xu, LiangJun; Fu, FengFu

2016-04-01

A simple dispersive solid-phase extraction (DSPE) used to extract and preconcentrate ultra-trace MeHg, EtHg and Hg(2+) from water sample, and a sensitive method for the simultaneous analysis of MeHg, EtHg and Hg(2+) by using capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) with field-amplified sample stacking injection (FASI) were first reported in this study. The DSPE used thiol cotton particles as adsorbent, and is simple and effective. It can be used to extract and preconcentrate ultra-trace mercury compounds in water samples within 30 min with a satisfied recovery and no mercury species alteration during the process. The FASI enhanced the sensitivity of CE-ICP-MS with 25-fold, 29-fold and 27-fold for MeHg, EtHg and Hg(2+) , respectively. Using FASI-CE-ICP-MS together with DSPE, we have successfully determined ultra-trace MeHg, EtHg and Hg(2+) in tap water with a limits of quantification (LOQs) of 0.26-0.45 pg/mL, an RSD (n = 3) < 6% and a recovery of 92-108%. Ultra-high sensitivity, as well as much less sample and reagent consumption and low operating cost, make our method a valuable technique to the speciation analysis of ultra-trace mercury. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-chromatographic speciation analysis of mercury by flow injection on-line preconcentration in combination with chemical vapor generation atomic fluorescence spectrometry

NASA Astrophysics Data System (ADS)

Wu, Hong; Jin, Yan; Han, Weiying; Miao, Qiang; Bi, Shuping

2006-07-01

A novel non-chromatographic approach for direct speciation of mercury, based on the selective retention inorganic mercury and methylmercury on the inner wall of a knotted reactor by using ammonium diethyl dithiophosphate and dithizone as complexing agents respectively, was developed for flow injection on-line sorption preconcentration coupled with chemical vapor generation non-dispersive atomic fluorescence spectrometry. With the sample pH kept at 2.0, the preconcentration of inorganic mercury on the inner walls of the knotted reactor was carried out based on the exclusive retention of Hg-DDP complex in the presence of methylmercury via on-line merging the sample solution with ammonium diethyl dithiophosphate solution, and selective preconcentration methylmercury was achieved with dithizone instead of ammonium diethyl dithiophosphate. A 15% (v/v) HCl was introduced to elute the retained mercury species and merge with KBH 4 solution for atomic fluorescence spectrometry detection. Under the optimal experimental conditions, the sample throughputs of inorganic mercury and methylmercury were 30 and 20 h - 1 with the enhancement factors of 13 and 24. The detection limits were found to be 3.6 ng l - 1 for Hg 2+ and 2.0 ng l - 1 for CH 3Hg +. The precisions (RSD) for the 11 replicate measurements of each 0.2 μg l - 1 of Hg 2+ and CH 3Hg + were 2.2% and 2.8%, respectively. The developed method was validated by the analysis of certified reference materials (simulated natural water, rice flour and pork) and by recovery measurements on spiked samples, and was applied to the determination of inorganic mercury and methylmercury in biological and environmental water samples.

Characteristics and distributions of atmospheric mercury ...

EPA Pesticide Factsheets

Continuous measurements of speciated atmospheric mercury (Hg), including gaseous elemental mercury (GEM), particulate mercury (PHg), and reactive gaseous mercury (RGM) were conducted in Guizhou Province, southwestern China. Guiyang Power Plant (GPP), Guiyang Wujiang Cement Plant, Guizhou Aluminum Plant (GAP), and Guiyang Forest Park (GFP) in Guiyang were selected as study sites. Automatic Atmospheric Mercury Speciation Analyzers (Tekran 2537A) were used for GEM analysis. PHg and RGM were simultaneously collected by a manual sampling system, including elutriator, coupler/impactor, KCl-coated annular denuder, and a filter holder. Results show that different emission sources dominate different species of Hg. The highest average GEM value was 22.2 ± 28.3 ng·m−3 and the lowest 6.1 ± 3.9 ng·m−3, from samples collected at GPP and GAP, respectively. The maximum average PHg was 1984.9 pg·m−3 and the minimum average 55.9 pg·m−3, also from GPP and GAP, respectively. Similarly, the highest average RGM of 68.8 pg·m−3 was measured at GPP, and the lowest level of 20.5 pg·m−3 was found at GAP. We conclude that coal combustion sources are still playing a key role in GEM; traffic contributes significantly to PHg; and domestic pollution dominates RGM. Mercury (Hg) is a persistent hazardous pollutant with adverse effects on human health and wildlife due mainly to bioaccumulation and biomagnification in aquatic food webs (Lindqvist et al. 1991; Schroeder and Munt

Mercury speciation and selenium in toothed-whale muscles.

PubMed

Sakamoto, Mineshi; Itai, Takaaki; Yasutake, Akira; Iwasaki, Toshihide; Yasunaga, Genta; Fujise, Yoshihiro; Nakamura, Masaaki; Murata, Katsuyuki; Chan, Hing Man; Domingo, José L; Marumoto, Masumi

2015-11-01

Mercury accumulates at high levels in marine mammal tissues. However, its speciation is poorly understood. The main goal of this investigation was to establish the relationships among mercury species and selenium (Se) concentrations in toothed-whale muscles at different mercury levels. The concentrations of total mercury (T-Hg), methylmercury (MeHg), inorganic mercury (I-Hg) and Se were determined in the muscles of four toothed-whale species: bottlenose dolphins (n=31), Risso's dolphins (n=30), striped dolphins (n=29), and short-finned pilot whales (n=30). In each species, the MeHg concentration increased with increasing T-Hg concentration, tending to reach a plateau. In contrast, the proportion of MeHg in T-Hg decreased from 90-100% to 20-40%. The levels of T-Hg and Se showed strong positive correlations. Se/I-Hg molar ratios rapidly decreased with the increase of I-Hg and reached almost 1 in all species. These results suggested that the demethylated MeHg immediately formed Se/I-Hg equimolar complex of mercury selenide (HgSe) in their muscles. In addition, an X-ray absorption fine structure analysis (XAFS) of a bottlenose dolphin muscle confirmed that the dominant chemical form of the Se/I-Hg equimolar complex was HgSe. HgSe was mainly localized in cells near the endomysium using electron probe microanalysis (EPMA). These results suggested that the demethylated MeHg finally deposits within muscle cells of bottlenose dolphin as an inert HgSe. Copyright © 2015 Elsevier Inc. All rights reserved.

Regional Scale Photochemical Model Evaluation of Total Mercury Wet Deposition and Speciated Ambient Mercury

EPA Science Inventory

Methylmercury is a known neurotoxin with deleterious health effects on humans and wildlife. Atmospheric deposition is the largest source of mercury loading to most terrestrial and aquatic ecosystems. Regional scale air quality models are needed to quantify mercury deposition resu...

THE IMPORTANCE OF EMISSIONS SPECIATION TO THE ATMOSPHERIC TRANSPORT AND DEPOSITION OF MERCURY

EPA Science Inventory

The atmospheric pathway of the global mercury cycle is believed to be the main source of mercury contamination to aquatic eco-systems throughout the United States and in most other nations where direct disposal of mercury to water has been largely eliminated. Although the spatia...

First field-based atmospheric observation of the reduction of reactive mercury driven by sunlight

NASA Astrophysics Data System (ADS)

de Foy, Benjamin; Tong, Yindong; Yin, Xiufeng; Zhang, Wei; Kang, Shichang; Zhang, Qianggong; Zhang, Guoshuai; Wang, Xuejun; Schauer, James J.

2016-06-01

Hourly speciated measurements of atmospheric mercury made in a remote, high-altitude site in the Tibetan Plateau revealed the first field observations of the reduction of reactive mercury in the presence of sunlight in the atmosphere. Measurements were collected over four winter months on the shore of Nam Co Lake in the inland Tibetan Plateau. The data was analyzed to identify sources and atmospheric transformations of the speciated mercury compounds. The absence of local anthropogenic sources provided a unique opportunity to examine chemical transformations of mercury. An optimization algorithm was used to determine the parameters of a chemical box model that would match the measured reactive mercury concentrations. This required the presence of a photolytic reduction reaction previously observed in laboratory studies and in power plant plumes. In addition, the model estimated the role of vertical mixing in diluting reactive gaseous mercury during the day, and the role of bromine chemistry in oxidizing gaseous elemental mercury to produce reactive gaseous mercury. This work provides further evidence of the need to add the photolytic reduction reaction of oxidized mercury into atmospheric transport models in order to better simulate mercury deposition.

Spatial distribution and speciation of mercury and methyl mercury in the surface water of East River (Dongjiang) tributary of Pearl River Delta, South China.

PubMed

Liu, Jinling; Feng, Xinbin; Zhu, Wei; Zhang, Xian; Yin, Runsheng

2012-01-01

The distribution and speciation of mercury in surface water of East River, Guangdong province, China were investigated. All told 63 water samples were collected during a bi-weekly sampling campaign from July 15th to 26th, 2009. Total mercury (THg) concentrations in water samples ranged from 11 to 49 ng/L. Maximum levels of THg were measured in the lower reaches of East River, where it passes through a major industrial area adjacent to Dongguang city. Higher ratios of dissolved mercury (THg (aq)) in proportion to THg were restricted to the downstream section of East River. Concentrations of the minor constituent methyl mercury varied in the range from 0.08 to 0.21 ng/L. On average, methyl mercury made up 0.8% and 0.56% of THg (aq) and THg, respectively. Dissolved species dominated the speciation of methyl mercury in proportions up to 81%, which may imply that methyl mercury is largely produced in situ within the river water. Environmental factors (such as water temperature, dissolved oxygen, etc.) are regarded to play an important role in Hg methylation processes were monitored and assessed. In an international perspective, East River must be classified as a polluted river with considerably sources within its industrial areas. The THg (aq) and particle mercury fluxes to the Pearl River Estuary by East River run-off were estimated to be 0.31 ± 0.11 and 0.17 ± 0.13 t/year, respectively. Hence, in total nearly 0.5 t Hg is annually released to the sea from the East River tributary.

Ion-pairing reversed-phase chromatography coupled to inductively coupled plasma mass spectrometry as a tool to determine mercurial species in freshwater fish.

PubMed

Cheng, Heyong; Chen, Xiaopan; Shen, Lihuan; Wang, Yuanchao; Xu, Zigang; Liu, Jinhua

2018-01-05

Most of analytical community is focused on reversed phase high performance liquid chromatography (RP-HPLC) for mercury speciation by employing mobile phases comprising of high salts and moderate amounts of organic solvents. This study aims at rapid mercury speciation analysis by ion-pairing RP-HPLC with inductively coupled plasma mass spectrometry (ICP-MS) detection only using low salts for the sake of green analytical chemistry. Two ion-pairing HPLC methods were developed on individual usage of positively and negatively charged ion-pairing reagents (tetrabutylammonium hydroxide -TBAH and sodium dodecylbenzene sulfonate -SDBS), where sodium 3-mercapto-1-propysulfonate (MPS) and l-cysteine (Cys) were individually added in mobile phases to transform mercury species into negative and positive Hg-complexes for good resolution. Addition of phenylalanine was also utilized for rapid baseline separation in combination of short C 18 guard columns. Optimum mobile phases of 2.0mM SDBS+2.0mM Cys+1.0mM Phe (pH 3.0) and 4.0mM TBAH+2.0mM MPS+2.0mM Phe (pH 6.0) both achieved baseline separation of inorganic mercury (Hg 2+ ), methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg) on two consecutive 12.5-mm C 18 columns. The former mobile phase was selected for mercury speciation in freshwater fish because of short separation time (3.0min). Detection limits of 0.015 for Hg 2+ , 0.014 for MeHg, 0.028 for EtHg and 0.042μgL -1 for PhHg were obtained along with satisfactory precisions of peak height and area (1.0-2.8% for 5.0μgL -1 Hg-mixture standard). Good accordance of determined values of MeHg and total mercury in certified reference materials of fish tissue (GBW 10029) and tuna fish (BCR-463) with certified values as well as good recoveries (91-106%) proved good accuracy of the proposed method. An example application to freshwater fish indicated its potential in routine analysis, where MeHg was presented at 3.7-20.3μgkg -1 as the dominate species. Copyright © 2017 Elsevier B.V. All rights reserved.

SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

EPA Science Inventory

The report details an investigation on the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury at power plants. If SCR and/or SNCR systems enhance mercury conversion/capture, t...

THERMODYNAMIC REACTION CONSTANTS FOR MODELING AQUEOUS ENVIRONMENTAL MERCURY SPECIATION

EPA Science Inventory

Unacceptably high fish tissue mercury residues are responsible for the majority of fish consumption advisories issued in 48 states of the United States of America. Mercury also has emerged as a transboundary contaminant of global concern. Although monomethylmercury is generally...

Understanding atmospheric mercury speciation and mercury in snow over time at Alert, Canada

NASA Astrophysics Data System (ADS)

Steffen, A.; Bottenheim, J.; Cole, A.; Ebinghaus, R.; Lawson, G.; Leaitch, W. R.

2013-06-01

Ten years of atmospheric mercury speciation data and 14 yr of mercury in snow data from Alert, Nunavut, Canada are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentrations of PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pg m-3 and RGM is 23.9 pg m-3 from March to June in comparison to the annual median concentrations of 11.3 and 3.2 -3 for PHg and RGM, respectively. In each of the ten years of sampling, PHg increases steadily from January through March and is higher than RGM. This pattern begins to change in April with very high levels of PHg and increasing RGM. In May, RGM transitions to be significantly higher than PHg and continues into June whereas PHg sharply drops down. The transition is thought to be driven by a combination of air temperature and particle availability. Firstly, the ratio of PHg to RGM is favoured by low temperatures suggesting that oxidized mercury may partition to available particles to form PHg. Prior to the transition, the median air temperature is -24.8 °C and after the transition the median air temperature is -5.8 °C. Secondly, high aerosol levels in the spring are a strong driver for the high PHg concentrations. In February through April, partitioning of oxidized mercury to produce PHg was favoured by increased concentrations of particles that are principally the result of Arctic Haze and some sea salts. In the snow, the concentrations of mercury peak in May for all years. The highest deposition of mercury to the snow in the spring at Alert is during and after the transition of PHg to RGM in the atmosphere.

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants.

PubMed

Ochoa-González, R; Córdoba, P; Díaz-Somoano, M; Font, O; López-Antón, M A; Leiva, C; Martínez-Tarazona, M R; Querol, X; Pereira, C Fernández; Tomás, A; Gómez, P; Mesado, P

2011-10-01

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg2+ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive. Copyright © 2011 Elsevier Ltd. All rights reserved.

Method for removal and stabilization of mercury in mercury-containing gas streams

DOEpatents

Broderick, Thomas E.

2005-09-13

The present invention is directed to a process and apparatus for removing and stabilizing mercury from mercury-containing gas streams. A gas stream containing vapor phase elemental and/or speciated mercury is contacted with reagent, such as an oxygen-containing oxidant, in a liquid environment to form a mercury-containing precipitate. The mercury-containing precipitate is kept or placed in solution and reacts with one or more additional reagents to form a solid, stable mercury-containing compound.

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

USGS Publications Warehouse

Gandhi, N.; Bhavsar, S.P.; Diamond, M.L.; Kuwabara, J.S.; Marvin-DiPasquale, M.; Krabbenhoft, D.P.

2007-01-01

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)2, and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations. ?? 2007 SETAC.

STANDARDIZED AUTOMATED AND MANUAL METHODS TO SPECIATE MERCURY: FIELD AND LABORATORY STUDIES

EPA Science Inventory

The urban atmosphere contains a large number of air pollutants including mercury. Atmospheric mercury is predominantly present in the elemental form (Hg0). However emissions from industrial activities (e.g. incinerators, fossil fuel combustion sources and others) emit other f...

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boggess, A.

Existing models and simulants of tank disposition media at SRS have presumed the presence of high concentrations of inorganic mercury. However, recent quarterly tank analyses show that mercury is present as organomercurial species at concentrations that may present challenges to remediation and disposition and may exceed the Saltstone Waste Acceptance Criteria (WAC). To-date, methylmercury analysis for Savannah River Remediation (SRR) has been performed off-site by Eurofins Scientific (Lancaster, PA). A series of optimization and validation experiments has been performed at SRNL, which has resulted in the development of on-site organomercury speciation capabilities using purge and trap gas chromatography coupled withmore » thermal desorption cold vapor atomic fluorescence spectroscopy (P&T GC/CVAFS). Speciation has been achieved for methylmercury, with a method reporting limit (MRL) values of 1.42 pg for methylmercury. Results obtained by SRNL from the analysis of past quarterly samples from tanks 21, 40, and 50 have demonstrated statistically indistinguishable concentration values compared with the concentration data obtained from Eurofins, while the data from SRNL has demonstrated significantly improved precision and processing time.« less

EFFECTS OF FLUE GAS CONSTITUENTS ON MERCURY SPECIATION. (R827649)

EPA Science Inventory

Beginning with the 1990 Clean Air Act Amendments, there has been considerable interest in mercury emissions from coal-fired power plants. This past year, the U.S. Environmental Protection Agency (EPA) issued both the Mercury Study Report to Congress and the Study of Hazardous ...

VALIDATION OF MERCURY CEMS WHEN COFIRING BIOMASS AT MADISON ELECTRIC'S BLOUNT STATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dennis L. Laudal; Jeffrey S. Thompson

2000-09-30

The state of Wisconsin has been concerned about mercury deposition into its lakes and streams and has been evaluating strategies to reduce mercury emissions. As part of this effort, the Blount Station, owned and operated by Madison Gas and Electric Company (MGE), has undergone a project to evaluate the effects and potential mercury emissions reduction of cofiring preconsumer waste. MGE owns and operates the Blount Generating Station located in central Madison, Wisconsin. At present, Blount operates with nine boilers and six turbine generators. The two largest boilers at Blount produce 400,000 pounds of steam per hour at 950 F andmore » 1250 psi. These larger boilers, MGE's Boiler Nos. 8 and 9, have the capability of cofiring both paper and plastic. MGE's Blount Generating Station was one of the first electric generating stations in the United States to retrofit its existing steam boilers to successfully burn refuse-derived fuel and other alternate fuels including waste paper and wood. It is the No. 9 boiler that was the focus of this project to determine the effect of cofiring PDF (plastic- and paper-derived fuel) on speciated mercury emissions. The project was laid out to compare four different fuel combinations: (1) coal feed only, (2) coal with plastic, (3) coal with paper, and (4) coal with paper and plastic. The design was to run the boiler for 2 days at each condition, thus allowing four samples to be taken at each condition. This plan was aimed at getting at least three representative samples at each condition and allowed for difficulties in sampling and boiler operation. The following objectives were accomplished as part of the project to determine the effects of cofiring PDF on mercury emissions and speciation at MGE Blount Station: Successfully completed all of the mercury sampling for each of the four boiler/PDF conditions using the Ontario Hydro (OH) mercury speciation method; Determined mercury concentrations at the stack location using mercury continuous emission monitors (CEMs) for each of the four boiler/PDF conditions; Calculated the overall mercury mass balance for each of the runs; Determined chlorine concentrations at the stack location using EPA Method 26A for each of the four boiler/PDF conditions; and Calculated speciated mercury flow to determine removal and/or transformations before its exiting the unit at the stack for each of the four boiler/PDF conditions.« less

Sources of speciated atmospheric mercury at a residential neighborhood impacted by industrial sources.

PubMed

Manolopoulos, Helen; Snyder, David C; Schauer, James J; Hill, Jason S; Turner, Jay R; Olson, Mark L; Krabbenhoft, David P

2007-08-15

Speciated measurements of atmospheric mercury plumes were obtained at an industrially impacted residential area of East St. Louis, IL. These plumes were found to result in extremely high mercury concentrations at ground level that were composed of a wide distribution of mercury species. Ground level concentrations as high as 235 ng m(-3) for elemental mercury (Hg0) and 38 300 pg m(-3) for reactive mercury species (reactive gaseous (RGM) plus particulate (PHg) mercury) were measured. The highest mercury concentrations observed during the study were associated with plumes that contained high concentrations of all mercury species (Hg0, RGM, and PHg) and originated from a source located southwest of the sampling site. Variations in proportions of Hg0/RGM/PHg among plumes, with Hg0 dominating some plumes and RGM and/or PHg dominating others, were attributed to differences in emissions from different sources. Correlations between mercury plumes and elevated NO(x) were not observed; however, a correlation between elevated SO2 and mercury plumes was observed during some but not all plume events. Despite the presence of six coal-fired power plants within 60 km of the study site, wind direction data along with Hg/SO2 and Hg/NO(x) ratios suggest that high-concentration mercury plumes impacting the St. Louis-Midwest Particle Matter Supersite are attributable to local point sources within 5 km of the site.

Sources of speciated atmospheric mercury at a residential neighborhood impacted by industrial sources

USGS Publications Warehouse

Manolopoulos, H.; Snyder, D.C.; Schauer, J.J.; Hill, J.S.; Turner, J.R.; Olson, M.L.; Krabbenhoft, D.P.

2007-01-01

Speciated measurements of atmospheric mercury plumes were obtained at an industrially impacted residential area of East St. Louis, IL. These plumes were found to result in extremely high mercury concentrations at ground level that were composed of a wide distribution of mercury species. Ground level concentrations as high as 235 ng m-3 for elemental mercury (Hg 0) and 38 300 pg m-3 for reactive mercury species (reactive gaseous (RGM) plus particulate (PHg) mercury) were measured. The highest mercury concentrations observed during the study were associated with plumes that contained high concentrations of all mercury species (Hg 0, RGM, and PHg) and originated from a source located southwest of the sampling site. Variations in proportions of Hg0/RGM/PHg among plumes, with Hg0 dominating some plumes and RGM and/or PHg dominating others, were attributed to differences in emissions from different sources. Correlations between mercury plumes and elevated NOx were not observed; however, a correlation between elevated SO2 and mercury plumes was observed during some but not all plume events. Despite the presence of six coal-fired power plants within 60 km of the study site, wind direction data along with Hg/SO2 and Hg/NOx ratios suggest that high-concentration mercury plumes impacting the St. Louis-Midwest Particle Matter Supersite are attributable to local point sources within 5 km of the site. ?? 2007 American Chemical Society.

Mercury hair levels and factors that influence exposure for residents of Huancavelica, Peru

EPA Science Inventory

Between 1564 and 1810, nearly 17,000 metric tons of mercury (Hg) vapor were released to the environment during cinnabar refining in the small town of Huancavelica, Peru. The present study characterizes individual exposure to mercury using total and speciated Hg from residential s...

POWER PLANT EVALUATION OF THE EFFECT OF SCR TECHNOLOGY ON MERCURY

EPA Science Inventory

The paper presents results of research on the impact that selective catalytic reduction (SCR) systems have on speciation and total emissions of mercury. Although SCR systems are designed to reduce nitrogen oxides (NOx), they may oxidize elemental mercury (Hg0) to Hg2+, which is m...

MEASUREMENT AND MODELING OF ATMOSPHERIC MERCURY SPECIES AND RELATED POLLUTANTS IN SOUTH FLORIDA FROM 2000-2005

EPA Science Inventory

In 2000, Florida DEP, USEPA, and Broward EPD located an atmospheric mercury monitoring site adjacent to the Everglades in southeast Florida for the purposes of field testing the Tekran mercury speciation system under long-term operational conditions and evaluating the impact of e...

INVESTIGATING OXIDATION MECHANISMS OF HGO IN THE FREE TROPOSPHERE AND ITS INFLUENCE ON LONG RANGE MERCURY TRANSPORT

EPA Science Inventory

ORD initiated automated speciated mercury measurements at the NOAA Mauna Loa Observatory (MLO), a high altitude research station (~11,500 feet) in 2001. Mercury monitoring at MLO was supplemented with trace element aerosol, criteria gas, and gas and particulate halide measurement...

Coupling pervaporation to AAS for inorganic and organic mercury determination. A new approach to speciation of Hg in environmental samples.

PubMed

Fernandez-Rivas, C; Muñoz-Olivas, R; Camara, C

2001-12-01

The design and development of a new approach for Hg speciation in environmental samples is described in detail. This method, consisting of the coupling of pervaporation and atomic absorption spectrometry, is based on a membrane phenomenon that combines the evaporation of volatile analytes and their diffusion through a polymeric membrane. It is proposed here as an alternative to gas chromatography for speciation of inorganic and organic Hg compounds, as the latter compounds are volatile and can be separated by applying the principles mentioned above. The interest of this method lies in its easy handling, low cost, and rapidity for the analysis of liquid and solid samples. This method has been applied to Hg speciation in a compost sample provided by a waste water treatment plant.

Temporal trend and sources of speciated atmospheric mercury at Waliguan GAW station, northwestern China

NASA Astrophysics Data System (ADS)

Fu, X. W.; Feng, X.; Liang, P.; Deli-Geer; Zhang, H.; Ji, J.; Liu, P.

2011-11-01

Measurements of speciated atmospheric mercury were conducted at a remote mountain-top station (WLG) at the edge of northeastern part of the Qinghai-Xizang Plateau, western China. Mean concentrations of total gaseous mercury (TGM), particulate mercury (PHg), and reactive gaseous mercury (RGM) during the whole sampling campaign were 1.98 ± 0.98 ng m-3, 19.4 ± 18.1 pg m-3, and 7.4 ± 4.8 pg m-3, respectively. Levels of speciated Hg at WLG were slightly higher than those reported from remote areas of North America and Europe. Both regional emissions and long-rang transport played a remarkable role in the distribution of TGM and PHg in ambient air at WLG, whereas RGM showed major links to the regional sources, likely as well as the in-situ productions by photochemical processes. Regional sources for speciated Hg were mostly located to the east of WLG, which is the most developed areas of Qinghai province and accounted for most of the province's anthropogenic Hg emissions. Potential source contribution function (PSCF) results showed a strong impact of long-range transport from eastern Gansu, western Ningxia and Shanxi Province, with good accordance with locations of urban areas and industrial centers. Moreover, we found that northern India was also an important source region of WLG during the sampling campaign, and this is the first time of direct evidence of long-range transport of atmospheric Hg from India to northeastern Tibetan Plateau. Seasonal and diurnal variations of TGM were in contrast with most of the previous studies in China, with relatively higher levels in warm seasons and night, respectively. The temporal trend of TGM also highlighted the impact of long-range transport on the distribution of TGM in ambient air at WLG.

Pattern of atmospheric mercury speciation during episodes of elevated PM2.5 levels in a coastal city in the Yangtze River Delta, China.

PubMed

Hong, Youwei; Chen, Jinsheng; Deng, Junjun; Tong, Lei; Xu, Lingling; Niu, Zhenchuan; Yin, Liqian; Chen, Yanting; Hong, Zhenyu

2016-11-01

Measurement of atmospheric mercury speciation was conducted in a coastal city of the Yangtze River Delta, China from July 2013 to January 2014, in conjunction with air pollutants and meteorological parameters. The mean concentrations of gaseous elemental mercury (GEM), particulate bound mercury (HgP) and reactive gaseous mercury (RGM) were 3.26 ± 1.63 ng m -3 , 659 ± 931 pg m -3 , and 197 ± 246 pg m -3 , respectively. High percentages of HgP during haze days were found, due to the increase in direct emissions and gas-particle partitioning of RGM. The average gas-particle partitioning coefficients (Kp) during moderate or severe haze days (PM2.5 > 150 μg m -3 ) were obviously decreased. GEM and HgP were positively correlated with PM2.5, SO 2 , NO 2 and CO, suggesting a significant contribution of anthropogenic sources. Elevated HgP concentrations in cold seasons and in the morning were observed while RGM exhibited different seasonal and diurnal pattern. The ratio of HgP/SO 2 and Pearson correlation analysis suggested that coal combustion was the main cause of increasing atmospheric Hg concentrations. The monitoring site was affected by local, regional and interregional sources. The back trajectory analysis suggested that air mass from northwest China and Huabei Plain contributed to elevated atmospheric Hg in winter and autumn, while southeast China with clean air masses were the major contributor in summer. Copyright © 2016 Elsevier Ltd. All rights reserved.

Highly efficient electrocatalytic vapor generation of methylmercury based on the gold particles deposited glassy carbon electrode: A typical application for sensitive mercury speciation analysis in fish samples.

PubMed

Shi, Meng-Ting; Yang, Xin-An; Qin, Li-Ming; Zhang, Wang-Bing

2018-09-26

A gold particle deposited glassy carbon electrode (Au/GCE) was first used in electrochemical vapor generation (ECVG) technology and demonstrated to have excellent catalytic property for the electrochemical conversion process of aqueous mercury, especially for methylmercury (CH 3 Hg + ), to gaseous mercury. Systematical research has shown that the highly consistent or distinct difference between the atomic fluorescence spectroscopy signals of CH 3 Hg + and Hg 2+ can be achieved by controlling the electrolytic parameters of ECVG. Hereby, a new green and accurate method for mercury speciation analysis based on the distinguishing electrochemical reaction behavior of Hg 2+ and CH 3 Hg +  on the modified electrode was firstly established. Furthermore, electrochemical impedance spectra and the square wave voltammetry displayed that the ECVG reaction of CH 3 Hg +  may belong to the electrocatalytic mechanism. Under the selected conditions, the limits of detection of Hg 2+ and CH 3 Hg +  are 5.3 ng L -1 and 4.4 ng L -1 for liquid samples and 0.53 pg mg -1 and 0.44 pg mg -1 for solid samples, respectively. The precision of the 5 measurements is less than 6% within the concentration of Hg 2+ and CH 3 Hg +  ranging from 0.2 to 15.0 μg L -1 . The accuracy and practicability of the proposed method was verified by analyzing the mercury content in the certified reference material and several fish as well as water samples. Copyright © 2018 Elsevier B.V. All rights reserved.

Atmospheric mercury speciation and mercury in snow over time at Alert, Canada

NASA Astrophysics Data System (ADS)

Steffen, A.; Bottenheim, J.; Cole, A.; Ebinghaus, R.; Lawson, G.; Leaitch, W. R.

2014-03-01

Ten years of atmospheric mercury speciation data and 14 years of mercury in snow data from Alert, Nunavut, Canada, are examined. The speciation data, collected from 2002 to 2011, includes gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM). During the winter-spring period of atmospheric mercury depletion events (AMDEs), when GEM is close to being completely depleted from the air, the concentration of both PHg and RGM rise significantly. During this period, the median concentrations for PHg is 28.2 pgm-3 and RGM is 23.9 pgm-3, from March to June, in comparison to the annual median concentrations of 11.3 and 3.2 pgm-3 for PHg and RGM, respectively. In each of the ten years of sampling, the concentration of PHg increases steadily from January through March and is higher than the concentration of RGM. This pattern begins to change in April when the levels of PHg peak and RGM begin to increase. In May, the high PHg and low RGM concentration regime observed in the early spring undergoes a transition to a regime with higher RGM and much lower PHg concentrations. The higher RGM concentration continues into June. The transition is driven by the atmospheric conditions of air temperature and particle availability. Firstly, a high ratio of the concentrations of PHg to RGM is reported at low temperatures which suggests that oxidized gaseous mercury partitions to available particles to form PHg. Prior to the transition, the median air temperature is -24.8 °C and after the transition the median air temperature is -5.8 °C. Secondly, the high PHg concentrations occur in the spring when high particle concentrations are present. The high particle concentrations are principally due to Arctic haze and sea salts. In the snow, the concentrations of mercury peak in May for all years. Springtime deposition of total mercury to the snow at Alert peaks in May when atmospheric conditions favour higher levels of RGM. Therefore, the conditions in the atmosphere directly impact when the highest amount of mercury will be deposited to the snow during the Arctic spring.

Impact of Measurement Uncertainties on Receptor Modeling of Speciated Atmospheric Mercury.

PubMed

Cheng, I; Zhang, L; Xu, X

2016-02-09

Gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) measurement uncertainties could potentially affect the analysis and modeling of atmospheric mercury. This study investigated the impact of GOM measurement uncertainties on Principal Components Analysis (PCA), Absolute Principal Component Scores (APCS), and Concentration-Weighted Trajectory (CWT) receptor modeling results. The atmospheric mercury data input into these receptor models were modified by combining GOM and PBM into a single reactive mercury (RM) parameter and excluding low GOM measurements to improve the data quality. PCA and APCS results derived from RM or excluding low GOM measurements were similar to those in previous studies, except for a non-unique component and an additional component extracted from the RM dataset. The percent variance explained by the major components from a previous study differed slightly compared to RM and excluding low GOM measurements. CWT results were more sensitive to the input of RM than GOM excluding low measurements. Larger discrepancies were found between RM and GOM source regions than those between RM and PBM. Depending on the season, CWT source regions of RM differed by 40-61% compared to GOM from a previous study. No improvement in correlations between CWT results and anthropogenic mercury emissions were found.

Impact of Measurement Uncertainties on Receptor Modeling of Speciated Atmospheric Mercury

PubMed Central

Cheng, I.; Zhang, L.; Xu, X.

2016-01-01

Gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) measurement uncertainties could potentially affect the analysis and modeling of atmospheric mercury. This study investigated the impact of GOM measurement uncertainties on Principal Components Analysis (PCA), Absolute Principal Component Scores (APCS), and Concentration-Weighted Trajectory (CWT) receptor modeling results. The atmospheric mercury data input into these receptor models were modified by combining GOM and PBM into a single reactive mercury (RM) parameter and excluding low GOM measurements to improve the data quality. PCA and APCS results derived from RM or excluding low GOM measurements were similar to those in previous studies, except for a non-unique component and an additional component extracted from the RM dataset. The percent variance explained by the major components from a previous study differed slightly compared to RM and excluding low GOM measurements. CWT results were more sensitive to the input of RM than GOM excluding low measurements. Larger discrepancies were found between RM and GOM source regions than those between RM and PBM. Depending on the season, CWT source regions of RM differed by 40–61% compared to GOM from a previous study. No improvement in correlations between CWT results and anthropogenic mercury emissions were found. PMID:26857835

Effect of oxy-combustion flue gas on mercury oxidation.

PubMed

Fernández-Miranda, Nuria; Lopez-Anton, M Antonia; Díaz-Somoano, Mercedes; Martínez-Tarazona, M Rosa

2014-06-17

This study evaluates the effect of the gases present in a typical oxy-coal combustion atmosphere on mercury speciation and compares it with the mercury speciation produced in conventional air combustion atmospheres. The work was performed at laboratory scale at 150 °C. It was found that the minor constituents (SO2, NOx, and HCl) significantly modify the percentages of Hg(2+) in the gas. The influence of these species on mercury oxidation was demostrated when they were tested individually and also when they were blended in different gas compositions, although the effect was different to the sum of their individual effects. Of the minor constituents, NOx were the main species involved in oxidation of mercury. Moreover, it was found that a large concentration of H2O vapor also plays an important role in mercury oxidation. Around 50% of the total mercury was oxidized in atmospheres with H2O vapor concentrations typical of oxy-combustion conditions. When the atmospheres have similar concentrations of SO2, NO, NO2, HCl, and H2O, the proportion of Hg(0)/Hg(2+) is similar regardless of whether CO2 (oxy-fuel combustion) or N2 (air combustion) are the main components of the gas.

MERCURY SPECIATION AND CAPTURE

EPA Science Inventory

In December 2000, the U.S. Environmental Protection Agency (USEPA) announced its intent to regulate mercury emissions from coal-fired electric utility steam generating plants. Maximum achievable control technology (MACT) requirements are to be proposed by December 2003 and finali...

Biogeochemical controls on mercury methylation in the Allequash Creek wetland.

PubMed

Creswell, Joel E; Shafer, Martin M; Babiarz, Christopher L; Tan, Sue-Zanne; Musinsky, Abbey L; Schott, Trevor H; Roden, Eric E; Armstrong, David E

2017-06-01

We measured mercury methylation potentials and a suite of related biogeochemical parameters in sediment cores and porewater from two geochemically distinct sites in the Allequash Creek wetland, northern Wisconsin, USA. We found a high degree of spatial variability in the methylation rate potentials but no significant differences between the two sites. We identified the primary geochemical factors controlling net methylmercury production at this site to be acid-volatile sulfide, dissolved organic carbon, total dissolved iron, and porewater iron(II). Season and demethylation rates also appear to regulate net methylmercury production. Our equilibrium speciation modeling demonstrated that sulfide likely regulated methylation rates by controlling the speciation of inorganic mercury and therefore its bioavailability to methylating bacteria. We found that no individual geochemical parameter could explain a significant amount of the observed variability in mercury methylation rates, but we found significant multivariate relationships, supporting the widely held understanding that net methylmercury production is balance of several simultaneously occurring processes.

Mercury speciation and mobilization in a wastewater-contaminated groundwater plume

USGS Publications Warehouse

Lamborg, Carl H.; Kent, Doug B.; Swarr, Gretchen J.; Munson, Kathleen M.; Kading, Tristan; O'Connor, Alison E.; Fairchild, Gillian M.; LeBlanc, Denis R.; Wiatrowski, Heather A.

2013-01-01

We measured the concentration and speciation of mercury (Hg) in groundwater down-gradient from the site of wastewater infiltration beds operated by the Massachusetts Military Reservation, western Cape Cod, Massachusetts. Total mercury concentrations in oxic, mildly acidic, uncontaminated groundwater are 0.5–1 pM, and aquifer sediments have 0.5–1 ppb mercury. The plume of impacted groundwater created by the wastewater disposal is still evident, although inputs ceased in 1995, as indicated by anoxia extending at least 3 km down-gradient from the disposal site. Solutes indicative of a progression of anaerobic metabolisms are observed vertically and horizontally within the plume, with elevated nitrate concentrations and nitrate reduction surrounding a region with elevated iron concentrations indicating iron reduction. Mercury concentrations up to 800 pM were observed in shallow groundwater directly under the former infiltration beds, but concentrations decreased with depth and with distance down-gradient. Mercury speciation showed significant connections to the redox and metabolic state of the groundwater, with relatively little methylated Hg within the iron reducing sector of the plume, and dominance of this form within the higher nitrate/ammonium zone. Furthermore, substantial reduction of Hg(II) to Hg0 within the core of the anoxic zone was observed when iron reduction was evident. These trends not only provide insight into the biogeochemical factors controlling the interplay of Hg species in natural waters, but also support hypotheses that anoxia and eutrophication in groundwater facilitate the mobilization of natural and anthropogenic Hg from watersheds/aquifers, which can be transported down-gradient to freshwaters and the coastal zone.

Adsorptive behaviour of mercury on algal biomass: competition with divalent cations and organic compounds.

PubMed

Carro, Leticia; Barriada, José L; Herrero, Roberto; Sastre de Vicente, Manuel E

2011-08-15

Biosorption processes constitute an effective technique for mercury elimination. Sorption properties of native and acid-treated Sargassum muticum have been studied. Effect of pH, initial mercury concentration and contact time studies provided fundamental information about the sorption process. This information was used as the reference values to analyse mercury sorption under competition conditions. Saline effect has shown little influence in sorption, when only electrostatic modifications took place upon salt addition. On the contrary, if mercury speciation dramatically changed owing to the addition of an electrolyte, such as in the case of chloride salt, very large modifications in mercury sorption were observed. Competition with other divalent cations or organic compounds has shown little or none effect on mercury, indicating that a different mechanism is taking place during the removal of these pollutants. Finally, continuous flow experiments have clearly shown that a reduction process is also taking place during mercury removal. This fact is not obvious to elucidate under batch sorption experiments. Scanning Electron Microscopy analysis of the surface of the materials show deposits of mercury(I) and metallic mercury which is indicative of the reduction process proposed. Copyright © 2011 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jain, V.; Shah, H.; Bannochie, C. J.

Mercury (Hg) in the Savannah River Site Liquid Waste System (LWS) originated from decades of canyon processing where it was used as a catalyst for dissolving the aluminum cladding of reactor fuel. Approximately 60 metric tons of mercury is currently present throughout the LWS. Mercury has long been a consideration in the LWS, from both hazard and processing perspectives. In February 2015, a Mercury Program Team was established at the request of the Department of Energy to develop a comprehensive action plan for long-term management and removal of mercury. Evaluation was focused in two Phases. Phase I activities assessed themore » Liquid Waste inventory and chemical processing behavior using a system-by-system review methodology, and determined the speciation of the different mercury forms (Hg+, Hg++, elemental Hg, organomercury, and soluble versus insoluble mercury) within the LWS. Phase II activities are building on the Phase I activities, and results of the LWS flowsheet evaluations will be summarized in three reports: Mercury Behavior in the Salt Processing Flowsheet (i.e. this report); Mercury Behavior in the Defense Waste Processing Facility (DWPF) Flowsheet; and Mercury behavior in the Tank Farm Flowsheet (Evaporator Operations). The evaluation of the mercury behavior in the salt processing flowsheet indicates, inter alia, the following: (1) In the assembled Salt Batches 7, 8 and 9 in Tank 21, the total mercury is mostly soluble with methylmercury (MHg) contributing over 50% of the total mercury. Based on the analyses of samples from 2H Evaporator feed and drop tanks (Tanks 38/43), the source of MHg in Salt Batches 7, 8 and 9 can be attributed to the 2H evaporator concentrate used in assembling the salt batches. The 2H Evaporator is used to evaporate DWPF recycle water. (2) Comparison of data between Tank 21/49, Salt Solution Feed Tank (SSFT), Decontaminated Salt Solution Hold Tank (DSSHT), and Tank 50 samples suggests that the total mercury as well as speciated forms in the assembled salt batches in Tanks 21/49 pass through the Actinide Removal Process (ARP) / Modular Caustic Side Solvent Extraction Unit (MCU) process to Tank 50 with no significant change in the mercury chemistry. (3) In Tank 50, Decontaminated Salt Solution (DSS) from ARP/MCU is the major contributor to the total mercury including MHg. (4) Speciation analyses of TCLP leached solutions of the grout samples prepared from Tank 21, as well as Tank 50 samples, show the majority of the mercury released in the solution is MHg.« less

Mercury emission and speciation of coal-fired power plants in China

NASA Astrophysics Data System (ADS)

Wang, S. X.; Zhang, L.; Li, G. H.; Wu, Y.; Hao, J. M.; Pirrone, N.; Sprovieri, F.; Ancora, M. P.

2010-02-01

Comprehensive field measurements are needed to understand the mercury emissions from Chinese power plants and to improve the accuracy of emission inventories. Characterization of mercury emissions and their behavior were measured in six typical coal-fired power plants in China. During the tests, the flue gas was sampled simultaneously at inlet and outlet of Selective Catalytic Reduction (SCR), electrostatic precipitators (ESP), and flue gas desulfurization (FGD) using the Ontario Hydro Method (OHM). The pulverized coal, bottom ash, fly ash and gypsum were also sampled in the field. Mercury concentrations in coal burned in the measured power plants ranged from 17 to 385 μg/kg. The mercury mass balances for the six power plants varied from 87 to 116% of the input coal mercury for the whole system. The total mercury concentrations in the flue gas from boilers were at the range of 1.92-27.15 μg/m3, which were significantly related to the mercury contents in burned coal. The mercury speciation in flue gas right after the boiler is influenced by the contents of halogen, mercury, and ash in the burned coal. The average mercury removal efficiencies of ESP, ESP plus wet FGD, and ESP plus dry FGD-FF systems were 24%, 73% and 66%, respectively, which were similar to the average removal efficiencies of pollution control device systems in other countries such as US, Japan and South Korea. The SCR system oxidized 16% elemental mercury and reduced about 32% of total mercury. Elemental mercury, accounting for 66-94% of total mercury, was the dominant species emitted to the atmosphere. The mercury emission factor was also calculated for each power plant.

Mercury emission and speciation of coal-fired power plants in China

NASA Astrophysics Data System (ADS)

Wang, S.; Zhang, L.; Li, G.; Wu, Y.; Hao, J.; Pirrone, N.; Sprovieri, F.; Ancora, M. P.

2009-11-01

Comprehensive field measurements are needed to understand the mercury emissions from Chinese power plants and to improve the accuracy of emission inventories. Characterization of mercury emissions and their behavior were measured in six typical coal-fired power plants in China. During the tests, the flue gas was sampled simultaneously at inlet and outlet of selective catalyst reduction (SCR), electrostatic precipitators (ESP), and flue gas desulfurization (FGD) using the Ontario Hydro Method (OHM). The pulverized coal, bottom ash, fly ash and gypsum were also sampled in the field. Mercury concentrations in coal burned in the measured power plants ranged from 17 to 385 μg/kg. The mercury mass balances for the six power plants varied from 87 to 116% of the input coal mercury for the whole system. The total mercury concentrations in the flue gas from boilers were at the range of 1.92-27.15 μg/m3, which were significantly related to the mercury contents in burned coal. The mercury speciation in flue gas right after the boiler is influenced by the contents of halogen, mercury, and ash in the burned coal. The average mercury removal efficiencies of ESP, ESP plus wet FGD, and ESP plus dry FGD-FF systems were 24%, 73% and 66%, respectively, which were similar to the average removal efficiencies of pollution control device systems in other countries such as US, Japan and South Korea. The SCR system oxidized 16% elemental mercury and reduced about 32% of total mercury. Elemental mercury, accounting for 66-94% of total mercury, was the dominant species emitted to the atmosphere. The mercury emission factor was also calculated for each power plant.

Geochemical modeling of mercury speciation in surface water and implications on mercury cycling in the everglades wetland.

PubMed

Jiang, Ping; Liu, Guangliang; Cui, Wenbin; Cai, Yong

2018-06-01

The geochemical model PHREEQC, abbreviated from PH (pH), RE (redox), EQ (equilibrium), and C (program written in C), was employed on the datasets generated by the USEPA Everglades Regional Environmental Monitoring and Assessment Program (R-EMAP) to determine the speciation distribution of inorganic mercury (iHg) in Everglades water and to explore the implications of iHg speciation on mercury cycling. The results suggest that sulfide and DOM were the key factors that regulate inorganic Hg speciation in the Everglades. When sulfide was present at measurable concentrations (>0.02 mg/L), Hg-S complexes dominated iHg species, occurring in the forms of HgS 2 2- , HgHS 2 - , and Hg(HS) 2 that were affected by a variety of environmental factors. When sulfide was assumed nonexistent, Hg-DOM complexes occurred as the predominant Hg species, accounting for almost 100% of iHg species. However, when sulfide was presumably present at a very low, environmentally relevant concentration (3.2 × 10 -7  mg/L), both Hg-DOM and Hg-S complexes were present as the major iHg species. These Hg-S species and Hg-DOM complex could be related to methylmercury (MeHg) in environmental matrices such floc, periphyton, and soil, and the correlations are dependent upon different circumstances (e.g., sulfide concentrations). The implications of the distribution of iHg species on MeHg production and fate in the Everglades were discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Development of a particle-trap preconcentration-soft ionization mass spectrometric technique for the quantification of mercury halides in air.

PubMed

Deeds, Daniel A; Ghoshdastidar, Avik; Raofie, Farhad; Guérette, Élise-Andrée; Tessier, Alain; Ariya, Parisa A

2015-01-01

Measurement of oxidized mercury, Hg(II), in the atmosphere poses a significant analytical challenge as Hg(II) is present at ultra-trace concentrations (picograms per cubic meter air). Current technologies are sufficiently sensitive to measure the total Hg present as Hg(II) but cannot determine the chemical speciation of Hg(II). We detail here the development of a soft ionization mass spectrometric technique coupled with preconcentration onto nano- or microparticle-based traps prior to analysis for the measurement of mercury halides in air. The current methodology has comparable detection limits (4-11 pg m(-3)) to previously developed techniques for the measurement of total inorganic mercury in air while allowing for the identification of HgX2 in collected samples. Both mercury chloride and mercury bromide have been sporadically detected in Montreal urban and indoor air using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). We discuss limitations and advantages of the current technique and discuss potential avenues for future research including quantitative trace measurements of a larger range of mercury compounds.

AN ASSESSMENT OF THERMODYNAMIC REACTION CONSTANTS FOR SIMULATING AQUEOUS ENVIRONMENTAL MONOMETHYLMERCURY SPECIATION

EPA Science Inventory

Monomethylmercury (CH3Hg+) is both the most ecologically significant and the least well characterized species of mercury in environmental settings. Our understanding of the environmental speciation behavior of this compound is limited both as the result of lesser available labor...

Behavior of Mercury Emissions from a Commercial Coal-Fired Utility Boiler: TheRelationship Between Stack Speciation and Near-Field Plume Measurements

EPA Science Inventory

The reduction of divalent gaseous mercury (Hg^II) to elemental gaseous mercury (Hg⁰) in a commercial coal-fired power plant (CFPP)exhaust plume was investigated by simultaneous measurement in-stack and in-plume as part of a collaborative study among the U.S....

Methyl mercury, but not inorganic mercury, associated with higher blood pressure during pregnancy.

PubMed

Wells, Ellen M; Herbstman, Julie B; Lin, Yu Hong; Hibbeln, Joseph R; Halden, Rolf U; Witter, Frank R; Goldman, Lynn R

2017-04-01

Prior studies addressing associations between mercury and blood pressure have produced inconsistent findings; some of this may result from measuring total instead of speciated mercury. This cross-sectional study of 263 pregnant women assessed total mercury, speciated mercury, selenium, and n-3 polyunsaturated fatty acids in umbilical cord blood and blood pressure during labor and delivery. Models with a) total mercury or b) methyl and inorganic mercury were evaluated. Regression models adjusted for maternal age, race/ethnicity, prepregnancy body mass index, neighborhood income, parity, smoking, n-3 fatty acids and selenium. Geometric mean total, methyl, and inorganic mercury concentrations were 1.40µg/L (95% confidence interval: 1.29, 1.52); 0.95µg/L (0.84, 1.07); and 0.13µg/L (0.10, 0.17), respectively. Elevated systolic BP, diastolic BP, and pulse pressure were found, respectively, in 11.4%, 6.8%, and 19.8% of mothers. In adjusted multivariable models, a one-tertile increase of methyl mercury was associated with 2.83mmHg (0.17, 5.50) higher systolic blood pressure and 2.99mmHg (0.91, 5.08) higher pulse pressure. In the same models, an increase of one tertile of inorganic mercury was associated with -1.18mmHg (-3.72, 1.35) lower systolic blood pressure and -2.51mmHg (-4.49, -0.53) lower pulse pressure. No associations were observed with diastolic pressure. There was a non-significant trend of higher total mercury with higher systolic blood pressure. We observed a significant association of higher methyl mercury with higher systolic and pulse pressure, yet higher inorganic mercury was significantly associated with lower pulse pressure. These results should be confirmed with larger, longitudinal studies. Copyright © 2017 Elsevier Inc. All rights reserved.

Investigation of a mercury speciation technique for flue gas desulfurization materials.

PubMed

Lee, Joo-Youp; Cho, Kyungmin; Cheng, Lei; Keener, Tim C; Jegadeesan, Gautham; Al-Abed, Souhail R

2009-08-01

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method. Potential candidates of pure mercury standards including mercuric chloride (HgCl2), mercurous chloride (Hg2Cl2), mercury oxide (HgO), mercury sulfide (HgS), and mercuric sulfate (HgSO4) were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg2Cl2 and HgCl2 could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury.

Investigation of a mercury speciation technique for flue gas desulfurization materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.Y.; Cho K.; Cheng L.

2009-08-15

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to benefit from the partial mercury control that these systems provide, some mercury is likely to be bound in with the FGD gypsum and wallboard. In this study, the feasibility of identifying mercury species in the FGD gypsum and wallboard samples was investigated using a large sample size thermal desorption method and samples from power plants in Pennsylvania. Potential candidatesmore » of pure mercury standards including mercuric chloride, mercurous chloride, mercury oxide, mercury sulfide, and mercuric sulfate were analyzed to compare their results with those obtained from FGD gypsum and dry wallboard samples. Although any of the thermal evolutionary curves obtained from these pure mercury standards did not exactly match with those of the FGD gypsum and wallboard samples, it was identified that Hg{sub 2}Cl{sub 2} and HgCl{sub 2} could be candidates. An additional chlorine analysis from the gypsum and wallboard samples indicated that the chlorine concentrations were approximately 2 orders of magnitude higher than the mercury concentrations, suggesting possible chlorine association with mercury. 21 refs., 5 figs., 3 tabs.« less

ASSESSING SPECIATION AND RELEASE OF HEAVY METALS FROM COAL COMBUSTION PRODUCTS

EPA Science Inventory

In this study, the speciation of heavy metals such as arsenic, selenium, lead, zinc and mercury in coal combustion products (CCPs) was evaluated using sequential extraction procedures. Coal fly ash, bottom ash and flue gas desulphurization (FGD) sludge samples were used in the ex...

THE ADVANTAGE OF ILLINOIS COAL FOR FGD REMOVAL OF MERCURY

EPA Science Inventory

The paper gives results of an investigation conducted to characterize and modify mercury (Hg) speciation in Illinois coal combustion flue gas so that a Hg control strategy can be implemented in conventional flue gas desulfurization (FGD) units. Hg, in trace concentration in coal,...

SELECTIVE CATALYTIC REDUCTION MERCURY FIELD SAMPLING PROJECT

EPA Science Inventory

A lack of data still exists as to the effect of selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas conditioning on the speciation and removal of mercury (Hg) at power plants. This project investigates the impact that SCR, SNCR, and flue gas...

Mercury accumulation by lower trophic-level organisms in lentic systems within the Guadalupe River watershed, California

USGS Publications Warehouse

Kuwabara, James S.; Topping, Brent R.; Moon, Gerald E.; Husby, Peter; Lincoff, Andrew; Carter, James L.; Croteau, Marie-Noële

2005-01-01

The water columns of four reservoirs (Almaden, Calero, Guadalupe and Lexington Reservoirs) and an abandoned quarry pit filled by Alamitos Creek drainage for recreational purposes (Lake Almaden) were sampled on September 14 and 15, 2004 to provide the first measurements of mercury accumulation by phytoplankton and zooplankton in lentic systems (bodies of standing water, as in lakes and reservoirs) within the Guadalupe River watershed, California. Because of widespread interest in ecosystem effects associated with historic mercury mining within and downgradient of the Guadalupe Riverwatershed, transfer of mercury to lower trophic-level organisms was examined. The propensity of mercury to bioaccumulate, particularly in phytoplankton and zooplankton at the base of the food web, motivated this attempt to provide information in support of developing trophic-transfer and solute-transport models for the watershed, and hence in support of subsequent evaluation of load-allocation strategies. Both total mercury and methylmercury were examined in these organisms. During a single sampling event, replicate samples from the reservoir water column were collected and processed for dissolved-total mercury, dissolved-methylmercury, phytoplankton mercury speciation, phytoplankton taxonomy and biomass, zooplankton mercury speciation, and zooplankton taxonomy and biomass. The timing of this sampling event was coordinated with sampling and analysis of fish from these five water bodies, during a period of the year when vertical stratification in the reservoirs generates a primary source of methylmercury to the watershed. Ancillary data, including dissolved organic carbon and trace-metal concentrations as well as vertical profiles of temperature, dissolved oxygen, specific conductance and pH, were gathered to provide a water-quality framework from which to compare the results for mercury. This work, in support of the Guadalupe River Mercury Total Maximum Daily Load (TMDL) Study, provides the first measurements of mercury trophic transfer through planktonic communities in this watershed. It is worth reemphasizing that this data set represents a single ?snap shot? of conditions in water bodies within the Guadalupe River watershed to: (1) fill gaps in trophic transfer information, and (2) provide a scientific basis for future process-based studies with enhanced temporal and spatial coverage. This electronic document was unconventionally formatted to enhance the accessibility of information to a wide range of interest groups.

Mercury Speciation by X-ray Absorption Fine Structure Spectroscopy and Sequential Chemical Extractions: A Comparison of Speciation Methods

USGS Publications Warehouse

Kim, C.S.; Bloom, N.S.; Rytuba, J.J.; Brown, Gordon E.

2003-01-01

Determining the chemical speciation of mercury in contaminated mining and industrial environments is essential for predicting its solubility, transport behavior, and potential bioavailability as well as for designing effective remediation strategies. In this study, two techniques for determining Hg speciation-X-ray absorption fine structure (XAFS) spectroscopy and sequential chemical extractions (SCE)-are independently applied to a set of samples with Hg concentrations ranging from 132 to 7539 mg/kg to determine if the two techniques provide comparable Hg speciation results. Generally, the proportions of insoluble HgS (cinnabar, metacinnabar) and HgSe identified by XAFS correlate well with the proportion of Hg removed in the aqua regia extraction demonstrated to remove HgS and HgSe. Statistically significant (> 10%) differences are observed however in samples containing more soluble Hg-containing phases (HgCl2, HgO, Hg3S2O 4). Such differences may be related to matrix, particle size, or crystallinity effects, which could affect the apparent solubility of Hg phases present. In more highly concentrated samples, microscopy techniques can help characterize the Hg-bearing species in complex multiphase natural samples.

Hg speciation by differential photochemical vapor generation at UV-B and UV-C wavelengths

USDA-ARS?s Scientific Manuscript database

Mercury speciation was accomplished by differential photochemical reduction at two UV wavelengths; the resulting Hg(O) vapor was quantified by atomic fluorescence spectrometry. After microwave digestion and centrifugation, analyte solutions were mixed with 20% (v/v) formic acid in a reactor coil, an...

Mercury speciation and selenium in toothed-whale muscles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakamoto, Mineshi, E-mail: sakamoto@nimd.go.jp; Itai, Takaaki; Yasutake, Akira

2015-11-15

Mercury accumulates at high levels in marine mammal tissues. However, its speciation is poorly understood. The main goal of this investigation was to establish the relationships among mercury species and selenium (Se) concentrations in toothed-whale muscles at different mercury levels. The concentrations of total mercury (T-Hg), methylmercury (MeHg), inorganic mercury (I-Hg) and Se were determined in the muscles of four toothed-whale species: bottlenose dolphins (n=31), Risso's dolphins (n=30), striped dolphins (n=29), and short-finned pilot whales (n=30). In each species, the MeHg concentration increased with increasing T-Hg concentration, tending to reach a plateau. In contrast, the proportion of MeHg in T-Hgmore » decreased from 90–100% to 20–40%. The levels of T-Hg and Se showed strong positive correlations. Se/I-Hg molar ratios rapidly decreased with the increase of I-Hg and reached almost 1 in all species. These results suggested that the demethylated MeHg immediately formed Se/I-Hg equimolar complex of mercury selenide (HgSe) in their muscles. In addition, an X-ray absorption fine structure analysis (XAFS) of a bottlenose dolphin muscle confirmed that the dominant chemical form of the Se/I-Hg equimolar complex was HgSe. HgSe was mainly localized in cells near the endomysium using electron probe microanalysis (EPMA). These results suggested that the demethylated MeHg finally deposits within muscle cells of bottlenose dolphin as an inert HgSe. - Highlights: • T-Hg, MeHg, I-Hg and Se were determined in the muscles of four toothed-whales. • MeHg increased with increasing T-Hg and tended to reach a plateau in all species. • Se/I-Hg molar ratios rapidly decreased with increase of I-Hg and reached almost 1. • XAFS of bottlenose dolphin muscle confirmed that HgSe was dominant chemical form. • EPMA of bottlenose dolphin muscle showed that HgSe deposited in muscle cells.« less

Current understanding of the driving mechanisms for spatiotemporal variations of atmospheric speciated mercury: a review

NASA Astrophysics Data System (ADS)

Mao, Huiting; Cheng, Irene; Zhang, Leiming

2016-10-01

Atmospheric mercury (Hg) is a global pollutant and thought to be the main source of mercury in oceanic and remote terrestrial systems, where it becomes methylated and bioavailable; hence, atmospheric mercury pollution has global consequences for both human and ecosystem health. Understanding of spatial and temporal variations of atmospheric speciated mercury can advance our knowledge of mercury cycling in various environments. This review summarized spatiotemporal variations of total gaseous mercury or gaseous elemental mercury (TGM/GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM) in various environments including oceans, continents, high elevation, the free troposphere, and low to high latitudes. In the marine boundary layer (MBL), the oxidation of GEM was generally thought to drive the diurnal and seasonal variations of TGM/GEM and GOM in most oceanic regions, leading to lower GEM and higher GOM from noon to afternoon and higher GEM during winter and higher GOM during spring-summer. At continental sites, the driving mechanisms of TGM/GEM diurnal patterns included surface and local emissions, boundary layer dynamics, GEM oxidation, and for high-elevation sites mountain-valley winds, while oxidation of GEM and entrainment of free tropospheric air appeared to control the diurnal patterns of GOM. No pronounced diurnal variation was found for Tekran measured PBM at MBL and continental sites. Seasonal variations in TGM/GEM at continental sites were attributed to increased winter combustion and summertime surface emissions, and monsoons in Asia, while those in GOM were controlled by GEM oxidation, free tropospheric transport, anthropogenic emissions, and wet deposition. Increased PBM at continental sites during winter was primarily due to local/regional coal and wood combustion emissions. Long-term TGM measurements from the MBL and continental sites indicated an overall declining trend. Limited measurements suggested TGM/GEM increasing from the Southern Hemisphere (SH) to the Northern Hemisphere (NH) due largely to the vast majority of mercury emissions in the NH, and the latitudinal gradient was insignificant in summer probably as a result of stronger meridional mixing. Aircraft measurements showed no significant vertical variation in GEM over the field campaign regions; however, depletion of GEM was observed in stratospherically influenced air masses. In examining the remaining questions and issues, recommendations for future research needs were provided, and among them is the most imminent need for GOM speciation measurements and fundamental understanding of multiphase redox kinetics.

Fluorescence dye tagging scheme for mercury quantification and speciation

DOEpatents

Jiao, Hong; Catterall, Hannah

2015-09-22

A fluorescent dye or fluorophore capable of forming complexes with mercury comprises 6,8-difluoro-7-hydroxy-2-oxo-2H-chromene-3-carboxylate amide, wherein the amide is formed by reacting the succinimidyl ester (Pacific Blue.TM.) with an amino acid containing a thiol group, such as cysteine or glutathione. Mercury complexes of the fluorophore fluoresce when excited by a UV or violet laser diode, and the detected intensity can be calibrated to quantify the concentration of mercury in a sample reacted with the fluorophore.

Investigation Of A Mercury Speciation Technique For Flue Gas Desulfurization Materials

EPA Science Inventory

Most of the synthetic gypsum generated from wet flue gas desulfurization (FGD) scrubbers is currently being used for wallboard production. Because oxidized mercury is readily captured by the wet FGD scrubber, and coal-fired power plants equipped with wet scrubbers desire to bene...

Speciation and bioaccessibility of mercury in adobe bricks and dirt floors in Huancavelica, Peru

EPA Science Inventory

Background: Huancavelica, Peru, a historic cinnabar refining site, is one of the most mercury (Hg) contaminated urban areas in the world. Residents’ exposures are amplified because residents build their adobe brick homes from contaminated soil. Objectives: The objectives of th...

EVALUATION OF SCR CATALYSTS FOR COMBINED CONTROL OF NOX AND MERCURY

EPA Science Inventory

The report documents two-task, bench- and pilot-scale research on the effect of selective catalytic reduction (SCR) catalysts on mercury speciation in Illinois and Powder River Basin (PRB) coal combustion flue gases. In task I, a bench-scale reactor was used to study the oxidatio...

STUDY OF SPECIATION OF MERCURY UNDER SIMULATED SCR NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

The paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. It describes the results of bench-scale experiments conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures wit...

INVESTIGATION OF SELECTIVE CATALYTIC REDUCTION IMPACT ON MERCURY SPECIATION UNDER SIMULATED NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

Selective catalytic reduction (SCR) technology is being increasingly applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury in the coal com...

Mercury Emission Measurement in Coal-Fired Boilers by Continuous Mercury Monitor and Ontario Hydro Method

NASA Astrophysics Data System (ADS)

Zhu, Yanqun; Zhou, Jinsong; He, Sheng; Cai, Xiaoshu; Hu, Changxin; Zheng, Jianming; Zhang, Le; Luo, Zhongyang; Cen, Kefa

2007-06-01

The mercury emission control approach attaches more importance. The accurate measurement of mercury speciation is a first step. Because OH method (accepted method) can't provide the real-time data and 2-week time for results attained, it's high time to seek on line mercury continuous emission monitors(Hg-CEM). Firstly, the gaseous elemental and oxidized mercury were conducted to measure using OH and CEM method under normal operation conditions of PC boiler after ESP, the results between two methods show good consistency. Secondly, through ESP, gaseous oxidized mercury decrease a little and particulate mercury reduce a little bit, but the elemental mercury is just the opposite. Besides, the WFGD system achieved to gaseous oxidized mercury removal of 53.4%, gaseous overall mercury and elemental mercury are 37.1% and 22.1%, respectively.

Atmospheric mercury and fine particulate matter in coastal New England: implications for mercury and trace element sources in the northeastern United States

USGS Publications Warehouse

Kolker, Allan; Engle, Mark A.; Peucker-Ehrenbrink, Bernhard; Geboy, Nicholas J.; Krabbenhotft, David P.; Bothner, Michael H.; Tate, Michael T.

2013-01-01

Intensive sampling of ambient atmospheric fine particulate matter was conducted at Woods Hole, Massachusetts over a four-month period from 3 April to 29 July, 2008, in conjunction with year-long deployment of the USGS Mobile Mercury Lab. Results were obtained for trace elements in fine particulate matter concurrently with determination of ambient atmospheric mercury speciation and concentrations of ancillary gasses (SO2, NOx, and O3). For particulate matter, trace element enrichment factors greater than 10 relative to crustal background values were found for As, Bi, Cd, Cu, Hg, Pb, Sb, V, and Zn, indicating contribution of these elements by anthropogenic sources. For other elements, enrichments are consistent with natural marine (Na, Ca, Mg, Sr) or crustal (Ba, Ce, Co, Cs, Fe, Ga, La, Rb, Sc, Th, Ti, U, Y) sources, respectively. Positive matrix factorization was used together with concentration weighted air-mass back trajectories to better define element sources and their locations. Our analysis, based on events exhibiting the 10% highest PM2.5 contributions for each source category, identifies coal-fired power stations concentrated in the U.S. Ohio Valley, metal smelting in eastern Canada, and marine and crustal sources showing surprisingly similar back trajectories, at times each sampling Atlantic coastal airsheds. This pattern is consistent with contribution of Saharan dust by a summer maximum at the latitude of Florida and northward transport up the Atlantic Coast by clockwise circulation of the summer Bermuda High. Results for mercury speciation show diurnal production of RGM by photochemical oxidation of Hg° in a marine environment, and periodic traverse of the study area by correlated RGM-SO2(NOx) plumes, indicative of coal combustion sources.

Mercury speciation and distribution in a 660-megawatt utility boiler in Taiwan firing bituminous coals.

PubMed

Hsi, Hsing-Cheng; Lee, Hsiu-Hsia; Hwang, Jyh-Feng; Chen, Wang

2010-05-01

Mercury speciation and distribution in a 660-MW tangential-fired utility boiler in Taiwan burning Australian and Chinese bituminous coal blends was investigated. Flue gases were simultaneously sampled at the selective catalytic reduction (SCR) inlet, the SCR outlet, the electrostatic precipitator (ESP) outlet, and the stack. Samplings of coal, lime, bottom ash/slag, fly ash, and gypsum slurry were also conducted. Results indicated that flue gases at the inlet to SCR contained a great potion of particle-bound mercury (Hg(p)), 59-92% of the total mercury. Removal of mercury was not observed for the SCR system. However, repartitioning of mercury species across the SCR occurred that significantly increased the portion of elemental mercury (Hg0) to up to 29% and oxidized mercury (Hg2+) to up to 33% in the SCR outlet gas. Overreporting of Hg(p) at the inlet of SCR may cause the observed repartitioning; the high ammonia/nitric oxide circumstance in the SCR unit was also speculated to cause the mercury desorption from ash particles and subsequent reentrance into the gas phase. ESP can remove up to 99% of Hg(p), and wet flue gas desulfurization (FGD) can remove up to 84% of Hg2+. Mercury mass balances were calculated to range between 81 and 127.4%, with an average of 95.7% wherein 56-82% was in ESP fly ash, 8.7-18.6% was retained in the FGD gypsum, and 6.2-26.1% was emitted from the stack. Data presented here suggest that mercury removal can be largely enhanced by increasing the conversion of Hg0 into Hg(p) and Hg2+.

Simultaneous determination of arsenic and mercury species in rice by ion-pairing reversed phase chromatography with inductively coupled plasma mass spectrometry.

PubMed

Fang, Yong; Pan, Yushi; Li, Peng; Xue, Mei; Pei, Fei; Yang, Wenjian; Ma, Ning; Hu, Qiuhui

2016-12-15

An analytical method using reversed phase chromatography-inductively coupled plasma mass spectrometry for arsenic and mercury speciation analysis was described. The effect of ion-pairing reagent on simultaneous separation of four arsenic (arsenite, arsenate, monomethlyarsonate and dimethylarsinate) and three mercury species (inorganic mercury (Hg(II)), methylmecury and ethylmercury) was investigated. Parameters including concentrations and pH of the mobile phase were optimized. The separation and re-equilibration time was attained within 20min. Meanwhile, a sequential extraction method for arsenic and mercury in rice was tested. Subsequently, 1% HNO3 microwave-assisted extraction was chosen. Calibration curves based on peak area measurements were linear with correlation coefficient greater than 0.9958 for each species in the range studied. The detection limits of the species were in the range of 0.84-2.41μg/L for arsenic and 0.01-0.04μg/L for mercury, respectively. The proposed method was then successfully applied for the simultaneous determination of arsenic and mercury species in rice flour standard material and two kinds of rice from local markets. Copyright © 2016 Elsevier Ltd. All rights reserved.

Analysis of Halogen-Mercury Reactions in Flue Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paula Buitrago; Geoffrey Silcox; Constance Senior

2010-01-01

Oxidized mercury species may be formed in combustion systems through gas-phase reactions between elemental mercury and halogens, such as chorine or bromine. This study examines how bromine species affect mercury oxidation in the gas phase and examines the effects of mixtures of bromine and chlorine on extents of oxidation. Experiments were conducted in a bench-scale, laminar flow, methane-fired (300 W), quartz-lined reactor in which gas composition (HCl, HBr, NO{sub x}, SO{sub 2}) and temperature profile were varied. In the experiments, the post-combustion gases were quenched from flame temperatures to about 350 C, and then speciated mercury was measured using amore » wet conditioning system and continuous emissions monitor (CEM). Supporting kinetic calculations were performed and compared with measured levels of oxidation. A significant portion of this report is devoted to sample conditioning as part of the mercury analysis system. In combustion systems with significant amounts of Br{sub 2} in the flue gas, the impinger solutions used to speciate mercury may be biased and care must be taken in interpreting mercury oxidation results. The stannous chloride solution used in the CEM conditioning system to convert all mercury to total mercury did not provide complete conversion of oxidized mercury to elemental, when bromine was added to the combustion system, resulting in a low bias for the total mercury measurement. The use of a hydroxylamine hydrochloride and sodium hydroxide solution instead of stannous chloride showed a significant improvement in the measurement of total mercury. Bromine was shown to be much more effective in the post-flame, homogeneous oxidation of mercury than chlorine, on an equivalent molar basis. Addition of NO to the flame (up to 400 ppmv) had no impact on mercury oxidation by chlorine or bromine. Addition of SO{sub 2} had no effect on mercury oxidation by chlorine at SO{sub 2} concentrations below about 400 ppmv; some increase in mercury oxidation was observed at SO{sub 2} concentrations of 400 ppmv and higher. In contrast, SO{sub 2} concentrations as low as 50 ppmv significantly reduced mercury oxidation by bromine, this reduction could be due to both gas and liquid phase interactions between SO{sub 2} and oxidized mercury species. The simultaneous presence of chlorine and bromine in the flue gas resulted in a slight increase in mercury oxidation above that obtained with bromine alone, the extent of the observed increase is proportional to the chlorine concentration. The results of this study can be used to understand the relative importance of gas-phase mercury oxidation by bromine and chlorine in combustion systems. Two temperature profiles were tested: a low quench (210 K/s) and a high quench (440 K/s). For chlorine the effects of quench rate were slight and hard to characterize with confidence. Oxidation with bromine proved sensitive to quench rate with significantly more oxidation at the lower rate. The data generated in this program are the first homogeneous laboratory-scale data on bromine-induced oxidation of mercury in a combustion system. Five Hg-Cl and three Hg-Br mechanisms, some published and others under development, were evaluated and compared to the new data. The Hg-halogen mechanisms were combined with submechanisms from Reaction Engineering International for NO{sub x}, SO{sub x}, and hydrocarbons. The homogeneous kinetics under-predicted the levels of mercury oxidation observed in full-scale systems. This shortcoming can be corrected by including heterogeneous kinetics in the model calculations.« less

Effects of the soil microbial community on mobile proportions and speciation of mercury (Hg) in contaminated soil.

PubMed

Száková, Jiřina; Havlíčková, Jitka; Šípková, Adéla; Gabriel, Jiří; Švec, Karel; Baldrian, Petr; Sysalová, Jiřina; Coufalík, Pavel; Červenka, Rostislav; Zvěřina, Ondřej; Komárek, Josef; Tlustoš, Pavel

2016-01-01

The precise characterization of the behavior of individual microorganisms in the presence of increased mercury contents in soil is necessary for better elucidation of the fate of mercury in the soil environment. In our investigation, resistant bacterial strains isolated from two mercury contaminated soils, represented by Paenibacillus alginolyticus, Burkholderia glathei, Burkholderia sp., and Pseudomonas sp., were used. Two differently contaminated soils (0.5 and 7 mg kg(-1) total mercury) were chosen. Preliminary soil analysis showed the presence of methylmercury and phenylmercury with the higher soil mercury level. Modified rhizobox experiments were performed to assess the ability of mercury accumulating strains to deplete the mobile and mobilizable mercury portions in the soil by modification; microbial agar cultures were used rather than the plant root zone. A sequential extraction procedure was performed to release the following mercury fractions: water soluble, extracted in acidic conditions, bound to humic substances, elemental, and bound to complexes, HgS and residual. Inductively coupled plasma mass spectrometry (ICP-MS) and a single-purpose atomic absorption spectrometer (AMA-254) were applied for mercury determination in the samples and extracts. Gas chromatography coupled to atomic fluorescence spectrometry (GC-AFS) was used for the determination of organomercury compounds. The analysis of the microbial community at the end of the experiment showed a 42% abundance of Paenibacillus sp. followed by Acetivibrio sp., Brevibacillus sp., Cohnella sp., Lysinibacillus sp., and Clostridium sp. not exceeding 2% abundance. The results suggest importance of Paenibacillus sp. in Hg transformation processes. This genus should be tested for potential bioremediation use in further research.

Multi-model study of mercury dispersion in the atmosphere: vertical and interhemispheric distribution of mercury species

NASA Astrophysics Data System (ADS)

Bieser, Johannes; Slemr, Franz; Ambrose, Jesse; Brenninkmeijer, Carl; Brooks, Steve; Dastoor, Ashu; DeSimone, Francesco; Ebinghaus, Ralf; Gencarelli, Christian N.; Geyer, Beate; Gratz, Lynne E.; Hedgecock, Ian M.; Jaffe, Daniel; Kelley, Paul; Lin, Che-Jen; Jaegle, Lyatt; Matthias, Volker; Ryjkov, Andrei; Selin, Noelle E.; Song, Shaojie; Travnikov, Oleg; Weigelt, Andreas; Luke, Winston; Ren, Xinrong; Zahn, Andreas; Yang, Xin; Zhu, Yun; Pirrone, Nicola

2017-06-01

Atmospheric chemistry and transport of mercury play a key role in the global mercury cycle. However, there are still considerable knowledge gaps concerning the fate of mercury in the atmosphere. This is the second part of a model intercomparison study investigating the impact of atmospheric chemistry and emissions on mercury in the atmosphere. While the first study focused on ground-based observations of mercury concentration and deposition, here we investigate the vertical and interhemispheric distribution and speciation of mercury from the planetary boundary layer to the lower stratosphere. So far, there have been few model studies investigating the vertical distribution of mercury, mostly focusing on single aircraft campaigns. Here, we present a first comprehensive analysis based on various aircraft observations in Europe, North America, and on intercontinental flights. The investigated models proved to be able to reproduce the distribution of total and elemental mercury concentrations in the troposphere including interhemispheric trends. One key aspect of the study is the investigation of mercury oxidation in the troposphere. We found that different chemistry schemes were better at reproducing observed oxidized mercury patterns depending on altitude. High concentrations of oxidized mercury in the upper troposphere could be reproduced with oxidation by bromine while elevated concentrations in the lower troposphere were better reproduced by OH and ozone chemistry. However, the results were not always conclusive as the physical and chemical parameterizations in the chemistry transport models also proved to have a substantial impact on model results.

Methods for Investigating Mercury Speciation, Transport, Methylation, and Bioaccumulation in Watersheds Affected by Historical Mining

NASA Astrophysics Data System (ADS)

Alpers, C. N.; Marvin-DiPasquale, M. C.; Fleck, J.; Ackerman, J. T.; Eagles-Smith, C.; Stewart, A. R.; Windham-Myers, L.

2016-12-01

Many watersheds in the western U.S. have mercury (Hg) contamination from historical mining of Hg and precious metals (gold and silver), which were concentrated using Hg amalgamation (mid 1800's to early 1900's). Today, specialized sampling and analytical protocols for characterizing Hg and methylmercury (MeHg) in water, sediment, and biota generate high-quality data to inform management of land, water, and biological resources. Collection of vertically and horizontally integrated water samples in flowing streams and use of a Teflon churn splitter or cone splitter ensure that samples and subsamples are representative. Both dissolved and particulate components of Hg species in water are quantified because each responds to different hydrobiogeochemical processes. Suspended particles trapped on pre-combusted (Hg-free) glass- or quartz-fiber filters are analyzed for total mercury (THg), MeHg, and reactive divalent mercury. Filtrates are analyzed for THg and MeHg to approximate the dissolved fraction. The sum of concentrations in particulate and filtrate fractions represents whole water, equivalent to an unfiltered sample. This approach improves upon analysis of filtered and unfiltered samples and computation of particulate concentration by difference; volume filtered is adjusted based on suspended-sediment concentration to minimize particulate non-detects. Information from bed-sediment sampling is enhanced by sieving into multiple size fractions and determining detailed grain-size distribution. Wet sieving ensures particle disaggregation; sieve water is retained and fines are recovered by centrifugation. Speciation analysis by sequential extraction and examination of heavy mineral concentrates by scanning electron microscopy provide additional information regarding Hg mineralogy and geochemistry. Biomagnification of MeHg in food webs is tracked using phytoplankton, zooplankton, aquatic and emergent vegetation, invertebrates, fish, and birds. Analysis of zooplankton in multiple size fractions from multiple depths in reservoirs can provide insight into food-web dynamics. The presentation will highlight application of these methods in several Hg-contaminated watersheds, with emphasis on understanding seasonal variability in designing effective sampling strategies.

SPECIATION OF MERCURY IN THE PRESENCE OF COAL AND WASTE COMBUSTION FLY ASHES

EPA Science Inventory

The paper gives results of a study that focused on the oxidation of elemental mercury (Hgo) in the presence of both complex, four-component, model fly ashes, and actual coal combustion fly ashes collected from a pilot plant. Steady-state oxidation of Hgo promoted by the four-com...

Intracellular speciation and transformation of inorganic mercury in marine phytoplankton.

PubMed

Wu, Yun; Wang, Wen-Xiong

2014-03-01

Metal speciation is closely related to toxicity in aquatic organisms, but quantitative study of mercury transformation has rarely been reported. In this study, the ability of three marine phytoplankton species, including a green alga Chlorella autotrophica, a flagellate Isochrysis galbana and a diatom Thalassiosira weissflogii, to convert inorganic mercury were examined. We found that all algae tested were able to transform Hg(II) into dissolved gaseous mercury (DGM), phytochelatin (PC) complexes and metacinnabar (β-HgS). The most tolerant species, T. weissflogii, generally produced the highest level of PCs and β-HgS. Attributed to the highest DGM production ability, C. autotrophica accumulated the least Hg, but was the most sensitive due to low PC induction and β-HgS formation. Of the added Hg(II), less than 5% was reduced to DGM per day in all species. Of the intracellular Hg, <20% and 20-90% were chelated by PCs and transformed into β-HgS, respectively. These results suggest that intracellular biotransformation might be more important than bioavailability regulation in Hg(II) detoxification in marine phytoplankton. Copyright © 2014 Elsevier B.V. All rights reserved.

Selenium inhibits the phytotoxicity of mercury in garlic (Allium sativum)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Jiating; Gao, Yuxi, E-mail: gaoyx@ihep.ac.cn; Li, Yu-Feng

2013-08-15

To investigate the influence of selenium on mercury phytotoxicity, the levels of selenium and mercury were analyzed with inductively coupled plasma-mass spectrometry (ICP-MS) in garlic tissues upon exposure to different dosages of inorganic mercury (Hg{sup 2+}) and selenite (SeO{sub 3}{sup 2−}) or selenate (SeO{sub 4}{sup 2−}). The distributions of selenium and mercury were examined with micro-synchrotron radiation X-ray fluorescence (μ-SRXRF), and the mercury speciation was investigated with micro-X-ray absorption near edge structure (μ-XANES). The results show that Se at higher exposure levels (>1 mg/L of SeO{sub 3}{sup 2−} or SeO{sub 4}{sup 2−}) would significantly inhibit the absorption and transportation ofmore » Hg when Hg{sup 2+} levels are higher than 1 mg/L in culture media. SeO{sub 3}{sup 2−} and SeO{sub 4}{sup 2−} were found to be equally effective in reducing Hg accumulation in garlic. The inhibition of Hg uptake by Se correlates well with the influence of Se on Hg phytotoxicity as indicated by the growth inhibition factor. Elemental imaging using μ-SRXRF also shows that Se could inhibit the accumulation and translocation of Hg in garlic. μ-XANES analysis shows that Hg is mainly present in the forms of Hg–S bonding as Hg(GSH){sub 2} and Hg(Met){sub 2}. Se exposure elicited decrease of Hg–S bonding in the form of Hg(GSH){sub 2}, together with Se-mediated alteration of Hg absorption, transportation and accumulation, may account for attenuated Hg phytotoxicity by Se in garlic. -- Highlights: ► Hg phytotoxicity can be mitigated by Se supplement in garlic growth. ► Se can inhibit the accumulation and transportation of Hg in garlic tissues. ► Localization and speciation of Hg in garlic can be modified by Se.« less

Mercury emissions during cofiring of sub-bituminous coal and biomass (chicken waste, wood, coffee residue, and tobacco stalk) in a laboratory-scale fluidized bed combustor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan Cao; Hongcang Zhou; Junjie Fan

Four types of biomass (chicken waste, wood pellets, coffee residue, and tobacco stalks) were cofired at 30 wt % with a U.S. sub-bituminous coal (Powder River Basin Coal) in a laboratory-scale fluidized bed combustor. A cyclone, followed by a quartz filter, was used for fly ash removal during tests. The temperatures of the cyclone and filter were controlled at 250 and 150{sup o}C, respectively. Mercury speciation and emissions during cofiring were investigated using a semicontinuous mercury monitor, which was certified using ASTM standard Ontario Hydra Method. Test results indicated mercury emissions were strongly correlative to the gaseous chlorine concentrations, butmore » not necessarily correlative to the chlorine contents in cofiring fuels. Mercury emissions could be reduced by 35% during firing of sub-bituminous coal using only a quartz filter. Cofiring high-chlorine fuel, such as chicken waste (Cl = 22340 wppm), could largely reduce mercury emissions by over 80%. When low-chlorine biomass, such as wood pellets (Cl = 132 wppm) and coffee residue (Cl = 134 wppm), is cofired, mercury emissions could only be reduced by about 50%. Cofiring tobacco stalks with higher chlorine content (Cl = 4237 wppm) did not significantly reduce mercury emissions. Gaseous speciated mercury in flue gas after a quartz filter indicated the occurrence of about 50% of total gaseous mercury to be the elemental mercury for cofiring chicken waste, but occurrence of above 90% of the elemental mercury for all other cases. Both the higher content of alkali metal oxides or alkali earth metal oxides in tested biomass and the occurrence of temperatures lower than 650{sup o}C in the upper part of the fluidized bed combustor seemed to be responsible for the reduction of gaseous chlorine and, consequently, limited mercury emissions reduction during cofiring. 36 refs., 3 figs. 1 tab.« less

Impact of the addition of chicken litter on mercury speciation and emissions from coal combustion in a laboratory-scale fluidized bed combustor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Songgeng Li; Shuang Deng; Andy Wu

Co-combustion of chicken litter with coal was performed in a laboratory-scale fluidized bed combustor to investigate the effect of chicken litter addition on the partitioning behavior of mercury. Gaseous total and elemental mercury concentrations in the flue gas were measured online, and ash was analyzed for particle-bound mercury along with other elemental and surface properties. The mercury mass balance was between 85 and 105%. The experimental results show that co-combustion of chicken litter decreases the amount of elemental and total mercury in the gas phase. Mercury content in fly ash increases with an increasing chicken litter share. 22 refs., 6more » figs., 5 tabs.« less

Nested-grid simulation of mercury over North America

NASA Astrophysics Data System (ADS)

Zhang, Y.; Jaeglé, L.; van Donkelaar, A.; Martin, R. V.; Holmes, C. D.; Amos, H. M.; Wang, Q.; Talbot, R.; Artz, R.; Brooks, S.; Luke, W.; Holsen, T. M.; Felton, D.; Miller, E. K.; Perry, K. D.; Schmeltz, D.; Steffen, A.; Tordon, R.; Weiss-Penzias, P.; Zsolway, R.

2012-01-01

We have developed a new high-resolution (1/2° latitude by 2/3° longitude) nested-grid mercury (Hg) simulation over North America employing the GEOS-Chem global chemical transport model. Emissions, chemistry, deposition, and meteorology are self-consistent between the global and nested domains. Compared to the global model (4° latitude by 5° longitude), the nested model shows improved skill at capturing the high spatial and temporal variability of Hg wet deposition over North America observed by the Mercury Deposition Network (MDN) in 2008-2009. The nested simulation resolves features such as land/ocean contrast and higher deposition due to orographic precipitation, and predicts more efficient convective rain scavenging of Hg over the southeast United States. However, the nested model overestimates Hg wet deposition over the Ohio River Valley region (ORV) by 27%. We modify anthropogenic emission speciation profiles in the US EPA National Emission Inventory (NEI) to account for the rapid in-plume reduction of reactive to elemental Hg (IPR simulation). This leads to a decrease in the model bias to +3% over the ORV region. Over the contiguous US, the correlation coefficient (r) between MDN observations and our IPR simulation increases from 0.63 to 0.78. The IPR nested simulation generally reproduces the seasonal cycle in surface concentrations of speciated Hg from the Atmospheric Mercury Network (AMNet) and Canadian Atmospheric Mercury Network (CAMNet). In the IPR simulation, annual mean reactive gaseous and particulate-bound Hg are within 80% and 10% of observations, respectively. In contrast, the simulation with unmodified anthropogenic Hg speciation profiles overestimates these observations by factors of 2 to 4. The nested model shows improved skill at capturing the horizontal variability of Hg observed over California during the ARCTAS aircraft campaign. We find that North American anthropogenic emissions account for 10-22% of Hg wet deposition flux over the US, depending on the anthropogenic emissions speciation profile assumed. The percent contribution can be as high as 60% near large point emission sources in ORV. The contribution for the dry deposition is 13-20%.

Self-Assembled Mercaptan on Mesoporous Silica (SAMMS) technology of mercury removal and stabilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Xiangdong; Liu, Jun; Fryxell, G.E.

1997-09-01

This paper explains the technology developed to produce Self-Assembled Mercaptan on Mesoporous Silica (SAMMS) for mercury removal from aqueous wastewater and from organic wastes. The characteristics of SAMMS materials, including physical characteristics and mercury loading, and its application for mercury removal and stabilization are discussed. Binding kinetics and binding speciations are reported. Preliminary cost estimates are provided for producing SAMMS materials and for mercury removal from wastewater. The characteristics of SAMMS in mercury separation were studied at PNNL using simulated aqueous tank wastes and actual tritiated pump oil wastes from Savannah River Site; preliminary results are outlined. 47 refs., 16more » figs., 16 tabs.« less

How incense and joss paper burning during the worship activities influences ambient mercury concentrations in indoor and outdoor environments of an Asian temple?

PubMed

Shen, Huazhen; Tsai, Cheng-Mou; Yuan, Chung-Shin; Jen, Yi-Hsiu; Ie, Iau-Ren

2017-01-01

This study firstly investigated the species, concentration variation, and emission factors of mercury emitted from the burning of incenses and joss papers in an Asian temple. Both indoor and outdoor speciated mercury (GEM, GOM, and PHg) were sampled by manual samplers, while ambient GEM at an indoor site was in-situ monitored by a continuous GEM monitor. Field measurement results showed that the total atmospheric mercury (TAM) concentrations in indoor and outdoor environments were in the range of 8.03-35.72 and 6.03-31.35 ng/m 3 , respectively. The indoor and outdoor ratios (I/O) of TAM in the daytime and at nighttime were in the range of 0.64-0.90 and 1.50-2.04, respectively. The concentrations of GEM, GOM, and PHg during the holiday periods were approximately 1-4 times higher than those during the non-holiday periods. GEM was the dominant mercury species in the indoor and outdoor environments and accounted for 63-81% of TAM, while the oxidized mercury accounted for 19-37% of TAM. Burning incenses and joss papers in a combustion chamber showed that the concentration of GEM from joss paper burning ranged from 4.07 to 11.62 μg/m 3 , or about 13.97 times higher than that of incense burning, while the concentration of PHg from incense burning ranged from 95.91 to 135.07 ng/m 3 , or about 3.29 times higher than that of joss paper burning. The emission factors of incense burning were 10.39 ng/g of GEM and 1.40 ng/g of PHg, while those of joss paper burning were 12.65 ng/g of GEM and 1.27 ng/g of PHg, respectively. This study revealed that speciated mercury emitted from worship activities had significant influence on the indoor and outdoor mercury concentrations in an Asian temple. Higher intensity of worship activities during holidays resulted in a higher concentration of speciated mercury in indoor and outdoor air, which might cause health threats to worshipers, staffs, and surrounding inhabitants through long-term exposure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ion-imprinted polymethacrylic microbeads as new sorbent for preconcentration and speciation of mercury.

PubMed

Dakova, Ivanka; Karadjova, Irina; Georgieva, Ventsislava; Georgiev, George

2009-04-30

Metal ion-imprinted polymer particles have been prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as cross-linking agent and 2,2'-azobisisobutyronitrile as initiator, in the presence of Hg(II)-1-(2-thiazolylazo)-2-naphthol complex. The separation and preconcentration characteristics of the Hg-ion-imprinted microbeads for inorganic mercury have been investigated by batch procedure. The optimal pH value for the quantitative sorption is 7. The adsorbed inorganic mercury is easily eluted by 2 mL 4M HNO(3). The adsorption capacity of the newly synthesized Hg ion-imprinted microbeads is 32.0 micromol g(-1) for dry copolymer. The selectivity of the copolymer toward inorganic mercury (Hg(II)) ion is confirmed through the comparison of the competitive adsorptions of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II)) and high values of the selectivity and distribution coefficients have been calculated. Experiments performed for selective determination of inorganic mercury in mineral and sea waters showed that the interfering matrix does not influence the extraction efficiency of Hg ion-imprinted microbeads. The detection limit for inorganic mercury is 0.006 microg L(-1) (3 sigma), determined by cold vapor atomic adsorption spectrometry. The relative standard deviation varied in the range 5-9 % at 0.02-1 microg L(-1) Hg levels. The new Hg-ion-imprinted microbeads have been tested and applied for the speciation of Hg in river and mineral waters: inorganic mercury has been determined selectively in nondigested sample, while total mercury e.g. sum of inorganic and methylmercury, has been determined in digested sample.

Uncertainty Assessment of Gaseous Oxidized Mercury Measurements Collected by Atmospheric Mercury Network.

PubMed

Cheng, Irene; Zhang, Leiming

2017-01-17

Gaseous oxidized mercury (GOM) measurement uncertainties undoubtedly impact the understanding of mercury biogeochemical cycling; however, there is a lack of consensus on the uncertainty magnitude. The numerical method presented in this study provides an alternative means of estimating the uncertainties of previous GOM measurements. Weekly GOM in ambient air was predicted from measured weekly mercury wet deposition using a scavenging ratio approach, and compared against field measurements of 2-4 hly GOM to estimate the measurement biases of the Tekran speciation instruments at 13 Atmospheric Mercury Network (AMNet) sites. Multiyear average GOM measurements were estimated to be biased low by more than a factor of 2 at six sites, between a factor of 1.5 and 1.8 at six other sites, and below a factor of 1.3 at one site. The differences between predicted and observed were significantly larger during summer than other seasons potentially because of higher ozone concentrations that may interfere with GOM sampling. The analysis data collected over six years at multiple sites suggests a systematic bias in GOM measurements, supporting the need for further investigation of measurement technologies and identifying the chemical composition of GOM.

Fate and transport of mercury in soil systems : a numerical model in HP1 and sensitivity analysis

NASA Astrophysics Data System (ADS)

Leterme, Bertrand; Jacques, Diederik

2013-04-01

Mercury (Hg) poses threats for human health and the environment, notably due to its persistence and its ability to bioaccumulate in ecosystems. Anthropogenic activities are major contributors of mercury release to soils. Main sources of contamination include manufacturing (chlor-alkali plants, manometer spill), mine tailings from mercury, gold and silver mining industries, wood preservation. The objective of this study was to develop a reactive transport model for simulating mercury fate and transport in the unsaturated zone, and to gain insight in the fate and transport of Hg following anthropogenic soil contamination. The present work is done in the framework of the IMaHg project, which aims at providing recommendations to improve management of sites contaminated by mercury within the SNOWMAN funding framework. A model of mercury fate and transport in soil systems was developed using the reactive transport code HP1 (Jacques and Šimůnek, 2010). The geochemical database THERMODDEM (Blanc et al., 2012) is used, augmented with some speciation data from (Skyllberg, 2012). The main processes accounted for in the model are : Hg aqueous speciation (including complexation with dissolved organic matter (DOM) - humic and fulvic acids, and thiol groups), Hg sorption to solid organic matter (SOM), dissolution of solid phase Hg (e.g. cinnabar HgS(s)), dissolution of Hg non-aqueous liquid phase (NAPL), sunlight-driven Hg(II) reduction to Hg(0), Hg(0) diffusion in the gas phase and volatilization, DOM sorption to soil minerals. Colloid facilitated transport is implicitly accounted for by solute transport of Hg-DOM complexes. Because we focused on soil systems having a high Hg contamination, some processes showing relatively smaller Hg fluxes could be neglected such as vegetation uptake and atmospheric wet and dry deposition. NAPL migration and entrapment is not modelled, as pollution is assumed to be historical and only residual NAPL to be present. Mercury methylation and demethylation was not implemented, because it could be neglected in an oxidising environment. However, if the model is to be tested in more reducing conditions (e.g. shallow groundwater table), methyl- and dimethylmercury formation can be non negligible. Using 50 year time series of daily weather observations in Dessel (Belgium) and a typical sandy soil with deep groundwater (free drainage, oxic conditions), a sensitivity analysis was performed to assess the relative importance of processes and parameters within the model. We used the elementary effects method (Morris, 1991; Campolongo et al., 2007), which draws trajectories across the parameter space to derive information on the global sensitivity of the selected input parameters. The impact of different initial contamination phases (solid, NAPL, aqueous and combinations of these) was also tested. Simulation results are presented in terms of (i) Hg volatilized to the atmosphere; (ii) Hg leached out of the soil profile; (iii) Hg still present in the soil horizon originally polluted; and (iv) Hg still present in the soil profile but below the original contaminated horizon. Processes and parameters identified as critical based on the sensitivity analysis differ from one scenario to the other ; depending on pollution type (cinnabar, NAPL, aqueous Hg), on the indicator assessed and on time (after 5, 25 or 50 years). However, in general DOM in soil water was the most critical parameter. Other important parameters were those related to Hg sorption on SOM (thiols, and humic and fulvic acids), and to Hg complexation with DOM. Initial Hg concentration was also often identified as a sensitive parameter. Interactions between factors and non linear effects as measured by the elementary effect method were generally important, but also dependent on the type of contamination and on time. No model calibration was performed until now. The numerical tool could greatly benefit from partial model calibration and/or validation. Ideally, detailed speciation data on a contaminated sites would be required, together with a good characterization of the pollution source. References : Blanc, P., Lassin, A. and Piantone, P. (2012), THERMODDEM a database devoted to waste minerals, BRGM, Orléans, France. http://thermoddem.brgm.fr Campolongo, F., Cariboni, J. and Saltelli, A. (2007), An effective screening design for sensitivity analysis of large models, Environmental Modelling & Software 22(10): 1509-1518. Jacques, D. and Šimůnek, J. (2010), Notes on HP1 - a software package for simulating variably-saturated water flow, heat transport, solute transport and biogeochemistry in porous media, HP1 Version 2.2 SCK•CEN-BLG-1068, Waste & Disposal Department, SCK•CEN, Mol, Belgium: 113 p. Morris, M. D. (1991), Factorial Sampling Plans for Preliminary Computational Experiments, Technometrics 33(2): 161-174. Skyllberg, U. (2012), Chemical Speciation of Mercury in Soil and Sediment. Environmental Chemistry and Toxicology of Mercury, John Wiley & Sons, Inc.: 219-258.

Diversity, community structure, and bioremediation potential of mercury-resistant marine bacteria of estuarine and coastal environments of Odisha, India.

PubMed

Dash, Hirak R; Das, Surajit

2016-04-01

Both point and non-point sources increase the pollution status of mercury and increase the population of mercury-resistant marine bacteria (MRMB). They can be targeted as the indicator organism to access marine mercury pollution, besides utilization in bioremediation. Thus, sediment and water samples were collected for 2 years (2010-2012) along Odisha coast of Bay of Bengal, India. Mercury content of the study sites varied from 0.47 to 0.99 ppb irrespective of the seasons of sampling. A strong positive correlation was observed between mercury content and MRMB population (P < 0.05) suggesting the utilization of these bacteria to assess the level of mercury pollution in the marine environment. Seventy-eight percent of the MRMB isolates were under the phylum Firmicutes, and 36 and 31% of them could resist mercury by mer operon-mediated volatilization and mercury biosorption, respectively. In addition, most of the isolates could resist a number of antibiotics and toxic metals. All the MRMB isolates possess the potential of growth and survival at cardinal pH (4-8), temperature (25-37 °C), and salinity (5-35 psu). Enterobacteria repetitive intergenic consensus (ERIC) and repetitive element palindromic PCR (REP-PCR) produced fingerprints corroborating the results of 16S rRNA gene sequencing. Fourier transform infrared (FTIR) spectral analysis also revealed strain-level speciation and phylogenetic relationships.

Legacy Mercury in Alviso Slough, South San Francisco Bay, California: Concentration, Speciation and Mobility

USGS Publications Warehouse

Marvin-DiPasquale, Mark; Cox, Marisa H.

2007-01-01

Mercury (Hg) is a significant contaminant in the waters, sediment and biota of San Francisco Bay, largely resulting from extensive historic regional mining activities. Alviso Slough represents one of the most mercury contaminated waterways entering south San Francisco Bay, as it is associated with the drainage of the New Almaden mercury mining district. Wetland habitat restoration of former salt manufacturing ponds adjacent to Alviso Slough is currently being planned. One management scenario being considered is a levee breach between Alviso Slough and Pond A8, which will allow reconnection of the salt pond with the tidal slough. This action is projected to increase the tidal prism within Alviso Slough and result in some degree of sediment remobilization as the main channel deepens and widens. The focus of the current study is to assess: a) the current mercury species composition and concentration in sediments within the Alviso Slough main channel and its associated fringing marsh plain, b) how much of each mercury species will be mobilized as a result of projected channel deepening and widening, and c) potential changes in inorganic reactive mercury bioavailability (for conversion to toxic methylmercury) associated with the mobilized sediment fraction. The current report details the field sampling approach and all laboratory analyses conducted, as well as provides the complete dataset associated with this project including a) a quantitative assessment of mercury speciation (total mercury, reactive mercury and methylmercury), b) estimates of the quantity of sediment and mercury mobilized based on 20-foot and 40-foot levee wall notch scenarios, and c) results from a sediment scour experiment examining the changes in the reactive mercury pool under four treatment conditions (high / low salinity and oxic / anoxic water). Ancillary sediment data also collected and reported herein include bulk density, organic content, magnetic susceptibility, percent dry weight, grain size, pH, oxidation-reduction potential, core photography, and detailed lithographic descriptions.

MERCURY SPECIATION IN COMBUSTION SYSTEMS: STUDIES WITH SIMULATED FLUE GASES AND MODEL FLY ASHES

EPA Science Inventory

The paper gives results of a bench-scale study of the effects of flue gas and fly ash parameters on the oxidation of elemental mercury in simulated flue gases containing hydrogen chloride (HCl), nitric oxide (NO), nitrogen dioxide (NO2), sulfur dioxide (SO2), and water vapor (H2O...

Phytoremediation of ionic and methylmercury pollution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meagher, Richard B.

2010-04-28

Our long-term goal is to enable highly productive plant species to extract, resist, detoxify, and sequester the toxic elemental pollutants, like the heavy metal mercury. Our current working hypothesis is that transgenic plants controlling the transport, chemical speciation, electrochemical state. volatilization, and aboveground binding of mercury will: a) tolerate mercury and grow rapidly in mercury contaminated environments; b) prevent methylmercury from entering the food chain; c) remove mercury from polluted soil and water; and d) hyperaccumulate mercury in aboveground tissues for later harvest. Progress toward these specific aims is reported: to increase the transport of mercury into roots and tomore » aboveground vegetative organs; to increase biochemical sinks and storage for mercury in leaves; to increase leaf cell vacuolar storage of mercury; and to demonstrate that several stacked transgenes, when functioning in concert, enhance mercury resistance and hyperaccumulation to high levels.« less

Mercury speciation in piscivorous fish from mining-impacted reservoirs

USGS Publications Warehouse

Kuwabara, J.S.; Arai, Y.; Topping, B.R.; Pickering, I.J.; George, G.N.

2007-01-01

Guadalupe Reservoir (GUA), California, and Lahontan Reservoir (LAH), Nevada, U.S. are both affected either directly or indirectly by the legacy of gold and silver mining in the Sierra Nevada during the nineteenth century. Analysis of total mercury in fish from these lentic systems consistently indicate elevated concentrations (>1 ??g??g-1 wet weight; hereinafter, all concentrations are reported as wet weight unless indicated otherwise) well above the U.S. Environmenal Protection Agency's human consumption advisory level for fish (<0.3 ??g??g-1). Replicate X-ray absorption near edge structure (XANES) analyses on largemouth bass and hybrid striped bass from GUA and LAH were performed to determine predominant chemical species of mercury accumulated by these high-trophic-level piscivores that are exposed to elevated mercury through trophic transfer in mining-impacted lentic systems. Despite distinct differences in mercury source, the proximity of the source, and concentrations of complexing ligands, results of XANES analysis clearly indicated that mercury accumulated in these individual fish from the two reservoirs were dominated by methylmercury cysteine complexes. These findings are consistent with results from commercial fish species inhabiting marine environments which are presumed to include differing mercury sources (e.g., atmospheric, hydrothermal, or benthic). The dominance of methylmercury cysteine complexes in muscle tissues of fish obtained from such contrasting environments and exposure conditions suggests that a generic toxicological model for the consumption of fish could be applicable over a wide range of ecologic settings. ?? 2007 American Chemical Society.

Environmental controls on the speciation and distribution of mercury in surface sediments of a tropical estuary, India.

PubMed

Chakraborty, Parthasarathi; Babu, P V Raghunadh

2015-06-15

Distribution and speciation of mercury (Hg) in the sediments from a tropical estuary (Godavari estuary) was influenced by the changing physico-chemical parameters of the overlying water column. The sediments from the upstream and downstream of the estuary were uncontaminated but the sediments from the middle of the estuary were contaminated by Hg. The concentrations of Hg became considerably less during the monsoon and post monsoon period. Total Hg concentrations and its speciation (at the middle of the estuary) were dependent on the salinity of the overlying water column. However, salinity had little or no effect on Hg association with organic phases in the sediments at downstream. Increasing pH of the overlying water column corresponded with an increase in the total Hg content in the sediments. Total organic carbon in the sediments played an important role in controlling Hg partitioning in the system. Uncomplexed Hg binding ligands were available in the sediments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Speciation of mercury in sludge solids: washed sludge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.; Lourie, A. P.

2017-10-24

The objective of this applied research task was to study the type and concentration of mercury compounds found within the contaminated Savannah River Site Liquid Waste System (SRS LWS). A method of selective sequential extraction (SSE), developed by Eurofins Frontier Global Sciences1,2 and adapted by SRNL, utilizes an extraction procedure divided into seven separate tests for different species of mercury. In the SRNL’s modified procedure four of these tests were applied to a washed sample of high level radioactive waste sludge.

Method development estimating ambient mercury concentration from monitored mercury wet deposition

NASA Astrophysics Data System (ADS)

Chen, S. M.; Qiu, X.; Zhang, L.; Yang, F.; Blanchard, P.

2013-05-01

Speciated atmospheric mercury data have recently been monitored at multiple locations in North America; but the spatial coverage is far less than the long-established mercury wet deposition network. The present study describes a first attempt linking ambient concentration with wet deposition using Beta distribution fitting of a ratio estimate. The mean, median, mode, standard deviation, and skewness of the fitted Beta distribution parameters were generated using data collected in 2009 at 11 monitoring stations. Comparing the normalized histogram and the fitted density function, the empirical and fitted Beta distribution of the ratio shows a close fit. The estimated ambient mercury concentration was further partitioned into reactive gaseous mercury and particulate bound mercury using linear regression model developed by Amos et al. (2012). The method presented here can be used to roughly estimate mercury ambient concentration at locations and/or times where such measurement is not available but where wet deposition is monitored.

Magnetic solid phase extraction coupled with inductively coupled plasma mass spectrometry for the speciation of mercury in environmental water and human hair samples.

PubMed

Ma, Shishuai; He, Man; Chen, Beibei; Deng, Wenchao; Zheng, Qi; Hu, Bin

2016-01-01

In this work, γ-mercaptopropyltrimethoxysilane (γ-MPTS) modified Fe3O4@SiO2 magnetic nanoparticles (MNPs) was successfully prepared, and characterized by Fourier transform infrared spectrometer (FT-IR), Transmission electron microscope (TEM) and Vibrating sample magnetometer (VSM). The sorption performance of the prepared Fe3O4@SiO2@γ-MPTS MNPs towards methylmercury (CH3Hg(+)) and inorganic mercury (Hg(2+)) was investigated. It was found that CH3Hg(+) and Hg(2+) could be simultaneously retained on the prepared Fe3O4@SiO2@γ-MPTS MNPs, and the quantitative elution of CH3Hg(+) and total mercury (THg) was achieved by using 1.5 mol L(-1) HCl containing 0.01% and 3% thiourea (m/v), respectively. And the levels of Hg(2+) were obtained by subtracting CH3Hg(+) from THg. Based on the above facts, a method of magnetic solid phase extraction (MSPE) combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for the speciation of CH3Hg(+) and Hg(2+). Various experimental parameters affecting MSPE of CH3Hg(+) and Hg(2+) such as pH, eluent, sample volume, and co-existing ions have been studied. Under the optimized conditions, the limits of detection (LODs) for CH3Hg(+) and THg were 1.6 and 1.9 ng L(-1), respectively. The accuracy of the proposed method was validated by analysis of a Certified Reference Material NRCC DORM-2 dogfish muscle, and the determined values are in good agreement with the certified values. The proposed method has also been successfully applied for the speciation of CH3Hg(+) and Hg(2+) in environmental water and human hair samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparion of Mercury Emissions Between Circulating Fluidized Bed Boiler and Pulverized Coal Boiler

NASA Astrophysics Data System (ADS)

Wang, Y. J.; Duan, Y. F.; Zhao, C. S.

Mercury emissions between a circulating fluidized bed (CFB) utility boiler and two pulverized coal (PC) boilers equipped with electrostatic precipitators (ESP) were in situ measured and compared. The standard Ontario Hydro Method (OHM) was used to sample the flue gas before and after the ESP. Various mercury speciations such as Hg0, Hg2+ and Hgp in flue gas and total mercury in fly ashes were analyzed. The results showed that the mercury removal rate of the CFB boiler is nearly 100%; the mercury emission in stack is only 0.028 g/h. However, the mercury removal rates of the two PC boilers are 27.56% and 33.59% respectively, the mercury emissions in stack are 0.80 and 51.78 g/h respectively. It concluded that components of the ESP fly ashes especially their unburnt carbons have remarkable influence on mercury capture. Pore configurations of fine fly ash particles have non-ignored impacts on mercury emissions.

Mercury speciation on three European mining districts by XANES techniques

NASA Astrophysics Data System (ADS)

Esbri, J. M.; Garcia-Noguero, E. M.; Guerrero, B.; Kocman, D.; Bernaus, A.; Gaona, X.; Higueras, P.; Alvarez, R.; Loredo, J.; Horvat, M.; Ávila, M.

2009-04-01

The mobility, bioavailability and toxicity of mercury in the environment depend on the chemical species in which is present in soil, sediments, water or air. In this work we used synchrotron radiation to determine mercury species in geological samples of three mercury mining districts: Almadén (Spain), Idria (Slovenia) and Asturias (Spain). The aim of this study was to find differences on mobility and bioavailability of mercury on three mining districts with different type of mineralization. For this porpoises we selected samples of ore, calcines, soils and stream sediments from the three sites, completely characterized by the Almadén School of Mines, Josef Stefan Institute of Ljubljana and Oviedo School of Mines. Speciation of mercury was carried out on Synchrotron Laboratories of Hamburg (HASYLAB) by XANES techniques. Spectra of pure compounds [HgCl2, HgSO4, HgO, CH3HgCl, Hg2Cl2 (calomel), HgSred (cinnabar), HgSblack (metacinnabar), Hg2NCl0.5(SO4)0.3(MoO4)0.1(CO3)0.1(H2O) (mosesite), Hg3S2Cl2 (corderoite), Hg3(SO4)O2 (schuetteite) y Hg2ClO (terlinguaite)] were obtained on transmittance mode. The number and type of the compounds required to reconstruct experimental spectra for each sample was obtained by PCA analysis and linear fitting of minimum quadratics of the pure compounds spectra. This offers a semiquantitative approach to the mineralogical constitution of each analyzed sample. The results put forward differences on the efficiency of roasting furnaces from the three studied sites, evidenced by the presence of metacinnabar on the less efficient (Almadén and Asturias) and absence on the most efficient (Idria). For the three studied sites, sulfide species (cinnabar and metacinnabar) were largely more abundant than soluble species (chlorides and sulfates). On the other hand, recent results on the mobility of both Hg and As on the target sites will be presented. These results correlate with the related chemical species found by XANES techniques.

Impacts of the Minamata Convention for Mercury Emissions from Coal-fired Power Generation in Asia

NASA Astrophysics Data System (ADS)

Giang, A.; Stokes, L. C.; Streets, D. G.; Corbitt, E. S.; Selin, N. E.

2014-12-01

We explore the potential implications of the recently signed United Nations Minamata Convention on Mercury for emissions from coal-fired power generation in Asia, and the impacts of these emissions changes on deposition of mercury worldwide by 2050. We use qualitative interviews, document analysis, and engineering analysis to create plausible technology scenarios consistent with the Convention, taking into account both technological and political factors. We translate these scenarios into possible emissions inventories for 2050, based on IPCC development scenarios, and then use the GEOS-Chem global transport model to evaluate the effect of these different technology choices on mercury deposition over geographic regions and oceans. We find that China is most likely to address mercury control through co-benefits from technologies for SO2, NOx, and particulate matter (PM) capture that will be required to attain its existing air quality goals. In contrast, India is likely to focus on improvements to plant efficiency such as upgrading boilers, and coal washing. Compared to current technologies, we project that these changes will result in emissions decreases of approximately 140 and 190 Mg/yr for China and India respectively in 2050, under an A1B development scenario. With these emissions reductions, simulated average gross deposition over India and China are reduced by approximately 10 and 3 μg/m2/yr respectively, and the global average concentration of total gaseous mercury (TGM) is reduced by approximately 10% in the Northern hemisphere. Stricter, but technologically feasible, requirements for mercury control in both countries could lead to an additional 200 Mg/yr of emissions reductions. Modeled differences in concentration and deposition patterns between technology suites are due to differences in both the mercury removal efficiency of technologies and their resulting stack speciation.

Final Technical Report: Mercury Release from Organic Matter (OM) and OM-Coated Mineral Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagy, Kathryn L.

2015-08-18

Chemical reactions between mercury, a neurotoxin, and sulfur, an essential nutrient, in the environment control to a large extent the distribution and amount of mercury available for uptake by living organisms. The largest reservoir of sulfur in soils is in living, decaying, and dissolved natural organic matter. The decaying and dissolved organic matter can also coat the surfaces of minerals in the soil. Mercury (as a divalent cation) can bind to the sulfur species in the organic matter as well as to the bare mineral surfaces, but the extent of binding and release of this mercury is not well understood.more » The goals of the research were to investigate fundamental relationships among mercury, natural organic matter, and selected minerals to better understand specifically the fate and transport of mercury in contaminated soils downstream from the Y-12 plant along East Fork Poplar Creek, Tennessee, and more generally in any contaminated soil. The research focused on (1) experiments to quantify the uptake and release of mercury from two clay minerals in the soil, kaolinite and vermiculite, in the presence and absence of dissolved organic matter; (2) release of mercury from cinnabar under oxic and anoxic conditions; (3) characterization of the forms of mercury in the soil using synchrotron X-ray absorption spectroscopic techniques; and, (4) determination of molecular forms of mercury in the presence of natural organic matter. We also leveraged funding from the National Science Foundation to (5) evaluate published approaches for determining sulfur speciation in natural organic matter by fitting X-ray Absorption Near Edge Structure (XANES) spectra obtained at the sulfur K-edge and apply optimized fitting schemes to new measurements of sulfur speciation in a suite of dissolved organic matter samples from the International Humic Substances Society. Lastly, in collaboration with researchers at the University of Colorado and the U.S. Geological Survey in Boulder, Colorado, (6) we investigated the biogeochemical controls on the release of mercury in simulated flooding experiments using loose soils and intact soil cores from East Fork Poplar Creek.« less

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques.

PubMed

Terzano, Roberto; Santoro, Anna; Spagnuolo, Matteo; Vekemans, Bart; Medici, Luca; Janssens, Koen; Göttlicher, Jörg; Denecke, Melissa A; Mangold, Stefan; Ruggiero, Pacifico

2010-08-01

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg(-1). Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as mu-XRF, mu-XRD and mu-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 microm. The main Hg-species found in the soil samples were metacinnabar (beta-HgS), cinnabar (alpha-HgS), corderoite (Hg(3)S(2)Cl(2)), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 microm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution. Copyright 2010 Elsevier Ltd. All rights reserved.

Mercury in aqueous tank waste at the Savannah River Site: Facts, forms, and impacts

DOE PAGES

Bannochie, C. J.; Fellinger, T. L.; Garcia-Strickland, P.; ...

2017-03-28

Over the past two years, there has been an intense effort to understand the chemistry of mercury across the Savannah River Site’s high-level liquid waste system to determine the impacts of various mercury species. This effort started after high concentrations of mercury were measured in the leachates from a toxicity characteristic leaching procedure (TCLP) test on the low-level cementitious waste form produced in the Savannah River Saltstone facility. Speciation showed the dominant form of leached mercury to be the methylmercury cation. Neither the source of the methylmercury nor its concentration in the Saltstone feed was well established at the timemore » of the testing. Finally, this assessment of mercury was necessary to inform points in the process operations that may be subject to new separation technologies for the removal of mercury.« less

Mercury in aqueous tank waste at the Savannah River Site: Facts, forms, and impacts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.; Fellinger, T. L.; Garcia-Strickland, P.

Over the past two years, there has been an intense effort to understand the chemistry of mercury across the Savannah River Site’s high-level liquid waste system to determine the impacts of various mercury species. This effort started after high concentrations of mercury were measured in the leachates from a toxicity characteristic leaching procedure (TCLP) test on the low-level cementitious waste form produced in the Savannah River Saltstone facility. Speciation showed the dominant form of leached mercury to be the methylmercury cation. Neither the source of the methylmercury nor its concentration in the Saltstone feed was well established at the timemore » of the testing. Finally, this assessment of mercury was necessary to inform points in the process operations that may be subject to new separation technologies for the removal of mercury.« less

In situ remediation technologies for mercury-contaminated soil

DOE PAGES

He, Feng; Gao, Jie; Pierce, Eric; ...

2015-04-09

A pollutant that poses significant risks to humans and the environment is mercury from anthropogenic activities. In soils, mercury remediation can be technically challenging and costly, depending on the subsurface mercury distribution, the types of mercury species, and the regulatory requirements. Our paper introduces the chemistry of mercury and its implications for in situ mercury remediation, which is followed by a detailed discussion of several in situ Hg remediation technologies in terms of applicability, cost, advantages, and disadvantages. The effect of Hg speciation on remediation performance, as well as Hg transformation during different remediation processes, was detailed. Thermal desorption, electrokinetic,more » and soil flushing/washing treatments are removal technologies that mobilize and capture insoluble Hg species, while containment, solidification/stabilization, and vitrification immobilize Hg by converting it to less soluble forms. We also discussed two emerging technologies, phytoremediation and nanotechnology, in this review.« less

In situ remediation technologies for mercury-contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Feng; Gao, Jie; Pierce, Eric

A pollutant that poses significant risks to humans and the environment is mercury from anthropogenic activities. In soils, mercury remediation can be technically challenging and costly, depending on the subsurface mercury distribution, the types of mercury species, and the regulatory requirements. Our paper introduces the chemistry of mercury and its implications for in situ mercury remediation, which is followed by a detailed discussion of several in situ Hg remediation technologies in terms of applicability, cost, advantages, and disadvantages. The effect of Hg speciation on remediation performance, as well as Hg transformation during different remediation processes, was detailed. Thermal desorption, electrokinetic,more » and soil flushing/washing treatments are removal technologies that mobilize and capture insoluble Hg species, while containment, solidification/stabilization, and vitrification immobilize Hg by converting it to less soluble forms. We also discussed two emerging technologies, phytoremediation and nanotechnology, in this review.« less

Trace-Level Automated Mercury Speciation Analysis

PubMed Central

Taylor, Vivien F.; Carter, Annie; Davies, Colin; Jackson, Brian P.

2011-01-01

An automated system for methyl Hg analysis by purge and trap gas chromatography (GC) was evaluated, with comparison of several different instrument configurations including chromatography columns (packed column or capillary), detector (atomic fluorescence, AFS, or inductively coupled plasma mass spectrometry, ICP-MS, using quadrupole and sector field ICP- MS instruments). Method detection limits (MDL) of 0.042 pg and 0.030 pg for CH3Hg+ were achieved with the automated Hg analysis system configured with AFS and ICPMS detection, respectively. Capillary GC with temperature programming was effective in improving resolution and decreasing retention times of heavier Hg species (in this case C3H7Hg+) although carryover between samples was increased. With capillary GC, the MDL for CH3Hg+ was 0.25 pg for AFS detection and 0.060 pg for ICP-MS detection. The automated system was demonstrated to have high throughput (72 samples analyzed in 8 hours) requiring considerably less analyst time than the manual method for methyl mercury analysis described in EPA 1630. PMID:21572543

Comparative study of atomic fluorescence spectroscopy and inductively coupled plasma mass spectrometry for mercury and arsenic multispeciation.

PubMed

Gómez-Ariza, José Luis; Lorenzo, Fernando; García-Barrera, Tamara

2005-05-01

Mercury and arsenic are two elements of undoubted importance owing to their toxic character. Although speciation of these elements has been developed separately, in this work for the first time the speciation of As and Hg using two atomic fluorescence detectors in a sequential ensemble is presented. A coupling based on the combination of high-performance liquid chromatography (where mercury and arsenic species are separated) and two atomic fluorescence detectors in series, with several online treatments, including photooxidation (UV) and hydride generation, has allowed the determination of mercury and arsenic compounds simultaneously. The detection limits for this device were 16, 3, 17, 12 and 8 ng mL(-1) for As(III), monomethylarsinic acid, As(V), Hg2+ and methylmercury, respectively. This coupling was compared with an analogous one based on inductively coupled plasma-mass spectrometry (ICP-MS) detection, with detection limits of 0.7, 0.5, 0.8, 0.9 and 1.1 ng mL(-1), respectively. Multispeciation based on ICP-MS exhibits better sensitivity than the coupling based on tandem atomic fluorescence, but this second device is a very robust system and exhibits obvious advantages related to the low cost of acquisition and maintenance, as well as easy handling, which makes it a suitable system for routine laboratories.

Solid-phase extraction-gas chromatography-mass spectrometry using a fullerene sorbent for the determination of inorganic mercury(II), methylmercury(I) and ethylmercury(I) in surface waters at sub-ng/ml levels.

PubMed

Muñoz, J; Gallego, M; Valcárcel, M

2004-11-05

A novel, straightforward solid-phase extraction system for the determination of inorganic mercury and organomercury compounds in water is proposed. The analytes, in a buffer medium at pH 4.5, are sorbed as diethyldithiocarbamate complexes on a C60 fullerene column an subsequently eluted and derivatized with sodium tetra-n-propylborate in ethyl acetate. Following elution, 1 microl of extract is injected into a gas chromatograph-mass spectrometer system. The proposed gas chromatography-mass spectrometry speciation method exhibits a linear range of 4-1 ng/ml, and a detection limit of 1.5 ng/l (sample volume, 50 ml). Its repeatibility, as relative standard deviation (RSD) (from 11 standards containing 50 ng/l for each analyte), is ca. 7%. No interferences from metals ions, such as Zn2+, Fe3+, Sb3+, As3+, Pb2+, Ni2+, Cu2+, Sn2+, Co2+, Mn2+ and Cd2+ were encountered at concentrations 1000 times higher than those of the mercury compounds. The method was used for the speciation of inorganic mercury, methylmercury and ethylmercury in various types of water including sea and waste water.

Fate and Transport of Mercury in Environmental Media and Human Exposure

PubMed Central

Kim, Moon-Kyung

2012-01-01

Mercury is emitted to the atmosphere from various natural and anthropogenic sources, and degrades with difficulty in the environment. Mercury exists as various species, mainly elemental (Hg0) and divalent (Hg2+) mercury depending on its oxidation states in air and water. Mercury emitted to the atmosphere can be deposited into aqueous environments by wet and dry depositions, and some can be re-emitted into the atmosphere. The deposited mercury species, mainly Hg2+, can react with various organic compounds in water and sediment by biotic reactions mediated by sulfur-reducing bacteria, and abiotic reactions mediated by sunlight photolysis, resulting in conversion into organic mercury such as methylmercury (MeHg). MeHg can be bioaccumulated through the food web in the ecosystem, finally exposing humans who consume fish. For a better understanding of how humans are exposed to mercury in the environment, this review paper summarizes the mechanisms of emission, fate and transport, speciation chemistry, bioaccumulation, levels of contamination in environmental media, and finally exposure assessment of humans. PMID:23230463

Distribution, speciation, and transport of mercury in stream-sediment, stream-water, and fish collected near abandoned mercury mines in southwestern Alaska, USA

USGS Publications Warehouse

Gray, J.E.; Theodorakos, P.M.; Bailey, E.A.; Turner, R.R.

2000-01-01

Concentrations of total Hg, Hg (II), and methylmercury were measured in stream-sediment, stream-water, and fish collected downstream from abandoned mercury mines in south-western Alaska to evaluate environmental effects to surrounding ecosystems. These mines are found in a broad belt covering several tens of thousands of square kilometers, primarily in the Kuskokwim River basin. Mercury ore is dominantly cinnabar (HgS), but elemental mercury (Hg(o)) is present in ore at one mine and near retorts and in streams at several mine sites. Approximately 1400 t of mercury have been produced from the region, which is approximately 99% of all mercury produced from Alaska. These mines are not presently operating because of low prices and low demand for mercury. Stream-sediment samples collected downstream from the mines contain as much as 5500 ??g/g Hg. Such high Hg concentrations are related to the abundance of cinnabar, which is highly resistant to physical and chemical weathering, and is visible in streams below mine sites. Although total Hg concentrations in the stream-sediment samples collected near mines are high, Hg speciation data indicate that concentrations of Hg (II) are generally less than 5%, and methylmercury concentrations are less than 1% of the total Hg. Stream waters below the mines are neutral to slightly alkaline (pH 6.8-8.4), which is a result of the insolubility of cinnabar and the lack of acid- generating minerals such as pyrite in the deposits. Unfiltered stream-water samples collected below the mines generally contain 500-2500 ng/l Hg; whereas, corresponding stream-water samples filtered through a 0.45-??m membrane contain less than 50 ng/l Hg. These stream-water results indicate that most of the Hg transported downstream from the mines is as finely- suspended material rather than dissolved Hg. Mercury speciation data show that concentrations of Hg (II) and methylmercury in stream-water samples are typically less than 22 ng/l, and generally less than 5% of the total Hg. Muscle samples of fish collected downstream from mines contain as much as 620 ng/g Hg (wet wt.), of which 90-100% is methylmercury. Although these Hg concentrations are several times higher than that in fish collected from regional baseline sites, the concentration of Hg in fish is below the 1000 ng/g action level for edible fish established by the US Food and Drug Administration (FDA). Salmon contain less than 100 ng/g Hg, which are among the lowest Hg contents observed for fish in the study, and well below the FDA action level. (C) 2000 Elsevier Science B.V.

Automated Calibration of Atmospheric Oxidized Mercury Measurements.

PubMed

Lyman, Seth; Jones, Colleen; O'Neil, Trevor; Allen, Tanner; Miller, Matthieu; Gustin, Mae Sexauer; Pierce, Ashley M; Luke, Winston; Ren, Xinrong; Kelley, Paul

2016-12-06

The atmosphere is an important reservoir for mercury pollution, and understanding of oxidation processes is essential to elucidating the fate of atmospheric mercury. Several recent studies have shown that a low bias exists in a widely applied method for atmospheric oxidized mercury measurements. We developed an automated, permeation tube-based calibrator for elemental and oxidized mercury, and we integrated this calibrator with atmospheric mercury instrumentation (Tekran 2537/1130/1135 speciation systems) in Reno, Nevada and at Mauna Loa Observatory, Hawaii, U.S.A. While the calibrator has limitations, it was able to routinely inject stable amounts of HgCl 2 and HgBr 2 into atmospheric mercury measurement systems over periods of several months. In Reno, recovery of injected mercury compounds as gaseous oxidized mercury (as opposed to elemental mercury) decreased with increasing specific humidity, as has been shown in other studies, although this trend was not observed at Mauna Loa, likely due to differences in atmospheric chemistry at the two locations. Recovery of injected mercury compounds as oxidized mercury was greater in Mauna Loa than in Reno, and greater still for a cation-exchange membrane-based measurement system. These results show that routine calibration of atmospheric oxidized mercury measurements is both feasible and necessary.

Multidrug Efflux Transporters Limit Accumulation of Inorganic, but Not Organic, Mercury in Sea Urchin Embryos

PubMed Central

Bošnjak, Ivana; Uhlinger, Kevin R.; Heim, Wesley; Smital, Tvrtko; Franekić-Čolić, Jasna; Coale, Kenneth; Epel, David; Hamdoun, Amro

2011-01-01

Mercuric compounds are persistent global pollutants that accumulate in marine organisms and in humans who consume them. While the chemical cycles and speciation of mercury in the oceans are relatively well described, the cellular mechanisms that govern which forms of mercury accumulate in cells and why they persist are less understood. In this study we examined the role of multidrug efflux transport in the differential accumulation of inorganic (HgCl2) and organic (CH3HgCl) mercury in sea urchin (Strongylocentrotus purpuratus) embryos. We found that inhibition of MRP/ABCC-type transporters increases intracellular accumulation of inorganic mercury but had no effect on accumulation of organic mercury. Similarly, pharmacological inhibition of metal conjugating enzymes by ligands GST/GSH significantly increases this antimitotic potency of inorganic mercury, but had no effect on the potency of organic mercury. Our results point to MRP-mediated elimination of inorganic mercury conjugates as a cellular basis for differences in the accumulation and potency of the two major forms of mercury found in marine environments. PMID:19924972

Mercury speciation in the Mt. Amiata mining district (Italy): interplay between urban activities and mercury contamination

USGS Publications Warehouse

Rimondi, Valentina; Bardelli, Fabrizio; Benvenuti, Marco; Costagliola, Pilario; Gray, John E.; Lattanzi, Pierfranco

2014-01-01

A fundamental step to evaluate the biogeochemical and eco-toxicological significance of Hg dispersion in the environment is to determine speciation of Hg in solid matrices. In this study, several analytical techniques such as scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), sequential chemical extractions (SCEs), and X-ray absorption spectroscopy (XANES) were used to identify Hg compounds and Hg speciation in samples collected from the Mt. Amiata Hg mining district, southern Tuscany, Italy. Different geological materials, such as mine waste calcine (retorted ore), soil, stream sediment, and stream water suspended particulate matter were analyzed. Results show that the samples were generally composed of highly insoluble Hg compounds such as sulphides (HgS, cinnabar and metacinnabar), and more soluble Hg halides such as those associated with the mosesite group. Other moderately soluble Hg compounds, HgCl2, HgO and Hg0, were also identified in stream sediments draining the mining area. The presence of these minerals suggests active and continuous runoff of soluble Hg compounds from calcines, where such Hg compounds form during retorting, or later in secondary processes. Specifically, we suggest that, due to the proximity of Hg mines to the urban center of Abbadia San Salvatore, the influence of other anthropogenic activities was a key factor for Hg speciation, resulting in the formation of unusual Hg-minerals such as mosesite.

Speciation of Mercury in Selected Areas of the Petroleum Value Chain.

PubMed

Avellan, Astrid; Stegemeier, John P; Gai, Ke; Dale, James; Hsu-Kim, Heileen; Levard, Clément; O'Rear, Dennis; Hoelen, Thomas P; Lowry, Gregory V

2018-02-06

Petroleum, natural gas, and natural gas condensate can contain low levels of mercury (Hg). The speciation of Hg can affect its behavior during processing, transport, and storage so efficient and safe management of Hg requires an understanding of its chemical form in oil, gas and byproducts. Here, X-ray absorption spectroscopy was used to determine the Hg speciation in samples of solid residues collected throughout the petroleum value chain including stabilized crude oil residues, sediments from separation tanks and condensate glycol dehydrators, distillation column pipe scale, and biosludge from wastewater treatment. In all samples except glycol dehydrators, metacinnabar (β-HgS) was the primary form of Hg. Electron microscopy on particles from a crude sediment showed nanosized (<100 nm) particles forming larger aggregates, and confirmed the colocalization of Hg and sulfur. In sediments from glycol dehydrators, organic Hg(SR) 2 accounted for ∼60% of the Hg, with ∼20% present as β-HgS and/or Hg(SR) 4 species. β-HgS was the predominant Hg species in refinery biosludge and pipe scale samples. However, the balance of Hg species present in these samples depended on the nature of the crude oil being processed, i.e. sweet (low sulfur crudes) vs sour (higher sulfur crudes). This information on Hg speciation in the petroleum value chain will inform development of better engineering controls and management practices for Hg.

Particulate-phase mercury emissions from biomass burning ...

EPA Pesticide Factsheets

Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg (Hg0(g)). However, little is known about the fraction of Hg bound to particulate matter (HgP) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric HgP concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improve

HgL(3) XANES Study of Mercury Methylation in Shredded Eichhornia Crassipes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajan, M.; Darrow, J.; Hua, M.

2009-05-21

Eichhornia crassipes (water hyacinth) is a non-native plant found in abundance in the Sacramento-San Joaquin River Delta (hereafter called Delta). This species has become a problem, clogging waterways and wetlands. Water hyacinth are also known to accumulate mercury. Recent attempts to curb its proliferation have included shredding with specialized boats. The purpose of this research is to better understand the ability of water hyacinth to phytoremediate mercury and to determine the effect of shredding and anoxic conditions on mercury speciation in plant tissue. In the field assessment, total mercury levels in sediment from the Dow Wetlands in the Delta weremore » found to be 0.273 {+-} 0.070 ppm Hg, and levels in hyacinth roots and shoots from this site were 1.17 {+-} 0.08 ppm and 1.03 {+-} 0.52 ppm, respectively, indicating bioaccumulation of mercury. Plant samples collected at this site were also grown in nutrient solution with 1 ppm HgCl{sub 2} under (1) aerobic conditions, (2) anaerobic conditions, and (3) with shredded plant material only. The greatest accumulation was found in the roots of whole plants. Plants grown in these conditions were also analyzed at Stanford Synchrotron Radiation Laboratory using Hg L{sub 3} X-ray Absorption Near Edge Spectroscopy (XANES), a method to examine speciation that is element-specific and noninvasive. Least-squares fitting of the XANES data to methylated and inorganic mercury(II) model compounds revealed that in plants grown live and aerobically, 5 {+-} 3% of the mercury was in the form of methylmercury, in a form similar to methylmercury cysteine. This percentage increased to 16 {+-} 4% in live plants grown anaerobically and to 22 {+-} 6% in shredded anaerobic plants. We conclude that shredding of the hyacinth plants and, in fact, subjection of plants to anaerobic conditions (e.g., as in normal decay, or in crowded growth conditions) increases mercury methylation. Mechanical removal of the entire plant is significantly more expensive than shredding, but it may be necessary to avoid increased biomagnification of mercury in infested areas.« less

Usage Proposal of a common urban decorative tree (Salix alba L.) to monitor the dispersion of gaseous mercury: A case study from Turda (Romania).

PubMed

Esbrí, J M; Cacovean, H; Higueras, P

2018-02-01

Closure of chloralkali plants poses a risk of abandonment of important sources of gaseous mercury. In this work, an assessment has been made of the potential for pollution from one of these plants in the proximity of a densely populated town in central Romania. The work involved a comparison between two major types of monitoring survey: biomonitoring using leaves of a tree common in urban environments; and LUMEX-based gaseous mercury analysis. For biomonitoring, 21 samples from Salix alba L. trees were taken in Turda area. Atmospheric monitoring included two mobile surveys and one at a fixed location. The results from both monitoring systems show similarities in gaseous mercury dispersion patterns, with high mercury contents clearly related to the presence of the chloralkali plant. Particularly high levels were measured in the following situations: (i) in a 'smog' area related with thermal inversion and (ii) during dusk. Direct monitoring suffered from limitations in acquiring information, especially in a medium-long time range, but biomonitoring provided these data and is capable of covering studies on temporary trends or comparative assessments between European cities with contrasting gaseous mercury sources. The thermal speciation of mercury contents indicates that the whole fraction of mercury in leaves corresponds to organic mercury. This finding implies a non-reversible uptake process, which in turn ensures the applicability of this technique to biomonitor long-term exposure. As a conclusion, the assessment of gaseous mercury pollution based on biomonitoring using S. alba has proven to be a useful, reliable and cost-effective methodology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Automated dynamic hollow fiber liquid-liquid-liquid microextraction combined with capillary electrophoresis for speciation of mercury in biological and environmental samples.

PubMed

Li, Pingjing; He, Man; Chen, Beibei; Hu, Bin

2015-10-09

A simple home-made automatic dynamic hollow fiber based liquid-liquid-liquid microextraction (AD-HF-LLLME) device was designed and constructed for the simultaneous extraction of organomercury and inorganic mercury species with the assistant of a programmable flow injection analyzer. With 18-crown-6 as the complexing reagent, mercury species including methyl-, ethyl-, phenyl- and inorganic mercury were extracted into the organic phase (chlorobenzene), and then back-extracted into the acceptor phase of 0.1% (m/v) 3-mercapto-1-propanesulfonic acid (MPS) aqueous solution. Compared with automatic static (AS)-HF-LLLME system, the extraction equilibrium of target mercury species was obtained in shorter time with higher extraction efficiency in AD-HF-LLLME system. Based on it, a new method of AD-HF-LLLME coupled with large volume sample stacking (LVSS)-capillary electrophoresis (CE)/UV detection was developed for the simultaneous analysis of methyl-, phenyl- and inorganic mercury species in biological samples and environmental water. Under the optimized conditions, AD-HF-LLLME provided high enrichment factors (EFs) of 149-253-fold within relatively short extraction equilibrium time (25min) and good precision with RSD between 3.8 and 8.1%. By combining AD-HF-LLLME with LVSS-CE/UV, EFs were magnified up to 2195-fold and the limits of detection (at S/N=3) for target mercury species were improved to be sub ppb level. Copyright © 2015 Elsevier B.V. All rights reserved.

The cycling and sea-air exchange of mercury in the waters of the Eastern Mediterranean during the 2010 MED-OCEANOR cruise campaign.

PubMed

Fantozzi, L; Manca, G; Ammoscato, I; Pirrone, N; Sprovieri, F

2013-03-15

An oceanographic cruise campaign on-board the Italian research vessel Urania was carried out from the 26th of August to the 13th of September 2010 in the Eastern Mediterranean. The campaign sought to investigate the mercury cycle at coastal and offshore locations in different weather conditions. The experimental activity focused on measuring mercury speciation in both seawater and in air, and using meteorological parameters to estimate elemental mercury exchange at the sea-atmosphere interface. Dissolved gaseous mercury (DGM), unfiltered total mercury (UTHg) and filtered total mercury (FTHg) surface concentrations ranged from 16 to 114, 300 to 18,760, and 230 to 10,990pgL(-1), respectively. The highest DGM, UTHg and FTHg values were observed close to Augusta (Sicily), a highly industrialized area of the Mediterranean region, while the lowest values were recorded at offshore stations. DGM vertical profiles partially followed the distribution of sunlight, as a result of the photoinduced transformations of elemental mercury in the surface layers of the water column. However, at some stations, we observed higher DGM concentrations in samples taken from the bottom of the water column, suggesting biological mercury production processes or the presence of tectonic activity. Moreover, two days of continuous measurement at one location demonstrated that surface DGM concentration is affected by solar radiation and atmospheric turbulence intensity. Atmospheric measurements of gaseous elemental mercury (GEM) showed an average concentration (1.6ngm(-3)) close to the background level for the northern hemisphere. For the first time this study used a numerical scheme based on a two-thin film model with a specific parameterization for mercury to estimate elemental mercury flux. The calculated average mercury flux during the entire cruise was 2.2±1.5ngm(-2)h(-1). The analysis of flux data highlights the importance of the wind speed on the mercury evasion from sea surfaces. Copyright © 2012 Elsevier B.V. All rights reserved.

The effect of aqueous speciation and cellular ligand binding on the biotransformation and bioavailability of methylmercury in mercury-resistant bacteria.

PubMed

Ndu, Udonna; Barkay, Tamar; Schartup, Amina Traore; Mason, Robert P; Reinfelder, John R

2016-02-01

Mercury resistant bacteria play a critical role in mercury biogeochemical cycling in that they convert methylmercury (MeHg) and inorganic mercury to elemental mercury, Hg(0). To date there are very few studies on the effects of speciation and bioavailability of MeHg in these organisms, and even fewer studies on the role that binding to cellular ligands plays on MeHg uptake. The objective of this study was to investigate the effects of thiol complexation on the uptake of MeHg by measuring the intracellular demethylation-reduction (transformation) of MeHg to Hg(0) in Hg-resistant bacteria. Short-term intracellular transformation of MeHg was quantified by monitoring the loss of volatile Hg(0) generated during incubations of bacteria containing the complete mer operon (including genes from putative mercury transporters) exposed to MeHg in minimal media compared to negative controls with non-mer or heat-killed cells. The results indicate that the complexes MeHgOH, MeHg-cysteine, and MeHg-glutathione are all bioavailable in these bacteria, and without the mer operon there is very little biological degradation of MeHg. In both Pseudomonas stutzeri and Escherichia coli, there was a pool of MeHg that was not transformed to elemental Hg(0), which was likely rendered unavailable to Mer enzymes by non-specific binding to cellular ligands. Since the rates of MeHg accumulation and transformation varied more between the two species of bacteria examined than among MeHg complexes, microbial bioavailability, and therefore microbial demethylation, of MeHg in aquatic systems likely depends more on the species of microorganism than on the types and relative concentrations of thiols or other MeHg ligands present.

Precise spectroscopic analysis of solar-type stars with moderate and fast rotation

NASA Astrophysics Data System (ADS)

Tsantaki, Maria

In the present work the performance and applicability of the thin mercury film electrode (TMFE) in the dynamic speciation of trace metals was investigated. Two different electroanalytical stripping techniques were used: the classical anodic stripping voltammetry (ASV) and a recent developed technique, scanning stripping chronopotentiometry (SSCP). The ion-exchange and the mass transport features of novel mixed coatings of two sulfonated cation-exchange polymers with dissimilar characteristics, Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS) were evaluated, prior to its application in the field of trace metal analysis. Suitable NA-PSS polymer coatings could be used in the modification of TMFE, presenting a high sensitivity, reproducibility, mechanical stability and adequate antifouling properties in the ASV determination of trace metal cations in complex media. Also the features of the PSS polyelectrolyte layers for ion-exchange voltammetry (IEV) were evaluated. The goal was to search for the best conditions to obtain stable PSS coated electrodes, which could present high negative charge densities in order to enhance the electrostatic accumulation of cations within the film, thus enlarging the ASV signal. The applicability and performance of the TMFE in the trace metal speciation studies, by SSCP, were for the first time exploited. The optimized TMFE presented a high sensitivity and resolution, being an excellent complement to the conventional mercury electrodes and could be use for 1-day term with no significant variation in the SCP analytical signal and no apparent degradation. The calculated SSCP curves were in excellent agreement with experimental data at the TMFE and the stability constant (K), calculated from the shift in the SSCP half-wave potential, of two labile metal-complex systems were in good agreement with the ones obtained using the conventional Hanging mercury drop electrode (HMDE) and those predicted by theory. Additionally, the experimental lability diagnosis inherent to the SSCP technique was validated and a rigorous quantification of the lability degree was made. Due to the well defined hydrodynamic conditions at the thin mercury film rotating disk electrode (TMF-RDE), during the deposition step, this electrode is quite valuable in the determination of kinetic parameters, like the association rate constants (ka).

Global Sources and Pathways of Mercury in the Context of Human Health.

PubMed

Sundseth, Kyrre; Pacyna, Jozef M; Pacyna, Elisabeth G; Pirrone, Nicola; Thorne, Rebecca J

2017-01-22

This paper reviews information from the existing literature and the EU GMOS (Global Mercury Observation System) project to assess the current scientific knowledge on global mercury releases into the atmosphere, on global atmospheric transport and deposition, and on the linkage between environmental contamination and potential impacts on human health. The review concludes that assessment of global sources and pathways of mercury in the context of human health is important for being able to monitor the effects from implementation of the Minamata Convention targets, although new research is needed on the improvement of emission inventory data, the chemical and physical behaviour of mercury in the atmosphere, the improvement of monitoring network data, predictions of future emissions and speciation, and on the subsequent effects on the environment, human health, as well as the economic costs and benefits of reducing these aspects.

Sampling and analysis of natural gas trace constituents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Attari, A.; Chao, S.

1993-09-01

Major and minor components of natural gas are routinely analyzed by gas chromatography (GC), using a thermal conductivity (TC). The best results obtained by these methods can report no better than 0.01 mole percent of each measured component. Even the extended method of analysis by flame ionization detector (FID) can only improve on the detection limit of hydrocarbons. The gas industry needs better information on all trace constituents of natural gas, whether native or inadvertently added during gas processing that may adversely influence the operation of equipment or the safety of the consumer. The presence of arsenic and mercury inmore » some gas deposits have now been documented in international literature as causing not only human toxicity but also damaging to the field equipment. Yet, no standard methods of sampling and analysis exist to provide this much needed information. In this paper the authors report the results of a three-year program to develop an extensive array of sampling and analysis methods for speciation and measurement of trace constituents of natural gas. A cryogenic sampler operating at near 200 K ({minus}99 F) and at pipeline pressures up to 12.4 {times} 10{sup 6}Pa (1800 psig) has been developed to preconcentrate and recover all trace constituents with boiling points above butanes. Specific analytical methods have been developed for speciating and measurement of many trace components (corresponding to US EPA air toxics) by GC-AED and GC-MS, and for determining various target compounds by other techniques. Moisture, oxygen and sulfur contents are measured on site using dedicated field instruments. Arsenic, mercury and radon are sampled by specific solid sorbents for subsequent laboratory analysis.« less

Mercury behaviour and C, N, and P biogeochemical cycles during ecological restoration processes of old mining sites in French Guiana.

PubMed

Couic, Ewan; Grimaldi, Michel; Alphonse, Vanessa; Balland-Bolou-Bi, Clarisse; Livet, Alexandre; Giusti-Miller, Stéphanie; Sarrazin, Max; Bousserrhine, Noureddine

2018-04-25

Several decades of gold mining extraction activities in the Amazonian rainforest have caused deforestation and pollution. While ecological rehabilitation is essential for restoring biodiversity and decreasing erosion on deforested lands, few studies note the behaviour or toxicity of trace elements during the rehabilitation process. Our original study focused on the potential use of microbial activity and Hg speciation and compared them with As, Cu, Zn and Cr speciation in assessing the chemical and biological quality of ecological restoration efforts. We sampled two sites in French Guyana 17 years after rehabilitation efforts began. The former site was actively regenerated (R) with the leguminous species Clitoria racemosa and Acacia mangium, and the second site was passively regenerated with spontaneous vegetation (Sv). We also sampled soil from a control site without a history of gold mining (F). We performed microcosm soil experiments for 30 days, where trace element speciation and enzyme activities (i.e., FDA, dehydrogenase, β-glucosidase, urease, alkaline and acid phosphatase) were estimated to characterise the behaviour of trace elements and the soil microbial activity. As bioindicators, the use of soil microbial carbon biomass and soil enzyme activities related to the carbon and phosphorus cycles seems to be relevant for assessing soil quality in rehabilitated and regenerated old mining sites. Our results showed that restoration with leguminous species had a positive effect on soil chemical quality and on soil microbial bioindicators, with activities that tended toward natural non-degraded soil (F). Active restoration processes also had a positive effect on Hg speciation by reducing its mobility. While in Sv we found more exchangeable and soluble mercury, in regenerated sites, Hg was mostly bound to organic matter. These results also suggested that enzyme activities and mercury cycles are sensitive to land restoration and must be considered when evaluating the efficiency of restoration processes.

General trends of atmospheric mercury concentrations in urban and rural areas in Korea and characteristics of high-concentration events

NASA Astrophysics Data System (ADS)

Han, Young-Ji; Kim, Jung-Eun; Kim, Pyung-Rae; Kim, Woo-Jin; Yi, Seung-Muk; Seo, Yong-Seok; Kim, Seung-Hee

2014-09-01

Long-term measurement of speciated Hg concentrations is the first step toward identifying the seasonal and spatial characteristics of Hg concentrations; however, atmospheric Hg research is scarce in Korea. In this study, total gaseous mercury (TGM), gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) were measured in urban (Seoul) and rural (Chuncheon) areas over a more than 3 year period in order to improve the understanding of speciated Hg transport. The mean concentrations of TGM, GOM and PBM were 3.72 ± 2.96 (0.19-149.84) ng m-3, 11.3 ± 9.5 (0.9-57.3) pg m-3, and 13.4 ± 12.0 (2.1-64.3) pg m-3 at the Seoul site and 2.12 ± 1.47 (0.26-10.75) ng m-3, 2.7 ± 2.7 (0.1-16.9) pg m-3, and 3.7 ± 5.7 (0.1-30.0) pg m-3 in Chuncheon. Both long-range transport and local sources caused high TGM concentration events, while local coal combustion was a main cause of enhancing the GOM and PBM concentrations in Seoul. However, there was no correlation between the pollutants emitted from coal combustion and the speciated Hg concentration in Chuncheon, indicating that other mechanisms were involved in the Hg increase. We found a positive correlation between the GOM and the O3 concentrations and a negative correlation between the GEM and the GOM concentrations, especially on foggy days, suggesting that the oxidation of GEM was an important source for GOM in Chuncheon. In addition, the ratio of PBM/GOM was inversely proportional to the atmospheric temperature and directly proportional to the relative humidity, which suggests that the in-situ formation of PBM through gas-particle partitioning of GOM was important in rural areas.

Distribution and fractionation of mercury in the soils of a unique tropical agricultural wetland ecosystem, southwest coast of India.

PubMed

Navya, C; Gopikrishna, V G; Arunbabu, V; Mohan, Mahesh

2015-12-01

Mercury biogeochemistry is highly complex in the aquatic ecosystems and it is very difficult to predict. The speciation of mercury is the primary factor controlling its behavior, movement, and fate in these systems. The fluctuating water levels in wetlands could play a major role in the mercury transformations and transport. Hence, the agricultural wetlands may have a significant influence on the global mercury cycling. Kuttanad agricultural wetland ecosystem is a unique one as it is lying below the sea level and most of the time it is inundated with water. To understand the mobility and bioavailability of Hg in the soils of this agricultural wetland ecosystem, the present study analyzed the total mercury content as well as the different fractions of mercury. Mercury was detected using cold vapor atomic fluorescence spectrophotometer. The total mercury content varied from 0.002 to 0.683 mg/kg, and most of the samples are having concentrations below the background value. The percentage of mercury found in the initial three fractions F1, F2, and F3 are more available and it may enhance the methylation potential of the Kuttanad agroecosystem.

Evaluation of the Emission, Transport, and Deposition of Mercury, Fine Particulate Matter, and Arsenic from Coal-Based Power Plants in the Ohio River Valley Region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin Crist

2005-10-02

Ohio University, in collaboration with CONSOL Energy, Advanced Technology Systems, Inc (ATS) and Atmospheric and Environmental Research, Inc. (AER) as subcontractors, is evaluating the impact of emissions from coal-fired power plants in the Ohio River Valley region as they relate to the transport and deposition of mercury, arsenic, and associated fine particulate matter. This evaluation will involve two interrelated areas of effort: ambient air monitoring and regional-scale modeling analysis. The scope of work for the ambient air monitoring will include the deployment of a surface air monitoring (SAM) station in southeastern Ohio. The SAM station will contain sampling equipment tomore » collect and measure mercury (including speciated forms of mercury and wet and dry deposited mercury), arsenic, particulate matter (PM) mass, PM composition, and gaseous criteria pollutants (CO, NOx, SO{sub 2}, O{sub 3}, etc.). Laboratory analysis of time-integrated samples will be used to obtain chemical speciation of ambient PM composition and mercury in precipitation. Near-real-time measurements will be used to measure the ambient concentrations of PM mass and all gaseous species including Hg{sup 0} and RGM. Approximately of 18 months of field data will be collected at the SAM site to validate the proposed regional model simulations for episodic and seasonal model runs. The ambient air quality data will also provide mercury, arsenic, and fine particulate matter data that can be used by Ohio Valley industries to assess performance on multi-pollutant control systems. The scope of work for the modeling analysis will include (1) development of updated inventories of mercury and arsenic emissions from coal plants and other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric chemical transport model to incorporate recent advancements in the understanding of mercury transformations in the atmosphere; (3) analyses of the flux of Hg0, RGM, arsenic, and fine particulate matter in the different sectors of the study region to identify key transport mechanisms; (4) comparison of cross correlations between species from the model results to observations in order to evaluate characteristics of specific air masses associated with long-range transport from a specified source region; and (5) evaluation of the sensitivity of these correlations to emissions from regions along the transport path. This will be accomplished by multiple model runs with emissions simulations switched on and off from the various source regions. To the greatest extent possible, model results will also be compared to field data collected at other air monitoring sites in the Ohio Valley region, operated independently of this project. These sites may include (1) the DOE National Energy Technologies Laboratory's monitoring site at its suburban Pittsburgh, PA facility; (2) sites in Pittsburgh (Lawrenceville) PA and Holbrook, PA operated by ATS; (3) sites in Steubenville, OH and Pittsburgh, PA operated by U.S. EPA and/or its contractors; and (4) sites operated by State or local air regulatory agencies. Field verification of model results and predictions will provide critical information for the development of cost effective air pollution control strategies by the coal-fired power plants in the Ohio River Valley region.« less

Evaluation of the Emission, Transport, and Deposition of Mercury, Fine Particulate Matter, and Arsenic from Coal-Based Power Plants in the Ohio River Valley Region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin Crist

2006-04-02

As stated in the proposal: Ohio University, in collaboration with CONSOL Energy, Advanced Technology Systems, Inc (ATS) and Atmospheric and Environmental Research, Inc. (AER) as subcontractors, is evaluating the impact of emissions from coal-fired power plants in the Ohio River Valley region as they relate to the transport and deposition of mercury, arsenic, and associated fine particulate matter. This evaluation will involve two interrelated areas of effort: ambient air monitoring and regional-scale modeling analysis. The scope of work for the ambient air monitoring will include the deployment of a surface air monitoring (SAM) station in southeastern Ohio. The SAM stationmore » will contain sampling equipment to collect and measure mercury (including speciated forms of mercury and wet and dry deposited mercury), arsenic, particulate matter (PM) mass, PM composition, and gaseous criteria pollutants (CO, NO{sub x}, SO{sub 2}, O{sub 3}, etc.). Laboratory analysis of time-integrated samples will be used to obtain chemical speciation of ambient PM composition and mercury in precipitation. Near-real-time measurements will be used to measure the ambient concentrations of PM mass and all gaseous species including Hg0 and RGM. Approximately 18 months of field data will be collected at the SAM site to validate the proposed regional model simulations for episodic and seasonal model runs. The ambient air quality data will also provide mercury, arsenic, and fine particulate matter data that can be used by Ohio Valley industries to assess performance on multi-pollutant control systems. The scope of work for the modeling analysis will include (1) development of updated inventories of mercury and arsenic emissions from coal plants and other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric chemical transport model to incorporate recent advancements in the understanding of mercury transformations in the atmosphere; (3) analyses of the flux of Hg{sup 0}, RGM, arsenic, and fine particulate matter in the different sectors of the study region to identify key transport mechanisms; (4) comparison of cross correlations between species from the model results to observations in order to evaluate characteristics of specific air masses associated with long-range transport from a specified source region; and (5) evaluation of the sensitivity of these correlations to emissions from regions along the transport path. This will be accomplished by multiple model runs with emissions simulations switched on and off from the various source regions. To the greatest extent possible, model results will also be compared to field data collected at other air monitoring sites in the Ohio Valley region, operated independently of this project. These sites may include (1) the DOE National Energy Technologies Laboratory's monitoring site at its suburban Pittsburgh, PA facility; (2) sites in Pittsburgh (Lawrenceville) PA and Holbrook, PA operated by ATS; (3) sites in Steubenville, OH and Pittsburgh, PA operated by the USEPA and/or its contractors; and (4) sites operated by State or local air regulatory agencies. Field verification of model results and predictions will provide critical information for the development of cost effective air pollution control strategies by the coal-fired power plants in the Ohio River Valley region.« less

EVALUATION OF THE EMISSION, TRANSPORT, AND DEPOSITION OF MERCURY, FINE PARTICULATE MATTER, AND ARSENIC FROM COAL-BASED POWER PLANTS IN THE OHIO RIVER VALLEY REGION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin Crist

2005-04-02

Ohio University, in collaboration with CONSOL Energy, Advanced Technology Systems, Inc (ATS) and Atmospheric and Environmental Research, Inc. (AER) as subcontractors, is evaluating the impact of emissions from coal-fired power plants in the Ohio River Valley region as they relate to the transport and deposition of mercury, arsenic, and associated fine particulate matter. This evaluation will involve two interrelated areas of effort: ambient air monitoring and regional-scale modeling analysis. The scope of work for the ambient air monitoring will include the deployment of a surface air monitoring (SAM) station in southeastern Ohio. The SAM station will contain sampling equipment tomore » collect and measure mercury (including speciated forms of mercury and wet and dry deposited mercury), arsenic, particulate matter (PM) mass, PM composition, and gaseous criteria pollutants (CO, NO{sub x}, SO{sub 2}, O{sub 3}, etc.). Laboratory analysis of time-integrated samples will be used to obtain chemical speciation of ambient PM composition and mercury in precipitation. Near-real-time measurements will be used to measure the ambient concentrations of PM mass and all gaseous species including Hg{sup 0} and RGM. Approximately of 18 months of field data will be collected at the SAM site to validate the proposed regional model simulations for episodic and seasonal model runs. The ambient air quality data will also provide mercury, arsenic, and fine particulate matter data that can be used by Ohio Valley industries to assess performance on multi-pollutant control systems. The scope of work for the modeling analysis will include (1) development of updated inventories of mercury and arsenic emissions from coal plants and other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric chemical transport model to incorporate recent advancements in the understanding of mercury transformations in the atmosphere; (3) analyses of the flux of Hg{sup 0}, RGM, arsenic, and fine particulate matter in the different sectors of the study region to identify key transport mechanisms; (4) comparison of cross correlations between species from the model results to observations in order to evaluate characteristics of specific air masses associated with long-range transport from a specified source region; and (5) evaluation of the sensitivity of these correlations to emissions from regions along the transport path. This will be accomplished by multiple model runs with emissions simulations switched on and off from the various source regions. To the greatest extent possible, model results will also be compared to field data collected at other air monitoring sites in the Ohio Valley region, operated independently of this project. These sites may include (1) the DOE National Energy Technologies Laboratory's monitoring site at its suburban Pittsburgh, PA facility; (2) sites in Pittsburgh (Lawrenceville) PA and Holbrook, PA operated by ATS; (3) sites in Steubenville, OH and Pittsburgh, PA operated by U.S. EPA and/or its contractors; and (4) sites operated by State or local air regulatory agencies. Field verification of model results and predictions will provide critical information for the development of cost effective air pollution control strategies by the coal-fired power plants in the Ohio River Valley region.« less

EVALUATION OF THE EMISSION, TRANSPORT, AND DEPOSITION OF MERCURY, FINE PARTICULATE MATTER, AND ARSENIC FROM COAL-BASED POWER PLANTS IN THE OHIO RIVER VALLEY REGION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin Crist

2004-10-02

Ohio University, in collaboration with CONSOL Energy, Advanced Technology Systems, Inc (ATS) and Atmospheric and Environmental Research, Inc. (AER) as subcontractors, is evaluating the impact of emissions from coal-fired power plants in the Ohio River Valley region as they relate to the transport and deposition of mercury, arsenic, and associated fine particulate matter. This evaluation will involve two interrelated areas of effort: ambient air monitoring and regional-scale modeling analysis. The scope of work for the ambient air monitoring will include the deployment of a surface air monitoring (SAM) station in southeastern Ohio. The SAM station will contain sampling equipment tomore » collect and measure mercury (including speciated forms of mercury and wet and dry deposited mercury), arsenic, particulate matter (PM) mass, PM composition, and gaseous criteria pollutants (CO, NOx, SO{sub 2}, O{sub 3}, etc.). Laboratory analysis of time-integrated samples will be used to obtain chemical speciation of ambient PM composition and mercury in precipitation. Near-real-time measurements will be used to measure the ambient concentrations of PM mass and all gaseous species including Hg{sup 0} and RGM. Approximately of 18 months of field data will be collected at the SAM site to validate the proposed regional model simulations for episodic and seasonal model runs. The ambient air quality data will also provide mercury, arsenic, and fine particulate matter data that can be used by Ohio Valley industries to assess performance on multi-pollutant control systems. The scope of work for the modeling analysis will include (1) development of updated inventories of mercury and arsenic emissions from coal plants and other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric chemical transport model to incorporate recent advancements in the understanding of mercury transformations in the atmosphere; (3) analyses of the flux of Hg{sup 0}, RGM, arsenic, and fine particulate matter in the different sectors of the study region to identify key transport mechanisms; (4) comparison of cross correlations between species from the model results to observations in order to evaluate characteristics of specific air masses associated with long-range transport from a specified source region; and (5) evaluation of the sensitivity of these correlations to emissions from regions along the transport path. This will be accomplished by multiple model runs with emissions simulations switched on and off from the various source regions. To the greatest extent possible, model results will also be compared to field data collected at other air monitoring sites in the Ohio Valley region, operated independently of this project. These sites may include (1) the DOE National Energy Technologies Laboratory's monitoring site at its suburban Pittsburgh, PA facility; (2) sites in Pittsburgh (Lawrenceville) PA and Holbrook, PA operated by ATS; (3) sites in Steubenville, OH and Pittsburgh, PA operated by U.S. EPA and/or its contractors; and (4) sites operated by State or local air regulatory agencies. Field verification of model results and predictions will provide critical information for the development of cost effective air pollution control strategies by the coal-fired power plants in the Ohio River Valley region.« less

Global Sources and Pathways of Mercury in the Context of Human Health

PubMed Central

Sundseth, Kyrre; Pacyna, Jozef M.; Pacyna, Elisabeth G.; Pirrone, Nicola; Thorne, Rebecca J.

2017-01-01

This paper reviews information from the existing literature and the EU GMOS (Global Mercury Observation System) project to assess the current scientific knowledge on global mercury releases into the atmosphere, on global atmospheric transport and deposition, and on the linkage between environmental contamination and potential impacts on human health. The review concludes that assessment of global sources and pathways of mercury in the context of human health is important for being able to monitor the effects from implementation of the Minamata Convention targets, although new research is needed on the improvement of emission inventory data, the chemical and physical behaviour of mercury in the atmosphere, the improvement of monitoring network data, predictions of future emissions and speciation, and on the subsequent effects on the environment, human health, as well as the economic costs and benefits of reducing these aspects. PMID:28117743

Characterization of soils from an industrial complex contaminated with elemental mercury

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Carrie L., E-mail: millercl@ornl.gov; Watson, David B.; Lester, Brian P.

2013-08-15

Historical use of liquid elemental mercury (Hg(0){sub l}) at the Y-12 National Security Complex in Oak Ridge, TN, USA, resulted in large deposits of Hg(0){sub l} in the soils. The fate and distribution of the spilled Hg(0) are not well characterized. In this study we evaluated analytical tools for characterizing the speciation of Hg in the contaminated soils and then used the analytical techniques to examine the speciation of Hg in two soil cores collected at the site. These include x-ray fluorescence (XRF), soil Hg(0) headspace analysis, and total Hg determination by acid digestion coupled with cold vapor atomic absorptionmore » (HgT). XRF was not found to be suitable for evaluating Hg concentrations in heterogeneous soils containing low concentration of Hg or Hg(0) because Hg concentrations determined using this method were lower than those determined by HgT analysis and the XRF detection limit is 20 mg/kg. Hg(0){sub g} headspace analysis coupled with HgT measurements yielded good results for examining the presence of Hg(0){sub l} in soils and the speciation of Hg. The two soil cores are highly heterogeneous in both the depth and extent of Hg contamination, with Hg concentrations ranging from 0.05 to 8400 mg/kg. In the first core, Hg(0){sub l} was distributed throughout the 3.2 m depth, whereas the second core, from a location 12 m away, contained Hg(0){sub l} in a 0.3 m zone only. Sequential extractions showed organically associated Hg dominant at depths with low Hg concentration. Soil from the zone of groundwater saturation showed reducing conditions and the Hg is likely present as Hg-sulfide species. At this depth, lateral Hg transport in the groundwater may be a source of Hg detected in the soil at the deeper soil depths. Overall, characterization of soils containing Hg(0){sub l} is difficult because of the heterogeneous distribution of Hg within the soils. This is exacerbated in industrial facilities where fill materials make up much of the soils and historical and continued reworking of the subsurface has remobilized the Hg. -- Highlights: • Presence of Hg(0) and chemical transformations control the Hg speciation in soil. • Redox reactions can result in the mobilization and sequestration of Hg in soils. • Analysis of soils containing Hg(0) is complex due to sample heterogeneity.« less

Adding to the Mercury Speciation Toolbox

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Northrup, P. A.; Chidambaram, D.; Kalb, P. D.

2007-12-01

Mercury was used to separate lithium-6 isotope for weapons production at the Y-12 Plant in Oak Ridge, TN in the 1950s and 1960s. A large portion of the waste Hg entered the environment and continues to move throughout the sub-surface and surface waters in the area. Environmental management of Hg contamination within this complex hydrologic system, where Hg speciation and the mobile fraction have been found to vary widely, will require ongoing characterization and predictive modeling of Hg speciation. State-of-the-art spectroscopic tools that can directly probe Hg speciation in preserved aqueous and sediment samples with greater sensitivity, however, are required to determine rates and mechanisms of biogeochemical reactions. We will present the first results demonstrating the use of x-ray absorption spectroscopy (XAS) at the Hg M5 edge (2295 eV) to fingerprint Hg species. Heavy-metal M5 absorption edges can have very sharp features due to local electron transitions, and therefore, we are developing this edge as a tool for quantitative measurement of Hg species. In addition, sulfur speciation using the sulfur K absorption edge, which is at a similar energy (2472 eV), can be measured in the same scan as the Hg M5 edge. Potentially important organic and inorganic sulfur species (sulfide, disulfide, elemental sulfur, sulfite and sulfate) are readily differentiated, and thereby, provides an independent method for monitoring the redox state of the system along with changes in S-Hg bonding. We will also present x-ray microprobe 2-D concentration maps of Hg and other elements at the grain and pore scales to identify its microscopic distribution and chemical associations. When used in combination with established sequential extraction and direct spectroscopic methods, the addition of XAS at the Hg M5 edge should provide a significant advancement in the determination of Hg speciation in complex biogeochemical environments.

Characteristics and sources of atmospheric mercury speciation in a coastal city, Xiamen, China.

PubMed

Xu, Lingling; Chen, Jinsheng; Yang, Liming; Niu, Zhenchuan; Tong, Lei; Yin, Liqian; Chen, Yanting

2015-01-01

Semi-continental monitoring of gaseous elemental mercury (GEM), particulate mercury (Hgp), and reactive gaseous mercury (RGM) was conducted in the Institute of Urban Environment, CAS in Xiamen, China from March 2012 to February 2013. The average concentrations and relative standard deviations (RSD) were 3.50 (34.6%) ng m(-3), 174.41 (160.9%) pg m(-3), and 61.05 (113.7%) pg m(-3) for GEM, Hgp, and RGM, respectively. The higher concentrations of GEM and Hgp were observed in spring and winter months, indicating the combustion source, while RGM showed the different seasonal variation with highest concentration in spring and the minimum value in winter. The concentrations of Hg species were generally elevated in nighttime and low in daytime to reflect the diurnal changes in meteorology, especially the mixing condition of the air masses. The high Hg concentrations were observed in SWW-NW sectors due to calm wind while the low levels in NE-SE due to high speed wind, and the amplitude was much larger for Hgp and RGM. Backward trajectories calculation indicated that summer air masses were much more from ocean with lower Hg while the air masses were mainly from inland area in other seasons. Principal component analysis suggested that combustion and road traffic emissions were the dominant anthropogenic mercury sources for the study area, and the temporal distribution of atmospheric mercury was mainly the result of climatological change. Copyright © 2014 Elsevier Ltd. All rights reserved.

Evaluation of the Emission, Transport, and Deposition of Mercury and Fine Particulate Matter from Coal-Based Power Plants in the Ohio River Valley Region

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kevin Crist

2008-12-31

As stated in the proposal: Ohio University, in collaboration with CONSOL Energy, Advanced Technology Systems, Inc (ATS) and Atmospheric and Environmental Research, Inc. (AER) as subcontractors, evaluated the impact of emissions from coal-fired power plants in the Ohio River Valley region as they relate to the transport and deposition of mercury and associated fine particulate matter. This evaluation involved two interrelated areas of effort: ambient air monitoring and regional-scale modeling analysis. The scope of work for the ambient air monitoring included the deployment of a surface air monitoring (SAM) station in southeastern Ohio. The SAM station contains sampling equipment tomore » collect and measure mercury (including speciated forms of mercury and wet and dry deposited mercury), particulate matter (PM) mass, PM composition, and gaseous criteria pollutants (CO, NOx, SO2, O3, etc.). Laboratory analyses of time-integrated samples were used to obtain chemical speciation of ambient PM composition and mercury in precipitation. Nearreal- time measurements were used to measure the ambient concentrations of PM mass and all gaseous species including Hg0 and RGM. Approximately 30 months of field data were collected at the SAM site to validate the proposed regional model simulations for episodic and seasonal model runs. The ambient air quality data provides mercury, and fine particulate matter data that can be used by Ohio Valley industries to assess performance on multi-pollutant control systems. The scope of work for the modeling analysis includes (1) development of updated inventories of mercury emissions from coal plants and other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric chemical transport model to incorporate recent advancements in the understanding of mercury transformations in the atmosphere; (3) analyses of the flux of Hg0, RGM, and fine particulate matter in the different sectors of the study region to identify key transport mechanisms; (4) comparison of cross correlations between species from the model results to observations in order to evaluate characteristics of specific air masses associated with long-range transport from a specified source region; and (5) evaluation of the sensitivity of these correlations to emissions from regions along the transport path. This is accomplished by multiple model runs with emissions simulations switched on and off from the various source regions. To the greatest extent possible, model results were compared to field data collected at other air monitoring sites in the Ohio Valley region, operated independently of this project. These sites may include (1) the DOE National Energy Technologies Laboratory’s monitoring site at its suburban Pittsburgh, PA facility; (2) sites in Pittsburgh (Lawrenceville) PA and Holbrook, PA operated by ATS; (3) sites in Steubenville, OH and Pittsburgh, PA operated by the USEPA and/or its contractors; and (4) sites operated by State or local air regulatory agencies. Field verification of model results and predictions provides critical information for the development of cost effective air pollution control strategies by the coal-fired power plants in the Ohio River Valley region.« less

A comparison of speciated atmospheric mercury at an urban center and an upwind rural location

USGS Publications Warehouse

Rutter, A.P.; Schauer, J.J.; Lough, G.C.; Snyder, D.C.; Kolb, C.J.; Von Klooster, S.; Rudolf, T.; Manolopoulos, H.; Olson, M.L.

2008-01-01

Gaseous elemental mercury (GEM), particulate mercury (PHg) and reactive gaseous mercury (RGM) were measured every other hour at a rural location in south central Wisconsin (Devil's Lake State Park, WI, USA) between April 2003 and March 2004, and at a predominantly downwind urban site in southeastern Wisconsin (Milwaukee, WI, USA) between June 2004 and May 2005. Annual averages of GEM, PHg, and RGM at the urban site were statistically higher than those measured at the rural site. Pollution roses of GEM and reactive mercury (RM; sum of PHg and RGM) at the rural and urban sites revealed the influences of point source emissions in surrounding counties that were consistent with the US EPA 1999 National Emission Inventory and the 2003-2005 US EPA Toxics Release Inventory. Source-receptor relationships at both sites were studied by quantifying the impacts of point sources on mercury concentrations. Time series of GEM, PHg, and RGM concentrations were sorted into two categories; time periods dominated by impacts from point sources, and time periods dominated by mercury from non-point sources. The analysis revealed average point source contributions to GEM, PHg, and RGM concentration measurements to be significant over the year long studies. At the rural site, contributions to annual average concentrations were: GEM (2%; 0.04 ng m-3); and, RM (48%; 5.7 pg m-3). At the urban site, contributions to annual average concentrations were: GEM (33%; 0.81 ng m-3); and, RM (64%; 13.8 pg m-3). ?? The Royal Society of Chemistry.

Micro-columns packed with Chlorella vulgaris immobilised on silica gel for mercury speciation.

PubMed

Tajes-Martínez, P; Beceiro-González, E; Muniategui-Lorenzo, S; Prada-Rodríguez, D

2006-02-28

A method has been developed for mercury speciation in water by using columns packed with Chlorella vulgaris immobilised on silica gel. The method involves the retention of CH(3)Hg(+) and Hg(2+) in micro-columns prepared by packing immobilised algae in polypropylene tubes, followed by selective and sequential elution with 0.03 and 1.5M HCl for CH(3)Hg(+) and Hg(2+), respectively. The adsorption capacity of the micro-algae for Hg(2+) and CH(3)Hg(+) has been evaluated using free and immobilised C. vulgaris. The efficiency uptake for both species at pH 3 was higher than 97%. Studies were carried out on the effect of retention and elution conditions for both species. Furthermore, the stability of mercury species retained on algae-silica gel micro-columns and lifetime of the columns were also investigated. Hg(2+) showed a higher stability than CH(3)Hg(+) at 0 degrees C (21 and 3 days, respectively) and a better lifetime than for the organic species. The developed method was applied to the analysis of spiked tap, sea and wastewater samples. Recovery studies on tap and filtered seawater provided results between 96+/-3 and 106+/-2 for Hg(2+) and from 98+/-5 to 107+/-5 for CH(3)Hg(+), for samples spiked with single species. For samples spiked with both CH(3)Hg(+) and Hg(2+), the average recoveries varied from 96+/-5 to 99+/-3 and from 103+/-6 to 115+/-5 for Hg(2+) and CH(3)Hg(+), respectively. However, the percentages of retention and elution on wastewater and unfiltered seawater were only adequate for the inorganic species.

Mercury speciation and dispersion from an active gold mine at the West Wits area, South Africa.

PubMed

Lusilao-Makiese, J G; Tessier, E; Amouroux, D; Tutu, H; Chimuka, L; Weiersbye, I; Cukrowska, E M

2016-01-01

Total mercury (HgTOT), inorganic mercury (IHg), and methylmercury (MHg) were determined in dry season waters, sediments, and tailings from an active mine which has long history of gold exploitation. Although HgTOT in waters was generally low (0.03 to 19.60 ng L(-1)), the majority of the samples had proportions of MHg of at least 90 % of HgTOT which denotes a substantial methylation potential of the mine watersheds. Mercury was relatively high in tailing materials (up to 867 μg kg(-1)) and also in the mine sediments (up to 837 μg kg(-1)) especially in samples collected near tailing storage facilities and within a receiving water dam. Sediment profiles revealed mercury enrichment and enhanced methylation rate at deeper layers. The presence of IHg and decaying plants (organic matter) in the watersheds as well as the anoxic conditions of bulk sediments are believed to be some of the key factors favoring the mercury methylation at the site.

The impact of eutrophication on the biogeochemical cycling of mercury species in a reservoir: a case study from Hongfeng Reservoir, Guizhou, China.

PubMed

He, Tianrong; Feng, Xinbin; Guo, Yanna; Qiu, Guangle; Li, Zhonggen; Liang, Lian; Lu, Julia

2008-07-01

The mercury distribution and speciation in the water column were investigated from November 2003 to September 2004. The distribution and concentrations of total mercury (THg) and particulate mercury (PHg) showed that algae had a large capacity to bind mercury in late spring (e.g. in May). It is shown that dissolved gaseous mercury (DGM) concentrations may also be affected by algae activities. The MeHg profile in the water column at a highly eutrophied site in Hongfeng Reservoir demonstrated that most of the MeHg was produced in the hypolimnion, whereas the MeHg profile pattern at another site with less eutrophication indicated that MeHg in water was largely ascribed to release from sediment. In September, the outflow of the reservoir was enriched with MeHg, which was 5.5 times higher than that in the inflows. The discharge of MeHg-concentrated water from the anoxic hypolimnion in the reservoir may pose a risk to downstream fauna.

The Atmospheric Mercury Network: measurement and initial examination of an ongoing atmospheric mercury record across North America

NASA Astrophysics Data System (ADS)

Gay, D. A.; Schmeltz, D.; Prestbo, E.; Olson, M.; Sharac, T.; Tordon, R.

2013-04-01

The National Atmospheric Deposition Program (NADP) developed and operates a collaborative network of atmospheric mercury monitoring sites based in North America - the Atmospheric Mercury Network (AMNet). The justification for the network was growing interest and demand from many scientists and policy makers for a robust database of measurements to improve model development, assess policies and programs, and improve estimates of mercury dry deposition. Many different agencies and groups support the network, including federal, state, tribal, and international governments, academic institutions, and private companies. AMNet has added two high elevation sites outside of continental North America in Hawaii and Taiwan because of new partnerships forged within NADP. Network sites measure concentrations of atmospheric mercury fractions using automated, continuous mercury speciation systems. The procedures that NADP developed for field operations, data management, and quality assurance ensure that the network makes scientifically valid and consistent measurements. AMNet reports concentrations of hourly gaseous elemental mercury (GEM), two-hour gaseous oxidized mercury (GOM), and two-hour particulate-bound mercury less than 2.5 microns in size (PBM2.5). As of January 2012, over 450 000 valid observations are available from 30 stations. The AMNet also collects ancillary meteorological data and information on land-use and vegetation, when available. We present atmospheric mercury data comparisons by time (3 yr) at 22 unique site locations. Highlighted are contrasting values for site locations across the network: urban versus rural, coastal versus high-elevation and the range of maximum observations. The data presented should catalyze the formation of many scientific questions that may be answered through further in-depth analysis and modeling studies of the AMNet database. All data and methods are publically available through an online database on the NADP website (http://nadp.isws.illinois.edu/amn/). Future network directions are to foster new network partnerships and continue to collect, quality assure, and post data, including dry deposition estimates, for each fraction.

The Atmospheric Mercury Network: measurement and initial examination of an ongoing atmospheric mercury record across North America

NASA Astrophysics Data System (ADS)

Gay, D. A.; Schmeltz, D.; Prestbo, E.; Olson, M.; Sharac, T.; Tordon, R.

2013-11-01

The National Atmospheric Deposition Program (NADP) developed and operates a collaborative network of atmospheric-mercury-monitoring sites based in North America - the Atmospheric Mercury Network (AMNet). The justification for the network was growing interest and demand from many scientists and policy makers for a robust database of measurements to improve model development, assess policies and programs, and improve estimates of mercury dry deposition. Many different agencies and groups support the network, including federal, state, tribal, and international governments, academic institutions, and private companies. AMNet has added two high-elevation sites outside of continental North America in Hawaii and Taiwan because of new partnerships forged within NADP. Network sites measure concentrations of atmospheric mercury fractions using automated, continuous mercury speciation systems. The procedures that NADP developed for field operations, data management, and quality assurance ensure that the network makes scientifically valid and consistent measurements. AMNet reports concentrations of hourly gaseous elemental mercury (GEM), two-hour gaseous oxidized mercury (GOM), and two-hour particulate-bound mercury less than 2.5 microns in size (PBM2.5). As of January 2012, over 450 000 valid observations are available from 30 stations. AMNet also collects ancillary meteorological data and information on land use and vegetation, when available. We present atmospheric mercury data comparisons by time (3 yr) at 21 individual sites and instruments. Highlighted are contrasting values for site locations across the network: urban versus rural, coastal versus high elevation and the range of maximum observations. The data presented should catalyze the formation of many scientific questions that may be answered through further in-depth analysis and modeling studies of the AMNet database. All data and methods are publically available through an online database on the NADP website (http://nadp.sws.uiuc.edu/amn/). Future network directions are to foster new network partnerships and continue to collect, quality assure, and post data, including dry deposition estimates, for each fraction.

XANES study of elemental mercury oxidation over RuO 2/TiO 2 and selective catalytic reduction catalysts for mercury emissions control

DOE PAGES

Liu, Zhouyang; Li, Can; Sriram, Vishnu; ...

2016-07-25

Linear combination fitting of the X-ray Absorption Near Edge Spectroscopy (XANES) was used to quantify oxidized mercury species over RuO 2/TiO 2 and Selective Catalytic Reduction (SCR) catalysts under different simulated flue gas conditions. Halogen gases play a major role in mercury oxidation. In the absence of halogen gas, elemental mercury can react with sulfur that is contained in both the RuO2/TiO2 and SCR catalysts to form HgS and HgSO 4. In the presence of HCl or HBr gas, HgCl 2 or HgBr 2 is the main oxidized mercury species. When both HCl and HBr gases are present, HgBr2 ismore » the preferred oxidation product and no HgCl 2 can be found. The formation of HgO and HgS cannot be neglected with or without halogen gas. Other simulated flue gas components such as NO, NH 3, SO 2 and CO 2 do not have significant effect on oxidized mercury speciation when halogen gas is present.« less

Total mercury, methylmercury, and selected elements in soils of the Fishing Brook watershed, Hamilton County, New York, and the McTier Creek watershed, Aiken County, South Carolina, 2008

USGS Publications Warehouse

Woodruff, Laurel G.; Cannon, William F.; Knightes, Christopher D.; Chapelle, Francis H.; Bradley, Paul M.; Burns, Douglas A.; Brigham, Mark E.; Lowery, Mark A.

2010-01-01

Mercury is an element of on-going concern for human and aquatic health. Mercury sequestered in upland and wetland soils represents a source that may contribute to mercury contamination in sensitive ecosystems. An improved understanding of mercury cycling in stream ecosystems requires identification and quantification of mercury speciation and transport dynamics in upland and wetland soils within a watershed. This report presents data for soils collected in 2008 from two small watersheds in New York and South Carolina. In New York, 163 samples were taken from multiple depths or soil horizons at 70 separate locations near Fishing Brook, located in Hamilton County. At McTier Creek, in Aiken County, South Carolina, 81 samples from various soil horizons or soil depths were collected from 24 locations. Sample locations within each watershed were selected to characterize soil geochemistry in distinct land-cover compartments. Soils were analyzed for total mercury, selenium, total and carbonate carbon, and 42 other elements. A subset of the samples was also analyzed for methylmercury.

Comparison of atmospheric mercury speciation and deposition at nine sites across central and eastern North America

USGS Publications Warehouse

Engle, Mark A.; Tate, Michael T.; Krabbenhoft, David P.; Schauer, James J; Kolker, Allan; Shanley, James B.; Bothner, Michael

2010-01-01

was observed but was highly dependant upon inclusion of data from two sites with exceptionally high deposition. Findings from this study highlight the importance of environmental setting on atmospheric Hg cycling and deposition rates.

MERCURY SPECIATION IN THE PRESENCE OF POLYSULFIDES. (R824778,R827915)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Mercury (II) reduction and co-precipitation of metallic mercury on hydrous ferric oxide in contaminated groundwater.

PubMed

Richard, Jan-Helge; Bischoff, Cornelia; Ahrens, Christian G M; Biester, Harald

2016-01-01

Mercury (Hg) speciation and sorption analyses in contaminated aquifers are useful for understanding transformation, retention, and mobility of Hg in groundwater. In most aquifers hydrous ferric oxides (HFOs) are among the most important sorbents for trace metals; however, their role in sorption or mobilization of Hg in aquifers has been rarely analyzed. In this study, we investigated Hg chemistry and Hg sorption to HFO under changing redox conditions in a highly HgCl2-contaminated aquifer (up to 870μgL(-1) Hg). Results from aqueous and solid phase Hg measurements were compared to modeled (PHREEQC) data. Speciation analyses of dissolved mercury indicated that Hg(II) forms were reduced to Hg(0) under anoxic conditions, and adsorbed to or co-precipitated with HFO. Solid phase Hg thermo-desorption measurements revealed that between 55 and 93% of Hg bound to HFO was elemental Hg (Hg(0)). Hg concentrations in precipitates reached more than 4 weight %, up to 7000 times higher than predicted by geochemical models that do not consider unspecific sorption to and co-precipitation of elemental Hg with HFO. The observed process of Hg(II) reduction and Hg(0) formation, and its retention and co-precipitation by HFO is thought to be crucial in HgCl2-contaminated aquifers with variable redox-conditions regarding the related decrease in Hg solubility (factor of ~10(6)), and retention of Hg in the aquifer. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions.

PubMed

Lee, Chun W; Srivastava, Ravi K; Ghorishi, S Behrooz; Hastings, Thomas W; Stevens, Frank M

2004-12-01

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.

Mercury emissions and species during combustion of coal and waste

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong Yao; Guangqian Luo; Minghou Xu

2006-10-15

The behaviors of mercury evolution for three types of coal and three types of dried sewage sludge are studied using a thermogravimetric (TG) analyzer. The mercury speciations in the flue gas from coal and sludge combustion are also analyzed by implementing a horizontal electrically heated tube furnace. Furthermore, the kinetic calculations of mercury oxidizing processes are carried out using the software package CHEMKIN in order to interpret the homogeneous mechanism of mercury oxidization. The results obtained show that the sulfur content in the sludge inhibits the evolution of mercury at low temperature if the Cl concentration is high enough. Chlorinemore » enhances mercury evolution in the coal combustion, whereas there is no relationship when the Cl concentration is high. Fixed carbon content plays a role in depression of the mercury evolution. Formation of oxidized mercury (HgCl{sub 2}) does not relate to the chlorine concentration in the raw coal and sludge. Whereas the ash and sulfur content in the sludge affects the Hg oxidization, kinetic calculations show that HgCl, Cl{sub 2}, and HOCl formation is important in producing the oxidized mercury during combustion of coal and sludge at 873 K. A suitable temperature for Hg oxidization when Cl{sub 2} is the oxidization resource is 700-1200 K. 32 refs., 10 figs., 5 tabs.« less

Aerobic Mercury-resistant bacteria alter Mercury speciation and retention in the Tagus Estuary (Portugal).

PubMed

Figueiredo, Neusa L; Canário, João; O'Driscoll, Nelson J; Duarte, Aida; Carvalho, Cristina

2016-02-01

Aerobic mercury-resistant bacteria were isolated from the sediments of two highly mercury-polluted areas of the Tagus Estuary (Barreiro and Cala do Norte) and one natural reserve area (Alcochete) in order to test their capacity to transform mercury. Bacterial species were identified using 16S rRNA amplification and sequencing techniques and the results indicate the prevalence of Bacillus sp. Resistance patterns to mercurial compounds were established by the determination of minimal inhibitory concentrations. Representative Hg-resistant bacteria were further tested for transformation pathways (reduction, volatilization and methylation) in cultures containing mercury chloride. Bacterial Hg-methylation was carried out by Vibrio fluvialis, Bacillus megaterium and Serratia marcescens that transformed 2-8% of total mercury into methylmercury in 48h. In addition, most of the HgR bacterial isolates showed Hg(2+)-reduction andHg(0)-volatilization resulting 6-50% mercury loss from the culture media. In summary, the results obtained under controlled laboratory conditions indicate that aerobic Hg-resistant bacteria from the Tagus Estuary significantly affect both the methylation and reduction of mercury and may have a dual face by providing a pathway for pollution dispersion while forming methylmercury, which is highly toxic for living organisms. Copyright © 2015 Elsevier Inc. All rights reserved.

Chemical Form Matters: Differential Accumulation of Mercury Following Inorganic and Organic Mercury Exposures in Zebrafish Larvae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korbas, Malgorzata; MacDonald, Tracy C.; Pickering, Ingrid J.

2013-04-08

Mercury, one of the most toxic elements, exists in various chemical forms each with different toxicities and health implications. Some methylated mercury forms, one of which exists in fish and other seafood products, pose a potential threat, especially during embryonic and early postnatal development. Despite global concerns, little is known about the mechanisms underlying transport and toxicity of different mercury species. To investigate the impact of different mercury chemical forms on vertebrate development, we have successfully combined the zebrafish, a well-established developmental biology model system, with synchrotron-based X-ray fluorescence imaging. Our work revealed substantial differences in tissue-specific accumulation patterns ofmore » mercury in zebrafish larvae exposed to four different mercury formulations in water. Methylmercury species not only resulted in overall higher mercury burdens but also targeted different cells and tissues than their inorganic counterparts, thus revealing a significant role of speciation in cellular and molecular targeting and mercury sequestration. For methylmercury species, the highest mercury concentrations were in the eye lens epithelial cells, independent of the formulation ligand (chloride versus L-cysteine). For inorganic mercury species, in absence of L-cysteine, the olfactory epithelium and kidney accumulated the greatest amounts of mercury. However, with L-cysteine present in the treatment solution, mercuric bis-L-cysteineate species dominated the treatment, significantly decreasing uptake. Our results clearly demonstrate that the common differentiation between organic and inorganic mercury is not sufficient to determine the toxicity of various mercury species.« less

Global Mercury Pathways in the Arctic Ecosystem

NASA Astrophysics Data System (ADS)

Lahoutifard, N.; Lean, D.

2003-12-01

The sudden depletions of atmospheric mercury which occur during the Arctic spring are believed to involve oxidation of gaseous elemental mercury, Hg(0), rendering it less volatile and more soluble. The Hg(II) oxidation product(s) are more susceptible to deposition, consistent with the observation of dramatic increases in snow mercury levels during depletion events. Temporal correlations with ozone depletion events and the proliferation of BrO radicals support the hypothesis that oxidation of Hg(0) occurs in the gas phase and results in its conversion to RGM (Reactive Gaseous Mercury). The mechanisms of Hg(0) oxidation and particularly Hg(II) reduction are as yet unproven. In order to evaluate the feasibility of proposed chemical processes involving mercury in the Arctic atmosphere and its pathway after deposition on the snow from the air, we investigated mercury speciation in air and snow pack at Resolute, Nunavut, Canada (latitude 75° N) prior to and during snow melt during spring 2003. Quantitative, real-time information on emission, air transport and deposition were combined with experimental studies of the distribution and concentrations of different mercury species, methyl mercury, anions, total organic carbon and total inorganic carbon in snow samples. The effect of solar radiation and photoreductants on mercury in snow samples was also investigated. In this work, we quantify mercury removed from the air, and deposited on the snow and the transformation to inorganic and methyl mercury.

ARTIFICIAL INTELLIGENCE-BASED ESTIMATION OF MERCURY SPECIATION IN COMBUSTION FLUE GASES. (R827649)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Mercury speciation in plankton from the Cabo Frio Bay, SE--Brazil.

PubMed

Silva-Filho, Emmanoel V; Kütter, Vinicius T; Figueiredo, Thiago S; Tessier, Emmanuel; Rezende, Carlos E; Teixeira, Daniel C; Silva, Carlos A; Donard, Olivier F X

2014-12-01

Mercury (Hg) is considered a global pollutant, and the scientific community has shown great concern about its toxicity as it may affect the biota of entire systems, through bioaccumulation and bioamplification processes of its organic form, methylmercury (MeHg), along food web. However, few research studies deal with bioaccumulation of Hg from marine primary producers and the first-order consumers. So, this study aims to determine Hg distribution and concentration levels in phytoplankton and zooplankton in the Cabo Frio Bay, Brazil, a site influenced by coastal upwelling. The results from Hg speciation analyses show that inorganic mercury Hg(II) was the predominant specie in plankton from this bay. The annual Hg species distribution in plankton shown mean concentration of 2.00 ± 1.28 ng Hg(II) g(-1) and 0.15 ± 0.08 ng MeHg g(-1) wet weight (phytoplankton) and 2.5 ± 2.03 ng Hg(II) g(-1) and 0.25 ± 0.09 ng MeHg g(-1) wet weight (zooplankton). Therefore, upwelling zones should be considered in the Hg biogeochemical cycle models as a process that enhances Hg(II) bioaccumulation in plankton, raising its bioavailability and shelf deposition.

The influence of avian biovectors on mercury speciation in a bog ecosystem.

PubMed

Kickbush, Jocelyn C; Mallory, Mark L; Murimboh, John D; Rand, Jennie; Klapstein, Sara J; Loder, Amanda L; Hill, Nicholas M; O'Driscoll, Nelson J

2018-05-08

Methylmercury (MeHg) is a neurotoxin and endocrine disruptor that bioaccumulates and biomagnifies through trophic levels, resulting in potentially hazardous concentrations. Although wetlands are known hotspots for mercury (Hg) methylation, the effects of avian biovectors on these processes are poorly understood. We examined Hg speciation and distribution in shallow groundwater and surface water from a raised-bog with over 30years of avian biovector (herring gulls Larus argentatus and great black-backed gulls Larus marinus) colonization and guano input. Compared to the reference site, the avian-impacted bog had elevated concentrations of total dissolved organic carbon (TOC), total Hg, MeHg, phosphate (PO 4 3- ), and other trace metals, notably Pb, As, Cd and Ni. Spatial interpolation showed that the densest area of gull nesting was co-located with areas that had the highest concentrations of PO 4 3- , MeHg, As and Cd, but not total mercury (THg), and models suggested that Mn, PO 4 3- , and dissolved TOC were strong predictors of MeHg. Our findings suggest that while these gulls may not be a significant source of Hg, the excess of PO 4 3- (a well recognised component of guano) and the subsequent changes in water chemistry due to avian biovector subsidies may increase net Hg methylation. Copyright © 2018 Elsevier B.V. All rights reserved.

Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

PubMed

Li, Tao; Wang, Yan; Mao, Huiting; Wang, Shuxiao; Talbot, Robert W; Zhou, Ying; Wang, Zhe; Nie, Xiaoling; Qie, Guanghao

2018-05-01

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L -1 , respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( N d ) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients K ad (5.9-362.7 L g -1 ) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation.

PubMed

Gencarelli, Christian Natale; De Simone, Francesco; Hedgecock, Ian Michael; Sprovieri, Francesca; Pirrone, Nicola

2014-03-01

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model's ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year(-1) of elemental Hg.

Speciation of mercury and mode of transport from placer gold mine tailings

USGS Publications Warehouse

Slowey, A.J.; Rytuba, J.J.; Brown, Gordon E.

2005-01-01

Historic placer gold mining in the Clear Creek tributary to the Sacramento River (Redding, CA) has highly impacted the hydrology and ecology of an important salmonid spawning stream. Restoration of the watershed utilized dredge tailings contaminated with mercury (Hg) introduced during gold mining, posing the possibility of persistent Hg release to the surrounding environment, including the San Francisco Bay Delta. Column experiments have been performed to evaluate the extent of Hg transport under chemical conditions potentially similar to those in river restoration projects utilizing dredge tailings such as at Clear Creek. Physicochemical perturbations, in the form of shifts in column influent ionic strength and the presence of a low molecular weight organic acid, were applied to coarse and fine sand placer tailings containing 109-194 and 69-90 ng of Hg/g, respectively. Significant concentrations of mercury, up to 16 ??g/L, leach from these sediments in dissolved and particle-associated forms. Sequential chemical extractions (SCE) of these tailings indicate that elemental Hg initially introduced during gold mining has been transformed to readily soluble species, such as mercury oxides and chlorides (3-4%), intermediately extractable phases that likely include (in)organic sorption complexes and amalgams (75-87%), and fractions of highly insoluble forms such as mercury sulfides (6-20%; e.g., cinnabar and metacinnabar). Extended X-ray absorption fine structure (EXAFS) spectroscopic analysis of colloids obtained from column effluent identified cinnabar particles as the dominant mobile mercury-bearing phase. The fraction of intermediately extractable Hg phases also likely includes mobile colloids to which Hg is adsorbed. ?? 2005 American Chemical Society.

Selenium inhibits the phytotoxicity of mercury in garlic (Allium sativum).

PubMed

Zhao, Jiating; Gao, Yuxi; Li, Yu-Feng; Hu, Yi; Peng, Xiaomin; Dong, Yuanxing; Li, Bai; Chen, Chunying; Chai, Zhifang

2013-08-01

To investigate the influence of selenium on mercury phytotoxicity, the levels of selenium and mercury were analyzed with inductively coupled plasma-mass spectrometry (ICP-MS) in garlic tissues upon exposure to different dosages of inorganic mercury (Hg(2+)) and selenite (SeO3(2-)) or selenate (SeO4(2-)). The distributions of selenium and mercury were examined with micro-synchrotron radiation X-ray fluorescence (μ-SRXRF), and the mercury speciation was investigated with micro-X-ray absorption near edge structure (μ-XANES). The results show that Se at higher exposure levels (>1mg/L of SeO3(2-) or SeO4(2-)) would significantly inhibit the absorption and transportation of Hg when Hg(2+) levels are higher than 1mg/L in culture media. SeO3(2-) and SeO4(2-) were found to be equally effective in reducing Hg accumulation in garlic. The inhibition of Hg uptake by Se correlates well with the influence of Se on Hg phytotoxicity as indicated by the growth inhibition factor. Elemental imaging using μ-SRXRF also shows that Se could inhibit the accumulation and translocation of Hg in garlic. μ-XANES analysis shows that Hg is mainly present in the forms of Hg-S bonding as Hg(GSH)2 and Hg(Met)2. Se exposure elicited decrease of Hg-S bonding in the form of Hg(GSH)2, together with Se-mediated alteration of Hg absorption, transportation and accumulation, may account for attenuated Hg phytotoxicity by Se in garlic. Copyright © 2013 Elsevier Inc. All rights reserved.

Chemical speciation of heavy metals by surface-enhanced Raman scattering spectroscopy: identification and quantification of inorganic- and methyl-mercury in water

NASA Astrophysics Data System (ADS)

Guerrini, Luca; Rodriguez-Loureiro, Ignacio; Correa-Duarte, Miguel A.; Lee, Yih Hong; Ling, Xing Yi; García de Abajo, F. Javier; Alvarez-Puebla, Ramon A.

2014-06-01

Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms.Chemical speciation of heavy metals has become extremely important in environmental and analytical research because of the strong dependence that toxicity, environmental mobility, persistence and bioavailability of these pollutants have on their specific chemical forms. Novel nano-optical-based detection strategies, capable of overcoming the intrinsic limitations of well-established analytic methods for the quantification of total metal ion content, have been reported, but the speciation of different chemical forms has not yet been achieved. Here, we report the first example of a SERS-based sensor for chemical speciation of toxic metal ions in water at trace levels. Specifically, the inorganic Hg2+ and the more toxicologically relevant methylmercury (CH3Hg+) are selected as analytical targets. The sensing platform consists of a self-assembled monolayer of 4-mercaptopyridine (MPY) on highly SERS-active and robust hybrid plasmonic materials formed by a dense layer of interacting gold nanoparticles anchored onto polystyrene microbeads. The co-ordination of Hg2+ and CH3Hg+ to the nitrogen atom of the MPY ring yields characteristic changes in the vibrational SERS spectra of the organic chemoreceptor that can be qualitatively and quantitatively correlated to the presence of the two different mercury forms. Electronic supplementary information (ESI) available: Representative TEM and ESEM images of AuNPs and PS@Au particles. Optical extinction spectra of AuNPs and PS@Au suspensions. SERS spectra of unmodified PS@Au suspension before and after the addition of CH3Hg+. SERS spectra of PS@Au-MPY upon addition of several metal solutions. Detailed SERS study of the MPY response to high concentration of CH3Hg+. See DOI: 10.1039/c4nr01464b

Local and regional factors affecting atmospheric mercury speciation at a remote location

USGS Publications Warehouse

Manolopoulos, H.; Schauer, J.J.; Purcell, M.D.; Rudolph, T.M.; Olson, M.L.; Rodger, B.; Krabbenhoft, D.P.

2007-01-01

Atmospheric concentrations of elemental (Hg0), reactive gaseous (RGM), and particulate (PHg) mercury were measured at two remote sites in the midwestern United States. Concurrent measurements of Hg0, PHg, and RGM obtained at Devil's Lake and Mt. Horeb, located approximately 65 km apart, showed that Hg0 and PHg concentrations were affected by regional, as well as local sources, while RGM was mainly impacted by local sources. Plumes reaching the Devil's Lake site from a nearby coal-fired power plant significantly impacted SO2 and RGM concentrations at Devil's Lake, but had little impact on Hg0. Our findings suggest that traditional modeling approaches to assess sources of mercury deposited that utilize source emissions and large-scale grids may not be sufficient to predict mercury deposition at sensitive locations due to the importance of small-scale sources and processes. We suggest the use of a receptor-based monitoring to better understand mercury source-receptor relationships. ?? 2007 NRC Canada.

Adsorbents for capturing mercury in coal-fired boiler flue gas.

PubMed

Yang, Hongqun; Xu, Zhenghe; Fan, Maohong; Bland, Alan E; Judkins, Roddie R

2007-07-19

This paper reviews recent advances in the research and development of sorbents used to capture mercury from coal-fired utility boiler flue gas. Mercury emissions are the source of serious health concerns. Worldwide mercury emissions from human activities are estimated to be 1000 to 6000 t/annum. Mercury emissions from coal-fired power plants are believed to be the largest source of anthropogenic mercury emissions. Mercury emissions from coal-fired utility boilers vary in total amount and speciation, depending on coal types, boiler operating conditions, and configurations of air pollution control devices (APCDs). The APCDs, such as fabric filter (FF) bag house, electrostatic precipitator (ESP), and wet flue gas desulfurization (FGD), can remove some particulate-bound and oxidized forms of mercury. Elemental mercury often escapes from these devices. Activated carbon injection upstream of a particulate control device has been shown to have the best potential to remove both elemental and oxidized mercury from the flue gas. For this paper, NORIT FGD activated carbon was extensively studied for its mercury adsorption behavior. Results from bench-, pilot- and field-scale studies, mercury adsorption by coal chars, and a case of lignite-burned mercury control were reviewed. Studies of brominated carbon, sulfur-impregnated carbon and chloride-impregnated carbon were also reviewed. Carbon substitutes, such as calcium sorbents, petroleum coke, zeolites and fly ash were analyzed for their mercury-adsorption performance. At this time, brominated activated carbon appears to be the best-performing mercury sorbent. A non-injection regenerable sorbent technology is briefly introduced herein, and the issue of mercury leachability is briefly covered. Future research directions are suggested.

Characterization of soils from an industrial complex contaminated with elemental mercury

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Carrie L; Watson, David B; Liang, Liyuan

2013-01-01

Historic use of liquid elemental mercury (Hg(0)l) at the Y-12 National Security Complex in Oak Ridge, TN, USA resulted in large deposits of Hg(0)l in the soils. An evaluation of analytical tools for characterizing the speciation of Hg in the soils at the Y-12 facility was conducted and these tequniques were used to examine the speciation of Hg in two soil cores collect at the site. These include X-ray fluorescence (XRF), soil Hg(0) headspace analysis, and total Hg determination by acid digestion coupled with cold vapor atomic absorption. Hg concentrations determined using XRF, a tool that has been suggestions formore » quick onsite characterization of soils, were lower than concentrations determined by HgT analysis and as a result this technique is not suitable for the evaluation of Hg concentrations in heterogeneous soils containing Hg(0)l. Hg(0)g headspace analysis can be used to examine the presence of Hg(0)l in soils and when coupled with HgT analysis an understanding of the speciation of Hg in soils can be obtained. Two soil cores collected within the Y-12 complex highlight the heterogeneity in the depth and extent of Hg contamination, with Hg concentrations ranging from 0.05 to 8400 mg/kg. At one location Hg(0)l was distributed throughout 3.2 meters of core whereas the core from a location only 12 meters away only contained Hg(0)l in 0.3 m zone of the core. Sequential extractions, used to examine the forms of Hg in the soils, indicated that at depths within the core that have low Hg concentrations organically associated Hg is dominant. Soil from the zone of groundwater inundation showed reduced characteristics and the Hg is likely present as Hg-sulfide species. At this location it appears that Hg transported within the groundwater is a source of Hg to the soil. Overall the characterization of Hg in soils containing Hg(0) l is difficult due to the heterogeneous distribution within the soils and this challenge is enhanced in industrial facilities in which fill material comprise most of the soils and historical and continuing reworking of the subsurface has remobilized the Hg.« less

In situ and denuder-based measurements of elemental and reactive gaseous mercury with analysis by laser-induced fluorescence - results from the Reno Atmospheric Mercury Intercomparison Experiment

NASA Astrophysics Data System (ADS)

Hynes, Anthony J.; Everhart, Stephanie; Bauer, Dieter; Remeika, James; Tatum Ernest, Cheryl

2017-01-01

The University of Miami (UM) deployed a sequential two-photon laser-induced fluorescence (2P-LIF) instrument for the in situ measurement of gaseous elemental mercury, Hg(0), during the Reno Atmospheric Mercury Intercomparison Experiment (RAMIX) campaign. A number of extended sampling experiments, typically lasting 6-8 h but on one occasion extending to ˜ 24 h, were conducted, allowing the 2P-LIF measurements of Hg(0) concentrations to be compared with two independently operated instruments using gold amalgamation sampling coupled with cold vapor atomic fluorescence spectroscopic (CVAFS) analysis. At the highest temporal resolution, ˜ 5 min samples, the three instruments measured concentrations that agreed to within 10-25 %. Measurements of total mercury (TM) were made by using pyrolysis to convert total oxidized mercury (TOM) to Hg(0). TOM was then obtained by difference. Variability in the ambient Hg(0) concentration limited our sensitivity for measurement of ambient TOM using this approach. In addition, manually sampled KCl-coated annular denuders were deployed and analyzed using thermal dissociation coupled with single-photon LIF detection of Hg(0). The TOM measurements obtained were normally consistent with KCl denuder measurements obtained with two Tekran speciation systems and with the manual KCl denuder measurements but with very large uncertainty. They were typically lower than measurements reported by the University of Washington (UW) Detector for Oxidized Hg Species (DOHGS) system. The ability of the 2P-LIF pyrolysis system to measure TM was demonstrated during one of the manifold HgBr2 spikes but the results did not agree well with those reported by the DOHGS system. The limitations of the RAMIX experiment and potential improvements that should be implemented in any future mercury instrument intercomparison are discussed. We suggest that instrumental artifacts make a substantial contribution to the discrepancies in the reported measurements over the course of the RAMIX campaign. This suggests that caution should be used in drawing significant implications for the atmospheric cycling of mercury from the RAMIX results.

Speciation, Characterization, And Mobility Of As, Se and Hg In Flue Gas Desulphurization Residues

EPA Science Inventory

Flue gas from coal combustion contains significant amounts of volatile toxic trace elements such as arsenic (As), selenium (Se) and mercury (Hg). The capture of these elements in the flue gas desulphurization (FGD) scrubber unit has resulted in generation of a metal-laden residue...

Speciation, Characterization, And Mobility Of As, Se, and Hg In Flue Gas Desulphurization Residues

EPA Science Inventory

Flue gas from coal combustion contains significant amounts of volatile elements, such as arsenic (As), selenium (Se) and mercury (Hg), which could lead to serious environmental health risks. The capture of these toxic elements in the scrubber with a flue gas desulphurization (FGD...

APPLICATION OF COLD VAPOR ATOMIC ABSORPTION SPECTROSCOPY TO THE MEASUREMENT OF MERCURY SPECIATION IN SUBSTRATE. (R825249)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

ASSESSING AS, HG AND SE SPECIATION AND TRANSPORT IN FLUE GAS DESULPHURIZATION MATERIAL AND DRYWALL

EPA Science Inventory

The risk associated with the reuse of flue gas desulphurization (FGD) material in drywall manufacture is largely determined by the distribution or mineralogical fractionation of mercury(Hg), arsenic (As) and selenium (Se). During coal combustion, FGD material is enriched in volat...

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

PubMed

Hellal, Jennifer; Guédron, Stéphane; Huguet, Lucie; Schäfer, Jörg; Laperche, Valérie; Joulian, Catherine; Lanceleur, Laurent; Burnol, André; Ghestem, Jean-Philippe; Garrido, Francis; Battaglia-Brunet, Fabienne

2015-09-01

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation. Copyright © 2015 Elsevier B.V. All rights reserved.

Annual ambient atmospheric mercury speciation measurement from Longjing, a rural site in Taiwan.

PubMed

Fang, Guor-Cheng; Lo, Chaur-Tsuen; Cho, Meng-Hsien; Zhuang, Yuan-Jie; Tsai, Kai-Hsiang; Huang, Chao-Yang; Xiao, You-Fu

2017-08-01

The main purpose of this study was to monitor ambient air particulates and mercury species [RGM, Hg(p), GEM and total mercury] concentrations and dry depositions over rural area at Longjing in central Taiwan during October 2014 to September 2015. In addition, passive air sampler and knife-edge surrogate surface samplers were used to collect the ambient air mercury species concentrations and dry depositions, respectively, in this study. Moreover, direct mercury analyzer was directly used to detect the mercury Hg(p) and RGM concentrations. The result indicated that: (1) The average highest RGM, Hg(p), GEM and total mercury concentrations, and dry depositions were observed in January, prevailing dust storm occurred in winter season was the possible major reason responsible for the above findings. (2) The highest average RGM, Hg(p), GEM and total mercury concentrations, dry depositions and velocities were occurred in winter. This is because that China is the largest atmospheric mercury (Hg) emitter in the world. Its Hg emissions and environmental impacts need to be evaluated. (3) The results indicated that the total mercury ratios of Kaohsiung to that of this study were 5.61. This is because that Kaohsiung has the largest industry density (~60 %) in Taiwan. (4) the USA showed average lower mercury species concentrations when compared to those of the other world countries. The average ratios of China/USA values were 89, 76 and 160 for total mercury, RGM and Hg(p), respectively, during the years of 2000-2012.

Understanding reduced inorganic mercury accumulation in rice following selenium application: Selenium application routes, speciation and doses.

PubMed

Tang, Wenli; Dang, Fei; Evans, Douglas; Zhong, Huan; Xiao, Lin

2017-02-01

Selenium (Se) has recently been demonstrated to reduce inorganic mercury (IHg) accumulation in rice plants, while its mechanism is far from clear. Here, we aimed at exploring the potential effects of Se application routes (soil or foliar application with Se), speciation (selenite and selenate), and doses on IHg-Se antagonistic interactions in soil-rice systems. Results of our pot experiments indicated that soil application but not foliar application could evidently reduce tissue IHg concentrations (root: 0-48%, straw: 15-58%, and brown rice: 26-74%), although both application routes resulted in comparable Se accumulation in aboveground tissues. Meanwhile, IHg distribution in root generally increased with amended Se doses in soil, suggesting antagonistic interactions between IHg and Se in root. These results provided initial evidence that IHg-Se interactions in the rhizosphere (i.e., soil or rice root), instead of those in the aboveground tissues, could probably be more responsible for the reduced IHg bioaccumulation following Se application. Furthermore, Se dose rather than Se speciation was found to be more important in controlling IHg accumulation in rice. Our findings regarding the importance of IHg-Se interactions in the rhizosphere, together with the systematic investigation of key factors affecting IHg-Se antagonism and IHg bioaccumulation, advance our understanding of Hg dynamics in soil-rice systems. Copyright © 2016 Elsevier Ltd. All rights reserved.

Relationship between Extracellular Low-Molecular-Weight Thiols and Mercury Species in Natural Lake Periphytic Biofilms.

PubMed

Leclerc, Maxime; Planas, Dolors; Amyot, Marc

2015-07-07

The uptake of mercury by microorganisms is a key step in the production of methylmercury, a biomagnifiable toxin. Mercury complexation by low-molecular-weight (LMW) thiols can affect its bioavailability and thus the production of methylmercury. Freshwater biofilms were sampled in the summer using artificial Teflon substrates submerged for over a year to allow natural community colonization in the littoral zone of a Boreal Shield lake. Inside biofilms, concentrations of different extracellular thiol species (thioglycolic acid, l-cysteine-l-glycine, cysteine, and glutathione) were up to 3 orders of magnitude greater than in the surrounding water column, potentially more readily controlling mercury speciation than in the water column. All biofilm thiols except thioglycolic acid were highly correlated to chlorophyll a, likely indicating an algal origin. Extracellular total mercury represented 3 ± 1% of all biofilm mercury and was preferentially found in the capsular fraction. Levels of LMW thiols of presumed algal origins were highly correlated with total mercury in the mobile colloidal fraction of biofilms. We propose that periphytic phototrophic microorganisms such as algae likely affect the bioavailability of mercury through the exudation of LMW thiols, and thus they may play a key role in the production of methylmercury in biofilms.

Effects of in vivo exposure of Mya arenaria to organic and inorganic mercury on phagocytic activity of hemocytes.

PubMed

Fournier, M; Pellerin, J; Clermont, Y; Morin, Y; Brousseau, P

2001-03-28

Marine bivalves are aquatic invertebrate organisms which can be used as bioindicators in environmental monitoring. In vivo effects of mercuric chloride (HgCl(2)) and methylmercury (CH(3)HgCl) on phagocytic function of Mya arenaria hemocytes were evaluated in this study. Clams were exposed to single metal in water for up to 28 days at concentrations ranging from 10(-9) to 10(-5) M. Phagocytic activity of hemocytes was determined by uptake of fluorescent microspheres and flow cytometry. All clams exposed to 10(-5) M HgCl(2) died by day 7 of exposure. The viability of hemocytes was decreased only in clams exposed to 10(-6) M HgCl(2) for 28 days. A significant decrease in phagocytic activity of hemocytes was observed in clams exposed to 10(-6) M of HgCl(2) for 28 days. A similar pattern was observed with CH(3)HgCl, but at an earlier time. Chemical analysis performed on the tissues of the animals clearly show a greater uptake of the organic form of mercury by clams. Furthermore, a clear correlation was established between body burden of mercury and effects on phagocytic activity of hemocytes. Overall, the results of this study show that both speciations of mercury inhibited phagocytic function of Mya arenaria hemocytes following in vivo exposures.

Multiple regression analysis to assess the role of plankton on the distribution and speciation of mercury in water of a contaminated lagoon.

PubMed

Stoichev, T; Tessier, E; Amouroux, D; Almeida, C M; Basto, M C P; Vasconcelos, V M

2016-11-15

Spatial and seasonal variation of mercury species aqueous concentrations and distributions was carried out during six sampling campaigns at four locations within Laranjo Bay, the most mercury-contaminated area of the Aveiro Lagoon (Portugal). Inorganic mercury (IHg(II)) and methylmercury (MeHg) were determined in filter-retained (IHgPART, MeHgPART) and filtered (<0.45μm) fractions (IHg(II)DISS, MeHgDISS). The concentrations of IHgPART depended on site and on dilution with downstream particles. Similar processes were evidenced for MeHgPART, however, its concentrations increased for particles rich in phaeophytin (Pha). The concentrations of MeHgDISS, and especially those of IHg(II)DISS, increased with Pha concentrations in the water. Multiple regression models are able to depict MeHgPART, IHg(II)DISS and MeHgDISS concentrations with salinity and Pha concentrations exhibiting additive statistical effects and allowing separation of possible addition and removal processes. A link between phytoplankton/algae and consumers' grazing pressure in the contaminated area can be involved to increase concentrations of IHg(II)DISS and MeHgPART. These processes could lead to suspended particles enriched with MeHg and to the enhancement of IHg(II) and MeHg availability in surface waters and higher transfer to the food web. Copyright © 2016 Elsevier B.V. All rights reserved.

Speciated atmospheric mercury and its potential source in Guiyang, China

NASA Astrophysics Data System (ADS)

Fu, Xuewu; Feng, Xinbin; Qiu, Guangle; Shang, Lihai; Zhang, Hui

2011-08-01

Speciated atmospheric mercury (Hg) including gaseous elemental mercury (GEM), particulate Hg (PHg), and reactive gaseous Hg (RGM) were continuously measured at an urban site in Guiyang city, southwest China from August to December 2009. The averaged concentrations for GEM, PHg, and RGM were 9.72 ± 10.2 ng m -3, 368 ± 676 pg m -3, and 35.7 ± 43.9 pg m -3, respectively, which were all highly elevated compared to observations at urban sites in Europe and North America. GEM and PHg were characterized by similar monthly and diurnal patterns, with elevated levels in cold months and nighttime, respectively. In contrast, RGM did not exhibit clear monthly and diurnal variations. The variations of GEM, PHg, and RGM indicate the sampling site was significantly impacted by sources in the city municipal area. Sources identification implied that both residential coal burning and large point sources were responsible to the elevated GEM and PHg concentrations; whereas point sources were the major contributors to elevated RGM concentrations. Point sources played a different role in regulating GEM, PHg, and RGM concentrations. Aside from residential emissions, PHg levels was mostly affected by small-scale coal combustion boilers situated to the east of the sampling site, which were scarcely equipped or lacking particulate control devices; whereas point sources situated to the east, southeast, and southwest of the sampling played an important role on the distribution of atmospheric GEM and RGM.

Selenium and arsenic in biology: their chemical forms and biological functions.

PubMed

Shibata, Y; Morita, M; Fuwa, K

1992-01-01

Based on the recent development of analytical methods, sensitive systems for the analysis and speciation of selenium and arsenic have been established. A palladium addition technique was developed for the accurate determination of selenium in biological samples using graphite furnace atomic absorption analysis. For the speciation of the elements, combined methods of HPLC either with ICP-AES or with ICP-MS were found to work well. These systems were applied to the elucidation of the chemical form of the elements in natural samples. Some chemical properties of the selenium-mercury complex in dolphin liver were elucidated: i.e., it was a cationic, water-soluble, low molecular weight compound containing selenium and mercury in a 1:1 molar ratio, and was shown to be different from a known selenium-mercury complex, bis(methylmercuric)selenide. The major selenium compound excreted in human urine was revealed to be other than any of those previously identified (TMSe, selenate, and selenite). TMSe, a suspected major metabolite in urine, was found, if at all, in low levels. The major water-soluble, and lipid-soluble arsenic compounds in a brown seaweed, U. pinnatifida (WAKAME), were rigorously identified, and the results were compared with other data on marine algae and animals. The major organic arsenic compounds (termed "arseno-sugars") in marine algae commonly contain 5-deoxy-5-dimethylarsinyl-ribofuranoside moiety. There are various kinds of arseno-sugar derivatives containing different side-chains attached to the anomeric position of the sugar, and the distribution of each arsenic species seems to be related to algal species. The arseno-sugar (A-XI) is present in every alga so far examined, is metabolized to lipids, and possibly may play some specific role in the algal cells. On the other hand, the major arsenic compound in fish, crustacea and molluscs has been identified as arsenobetaine, which is an arseno-analog of glycinebetaine, a very common osmo-regulator in living organisms. Arsenobetaine is not detected in marine algae while arseno-sugars are not present in marine animals except for some molluscs which contain both compounds in considerable amounts. Arsenobetaine is present in the urine of human beings who have eaten foods derived from marine animals.

Direct determination and speciation of mercury compounds in environmental and biological samples by carbon bed atomic absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skelly, E.M.

A method was developed for the direct determination of mercury in water and biological samples using a unique carbon bed atomizer for atomic absorption spectroscopy. The method avoided sources of error such as loss of volatile mercury during sample digestion and contamination of samples through added reagents by eliminating sample pretreatment steps. The design of the atomizer allowed use of the 184.9 nm mercury resonance line in the vacuum ultraviolet region, which increased sensitivity over the commonly used spin-forbidden 253.7 nm line. The carbon bed atomizer method was applied to a study of mercury concentrations in water, hair, sweat, urine,more » blood, breath and saliva samples from a non-occupationally exposed population. Data were collected on the average concentration, the range and distribution of mercury in the samples. Data were also collected illustrating individual variations in mercury concentrations with time. Concentrations of mercury found were significantly higher than values reported in the literature for a ''normal'' population. This is attributed to the increased accuracy gained by eliminating pretreatment steps and increasing atomization efficiency. Absorption traces were obtained for various solutions of pure and complexed mercury compounds. Absorption traces of biological fluids were also obtained. Differences were observed in the absorption-temperatures traces of various compounds. The utility of this technique for studying complexation was demonstrated.« less

Mercury speciation by differential photochemical vapor generation at UV-B vs. UV-C wavelength

NASA Astrophysics Data System (ADS)

Chen, Guoying; Lai, Bunhong; Mei, Ni; Liu, Jixin; Mao, Xuefei

2017-11-01

Photochemical vapor generation (PVG) is an effective sample introduction scheme for volatile mercury (Hg). Speciation of Hg++ and MeHg+ was fulfilled for the first time by differential PVG under UV-B vs. UV-C wavelength and applied to fish oil supplements. After liquid-liquid extraction, the aqueous extract was mixed with 0.4% anthranilic acid (AA)-20% formic acid (FA) in a quartz coil, and exposed sequentially to 311 nm or 254 nm UV light. The resulting Hg0 vapor was detected by atomic fluorescence spectrometry (AFS). At each wavelength, the AFS intensity was a linear function of Hg++ and MeHg+ concentrations, which were solvable from a set of two equations. This method achieved ultrahigh sensitivity with 0.50 and 0.63 ng mL- 1 limits of detection for Hg++ and MeHg+, respectively, and 73% recovery for MeHg+ at 10 ng mL- 1. Validation was performed by ICP-MS on total Hg. Obviation of chemical or chromatographic separation rendered this method rapid, green, and cost-effective.

Characteristics and source appointment of atmospheric particulate mercury over East China Sea: Implication on the deposition of atmospheric particulate mercury in marine environment.

PubMed

Duan, Lian; Cheng, Na; Xiu, Guangli; Wang, Fujiang; Chen, Ying

2017-05-01

Total Suspended Particulate (TSP) samples were collected at Huaniao Island in northern East China Sea (ECS) from March 2012 to January 2013. Chemical analysis were conducted to measure the concentration of total particulate mercury (TPM) and speciated particulate mercury including HCl-soluble particulate mercury (HPM), elemental particulate mercury (EPM) and residual particulate mercury (RPM). The bromine (Br) and iodine (I) on particles were also detected. The mean concentration of TPM during the study period was 0.23 ± 0.15 ng m -3 , while the obviously seasonal variation was found that the concentrations of TPM in spring, summer, fall and winter were 0.34 ± 0.20 ng m -3 , 0.15 ± 0.03 ng m -3 , 0.15 ± 0.05 ng m -3 and 0.27 ± 0.26 ng m -3 , respectively. The statistically strong correlation of bromine and iodine to HPM was only found in spring with r = 0.81 and 0.77 (p < 0.01), respectively. While the strongest correlations between EPM and bromine and iodine were found in winter with r = 0.92 (Br) and 0.96 (I) (p < 0.01), respectively. The clustered 72-h backward trajectories of different seasons and the whole sampling period were categorized into 4 groups. In spring, the clusters passed a long distance across the East China Sea and brought about low concentration of mercury due to the deposition of mercury over the sea. The cluster of air mass across the sea had low concentration of HPM in winter, which suggested that the oxidation of mercury in winter might be related to other oxidants. During the whole sampling period, the air mass from the north of China contributed to the higher concentration of TPM in Huaniao Island. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mercury in the atmosphere, snow and melt water ponds in the North Atlantic Ocean during Arctic summer.

PubMed

Aspmo, Katrine; Temme, Christian; Berg, Torunn; Ferrari, Christophe; Gauchard, L Pierre-Alexis; Fain, Xavier; Wibetoe, Grethe

2006-07-01

Atmospheric mercury speciation measurements were performed during a 10 week Arctic summer expedition in the North Atlantic Ocean onboard the German research vessel RV Polarstern between June 15 and August 29, 2004. This expedition covered large areas of the North Atlantic and Arctic Oceans between latitudes 54 degrees N and 85 degrees N and longitudes 16 degrees W and 16 degrees E. Gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P) were measured during this study. In addition, total mercury in surface snow and meltwater ponds located on sea ice floes was measured. GEM showed a homogeneous distribution over the open North Atlantic Ocean (median 1.53 +/- 0.12 ng/m3), which is in contrast to the higher concentrations of GEM observed over sea ice (median 1.82 +/- 0.24 ng/m3). It is hypothesized that this results from either (re-) emission of mercury contained in snow and ice surfaces that was previously deposited during atmospheric mercury depletion events (AMDE) in the spring or evasion from the ocean due to increased reduction potential at high latitudes during Arctic summer. Measured concentrations of total mercury in surface snow and meltwater ponds were low (all samples <10 ng/L), indicating that marginal accumulation of mercury occurs in these environmental compartments. Results also reveal low concentrations of RGM and Hg-P without a significant diurnal variability. These results indicate that the production and deposition of these reactive mercury species do not significantly contribute to the atmospheric mercury cycle in the North Atlantic Ocean during the Arctic summer.

[Mercury Transport from Glacier to Runoff in Typical Inland Glacial Area in the Tibetan Plateau].

PubMed

Sun, Xue-jun; Wang, Kang; Guo, Jun-ming; Kang, Shi-chang; Zhang, Guo-shuai; Huang, Jie; Cong, Zhi-yuan; Zhang, Qiang-gong

2016-02-15

To investigate the transport of mercury from glacier to runoff in typical inland glacial area in the Tibetan Plateau, we selected Zhadang glacier and Qugaqie river Basin located in the Nyainqentanglha Range region and collected samples from snow pit, glacier melt-water and Qugaqie river water during 15th August to 9'h September 2011. Mercury speciation and concentrations were determined and their distribution and controlling factors in different environmental compartments were analyzed. The results showed that the average THg concentrations were (3.79 +/- 5.12) ng x L(-1), (1.06 +/- 0.77) ng x L(-1) and (1.02 +/- 0.24) ng x L(-1) for glacier snow, glacier melt-water and Qugaqie river water, respectively, all of which were at the global background levels. Particulate-bound mercury accounted for large proportion of mercury in all environmental matrices, while mercury in glacial melt-water was controlled by total suspended particle, and mercury in Qugaqie river water co-varied with runoff. With the increase of temperature, glacier melted and released water as well as mercury into glacier-fed river. Total mercury concentrations in glacier melt water, upstream and downstream peaked at 14:00, 16:00 and after 20:00, respectively, reflecting the process of mercury release from glacier and its subsequent transport in the glacier fed river. The transport of riverine mercury was controlled by multiple factors. Under the context of climate change, glacier ablation and the increasing runoff will play increasingly important roles in mercury release and transport.

Mercury speciation and exchanges at the air-water interface of a tropical artificial reservoir, French Guiana.

PubMed

Muresan, B; Cossa, D; Richard, S; Burban, B

2007-10-15

The distribution and speciation of mercury (Hg) in air, rain, and surface waters from the artificial tropical lake of Petit-Saut in French Guiana were investigated during the 2003/04 period. In the air, total gaseous mercury (TGM) at the dam station averaged 12+/-2 pmol m(-3) of which >98% was gaseous elemental mercury (GEM). GEM distribution depicted a day-night cycling with high concentrations (up to 15 pmol m(-3)) at dawn and low concentrations (down to 5 pmol m(-3)) at nightfall. Reactive gaseous mercury (RGM) represented <1% of the GEM with a mean concentration of 4+/-3 fmol m(-3). Diel RGM variations were negatively related to GEM. In the rain, the sum of all Hg species in the unfiltered (HgT(UNF)) averaged 16+/-12 pmol L(-1). Temporal distribution of HgT(UNF) exhibited a pattern of high concentrations during the late dry seasons (up to 57.5 pmol L(-1)) and low concentrations (down to 2.7 pmol L(-1)) in the course of the wet seasons. Unfiltered reactive (HgR(UNF)), dissolved gaseous (DGM) and monomethyl (MMHg(UNF)) Hg constituted 20, 5 and 5% of HgT(UNF), respectively. All measured Hg species were positively related and displayed negative relationships with the pH of the rain. In the reservoir surface waters, dissolved total mercury (HgT(D)) averaged 3.4+/-1.2 pmol L(-1) of which 10% consisted of DGM. DGM showed a trend of high concentrations during the dry seasons (480+/-270 fmol L(-1)) and lower (230+/-130 fmol L(-1)) in the course of the wet seasons. Diel variations included diurnal photo-induced DGM production (of about 60 fmol L(-1) h(-1)) coupled to minute to hour oxidation/reduction cycles (of >100 fmol L(-1) amplitude). Finally, calculated atmospheric Hg inputs to the Petit-Saut reservoir represented 14 mol yr(-1) whereas DGM evasion reached 23 mol yr(-1). Apportionment among forms of Hg deposition indicated that up to 75% of the total Hg invasive flux follows the rainfall pathway.

Sediment-water partitioning of inorganic mercury in estuaries.

PubMed

Turner, A; Millward, G E; Le Roux, S M

2001-12-01

The sediment-water partitioning and speciation of inorganic mercury have been studied under simulated estuarine conditions by monitoring the hydrophobicity and uptake of dissolved 203Hg(II) in samples from a variety of estuarine environments. A persistent increase in the distribution coefficientwith increasing salinity is inconsistent with inorganic speciation calculations, which predict an increase in the concentration of the soluble HgCl4(2-) complex (or reduction in sediment-water distribution coefficient) with increasing salinity. Partition data are, however, defined by an empirical equation relating to the salting out of nonelectrolytes via electrostriction and are characterized by salting constants between about 1.4 and 2.0 L mol(-1). Salting out of the neutral, covalent chloro-complex, HgCl2(0), is predicted but cannot account for the magnitude of salting out observed. Since Hg(II) strongly complexes with dissolved (and particulate) organic matter in natural environments, of more significance appears to be the salting out of Hg(II)-organic complexes. Operational measurements of the speciation of dissolved Hg(II) using Sep-Pak C18 columns indicate a reduction in the proportion of hydrophobic (C18-retained) dissolved Hg(II) complexes with increasing salinity, both in the presence and absence of suspended particles. Ratios of hydrophobic Hg(ll) before and after particle addition suggest a coupled salting out-sorption mechanism, with the precise nature of Hg(II) species salted out being determined bythe characteristics and concentrations of dissolved and sediment organic matter.

Mercury speciation and emissions from coal combustion in Guiyang, Southwest China.

PubMed

Tang, Shunlin; Feng, Xinbin; Qiu, Jianrong; Yin, Guoxun; Yang, Zaichan

2007-10-01

Although China has been regarded as one of the largest anthropogenic mercury emission source with coal combustion, so far the actual measurements of Hg species and Hg emissions from the combustion and the capture of Hg in Chinese emission control devices were very limited. Aiming at Hg mercury species measurements in Guiyang, the capital city of Guizhou province in Southwest China, we studied flue gases of medium-to-small-sized industrial steam coal-firing boiler (10-30 t/h) with no control devices, medium-to-small-sized industrial steam coal-firing boiler with WFGD and large-scale coal combustion with ESPs using Ontario Hytro method. We obtained mercury emission factors of the three representative coal combustion and estimated mercury emissions in Guiyang in 2003, as well as the whole province from 1986 to 2002. Coal combustion in Guiyang emitted 1898 kg mercury to the atmosphere, of which 36% Hg is released from power plants, 41% from industrial coal combustion, and 23% from domestic users, and 267 kg is Hg(p), 813 kg is Hg(2+) and 817 kg is Hg0. Mercury emission in Guizhou province increased sharply from 5.8 t in 1986 to 16.4 t in 2002. With the implementation of national economic strategy of China's Western Development, the annual mercury emission from coal combustion in the province is estimated to be about 32 t in 2015.

The distribution and speciation of mercury in the free troposphere of the Pacific Northwest

NASA Astrophysics Data System (ADS)

Swartzendruber, Philip C.

2009-12-01

Mercury (Hg) is a potent neurotoxin which has accumulated in aquatic ecosystems and has led to increased neurological and developmental health risks for wildlife and humans worldwide. This dissertation aims to improve our understanding of the global mercury cycle by investigating its distribution and chemistry in the free troposphere. A Hg speciation system was deployed at the summit station of Mt. Bachelor, OR (2.7 km asl) (MBO). It measured gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate mercury (PHg) from May-Aug 2005. The system detected RGM up to 600 pg/m3, or 40% of the total airborne Hg. The high RGM was not due to anthropogenic emissions, but was produced in situ. The GEOS-Chem chemical transport model (CTM) was unable to reproduce the magnitude of the highest RGM concentrations using the assumed OH and ozone oxidation mechanisms. The vertical distribution of mercury in the Pacific Northwest was investigated with an aircraft campaign in 2006 during the INTEX-B campaign. Three of the eight flights observed significant enhancements of GEM and CO in the free troposphere. The enhancement ratios (0.0067 (+/-0.0027) ng/m3 /ppb) were consistent with previous observations of Asian industrial influence at MBO and in Okinawa, Japan. Backtrajectories and GEOS-Chem CTM simulations supported Asian long range transport as the source of the influence. A technique was developed to measure RGM in an aircraft. In this technique, RGM is measured by difference and simultaneously is directly collected on a denuder. The system was tested in the laboratory with an RGM proxy, (HgCl 2 at ˜500 pg/m3), and the agreement of the denuder-difference techniques was 15% (+/-13%, relative percent difference). The instrument was tested in five flights from the surface to 5 km. A linear correlation of all denuder-difference data had a slope of 0.41. RGM enhancements (200-500 pg/m3) were observed with varying relationships to ozone and water vapor which suggests that upper tropospheric influence is not a controlling factor. There was no mean vertical trend in total Hg (GEM + RGM) up to 5 km. The only factor common to all high RGM, was low aerosol scattering (<2 M/m).

Modelling the long-term fate of mercury in a lowland tidal river. I. Description of two finite segment models.

PubMed

Braga, M Cristina B; Birkett, Jason W; Lester, John N; Shaw, George

2010-02-01

Crucial determinants of the potential effects of mercury in aquatic ecosystems are the speciation, partitioning, and cycling of its various species. These processes are affected by site-specific factors, such as water chemistry, sediment transport, and hydrodynamics. This study presents two different approaches to the development of one-dimensional/dynamic-deterministic models for the evaluation and prediction of mercury contamination in a lowland tidal river, the River Yare (Norfolk, UK). The models described here were developed to encompass the entire river system and address the mass balance of mercury in a multicompartment system, including tidal reversal and saline limit. The models were focused on river systems, with the River Yare being used as a case study because previous modelling studies have been centred on lakes and wetlands whilst there is a paucity of information for rivers. Initial comparisons with actual measured water parameters (salinity and suspended solids) indicate that both models exhibit good agreement with the actual values.

Bioavailable mercury cycling in polar snowpacks.

PubMed

Larose, Catherine; Dommergue, Aurélien; Marusczak, Nicolas; Coves, Jacques; Ferrari, Christophe P; Schneider, Dominique

2011-03-15

Polar regions are subject to contamination by mercury (Hg) transported from lower latitudes, severely impacting human and animal health. Atmospheric Mercury Depletion Events (AMDEs) are an episodic process by which Hg is transferred from the atmospheric reservoir to arctic snowpacks. The fate of Hg deposited during these events is the subject of numerous studies, but its speciation remains unclear, especially in terms of environmentally relevant forms such as bioavailable mercury (BioHg). Here, using a bacterial mer-lux biosensor, we report the fraction of newly deposited Hg at the surface and at the bottom of the snowpack that is bioavailable. Snow samples were collected over a two-month arctic field campaign in 2008. In surface snow, BioHg is related to atmospheric Hg deposition and snow fall events were shown to contribute to higher proportions of BioHg than AMDEs. Based on our data, AMDEs represent a potential source of 20 t.y(-1) of BioHg, while wet and dry deposition pathways may provide 135-225 t.y(-1) of BioHg to Arctic surfaces.

Phytoremediation of Ionic and Methyl Mercury Pollution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant.« less

Using X-ray Microscopy and Hg L3 XANES to study Hg Binding in the Rhizosphere of Spartina Cordgrass

PubMed Central

Patty, Cynthia; Barnett, Brandy; Mooney, Bridget; Kahn, Amanda; Levy, Silvio; Liu, Yijin; Pianetta, Piero; Andrews, Joy C

2009-01-01

San Francisco Bay has been contaminated historically by mercury from mine tailings as well as contemporary industrial sources. Native Spartina foliosa and non-native S. alterniflora-hybrid cordgrasses are dominant florae within the SF Bay estuary environment. Understanding mercury uptake and transformations in these plants will help to characterize the significance of their roles in mercury biogeochemical cycling in the estuarine environment. Methylated mercury can be biomagnified up the food web, resulting in levels in sport fish up to one million times greater than in surrounding waters and resulting in advisories to limit fish intake. Understanding the uptake and methylation of mercury in the plant rhizosphere can yield insight into ways to manage mercury contamination. The transmission x-ray microscope on beamline 6-2 at the Stanford Synchrotron Radiation Lightsource (SSRL) was used to obtain absorption contrast images and 3D tomography of Spartina foliosa roots that were exposed to 1 ppm Hg (as HgCl2) hydroponically for one week. Absorption contrast images of micron-sized roots from S. foliosa revealed dark particles, and dark channels within the root, due to Hg absorption. 3D tomography showed that the particles are on the root surface, and slices from the tomographic reconstruction revealed that the particles are hollow, consistent with microorganisms with a thin layer of Hg on the surface. Hg L3 XANES of ground-up plant roots and Hg L3 micro-XANES from microprobe analysis of micron-sized roots (60–120 microns in size) revealed three main types of speciation in both Spartina species: Hg-S ligation in a form similar to Hg(II) cysteine, Hg-S bonding as in cinnabar and metacinnabar, and methylmercury-carboxyl bonding in a form similar to methylmercury acetate. These results are interpreted within the context of obtaining a “snapshot” of mercury methylation in progress. PMID:19848152

Using X-ray microscopy and Hg L3 XANES to study Hg binding in the rhizosphere of Spartina cordgrass.

PubMed

Patty, Cynthia; Barnett, Brandy; Mooney, Bridget; Kahn, Amanda; Levy, Silvio; Liu, Yijin; Pianetta, Piero; Andrews, Joy C

2009-10-01

San Francisco Bay has been contaminated historically by mercury from mine tailings as well as contemporary industrial sources. Native Spartina foliosa and non-native S. alterniflora-hybrid cordgrasses are dominant florae within the SF Bay estuary environment. Understanding mercury uptake and transformations in these plants will help to characterize the significance of their roles in mercury biogeochemical cycling in the estuarine environment. Methylated mercury can be biomagnified up the food web, resulting in levels in sport fish up to 1 million times greater than in surrounding waters and resulting in advisories to limit fish intake. Understanding the uptake and methylation of mercury in the plant rhizosphere can yield insight into ways to manage mercury contamination. The transmission X-ray microscope on beamline 6-2 at the Stanford Synchrotron Radiation Lightsource (SSRL) was used to obtain absorption contrast images and 3D tomography of Spartina foliosa roots that were exposed to 1 ppm Hg (as HgCl2) hydroponically for 1 week. Absorption contrast images of micrometer-sized roots from S. foliosa revealed dark particles, and dark channels within the root, due to Hg absorption. 3D tomography showed that the particles are on the root surface, and slices from the tomographic reconstruction revealed that the particles are hollow, consistent with microorganisms with a thin layer of Hg on the surface. Hg L3 XANES of ground-up plant roots and Hg L3 micro-XANES from microprobe analysis of micrometer-sized roots (60-120 microm in size) revealed three main types of speciation in both Spartina species: Hg-S ligation in a form similar to Hg(II) cysteine, Hg-S bonding as in cinnabar and metacinnabar, and methylmercury-carboxyl bonding in a form similar to methylmercury acetate. These results are interpreted within the context of obtaining a "snapshot" of mercury methylation in progress.

Speciation and bioavailability of mercury in sediments impacted by gold mining in Colombia.

PubMed

Pinedo-Hernández, José; Marrugo-Negrete, José; Díez, Sergi

2015-01-01

Mercury (Hg) speciation and bioavailability were studied in surface sediments affected by artisanal and small-scale gold mining (ASGM) in the Mojana region of Colombia. The results demonstrated higher levels in sampling stations that receive water streams carrying Hg from mining areas. The T-Hg concentrations were slightly elevated with values between 196.2 and 1187.6 ng g(-1) dry weight (dw) (mean 524.2±256.8 ng g(-1) dw). The MeHg concentrations were significantly correlated with the T-Hg and organic matter (OM) and represent between 1.7% and 3.6% (mean: 2.6%) of the T-Hg. A five-step sequential extraction procedure shown that most of T-Hg in sediments occur primarily as organically bound Hg (Hg-o), which constitutes 48.4% of the T-Hg, followed by elemental Hg fraction (Hg-e) bound to amorphous compounds, such as Fe/Mn oxides with 26.5%, and the fraction bound to sulfur (Hg-s), which constitutes 18.7%. Exchangeable Hg (Hg-w; water-soluble Hg and stomach acid soluble mercury; Hg-h) represents between 1.7% and 4.7%. These fractions constitute a low percentage but exhibit a high level of risk when entering the water column, and they can bioaccumulate in organisms. The significant relationship between OM, T-Hg and MeHg suggests an important role in the control of the distribution, mobility and bioavailability of the Hg in the sediments. Copyright © 2014 Elsevier Ltd. All rights reserved.

Speciation and Attenuation of Arsenic and Selenium at Coal Combustion By-Product Management Facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

K. Ladwig

2005-12-31

The overall objective of this project was to evaluate the impact of key constituents captured from power plant air streams (principally arsenic and selenium) on the disposal and utilization of coal combustion products (CCPs). Specific objectives of the project were: (1) to develop a comprehensive database of field leachate concentrations at a wide range of CCP management sites, including speciation of arsenic and selenium, and low-detection limit analyses for mercury; (2) to perform detailed evaluations of the release and attenuation of arsenic species at three CCP sites; and (3) to perform detailed evaluations of the release and attenuation of seleniummore » species at three CCP sites. Each of these objectives was accomplished using a combination of field sampling and laboratory analysis and experimentation. All of the methods used and results obtained are contained in this report. For ease of use, the report is subdivided into three parts. Volume 1 contains methods and results for the field leachate characterization. Volume 2 contains methods and results for arsenic adsorption. Volume 3 contains methods and results for selenium adsorption.« less

Assessment of Gaseous Oxidized Mercury Measurement Accuracy at an Atmospheric Mercury Network (AMNet) Site

NASA Astrophysics Data System (ADS)

Luke, W. T.

2016-12-01

Recent laboratory and field research has documented and explored the biases and inaccuracies of the measurement of gaseous oxidized mercury (GOM) compounds using KCl-coated denuders. We report on the development of a simple, automated GOM calibration source and its deployment at NOAA/Air Resources Laboratory's Atmospheric Mercury Network (AMNet) site at the Mauna Loa Observatory (MLO) on the island of Hawaii. NOAA/ARL has developed a permeation-tube based calibration source with an extremely simple flow path that minimizes surface adsorptive effects and losses. The source was used to inject HgBr2 into one of two side-by-side Tekran® mercury speciation systems at MLO to characterize GOM measurement accuracy under a variety of atmospheric conditions. Due to its unique topography and meteorology, MLO experiences katabatic (upslope/downslope) mesoscale flow superimposed on the synoptic trade wind circulation of the tropics. Water vapor, ozone, and other trace atmospheric constituents often display pronounced diurnal variations at the site, which frequently encounters air characteristic of the middle free troposphere at night, and of the tropical marine boundary layer during the day. Results presented here will assist in the better understanding of the biases underlying GOM measurements in global mercury monitoring networks and may allow the development of correction factors for ambient data.

Dithizone-functionalized solid phase extraction-displacement elution-high performance liquid chromatography-inductively coupled plasma mass spectrometry for mercury speciation in water samples.

PubMed

Yin, Yong-guang; Chen, Ming; Peng, Jin-feng; Liu, Jing-fu; Jiang, Gui-bin

2010-06-15

A novel and simple solid phase extraction (SPE)-high performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) method was developed for determination of inorganic mercury (IHg), methylmercury MeHg and ethylmercury (EtHg) in water samples in the present work. The procedure involves pre-functionalization of the commercially available C18 SPE column with dithizone, loading water sample, displacement elution of mercury species by Na(2)S(2)O(3) solution, followed by HPLC-ICP-MS determination. Characterization and optimization of operation parameters of this new SPE procedure were discussed, including eluting reagent selection, concentration of eluting reagent, volume of eluting reagent, effect of NaCl and humic acid in sample matrix. At optimized conditions, the detection limits of mercury species for 100mL water sample were about 3ngL(-1) and the average recoveries were 93.7, 83.4, and 71.7% for MeHg, IHg and EtHg, respectively, by spiking 0.2microgL(-1) mercury species into de-ion water. Stability experiment reveals that both the dithizone-functionalized SPE cartridge and the mercury species incorporated were stable in the storage procedure. These results obtained demonstrate that SPE-HPLC-ICP-MS is a simple and sensitive technique for the determination of mercury species at trace level in water samples with high reproducibility and accuracy.

Observations of reactive gaseous mercury in the free troposphere at the Mount Bachelor Observatory

NASA Astrophysics Data System (ADS)

Swartzendruber, P. C.; Jaffe, D. A.; Prestbo, E. M.; Weiss-Penzias, P.; Selin, N. E.; Park, R.; Jacob, D. J.; Strode, S.; Jaeglé, L.

2006-12-01

We measured gaseous elemental mercury (GEM), particulate mercury (PHg), and reactive gaseous mercury (RGM), along with CO, ozone, and aerosol scatter at the Mount Bachelor Observatory (2.7 km above sea level), Oregon, from May to August 2005. The mean mercury concentrations (at standard conditions) were 1.54 ng/m3 (GEM), 5.2 pg/m3 (PHg), and 43 pg/m3 (RGM). RGM enhancements, up to 600 pg/m3, occurred at night and were linked to a diurnal pattern of upslope and downslope flows that mixed in boundary layer air during the day and free tropospheric air at night. During the night, RGM was inversely correlated (P < 0.0001) with CO (r = -0.36), GEM (r = -0.73), and H2O (r = -0.44), was positively correlated with ozone (r = 0.38), and could not be linked to recent anthropogenic emissions from local sources or long-range transport. Principal component analysis and a composite of change in RGM versus change in GEM during RGM enhancements indicate that a nearly quantitative shift in speciation is associated with increases in ozone and decreases in water vapor and CO. This argues that high concentrations of RGM are present in the free troposphere because of in situ oxidation of GEM to RGM. A global chemical transport model reproduces the RGM mean and diurnal pattern but underestimates the magnitude of the largest observed enhancements. Since the only modeled, in situ RGM production mechanisms are oxidation of GEM by ozone and OH, this implies that there are faster reaction rates or additional RGM production mechanisms in the free troposphere.

Sensitivity model study of regional mercury dispersion in the atmosphere

NASA Astrophysics Data System (ADS)

Gencarelli, Christian N.; Bieser, Johannes; Carbone, Francesco; De Simone, Francesco; Hedgecock, Ian M.; Matthias, Volker; Travnikov, Oleg; Yang, Xin; Pirrone, Nicola

2017-01-01

Atmospheric deposition is the most important pathway by which Hg reaches marine ecosystems, where it can be methylated and enter the base of food chain. The deposition, transport and chemical interactions of atmospheric Hg have been simulated over Europe for the year 2013 in the framework of the Global Mercury Observation System (GMOS) project, performing 14 different model sensitivity tests using two high-resolution three-dimensional chemical transport models (CTMs), varying the anthropogenic emission datasets, atmospheric Br input fields, Hg oxidation schemes and modelling domain boundary condition input. Sensitivity simulation results were compared with observations from 28 monitoring sites in Europe to assess model performance and particularly to analyse the influence of anthropogenic emission speciation and the Hg0(g) atmospheric oxidation mechanism. The contribution of anthropogenic Hg emissions, their speciation and vertical distribution are crucial to the simulated concentration and deposition fields, as is also the choice of Hg0(g) oxidation pathway. The areas most sensitive to changes in Hg emission speciation and the emission vertical distribution are those near major sources, but also the Aegean and the Black seas, the English Channel, the Skagerrak Strait and the northern German coast. Considerable influence was found also evident over the Mediterranean, the North Sea and Baltic Sea and some influence is seen over continental Europe, while this difference is least over the north-western part of the modelling domain, which includes the Norwegian Sea and Iceland. The Br oxidation pathway produces more HgII(g) in the lower model levels, but overall wet deposition is lower in comparison to the simulations which employ an O3 / OH oxidation mechanism. The necessity to perform continuous measurements of speciated Hg and to investigate the local impacts of Hg emissions and deposition, as well as interactions dependent on land use and vegetation, forests, peat bogs, etc., is highlighted in this study.

Influence of chemical speciation and biofilm composition on mercury accumulation by freshwater biofilms.

PubMed

Dranguet, P; Le Faucheur, S; Cosio, C; Slaveykova, V I

2017-01-25

Mercury (Hg) is a pollutant of high concern for aquatic systems due to the biomagnification of its methylated form along the food chain. However, in contrast to other metals, gaining knowledge of its bioavailable forms for aquatic microorganisms remains challenging, making Hg risk assessment difficult. Ubiquitous and sessile freshwater biofilms are well known to accumulate and to transform Hg present in their ambient environment. The present study thus aims to evaluate whether non-extractable (proxy of intracellular) Hg accumulated by biofilms could be a good indicator of Hg bioavailability for microorganisms in freshwater. To that end, the link between Hg concentration and speciation, as well as biofilm composition (percentage of abiotic, biotic, chlorophyll and phycocyanin-fractions and abundance of dsrA, gcs, merA and hgcA bacterial genes) and biofilm Hg accumulation was examined. The studied biofilms were grown on artificial substrata in four reservoirs along the Olt River (Romania), which was contaminated by Hg coming from chlor-alkali plant effluents. The 0.45 μm-filterable Hg concentrations in ambient waters were measured and inorganic IHg speciation was modelled. Biofilms were analyzed for their non-extractable IHg and methylmercury (MeHg) contents as well as for their composition. The non-extractable IHg content was related, but not significantly, to the concentration of total IHg (r 2 = 0.88, p = 0.061) whereas a significant correlation was found with the predicted IHg concentration that is not bound to dissolved organic matter (r 2 = 0.95, p = 0.027), despite its extremely low concentrations (10 -25 M), showing a limitation of the thermodynamic Hg modelling to predict Hg bioavailability. The studied biofilms were different in biomass and composition and a principal component analysis showed that the non-extractable IHg content correlated with the abundance of the merA and hgcA genes, while MeHg accumulation was only linked with the abundance of the rRNA 16S gene. The present study suggests that non-extractable IHg concentrations in biofilms are a useful proxy of IHg bioavailable forms in waters whereas the hgcA and merA genes are good biomarkers of both biofilm IHg exposure and bioavailability.

Adsorption of mercury by activated carbon prepared from dried sewage sludge in simulated flue gas.

PubMed

Park, Jeongmin; Lee, Sang-Sup

2018-04-25

Conversion of sewage sludge to activated carbon is attractive as an alternative method to ocean dumping for the disposal of sewage sludge. Injection of activated carbon upstream of particulate matter control devices has been suggested as a method to remove elemental mercury from flue gas. Activated carbon was prepared using various activation temperatures and times and was tested for their mercury adsorption efficiency using lab-scale systems. To understand the effect of the physical property of the activated carbon, its mercury adsorption efficiency was investigated as a function of their Brunauer-Emmett-Teller (BET) surface area. Two simulated flue gas conditions: (1) without hydrogen chloride (HCl) and (2) with 20 ppm HCl, were used to investigate the effect of flue gas composition on the mercury adsorption capacity of activated carbon. Despite very low BET surface area of the prepared sewage sludge activated carbons, their mercury adsorption efficiencies were comparable under both simulated flue gas conditions to those of pinewood and coal activated carbons. After injecting HCl into the simulated flue gas, all sewage sludge activated carbons demonstrated high adsorption efficiencies, i.e., more than 87%, regardless of their BET surface area. IMPLICATIONS We tested activated carbons prepared from dried sewage sludge to investigate the effect of their physical properties on their mercury adsorption efficiency. Using two simulated flue gas conditions, we conducted mercury speciation for the outlet gas. We found that the sewage sludge activated carbon had comparable mercury adsorption efficiency to pinewood and coal activated carbons, and the presence of HCl minimized the effect of physical property of the activated carbon on its mercury adsorption efficiency.

Interactions between Snow Chemistry, Mercury Inputs and Microbial Population Dynamics in an Arctic Snowpack

PubMed Central

Larose, Catherine; Prestat, Emmanuel; Cecillon, Sébastien; Berger, Sibel; Malandain, Cédric; Lyon, Delina; Ferrari, Christophe; Schneider, Dominique; Dommergue, Aurélien; Vogel, Timothy M.

2013-01-01

We investigated the interactions between snowpack chemistry, mercury (Hg) contamination and microbial community structure and function in Arctic snow. Snowpack chemistry (inorganic and organic ions) including mercury (Hg) speciation was studied in samples collected during a two-month field study in a high Arctic site, Svalbard, Norway (79°N). Shifts in microbial community structure were determined by using a 16S rRNA gene phylogenetic microarray. We linked snowpack and meltwater chemistry to changes in microbial community structure by using co-inertia analyses (CIA) and explored changes in community function due to Hg contamination by q-PCR quantification of Hg-resistance genes in metagenomic samples. Based on the CIA, chemical and microbial data were linked (p = 0.006) with bioavailable Hg (BioHg) and methylmercury (MeHg) contributing significantly to the ordination of samples. Mercury was shown to influence community function with increases in merA gene copy numbers at low BioHg levels. Our results show that snowpacks can be considered as dynamic habitats with microbial and chemical components responding rapidly to environmental changes. PMID:24282515

Mercury genomics in the Arctic Ocean

NASA Astrophysics Data System (ADS)

Bowman, K.; Lamborg, C. H.; Collins, E.; Hammerschmidt, C. R.; Agather, A. M.

2017-12-01

Methyl-mercury production in the ocean is likely dependent on microbial activity, however, methylation pathways remain elusive. In the Arctic, high concentrations of methyl-mercury are found in top predator marine mammals and seabirds. As a result of seafood consumption, pregnant women and women of child-bearing age in the Arctic often have blood Hg concentrations that exceed U.S. and Canadian safety guidelines. To understand the chemical cycling of mercury in the Arctic Ocean we participated in the 2015 U.S. GEOTRACES Arctic expedition (GN01) to measure Hg speciation in the water column of the Bering Sea, Makarov basin, and Canada basin between Dutch Harbor, Alaska and the North Pole. At select stations, seawater was filtered through 0.22 µm Sterivex filters and genomic DNA was collected using a phenol-chloroform extraction. Broad-range degenerate PCR primers were used to detect the presence of hgcAB, and clade-specific degenerate quantitative PCR primers were used to determine the abundance of hgcA. Metagenomic sequencing was done at three stations to identify taxonomic and functional groups, and to search for hgcA-like genes that the PCR primers may have missed.

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

PubMed

Zhong, Huan; Wang, Wen-Xiong

2008-01-01

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.

Results of Hg speciation testing on tank 39 and 1Q16 tank 50 samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.

2016-03-07

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team.i,ii The seventeenth shipment of samples was designated to include two Tank 39 samples and the 1Q16 Tank 50 Quarterly WAC sample. The surface Tank 39 sample was pulled at 262.1” from the tank bottom, and the depth Tank 39 sample was pulled at 95” from the tank bottom. The 1Q16 Tank 50 WAC sample was drawn from the 1-L variable depth sample received bymore » SRNL.« less

Observations of speciated atmospheric mercury at three sites in Nevada: Evidence for a free tropospheric source of reactive gaseous mercury

NASA Astrophysics Data System (ADS)

Weiss-Penzias, Peter; Gustin, Mae Sexauer; Lyman, Seth N.

2009-07-01

Air mercury (Hg) speciation was measured for 11 weeks (June-August 2007) at three sites simultaneously in Nevada, USA. Mean reactive gaseous Hg (RGM) concentrations were elevated at all sites relative to those reported for locations not directly influenced by known point sources. RGM concentrations at all sites displayed a regular diel pattern and were positively correlated with ozone (O3) and negatively correlated with elemental Hg (Hg0) and dew point temperature (Tdp). Superimposed on the diel changes were 2- to 7-day periods when RGM concentrations increased across all three sites, producing significant intersite correlations of RGM daily means (r = 0.53-0.76, p < 0.0001). During these periods, enhanced O3 concentrations and lower Tdp were also observed. Back trajectories were applied to develop gridded frequency distribution (GFD) plots and determine trajectory residence times (TRT) in specific source boxes. The GFD for the upper-quartile RGM daily means at one site showed a contributing airflow regime from the high-altitude subtropics with little precipitation, while that developed for the lower-quartile RGM concentrations indicated predominantly lower-altitude westerly flow and precipitation. Daily mean TRT in a subtropical high-altitude source box (>2 km and <35°N) explained a component of the daily mean RGM at two sites (r2 = 0.37 and 0.27, p < 0.05). These observations indicate that long-range transport of RGM from the free troposphere is a potentially important component of Hg input to rural areas of the western United States.

Speciation, behaviour, and fate of mercury under oxy-fuel combustion conditions.

PubMed

Córdoba, Patricia; Maroto-Valer, M; Delgado, Miguel Angel; Diego, Ruth; Font, Oriol; Querol, Xavier

2016-02-01

The work presented here reports the first study in which the speciation, behaviour and fate of mercury (Hg) have been evaluated under oxy-fuel combustion at the largest oxy-Pulverised Coal Combustion (oxy-PCC) demonstration plant to date during routine operating conditions and partial exhaust flue gas re-circulation to the boiler. The effect of the CO2-rich flue gas re-circulation on Hg has also been evaluated. Results reveal that oxy-PCC operational conditions play a significant role on Hg partitioning and fate because of the continuous CO2-rich flue gas re-circulations to the boiler. Mercury escapes from the cyclone in a gaseous form as Hg(2+) (68%) and it is the prevalent form in the CO2-rich exhaust flue gas (99%) with lower proportions of Hg(0) (1.3%). The overall retention rate for gaseous Hg is around 12%; Hg(0) is more prone to be retained (95%) while Hg(2+) shows a negative efficiency capture for the whole installation. The negative Hg(2+) capture efficiencies are due to the continuous CO2-rich exhaust flue gas recirculation to the boiler with enhanced Hg contents. Calculations revealed that 44mg of Hg were re-circulated to the boiler as a result of 2183 re-circulations of CO2-rich flue gas. Especial attention must be paid to the role of the CO2-rich exhaust flue gas re-circulation to the boiler on the Hg enrichment in Fly Ashes (FAs). Copyright © 2015 Elsevier Inc. All rights reserved.

Speciation and quantification of Hg in sediments contaminated by artisanal gold mining in the Gualaxo do Norte River, Minas Gerais, SE, Brazil.

PubMed

da Penha Rhodes, Valdilene; de Lena, Jorge Carvalho; Santolin, Camila Vidal Alves; da Silva Pinto, Thais; Mendes, Louise Aparecida; Windmöller, Cláudia Carvalhinho

2017-12-28

The Iron Quadrangle in SE Brazil was, in the eighteenth century, one of the most important Au producing regions of Brazil. In this region, gold is produced, even today, by artisanal methods that use Hg to increase the extraction efficiency with no control of Hg release to water systems and the atmosphere. In this context, the Gualaxo do Norte River is of particular interest; its springs are located in the Doce River basin, an important Brazilian basin that supplies water for 3.5 million people. The main goal of this work was to quantify and speciate the Hg in the sediments of the Gualaxo do Norte River using a direct mercury analyzer and gas chromatography-pyrolysis-atomic fluorescence detection system. Statistical analyses consisted of principal component analysis, aiming to assess interactions among elements and species and to group the variables in factors affecting the properties of sediment. The results show that total Hg (THg) and methylmercury (CH 3 Hg + ) concentrations in samples ranged from 209 to 1207 μg kg -1 and from 0.07 to 1.00 μg kg -1 , respectively (methylation percentages from 0.01 to 0.27%). Thermal desorption analysis showed that mercury is mainly present in the oxidized form, and correlation analyses pointed to a relationship between THg and MnO, indicating that manganese can oxidize and/or adsorb Hg. Together, MO and CH 3 Hg + are important parameters in the third principal component, indicating the influence of OM on the methylation process. This first investigation on Hg methylation in this small-scale gold mining area points to the possibility of Hg bioaccumulation and to the need of better understanding the biogeochemical cycle of Hg in this area. Samples were collected in 2012, prior to the 2015 Fundão Dam disaster. The results are also a record of the characteristics of the sediment prior to that event.

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions.

PubMed

Lee, Chun W; Serre, Shannon D; Zhao, Yongxin; Lee, Sung Jun; Hastings, Thomas W

2008-04-01

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.

Strategies for the engineered phytoremediation of toxic element pollution: mercury and arsenic.

PubMed

Meagher, Richard B; Heaton, Andrew C P

2005-12-01

Plants have many natural properties that make them ideally suited to clean up polluted soil, water, and air, in a process called phytoremediation. We are in the early stages of testing genetic engineering-based phytoremediation strategies for elemental pollutants like mercury and arsenic using the model plant Arabidopsis. The long-term goal is to develop and test vigorous, field-adapted plant species that can prevent elemental pollutants from entering the food-chain by extracting them to aboveground tissues, where they can be managed. To achieve this goal for arsenic and mercury, and pave the way for the remediation of other challenging elemental pollutants like lead or radionucleides, research and development on native hyperaccumulators and engineered model plants needs to proceed in at least eight focus areas: (1) Plant tolerance to toxic elementals is essential if plant roots are to penetrate and extract pollutants efficiently from heterogeneous contaminated soils. Only the roots of mercury- and arsenic-tolerant plants efficiently contact substrates heavily contaminated with these elements. (2) Plants alter their rhizosphere by secreting various enzymes and small molecules, and by adjusting pH in order to enhance extraction of both essential nutrients and toxic elements. Acidification favors greater mobility and uptake of mercury and arsenic. (3) Short distance transport systems for nutrients in roots and root hairs requires numerous endogenous transporters. It is likely that root plasma membrane transporters for iron, copper, zinc, and phosphate take up ionic mercuric ions and arsenate. (4) The electrochemical state and chemical speciation of elemental pollutants can enhance their mobility from roots up to shoots. Initial data suggest that elemental and ionic mercury and the oxyanion arsenate will be the most mobile species of these two toxic elements. (5) The long-distance transport of nutrients requires efficient xylem loading in roots, movement through the xylem up to leaves, and efficient xylem unloading aboveground. These systems can be enhanced for the movement of arsenic and mercury. (6) Aboveground control over the electrochemical state and chemical speciation of elemental pollutants will maximize their storage in leaves, stems, and vascular tissues. Our research suggests ionic Hg(II) and arsenite will be the best chemical species to trap aboveground. (7) Chemical sinks can increase the storage capacity for essential nutrients like iron, zinc, copper, sulfate, and phosphate. Organic acids and thiol-rich chelators are among the important chemical sinks that could trap maximal levels of mercury and arsenic aboveground. (8) Physical sinks such as subcellular vacuoles, epidermal trichome cells, and dead vascular elements have shown the evolutionary capacity to store large quantities of a few toxic pollutants aboveground in various native hyperaccumulators. Specific plant transporters may already recognize gluthione conjugates of Hg(II) or arsenite and pump them into vacuole.

Cork stoppers as an effective sorbent for water treatment: the removal of mercury at environmentally relevant concentrations and conditions.

PubMed

Lopes, Cláudia B; Oliveira, Joana R; Rocha, Luciana S; Tavares, Daniela S; Silva, Carlos M; Silva, Susana P; Hartog, Niels; Duarte, Armando C; Pereira, E

2014-02-01

The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 μg/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 μg/L.

Speciated atmospheric mercury in the marine boundary layer of the Bohai Sea and Yellow Sea

NASA Astrophysics Data System (ADS)

Wang, Chunjie; Ci, Zhijia; Wang, Zhangwei; Zhang, Xiaoshan; Guo, Jia

2016-04-01

The objectives of this study are to identify the spatial and temporal distributions of gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and fine particulate mercury (HgP2.5) in the marine boundary layer (MBL) of the Bohai Sea (BS) and Yellow Sea (YS), and to investigate the relationships between mercury species and meteorological parameters. The mean concentrations of GEM, RGM, and HgP2.5 were 2.03 ng m-3, 2.5 pg m-3, and 8.2 pg m-3 in spring, and 2.09 ng m-3, 4.3 pg m-3, and 8.3 pg m-3 in fall. Reactive mercury (RGM + HgP2.5) represented < 1% of total atmospheric mercury (GEM + RGM + HgP2.5), which indicated that most mercury export in the MBL was GEM and the direct outflow of reactive mercury was very small. Moreover, GEM concentrations over the BS were generally higher than those over the YS both in spring and fall. Although RGM showed a homogeneous distribution over the BS and YS both in spring and fall, the mean RGM concentration in fall was significantly higher than that in spring. In contrast, the spatial distribution of HgP2.5 generally reflected a gradient with high levels near the coast of China and low levels in the open sea, suggesting the significant atmospheric mercury outflow from China. Interestingly, the mean RGM concentrations during daytime were significantly higher than those during nighttime both in spring and fall, while the opposite results were observed for HgP2.5. Additionally, RGM positively correlates with air temperature while negatively correlates with relative humidity. In conclusion, the elevated atmospheric mercury levels in the BS and YS compared to other open seas suggested that the human activities had a significant influence on the oceanic mercury cycle downwind of China.

EFFECTS OF FLY ASH TRANSITION METAL CONTENT AND FLUE GAS HCL/SO2 RATIO ON MERCURY SPECIATION IN WASTE COMBUSTION

EPA Science Inventory

The paper presents results of research on the effect of sulfur dioxide (SO2):HCI ratio on heterogeneous Hg0 oxidation. The addition of SO2 to moist flue gas at high SO2:HCI ratios (4:1 to 10:1) caused a decrease in oxidation of Hg0 relative to flur gas without SO2. This is attrib...

Effect of secondary fuels and combustor temperature on mercury speciation in pulverized fuel co-combustion: part 1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shishir P. Sable; Wiebren de Jong; Ruud Meij

2007-08-15

The present work mainly involves bench scale studies to investigate partitioning of mercury in pulverized fuel co-combustion at 1000 and 1300{sup o}C. High volatile bituminous coal is used as a reference case and chicken manure, olive residue, and B quality (demolition) wood are used as secondary fuels with 10 and 20% thermal shares. The combustion experiments are carried out in an entrained flow reactor with a fuel input of 7-8 kWth. Elemental and total gaseous mercury concentrations in the flue gas of the reactor are measured on-line, and ash is analyzed for particulate mercury along with other elemental and surfacemore » properties. Animal waste like chicken manure behaves very differently from plant waste. The higher chlorine contents of chicken manure cause higher ionic mercury concentrations whereas even with high unburnt carbon, particulate mercury reduces with increase in the chicken manure share. This might be a problem due to coarse fuel particles, low surface area, and iron contents. B-wood and olive residue cofiring reduces the emission of total gaseous mercury and increases particulate mercury capture due to unburnt carbon formed, fine particles, and iron contents of the ash. Calcium in chicken manure does not show any effect on particulate or gaseous mercury. It is probably due to a higher calcium sulfation rate in the presence of high sulfur and chlorine contents. However, in plant waste cofiring, calcium may have reacted with chlorine to reduce ionic mercury to its elemental form. According to thermodynamic predictions, almost 50% of the total ash is melted to form slag at 1300{sup o}C in cofiring because of high calcium, iron, and potassium and hence mercury and other remaining metals are concentrated in small amounts of ash and show an increase at higher temperatures. No slag formation was predicted at 1000{sup o}C. 24 refs., 8 figs., 4 tabs.« less

Utility of ultrasound assisted-cloud point extraction and spectophotometry as a preconcentration and determination tool for the sensitive quantification of mercury species in fish samples

NASA Astrophysics Data System (ADS)

Altunay, Nail

2018-01-01

The current study reports, for the first time, the development of a new analytical method employing ultrasound assisted-cloud point extraction (UA-CPE) for the extraction of CH3Hg+ and Hg2 + species from fish samples. Detection and quantification of mercury species were performed at 550 nm by spectrophotometry. The analytical variables affecting complex formation and extraction efficiency were extensively evaluated and optimized by univariate method. Due to behave 14-fold more sensitive and selective of thiophene 2,5-dicarboxylic acid (H2TDC) to Hg2 + ions than CH3Hg+ in presence of mixed surfactant, Tween 20 and SDS at pH 5.0, the amounts of free Hg2 + and total Hg were spectrophotometrically established at 550 nm by monitoring Hg2 + in the pretreated- and extracted-fish samples in ultrasonic bath to speed up extraction using diluted acid mixture (1:1:1, v/v, 4 mol L- 1 HNO3, 4 mol L- 1 HCl, and 0.5 mol L- 1 H2O2), before and after pre-oxidation with permanganate in acidic media. The amount of CH3Hg+ was calculated from difference between total Hg and Hg2 + amounts. The UA-CPE method showed to be suitable for the extraction and determination of mercury species in certified reference materials. The results were in a good agreement (with Student's t-test at 95% confidence limit) with the certified values, and the relative standard deviation was lower than 3.2%. The limits of detection have been 0.27 and 1.20 μg L- 1, for Hg2 + from aqueous calibration solutions and matrix-matched calibration solutions spiked before digestion, respectively, while it is 2.43 μg L- 1 for CH3Hg+ from matrix-matched calibration solutions. A significant matrix effect was not observed from comparison of slopes of both calibration curves, so as to represent the sample matrix. The method was applied to fish samples for speciation analysis of Hg2 + and CH3Hg+. In terms of speciation, while total Hg is detected in range of 2.42-32.08 μg kg- 1, the distribution of mercury in fish were in range of 0.7-11.06 μg kg- 1 for CH3Hg+ and in range of 1.72-24.56 μg kg- 1 for Hg2 +.

Shipborne measurements of mercury in the marine boundary layer

NASA Astrophysics Data System (ADS)

Soerensen, A. L.; Skov, H.; Christensen, J.; Glasius, M.; Soerensen, B. T.; Steffen, A.; Jensen, B.; Christoffersen, C.; Madsen, H. W.; Johnson, M. S.

2008-12-01

Mercury accumulates in the human body, for example when consumed through fish and other aquatic animals. While it is poisonous to adults, only low doses are sufficient to cause severe effects in the development of foetuses where the source of mercury is through the mother's blood. From once being a problem restricted to certain populations, the negative effects of mercury consumption are becoming a global problem due to high anthropogenic emissions, long range transport in the atmosphere and bioaccumulation in the food chain after deposition. It is therefore important to understand the atmospheric photochemical pathways of mercury from source to sink. We have used a TEKRAN 2537A mercury vapor analyzer with a TEKRAN 1130 mercury speciation unit to measure gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) during an eight month circumnavigation of the Earth. This is the longest single track time series of mercury concentrations that we know of. This has offered the opportunity to give a global overview of the marine boundary layer (MBL) distribution of both GEM and RGM. Supplemented with earlier cruise measurements, we now have a broader knowledge of global GEM and RGM concentration in the MBL. The Galathea 3 cruise data offers new knowledge of the mechanisms causing the distribution patterns of GEM and RGM in the MBL. The first analysis of the Galathea 3 data indicates that measurements show a concentration difference between the northern and the southern hemispheres. In the northern hemisphere, the mean concentration in the free ocean is 2.06 ng/m3 and, including values down wind of Western Europe, an average value of 2.47 ng/m3 was found. Measurements in the southern hemisphere show a mean concentration of 1.24 ng/m3 and 1.57 ng/m3 where values close to the coast of West Africa are included. In contrast, the concentration levels of RGM are similar for the two hemispheres (northern hemisphere 3.40 pg/m3, southern hemisphere 3.95 pg/m3). Some interesting events involving coastal influence where observed during the cruise. For example, along the coast of Antarctica GEM and RGM peaked simultaneously with some of the highest observed concentrations of RGM during the cruise. Along the west coast of South Africa measurements of GEM were observed up to 10.16 ng/m3 with a mean of 5.17 ng/m3 between the 10th and 15th of November 2006.

The fate of Mercury in Arctic regions: New understanding of atmospheric chemical processes and mercury stability in snow.

NASA Astrophysics Data System (ADS)

Steffen, A.; Ferrari, C.; Dommergue, A.; Scherz, T.; Lawson, G.; Leiatch, R.

2006-12-01

Mercury is a known toxic pollutant in the Arctic environment. Atmospheric mercury depletion events (AMDEs) have been studied in the Arctic since 1995. While advances in understanding this newly discovered cycling of mercury in the atmosphere have been made, much of the chemistry and the impact of this annually reoccurring event to the Arctic ecosystem are not well understood. Four years of continuous measurements at Alert, Canada of so-called reactive gaseous mercury (RGM) and mercury associated to particles (PHg) coupled with ongoing snow sampling have produced new information on the atmospheric chemistry and deposition of these mercury species to the Arctic. A distinct pattern during the springtime period in the distribution of these atmospheric mercury species has emerged. This pattern is characterized by the predominance of PHg concentration at the onset of the AMDEs. During the latter part of the AMDE season, there is an obvious swicth in the speciation of mercury to RGM as the main component during AMDEs. This swicth from PHg to RGM is clearly linked to a significant increase of mercury in the snow. In addition, concentrations of PHg are clearly linked with particles in the air that are primarily associated with Arctic haze. Recently, similar results have also been observed in Ny-Alesund (Svalbard). Further observations indicate that once deposited, the deposited mercury appears to evolve chemically in the snow. This change in mercury may impact the transfer of mercury to the environment during snow melt. These first time observed links between atmospheric conditions and subsequent deposition of mercury may help to ascertain the conditions throughout the Arctic as to when significant deposition of mercury will occur. It is proposed that should the concentration of atmospheric particles increase in the Arctic due to long range transport from emission sources, an increase in the deposition of mercury to this environment will increase during the springtime period. Additionally, information from these data demonstrates that the primary product of the oxidation of gaseous elemental mercury (GEM) is RGM which will associate to the particles and exist as PHg when these particles are available in the atmosphere. The oxidation of GEM is, therefore, a result of homogeneous chemistry. Results from this ongoing study and the impacts of this pollutant to the Arctic environment will be presented.

New technique for quantification of elemental hg in mine wastes and its implications for mercury evasion into the atmosphere

USGS Publications Warehouse

Jew, A.D.; Kim, C.S.; Rytuba, J.J.; Gustin, M.S.; Brown, Gordon E.

2011-01-01

Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline ??-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica-carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica-carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range. ?? 2011 American Chemical Society.

How important is biomass burning in Canada to mercury contamination?

NASA Astrophysics Data System (ADS)

Fraser, Annemarie; Dastoor, Ashu; Ryjkov, Andrei

2018-05-01

Wildfire frequency has increased in past four decades in Canada and is expected to increase in future as a result of climate change (Wotton et al., 2010). Mercury (Hg) emissions from biomass burning are known to be significant; however, the impact of biomass burning on air concentration and deposition fluxes in Canada has not been previously quantified. We use estimates of burned biomass from FINN (Fire INventory from NCAR) and vegetation-specific emission factors (EFs) of mercury to investigate the spatiotemporal variability of Hg emissions in Canada. We use Environment and Climate Change Canada's GEM-MACH-Hg (Global Environmental Multi-scale, Modelling Air quality and Chemistry model, mercury version) to quantify the impact of biomass burning in Canada on spatiotemporal variability of air concentrations and deposition fluxes of mercury in Canada. We use North American gaseous elemental mercury (GEM) observations (2010-2015), GEM-MACH-Hg, and an inversion technique to optimize the EFs for GEM for five vegetation types represented in North American fires to constrain the biomass burning impacts of mercury. The inversion results suggest that EFs representing more vegetation types - specifically peatland - are required. This is currently limited by the sparseness of measurements of Hg from biomass burning plumes. More measurements of Hg concentration in the air, specifically downwind of fires, would improve the inversions. We use three biomass burning Hg emissions scenarios in Canada to conduct three sets of model simulations for 2010-2015: two scenarios where Hg is emitted only as GEM using literature or optimized EFs and a third scenario where Hg is emitted as GEM using literature EFs and particle bound mercury (PBM) emitted using the average GEM/PBM ratio from lab measurements. The three biomass burning emission scenarios represent a range of possible values for the impacts of Hg emissions from biomass burning in Canada on Hg concentration and deposition. We find total biomass burning Hg emissions to be highly variable from year to year and estimate average 2010-2015 total atmospheric biomass burning emissions of Hg in Canada to be between 6 and 14 t during the biomass burning season (i.e. from May to September), which is 3-7 times the mercury emission from anthropogenic sources in Canada for this period. On average, 65 % of the emissions occur in the provinces west of Ontario. We find that while emissions from biomass burning have a small impact on surface air concentrations of GEM averaged over individual provinces/territories, the impact at individual sites can be as high as 95 % during burning events. We estimate average annual mercury deposition from biomass burning in Canada to be between 0.3 and 2.8 t, compared to 0.14 t of mercury deposition from anthropogenic sources during the biomass burning season in Canada. Compared to the biomass burning emissions, the relative impact of fires on mercury deposition is shifted eastward, with on average 54 % percent of the deposition occurring in provinces west of Ontario. While the relative contribution of Canadian biomass burning to the total mercury deposition over each province/territory is no more than 9 % between 2010 and 2015, the local contribution in some locations (including areas downwind of biomass burning) can be as high as 80 % (e.g. northwest of Great Slave Lake in 2014) from May to September. We find that northern Alberta and Saskatchewan, central British Columbia, and the area around Great Slave Lake in the Northwest Territories are at greater risk of mercury contamination from biomass burning. GEM is considered to be the dominant mercury species emitted from biomass burning; however, there remains an uncertainty in the speciation of mercury released from biomass burning. We find that the impact of biomass burning emissions on mercury deposition is significantly affected by the uncertainty in speciation of emitted mercury because PBM is more readily deposited closer to the emission sources than GEM; an addition of ˜ 18 % percent of mercury emission from biomass burning in the form of PBM in the model increases the 6-year average deposition by ˜ 4 times.

Mercury and arsenic in the gold mining regions of the Ankobra River basin in Ghana

NASA Astrophysics Data System (ADS)

Bannerman, W.; Potin-Gautier, M.; Amoureux, D.; Tellier, S.; Rambaud, A.; Babut, M.; Adimado, A.; Beinhoff, C.

2003-05-01

The river Ankobra flows through the principal gold mining centres in Western Ghana, draining a total area of 8272 km^2 to join the Atlantic ocean. Mercury is used by thousands of small-scale miners in the region to amalgamate gold. Ores mined in some deep shafts and surface mines are arsenopyrites and the region is marked by the presence of heaps of arsenic - rich mine tailings from both past and recent activities. This study was conducted to assess the impact of mining activities on the distribution and speciation of arsenic and mercury in the aquatic environment of the Ankobra River. In all, water (filtered and non-filtered) and bed sediments were collected from various locations within the watershed. Principal parameters investigated include total mercury, arsenic (III), arsenic (V), monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA). Seasonal and spatial variations of these parameters were investigated. Quality control systems were adopted at both the environmental and analytical stages of the study. ln general, areas close to the mining centres are the most pollilited. As (V)/As (III) ratios in water are reversed after the first 100-km of the river length with the onset of industrial influence downstream.

Two new sources of reactive gaseous mercury in the free troposphere

NASA Astrophysics Data System (ADS)

Timonen, H.; Ambrose, J. L.; Jaffe, D. A.

2012-11-01

Mercury (Hg) is a neurotoxin that bioaccumulates in the food chain. Mercury is emitted to the atmosphere primarily in its elemental form, which has a long lifetime allowing global transport. It is known that atmospheric oxidation of gaseous elemental mercury (GEM) generates reactive gaseous mercury (RGM) which plays an important role in the atmospheric mercury cycle by enhancing the rate of mercury deposition to ecosystems. However, the primary GEM oxidants, and the sources and chemical composition of RGM are poorly known. Using speciated mercury measurements conducted at the Mt. Bachelor Observatory since 2005 we present two previously unidentified sources of RGM to the free troposphere (FT). Firstly, we observed elevated RGM concentrations, large RGM/GEM-ratios, and anti-correlation between RGM and GEM during Asian long-rang transport events, demonstrating that RGM is formed from GEM by in-situ oxidation in some anthropogenic pollution plumes in the FT. During the Asian pollution events the measured RGM/GEM-ratios reached peak values, up to ~0.20, which are significantly larger than ratios typically measured (RGM/GEM < 0.05) in the Asian source region. Secondly, we observed very high RGM levels - the highest reported in the FT - in clean air masses that were processed upwind of Mt. Bachelor Observatory over the Pacific Ocean. The high RGM concentrations (up to 700 pg m-3), high RGM/GEM-ratios (up to 1), and very low ozone levels during these events provide the first observational evidence indicating significant GEM oxidation in the lower FT. The identification of these processes changes our conceptual understanding of the formation and distribution of oxidized Hg in the global atmosphere.

[Research on the mercury species in Jiaozhou Bay in spring].

PubMed

Xu, Liao-Qi; Liu, Ru-Hai; Wang, Jin-Yu; Tang, Ai-Kun; Wang, Shu

2012-01-01

In April 2010, seawater samples collected every twenty minutes in the Jiaozhou Bay were separated and determined in-situ and indoor to study mercury speciation and its daily variation and to further understand the end-result and effect of mercury on offshore environment. Results showed that dissolved element mercury (DEM) concentration of seawater ranged from 38.2 pg x L(-1) to 156 pg x L(-1), with an average value of 97.5 pg x L(-1). The highest and the lowest value appeared at around 13:00 and 17:30 respectively under the influence of tide and light intensity. DEM concentration gradually declined with depth. DEM of surface sea primarily derived from photoreduction of bivalent mercury. Dissolved mercury (DHg) concentrations ranged from 7.32 ng x L(-1) to 49.1 ng x L(-1) (average value was 13.9 ng x L(-1)), from 4.39 ng x L(-1) to 19.3 ng x L(-1) (average value was 7.94 ng x L(-1)) for dissolved reactive mercury (RHg). The maximum peaks of DHg and RHg all appeared around 13:00, due to dirty seawater carried by tidal movement in the lowest tide. The variation trend with depth of RHg and DHg concentrations was similar at different time. Under the influence of the light and water temperature, the ratio of RHg to DHg was higher in the surface water. RHg accounted for 62% of DHg, so the mercury had relatively high activity and biological availability, and contributed to the form of DEM. The methylmercury concentration was low, with an average value of 0.30 ng x L(-1), and some samples were lower than the detection limit.

Biogenesis of Mercury-Sulfur Nanoparticles in Plant Leaves from Atmospheric Gaseous Mercury.

PubMed

Manceau, Alain; Wang, Jianxu; Rovezzi, Mauro; Glatzel, Pieter; Feng, Xinbin

2018-04-03

Plant leaves serve both as a sink for gaseous elemental mercury (Hg) from the atmosphere and a source of toxic mercury to terrestrial ecosystems. Litterfall is the primary deposition pathway of atmospheric Hg to vegetated soils, yet the chemical form of this major Hg input remains elusive. We report the first observation of in vivo formation of mercury sulfur nanoparticles in intact leaves of 22 native plants from six different species across two sampling areas from China. The plants grew naturally in soils from a mercury sulfide mining and retorting region at ambient-air gaseous-Hg concentrations ranging from 131 ± 19 to 636 ± 186 ng m -3 and had foliar Hg concentration between 1.9 and 31.1 ng Hg mg -1 dry weight (ppm). High energy resolution X-ray absorption near-edge structure (HR-XANES) spectroscopy shows that up to 57% of the acquired Hg is nanoparticulate, and the remainder speciated as a bis-thiolate complex (Hg(SR) 2 ). The fractional amount of nanoparticulate Hg is not correlated with Hg concentration. Variation likely depends on leaf age, plant physiology, and natural variability. Nanoparticulate Hg atoms are bonded to four sulfide or thiolate sulfur atoms arranged in a metacinnabar-type (β-HgS) coordination environment. The nanometer dimension of the mercury-sulfur clusters outmatches the known binding capacity of plant metalloproteins. These findings give rise to challenging questions on their exact nature, how they form, and their biogeochemical reactivity and fate in litterfall, whether this mercury pool is recycled or stored in soils. This study provides new evidence that metacinnabar-type nanoparticles are widespread in oxygenated environments.

Regression modeling of gas-particle partitioning of atmospheric oxidized mercury from temperature data

NASA Astrophysics Data System (ADS)

Cheng, Irene; Zhang, Leiming; Blanchard, Pierrette

2014-10-01

Models describing the partitioning of atmospheric oxidized mercury (Hg(II)) between the gas and fine particulate phases were developed as a function of temperature. The models were derived from regression analysis of the gas-particle partitioning parameters, defined by a partition coefficient (Kp) and Hg(II) fraction in fine particles (fPBM) and temperature data from 10 North American sites. The generalized model, log(1/Kp) = 12.69-3485.30(1/T) (R2 = 0.55; root-mean-square error (RMSE) of 1.06 m3/µg for Kp), predicted the observed average Kp at 7 of the 10 sites. Discrepancies between the predicted and observed average Kp were found at the sites impacted by large Hg sources because the model had not accounted for the different mercury speciation profile and aerosol compositions of different sources. Site-specific equations were also generated from average Kp and fPBM corresponding to temperature interval data. The site-specific models were more accurate than the generalized Kp model at predicting the observations at 9 of the 10 sites as indicated by RMSE of 0.22-0.5 m3/µg for Kp and 0.03-0.08 for fPBM. Both models reproduced the observed monthly average values, except for a peak in Hg(II) partitioning observed during summer at two locations. Weak correlations between the site-specific model Kp or fPBM and observations suggest the role of aerosol composition, aerosol water content, and relative humidity factors on Hg(II) partitioning. The use of local temperature data to parameterize Hg(II) partitioning in the proposed models potentially improves the estimation of mercury cycling in chemical transport models and elsewhere.

Speciation analysis of mercury by dispersive solid-phase extraction coupled with capillary electrophoresis.

PubMed

Li, Jinhua; Liu, Junying; Lu, Wenhui; Gao, Fangfang; Wang, Liyan; Ma, Jiping; Liu, Huitao; Liao, Chunyang; Chen, Lingxin

2018-04-23

A pretreatment method of dispersive solid-phase extraction (DSPE) along with back-extraction followed by CE-UV detector was developed for the determination of mercury species in water samples. Sulfhydryl-functionalized SiO 2 microspheres (SiO 2 -SH) were synthesized and used as DSPE adsorbents for selective extraction and enrichment of three organic mercury species namely ethylmercury (EtHg), methylmercury (MeHg), and phenylmercury (PhHg), along with L-cysteine (L-cys) containing hydrochloric acid as back-extraction solvent. Several main extraction parameters were systematically investigated including sample pH, amount of adsorbent, extraction and back-extraction time, volume of eluent, and concentration of hydrochloric acid. Under optimal conditions, good linearity was achieved with correlation coefficients over 0.9990, in the range of 4-200 μg/L for EtHg, and 2-200 μg/L for MeHg and PhHg. The LODs were obtained of 1.07, 0.34, and 0.24 μg/L for EtHg, MeHg, and PhHg, respectively, as well as the LOQs were 3.57, 1.13, and 0.79 μg/L, respectively, with enrichment factors ranging from 109 to 184. Recoveries were attained with tap and lake water samples in a range of 62.3-107.2%, with relative standard deviations of 3.5-10.1%. The results proved that the method of SiO 2 -SH based DSPE coupled with CE-UV was a simple, rapid, cost-effective, and eco-friendly alternative for the determination of mercury species in water samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mercury speciation, fluxes, and fate in the volcanically acidified fluids of Copahue volcano, Argentina

NASA Astrophysics Data System (ADS)

Kading, T.; Varekamp, J. C.; Andersson, M.; Balcom, P.; Mason, R. P.

2010-12-01

The behavior of mercury in volcanic acid springs and acidified rivers is poorly known, despite the potential impact this vector of contamination has on local surface and ground water quality. Mercury was measured in a volcanically acidified river system (pH<1 - 3), the Rio Agrio in the Neuquen province of Argentina, which discharges into a large glacial lake (Lake Caviahue, pH 2.2-3.0). The Hg concentration ranged from 2 - 600 pM throughout the fluvial system. Mercury in the hot, hyperacidic source fluids was dominated by dissolved ionic species, with only 2% of total mercury as dissolved elemental mercury, and 11% being particulate bound. The Hg flux from the volcano, determined from river water flux measurements and Hg concentrations, was modest and varied between the 3/2008 and 3/2009 sampling campaigns resp. from 0.7 to 1.1 moles/year. The Hg:S ratio of the acid fluids was ~10-8, several orders of magnitude lower than that typically found in volcanic plumes and fumaroles. The small Hg flux and low Hg:S values suggest that the system is either inherently Hg-poor or has lost Hg through vapor loss deeper in the hydrothermal system. Support for the latter comes from high Hg concentrations in geothermal vents and mudpots on the flank of the mountain (24 - 55 ppm Hg). Mercury concentrations decreased conservatively downstream in the river as based on Hg/Cl and Hg/SO4. Non-conservative depletion occurs in the less acidic Lake Caviahue, suggesting that mercury is removed from the water column by sorption to organic matter or other phases. Mercury analyses of a short lake sediment core confirm this (Hg = 0.01 to 0.70 ppm). No evidence was found for preferential uptake of mercury by jarosite, schwertmannite, or goethite, although the latter two phases precipitate in the most distal and Hg-depleted section of the fluvial system.

The mercury species and their association with carbonaceous compositions, bromine and iodine in PM2.5 in Shanghai.

PubMed

Duan, Lian; Xiu, Guangli; Feng, Ling; Cheng, Na; Wang, Chenggang

2016-03-01

PM2.5 samples were collected in south Shanghai from November 2013 to October 2014. The species of particulate bounded mercury (PBM), including hydrochloric soluble particle-phase mercury (HPM), element soluble particle-phase mercury (EPM) and residual soluble particle-phase mercury (RPM), were determined in PM2.5. The chemical composition of PM2.5 including organic carbon (OC) and elemental carbon (EC), total bromine and iodine were also analyzed. The results showed that the annual average concentration of PBM was 0.30 ± 0.31 ng m(-3) and 0.34 ± 0.32 ng m(-3) in winter, 0.31 ± 0.19 ng m(-3) in spring, 0.30 ± 0.45 ng m(-3) in fall and 0.28 ± 0.17 ng m(-3) in summer. HPM took the highest fraction 51.2% in PBM, followed by RPM 27.7% and EPM 21.1%. EC positively correlated to particle mercury, especially in winter (r = 0.70), the same for OC in winter (r = 0.72), which indicated that the carbonaceous composition may affect the transformation of Hg in the atmosphere. Mercury species showed different correlations with bromine and iodine in the four seasons. The strongest correlation between bromine, iodine and mercury was found in spring and fall, respectively. Bromine showed the stronger correlation with total mercury and speciated particle mercury than iodine. In addition, the days were classified into haze and non-haze days based on the visibility and relative humidity, while the ratio of HPM in haze days was much higher than that in non-haze days. EC strongly correlated with PBM during haze and non-haze days while OC only positively correlated with PBM in non-haze days, this may indicate that the different carbonaceous part may affect PBM differently. Copyright © 2015 Elsevier Ltd. All rights reserved.

Speciated mercury at marine, coastal, and inland sites in New England - Part 2: Relationships with atmospheric physical parameters

NASA Astrophysics Data System (ADS)

Mao, H.; Talbot, R.; Hegarty, J.; Koermer, J.

2011-10-01

Long-term continuous measurements of gaseous elemental mercury (Hgo), reactive gaseous mercury (RGM), and particulate phase mercury (Hgp) were conducted at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland (Pac Monadnock, denoted as PM) monitoring sites of the AIRMAP Observing Network. Diurnal, seasonal, annual, and interannual variability in Hgo, RGM, and Hgp from the three distinctly different environments were characterized and compared in Part 1. Here in Part 2 relationships between speciated mercury (i.e., Hgo, RGM, and Hgp) and climate variables (e.g., temperature, wind speed, humidity, solar radiation, and precipitation) were examined. The best point-to-point correlations were found between Hgo and temperature in summer at TF and spring at PM, but there was no similar correlation at AI. Subsets of data demonstrated regional impacts of episodic dynamic processes such as strong cyclonic systems on ambient levels of Hgo at all three sites, possibly through enhanced oceanic evasion of Hgo. A tendency of higher levels of RGM and Hgp was identified in spring and summer under sunny conditions in all environments. Specifically, the 10th, 25th, median, 75th, and 90th percentile mixing ratios of RGM and Hgp increased with stronger solar radiation at both the coastal and marine sites. These metrics decreased with increasing wind speed at AI indicating enhanced loss of RGM and Hgp through deposition. RGM and Hgp levels correlated with temperature positively in spring, summer and fall at the coastal and marine locations. In the coastal region relationships between RGM and relative humidity suggested a clear decreasing tendency in all metrics from <40% to 100% relative humidity in all seasons especially in spring, compared to less variability in the marine environment. The effect of precipitation on RGM at coastal and marine locations was similar. At the coastal site, RGM levels were a factor of 3-4 higher under dry conditions than rainy conditions in all seasons. In winter RGM mixing ratios appeared to be mostly above the limit of detection (LOD) during snowfalls suggesting less scavenging efficiency of snow. Mixing ratios of Hgp at the coastal and marine sites remained above the LOD under rainy conditions. Precipitation had negligible impact on the magnitude and pattern of diurnal variation of Hgp in all seasons in the marine environment.

Geochemical data for mercury, methylmercury, and other constituents in sediments from Englebright Lake, California, 2002

USGS Publications Warehouse

Alpers, Charles N.; Hunerlach, Michael P.; Marvin-DePasquale, Mark C.; Antweiler, Ronald C.; Lasorsa, Brenda K.; De Wild, John F.; Snyder, Noah P.

2006-01-01

Deep coring penetrated the full thickness of material deposited after 1940 at six locations in the reservoir; the cores reached a maximum depth of 32.8 meters below the reservoir floor. At the three deep coring sites closest to Englebright Dam, concentrations of HgT (dry basis) were consistently in the range of 100 to 500 ng/g (nanogram per gram), in sediment dominantly of silt size (median grain size of 0.004 to 0.063 mm [millimeter]). At the deep coring sites located farther upstream, the upper parts of the profile had lower concentrations of HgT, generally ranging from 2 to 100 ng/g, in sediment dominantly of sand size (median grain size from 0.063 to 2 mm). The lower part of the vertical profiles at three upstream coring sites had higher concentrations of HgT than the upper and middle parts of these profiles, and had finer median grain size. The highest median concentration of MeHg (1.1 ng/g) was in the top 2 cm (centimeter) of the shallow box cores. This vertical interval also had the highest value of the ratio of MeHg to HgT, 0.41 percent. Median concentrations of MeHg and median values of MeHg/HgT decreased systematically with depth from 0-4 to 4-8 to 8-12 cm in the shallow cores. However, similar systematic decreases were not observed at the meter scale in the deep cores of the MEM (MEthylMercury) series. The overall median of the ratio MeHg/HgT in the deep cores was 0.25 percent, not much less than the overall median value for the shallow cores (0.33 percent). Mercury-203 radiotracer divalent inorganic mercury (203Hg(II)) was used to determine microbial mercury-methylation potential rates for 11 samples collected from three reservoir locations and various depths in the sediment profile. For the five shallow mercury-methylation subsamples, ancillary geochemical parameters were assayed, including microbial sulfate reduction rates, sulfur speciation (sediment acid volatile sulfide, total reduced sulfur, and pore-water sulfate), iron speciation (sediment acid extractable iron(II), amorphous iron(III), crystalline iron(III) and pore-water iron(II)), pore-water chloride and dissolved organic carbon, and pH, oxidation-reduction potential (Eh) and whole-sediment organic content. The highest potential rates of microbial mercury methylation were measured in shallow (0 to 8 cm depth) sediments (5 to 30 nanograms of mercury per gram dry sediment per day), whereas potential rates for subsamples collected from depths greater than 500 cm were consistently below the detection limit of the radiotracer method (< 0.02 nanogram of mercury per gram dry sediment per day). Chemical analyses of trace and major elements in bed sediment are presented for 202 samples from deep cores from five locations in Englebright Lake. The mean values and standard deviations for selected trace elements were as follows (in micrograms per gram): antimony, 2.4 ? 1.6; arsenic, 69 ? 48; chromium, 134 ? 23; lead, 33 ? 25; and nickel, 87 ? 24. Concentrated samples of heavy-mineral grains, prepared using nine large-volume composite samples from

Fate and aqueous transport of mercury in light of the Clean Air Mercury Rule for coal-fired electric power plants

NASA Astrophysics Data System (ADS)

Arzuman, Anry

Mercury is a hazardous air pollutant emitted to the atmosphere in large amounts. Mercury emissions from electric power generation sources were estimated to be 48 metric tons/year, constituting the single largest anthropogenic source of mercury in the U.S. Settled mercury species are highly toxic contaminants of the environment. The newly issued Federal Clean Air Mercury Rule requires that the electric power plants firing coal meet the new Maximum Achievable Mercury Control Technology limit by 2018. This signifies that all of the air-phase mercury will be concentrated in solid phase which, based on the current state of the Air Pollution Control Technology, will be fly ash. Fly ash is utilized by different industries including construction industry in concrete, its products, road bases, structural fills, monifills, for solidification, stabilization, etc. Since the increase in coal combustion in the U.S. (1.6 percent/year) is much higher than the fly ash demand, large amounts of fly ash containing mercury and other trace elements are expected to accumulate in the next decades. The amount of mercury transferred from one phase to another is not a linear function of coal combustion or ash production, depends on the future states of technology, and is unknown. The amount of aqueous mercury as a function of the future removal, mercury speciation, and coal and aquifer characteristics is also unknown. This paper makes a first attempt to relate mercury concentrations in coal, flue gas, fly ash, and fly ash leachate using a single algorithm. Mercury concentrations in all phases were examined and phase transformation algorithms were derived in a form suitable for probabilistic analyses. Such important parameters used in the transformation algorithms as Soil Cation Exchange Capacity for mercury, soil mercury selectivity sequence, mercury activity coefficient, mercury retardation factor, mercury species soil adsorption ratio, and mercury Freundlich soil adsorption isotherm coefficients were derived. Mercury air-phase removal efficiency was studied as a function of dominant mercury species vapor pressures, the amount of chlorine, sorbent injection rate and adsorption capacities, and process temperature and modifications. A mercury air phase removal algorithm was derived which defines the future removal efficiencies as a function of activated carbon injection rate. Mercury adsorption on soil was studied as a function of Mercury Mass Law incorporating the dominant aquatic mercury species, pH, chlorine and sulfur concentrations, and the amount of complexed hydroxyl groups. Aquatic mercury longitudinal plume delineation was studied using the Domenico and Robbins function. A Monte Carlo simulation was performed using random number series (5000) for all of the variables in the Domenico and Robbins and mercury retardation functions. The probability that the Maximum Contaminant Level for mercury will be exceeded was found to be equal approximately 1 percent of all soil-related fly ash applications.

Mercury speciation in brain tissue of polar bears (Ursus maritimus) from the Canadian Arctic.

PubMed

Krey, Anke; Kwan, Michael; Chan, Hing Man

2012-04-01

Methylmercury (MeHg) is a neurotoxicant that has been found at elevated concentrations in the Arctic ecosystem. Little is known about its internal dose in wildlife such as polar bears. We measured concentrations of mercury (Hg) in three different brain regions (cerebellum, frontal lobe and brain stem) of 24 polar bears collected from the Nunavik, Canada between 2000 and 2003. Speciation of Hg was measured by High Performance Liquid Chromatography coupled to Inductively Coupled Plasma Mass Spectroscopy (HPLC-ICP-MS). Concentrations of mean total Hg in brain tissue were up to 625 times lower (0.28 ± 0.07 mg kg(-1) dry weight (dw) in frontal lobe, 0.23 ± 0.07 mg kg(-1) dw in cerebellum and 0.12 ± 0.0 3mg kg(-1) dw in brain stem) than the mean total Hg concentration previously reported in polar bear liver collected from Eastern Baffin Island. Methylmercury (MeHg) accounted for 100% of the Hg found in all three brain regions analyzed. These results suggest that polar bear might reduce the toxic effects of Hg by limiting the uptake into the brain and/or decrease the rate of demethylation so that Hg can be excreted from the brain more easily. The toxicokinetics and the blood-brain-barrier mechanisms of polar bears are still unknown and further research is required. Copyright © 2012 Elsevier Inc. All rights reserved.

Geological and anthropogenic factors influencing mercury speciation in mine wastes: An EXAFS spectroscopy study

USGS Publications Warehouse

Kim, C.S.; Rytuba, J.J.; Brown, Gordon E.

2004-01-01

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600??C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345??C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500-2000 ??m and <45 ??m size fractions (e.g., from 97-810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8-18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg LIII-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg3O2SO4), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments. ?? 2003 Elsevier Ltd. All rights reserved.

Preliminary report on mercury geochemistry of placer gold dredge tailings, sediments, bedrock, and waters in the Clear Creek restoration area, Shasta County, California

USGS Publications Warehouse

Ashley, Roger P.; Rytuba, James J.; Rogers, Ronald; Kotlyar, Boris B.; Lawler, David

2002-01-01

Clear Creek, one of the major tributaries of the upper Sacramento River, drains the eastern Trinity Mountains. Alluvial plain and terrace gravels of lower Clear Creek, at the northwest edge of the Sacramento Valley, contain placer gold that has been mined since the Gold Rush by various methods including dredging. In addition, from the 1950s to the 1980s aggregate-mining operations removed gravel from the lower Clear Creek flood plain. Since Clear Creek is an important stream for salmon production, a habitat restoration program is underway to repair damage from mining and improve conditions for spawning. This program includes using dredge tailings to fill in gravel pits in the flood plain, raising the concern that mercury lost to these tailings in the gold recovery process may be released and become available to biota. The purposes of our study are to determine concentrations and speciation of mercury in sediments, tailings, and water in the lower Clear Creek area, and to determine its mobility. Mercury concentrations in bedrock and unmined gravels both within and above the mined area are low, and are taken to represent background concentrations. Bulk mercury values in flood-plain sediments and dry tailings are elevated to several times these background concentrations. Mercury in sediments and tailings is associated with fine size fractions. Although methylmercury levels are generally low in sediments, shallow ponds in the flood plain may have above-normal methylation potential. Stream waters in the area show low mercury and methylmercury levels. Ponds with elevated methylmercury in sediments have more methylmercury in their waters as well. One seep in the area is highly saline, and enriched in mercury, lithium, and boron, similar to connate waters that are expelled along thrust faults to the south on the west side of the Sacramento Valley. This occurrence suggests that mercury in waters may at least in part be from sources other than placer mining.

Wet deposition of mercury at a remote site in the Tibetan Plateau: Concentrations, speciation, and fluxes

NASA Astrophysics Data System (ADS)

Huang, Jie; Kang, Shichang; Zhang, Qianggong; Yan, Haiyu; Guo, Junming; Jenkins, Matt G.; Zhang, Guoshuai; Wang, Kang

2012-12-01

Precipitation samples collected at a remote high elevation site (i.e., Nam Co Station, 4730 m a.s.l.) in the southern Tibetan Plateau were analyzed for total mercury (HgT) between July 2009 and 2011, particulate-bound mercury (HgP) between July 2010 and 2011 and methylmercury (MeHg) from July through August of 2009. The volume-weighted mean (VWM) concentrations and wet deposition fluxes of HgT and MeHg in precipitation were 4.8 ng L-1 and 1.75 μg m-2 yr-1, 0.031 ng L-1 and 0.01 μg m-2 yr-1, respectively. VWM HgT concentration was approximately two times higher during the non-monsoon season than during the monsoon season, while 83% of the HgT wet deposition fluxes occurred during the monsoon season. The HgT and MeHg concentrations are comparable to the reported data for some of the most remote alpine and polar regions worldwide (e.g., Churchill), but the wet deposition fluxes of HgT and MeHg were among the lowest in the world. Analysis of Hg speciation has presented that HgP and MeHg concentrations are high, making up 71.2% and 1.82% of the HgT on average (VWM), respectively. The high HgP%, as well as a significantly positive between HgT and HgP (R2 = 0.91; n = 44; p < 0.001), confirmed that atmospheric deposition of Hg in the Tibetan Plateau was occurring in the form of HgP. A decreasing trend in HgT concentrations with increasing amount of precipitation (R2 = 0.08; N = 101; p < 0.005) was found at Nam Co Station, indicative that scavenging of HgP from the atmosphere was an important mechanism contributing Hg to precipitation. The precipitation amount, rather than HgT concentration, was found to be the governing factor affecting HgT wet deposition flux. Moreover, a comparison between measured wet deposition flux of Hg at Nam Co Station and the estimates from environmental records indicated that both snowpits and lake sediments appear to be reliable archives for estimating historical Hg accumulation rates over the Tibetan Plateau.

Short-time variation of mercury speciation in the urban of Göteborg during GÖTE-2005

NASA Astrophysics Data System (ADS)

Li, Jing; Sommar, Jonas; Wängberg, Ingvar; Lindqvist, Oliver; Wei, Shi-qiang

Mercury species samples for gaseous elemental mercury (GEM) with a temporal resolution of 5 min, 5 h and 20 min integrated measurements of reactive gaseous mercury (RGM), and 24-h sampling of particulate mercury (HgP) at urban Femman and total gaseous mercury (TGM) at rural Rörvik were conducted during the measurement campaign GÖTE-2005 in Göteborg, Sweden. Results showed that average concentrations for GEM, RGM, HgP and TGM were 1.96 ± 0.38 ng m -3, 2.53 ± 4.09 pg m -3, 12.50 ± 5.88 pg m -3 and 1.63 ± 0.19 ng m -3, respectively. A reverse diurnal distribution pattern between GEM and RGM was observed, and early morning GEM concentration was elevated compared to daytime values which was likely due to activation of fossil fuel combustion, electric utilities, etc., by the formation of a nighttime inversion layer, less activity of GEM and reduced mixing. The subsequent decline and afternoon minimum were likely related to increase vertical mixing, photochemical reaction, and coupling with the coal combustion. However, the photochemical conversion from GEM during daytime and nocturnal behavior of "sticky" gases under higher relative humidity may result in strong diurnal cycles for RGM. Sampling site was heavily affected by anthropogenic sources from two distinguished wind sectors. One was ESE-SSW sector which was likely impacted by long distance transport from south highly industrialized region; the other was likely tied with local sources from N-NE sector.

Mercury Emission Measurement at a CFB Plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

John Pavlish; Jeffrey Thompson; Lucinda Hamre

2009-02-28

In response to pending regulation to control mercury emissions in the United States and Canada, several projects have been conducted to perform accurate mass balances at pulverized coal (pc)-fired utilities. Part of the mercury mass balance always includes total gaseous mercury as well as a determination of the speciation of the mercury emissions and a concentration bound to the particulate matter. This information then becomes useful in applying mercury control strategies, since the elemental mercury has traditionally been difficult to control by most technologies. In this instance, oxidation technologies have proven most beneficial for increased capture. Despite many years ofmore » mercury measurement and control projects at pc-fired units, far less work has been done on circulating fluidized-bed (CFB) units, which are able to combust a variety of feedstocks, including cofiring coal with biomass. Indeed, these units have proven to be more problematic because it is very difficult to obtain a reliable mercury mass balance. These units tend to have very different temperature profiles than pc-fired utility boilers. The flexibility of CFB units also tends to be an issue when a mercury balance is determined, since the mercury inputs to the system come from the bed material and a variety of fuels, which can have quite variable chemistry, especially for mercury. In addition, as an integral part of the CFB operation, the system employs a feedback loop to circulate the bed material through the combustor and the solids collection system (the primary cyclone), thereby subjecting particulate-bound metals to higher temperatures again. Despite these issues, CFB boilers generally emit very little mercury and show good native capture. The Energy & Environmental Research Center is carrying out this project for Metso Power in order to characterize the fate of mercury across the unit at Rosebud Plant, an industrial user of CFB technology from Metso. Appropriate solids were collected, and flue gas samples were obtained using the Ontario Hydro method, mercury continuous emission monitors, and sorbent trap methods. In addition, chlorine and fluorine were determined for solids and in the flue gas stream. Results of this project have indicated a very good mercury mass balance for Rosebud Plant, indicating 105 {+-} 19%, which is well within acceptable limits. The mercury flow through the system was shown to be primarily in with the coal and out with the flue gas, which falls outside of the norm for CFB boilers.« less

Intensive atmospheric mercury measurements at Terra Nova Bay in Antarctica during November and December 2000

NASA Astrophysics Data System (ADS)

Sprovieri, F.; Pirrone, N.; Hedgecock, I. M.; Landis, M. S.; Stevens, R. K.

2002-12-01

It is well known that due to its long atmospheric residence time, mercury is distributed on a global scale and aeolian transport is believed to be the major contributor to mercury in polar environments. No measurements of reactive gaseous mercury (RGM) at all have ever been performed in the Antarctic before. Hg0(g) concentrations were in the range 0.29 to 2.3 ng m-3, with an average value of 0.9 ± 0.3 ng m-3. RGM was measured using KCl-coated annular denuders and a speciation unit coupled to a TGM analyzer; concentrations ranged from 10.5 to 334 pg m-3, with an average of 116.2 ± 77.8 pg m-3. The Hg0(g) measurements are in good agreement with the few data available for such southerly latitudes. The RGM concentrations are as high as those found in some industrial environments; the high concentrations in the absence of local sources (anthropogenic or natural) show that in situ gas phase oxidation of Hg0 is the most important factor influencing RGM production and therefore also Hg deposition. The toxicity of Hg means that the consequences of high concentrations of oxidized and soluble Hg species depositing in the fragile Antarctic environment could be serious indeed.

Ultrasound-assisted vapor generation of mercury.

PubMed

Ribeiro, Anderson S; Vieira, Mariana A; Willie, Scott; Sturgeon, Ralph E

2007-06-01

Cold vapor generation arising from reduction of both Hg(2+) and CH(3)Hg(+) occurs using ultrasonic (US) fields of sufficient density to achieve both localized heating as well as radical-based attack in solutions of formic and acetic acids and tetramethylammonium hydroxide (TMAH). A batch sonoreactor utilizing an ultrasonic probe as an energy source and a flow through system based on a US bath were optimized for this purpose. Reduction of CH(3)Hg(+) to Hg(0) occurs only at relatively high US field density (>10 W cm(-3) of sample solution) and is thus not observed when a conventional US bath is used for cold vapor generation. Speciation of mercury is thus possible by altering the power density during the measurement process. Thermal reduction of Hg(2+) is efficient in formic acid and TMAH at 70 degrees C and occurs in the absence of the US field. Room temperature studies with the batch sonoreactor reveal a slow reduction process, producing temporally broad signals having an efficiency of approximately 68% of that arising from use of a conventional SnCl(2) reduction system. Molecular species of mercury are generated at high concentrations of formic and acetic acid. Factors affecting the generation of Hg(0) were optimized and the batch sonoreactor used for the determination of total mercury in SLRS-4 river water reference material.

Evaluation of the KCl Denuder Method for Gaseous Oxidized Mercury using HgBr2 at an In-Service AMNet Site

NASA Astrophysics Data System (ADS)

McClure, Crystal

During the summer of 2013, we examined the performance of KCl-coated denuders for measuring gaseous oxidized mercury (GOM) by calibrating with a known source of GOM (i.e., HgBr2) at the North Birmingham SouthEastern Aerosol Research and Characterization (SEARCH) site. We found that KCl-coated denuders have near 95% collection efficiency for HgBr2 in zero air (i.e., air scrubbed of mercury and ozone). However, in ambient air, the efficiency of KCl-coated denuders in capturing HgBr2 dropped to 20-54%. We also found that absolute humidity and ozone each demonstrate a significant inverse correlation with HgBr2 recovery in ambient air. Subsequent laboratory tests with HgBr2 and the KCl-coated denuder show that ozone and absolute humidity cause the release of gaseous elemental Hg from the denuder and thus appear to explain the low recovery in ambient air. Based on these findings, we infer that the KCl denuder method underestimates atmospheric GOM concentrations. A calibration system is needed to accurately measure GOM. The system described in this paper for HgBr2 could be implemented with existing mercury speciation instrumentation and this would improve our knowledge of the response to one potentially important GOM compound.

Mercury speciation in coastal sediments from the central east coast of India by modified BCR method.

PubMed

Chakraborty, Parthasarathi; Raghunadh Babu, P V; Vudamala, Krushna; Ramteke, Darwin; Chennuri, Kartheek

2014-04-15

This is the first study to describe distribution and speciation of Hg in coastal sediments from the central east coast of India. The concentrations of Hg in the studied sediments were found to be much lower than the Hg concentration recommended in coastal sediments by the United State Environmental Protection Agency and the Canadian Council of Ministers of the Environment for the protection of aquatic life. This study suggests that the interactions between Hg and coastal sediments are influenced by particle size (sand, silt and clay) of the sediments and the total organic carbon (TOC) content in the sediments. It was found that the coastal sediments from the central east coast of India could act as a sink for Hg. The availability of strong uncomplexed-Hg binding sites in the coastal sediments was observed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Degassing of reduced carbon from planetary basalts.

PubMed

Wetzel, Diane T; Rutherford, Malcolm J; Jacobsen, Steven D; Hauri, Erik H; Saal, Alberto E

2013-05-14

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential.

Natural causes of changes in marine environment: Mercury speciation and distribution in anchialine caves

NASA Astrophysics Data System (ADS)

Kwokal, Željko; Cukrov, Neven; Cuculić, Vlado

2014-12-01

Mercury speciation and distribution were assessed, for the first time, from the water, sediment, rock, soil and air of anchialine caves. We evaluated the origin and distribution of four mercury species (total (THg), reactive (RHg), dissolved gaseous mercury (DGM) and monomethylmercury (MeHg)) in water from Bjejajka cave (Bjejajka) and Lenga Pit (Lenga) in the Croatian Adriatic Sea from 2006 to 2011. Concentrations of all mercury species were elevated at both sites compared to adjacent seawater, which had concentration range of 0.5-2.4 ng L-1 for THg, 0.06-0.2 ng L-1 for RHg, 0.02-0.07 ng L-1 for DGM, and 0.01-0.02 ng L-1 for MeHg. In Bjejajka, the maximum THg concentration (350 ng L-1) in the middle layer (3-7 m) of the 12 m deep stratified water column was up to 3 orders of magnitude greater than in adjacent seawater. During and after the rainy sampling periods in January 2009 and 2010, mixing of Bjejajka water column resulted in elevated concentrations, up to 3700 ng L-1 of THg (4 orders of magnitude higher compared to values in nearby seawater) in the bottom water layer. MeHg concentrations in the Bjejajka water column were also considerably elevated (0.7-6.3 ng L-1) compared to the surrounding seawater (0.01-0.02 ng L-1). The vertical distribution of MeHg concentrations followed that of THg, however the ratio of MeHg/THg above the Bjejajka halocline was drastically higher (up to 57%) compared to MeHg proportion (1-2 %) below the halocline, which was similar to that of surface seawater. In sediment of Bjejajka, THg concentrations were up to 3.3 mg kg-1, considerably above concentrations in unpolluted Adriatic marine sediment (0.1-0.3 mg kg-1). The highest THg amounts found in soil and air were inside and in close proximity to Bjejajka, while THg in rock (≤0.01 mg kg-1) were below reported values for unaltered carbonates. Laboratory experiments indicate that bat guano was the major source of elevated mercury concentrations in the water column and sediment of Bjejajka. Concentrations of THg in bat guano were up to 0.45 mg kg-1, above the range of THg concentrations found in unpolluted marine sediment. Seventy-two days after the addition of bat guano in solution, a 100-fold higher Hg concentration was observed, from 2.5 up to 252 ng L-1. In Lenga bat guano was not spotted and THg water and sediment concentrations were drastically lower, mostly below 7 ng L-1 and 0.8 mg kg-1, respectively.

Phytoremediation of Ionic and Methyl Mercury Pollution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant. To advance this mercury phytoremediation strategy, our planned research focuses on the following Specific Aims: (1) to increase the transport of mercury to aboveground tissue; (2) to identify small mercury binding peptides that enhance hyperaccumulation aboveground; (3) to test the ability of multiple genes acting together to enhance resistance and hyperaccumulation; (4) to construct a simple molecular system for creating male/female sterility, allowing engineered grass, shrub, and tree species to be released indefinitely at contaminated sites; (5) to test the ability of transgenic cottonwood and rice plants to detoxify ionic mercury and prevent methylmercury release from contaminated sediment; and (6) to initiate field testing with transgenic cottonwood and rice for the remediation of methylmercury and ionic mercury. The results of these experiments will enable the phytoremediation of methyl- and ionic mercury by a wide spectrum of deep-rooted, fast-growing plants adapted to diverse environments. We have made significant progress on all six of these specific aims as summarized below.« less

Determination, speciation and distribution of mercury in soil in the surroundings of a former chlor-alkali plant: assessment of sequential extraction procedure and analytical technique

PubMed Central

2013-01-01

Background The paper presents the evaluation of soil contamination with total, water-available, mobile, semi-mobile and non-mobile Hg fractions in the surroundings of a former chlor-alkali plant in connection with several chemical soil characteristics. Principal Component Analysis and Cluster Analysis were used to evaluate the chemical composition variability of soil and factors influencing the fate of Hg in such areas. The sequential extraction EPA 3200-Method and the determination technique based on capacitively coupled microplasma optical emission spectrometry were checked. Results A case study was conducted in the Turda town, Romania. The results revealed a high contamination with Hg in the area of the former chlor-alkali plant and waste landfills, where soils were categorized as hazardous waste. The weight of the Hg fractions decreased in the order semi-mobile > non-mobile > mobile > water leachable. Principal Component Analysis revealed 7 factors describing chemical composition variability of soil, of which 3 attributed to Hg species. Total Hg, semi-mobile, non-mobile and mobile fractions were observed to have a strong influence, while the water leachable fraction a weak influence. The two-dimensional plot of PCs highlighted 3 groups of sites according to the Hg contamination factor. The statistical approach has shown that the Hg fate in soil is dependent on pH, content of organic matter, Ca, Fe, Mn, Cu and SO42- rather than natural components, such as aluminosilicates. Cluster analysis of soil characteristics revealed 3 clusters, one of which including Hg species. Soil contamination with Cu as sulfate and Zn as nitrate was also observed. Conclusions The approach based on speciation and statistical interpretation of data developed in this study could be useful in the investigation of other chlor-alkali contaminated areas. According to the Bland and Altman test the 3-step sequential extraction scheme is suitable for Hg speciation in soil, while the used determination method of Hg is appropriate. PMID:24252185

Speciated mercury at marine, coastal, and inland sites in New England - Part 2: Relationships with atmospheric physical parameters

NASA Astrophysics Data System (ADS)

Mao, H.; Talbot, R.; Hegarty, J.; Koermer, J.

2012-05-01

Long-term continuous measurements of gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate phase mercury (HgP) were conducted at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland rural (Pac Monadnock, denoted as PM) monitoring sites of the AIRMAP Observing Network. Diurnal, seasonal, annual, and interannual variability in Hg0, RGM, and HgP from the three distinctly different environments were characterized and compared in Part 1. Here in Part 2 relationships between speciated mercury (i.e., Hg0, RGM, and HgP) and climate variables (e.g., temperature, wind speed, humidity, solar radiation, and precipitation) were examined. The best point-to-point correlations were found between Hg0 and temperature in summer at TF and spring at PM, but there was no similar correlation at AI. Subsets of data demonstrated regional impacts of episodic dynamic processes such as strong cyclonic systems on ambient levels of Hg0 at all three sites, possibly through enhanced oceanic evasion of Hg0. A tendency of higher levels of RGM and HgP was identified in spring and summer under sunny conditions in all environments. Specifically, the 10th, 25th, median, 75th, and 90th percentile mixing ratios of RGM and HgP increased with stronger solar radiation at both the coastal and marine sites. These metrics decreased with increasing wind speed at AI indicating enhanced loss of RGM and HgP through deposition. RGM and HgP levels correlated with temperature positively in spring, summer and fall at the coastal and marine locations. At the coastal site relationships between RGM and relative humidity suggested a clear decreasing tendency in all metrics from <40% to 100% relative humidity in all seasons especially in spring, compared to less variability in the marine environment. The effect of precipitation on RGM at coastal and marine locations was similar. At the coastal site, RGM levels were a factor of 3-4 to two orders of magnitude higher under dry conditions than rainy conditions in all seasons. In winter RGM mixing ratios appeared to be mostly above the limit of detection (LOD) during snowfalls suggesting less scavenging efficiency of snow. Mixing ratios of HgP at the coastal and marine sites remained above the LOD under rainy conditions. Precipitation had negligible impact on the magnitude and pattern of diurnal variation of HgP in all seasons in the marine environment.

Impacts of Wildfires on Mercury Contamination in Canada

NASA Astrophysics Data System (ADS)

Dastoor, A.; Fraser, A.; Ryjkov, A.

2017-12-01

Wildfires frequency has increased in past four decades in Canada, and is expected to increase in future as a result of climate change. Biomass Burning Mercury Emissions (BBMEs) are known to be significant; however, the impact of biomass burning on Mercury (Hg) burden in Canada has not been previously quantified. We investigated the spatio-temporal variability of BBME in Canada, and used Environment and Climate Change Canada's air quality and mercury model, GEM-MACH-Hg, to quantify the impacts of BBME on spatio-temporal variability of air concentrations and deposition fluxes of Hg in Canada. We optimized the biomass burning Emission Factors (EFs) for gaseous elemental mercury (GEM) using observations, GEM-MACH-Hg and an inversion technique for five vegetation types represented in North American fires to constrain the BBME impacts of Hg. We used three BBME scenarios (i.e., two scenarios where mercury is emitted only as GEM using literature or optimized EFs, and a third scenario where mercury is emitted as GEM using literature EFs and particle bound mercury (PBM) emitted using a GEM/PBM ratio from lab measurements) in Canada to conduct three sets of model simulations for 2010-2015. The three BBME scenarios represent the range of possible values for the impacts of BBME in Canada on mercury concentration and deposition. We found total BBME and its spatial distribution to be highly variable from year to year, and total atmospheric BBME averaged for 2010-2015 in Canada to be between 6 - 14 tonnes, which is 3 - 7 times the mercury emission from anthropogenic sources in Canada during the biomass burning season (i.e., from May to September). We found that while BBME have a small impact on surface air concentrations of GEM and total Hg deposition averaged over individual provinces/territories, these impacts for individual ecosystems can be as high as 95% during the burning season. We found that northern Alberta and Saskatchewan, central British Columbia, and the area around Great Slave Lake in the Northwest Territories are at greater risk of mercury contamination from biomass burning. We analysed the uncertainties in BBME, and found that reducing uncertainty in the speciation of Hg in BBME would provide the largest benefit to constraining the mercury contamination from biomass burning source to Canadian ecosystems.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buitrago, Paula A.; Morrill, Mike; Lighty, JoAnn S.

This report presents experimental and modeling mercury oxidation and adsorption data. Fixed-bed and single-particle models of mercury adsorption were developed. The experimental data were obtained with two reactors: a 300-W, methane-fired, tubular, quartz-lined reactor for studying homogeneous oxidation reactions and a fixed-bed reactor, also of quartz, for studying heterogeneous reactions. The latter was attached to the exit of the former to provide realistic combustion gases. The fixed-bed reactor contained one gram of coconut-shell carbon and remained at a temperature of 150°C. All methane, air, SO 2, and halogen species were introduced through the burner to produce a radical pool representativemore » of real combustion systems. A Tekran 2537A Analyzer coupled with a wet conditioning system provided speciated mercury concentrations. At 150°C and in the absence of HCl or HBr, the mercury uptake was about 20%. The addition of 50 ppm HCl caused complete capture of all elemental and oxidized mercury species. In the absence of halogens, SO 2 increased the mercury adsorption efficiency to up to 30 percent. The extent of adsorption decreased with increasing SO 2 concentration when halogens were present. Increasing the HCl concentration to 100 ppm lessened the effect of SO 2. The fixed-bed model incorporates Langmuir adsorption kinetics and was developed to predict adsorption of elemental mercury and the effect of multiple flue gas components. This model neglects intraparticle diffusional resistances and is only applicable to pulverized carbon sorbents. It roughly describes experimental data from the literature. The current version includes the ability to account for competitive adsorption between mercury, SO 2, and NO 2. The single particle model simulates in-flight sorbent capture of elemental mercury. This model was developed to include Langmuir and Freundlich isotherms, rate equations, sorbent feed rate, and intraparticle diffusion. The Freundlich isotherm more accurately described in-flight mercury capture. Using these parameters, very little intraparticle diffusion was evident. Consistent with other data, smaller particles resulted in higher mercury uptake due to available surface area. Therefore, it is important to capture the particle size distribution in the model. At typical full-scale sorbent feed rates, the calculations under-predicted adsorption, suggesting that wall effects can account for as much as 50 percent of the removal, making it an important factor in entrained-mercury adsorption models.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buitrago, Paula A.; Morrill, Mike; Lighty, JoAnn S.

This report presents experimental and modeling mercury oxidation and adsorption data. Fixed-bed and single-particle models of mercury adsorption were developed. The experimental data were obtained with two reactors: a 300-W, methane-fired, tubular, quartz-lined reactor for studying homogeneous oxidation reactions and a fixed-bed reactor, also of quartz, for studying heterogeneous reactions. The latter was attached to the exit of the former to provide realistic combustion gases. The fixed-bed reactor contained one gram of coconut-shell carbon and remained at a temperature of 150°C. All methane, air, SO 2, and halogen species were introduced through the burner to produce a radical pool representativemore » of real combustion systems. A Tekran 2537A Analyzer coupled with a wet conditioning system provided speciated mercury concentrations. At 150°C and in the absence of HCl or HBr, the mercury uptake was about 20%. The addition of 50 ppm HCl caused complete capture of all elemental and oxidized mercury species. In the absence of halogens, SO 2 increased the mercury adsorption efficiency to up to 30 percent. The extent of adsorption decreased with increasing SO 2 concentration when halogens were present. Increasing the HCl concentration to 100 ppm lessened the effect of SO 2. The fixed-bed model incorporates Langmuir adsorption kinetics and was developed to predict adsorption of elemental mercury and the effect of multiple flue gas components. This model neglects intraparticle diffusional resistances and is only applicable to pulverized carbon sorbents. It roughly describes experimental data from the literature. The current version includes the ability to account for competitive adsorption between mercury, SO 2, and NO 2. The single particle model simulates in-flight sorbent capture of elemental mercury. This model was developed to include Langmuir and Freundlich isotherms, rate equations, sorbent feed rate, and intraparticle diffusion. The Freundlich isotherm more accurately described in-flight mercury capture. Using these parameters, very little intraparticle diffusion was evident. Consistent with other data, smaller particles resulted in higher mercury uptake due to available surface area. Therefore, it is important to capture the particle size distribution in the model. At typical full-scale sorbent feed rates, the calculations underpredicted adsorption, suggesting that wall effects can account for as much as 50 percent of the removal, making it an important factor in entrained-mercury adsorption models.« less

Mercury, trace elements and organic constituents in atmospheric fine particulate matter, Shenandoah National Park, Virginia, USA: A combined approach to sampling and analysis

USGS Publications Warehouse

Kolker, A.; Engle, M.A.; Orem, W.H.; Bunnell, J.E.; Lerch, H.E.; Krabbenhoft, D.P.; Olson, M.L.; McCord, J.D.

2008-01-01

Compliance with U.S. air quality regulatory standards for atmospheric fine particulate matter (PM2.5) is based on meeting average 24 hour (35 ?? m-3) and yearly (15 ??g m-3) mass-per-unit-volume limits, regardless of PM2.5 composition. Whereas this presents a workable regulatory framework, information on particle composition is needed to assess the fate and transport of PM2.5 and determine potential environmental/human health impacts. To address these important non-regulatory issues an integrated approach is generally used that includes (1) field sampling of atmospheric particulate matter on filter media, using a size-limiting cyclone, or with no particle-size limitation; and (2) chemical extraction of exposed filters and analysis of separate particulate-bound fractions for total mercury, trace elements and organic constituents, utilising different USGS laboratories optimised for quantitative analysis of these substances. This combination of sampling and analysis allowed for a more detailed interpretation of PM2.5 sources and potential effects, compared to measurements of PM2.5 abundance alone. Results obtained using this combined approach are presented for a 2006 air sampling campaign in Shenandoah National Park (Virginia, USA) to assess sources of atmospheric contaminants and their potential impact on air quality in the Park. PM2.5 was collected at two sampling sites (Big Meadows and Pinnacles) separated by 13.6 km. At both sites, element concentrations in PM2.5 were low, consistent with remote or rural locations. However, element/Zr crustal abundance enrichment factors greater than 10, indicating anthropogenic input, were found for Hg, Se, S, Sb, Cd, Pb, Mo, Zn and Cu, listed in decreasing order of enrichment. Principal component analysis showed that four element associations accounted for 84% of the PM 2.5 trace element variation; these associations are interpreted to represent: (1) crustal sources (Al, REE); (2) coal combustion (Se, Sb), (3) metal production and/or mobile sources (Mo, Cd, Pb, Cu, Zn) and (4) a transient marine source (Sr, Mg). Concentrations of Hg in PM2.5 at background levels in the single pg m-3 were shown by collection and analysis of PM2.5 on filters and by an automated speciation analyser set up at the Big Meadows air quality site. The speciation unit revealed periodic elevation of reactive gaseous mercury (RGM) that co-occurred with peaks in SO2, indicating an anthropogenic source. GC/MS total ion current chromatograms for the two sites were quite similar indicating that organic signatures were regional in extent and/or that the same compounds were present locally at each site. Calculated carbon preference index values for n-alkanes indicated that plant waxes rather than anthropogenic sources, were the dominant alkane source. Polycyclic aromatic hydrocarbons (PAHs) were detected, with a predominance of non-alkylated, and higher molecular weight PAHs in this fraction, suggestive of a combustion source (fossil fuel or forest fires). ?? 2008 The Authors. Journal compilation ?? 2008 International Association of Geoanalysts.

The Influence of Coastal Wetland Zonation on Surface Sediment and Porewater Mercury Speciation

NASA Astrophysics Data System (ADS)

Marvin-DiPasquale, M. C.; Windham-Myers, L.; Wilson, A. M.; Buck, T.; Smith, E.

2014-12-01

An investigation of mercury (Hg) speciation in saltmarsh surface sediment (top 0-2 cm) and porewater (integrated 0-50 cm) was conducted along two monitoring well transects established within North Inlet Estuary (S. Carolina, USA) as part of the NOAA sponsored National Estuarine Research Reserve (NERR) network. Transects were perpendicular to the shoreline, from the forested uplands to the edge of the tidal channel, and traversed a range of vegetated zones from the high marsh (pickleweed, rush, and salt panne-dominated) to the low marsh (cordgrass dominated), as mediated by elevation and tidal inundation. Sediment grain size and organic content explained 95% of the variability in the distribution of total Hg (THg) in surface sediment. Tin-reducible 'reactive' mercury (HgR) concentration was 10X greater in the high marsh, compared to the low marsh, and increased sharply with decreasing sediment pH values below pH=6. The percentage of THg as HgR decreased as sediment redox conditions became more reducing. There were no significant differences in surface sediment methylmercury (MeHg) concentrations between high and low marsh zones. In contrast, porewater MeHg concentrations were 5X greater in the high marsh compared to the low marsh. As a percentage of THg, mean porewater %MeHg was 23% in the low marsh and 51% in the high marsh, reaching levels of 73-89% in a number of high marsh sites. Calculations of partitioning between porewater and the solid phase suggest stronger binding to particles in the low marsh and a shift towards the dissolved phase in the high marsh for both THg and MeHg. These results are consistent with a conceptual model for coastal wetlands where the less frequently inundated high marsh zone may be important in terms of MeHg production and enhanced subsurface mobilization, partially due to the subsurface mixing of saline estuarine water and freshwater draining in from the uplands area.

Relative contributions of mercury bioavailability and microbial growth rate on net methylmercury production by anaerobic mixed cultures

DOE PAGES

Kucharzyk, Katarzyna H.; Deshusses, Marc A.; Porter, Kaitlyn A.; ...

2015-07-17

Monomethylmercury (MeHg) is produced in many aquatic environments by anaerobic microorganisms that take up and methylate inorganic forms of Hg(II). Net methylation of Hg(II) appears to be correlated with factors that affect the activity of the anaerobic microbial community and factors that increase the bioavailability of Hg(II) to these organisms. However, the relative importance of one versus the other is difficult to elucidate even though this information can greatly assist remediation efforts and risk assessments. Here in this study, we investigated the effects of Hg speciation (dissolved Hg and nanoparticulate HgS) and microbial activity on the net production of MeHgmore » using two mixed microbial cultures that were enriched from marine sediments under sulfate reducing conditions. The cultures were amended with dissolved Hg (added as a dissolved nitrate salt) and nanoparticulate HgS, and grown under different carbon substrate concentrations. The results indicated that net mercury methylation was the highest for cultures incubated in the greatest carbon substrate concentration (60 mM) compared to incubations with less carbon (0.6 and 6 mM), regardless of the form of mercury amended. Net MeHg production in cultures exposed to HgS nanoparticles was significantly slower than in cultures exposed to dissolved Hg; however, the difference diminished with slower growing cultures with low carbon addition (0.6 mM). The net Hg methylation rate was found to correlate with sulfate reduction rate in cultures exposed to dissolved Hg, while methylation rate was roughly constant for cultures exposed to nanoparticulate HgS. These results indicated a potential threshold of microbial productivity: below this point net MeHg production was limited by microbial activity, regardless of Hg bioavailability. Lastly, above this threshold of productivity, Hg speciation became a contributing factor towards net MeHg production.« less

Mercury speciation in sediments at a municipal sewage sludge marine disposal site.

PubMed

Shoham-Frider, E; Shelef, G; Kress, N

2007-12-01

Mercury speciation was performed in excess activated sewage sludge (ASS) and in marine sediments collected at the AAS disposal site off the Mediterranean coast of Israel in order to characterize the spatial and vertical distribution of different mercury species and assess their environmental impact. Total Hg (HgT) concentrations ranged between 0.19 and 1003ng/g at the polluted stations and 5.7 and 72.8ng/g at the background station, while the average concentration in ASS was 1181+/-273ng/g. Only at the polluted stations did HgT concentrations decrease exponentially with sediment depth, reaching background values at 16-20cm, the vertical distribution resulting from mixing of natural sediment with ASS solids and bioturbation by large populations of polycheates. Average Methyl Hg (MeHg) concentration in ASS was 39.7+/-7.1ng/g, ca. 3% of the HgT concentration, while the background concentrations ranged between 0.1 and 0.61ng/g. MeHg concentrations in surficial polluted sediments were 0.7-5.9ng/g (ca. 0.5% of the HgT) and decreased vertically, similar to HgT. A positive correlation between MeHg and Hg only at the polluted stations, higher MeHg concentrations at the surface of the sediment and not below the redoxline, and no seasonality in the concentrations suggest that the MeHg originated from the ASS and not from in situ methylation. By doing selective extractions, we found that ca. 80% of the total Hg in ASS and polluted sediments was strongly bound to amorphous organo-sulfur and to inorganic sulfide species that are not bioavailable. The fractions with potential bioaccessible Hg had maximal concentrations in the range in which biotic effects should be expected. Therefore, although no bioaccumulation was found in the biota in the area, the concentration in the polluted sediments are not negligible and should be carefully monitored.

Seasonal assessment of trace element contamination in intertidal sediments of the meso-macrotidal Hooghly (Ganges) River Estuary with a note on mercury speciation.

PubMed

Mondal, Priyanka; de Alcântara Mendes, Rosivaldo; Jonathan, M P; Biswas, Jayanta Kumar; Murugan, Kadarkarai; Sarkar, Santosh Kumar

2018-02-01

The spatial and seasonal distribution of trace elements (TEs) (n=16) in surficial sediment were examined along the Hooghly River Estuary (~175km), India. A synchronous elevation of majority of TEs concentration (mgkg -1 ) was encountered during monsoon with the following descending order: Al (67070); Fe (31300); Cd (5.73); Cr (71.17); Cu (29.09); Mn (658.74); Ni (35.89). An overall low and homogeneous concentration of total Hg (T Hg =17.85±4.98ngg -1 ) was recorded in which methyl mercury (MeHg) shared minor fraction (8-31%) of the T Hg . Sediment pollution indices, viz. geo-accumulation index (I geo ) and enrichment factor (EF) for Cd (I geo =1.92-3.67; EF=13.83-31.17) and Ba (I geo =0.79-5.03; EF=5.79-108.94) suggested high contamination from anthropogenic sources. From factor analysis it was inferred that TEs primarily originated from lithogenic sources. This study would provide the latest benchmark of TE pollution along with the first record of MeHg in this fluvial system which recommends reliable monitoring to safeguard geochemical health of this stressed environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Occurrence and speciation of arsenic and mercury in estuarine sediments affected by mining activities (Asturias, northern Spain).

PubMed

Garcia-Ordiales, Efrén; Covelli, Stefano; Rico, Jose Manuel; Roqueñí, Nieves; Fontolan, Giorgio; Flor-Blanco, German; Cienfuegos, Pablo; Loredo, Jorge

2018-05-01

Sediments contaminated by Hg and As from two historical mining areas have been deposited in the Nalón estuary (Asturias, northern Spain) since 1850. Total mercury (Hg total ) concentrations in the sediments range from 0.20 μg g -1 to 1.33 μg g -1 , most of it in the form of sulphides. Concentrations of methylmercury (303.20-865.40 pg g -1 ) are up to two orders of magnitude lower than the concentration of Hg total . Total As concentration (As total ) is enriched compared to the background level for the area. The relative abundance of As(V) on As(III) in the sediments ranges from 97.6% to 100%, whereas inorganic Hg accounts for more than 99% of the total Hg. The occurrence of the most toxic species, inorganic As(III) and organic methylmercury, seem to be related to redox conditions together with the amounts of sulphur which act as natural barriers which inhibit the biological and chemical speciation processes. Despite the high amounts of Hg and As present in the sediments, their transference to the water column appear to be limited thus converting sediments in an effective sink of both elements. Special attention should be paid to potential variations of the environmental conditions which might increase the element mobility and exchange between sediments and the water column. Copyright © 2018 Elsevier Ltd. All rights reserved.

Isotopic Composition of Gaseous Elemental Mercury in the Free Troposphere of the Pic du Midi Observatory, France.

PubMed

Fu, Xuewu; Marusczak, Nicolas; Wang, Xun; Gheusi, François; Sonke, Jeroen E

2016-06-07

Understanding the sources and transformations of mercury (Hg) in the free troposphere is a critical aspect of global Hg research. Here we present one year of observations of atmospheric Hg speciation and gaseous elemental Hg (GEM) isotopic composition at the high-altitude Pic du Midi Observatory (2860 m above sea level) in France. Biweekly integrated GEM from February 2012 to January 2013 revealed significant variations in δ(202)HgGEM (-0.04‰ to 0.52‰) but not in Δ(199)HgGEM (-0.17‰ to -0.27‰) or Δ(200)HgGEM (-0.10‰ to 0.05‰). δ(202)HgGEM was negatively correlated with CO and reflected air mass origins from Europe (high CO, low δ(202)HgGEM) and from the Atlantic Ocean (low CO, high δ(202)HgGEM). We suggest that the δ(202)HgGEM variations represent mixing of recent low δ(202)HgGEM European anthropogenic emissions with high δ(202)HgGEM northern hemispheric background GEM. In addition, Atlantic Ocean free troposphere air masses showed a positive correlation between δ(202)HgGEM and gaseous oxidized Hg (GOM) concentrations, indicative of mass-dependent Hg isotope fractionation during GEM oxidation. On the basis of atmospheric δ(202)HgGEM and speciated Hg observations, we suggest that the oceanic free troposphere is a reservoir within which GEM is readily oxidized to GOM.

Mercury in U.S. coal—Priorities for new U.S. Geological Survey studies

USGS Publications Warehouse

Kolker, Allan

2016-05-09

In 2011, the U.S. Environmental Protection Agency (EPA) introduced emissions standards, known as Mercury and Air Toxics Standards (MATS), for a range of toxic constituents from coal-fired utility power stations and other combustion sources. This report presents the findings of an expert panel convened in September 2014 to assess the role of the U.S. Geological Survey (USGS) in new coal investigations that would be useful to stakeholders under MATS. Panel input is provided as summaries of responses to a questionnaire distributed to participants. The panel suggests that the USGS continue its work on trace elements in coal and include more information about delivered coals and boiler feed coals, in comparison to previous USGS compilations that emphasized sampling representative of coals in the ground. To be useful under multipollutant regulatory standards, investigation of a range of constituents in addition to mercury would be necessary. These include other toxic metals proposed for regulation, such as arsenic, nickel, cadmium, and chromium, as well as the halogens chlorine and fluorine, which upon emission form harmful acid gases. Halogen determinations are also important because they influence mercury speciation in flue gas, which allows the effectiveness of mercury controls to be assessed and predicted. The panel suggests that the Illinois Basin and the Powder River Basin should have the highest priority for new coal quality investigations in the near term by the USGS, on the basis of current economic conditions and overall economic importance, respectively. As a starting point for new investigations, brief summaries of the distribution of mercury in each coal basin, and their potential for further investigation, are presented.

Biogeochemical transformations of mercury in solid waste landfills and pathways for release.

PubMed

Lee, Sung-Woo; Lowry, Gregory V; Hsu-Kim, Heileen

2016-02-01

Mercury (Hg) is present in a variety of solid wastes including industrial wastes, household products, consumer electronics, and medical wastes, some of which can be disposed in conventional landfills. The presence of this neurotoxic metal in landfills is a concern due to the potential for it to leach or volatilize from the landfill and impact local ecosystems. The objective of this review is to describe general practices for the disposal of mercury-bearing solid wastes, summarize previous studies on the release of mercury from landfills, and delineate the expected transformations of Hg within landfill environments that would influence transport of Hg via landfill gas and leachate. A few studies have documented the emissions of Hg as landfill gas, primarily as gaseous elemental Hg(0) and smaller amounts as methylated Hg species. Much less is known regarding the release of Hg in leachate. Landfill conditions are unique from other subsurface environments in that they can contain water with very high conductivity and organic carbon concentration. Landfills also experience large changes in redox potential (and the associated microbial community) that greatly influence Hg speciation, transformations, and mobilization potential. Generally, Hg is not likely to persist in large quantities as dissolved species, since Hg(0) tends to evolve in the gas phase and divalent Hg(ii) sorbs strongly to particulate phases including organic carbon and sulfides. However, Hg(ii) has the potential to associate with or form colloidal particles that can be mobilized in porous media under high organic carbon conditions. Moreover, the anaerobic conditions within landfills can foster the growth of microorganisms that produced monomethyl- and dimethyl-Hg species, the forms of mercury with high potential for bioaccumulation. Much advancement has recently been made in the mercury biogeochemistry research field, and this study seeks to incorporate these findings for landfill settings.

The local impact of a coal-fired power plant on inorganic mercury and methyl-mercury distribution in rice (Oryza sativa L.).

PubMed

Xu, Xiaohang; Meng, Bo; Zhang, Chao; Feng, Xinbin; Gu, Chunhao; Guo, Jianyang; Bishop, Kevin; Xu, Zhidong; Zhang, Sensen; Qiu, Guangle

2017-04-01

Emission from coal-fired power plants is one of the major anthropogenic sources of mercury (Hg) in the environment, because emitted Hg can be quickly deposited nearby the source, attention is paid to the effects of coal-burning facilities on levels of toxic methyl-mercury (MeHg) in biota near such sources. Since rice is an agricultural crop that can bio-accumulate MeHg, the potential effects of a large Hg-emitting coal-fired power plant in Hunan Province, China on both inorganic Hg (Hg(II)) and MeHg distributions in rice was investigated. Relatively high MeHg (up to 3.8 μg kg -1 ) and Hg(II) (up to 22 μg kg -1 ) concentrations were observed in rice samples collected adjacent to the plant, suggesting a potential impact of Hg emission from the coal fired power plant on the accumulation of Hg in rice in the area. Concentrations of MeHg in rice were positively correlated with soil MeHg, soil S, and gaseous elemental Hg (GEM) in ambient air. Soil MeHg was the most important factor controlling MeHg concentrations in rice. The methylation of Hg in soils may be controlled by factors such as the chemical speciation of inorganic Hg, soil S, and ambient GEM. Copyright © 2016 Elsevier Ltd. All rights reserved.

Simple interface of high-performance liquid chromatography-atomic fluorescence spectrometry hyphenated system for speciation of mercury based on photo-induced chemical vapour generation with formic acid in mobile phase as reaction reagent.

PubMed

Yin, Yongguang; Liu, Jingfu; He, Bin; Shi, Jianbo; Jiang, Guibin

2008-02-15

Photo-induced chemical vapour generation (CVG) with formic acid in mobile phase as reaction reagent was developed as interface to on-line couple HPLC with atomic fluorescence spectrometry for the separation and determination of inorganic mercury, methylmercury (MeHg), ethylmercury (EtHg) and phenylmercury (PhHg). In the developed procedure, formic acid in mobile phase was used to decompose organomercuries and reduce Hg(2+) to mercury cold vapour under UV irradiation. Therefore, no post-column reagent was used and the flow injection system in traditional procedure is omitted. A number of operating parameters including pH of mobile phase, concentration of formate, flow rate of mobile phase, length of PTFE reaction coil, flow rate of carrier gas and Na(2)S(2)O(3) in sample matrix were optimized. The limits of detection at the optimized conditions were 0.085, 0.033, 0.029 and 0.038 microg L(-1) for inorganic mercury, MeHg, EtHg and PhHg, respectively. The developed method was validated by determination of certified reference material DORM-2 and was further applied in analyses of seafood samples from Yantai port, China. The UV-CVG with formic acid simplifies the instrumentation and reduces the analytical cost significantly.

Urban-rural differences in atmospheric mercury speciation

NASA Astrophysics Data System (ADS)

Liu, Bian; Keeler, Gerald J.; Timothy Dvonch, J.; Barres, James A.; Lynam, Mary M.; Marsik, Frank J.; Morgan, Joy Taylor

2010-05-01

Measurements of gaseous elemental mercury (GEM), particulate mercury (Hg p), and reactive gaseous mercury (RGM) were concurrently recorded at an urban site in Detroit and a rural site in Dexter, both in Michigan for the calendar year 2004. Their average concentrations (±standard deviation) for the urban area were 2.5 ± 1.4 ng m -3, 18.1 ± 61.0 pg m -3, and 15.5 ± 54.9 pg m -3, respectively, while their rural counterparts were 1.6 ± 0.6 ng m -3, 6.1 ± 5.5 pg m -3, and 3.8 ± 6.6 pg m -3, respectively. The medians of urban-to-rural ratios of Hg concentrations indicate approximately 1-fold, 2-fold, and 3-fold gradients between Detroit and Dexter for GEM, Hg p, and RGM, respectively. The urban-rural differences in Hg also varied considerably on different temporal scales and with wind flow patterns, which was most evident in RGM. Our results show that while Hg at both sites was impacted by regional sources, meteorological conditions, and photochemical transformations, the extent of variations in the observed urban-to-rural gradients, particularly in RGM, cannot be fully accounted for by these processes. Both analyses of the annual data and case studies indicate that the more variable and episodic nature of Hg, particularly RGM, seen in Detroit compared with Dexter, was the result of direct impact from local anthropogenic sources.

Influence of soil mercury concentration and fraction on bioaccumulation process of inorganic mercury and methylmercury in rice (Oryza sativa L.).

PubMed

Zhou, Jun; Liu, Hongyan; Du, Buyun; Shang, Lihai; Yang, Junbo; Wang, Yusheng

2015-04-01

Recent studies showed that rice is the major pathway for methylmercury (MeHg) exposure to inhabitants in mercury (Hg) mining areas in China. There is, therefore, a concern regarding accumulation of Hg in rice grown in soils with high Hg concentrations. A soil pot experimental study was conducted to investigate the effects of Hg-contaminated soil on the growth of rice and uptake and speciation of Hg in the rice. Our results imply that the growth of rice promotes residual fraction of Hg transforming to organic-bound fraction in soil and increased the potential risks of MeHg production. Bioaccumulation factors deceased for IHg but relatively stabilized for MeHg with soil total mercury (THg) increasing. IHg in soil was the major source of Hg in the root and stalk, but leaf was contributed by Hg from both atmosphere and soil. Soluble and exchangeable Hg fraction can predict the bioavailability of IHg and MeHg in soils, and that can provide quantitative description of the rate of uptake of the bioavailable Hg. Soluble and exchangeable Hg fraction in paddy soil exceeding 0.0087 mg kg(-1) may cause THg concentration in rice grain above the permissible limit standard, and MeHg concentration in paddy soil more than 0.0091 mg kg(-1) may have the health risks to humans.

Measurements of mercury methylation rates and bioavailability in the Allequash Creek Wetland, Northern Wisconsin

NASA Astrophysics Data System (ADS)

Creswell, J. E.; Babiarz, C. L.; Shafer, M. M.; Armstrong, D. E.

2008-12-01

Wetlands are known to be hot spots for the production of methylmercury (MeHg) and subsequent export into other aquatic ecosystems. Because MeHg is a bioaccumulative neurotoxin, and because the primary route of human exposure to mercury is through the consumption of contaminated fish, understanding the processes by which MeHg is produced in the aquatic environment is important to the protection of human health. Inorganic Hg(II) is known to be methylated by bacteria in the anoxic zones of wetland sediments, but bioavailability plays a role in this process, as certain chemical complexes of mercury are unavailable to the microbial community. In the Allequash Creek wetland, a strong relationship has been observed between MeHg and Dissolved Organic Carbon (DOC) concentrations, but the observed relationship between MeHg and total Hg is weak. This observation implicates factors other than Hg(II) concentration as drivers of methylation. In this study, depth-resolved estimates of the bioavailability of inorganic Hg(II) were made by measuring the net mercury methylation rate potential in the hyporheic zone of the wetland. Gross mercury methylation was measured in sediment cores amended with stable isotope-enriched Hg(II), by analyzing isotopically-enriched methylmercury produced during an incubation. Demethylation was measured by amending replicate cores with stable isotope-enriched methylmercury and analyzing the amount consumed over the incubation period. Analyses were conducted using an inductively coupled plasma-quadrupole mass spectrometer. A method comparison was made between incubating cores intact, with mercury amendments injected through core tube walls, and incubating sectioned cores, with mercury amendments mixed into homogenized sediments. The value of incubating intact cores is that disturbance to the sediment and the microbial community is minimized, resulting in experimental conditions that more accurately mimic in situ conditions. The value of mixing mercury amendments into homogenized sediments is that this spreads the amended mercury throughout the core section, avoiding injection channel effects. The influence of Hg(II) speciation on methylation is also being examined. Preliminary results show gross mercury methylation occurring at both sites sampled, although net methylation is negative throughout most of the depth profile, suggesting that the chemical conditions controlling the bioavailability of Hg(II) are highly variable. Because this is the first time such measurements have been made in this system, these data provide an important baseline for future studies of mercury bioavailability in northern wetlands.

Methymercury Formation in Marine and Freshwater Systems: Sediment Characteristics, Microbial Activity and SRB Phylogeny Control Formation Rates and Food-Chain Exposure

NASA Astrophysics Data System (ADS)

King, J. K.; Saunders, F. M.

2004-05-01

Mercury research in freshwater and marine systems suggests that sediment characteristics such as organic substrate, mercury speciation, and sulfate/sulfide concentrations influence availability of inorganic mercury for methylation. Similarly, sediment characteristics also influence sulfate-reducing bacterial (SRB) respiration as well as the presence/distribution of phylogenetic groups responsible for mercury methylation. Our work illustrates that the process of methylmercury formation in freshwater and marine systems are not dissimilar. Rather, the same geochemical parameters and SRB phylogenetic groups determine the propensity for methylmercury formation and are applicable in both fresh- and marine-water systems. The presentation will include our integration of sediment geochemical and microbial parameters affecting mercury methylation in specific freshwater and marine systems. Constructed wetlands planted with Schoenoplectus californicus and amended with gypsum (CaSO4) have demonstrated a capacity to remove inorganic mercury from industrial outfalls. However, bioaccumulation studies of periphyton, eastern mosquitofish (Gambusia holbrooki) and lake chubsucker (Erimyzon sucetta) were conducted in order to ascertain the availability of wetland-generated methylmercury to biota. Total mercury concentrations in mosquitofish from non-sulfate treated controls and the reference location were significantly lower than those from the low and high sulfate treatments while mean total mercury concentrations in lake chubsuckers were also significantly elevated in the high sulfate treatment compared to the low sulfate, control and reference populations. Methylmercury concentrations in periphyton also corresponded with mercury levels found in the tissue of the lake chubsuckers, and these findings fit well given the trophic levels identified for both species of fish. Overall, data from this study suggest that the initial use of gypsum to accelerate the maturity of a constructed wetland may not prove beneficial with respect to the ultimate objective of mercury sequestration. Current regulations place strict requirements on dredge material placed in confined disposal facilities (CDF) as well as associated effluent waters. Although regulatory guidelines typically address total mercury concentrations, historical data specific to bioaccumulation of mercury suggest that methylmercury concentrations found in sediments and water require attention. Resource agencies are now interested in knowing the likelihood of methylmercury formation in dredge spoil since birds and fish are frequently found feeding in CDFs and the associated mixing zones. Mechanisms that influence methylmercury formation in sediments dictate that dredging of mercury-containing sediments will result in an increased availability of inorganic mercury for methylation. Prior to dredging, the undisturbed sediment contains inorganic mercury complexed to sulfide in an insoluble, unavailable form. However, hydraulic or clamshell dredging can result in an oxidation of sediments and remobilization of mercury-sulfide species thus increasing its availability for methylation. Once sediments are disposed in a CDF, sulfate-reducing bacteria profiles are re-established vertically in dredge spoil and methylmercury synthesis can readily occur.

Variation in concentrations of three mercury (Hg) forms at a rural and a suburban site in New York State.

PubMed

Choi, Hyun-Deok; Huang, Jiaoyan; Mondal, Sumona; Holsen, Thomas M

2013-03-15

Tekran® Hg speciation systems were used at a rural site (Huntington Forest, NY; HF) and a suburban site (Rochester, NY; ROC) to measure gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), and fine particulate-bound mercury (PBM2.5) concentrations for two years (December 2007 to November 2009). Ancillary data were also available from the New York State Department of Environmental Conservation and the United States Environmental Protection Agency Clean Air Status and Trends Network. Seasonal GEM concentrations were similar at both sites and influenced by factors such as the planet boundary layer (PBL) height and mercury emissions from snow, soil, and point sources. In some seasons, O3 was negatively correlated with GEM at ROC and positively correlated with GEM at HF. At HF, O3 was correlated with GOM and was typically higher in the afternoon. The cause of this pattern may be photochemical reactions during the day, and the GOM diel pattern may also be due to deposition which is enhanced by dew formation during the night and early morning. PBM2.5 concentrations were higher in winter at both sites. This is indicative of local wood combustion for space heating in winter, increased sorption to particles at lower temperatures, and lower PBL in the winter. At the suburban site, 2 of 12 events with enhanced GEM/CO ratios were poorly correlated with SO2/GOM, implying that these two events were due either to long range transport or regional metallurgical industries in Canada. Copyright © 2012 Elsevier B.V. All rights reserved.

Applications of optical measurement technology in pollution gas monitoring at thermal power plants

NASA Astrophysics Data System (ADS)

Wang, Jian; Yu, Dahai; Ye, Huajun; Yang, Jianhu; Ke, Liang; Han, Shuanglai; Gu, Haitao; Chen, Yingbin

2011-11-01

This paper presents the work of using advanced optical measurement techniques to implement stack gas emission monitoring and process control. A system is designed to conduct online measurement of SO2/NOX and mercury emission from stacks and slipping NH3 of de-nitrification process. The system is consisted of SO2/NOX monitoring subsystem, mercury monitoring subsystem, and NH3 monitoring subsystem. The SO2/NOX monitoring subsystem is developed based on the ultraviolet differential optical absorption spectroscopy (UV-DOAS) technique. By using this technique, a linearity error less than +/-1% F.S. is achieved, and the measurement errors resulting from optical path contamination and light fluctuation are removed. Moreover, this subsystem employs in situ extraction and hot-wet line sampling technique to significantly reduce SO2 loss due to condensation and protect gas pipeline from corrosion. The mercury monitoring subsystem is used to measure the concentration of element mercury (Hg0), oxidized mercury (Hg2+), and total gaseous mercury (HgT) in the flue gas exhaust. The measurement of Hg with a low detection limit (0.1μg/m3) and a high sensitivity is realized by using cold vapor atom fluorescence spectroscopy (CVAFS) technique. This subsystem is also equipped with an inertial separation type sampling technique to prevent gas pipeline from being clogged and to reduce speciation mercury measurement error. The NH3 monitoring subsystem is developed to measure the concentration of slipping NH3 and then to help improving the efficiency of de-nitrification. The NH3 concentration as low as 0.1ppm is able to be measured by using the off-axis integrated cavity output spectroscopy (ICOS) and the tunable diode laser absorption spectroscopy (TDLAS) techniques. The problem of trace NH3 sampling loss is solved by applying heating the gas pipelines when the measurement is running.

Degassing of reduced carbon from planetary basalts

PubMed Central

Wetzel, Diane T.; Rutherford, Malcolm J.; Jacobsen, Steven D.; Hauri, Erik H.; Saal, Alberto E.

2013-01-01

Degassing of planetary interiors through surface volcanism plays an important role in the evolution of planetary bodies and atmospheres. On Earth, carbon dioxide and water are the primary volatile species in magmas. However, little is known about the speciation and degassing of carbon in magmas formed on other planets (i.e., Moon, Mars, Mercury), where the mantle oxidation state [oxygen fugacity (fO2)] is different from that of the Earth. Using experiments on a lunar basalt composition, we confirm that carbon dissolves as carbonate at an fO2 higher than -0.55 relative to the iron wustite oxygen buffer (IW-0.55), whereas at a lower fO2, we discover that carbon is present mainly as iron pentacarbonyl and in smaller amounts as methane in the melt. The transition of carbon speciation in mantle-derived melts at fO2 less than IW-0.55 is associated with a decrease in carbon solubility by a factor of 2. Thus, the fO2 controls carbon speciation and solubility in mantle-derived melts even more than previous data indicate, and the degassing of reduced carbon from Fe-rich basalts on planetary bodies would produce methane-bearing, CO-rich early atmospheres with a strong greenhouse potential. PMID:23569260

Evaluating mercury bioaccumulation rates in fish using mark-recapture techniques

NASA Astrophysics Data System (ADS)

Mathews, T.; Surendran Nair, S.; McManamay, R.

2017-12-01

Mercury (Hg) bioaccumulation can be described by models of varying complexity, from the simplified bioconcentration factor which describes the partitioning of contaminants between water and the organism, to more sophisticated models which take into consideration speciation, complexation, and/or bioavailability. At contaminated sites, especially those that are undergoing remediation, it is helpful to have a dynamic framework to identify critical Hg sources and processes, and to predict time scales to recovery. However, understanding the relationship between changes in exposure concentrations and bioaccumulation rates remains a challenge. East Fork Poplar Creek (EFPC) is a Hg-contaminated stream located in East Tennessee. Over the past 30 years, various remediation actions have succeeded in significantly reducing Hg inputs to this stream. One of the major goals of remediation is to reduce Hg bioaccumulation in resident sunfish in order to meet human health guidelines. Mercury is measured in sunfish fillets bi-annually at various sites along the stream. Because Hg analysis requires only 100 mg of tissue, fish can be sampled non-lethally and released at the site of capture. Since 2008, passive induced transponder (PIT) tags have been used to identify individual fish that are collected from EFPC for Hg analysis. Approximately 10% of PIT tagged fish were recaptured, allowing for the measurement of growth rates and Hg bioaccumulation rates in individual fish. While traditional biomonitoring studies conducted in EFPC have found that the average Hg concentrations in sacrificed fish have not responded to changes in aqueous Hg concentrations over the past 10 years, data from the mark-recapture study show that individual fish may respond to changes in aqueous inorganic Hg concentrations on shorter time scales. Rapid changes in aqueous Hg concentrations over a four year period resulted in measurable increases and decreases in Hg concentrations in individual fish that could not be explained by growth dilution. These findings are relevant to remediation decisions in EFPC and other Hg-contaminated sites.

Reactive Gaseous Mercury Formation Over The North Pacific Ocean: Influence Of Environmental Parameters On Elemental Mercury Oxidation In The Marine Boundary Layer

NASA Astrophysics Data System (ADS)

Laurier, F. J.

2002-12-01

Global mercury models have identified wet and dry particle deposition and evasion of dissolved gaseous mercury from the ocean and from land as key controls over global mercury cycling (1,2). Recent ocean studies (3,4) however, have indicated that estimated mercury evasion rates from the ocean substantially exceed estimated deposition. Oxidized reactive gaseous mercury species (RGHg) are now known to play a major role in the global mercury cycle (2,5). RGHg species are water-soluble, exhibit a much shorter atmospheric lifetime than elemental mercury, and contribute to a large extent to atmospheric mercury deposition (2,3,6). Although recent global mercury models have accounted for the dry deposition of RGHg derived from point source emissions (6,7), the formation and deposition of RGHg in remote areas have not been incorporated. We suggest that the oxidation of elemental mercury over the ocean, by gas phase or heterogeneous reactions, is an important part the global mercury cycle. In agreement with previous studies (3,8,9) our recent data from atmospheric collections over the North Pacific Ocean support the notion of enhanced oxidation in the marine boundary layer. Our results show an inverse correlation between RGHg production and ozone, and a diurnal cycle with highest concentrations during periods of highest UV irradiation. In addition, the relationship between RGHg and other parameters measured during the cruise will be discussed. Our results clearly show that RGHg deposition to the ocean must be an important Hg source, and a crucial part of the global Hg cycle. (1) Mason R.P., Fitzgerald W.F., and Morel F.M.M. (1994), The biogeochemical cycling of elemental mercury: Anthropogenic influences, Geochim. Cosmochim. Acta, 58: 3191-3198 (2) Shia R.L., Seigneur C., Pai P., Ko M., and Sze N.-D. (1999), Global simulation of atmospheric mercury concentrations and deposition fluxes, J. Geophy. Res., 104(D19), 23, 747-23, 760 (3) Mason, R.P., Lawson N.M., and Sheu G.-R. (2001), Mercury in the Atlantic Ocean: factors controlling air-sea exchange of mercury and its distribution in the upper water, Deep-Sea Res. II, 2829-2853 (4) Lamborg, C.H., Rolfus K.R., and Fitzgerald W.F. (1999), The atmospheric cycling and air-sea exchange of mercury species in the south and equatorial Atlantic Ocean, Deep-Sea Res. II, 957-977 (5) Lindberg S.E., Brooks S., Lin C.-J., Scott K. J., Landis M. S., Stevens R.K., Goodsite M., and Richter A. (2002), Dynamic oxidation of gaseous mercury in the arctic troposphere at polar sunrise, Environ. Sci. Technol., 1245-1256 (6) Bullock O.R. (2000), Modeling assessment of transport and deposition patterns of anthropogenic mercury air emissions in the United States and Canada, Sci Total Environ., 259(1-3), 145-157 (7) Xu X., Yang X., Miller d.R., Helble J.J., and Carley R.J. (2000), a regional scale modelling study of atmospheric transport and formation of mercury. II. Simulation results for the northeast United states, Atmos. Environ., 34: 4945-4955 (8) Sheu G.-R. (2001), Speciation and distribution of atmospheric mercury: Significance of reactive gaseous mercury in the global mercury cycle. PhD. thesis, University of Maryland, College park, pp. 170 (9) Guentzel J.L., Landing W.M., Gill G.A., and Pollman C.D. (2001), Processes influencing rainfall deposition of mercury in Florida, Environ. Sci. Technol., 35: 863-873

Mercury conversion processes in Amazon soils evaluated by thermodesorption analysis.

PubMed

do Valle, Cláudia M; Santana, Genilson P; Windmöller, Cláudia C

2006-12-01

This paper reports on the speciation study and the Hg redox behavior in Amazon soils not influenced by gold mining and collected near Manaus, AM, Brazil. The samples were incubated by adding Hg(0) and HgCl(2) to dry soil. Solid phase Hg speciation analysis was carried out using a Hg thermodesorption technique with the aim of distinguishing elemental Hg(0) from Hg(II) binding forms. In the first case, we observed the conversion of Hg(0) to Hg(II) binding forms in the range of 28-68% and a correlation between the percent of oxidation and OM content. Samples incubated with Hg(II) showed the formation of Hg(I) and/or Hg(0) in the range of 19-69%. The lowest values corresponded to the samples with the lowest clay contents. The kinetics of conversion of Hg(0) as well as HgCl(2) were roughly fitted to the two first order reactions, a fast one and a slow one. It was not possible to evaluate differences between sampling sites and types of soils, but the mean half-life of the first order reaction obtained by the addition of Hg(II) was slower (t(1/2)=365d) than the one obtained by the addition of Hg(0) (t(1/2)=148d). Previous studies have shown the predominance of organically bound Hg in these samples. Thus, the kinetic difference between Hg oxidation and reduction in combination with the efficient retention processes by OM may explain the high background values found in Amazon soils.

Air-snowpack exchange of bromine, ozone and mercury in the springtime Arctic simulated by the 1-D model PHANTAS - Part 2: Mercury and its speciation

NASA Astrophysics Data System (ADS)

Toyota, K.; Dastoor, A. P.; Ryzhkov, A.

2014-04-01

Atmospheric mercury depletion events (AMDEs) refer to a recurring depletion of mercury occurring in the springtime Arctic (and Antarctic) boundary layer, in general, concurrently with ozone depletion events (ODEs). To close some of the knowledge gaps in the physical and chemical mechanisms of AMDEs and ODEs, we have developed a one-dimensional model that simulates multiphase chemistry and transport of trace constituents throughout porous snowpack and in the overlying atmospheric boundary layer (ABL). This paper constitutes Part 2 of the study, describing the mercury component of the model and its application to the simulation of AMDEs. Building on model components reported in Part 1 ("In-snow bromine activation and its impact on ozone"), we have developed a chemical mechanism for the redox reactions of mercury in the gas and aqueous phases with temperature dependent reaction rates and equilibrium constants accounted for wherever possible. Thus the model allows us to study the chemical and physical processes taking place during ODEs and AMDEs within a single framework where two-way interactions between the snowpack and the atmosphere are simulated in a detailed, process-oriented manner. Model runs are conducted for meteorological and chemical conditions that represent the springtime Arctic ABL characterized by the presence of "haze" (sulfate aerosols) and the saline snowpack on sea ice. The oxidation of gaseous elemental mercury (GEM) is initiated via reaction with Br-atom to form HgBr, followed by competitions between its thermal decomposition and further reactions to give thermally stable Hg(II) products. To shed light on uncertain kinetics and mechanisms of this multi-step oxidation process, we have tested different combinations of their rate constants based on published laboratory and quantum mechanical studies. For some combinations of the rate constants, the model simulates roughly linear relationships between the gaseous mercury and ozone concentrations as observed during AMDEs/ODEs by including the reaction HgBr + BrO and assuming its rate constant to be the same as for the reaction HgBr + Br, while for other combinations the results are more realistic by neglecting the reaction HgBr + BrO. Speciation of gaseous oxidized mercury (GOM) changes significantly depending on whether or not BrO is assumed to react with HgBr to form Hg(OBr)Br. Similarly to ozone (reported in Part 1), GEM is depleted via bromine radical chemistry more vigorously in the snowpack interstitial air than in the ambient air. However, the impact of such in-snow sink of GEM is found to be often masked by the re-emissions of GEM from the snow following the photo-reduction of Hg(II) deposited from the atmosphere. GOM formed in the ambient air is found to undergo fast "dry deposition" to the snowpack by being trapped on the snow grains in the top ~1 mm layer. We hypothesize that liquid-like layers on the surface of snow grains are connected to create a network throughout the snowpack, thereby facilitating the vertical diffusion of trace constituents trapped on the snow grains at much greater rates than one would expect inside solid ice crystals. Nonetheless, on the timescale of a week simulated in this study, the signal of atmospheric deposition does not extend notably below the top 1 cm of the snowpack. We propose and show that particulate-bound mercury (PBM) is produced mainly as HgBr42- by taking up GOM into bromide-enriched aerosols after ozone is significantly depleted in the air mass. In the Arctic, "haze" aerosols may thus retain PBM in ozone-depleted air masses, allowing the airborne transport of oxidized mercury from the area of its production farther than in the form of GOM. Temperature dependence of thermodynamic constants calculated in this study for Henry's law and aqueous-phase halide complex formation of Hg(II) species is a critical factor for this proposition, calling for experimental verification. The proposed mechanism may explain observed changes in the GOM-PBM partitioning with seasons, air temperature and the concurrent progress of ozone depletion in the high Arctic. The net deposition of mercury to the surface snow is shown to increase with the thickness of the turbulent ABL and to correspond well with the column amount of BrO in the atmosphere.

Updated atmospheric speciated mercury emissions from iron and steel production in China during 2000-2015

NASA Astrophysics Data System (ADS)

Wu, Qingru; Gao, Wei; Wang, Shuxiao; Hao, Jiming

2017-09-01

Iron and steel production (ISP) is one of the significant atmospheric Hg emission sources in China. Atmospheric mercury (Hg) emissions from ISP during 2000-2015 were estimated by using a technology-based emission factor method. To support the application of this method, databases of Hg concentrations in raw materials, technology development trends, and Hg removal efficiencies of air pollution control devices (APCDs) were constructed through national sampling and literature review. Hg input to ISP increased from 21.6 t in 2000 to 94.5 t in 2015. In the various types of raw materials, coking coal and iron concentrates contributed 35-46 and 25-32 % of the total Hg input. Atmospheric Hg emissions from ISP increased from 11.5 t in 2000 to 32.7 t in 2015 with a peak of 35.6 t in 2013. Pollution control promoted the increase in average Hg removal efficiency, from 47 % in 2000 to 65 % in 2015. During the study period, sinter/pellet plants and blast furnaces were the largest two emission processes. However, emissions from roasting plants and coke ovens cannot be ignored, which accounted for 22-34 % of ISP's emissions. Overall, Hg speciation shifted from 50/44/6 (gaseous elemental Hg (Hg0)/gaseous oxidized Hg (HgII)/particulate-bound Hg (Hgp)) in 2000 to 40/59/1 in 2015, which indicated a higher proportion of Hg deposition around the emission points. Future emissions of ISP were expected to decrease based on the comprehensive consideration crude-steel production, steel scrap utilization, energy saving, and pollution control measures.

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real, Spain) as a case of study.

PubMed

Patiño Ropero, M J; Rodríguez Fariñas, N; Mateo, R; Berzas Nevado, J J; Rodríguez Martín-Doimeadios, R C

2016-04-01

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n = 41) and wild boar (Sus scrofa; n = 16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81%), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46% in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.

Dissolved organic matter kinetically controls mercury bioavailability to bacteria.

PubMed

Chiasson-Gould, Sophie A; Blais, Jules M; Poulain, Alexandre J

2014-03-18

Predicting the bioavailability of inorganic mercury (Hg) to bacteria that produce the potent bioaccumulative neurotoxin monomethylmercury remains one of the greatest challenges in predicting the environmental fate and transport of Hg. Dissolved organic matter (DOM) affects mercury methylation due to its influence on cell physiology (as a potential nutrient) and its influence on Hg(II) speciation in solution (as a complexing agent), therefore controlling Hg bioavailability. We assessed the role of DOM on Hg(II) bioavailability to a gram-negative bacterium bioreporter under oxic pseudo- and nonequilibrium conditions, using defined media and field samples spanning a wide range of DOM levels. Our results showed that Hg(II) was considerably more bioavailable under nonequilibrium conditions than when DOM was absent or when Hg(II) and DOM had reached pseudoequilibrium (24 h) prior to cell exposure. Under these enhanced uptake conditions, Hg(II) bioavailability followed a bell shaped curve as DOM concentrations increased, both for defined media and natural water samples, consistent with bioaccumulation results in a companion paper (this issue) observed for amphipods. Experiments also suggest that DOM may not only provide shuttle molecules facilitating Hg uptake, but also alter cell wall properties to facilitate the first steps toward Hg(II) internalization. We propose the existence of a short-lived yet critical time window (<24 h) during which DOM facilitates the entry of newly deposited Hg(II) into aquatic food webs, suggesting that the bulk of mercury incorporation in aquatic food webs would occur within hours following its deposition from the atmosphere.

Mercury speciation and transport via submarine groundwater discharge at a southern California coastal lagoon system.

PubMed

Ganguli, P M; Conaway, C H; Swarzenski, P W; Izbicki, J A; Flegal, A R

2012-02-07

We measured total mercury (Hg(T)) and monomethylmercury (MMHg) concentrations in coastal groundwater and seawater over a range of tidal conditions near Malibu Lagoon, California, and used (222)Rn-derived estimates of submarine groundwater discharge (SGD) to assess the flux of mercury species to nearshore seawater. We infer a groundwater-seawater mixing scenario based on salinity and temperature trends and suggest that increased groundwater discharge to the ocean during low tide transported mercury offshore. Unfiltered Hg(T) (U-Hg(T)) concentrations in groundwater (2.2-5.9 pM) and seawater (3.3-5.2 pM) decreased during a falling tide, with groundwater U-Hg(T) concentrations typically lower than seawater concentrations. Despite the low Hg(T) in groundwater, bioaccumulative MMHg was produced in onshore sediment as evidenced by elevated MMHg concentrations in groundwater (0.2-1 pM) relative to seawater (∼0.1 pM) throughout most of the tidal cycle. During low tide, groundwater appeared to transport MMHg to the coast, resulting in a 5-fold increase in seawater MMHg (from 0.1 to 0.5 pM). Similarly, filtered Hg(T) (F-Hg(T)) concentrations in seawater increased approximately 7-fold during low tide (from 0.5 to 3.6 pM). These elevated seawater F-Hg(T) concentrations exceeded those in filtered and unfiltered groundwater during low tide, but were similar to seawater U-Hg(T) concentrations, suggesting that enhanced SGD altered mercury partitioning and/or solubilization dynamics in coastal waters. Finally, we estimate that the SGD Hg(T) and MMHg fluxes to seawater were 0.41 and 0.15 nmol m(-2) d(-1), respectively - comparable in magnitude to atmospheric and benthic fluxes in similar environments.

Mercury speciation and transport via submarine groundwater discharge at a southern California coastal lagoon system

USGS Publications Warehouse

Ganguli, P.M.; Conaway, C.H.; Swarzenski, P.W.; Izbicki, J.A.; Flegal, A.R.

2012-01-01

We measured total mercury (Hg T) and monomethylmercury (MMHg) concentrations in coastal groundwater and seawater over a range of tidal conditions near Malibu Lagoon, California, and used 222Rn-derived estimates of submarine groundwater discharge (SGD) to assess the flux of mercury species to nearshore seawater. We infer a groundwater-seawater mixing scenario based on salinity and temperature trends and suggest that increased groundwater discharge to the ocean during low tide transported mercury offshore. Unfiltered Hg T (U-Hg T) concentrations in groundwater (2.2-5.9 pM) and seawater (3.3-5.2 pM) decreased during a falling tide, with groundwater U-Hg T concentrations typically lower than seawater concentrations. Despite the low Hg T in groundwater, bioaccumulative MMHg was produced in onshore sediment as evidenced by elevated MMHg concentrations in groundwater (0.2-1 pM) relative to seawater (???0.1 pM) throughout most of the tidal cycle. During low tide, groundwater appeared to transport MMHg to the coast, resulting in a 5-fold increase in seawater MMHg (from 0.1 to 0.5 pM). Similarly, filtered Hg T (F-Hg T) concentrations in seawater increased approximately 7-fold during low tide (from 0.5 to 3.6 pM). These elevated seawater F-Hg T concentrations exceeded those in filtered and unfiltered groundwater during low tide, but were similar to seawater U-Hg T concentrations, suggesting that enhanced SGD altered mercury partitioning and/or solubilization dynamics in coastal waters. Finally, we estimate that the SGD Hg T and MMHg fluxes to seawater were 0.41 and 0.15 nmol m -2 d -1, respectively - comparable in magnitude to atmospheric and benthic fluxes in similar environments. ?? 2012 American Chemical Society.

Comparison of Mercury Measurement Methods Using Two Active Filter Measurement Methods and a Tekran Speciation Unit

NASA Astrophysics Data System (ADS)

Pierce, A.; Gustin, M. S.; Huang, J.; Heidecorn, K.

2014-12-01

Three active mercury (Hg) measurement methods were operated side by side at an urban site (University of Nevada, Reno College of Agriculture Greenhouse facility, elev. 1370 m) in Reno, and at a high elevation site (Peavine Peak, elev. 2515 m) adjacent to Reno from December 2013 to October 2014. A model 602 BetaPlus Teledyne Advanced Pollution Instrumentation (TAPI, San Diego, CA USA) particulate measurement system was used to collect particulate matter on a 47 mm diameter cation exchange membrane (CEM, PN# MSTGS3R Mustang S, Pall Corp. Port Washington, NY) at a rate of 16.7 lpm for 24 hours to four days. Particulate concentrations were calculated using beta attenuation across the filters (non-destructive to filter material); the CEM filters were then analyzed for total Hg on a Tekran Total Hg Analysis system (model 2600, Tekran Instruments Corp. Knoxville, TN, USA). Concurrently, samples were collected on an active Hg membrane system. The active Hg membrane system consisted of 3 CEM filters sampling at a rate of 1 lpm for one to two weeks. CEM filters were then analyzed on the Tekran 2600. A Tekran speciation unit (model 1130, 1135, 2537) was also in operation and ambient air samples were analyzed for gaseous elemental Hg (GEM), gaseous oxidized Hg (GOM), and particulate bound Hg (PBM). Both the 602 BetaPlus system and the active Hg membrane system should collect RM on the CEM filters. The active Hg membrane system most likely captures mainly GOM based on previous tests with the Teflon inlet setup that indicated there was high static electricity effective in removing particulate matter. Flow rate and length of measurement (24 hours vs. four days) affected the Hg concentrations on the 602 BetaPlus system. Based on these measurements we hypothesize that, due to the high flow rate, and therefore short retention time, the 602 BetaPlus only captured PBM. It is also possible that there was loss of Hg to inlet walls due to the longer inlet on the 602 BetaPlus system compared to the active Hg membrane system.

Mercury species in dab (Limanda limanda) from the North Sea, Baltic Sea and Icelandic waters in relation to host-specific variables.

PubMed

Lang, Thomas; Kruse, Reinhard; Haarich, Michael; Wosniok, Werner

2017-03-01

In the framework of the ICON project (Integrated Assessment of Contaminant Impacts on the North Sea), muscle tissue from a total of 135 common dab (Limanda limanda) (20-28 cm total length) was collected in seven offshore sampling areas in the North Sea, at Iceland and in the Baltic Sea during Aug/Sept and December 2008 for a chemical mercury speciation analysis by means of gas chromatography and detection by cold vapour atomic fluorescence spectroscopy (GC-CVAFS). There was a highly significant correlation between concentrations of methylmercury (MeHg + ) and inorganic mercury (Hg 2+ ) in individual fish, and the mean ratio of MeHg + compared to Σ Hg (MeHg +  + Hg 2+ ) was 94.0%. The results revealed statistically significant differences in concentrations of MeHg + and Hg 2+ , respectively, between sampling areas. Mean concentrations in the German Bight (North Sea), in Icelandic waters and in Mecklenburg Bight (Baltic Sea) were low (MeHg + : 0.023-0.036; Hg 2+ : 0.001-0.002 mg/kg wet weight), while concentrations in dab from the Dogger Bank, Firth of Forth and the vicinity of the Ekofisk oil field (all North Sea) were significantly higher (MeHg + : 0.059-0.101; Hg 2+ : 0.003-0.004 mg/kg wet weight). Statistical correlation analysis on effects of host-specific factors revealed that neither length, weight, age, sex nor condition factor showed a significant relationship with Hg concentrations. However, Hg concentrations were significantly correlated with the Fish Disease Index (FDI), indicating a relationship between Hg concentrations and the health status of dab. Multiple linear regression analysis aiming to find factors affecting Hg concentrations revealed that only the sampling area had a highly significant main effect on Hg concentrations, and in some cases, additionally the condition factor contributed significantly to the final model. From the results, it cannot be excluded that elevated Hg concentration recorded in dab were linked to discharges from offshore oil and gas installations and that Hg affected the health status of dab. Copyright © 2016 Elsevier Ltd. All rights reserved.

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations.

PubMed

Niksa, Stephen; Fujiwara, Naoki

2005-07-01

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.

Sediment-porewater partitioning, total sulfur, and methylmercury production in estuaries.

PubMed

Schartup, Amina T; Balcom, Prentiss H; Mason, Robert P

2014-01-21

Mercury (Hg) speciation and the activity of Hg(II)-methylating bacteria are responsible for the rate of methylmercury production and thus bioaccumulation in marine foodwebs. Factors affecting porewater partitioning (Kd) and methylation of Hg(II) were examined at 11 sites in sediment of 4 biogeochemically diverse estuaries in the Northeast U.S. In Long Island Sound, 88% of total mercury (HgT) log Kd variability was described by porewater dissolved organic carbon concentration and sediment total sulfur (S) content. Whereas across all estuaries, regression analyses showed that S alone drives about 70% of Kd variability and 50% of changes in methylation rates; and the inclusion of DOC and sulfides did not improve the prediction. Thus, we demonstrated that S is a better predictor of HgT log Kd than the sediment organic matter across multiple estuaries, and while organic matter and S are interchangeable in small-scale studies, on a larger scale, sediment S content is the simplest and most effective variable to measure.

Mercury in the sediments of the Marano and Grado Lagoon (northern Adriatic Sea): Sources, distribution and speciation

NASA Astrophysics Data System (ADS)

Acquavita, Alessandro; Covelli, Stefano; Emili, Andrea; Berto, Daniela; Faganeli, Jadran; Giani, Michele; Horvat, Milena; Koron, Neža; Rampazzo, Federico

2012-11-01

The existence of mining tailings in Idrija (Slovenia) and their subsequent transportation via the Isonzo River has been the primary source of mercury (Hg) in the northern Adriatic Sea for almost 500 years, making the Gulf of Trieste and the adjacent Marano and Grado Lagoon two of the most contaminated marine areas in the world. A further, more recent, contribution of Hg has been added by the operation of a chlor-alkali plant (CAP) located in the drainage basin flowing into the Lagoon. On the basis of previous research, as well as new data obtained from the "MIRACLE" project (Mercury Interdisciplinary Research for Appropriate Clam farming in a Lagoon Environment), the spatial distribution of Hg and its relationships with methylmercury (MeHg), organic matter and several geochemical parameters in surface sediments were investigated. The predominant and long-term impacts of the cinnabar-rich Isonzo River particulate matter in the Lagoon surface sediments are evident and confirmed by a decreasing concentration gradient from east (>11 μg g-1) to west (0.7 μg g-1). Hg originated from the CAP is only significant in the central sector of the Lagoon. Hg is primarily associated with fine-grained sediments (<16 μm), as a consequence of transport and dispersion from the fluvial source through littoral and tidal currents. However, speciation analyses highlighted the presence of Hg sulphides in the coarse sandy fraction of sediments from the eastern area, as expected given the origin of the sedimentary material. Unlike Hg, the distribution of MeHg (0.47-7.85 ng g-1) does not show a clear trend. MeHg constitutes, on average, 0.08% of total Hg and percentages are comparable to those obtained in similar lagoon environments. Higher MeHg concentrations in low to intermediate Hg-contaminated sediments indicate that the metal availability is not a limiting factor for MeHg occurrence, thus suggesting a major role played by environmental conditions and/or speciation. The reasonably good correlation between MeHg normalized to humic acid (HA) content and humic δ13C indicates that MeHg is preferentially associated with autochthonous δ13C-enriched HAs in lagoon surface sediments, suggesting that the structure of "marine" HAs, less refractory and less aromatic, could favor MeHg binding and/or production. In the context of the potential hazard of Hg and MeHg accumulation in reared clams, the choice of a site for the extension of farming activities inside the Marano and Grado Lagoon is dependent on several factors and cannot be decided solely on the basis of the total Hg content in the sediment.

Natural and anthropogenic atmospheric mercury in the European Arctic: a speciation study

NASA Astrophysics Data System (ADS)

Steen, A. O.; Berg, T.; Dastoor, A. P.; Durnford, D. A.; Hole, L. R.; Pfaffhuber, K. A.

2010-11-01

It is agreed that gaseous elemental mercury (GEM) is converted to reactive gaseous mercury (RGM) during springtime Atmospheric Mercury Depletion Event (AMDE). RGM is associated with aerosols (PHg) provided that there are sufficient aerosols available for the conversion from RGM to PHg to occur. This study reports the longest time series of GEM, RGM and PHg concentrations from a European Arctic site. From 27 April 2007 until 31 December 2008 composite GEM, RGM and PHg measurements were conducted in Ny-Ålesund (78°54' N, 11°53' E). The average concentrations of the complete dataset were 1.62±0.3 ng m-3, 8±13 pgm-3 and 8±25 pgm-3 for GEM, RGM and PHg, respectively. The study revealed a clear seasonal distribution of GEM, RGM and PHg previously undiscovered. For the complete dataset the atmospheric mercury distribution was 99% GEM, whereas RGM and PHg constituted <1%. Increased PHg concentration occurred exclusively from March through April, and constituted on average 75% of the reactive mercury species in the respective period. RGM was suggested as the precursor for the PHg existence, but long range transportation of PHg has to be taken into consideration. Surprisingly, RGM was not solely formed during the spring AMDE season. Environment Canada's Global/Regional Atmospheric Heavy Metal model (GRAHM) suggested that in situ oxidation of GEM by ozone may be producing the increased RGM concentrations from March through August. Most likely, in situ oxidation of GEM by BrO produced the observed RGM from March through August. The AMDEs occurred from late March until mid June and were thought to be of non-local origin, with GEM being transported to the study site by a wide variety of air masses. With some exceptions, no clear meteorological regime was associated with the GEM, RGM and PHg concentrations.

Statistical estimate of mercury removal efficiencies for air pollution control devices of municipal solid waste incinerators.

PubMed

Takahashi, Fumitake; Kida, Akiko; Shimaoka, Takayuki

2010-10-15

Although representative removal efficiencies of gaseous mercury for air pollution control devices (APCDs) are important to prepare more reliable atmospheric emission inventories of mercury, they have been still uncertain because they depend sensitively on many factors like the type of APCDs, gas temperature, and mercury speciation. In this study, representative removal efficiencies of gaseous mercury for several types of APCDs of municipal solid waste incineration (MSWI) were offered using a statistical method. 534 data of mercury removal efficiencies for APCDs used in MSWI were collected. APCDs were categorized as fixed-bed absorber (FA), wet scrubber (WS), electrostatic precipitator (ESP), and fabric filter (FF), and their hybrid systems. Data series of all APCD types had Gaussian log-normality. The average removal efficiency with a 95% confidence interval for each APCD was estimated. The FA, WS, and FF with carbon and/or dry sorbent injection systems had 75% to 82% average removal efficiencies. On the other hand, the ESP with/without dry sorbent injection had lower removal efficiencies of up to 22%. The type of dry sorbent injection in the FF system, dry or semi-dry, did not make more than 1% difference to the removal efficiency. The injection of activated carbon and carbon-containing fly ash in the FF system made less than 3% difference. Estimation errors of removal efficiency were especially high for the ESP. The national average of removal efficiency of APCDs in Japanese MSWI plants was estimated on the basis of incineration capacity. Owing to the replacement of old APCDs for dioxin control, the national average removal efficiency increased from 34.5% in 1991 to 92.5% in 2003. This resulted in an additional reduction of about 0.86Mg emission in 2003. Further study using the methodology in this study to other important emission sources like coal-fired power plants will contribute to better emission inventories. Copyright © 2010 Elsevier B.V. All rights reserved.

Effects of sulfide concentration and dissolved organic matter characteristics on the structure of nanocolloidal metacinnabar

USGS Publications Warehouse

Poulin, Brett; Gerbig, Chase A.; Kim, Christopher S.; Stegemeier, John P.; Ryan, Joseph N.; Aiken, George R.

2017-01-01

Understanding the speciation of divalent mercury (Hg(II)) in aquatic systems containing dissolved organic matter (DOM) and sulfide is necessary to predict the conversion of Hg(II) to bioavailable methylmercury. We used X-ray absorption spectroscopy to characterize the structural order of mercury in Hg(II)–DOM–sulfide systems for a range of sulfide concentration (1–100 μM), DOM aromaticity (specific ultraviolet absorbance (SUVA254)), and Hg(II)–DOM and Hg(II)–DOM–sulfide equilibration times (4–142 h). In all systems, Hg(II) was present as structurally disordered nanocolloidal metacinnabar (β-HgS). β-HgS nanocolloids were significantly smaller or less ordered at lower sulfide concentration, as indicated by under-coordination of Hg(II) in β-HgS. The size or structural order of β-HgS nanocolloids increased with increasing sulfide abundance and decreased with increasing SUVA254 of the DOM. The Hg(II)–DOM or Hg(II)–DOM–sulfide equilibration times did not significantly influence the extent of structural order in nanocolloidal β-HgS. Geochemical factors that control the structural order of nanocolloidal β-HgS, which are expected to influence nanocolloid surface reactivity and solubility, should be considered in the context of mercury bioavailability.

Distribution of mercury species and mercury isotope ratios in soils and river suspended matter of a mercury mining area.

PubMed

Baptista-Salazar, Carluvy; Hintelmann, Holger; Biester, Harald

2018-04-25

Mercury (Hg) released by mining activities can be dispersed in the environment, where it is subject to species transformations. Hg isotope ratios have been used to track sources in Hg contaminated areas, although it is unclear to what extent variations in δ-values are attributed to distinct Hg species. Hg was mined as Hg sulphide (cinnabar) in Idrija, Slovenia for centuries. Sediments are loaded with mining-residues (cinnabar and calcine), whereas contaminated soils mainly contain Hg bound to natural organic matter (NOM-Hg) related to atmospheric Hg deposition. Hg released from soils and sediments is transported as suspended matter (SM) in the Idrijca river to the Gulf of Trieste (GT), Italy. We determine Hg isotope ratios in river SM, sediments and soils from the Idrijca-catchment to decipher the Hg isotope ratio variability related to Hg species distribution in different grain-size fractions. δ202Hg values of SM collected from tributaries corresponded to those found in soils ranging from -2.58 to 0.19‰ and from -2.27 to -0.88‰, respectively. Speciation measurements reveal that fine fractions (0.45-20 μm) are dominated by NOM-Hg, while larger fractions contain more cinnabar. More negative δ202Hg values were related to higher proportions of NOM-Hg, which are predominant in soils and SM. Rain events increase SM-loads in the river, mainly due to resuspension of coarse grain-size fractions of bottom sediments bearing larger proportions of cinnabar, which leads to more positive δ202Hg values. The large magnitude of variation in δ202Hg and the smaller magnitude of variation in Δ199Hg (-0.37 to 0.09‰) are likely related to fractionation during ore roasting. Soil samples with high NOM-Hg content show more negative δ202Hg values and larger variation of Δ199Hg. More negative δ202Hg values in GT sediments were rather linked to distant sedimentation of soil derived NOM-Hg than to sedimentation of autochthonous marine material. Heterogeneity in the Idrija ore and ore processing likely produce large variations in the Hg isotopic composition of cinnabar and released metallic Hg, which complicate the differentiation of Hg sources. Combining Hg isotope measurements with solid phase Hg speciation reveals that Hg isotope ratios rather indicate different Hg species and are not necessarily symptomatic for Hg pollution sources.

Albatross as Sentinels of Heavy Metal Pollution: Local and Global Factors

NASA Astrophysics Data System (ADS)

Sentman, W.; Edwards, S. V.; Vo, A. E.; Bank, M. S.

2012-12-01

Heavy metal pollution in the Pacific Ocean has garnered significant attention in recent years, especially with regard to rising mercury emissions from Asia. Uncertainty exists over the extent to which mercury in biota may have resulted from increases in anthropogenic emissions over time. Albatrosses, including those inhabiting the North Pacific, are wide-ranging, long-lived, keystone, avian predators. Consequently, they serve as ideal sentinel species for investigating the effects of historical and contemporary pollution as well as local and global factors related to heavy metal bioaccumulation, exposure, and ecotoxicological risk. To date, high levels of mercury and lead have been documented in albatross species throughout the Pacific. To address biotic exposure to these multiple stressors, here we synthesize and conduct meta-analyses of total mercury, methylmercury, and lead exposure data in Black-footed albatross (Phoebastria nigripes) and Laysan albatross (Phoebastria immutabilis). Our approach uses data from the field and literature and for methyl mercury uses museum feathers spanning the past 130 years for Black-Footed albatross. We discuss the use and application of stable isotopes (δ15N and δ13C) as a way to control for temporal changes in trophic structure and diet and the importance of conducting speciation analyses, for mercury, to account for curator mediated inorganic mercury in older specimens. Our data showed higher levels of inorganic mercury in older specimens of Black-Footed albatross as well as two non-pelagic species (control samples) lacking historical sources of bioavailable mercury exposure, which suggests that studies on bioaccumulation should measure methylmercury rather than total mercury when utilizing museum collections. Additionally, at the local scale, previous research has reported that lead paint exposure from buildings was also an important environmental stressor for Laysan albatross, suggesting that albatross species face heavy metal exposure threats at both local (lead) and global scales (mercury). Specific types of plastic pollution entering marine environments have been documented to contain heavy metals at levels, which if bio-available, may present a non-localized source of lead exposure in albatross species known to ingest (and regurgitate to their young) large amounts of marine plastic. Changes in methylmercury levels, in Black-Footed albatross, were consistent with historical global and recent regional increases observed among published estimates and proxies of anthropogenic mercury emissions. Heavy metal toxicity along with other stressors may undermine current and future reproductive outcomes in these seabird species. Collectively, our findings, and review of the literature, suggest that albatrosses in this region can be considered to be an effective marine flagship species and raising the profile of these organisms likely would successfully support broader biodiversity conservation efforts in the North Pacific.

Atmospheric mercury speciation in Shanghai, China.

PubMed

Duan, Lian; Wang, Xiaohao; Wang, Dongfang; Duan, Yusen; Cheng, Na; Xiu, Guangli

2017-02-01

GEM (Gaseous elemental mercury), fine fraction (<2.5μm) PBM (Particle-bound mercury) and GOM (Gaseous oxidized mercury) were continuously monitored from Jun 1 to Dec 31 2014 at a suburban site in Shanghai. The average concentrations of GEM, PBM and GOM were 4.19±9.13ng·m -3 , 197±877pg·m -3 , 21±100pg·m -3 , respectively, which were all much higher than those at urban sites in Europe and North America and rural areas of China, but lower than those at urban sites of China. The concentrations of the three mercury species were all found with the highest concentration in December than those in summer. Overall, GEM varied little and PBM exhibited higher level during the night, while GOM typically peaked in the noon and afternoon which is consistent with that of ozone, indicating that GOM may depend on the stronger photochemical reactions during the daytime. Despite of the weak correlations of GEM with SO 2 (r=0.14, p<0.0001) and NO X (r=0.17, p<0.0001), GEM, PBM, SO 2 and NO x exhibited similar diurnal trend, suggesting that coal combustion might be the important sources of mercury in Shanghai because there is no mercury mining companies and few mercuric manufacturers in Shanghai. The strong correlation of PBM with GEM and GOM showed that directly anthropogenic emission was an important source of GEM and PBM, but the gas-particle partitioning of GOM and GEM might be also another source of PBM. The lower GEM/CO ratio of 3.9 (ng·m -3 ·ppmv -1 ) in Shanghai than that for mainland China and non-ferrous smelting factories were related to the few non-ferrous smelting factories around Shanghai. The results from the potential source contribution function (PSCF) model furtherly illustrated that in Shanghai the concentration of GEM in summer and autumn might be highly impacted by the local and regional source but wasn't heavily affected by long-range transport. Copyright © 2016 Elsevier B.V. All rights reserved.

Role of mariculture in the loading and speciation of mercury at the coast of the East China Sea.

PubMed

Liang, Peng; Gao, Xuefei; You, Qiongzhi; Zhang, Jin; Cao, Yucheng; Zhang, Chan; Wong, Ming-Hung; Wu, Sheng-Chun

2016-11-01

The effects of mariculture on mercury (Hg) contamination and speciation in water, sediment and cultured fish in a typical mariculture zone located in Xiangshan bay, Zhejiang province, east China, were studied. Water, sediment and fish samples were collected from mariculture sites (MS) and from corresponding reference sites (RS) 2500 m away from the MS. The THg concentration in overlying water in Xiangshan bay reached as high as 16.6 ± 19.5 ng L -1 , indicating that anthropogenic sources in this bay may contribution on Hg contamination in overlying water. Mariculture activities resulted in an increase in THg concentration in water from surface and bottom layers, which may be attributed to the discharge of domestic sewage and the accumulation of unconsumed fish feed and fish excreta in the benthic environment. Methylmercury (MeHg) concentrations in the bottom layer of overlying water and top surface layer of porewater underneath MS were higher than at RS, implying that mariculture activities promote Hg methylation in the interface between sediments and water. In addition, the concentrations of MeHg in sediment and porewater were significantly higher in summer than winter. It was observed that THg and MeHg contents in the muscle of blackhead seabream (Acanthopagrus schlegelii) (fed by the trash fish) were significantly higher (p < 0.001) than those in red snapper (Lutjanus campechanus) or perch (Perca fluviatilis) (fed by pellet fish feed). The THg and MeHg concentrations in the fish meat were closely related to the feeding mode, which indicate that fish feed rather than environmental media is the major pathway for Hg accumulation in fish muscle. Copyright © 2016 Elsevier Ltd. All rights reserved.

Mercury in a stream-lake network of Andean Patagonia (Southern Volcanic Zone): Partitioning and interaction with dissolved organic matter.

PubMed

Soto Cárdenas, Carolina; Diéguez, María Del Carmen; Queimaliños, Claudia; Rizzo, Andrea; Fajon, Vesna; Kotnik, Jože; Horvat, Milena; Ribeiro Guevara, Sergio

2018-04-01

Lake Nahuel Huapi (NH) is a large, ultraoligotrophic deep system located in Nahuel Huapi National Park (NHNP) and collecting a major headwater network of Northwestern Patagonia (Argentina). Brazo Rincón (BR), the westernmost branch of NH, is close to the active volcanic formation Puyehue-Cordón Caulle. In BR, aquatic biota and sediments display high levels of total Hg (THg), ranging in contamination levels although it is an unpolluted region. In this survey, Hg species and fractionation were assessed in association with dissolved organic matter (DOM) in several aquatic systems draining to BR. THg varied between 16.8 and 363 ng L -1 , with inorganic Hg (Hg 2+ ) contributing up to 99.8% and methyl mercury (MeHg) up to 2.10%. DOC levels were low (0.31-1.02 mg L -1 ) resulting in high THg:DOC and reflecting in high Hg 2+ availability for binding particles (partitioning coefficient log K d up to 6.03). In streams, Hg fractionation and speciation related directly with DOM terrestrial prints, indicating coupled Hg-DOM inputs from the catchment. In the lake, DOM quality and photochemical and biological processing drive Hg fractionation, speciation and vertical levels. Dissolved gaseous Hg (Hg 0 ) reached higher values in BR (up to 3.8%), particularly in upper lake layers where solar radiation enhances the photoreduction of Hg 2+ and Hg-DOM complexes. The environmental conditions in BR catchment promote Hg 2+ binding to abiotic particles and bioaccumulation and the production of Hg 0 , features enhancing Hg mobilization among ecosystem compartments. Overall, the aquatic network studied can be considered a "natural Hg hotspot" within NHNP. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mercury methylation dynamics in estuarine and coastal marine environments — A critical review

NASA Astrophysics Data System (ADS)

Merritt, Karen A.; Amirbahman, Aria

2009-09-01

Considerable recent research has focused on methylmercury (MeHg) cycling within estuarine and coastal marine environments. Because MeHg represents a potent neurotoxin that may magnify in marine foodwebs, it is important to understand the mechanisms and environmental variables that drive or constrain methylation dynamics in these environments. This critical review article explores the mechanisms hypothesized to influence aqueous phase and sediment solid phase MeHg concentrations and depth-specific inorganic Hg (II) (Hg i) methylation rates (MMR) within estuarine and coastal marine environments, and discusses issues of terminology or methodology that complicate mechanism-oriented interpretation of field and laboratory data. Mechanisms discussed in this review article include: 1) the metabolic activity of sulfate reducing bacteria (SRB), the microbial group thought to dominate mercury methylation in these environments; 2) the role that Hg i concentration and/or speciation play in defining depth-specific Hg i methylation rates; and 3) the depth-dependent balance between MeHg production and consumption within the sedimentary environment. As discussed in this critical review article, the hypothesis of SRB community control on the Hg i methylation rate in estuarine and coastal marine environments is broadly supported by the literature. Although Hg i speciation, as a function of porewater inorganic sulfide and/or dissolved organic matter concentration and/or pH, may also play a role in observed variations in MMR, the nature and function of the controlling ligand(s) has not yet been adequately defined. Furthermore, although it is generally recognized that the processes responsible for MeHg production and consumption overlap spatially and/or kinetically in the sedimentary environment, and likely dictate the extent to which MeHg accumulates in the aqueous and/or sediment solid phase, this conceptual interpretation requires refinement, and would benefit greatly from the application of kinetic modeling.

Results of Hg speciation testing on DWPF SMECT-8, OGCT-1, AND OGCT-2 samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C.

2016-02-22

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The sixteenth shipment of samples was designated to include a Defense Waste Processing Facility (DWPF) Slurry Mix Evaporator Condensate Tank (SMECT) sample from Sludge Receipt and Adjustment Tank (SRAT) Batch 738 processing and two Off-Gas Condensate Tank (OGCT) samples, one following Batch 736 and one following Batch 738. The DWPF sample designations for the three samples analyzed are provided. The Batch 738 ‘End ofmore » SME Cycle’ SMECT sample was taken at the conclusion of Slurry Mix Evaporator (SME) operations for this batch and represents the fourth SMECT sample examined from Batch 738. Batch 738 experienced a sludge slurry carryover event, which introduced sludge solids to the SMECT that were particularly evident in the SMECT-5 sample, but less evident in the ‘End of SME Cycle’ SMECT-8 sample.« less

Long-term trends of surface-water mercury and methylmercury concentrations downstream of historic mining within the Carson River watershed

USGS Publications Warehouse

Morway, Eric D.; Thodal, Carl E.; Marvin-DiPasquale, Mark C.

2017-01-01

The Carson River is a vital water resource for local municipalities and migratory birds travelling the Pacific Flyway. Historic mining practices that used mercury (Hg) to extract gold from Comstock Lode ore has left much of the river system heavily contaminated with Hg, a practice that continues in many parts of the world today. Between 1998 and 2013, the United States Geological Survey (USGS) collected and analyzed Carson River water for Hg and methylmercury (MeHg) concentrations resulting in a sixteen year record of unfiltered total mercury (uf.THg), filtered (dissolved) Hg (f.THg), total methylmercury (uf.MeHg), filtered MeHg (f.MeHg), and particulate-bound THg (p.THg) and MeHg (p.MeHg) concentrations. This represents one of the longest continuous records of Hg speciation data for any riverine system, thereby providing a unique opportunity to evaluate long-term trends in concentrations and annual loads. During the period of analysis, uf.THg concentration and load trended downward at rates of −0.85% and −1.8% per year, respectively. Conversely, the f.THg concentration increased at a rate of 1.7% per year between 1998 and 2005, and 4.9% per year between 2005 and 2013. Trends in flow-normalized partition coefficients for both Hg and MeHg suggest a statistically significant shift from the particulate to the filtered phase. The upwardly accelerating f.THg concentration and observed shift from the solid phase to the aqueous phase among the pools of Hg and MeHg within the river water column signals an increased risk of deteriorating ecological conditions in the lower basin with respect to Hg contamination. More broadly, the 16-year trend analysis, completed 140 years after the commencement of major Hg releases to the Carson River, provides a poignant example of the ongoing legacy left behind by gold and silver mining techniques that relied on Hg amalgamation, and a cautionary tale for regions still pursuing the practice in other countries.

Flux model to estimate the transport of mercury species in a contaminated lagoon (Ria de Aveiro, Portugal).

PubMed

Stoichev, Teodor; Tessier, Emmanuel; Almeida, Cristina Marisa R; Basto, Maria Clara P; Vasconcelos, Vitor M; Amouroux, David

2018-04-13

The concentrations of dissolved and particulate inorganic mercury (IHg(II)) and methylmercury (MeHg) from the contaminated Laranjo Bay (main freshwater discharge from the Antuã River) were measured by species-specific isotope dilution during six sampling campaigns at high and at low tide. Different effective riverine concentrations were calculated, based on salinity profiles, for specific hydrological conditions. The export fluxes of total Hg and MeHg (324 and 1.24 mol year -1 , respectively) from the bay to the rest of the Aveiro Lagoon are much higher than the input fluxes from the Hg source (3.9 and 0.05 mol year -1 ) and from the Antuã River (10.4 and 0.10 mol year -1 ). Resuspension of contaminated sediments from Laranjo Bay is crucial for the transport of both IHg(II) and MeHg. Methylation and/or selective enrichment into biogenic particles is responsible for the mobilization of MeHg. Sorption of dissolved IHg(II) onto suspended particles limits its export flux. This is one of the rarest examples where both speciation fluxes and partitioning of mercury are studied in a contaminated coastal environment. Despite the lower fraction of total MeHg (relative to total Hg), the contaminated lagoon may have an impact on coastal areas, particularly if change in the lagoon geometry occurs, due to sea level rise.

Photochemical Oxidation of Dissolved Elemental Mercury by Carbonate Radicals in Water

DOE PAGES

He, Feng; Zhao, Weirong; Liang, Liyuan; ...

2014-11-11

Photochemical oxidation of dissolved elemental mercury [Hg(0)] affects mercury chemical speciation and its transfer at the water-air interface in the aquatic environment. The mechanisms and factors that control Hg(0) photooxidation, however, are not completely understood, especially in natural freshwaters containing dissolved organic matter (DOM) and carbonate. Here, we evaluate Hg(0) photooxidation rates affected by various reactive ionic species [e.g., DOM, CO 3 2-, NO 3 -] and free radicals in a creek water and a phosphate buffer solution (pH=8) under simulated solar irradiation. We report a high Hg(0) photooxidation rate (k = 1.44 h -1) in the presence of bothmore » HCO 3 2- and NO 3 -, whereas HCO 3 2-, NO 3 -, or DOM alone increased the oxidation rate slightly (k = 0.1 0.17 h -1). Using scavengers and enhancers for singlet oxygen ( 1O 2) and hydroxyl (HO ∙ ) radicals, as well as electron paramagnetic resonance spectroscopy, we identify that carbonate radicals (CO 3 ∙-) primarily drive the Hg(0) photooxidation, whereas addition of DOM resulted in a 2-fold decrease in Hg(0) oxidation. This study identifies an unrecognized pathway of Hg(0) photooxidation by CO 3 ∙- radicals and the inhibitory effect of DOM, which could be important in assessing Hg transformation and fate in water containing carbonate such as hard water and seawater.« less

ECONOMIC AND ENVIRONMENTAL ANALYSIS OF TECHNOLOGIES TO TREAT MERCURY AND DISPOSE IN A WASTE CONTAINMENT FACILITY

EPA Science Inventory

This report is intended to describe an economic and environmental analysis of a number of technologies for the treatment and disposal of elemental mercury. The analysis considers three treatment technologies that convert elemental mercury into a stable form of mercury. The techno...

Mercury Emission Control Technologies for PPL Montana-Colstrip Testing

DOE Office of Scientific and Technical Information (OSTI.GOV)

John P. Kay; Michael L. Jones; Steven A. Benson

2007-04-01

The Energy & Environmental Research Center (EERC) was asked by PPL Montana LLC (PPL) to provide assistance and develop an approach to identify cost-effective options for mercury control at its coal-fired power plants. The work conducted focused on baseline mercury level and speciation measurement, short-term parametric testing, and week long testing of mercury control technology at Colstrip Unit 3. Three techniques and various combinations of these techniques were identified as viable options for mercury control. The options included oxidizing agents or sorbent enhancement additives (SEAs) such as chlorine-based SEA1 and an EERC proprietary SEA2 with and without activated carbon injection.more » Baseline mercury emissions from Colstrip Unit 3 are comparatively low relative to other Powder River Basin (PRB) coal-fired systems and were found to range from 5 to 6.5 g/Nm3 (2.9 to 3.8 lb/TBtu), with a rough value of approximately 80% being elemental upstream of the scrubber and higher than 95% being elemental at the outlet. Levels in the stack were also greater than 95% elemental. Baseline mercury removal across the scrubber is fairly variable but generally tends to be about 5% to 10%. Parametric results of carbon injection alone yielded minimal reduction in Hg emissions. SEA1 injection resulted in 20% additional reduction over baseline with the maximum rate of 400 ppm (3 gal/min). Week long testing was conducted with the combination of SEA2 and carbon, with injection rates of 75 ppm (10.3 lb/hr) and 1.5 lb/MMacf (40 lb/hr), respectively. Reduction was found to be an additional 30% and, overall during the testing period, was measured to be 38% across the scrubber. The novel additive injection method, known as novel SEA2, is several orders of magnitude safer and less expensive than current SEA2 injection methods. However, used in conjunction with this plant configuration, the technology did not demonstrate a significant level of mercury reduction. Near-future use of this technique at Colstrip is not seen. All the additives injected resulted in some reduction in mercury emissions. However, the target reduction of 55% was not achieved. The primary reason for the lower removal rates is because of the lower levels of mercury in the flue gas stream and the lower capture level of fine particles by the scrubbers (relative to that for larger particles). The reaction and interaction of the SEA materials is with the finer fraction of the fly ash, because the SEA materials are vaporized during the combustion or reaction process and condense on the surfaces of entrained particles or form very small particles. Mercury will have a tendency to react and interact with the finer fraction of entrained ash and sorbent as a result of the higher surface areas of the finer particles. The ability to capture the finer fraction of fly ash is the key to controlling mercury. Cost estimates for mercury removal based on the performance of each sorbent during this project are projected to be extremely high. When viewed on a dollar-per-pound-of-mercury removed basis activated carbon was projected to cost nearly $1.2 million per pound of mercury removed. This value is roughly six times the cost of other sorbent-enhancing agents, which were projected to be closer to $200,000 per pound of mercury removed.« less

Multielemental speciation analysis by advanced hyphenated technique - HPLC/ICP-MS: A review.

PubMed

Marcinkowska, Monika; Barałkiewicz, Danuta

2016-12-01

Speciation analysis has become an invaluable tool in human health risk assessment, environmental monitoring or food quality control. Another step is to develop reliable multielemental speciation methodologies, to reduce costs, waste and time needed for the analysis. Separation and detection of species of several elements in a single analytical run can be accomplished by high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC/ICP-MS). Our review assembles articles concerning multielemental speciation determination of: As, Se, Cr, Sb, I, Br, Pb, Hg, V, Mo, Te, Tl, Cd and W in environmental, biological, food and clinical samples analyzed with HPLC/ICP-MS. It addresses the procedures in terms of following issues: sample collection and pretreatment, selection of optimal conditions for elements species separation by HPLC and determination using ICP-MS as well as metrological approach. The presented work is the first review article concerning multielemental speciation analysis by advanced hyphenated technique HPLC/ICP-MS. Copyright © 2016 Elsevier B.V. All rights reserved.

Preconstruction Biogeochemical Analysis of Mercury in Wetlands Bordering the Hamilton Army Airfield (HAAF) Wetlands Restoration Site. Part 3

DTIC Science & Technology

2009-12-01

ER D C/ EL T R- 09 -2 1 Preconstruction Biogeochemical Analysis of Mercury in Wetlands Bordering the Hamilton Army Airfield (HAAF) Wetlands...Preconstruction Biogeochemical Analysis of Mercury in Wetlands Bordering the Hamilton Army Airfield (HAAF) Wetlands Restoration Site Part 3 Elly P. H... mercury methylation and demethylation, and biogeochemical parameters related to the mercury cycle as measured by both conventional and emerging methods

Geochemistry of mercury and other constituents in subsurface sediment—Analyses from 2011 and 2012 coring campaigns, Cache Creek Settling Basin, Yolo County, California

USGS Publications Warehouse

Arias, Michelle R.; Alpers, Charles N.; Marvin-DiPasquale, Mark C.; Fuller, Christopher C.; Agee, Jennifer L.; Sneed, Michelle; Morita, Andrew Y.; Salas, Antonia

2017-10-31

Cache Creek Settling Basin was constructed in 1937 to trap sediment from Cache Creek before delivery to the Yolo Bypass, a flood conveyance for the Sacramento River system that is tributary to the Sacramento–San Joaquin Delta. Sediment management options being considered by stakeholders in the Cache Creek Settling Basin include sediment excavation; however, that could expose sediments containing elevated mercury concentrations from historical mercury mining in the watershed. In cooperation with the California Department of Water Resources, the U.S. Geological Survey undertook sediment coring campaigns in 2011–12 (1) to describe lateral and vertical distributions of mercury concentrations in deposits of sediment in the Cache Creek Settling Basin and (2) to improve constraint of estimates of the rate of sediment deposition in the basin.Sediment cores were collected in the Cache Creek Settling Basin, Yolo County, California, during October 2011 at 10 locations and during August 2012 at 5 other locations. Total core depths ranged from approximately 4.6 to 13.7 meters (15 to 45 feet), with penetration to about 9.1 meters (30 feet) at most locations. Unsplit cores were logged for two geophysical parameters (gamma bulk density and magnetic susceptibility); then, selected cores were split lengthwise. One half of each core was then photographed and archived, and the other half was subsampled. Initial subsamples from the cores (20-centimeter composite samples from five predetermined depths in each profile) were analyzed for total mercury, methylmercury, total reduced sulfur, iron speciation, organic content (as the percentage of weight loss on ignition), and grain-size distribution. Detailed follow-up subsampling (3-centimeter intervals) was done at six locations along an east-west transect in the southern part of the Cache Creek Settling Basin and at one location in the northern part of the basin for analyses of total mercury; organic content; and cesium-137, which was used for dating. This report documents site characteristics; field and laboratory methods; and results of the analyses of each core section and subsample of these sediment cores, including associated quality-assurance and quality-control data.

The use of a mercury biosensor to evaluate the bioavailability of mercury-thiol complexes and mechanisms of mercury uptake in bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ndu, Udonna; Barkay, Tamar; Mason, Robert P.

We discuss as mercury (Hg) biosensors are sensitive to only intracellular Hg, they are useful in the investigation of Hg uptake mechanisms and the effects of speciation on Hg bioavailability to microbes. In this study, bacterial biosensors were used to evaluate the roles that several transporters such as the glutathione, cystine/cysteine, and Mer transporters play in the uptake of Hg from Hg-thiol complexes by comparing uptake rates in strains with functioning transport systems to strains where these transporters had been knocked out by deletion of key genes. The Hg uptake into the biosensors was quantified based on the intracellular conversionmore » of inorganic mercury (Hg(II)) to elemental mercury (Hg(0)) by the enzyme MerA. It was found that uptake of Hg from Hg-cysteine (Hg(CYS) 2) and Hg-glutathione (Hg(GSH) 2) complexes occurred at the same rate as that of inorganic complexes of Hg(II) into Escherichia coli strains with and without intact Mer transport systems. However, higher rates of Hg uptake were observed in the strain with a functioning Mer transport system. These results demonstrate that thiol-bound Hg is bioavailable to E. coli and that this bioavailability is higher in Hg-resistant bacteria with a complete Mer system than in non-resistant strains. No difference in the uptake rate of Hg from Hg(GSH) 2 was observed in E. coli strains with or without functioning glutathione transport systems. There was also no difference in uptake rates between a wildtype Bacillus subtilis strain with a functioning cystine/cysteine transport system, and a mutant strain where this transport system had been knocked out. These results cast doubt on the viability of the hypothesis that the entire Hg-thiol complex is taken up into the cell by a thiol transporter. It is more likely that the Hg in the Hg-thiol complex is transferred to a transport protein on the cell membrane and is subsequently internalized.« less

The use of a mercury biosensor to evaluate the bioavailability of mercury-thiol complexes and mechanisms of mercury uptake in bacteria

DOE PAGES

Ndu, Udonna; Barkay, Tamar; Mason, Robert P.; ...

2015-09-15

We discuss as mercury (Hg) biosensors are sensitive to only intracellular Hg, they are useful in the investigation of Hg uptake mechanisms and the effects of speciation on Hg bioavailability to microbes. In this study, bacterial biosensors were used to evaluate the roles that several transporters such as the glutathione, cystine/cysteine, and Mer transporters play in the uptake of Hg from Hg-thiol complexes by comparing uptake rates in strains with functioning transport systems to strains where these transporters had been knocked out by deletion of key genes. The Hg uptake into the biosensors was quantified based on the intracellular conversionmore » of inorganic mercury (Hg(II)) to elemental mercury (Hg(0)) by the enzyme MerA. It was found that uptake of Hg from Hg-cysteine (Hg(CYS) 2) and Hg-glutathione (Hg(GSH) 2) complexes occurred at the same rate as that of inorganic complexes of Hg(II) into Escherichia coli strains with and without intact Mer transport systems. However, higher rates of Hg uptake were observed in the strain with a functioning Mer transport system. These results demonstrate that thiol-bound Hg is bioavailable to E. coli and that this bioavailability is higher in Hg-resistant bacteria with a complete Mer system than in non-resistant strains. No difference in the uptake rate of Hg from Hg(GSH) 2 was observed in E. coli strains with or without functioning glutathione transport systems. There was also no difference in uptake rates between a wildtype Bacillus subtilis strain with a functioning cystine/cysteine transport system, and a mutant strain where this transport system had been knocked out. These results cast doubt on the viability of the hypothesis that the entire Hg-thiol complex is taken up into the cell by a thiol transporter. It is more likely that the Hg in the Hg-thiol complex is transferred to a transport protein on the cell membrane and is subsequently internalized.« less

An evaluation of a reagentless method for the determination of total mercury in aquatic life

USGS Publications Warehouse

Haynes, Sekeenia; Gragg, Richard D.; Johnson, Elijah; Robinson, Larry; Orazio, Carl E.

2006-01-01

Multiple treatment (i.e., drying, chemical digestion, and oxidation) steps are often required during preparation of biological matrices for quantitative analysis of mercury; these multiple steps could potentially lead to systematic errors and poor recovery of the analyte. In this study, the Direct Mercury Analyzer (Milestone Inc., Monroe, CT) was utilized to measure total mercury in fish tissue by integrating steps of drying, sample combustion and gold sequestration with successive identification using atomic absorption spectrometry. We also evaluated the differences between the mercury concentrations found in samples that were homogenized and samples with no preparation. These results were confirmed with cold vapor atomic absorbance and fluorescence spectrometric methods of analysis. Finally, total mercury in wild captured largemouth bass (n = 20) were assessed using the Direct Mercury Analyzer to examine internal variability between mercury concentrations in muscle, liver and brain organs. Direct analysis of total mercury measured in muscle tissue was strongly correlated with muscle tissue that was homogenized before analysis (r = 0.81, p < 0.0001). Additionally, results using this integrated method compared favorably (p < 0.05) with conventional cold vapor spectrometry with atomic absorbance and fluorescence detection methods. Mercury concentrations in brain were significantly lower than concentrations in muscle (p < 0.001) and liver (p < 0.05) tissues. This integrated method can measure a wide range of mercury concentrations (0-500 ??g) using small sample sizes. Total mercury measurements in this study are comparative to the methods (cold vapor) commonly used for total mercury analysis and are devoid of laborious sample preparation and expensive hazardous waste. ?? Springer 2006.

Thiol-Based Selective Extraction Assay to Comparatively Assess Bioavailable Mercury in Sediments

PubMed Central

Ticknor, Jonathan L.; Kucharzyk, Katarzyna H.; Porter, Kaitlyn A.; Deshusses, Marc A.; Hsu-Kim, Heileen

2015-01-01

Abstract Bioaccumulation of methylmercury in the aquatic food web is governed in part by the methylation of inorganic divalent mercury (Hg(II)) by anaerobic microorganisms. In sulfidic settings, a small fraction of total Hg(II) is typically bioavailable to methylating microorganisms. Quantification of this fraction is difficult due to uncertainties in the speciation of Hg(II) and the mechanisms of uptake by methylating microbes. However, recent studies have shown that the bioavailable fraction is likely to include a portion of Hg(II) associated with solid phases, that is, nanostructured mercuric sulfides. Moreover, addition of thiols to suspensions of methylating cultures coincides with increased uptake into cells and methylmercury production. Here, we present a thiol-based selective extraction assay to provide information on the bioavailable Hg fraction in sediments. In the procedure, sediment samples were exposed to a nitrogen-purged solution of glutathione (GSH) for 30 min and the amount of GSH-leachable mercury was quantified. In nine sediment samples from a marine location, the relative GSH-leachable mercury concentration was strongly correlated to the relative amount of methylmercury in the sediments (r2=0.91, p<0.0001) across an order of magnitude of methylmercury concentration values. The approach was further applied to anaerobic sediment slurry microcosm experiments in which sediments were cultured under the same microbial growth conditions but were amended with multiple forms of Hg with a known spectrum of bioavailability. GSH-leachable Hg concentrations increased with observed methylmercury concentrations in the microcosms, matching the trend of species bioavailability in our previous work. Results suggest that a thiol-based selective leaching approach is an improvement compared with other proposed methods to assess Hg bioavailability in sediment and that this approach could provide a basis for comparison of sites where Hg methylation is a concern. PMID:26244001

Sulfur Speciation in Peat: a Time-zero Signature for the " Spruce and Peatland Responses Under Climate and Environmental Change" Experiment

NASA Astrophysics Data System (ADS)

Furman, O.; Toner, B. M.; Sebestyen, S. D.; Kolka, R. K.; Nater, E. A.

2014-12-01

As part of the "Spruce and Peatland Responses Under Climate and Environmental Change" (SPRUCE) experiment, we made initial measurements of sulfur speciation in peat. These observations represent a "time-zero" relative to the intended soil warming experiment which begins in 2015. Total sulfur and sulfur speciation were measured in peat cores (solid phase) from nine plots (hollows and hummocks) to a depth of 2 m. Peat samples were packed under nitrogen and frozen in the field immediately after collection. All subsequent sample storage, handling, and processing were conducted under inert gas. Sulfur speciation was measured using bulk sulfur 1s X-ray absorption near edge structure (XANES) spectroscopy at the SXRMB instrument at the Canadian Light Source, Saskatoon, SK, Canada and at the 9-BM instrument, Advanced Photon Source, Argonne National Laboratory, IL, USA. Total sulfur concentrations ranged from 968 to 4077 mg sulfur / kg dry peat. Sulfur content increased with depth from 2 g sulfur / m2 in the 0-10 cm increment to a maximum value of 38 g sulfur / m2 in the 50-60 cm increment. These sulfur loadings produced high quality XANES spectra. The nine cores exhibited reproducible trends with depth in both total sulfur and specific sulfur species; however, variability in sulfur speciation was greatest in the top 40 cm. All sulfur detected within the peat solids was in an organic form. The most abundant sulfur species group was composed of organic mono-sulfide and thiol forms, representing approximately half of the total sulfur at all depths. Sulfonate and ester-sulfate species were 10-15 mol% of sulfur and exhibited low variability with depth. A subsurface maximum in organic di-sulfide was observed in the 20-30 cm depth increment, which is the transition zone between transiently oxidized acrotelm and permanently saturated anaerobic catotelm. Quantification of major sulfur pools is important for the SPRUCE experiment as they are likely to be indicators of changes in the oxidation-reduction (redox) status, and mercury methylation potential, of the peat in response to warming and enhanced carbon dioxide.

Concentration and dry deposition of mercury species in arid south central New Mexico (2001-2002)

USGS Publications Warehouse

Caldwell, Colleen A.; Swartzendruber, Philip; Prestbo, Eric

2006-01-01

This research was initiated to characterize atmospheric deposition of reactive gaseous mercury (RGM), particulate mercury (HgP; <2.5 μm), and gaseous elemental mercury (Hg0) in the arid lands of south central New Mexico. Two methods were field-tested to estimate dry deposition of three mercury species. A manual speciation sampling train consisting of a KCl-coated denuder, 2.5 μm quartz fiber filters, and gold-coated quartz traps and an ion-exchange membrane (as a passive surrogate surface) were deployed concurrently over 24-h intervals for an entire year. The mean 24-h atmospheric concentration for RGM was 6.8 pg m-3 with an estimated deposition of 0.10 ng m-2h-1. The estimated deposition of mercury to the passive surrogate surface was much greater (4.0 ng m-2h-1) but demonstrated a diurnal pattern with elevated deposition from late afternoon to late evening (1400−2200; 8.0 ng m-2h-1) and lowest deposition during the night just prior to sunrise (2200−0600; 1.7 ng m-2h-1). The mean 24-h atmospheric concentrations for HgP and Hg0 were 1.52 pg m-3 and 1.59 ng m-3, respectively. Diurnal patterns were observed for RGM with atmospheric levels lowest during the night prior to sunrise (3.8 pg m-3) and greater during the afternoon and early evening (8.9 pg m-3). Discernible diurnal patterns were not observed for either HgP or Hg0. The total dry deposition of Hg was 5.9 μg m-2 year-1 with the contribution from the three species as follows:  RGM (0.88 μg m-2 year-1), HgP (0.025 μg m-2 year-1), and Hg0 (5.0 μg m-2 year-1). The annual wet deposition for total mercury throughout the same collection duration was 4.2 μg m-2 year-1, resulting in an estimated total deposition of 10.1 μg m-2 year-1 for Hg. On one sampling date, enhanced HgP (12 pg m-3) was observed due to emissions from a wildfire approximately 250 km to the east.

Mercury(II) Complex Formation With Glutathione in Alkaline Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mah, V.; Jalilehvand, F.

2009-05-19

The structure and speciation of the complexes formed between mercury(II) ions and glutathione (GSH = L-glutamyl-L-cysteinyl-glycine) have been studied for a series of alkaline aqueous solutions (C{sub Hg{sup 2+}} {approx} 18 mmol dm{sup -3} and C{sub GSH} = 40-200 mmol dm{sup -3} at pH {approx} 10.5) by means of extended X-ray absorption fine structure (EXAFS) and {sup 199}Hg NMR spectroscopy at ambient temperature. The dominant complexes are [Hg(GS){sub 2}]{sup 4-} and [Hg(GS){sub 3}]{sup 7-}, with mean Hg-S bond distances of 2.32(1) and 2.42(2) {angstrom} observed in digonal and trigonal Hg-S coordination, respectively. The proportions of the Hg{sup 2+}-glutathione complexes weremore » evaluated by fitting linear combinations of model EXAFS oscillations representing each species to the experimental EXAFS spectra. The [Hg(GS){sub 4}]{sup 10-} complex, with four sulfur atoms coordinated at a mean Hg-S bond distance of 2.52(2) {angstrom}, is present in minor amounts (<30%) in solutions containing a large excess of glutathione (C{sub GSH} {ge} 160 mmol dm{sup -3}). Comparable alkaline mercury(II) cysteine (H{sub 2}Cys) solutions were also investigated and a reduced tendency to form higher complexes was observed, because the deprotonated amino group of Cys{sup 2-} allows the stable [Hg(S,N-Cys){sub 2}]{sup 2-} chelate to form. The effect of temperature on the distribution of the Hg{sup 2+}-glutathione complexes was studied by comparing the EXAFS spectra at ambient temperature and at 25 K of a series of glycerol/water (33/67, v/v) frozen glasses with and C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3} and C{sub GSH} = 16-81 mmol dm{sup -3}. Complexes with high Hg-S coordination numbers, [Hg(GS){sub 3}]{sup 7-} and [Hg(GS){sub 4}]{sup 10-}, became strongly favored when just a moderate excess of glutathione (C{sub GSH} {ge} 28 mmol dm{sup -3}) was used in the glassy samples, as expected for a stepwise exothermic bond formation. Addition of glycerol had no effect on the Hg(II)-glutathione speciation, as shown by the similarity of the EXAFS spectra obtained at room temperature for two parallel series of Hg(II)-glutathione solutions with C{sub Hg{sup 2+}} {approx} 7 mmol dm{sup -3}, with and without 33% glycerol. Also, the {sup 199}Hg NMR chemical shifts of a series of {approx} 18 mmol dm{sup -3} mercury(II) glutathione solutions with 33% glycerol were not significantly different from those of the corresponding series in aqueous solution.« less

Gas and liquid chromatography with inductively coupled plasma mass spectrometry detection for environmental speciation analysis — advances and limitations

NASA Astrophysics Data System (ADS)

Szpunar, Joanna; McSheehy, Shona; Połeć, Kasia; Vacchina, Véronique; Mounicou, Sandra; Rodriguez, Isaac; Łobiński, Ryszard

2000-07-01

Recent advances in the coupling of gas chromatography (GC) and high performance liquid chromatography (HPLC) with inductively coupled plasma mass spectrometry (ICP MS) and their role in trace element speciation analysis of environmental materials are presented. The discussion is illustrated with three research examples concerning the following topics: (i) development and coupling of multicapillary microcolumn GC with ICP MS for speciation of organotin in sediment and biological tissue samples; (ii) speciation of arsenic in marine algae by size-exclusion-anion-exchange HPLC-ICP MS; and (iii) speciation of cadmium in plant cell cultures by size-exclusion HPLC-ICP MS. Particular attention is paid to the problem of signal identification in ICP MS chromatograms; the potential of electrospray MS/MS for this purpose is highlighted.

Considerations in As analysis and speciation

USGS Publications Warehouse

Edwards, M.; Patel, S.; McNeil, L.; Chen, H.W.; Frey, M.; Eaton, A.D.; Antweiler, Ronald C.; Taylor, Howard E.

1998-01-01

This article summarizes recent experiences in arsenic (As) quantification, preservation, and speciation developed during AWWA Research Foundation (AWWARF) and Water Industry Technical Action Fund (WITAF) projects. The goal of this article is to alert analysts and decision-makers to potential problems in As analysis and speciation, because there appear to be several unresolved problems with routine analytical approaches. In true split drinking water samples As was quantified by three accepted analytical methods in three laboratories. The techniques used were graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation inductively coupled plasma-emission spectrometry (HG-ICP-AES). Experimental findings are organized into sections on As analysis, particulate As in water supplies, and examination of As speciation methods.

Selenium Metabolism in Cancer Cells: The Combined Application of XAS and XFM Techniques to the Problem of Selenium Speciation in Biological Systems

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Finney, Lydia; Vogt, Stefan; Witting, Paul K.; Harris, Hugh H.

2013-01-01

Determining the speciation of selenium in vivo is crucial to understanding the biological activity of this essential element, which is a popular dietary supplement due to its anti-cancer properties. Hyphenated techniques that combine separation and detection methods are traditionally and effectively used in selenium speciation analysis, but require extensive sample preparation that may affect speciation. Synchrotron-based X-ray absorption and fluorescence techniques offer an alternative approach to selenium speciation analysis that requires minimal sample preparation. We present a brief summary of some key HPLC-ICP-MS and ESI-MS/MS studies of the speciation of selenium in cells and rat tissues. We review the results of a top-down approach to selenium speciation in human lung cancer cells that aims to link the speciation and distribution of selenium to its biological activity using a combination of X-ray absorption spectroscopy (XAS) and X-ray fluorescence microscopy (XFM). The results of this approach highlight the distinct fates of selenomethionine, methylselenocysteine and selenite in terms of their speciation and distribution within cells: organic selenium metabolites were widely distributed throughout the cells, whereas inorganic selenium metabolites were compartmentalized and associated with copper. New data from the XFM mapping of electrophoretically-separated cell lysates show the distribution of selenium in the proteins of selenomethionine-treated cells. Future applications of this top-down approach are discussed. PMID:23698165

Mercury profiles in sediment from the marginal high of Arabian Sea: an indicator of increasing anthropogenic Hg input.

PubMed

Chakraborty, Parthasarathi; Vudamala, Krushna; Chennuri, Kartheek; Armoury, Kazip; Linsy, P; Ramteke, Darwin; Sebastian, Tyson; Jayachandran, Saranya; Naik, Chandan; Naik, Richita; Nath, B Nagender

2016-05-01

Total Hg distributions and its speciation were determined in two sediment cores collected from the western continental marginal high of India. Total Hg content in the sediment was found to gradually increase (by approximately two times) towards the surface in both the cores. It was found that Hg was preferentially bound to sulfide under anoxic condition. However, redox-mediated reactions in the upper part of the core influenced the total Hg content in the sediment cores. This study suggests that probable increase in authigenic and allogenic Hg deposition attributed to the increasing Hg concentration in the surface sediment in the study area.

Results of Hg speciation testing on MCU strip effluent hold tank (SEHT) and decontaminated salt solution hold tank (DSSHT) materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.

2015-09-17

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team.i,ii The tenth shipment of samples was designated to include Modular Caustic Side Solvent Extraction Unit (MCU) Strip Effluent Hold Tank (SEHT) and MCU Decontaminated Salt Solution Hold Tank (DSSHT) materials from processing Salt Batch 7b. The MCU SEHT (MCU-15-722) and DSSHT (MCU-15-709) samples were pulled on June 15, 2015. All MCU samples were received at SRNL on June 16, 2015. The DSSHT sample wasmore » moved the same day to refrigeration, while the SEHT sample was placed in the Shielded Cells. On July 9, 2015 it was opened and an aliquot diluted 1:100 with Eurofins deionized water and a portion of the diluted sample transferred to a Teflon® bottle prior to moving it to refrigeration that same day. All samples were kept in the dark and refrigerated until final dilutions were prepared for shipment to Eurofins.« less

Characterization of typical heavy metals in pyrolysis MSWI fly ash.

PubMed

Xu, Tengtun; Wang, Li'ao; Zeng, Yunmin; Zhao, Xue; Wang, Lei; Zhan, Xinyuan; Li, Tong; Yang, Lu

2018-06-07

Thermal treatment methods are used extensively in the process of municipal solid waste incineration fly ash. However, the characterization of heavy metals during this process should be understood more clearly in order to control secondary pollution. In this paper, the content, speciation and leaching toxicity of mercury (Hg), plumbum (Pb), cadmium (Cd) and zinc (Zn) in fly ash treated under different temperatures and time were firstly analysed as pre-tests. Later, pilot-scale pyrolysis equipment was used to explore the concentration and speciation changes in the heavy metals of fly ash. Finally, the phase constitution and microstructure changes in fly ash were compared before and after pyrolysis using X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The results showed that (a) The appropriate processing temperature was between 400°C and 450°C, and the processing time should be 1 h. (b) The stability of heavy metals in fly ash increased after pyrolysis. (c) XRD and SEM results indicated that phase constitution changed a little, but the microstructure varied to a porous structure similar to that of a coral reef after pyrolysis. These results suggest that pyrolysis could be an effective method in controlling heavy metal pollution in fly ash.

High Throughput Determination of Mercury in Tobacco and Mainstream Smoke from Little Cigars

PubMed Central

Fresquez, Mark R.; Gonzalez-Jimenez, Nathalie; Gray, Naudia; Watson, Clifford H.; Pappas, R. Steven

2015-01-01

A method was developed that utilizes a platinum trap for mercury from mainstream tobacco smoke which represents an improvement over traditional approaches that require impingers and long sample preparation procedures. In this approach, the trapped mercury is directly released for analysis by heating the trap in a direct mercury analyzer. The method was applied to the analysis of mercury in the mainstream smoke of little cigars. The mercury levels in little cigar smoke obtained under Health Canada Intense smoking machine conditions ranged from 7.1 × 10−3 mg/m3 to 1.2 × 10−2 mg/m3. These air mercury levels exceed the chronic inhalation Minimal Risk Level corrected for intermittent exposure to metallic mercury (e.g., 1 or 2 hours per day, 5 days per week) determined by the Agency for Toxic Substances and Disease Registry. Multivariate statistical analysis was used to assess associations between mercury levels and little cigar physical design properties. Filter ventilation was identified as the principal physical parameter influencing mercury concentrations in mainstream little cigar smoke generated under ISO machine smoking conditions. With filter ventilation blocked under Health Canada Intense smoking conditions, mercury concentrations in tobacco and puff number (smoke volume) were the primary physical parameters that influenced mainstream smoke mercury concentrations. PMID:26051388

Mercury and gold concentrations of highly polluted environmental samples determined using prompt gamma-ray analysis and instrument neutron activation analysis

NASA Astrophysics Data System (ADS)

Osawa, Takahito; Hatsukawa, Yuichi; Appel, Peter W. U.; Matsue, Hideaki

2011-04-01

The authors have established a method of determining mercury and gold in severely polluted environmental samples using prompt gamma-ray analysis (PGA) and instrumental neutron activation analysis (INAA). Since large amounts of mercury are constantly being released into the environment by small-scale gold mining in many developing countries, the mercury concentration in tailings and water has to be determined to mitigate environmental pollution. Cold-vapor atomic absorption analysis, the most pervasive method of mercury analysis, is not suitable because tailings and water around mining facilities have extremely high mercury concentrations. On the other hand, PGA can determine high mercury concentrations in polluted samples as it has an appropriate level of sensitivity. Moreover, gold concentrations can be determined sequentially by using INAA after PGA. In conclusion, the analytical procedure established in this work using PGA and INAA is the best way to evaluate the degree of pollution and the tailing resource value. This method will significantly contribute to mitigating problems in the global environment.

The importance of trace element speciation in biomedical science.

PubMed

Templeton, Douglas M

2003-04-01

According to IUPAC terminology, trace element speciation reflects differences in chemical composition at multiple levels from nuclear and electronic structure to macromolecular complexation. In the medical sciences, all levels of composition are important in various circumstances, and each can affect the bioavailability, distribution, physiological function, toxicity, diagnostic utility, and therapeutic potential of an element. Here we discuss, with specific examples, three biological principles in the intimate relation between speciation and biological behavior: i) the kinetics of interconversion of species determines distribution within the organism, ii) speciation governs transport across various biological barriers, and iii) speciation can limit potentially undesirable interactions between physiologically essential elements. We will also describe differences in the speciation of iron in states of iron overload, to illustrate how speciation analysis can provide insight into cellular processes in human disease.

Sediment-water interactions affecting dissolved-mercury distributions in Camp Far West Reservoir, California

USGS Publications Warehouse

Kuwabara, James S.; Alpers, Charles N.; Marvin-DiPasquale, Mark; Topping, Brent R.; Carter, James L.; Stewart, A. Robin; Fend, Steven V.; Parcheso, Francis; Moon, Gerald E.; Krabbenhoft, David P.

2003-01-01

Field and laboratory studies were conducted in April and November 2002 to provide the first direct measurements of the benthic flux of dissolved (0.2-micrometer filtered) mercury species (total and methylated forms) between the bottom sediment and water column at three sampling locations within Camp Far West Reservoir, California: one near the Bear River inlet to the reservoir, a second at a mid-reservoir site of comparable depth to the inlet site, and the third at the deepest position in the reservoir near the dam (herein referred to as the inlet, midreservoir and near-dam sites, respectively; Background, Fig. 1). Because of interest in the effects of historic hydraulic mining and ore processing in the Sierra Nevada foothills just upstream of the reservoir, dissolved-mercury species and predominant ligands that often control the mercury speciation (represented by dissolved organic carbon, and sulfides) were the solutes of primary interest. Benthic flux, sometimes referred to as internal recycling, represents the transport of dissolved chemical species between the water column and the underlying sediment. Because of the affinity of mercury to adsorb onto particle surfaces and to form insoluble precipitates (particularly with sulfides), the mass transport of mercury in mining-affected watersheds is typically particle dominated. As these enriched particles accumulate at depositional sites such as reservoirs, benthic processes facilitate the repartitioning, transformation, and transport of mercury in dissolved, biologically reactive forms (dissolved methylmercury being the most bioavailable for trophic transfer). These are the forms of mercury examined in this study. In contrast to typical scientific manuscripts, this report is formatted in a pyramid-like structure to serve the needs of diverse groups who may be interested in reviewing or acquiring information at various levels of technical detail (Appendix 1). The report enables quick transitions between the initial summary information (figuratively at the top of the pyramid) and the later details of methods or results (figuratively towards the base of the pyramid) using hyperlinks to supporting figures and tables, and an electronically linked Table of Contents. During two sampling events, two replicate sediment cores (Coring methods; Fig. 2) from each of three reservoir locations (Fig. 1) were used in incubation experiments to provide flux estimates and benthic biological characterizations. Incubation of these cores provided ?snapshots? of solute flux across the sediment-water interface in the reservoir, under benthic, environmental conditions representative of the time and place of collection. Ancillary data, including nutrient and ligand fluxes, were gathered to provide a water-quality framework from which to compare the results for mercury. The following major observations from interdependent physical, biological, and chemical data were made:

Speciated mercury at marine, coastal, and inland sites in New England - Part 1: Temporal variability

NASA Astrophysics Data System (ADS)

Mao, H.; Talbot, R.

2011-12-01

A comprehensive analysis was conducted using long-term continuous measurements of gaseous elemental mercury (Hgo), reactive mercury (RGM), and particulate phase mercury (HgP) at coastal (Thompson Farm, denoted as TF), marine (Appledore Island, denoted as AI), and elevated inland (Pac Monadnock, denoted as PM) sites from the AIRMAP Observatories. Decreasing trends in background Hgo were identified in the 7- and 5-yr records at TF and PM with decline rates of 3.3 parts per quadrillion by volume (ppqv) yr-1 and 6.3 ppqv yr-1, respectively. Common characteristics at these sites were the reproducible annual cycle of Hgo with its maximum in winter-spring and minimum in fall as well as a decline/increase trend in the warm/cool season. The coastal site TF differed from the other two sites with its exceptionally low levels (as low as below 50 ppqv) in the nocturnal inversion layer probably due to dissolution in dew water. Year-to-year variability was observed in the warm season decline in Hgo at TF varying from a minimum total seasonal loss of 20 ppqv in 2010 to a maximum of 92 ppqv in 2005, whereas variability remained small at AI and PM. Measurements of Hgo at PM, an elevated inland rural site, exhibited the smallest diurnal to annual variability among the three environments, where peak levels rarely exceeded 250 ppqv and the minimum was typically 100 ppqv. It should be noted that summertime diurnal patterns at TF and AI are opposite in phase indicating strong sink(s) for Hgo during the day in the marine boundary layer, which is consistent with the hypothesis of Hgo oxidation by halogen radicals there. Mixing ratios of RGM in the coastal and marine boundary layers reached annual maximum in spring and minimum in fall, whereas at PM levels were generally below the limit of detection (LOD) except in spring. RGM levels at AI were higher than at TF and PM indicating a stronger source strength(s) in the marine environment. Mixing ratios of HgP at AI and TF were close in magnitude to RGM levels and were mostly below 1 ppqv. Diurnal variation in HgP was barely discernible at TF and AI in spring and summer with higher levels during the day and smaller but above the LOD at night.

Substance flow analysis of mercury in Turkey for policy decision support.

PubMed

Civancik, Didem; Yetis, Ulku

2018-02-01

Identification and quantification of mercury flows in Turkey are essential for better policy development regarding to the implementation of water-related legislation. To this end, substance flow analysis (SFA) of mercury in Turkey was conducted in order to identify and quantify mercury releases to different environmental compartments and help policy decision makers to better understand their options to reduce mercury flows. For the quantification of mercury flows, United Nations Environment Programme (UNEP) Mercury Toolkit, which is develop by UNEP Chemicals Branch with the aim of assisting countries to develop their own mercury inventory, was used. Results of the study showed that a total of 34.61 t of mercury is released annually from the activities in Turkey to different environmental compartments. It was found that most of the mercury releases were to the atmosphere (74 %) and smaller amounts were to land (21 %) and to water (5 %). Mercury naturally found in the lithosphere was found to be responsible for most of the releases while intentional mercury uses have smaller shares and decreasing importance because of the phasing out of mercury.

Mercury in soils of the agro-industrial zone of Zima city (Irkutsk oblast)

NASA Astrophysics Data System (ADS)

Butakov, E. V.; Kuznetsov, P. V.; Kholodova, M. S.; Grebenshchikova, V. I.

2017-11-01

Data on mercury concentrations in soils of the agro-industrial zone of Zima city in Irkutsk oblast are discussed. It is shown that mercury concentrations in the plow horizon of studied soils exceed background values. The distribution pattern of mercury in soils of the investigated area is characterized. The revealed mercury anomalies are allocated to the industrial zone of the Sayanskkhimprom plant. The combined analysis of data on mercury concentrations in the plow and subplow horizons and on the chemical composition of snow indicates that mercury enters the soil mainly with atmospheric precipitation and is present there in the adsorbed form. The correlation analysis indicates that the local thermal power station plays a significant role as the source of mercury emission to the atmosphere. Close relationships between mercury concentrations and concentrations of mobile forms of elements attest to the presence of mobile organomineral mercury compounds in the studied soils.

Spatially Oscillating Activity and Microbial Succession of Mercury-Reducing Biofilms in a Technical-Scale Bioremediation System

PubMed Central

von Canstein, Harald; Li, Ying; Leonhäuser, Johannes; Haase, Elke; Felske, Andreas; Deckwer, Wolf-Dieter; Wagner-Döbler, Irene

2002-01-01

Mercury-contaminated chemical wastewater of a mercury cell chloralkali plant was cleaned on site by a technical-scale bioremediation system. Microbial mercury reduction of soluble Hg(II) to precipitating Hg(0) decreased the mercury load of the wastewater during its flow through the bioremediation system by up to 99%. The system consisted of a packed-bed bioreactor, where most of the wastewater's mercury load was retained, and an activated carbon filter, where residual mercury was removed from the bioreactor effluent by both physical adsorption and biological reduction. In response to the oscillation of the mercury concentration in the bioreactor inflow, the zone of maximum mercury reduction oscillated regularly between the lower and the upper bioreactor horizons or the carbon filter. At low mercury concentrations, maximum mercury reduction occurred near the inflow at the bottom of the bioreactor. At high concentrations, the zone of maximum activity moved to the upper horizons. The composition of the bioreactor and carbon filter biofilms was investigated by 16S-23S ribosomal DNA intergenic spacer polymorphism analysis. Analysis of spatial biofilm variation showed an increasing microbial diversity along a gradient of decreasing mercury concentrations. Temporal analysis of the bioreactor community revealed a stable abundance of two prevalent strains and a succession of several invading mercury-resistant strains which was driven by the selection pressure of high mercury concentrations. In the activated carbon filter, a lower selection pressure permitted a steady increase in diversity during 240 days of operation and the establishment of one mercury-sensitive invader. PMID:11916716

Measurement of atmospheric mercury species with manual sampling and analysis methods in a case study in Indiana

USGS Publications Warehouse

Risch, M.R.; Prestbo, E.M.; Hawkins, L.

2007-01-01

Ground-level concentrations of three atmospheric mercury species were measured using manual sampling and analysis to provide data for estimates of mercury dry deposition. Three monitoring stations were operated simultaneously during winter, spring, and summer 2004, adjacent to three mercury wet-deposition monitoring stations in northern, central, and southern Indiana. The monitoring locations differed in land-use setting and annual mercury-emissions level from nearby sources. A timer-controlled air-sampling system that contained a three-part sampling train was used to isolate reactive gaseous mercury, particulate-bound mercury, and elemental mercury. The sampling trains were exchanged every 6 days, and the mercury species were quantified in a laboratory. A quality-assurance study indicated the sampling trains could be held at least 120 h without a significant change in reactive gaseous or particulate-bound mercury concentrations. The manual sampling method was able to provide valid mercury concentrations in 90 to 95% of samples. Statistical differences in mercury concentrations were observed during the project. Concentrations of reactive gaseous and elemental mercury were higher in the daytime samples than in the nighttime samples. Concentrations of reactive gaseous mercury were higher in winter than in summer and were highest at the urban monitoring location. The results of this case study indicated manual sampling and analysis could be a reliable method for measurement of atmospheric mercury species and has the capability for supplying representative concentrations in an effective manner from a long-term deposition-monitoring network. ?? 2007 Springer Science+Business Media B.V.

Characterization of mercury contamination in the Androscoggin River, Coos County, New Hampshire

USGS Publications Warehouse

Chalmers, Ann; Marvin-DiPasquale, Mark C.; Degnan, James R.; Coles, James; Agee, Jennifer L.; Luce, Darryl

2013-01-01

Concentrations of total mercury (THg) and MeHg in sediment, pore water, and biota in the Androscoggin River were elevated downstream from the former chloralkali facility compared with those upstream from reference sites. Sequential extraction of surface sediment showed a distinct difference in Hg speciation upstream compared with downstream from the contamination site. An upstream site was dominated by potassium hydroxide-extractable forms (for example, organic-Hg or particle-bound Hg(II)), whereas sites downstream from the point source were dominated by more chemically recalcitrant forms (largely concentrated nitric acid-extractable), indicative of elemental mercury or mercurous chloride. At all sites, only a minor fraction (less than 0.1 percent) of THg existed in chemically labile forms (for example, water extractable or weak acid extractable). All metrics indicated that a greater percentage of mercury at an upstream site was available for Hg(II)-methylation compared with sites downstream from the point source, but the absolute concentration of bioavailable Hg(II) was greater downstream from the point source. In addition, the concentration of tin-reducible inorganic reactive mercury, a surrogate measure of bioavailable Hg(II) generally increased with distance downstream from the point source. Whereas concentrations of mercury species on a sediment-dry-weight basis generally reflected the relative location of the sample to the point source, river-reach integrated mercury-species inventories and MeHg production potential (MPP) rates reflected the amount of fine-grained sediment in a given reach. THg concentrations in biota were significantly higher downstream from the point source compared with upstream reference sites for smallmouth bass, white sucker, crayfish, oligochaetes, bat fur, nestling tree swallow blood and feathers, adult tree swallow blood, and tree swallow eggs. As with tin-reducible inorganic reactive mercury, THg in smallmouth bass also increased with distance downstream from the point source. Toxicity tests and invertebrate community assessments suggested that invertebrates were not impaired at the current (2009 and 2010) levels of mercury contamination downstream from the point source. Concentrations of THg and MeHg in most water and sediment samples from the Androscoggin River were below U.S. Environmental Protection Agency (USEPA), the Canadian Council of Ministers of the Environment, and probable effects level guidelines. Surface-water and sediment samples from the Androscoggin River had similar THg concentrations but lower MeHg concentrations compared with other rivers in the region. Concentrations of THg in fish tissue were all above regional and U.S. Environmental Protection Agency guidelines. Moreover, median THg concentrations in smallmouth bass from the Androscoggin River were significantly higher than those reported in regional surveys of river and streams nationwide and in the Northeastern United States and Canada. The higher concentrations of mercury in smallmouth bass suggest conditions may be more favorable for Hg(II)-methylation and bioaccumulation in the Androscoggin River compared with many other rivers in the United States and Canada.

Mercury speciation in the Valdeazogues River-La Serena Reservoir system: influence of Almadén (Spain) historic mining activities.

PubMed

Berzas Nevado, Juan J; Rodríguez Martín-Doimeadios, Rosa C; Moreno, María Jiménez

2009-03-15

Mercury (Hg) speciation and partitioning have been investigated in a river-reservoir system impacted by the Almadén mining activities, the world's largest Hg district. This study is the first to simultaneously investigate Hg dynamics from above the mining district and into the La Serena Reservoir (3219 Hm(3)), being the third largest reservoir in Europe and the largest in Spain. Water, sediment and biota were sampled at different seasons during a 2-year study from the Valdeazogues River, which flows east-west from the mining District, to La Serena Reservoir. Simultaneously, a comprehensive study was undertaken to determine the influence of some major physico-chemical parameters that potentially influence the fate of Hg within the watershed. Concentrations of dissolved Hg in water were below 0.14 microg/L, whereas particulate Hg ranged from 0.1 to 87 microg/g, with significant seasonal variation. Total Hg concentrations varied from 7 to 74 microg/g in sediment from the Valdeazogues River, while in sediments from La Serena Reservoir were below 2 microg/g. On the other hand, methyl-Hg reached concentrations up to 0.3 ng/L in water and 6 ng/g in sediment from La Serena Reservoir, whereas maximum concentrations in Valdeazogues River were 5 ng/L and 880 ng/g in water and sediment, respectively. The distribution of Hg species in the Valdeazogues River-La Serena Reservoir system indicated a source of Hg from the mine waste distributed along the river. Total Hg in water was strongly correlated with total dissolved solids and chlorophyll a concentrations, whereas organic carbon and Fe concentrations seem to play a role in methylation of inorganic Hg in sediment. Total Hg concentrations were low in fish from Valdeazogues River (0.8-8.6 ng/g, wet weight) and bivalves from La Serena Reservoir (10-110 ng/g, wet weight), but most was present as methyl-Hg.

Mercury contamination level and speciation inventory in Lakes Titicaca & Uru-Uru (Bolivia): Current status and future trends.

PubMed

Guédron, S; Point, D; Acha, D; Bouchet, S; Baya, P A; Tessier, E; Monperrus, M; Molina, C I; Groleau, A; Chauvaud, L; Thebault, J; Amice, E; Alanoca, L; Duwig, C; Uzu, G; Lazzaro, X; Bertrand, A; Bertrand, S; Barbraud, C; Delord, K; Gibon, F M; Ibanez, C; Flores, M; Fernandez Saavedra, P; Ezpinoza, M E; Heredia, C; Rocha, F; Zepita, C; Amouroux, D

2017-12-01

Aquatic ecosystems of the Bolivian Altiplano (∼3800 m a.s.l.) are characterized by extreme hydro-climatic constrains (e.g., high UV-radiations and low oxygen) and are under the pressure of increasing anthropogenic activities, unregulated mining, agricultural and urban development. We report here a complete inventory of mercury (Hg) levels and speciation in the water column, atmosphere, sediment and key sentinel organisms (i.e., plankton, fish and birds) of two endorheic Lakes of the same watershed differing with respect to their size, eutrophication and contamination levels. Total Hg (THg) and monomethylmercury (MMHg) concentrations in filtered water and sediment of Lake Titicaca are in the lowest range of reported levels in other large lakes worldwide. Downstream, Hg levels are 3-10 times higher in the shallow eutrophic Lake Uru-Uru than in Lake Titicaca due to high Hg inputs from the surrounding mining region. High percentages of MMHg were found in the filtered and unfiltered water rising up from <1 to ∼50% THg from the oligo/hetero-trophic Lake Titicaca to the eutrophic Lake Uru-Uru. Such high %MMHg is explained by a high in situ MMHg production in relation to the sulfate rich substrate, the low oxygen levels of the water column, and the stabilization of MMHg due to abundant ligands present in these alkaline waters. Differences in MMHg concentrations in water and sediments compartments between Lake Titicaca and Uru-Uru were found to mirror the offset in MMHg levels that also exist in their respective food webs. This suggests that in situ MMHg baseline production is likely the main factor controlling MMHg levels in fish species consumed by the local population. Finally, the increase of anthropogenic pressure in Lake Titicaca may probably enhance eutrophication processes which favor MMHg production and thus accumulation in water and biota. Copyright © 2017 Elsevier Ltd. All rights reserved.

The redox processes in Hg-contaminated soils from Descoberto (Minas Gerais, Brazil): implications for the mercury cycle.

PubMed

Windmöller, Cláudia C; Durão Júnior, Walter A; de Oliveira, Aline; do Valle, Cláudia M

2015-02-01

Investigations of the redox process and chemical speciation of Hg(II) lead to a better understanding of biogeochemical processes controlling the transformation of Hg(II) into toxic and bioaccumulative monomethyl mercury, mainly in areas contaminated with Hg(0). This study investigates the speciation and redox processes of Hg in soil samples from a small area contaminated with Hg(0) as a result of gold mining activities in the rural municipality of Descoberto (Minas Gerais, Brazil). Soil samples were prepared by adding Hg(0) and HgCl2 separately to dry soil, and the Hg redox process was monitored using thermodesorption coupled to atomic absorption spectrometry. A portion of the Hg(0) added was volatilized (up to 37.4±2.0%) or oxidized (from 36±7% to 88±16%). A correlation with Mn suggests that this oxidation is favored, but many other factors must be evaluated, such as the presence of microorganisms and the types of organic matter present. The interaction of Hg with the matrix is suggested to involve Hg(II)-complexes formed with inorganic and organic sulfur ligands and/or nonspecific adsorption onto oxides of Fe, Al and/or Mn. The kinetics of the oxidation reaction was approximated for two first-order reactions; the faster reaction was attributed to the oxidation of Hg(0)/Hg(I), and the slower reaction corresponded to Hg(I)/Hg(II). The second stage was 43-139 times slower than the first. The samples spiked with Hg(II) showed low volatilization and a shifting of the signal of Hg(II) to lower temperatures. These results show that the extent, rate and type of redox process can be adverse in soils. Descoberto can serve as an example for areas contaminated with Hg(0). Copyright © 2014 Elsevier Inc. All rights reserved.

ARSENIC SPECIATION ANALYSIS IN HUMAN SALIVA

EPA Science Inventory

Background: Determination of arsenic species in human saliva is potentially useful for biomonitoring of human exposure to arsenic and for studying arsenic metabolism. However, there is no report on the speciation analysis of arsenic in saliva. Methods: Arsenic species in saliva ...

Modeling study of natural emissions, source apportionment, and emission control of atmospheric mercury

NASA Astrophysics Data System (ADS)

Shetty, Suraj K.

Mercury (Hg) is a toxic pollutant and is important to understand its cycling in the environment. In this dissertation, a number of modeling investigations were conducted to better understand the emission from natural surfaces, the source-receptor relationship of the emissions, and emission reduction of atmospheric mercury. The first part of this work estimates mercury emissions from vegetation, soil and water surfaces using a number of natural emission processors and detailed (LAI) Leaf Area Index data from GIS (Geographic Information System) satellite products. East Asian domain was chosen as it contributes nearly 50% of the global anthropogenic mercury emissions into the atmosphere. The estimated annual natural mercury emissions (gaseous elemental mercury) in the domain are 834 Mg yr-1 with 462 Mg yr-1 contributing from China. Compared to anthropogenic sources, natural sources show greater seasonal variability (highest in simmer). The emissions are significant, sometimes dominant, contributors to total mercury emission in the regions. The estimates provide possible explanation for the gaps between the anthropogenic emission estimates based on activity data and the emission inferred from field observations in the regions. To understand the contribution of domestic emissions to mercury deposition in the United States, the second part of the work applies the mercury model of Community Multi-scale Air Quality Modeling system (CMAQ-Hg v4.6) to apportion the various emission sources attributing to the mercury wet and dry deposition in the 6 United States receptor regions. Contributions to mercury deposition from electric generating units (EGU), iron and steel industry (IRST), industrial point sources excluding EGU and IRST (OIPM), the remaining anthropogenic sources (RA), natural processes (NAT), and out-of-boundary transport (BC) in domain was estimated. The model results for 2005 compared reasonably well to field observations made by MDN (Mercury Deposition Network) and CAMNet (Canadian Atmospheric Mercury Measurement Network). The model estimated a total deposition of 474 Mg yr-1 to the CONUS (Contiguous United States) domain, with two-thirds being dry deposited. Reactive gaseous mercury contributed the most to 60% of deposition. Emission speciation distribution is a key factor for local deposition as contribution from large point sources can be as high as 75% near (< 100 km) the emission sources, indicating that emission reduction may result in direct deposition decrease near the source locations. Among the sources, BC contributes to about 68% to 91% of total deposition. Excluding the BC's contribution, EGU contributes to nearly 50% of deposition caused by CONUS emissions in the Northeast, Southeast and East Central regions, while emissions from natural processes are more important in the Pacific and West Central regions (contributing up to 40% of deposition). The modeling results implies that implementation of the new emission standards proposed by USEPA (United States Environmental Protection Agency) would significantly benefit regions that have larger contributions from EGU sources. Control of mercury emissions from coal combustion processes has attracted great attention due to its toxicity and the emission-control regulations and has lead to advancement in state-of-the-art control technologies that alleviate the impact of mercury on ecosystem and human health. This part of the work applies a sorption model to simulate adsorption of mercury in flue gases, onto a confined-bed of activated carbon. The model's performances were studied at various flue gas flow rates, inlet mercury concentrations and adsorption bed temperatures. The process simulated a flue gas, with inlet mercury concentration of 300 ppb, entering at a velocity of 0.3 m s-1 from the bottom into a fixed bed (inside bed diameter of 1 m and 3 m bed height; bed temperature of 25 °C) of activated carbon (particle size of 0.004 m with density of 0.5 g cm-3 and surface area of 90.25 cm2 g -1). The model result demonstrated that a batch of activated carbon bed was capable of controlling mercury emission for approximately 275 days after which further mercury uptake starts to decrease till it reaches about 500 days when additional control ceases. An increase in bed temperature significantly reduces mercury sorption capacity of the activated carbon. Increase in flue gas flow rate may result in faster consumption of sorption capacity initially but at a later stage, the sorption rate decreases due to reduced sorption capacity. Thus, overall sorption rate remains unaffected. The activated carbon's effective life (time to reach saturation) is not affected by inlet mercury concentration, implying that the designing and operation of a mercury sorption process can be done independently. The results provide quantitative indication for designing efficient confined-bed process to remove mercury from flue gases.

Sexual selection drives speciation in an Amazonian frog

USGS Publications Warehouse

Boul, K.E.; Funk, W.C.; Darst, C.R.; Cannatella, D.C.; Ryan, M.J.

2007-01-01

One proposed mechanism of speciation is divergent sexual selection, whereby divergence in female preferences and male signals results in behavioural isolation. Despite the appeal of this hypothesis, evidence for it remains inconclusive. Here, we present several lines of evidence that sexual selection is driving behavioural isolation and speciation among populations of an Amazonian frog (Physalaemus petersi). First, sexual selection has promoted divergence in male mating calls and female preferences for calls between neighbouring populations, resulting in strong behavioural isolation. Second, phylogenetic analysis indicates that populations have become fixed for alternative call types several times throughout the species' range, and coalescent analysis rejects genetic drift as a cause for this pattern, suggesting that this divergence is due to selection. Finally, gene flow estimated with microsatellite loci is an average of 30 times lower between populations with different call types than between populations separated by a similar geographical distance with the same call type, demonstrating genetic divergence and incipient speciation. Taken together, these data provide strong evidence that sexual selection is driving behavioural isolation and speciation, supporting sexual selection as a cause for speciation in the wild. ?? 2006 The Royal Society.

Bioconcentration and arsenic speciation analysis in ragworm, Hediste diversicolor (Muller 1776).

PubMed

Gaion, Andrea; Scuderi, Alice; Pellegrini, David; Sartori, Davide

2013-01-01

This study focused on bioconcentrations of arsenic in Hediste diversicolor (Müller 1776) after exposure to three different molecule solutions: arsenate, dimethyl-arsinate and arsenobetaine. Speciation analysis was carried out after exposing the organisms to these solutions in order to investigate their arsenic biotransformation capacity. Arsenic reached to the maximum level in these tissues after 15 days' exposure to a solution of 100 μg L(-1) of arsenobetaine, although a significant increase was obtained in worms exposed to arsenate. Speciation analysis shows that trimethyl-arsine oxide is the slowest detoxification phase recorded in experiment.

Economic analysis of atmospheric mercury emission control for coal-fired power plants in China.

PubMed

Ancora, Maria Pia; Zhang, Lei; Wang, Shuxiao; Schreifels, Jeremy; Hao, Jiming

2015-07-01

Coal combustion and mercury pollution are closely linked, and this relationship is particularly relevant in China, the world's largest coal consumer. This paper begins with a summary of recent China-specific studies on mercury removal by air pollution control technologies and then provides an economic analysis of mercury abatement from these emission control technologies at coal-fired power plants in China. This includes a cost-effectiveness analysis at the enterprise and sector level in China using 2010 as a baseline and projecting out to 2020 and 2030. Of the control technologies evaluated, the most cost-effective is a fabric filter installed upstream of the wet flue gas desulfurization system (FF+WFGD). Halogen injection (HI) is also a cost-effective mercury-specific control strategy, although it has not yet reached commercial maturity. The sector-level analysis shows that 193 tons of mercury was removed in 2010 in China's coal-fired power sector, with annualized mercury emission control costs of 2.7 billion Chinese Yuan. Under a projected 2030 Emission Control (EC) scenario with stringent mercury limits compared to Business As Usual (BAU) scenario, the increase of selective catalytic reduction systems (SCR) and the use of HI could contribute to 39 tons of mercury removal at a cost of 3.8 billion CNY. The economic analysis presented in this paper offers insights on air pollution control technologies and practices for enhancing atmospheric mercury control that can aid decision-making in policy design and private-sector investments. Copyright © 2015. Published by Elsevier B.V.

ATMOSPHERIC MERCURY SIMULATION USING THE CMAQ MODEL: FORMULATION DESCRIPTION AND ANALYSIS OF WET DEPOSITION RESULTS

EPA Science Inventory

The Community Multiscale Air Quality (CMAQ) modeling system has recently been adapted to simulate the emission, transport, transformation and deposition of atmospheric mercury in three distinct forms; elemental mercury gas, reactive gaseous mercury, and particulate mercury. Emis...

Results of Hg speciation testing on tanks 30, 32, and 37 depth samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.

2015-11-30

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The twelfth shipment of samples was designated to include 3H evaporator system Tank 30, 32, and 37 depth samples. The Tank 30 depth sample (HTF-30-15-70) was taken at 190 inches from the tank bottom and the Tank 32 depth sample (HTF-32-15-68) was taken at 89 inches from the tank bottom and both were shipped to SRNL on June 29, 2015 in an 80 mLmore » stainless steel dip bottles. The Tank 37 surface sample (HTF-37-15-94) was taken around 253.4 inches from the tank bottom and shipped to SRNL on July 21, 2015 in an 80 mL stainless steel dip bottle. All samples were placed in the SRNL Shielded Cells and left unopened until intermediate dilutions were made on July 24, 2015 using 1.00 mL of sample diluted to 100.00 mL with deionized H 2O. A 30 mL Teflon® bottle was rinsed twice with the diluted tank sample and then filled leaving as little headspace as possible. It was immediately removed from the Shielded Cells and transferred to refrigerated storage where it remained at 4 °C until final dilutions were made on October 20. A second portion of the cells diluted tank sample was poured into a shielded polyethylene bottle and transferred to Analytical Development for radiochemical analysis data needed for Hazardous Material Transportation calculations.« less

Selenium Speciation and Management in Wet FGD Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Searcy, K; Richardson, M; Blythe, G

2012-02-29

This report discusses results from bench- and pilot-scale simulation tests conducted to determine the factors that impact selenium speciation and phase partitioning in wet FGD systems. The selenium chemistry in wet FGD systems is highly complex and not completely understood, thus extrapolation and scale-up of these results may be uncertain. Control of operating parameters and application of scrubber additives have successfully demonstrated the avoidance or decrease of selenite oxidation at the bench and pilot scale. Ongoing efforts to improve sample handling methods for selenium speciation measurements are also discussed. Bench-scale scrubber tests explored the impacts of oxidation air rate, tracemore » metals, scrubber additives, and natural limestone on selenium speciation in synthetic and field-generated full-scale FGD liquors. The presence and concentration of redox-active chemical species as well as the oxidation air rate contribute to the oxidation-reduction potential (ORP) conditions in FGD scrubbers. Selenite oxidation to the undesirable selenate form increases with increasing ORP conditions, and decreases with decreasing ORP conditions. Solid-phase manganese [Mn(IV)] appeared to be the significant metal impacting the oxidation of selenite to selenate. Scrubber additives were tested for their ability to inhibit selenite oxidation. Although dibasic acid and other scrubber additives showed promise in early clear liquor (sodium based and without calcium solids) bench-scale tests, these additives did not show strong inhibition of selenite oxidation in tests with higher manganese concentrations and with slurries from full-scale wet FGD systems. In bench-tests with field liquors, addition of ferric chloride at a 250:1 iron-to-selenium mass ratio sorbed all incoming selenite to the solid phase, although addition of ferric salts had no impact on native selenate that already existed in the field slurry liquor sample. As ORP increases, selenite may oxidize to selenate more rapidly than it sorbs to ferric solids. Though it was not possible to demonstrate a decrease in selenium concentrations to levels below the project'ale testing were evident at the pilot scale. Specifically, reducing oxidation air rate and ORP tends to either retain selenium as selenite in the liquor or shift selenium phase partitioning to the solid phase. Oxidation air flow rate control may be one option for managing selenium behavior in FGD scrubbers. Units that cycle load widely may find it more difficult to impact ORP conditions with oxidation air flow rate control alone. Because decreasing oxidation air rates to the reaction tank showed that all new selenium reported to the solids, the addition of ferric chloride to the pilot scrubber could not show further improvements in selenium behavior. Ferric chloride addition did shift mercury to the slurry solids, specifically to the fine particles. Several competing pathways may govern the reporting of selenium to the slurry solids: co-precipitation with gypsum into the bulk solids and sorption or co-precipitation with iron into the fine particles. Simultaneous measurement of selenium and mercury behavior suggests a holistic management strategy is best to optimize the fate of both of these elements in FGD waters. Work conducted under this project evaluated sample handling and analytical methods for selenium speciation in FGD waters. Three analytical techniques and several preservation methods were employed. Measurements of selenium speciation over time indicated that for accurate selenium speciation, it is best to conduct measurements on unpreserved, filtered samples as soon after sampling as possible. The capital and operating costs for two selenium management strategies were considered: ferric chloride addition and oxidation air flow rate control. For ferric chloride addition, as might be expected the reagent makeup costs dominate the overall costs, and range from 0.22 to 0.29 mills/kWh. For oxidation air flow rate control, a cursory comparison of capital costs and turndown capabilities for multi-stage and single-stage centrifugal blowers and several flow control methods was completed. For greenfield systems, changing the selection of blower type and flow control method may have payback periods of 4 to 5 years or more if based on energy savings alone. However, the benefits to managing redox chemistry in the scrubber could far outweigh the savings in electricity costs under some circumstances.« less

Emissions of mercury in southern Africa derived from long-term observations at Cape Point, South Africa

NASA Astrophysics Data System (ADS)

Brunke, E.-G.; Ebinghaus, R.; Kock, H. H.; Labuschagne, C.; Slemr, F.

2012-08-01

Mercury emissions in South Africa have so far been estimated only by a bottom-up approach from activities and emission factors for different processes. In this paper we derive GEM/CO (GEM being gaseous elemental mercury, Hg0), GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios from plumes observed during long-term monitoring of these species at Cape Point between March 2007 and December 2009. The average observed GEM/CO, GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios were 2.40 ± 2.65 pg m-3 ppb-1 (n = 47), 62.7 ± 80.2 pg m-3 ppm-1 (n = 44), 3.61 ± 4.66 pg m-3 ppb-1 (n = 46), 35.6 ± 25.4 ppb ppm-1 (n = 52), 20.2 ± 15.5 ppb ppm-1 (n = 48), and 0.876 ± 1.106 ppb ppb-1 (n = 42), respectively. The observed CO/CO2, CH4/CO2, and CH4/CO emission ratios agree within the combined uncertainties of the observations and emissions with the ratios calculated from EDGAR (version 4.2) CO2, CO, and CH4 inventories for South Africa and southern Africa (South Africa, Lesotho, Swaziland, Namibia, Botswana, Zimbabwe, and Mozambique) in 2007 and 2008 (inventories for 2009 are not available yet). Total elemental mercury emission of 13.1, 15.2, and 16.1 t Hg yr-1 are estimated independently using the GEM/CO, GEM/CO2, and GEM/CH4 emission ratios and the annual mean CO, CO2, and CH4 emissions, respectively, of South Africa in 2007 and 2008. The average of these independent estimates of 14.8 t GEM yr-1 is much less than the total emission of 257 t Hg yr-1 shown by older inventories which are now considered to be wrong. Considering the uncertainties of our emission estimate, of the emission inventories, and the fact that emission of GEM represents 50-78 % of all mercury emissions, our estimate is comparable to the currently cited GEM emissions in 2004 and somewhat smaller than emissions in 2006. A further increase of mercury emissions due to increasing electricity consumption will lead to a more pronounced difference. A quantitative assessment of the difference and its significance, however, will require emission inventories for the years of observations (2007-2009) as well as better data on the speciation of the total mercury emissions in South Africa.

An Analysis of Simulated Wet Deposition of Mercury from the North American Mercury Model Intercomparison Study

EPA Science Inventory

A previous intercomparison of atmospheric mercury models in North America has been extended to compare simulated and observed wet deposition of mercury. Three regional-scale atmospheric mercury models were tested; CMAQ, REMSAD and TEAM. These models were each employed using thr...

[The progress in speciation analysis of trace elements by atomic spectrometry].

PubMed

Wang, Zeng-Huan; Wang, Xu-Nuo; Ke, Chang-Liang; Lin, Qin

2013-12-01

The main purpose of the present work is to review the different non-chromatographic methods for the speciation analysis of trace elements in geological, environmental, biological and medical areas. In this paper, the sample processing methods in speciation analysis were summarized, and the main strategies for non-chromatographic technique were evaluated. The basic principles of the liquid extractions proposed in the published literatures recently and their advantages and disadvantages were discussed, such as conventional solvent extraction, cloud point extraction, single droplet microextraction, and dispersive liquid-liquid microextraction. Solid phase extraction, as a non-chromatographic technique for speciation analysis, can be used in batch or in flow detection, and especially suitable for the online connection to atomic spectrometric detector. The developments and applications of sorbent materials filled in the columns of solid phase extraction were reviewed. The sorbents include chelating resins, nanometer materials, molecular and ion imprinted materials, and bio-sorbents. Other techniques, e. g. hydride generation technique and coprecipitation, were also reviewed together with their main applications.

Recent Advances in On-Line Methods Based on Extraction for Speciation Analysis of Chromium in Environmental Matrices.

PubMed

Trzonkowska, Laura; Leśniewska, Barbara; Godlewska-Żyłkiewicz, Beata

2016-07-03

The biological activity of Cr(III) and Cr(VI) species, their chemical behavior, and toxic effects are dissimilar. The speciation analysis of Cr(III) and Cr(VI) in environmental matrices is then of great importance and much research has been devoted to this area. This review presents recent developments in on-line speciation analysis of chromium in such samples. Flow systems have proved to be excellent tools for automation of sample pretreatment, separation/preconcentration of chromium species, and their detection by various instrumental techniques. Analytical strategies used in chromium speciation analysis discussed in this review are divided into categories based on selective extraction/separation of chromium species on solid sorbents and liquid-liquid extraction of chromium species. The most popular strategy is that based on solid-phase extraction. Therefore, this review shows the potential of novel materials designed and used for selective binding of chromium species. The progress in miniaturization of measurement systems is also presented.

Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

Speciation has a spatial scale that depends on levels of gene flow.

PubMed

Kisel, Yael; Barraclough, Timothy G

2010-03-01

Area is generally assumed to affect speciation rates, but work on the spatial context of speciation has focused mostly on patterns of range overlap between emerging species rather than on questions of geographical scale. A variety of geographical theories of speciation predict that the probability of speciation occurring within a given region should (1) increase with the size of the region and (2) increase as the spatial extent of intraspecific gene flow becomes smaller. Using a survey of speciation events on isolated oceanic islands for a broad range of taxa, we find evidence for both predictions. The probability of in situ speciation scales with island area in bats, carnivorous mammals, birds, flowering plants, lizards, butterflies and moths, and snails. Ferns are an exception to these findings, but they exhibit high frequencies of polyploid and hybrid speciation, which are expected to be scale independent. Furthermore, the minimum island size for speciation correlates across groups with the strength of intraspecific gene flow, as is estimated from a meta-analysis of published population genetic studies. These results indicate a general geographical model of speciation rates that are dependent on both area and gene flow. The spatial scale of population divergence is an important but neglected determinant of broad-scale diversity patterns.

Speciation genetics: current status and evolving approaches

PubMed Central

Wolf, Jochen B. W.; Lindell, Johan; Backström, Niclas

2010-01-01

The view of species as entities subjected to natural selection and amenable to change put forth by Charles Darwin and Alfred Wallace laid the conceptual foundation for understanding speciation. Initially marred by a rudimental understanding of hereditary principles, evolutionists gained appreciation of the mechanistic underpinnings of speciation following the merger of Mendelian genetic principles with Darwinian evolution. Only recently have we entered an era where deciphering the molecular basis of speciation is within reach. Much focus has been devoted to the genetic basis of intrinsic postzygotic isolation in model organisms and several hybrid incompatibility genes have been successfully identified. However, concomitant with the recent technological advancements in genome analysis and a newfound interest in the role of ecology in the differentiation process, speciation genetic research is becoming increasingly open to non-model organisms. This development will expand speciation research beyond the traditional boundaries and unveil the genetic basis of speciation from manifold perspectives and at various stages of the splitting process. This review aims at providing an extensive overview of speciation genetics. Starting from key historical developments and core concepts of speciation genetics, we focus much of our attention on evolving approaches and introduce promising methodological approaches for future research venues. PMID:20439277

Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique

PubMed Central

Jabłońska-Czapla, Magdalena

2015-01-01

Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis. PMID:25873962

Mercury in human hair due to environment and diet: a review.

PubMed Central

Airey, D

1983-01-01

Hair mercury levels increase with the amount of fish in the diet and the amount of mercury in the fish species consumed. If hair mercury levels in people throughout the world were monitored by a standard analytical procedure, the results would indicate locations where people's body burden of mercury is high enough to be subclinically unhealthy and where controls on environmental emissions might be beneficial. The relationship of hair mercury concentration to the method of sampling and analysis of hair, the analysis of the results, the amount of fish consumed, the country and location from which samples were taken and the age, sex and occupation of the donor is discussed. PMID:6653535

Mercury Speciation and Trophic Magnification Slopes in Giant Salamander Larvae from the Pacific Northwest, USA

NASA Astrophysics Data System (ADS)

Bank, M. S.; Crocker, J.; Wachtl, J.; Kleeman, P.; Fellers, G.; Currens, C.; Hothem, R.; Madej, M. A.

2014-12-01

Mercury (Hg) contamination of stream salamanders in the Pacific Northwest region of the United States has received little attention. Here we report total Hg (HgT) and methyl mercury (MeHg) concentrations in larval giant salamanders (Dicamptodon spp.) and surface water from forested and chaparral lotic ecosystems distributed along a latitudinal gradient throughout Northern California and Washington. To test hypotheses related to potential effects from mining land-use activities, salamander larvae were also sampled from a reference site at Whiskeytown National Recreation Area, California, and at a nearby, upstream site (Shasta county) on Bureau of Land Management land where Hg contamination from gold mining activities has been documented. HgT concentrations in whole body larvae ranged from 4.6 to 74.5 ng/g wet wt. and percent MeHg ranged from 67% to 86%. Both HgT and MeHg larval tissue concentrations were significantly higher at the mining site in comparison to measured background levels (P < 0.001). We conclude that salamander larvae in remote stream ecosystems, where Hg sources were dominated by atmospheric deposition, were generally low in HgT and MeHg and, in comparison, watersheds with a legacy of land-use practices (i.e., mining operations) had approximately 4.5 - 5.5 times the level of HgT bioaccumulation. Moreover, trophic magnification slopes were highest in the Shasta county region where mining was present. These findings suggest that mining activities increase HgT and MeHg exposure to salamander larvae in the region and may present a threat to other higher trophically positioned organisms, and their associated food webs.

Mercury Speciation in Hair of Children in Three Communities of the Amazon, Brazil

PubMed Central

Marinho, Jamile Salim; Lima, Marcelo Oliveira; Santos, Elisabeth Conceição de Oliveira; de Jesus, Iracina Maura; Pinheiro, Maria da Conceição N.; Alves, Cláudio Nahum; Muller, Regina Celi Sarkis

2014-01-01

Children from riverside communities located downstream of gold mining areas may be chronically exposed to relatively high levels of MeHg through the consumption of fish of this region. The objective of this study was to evaluate and compare levels of THg and MeHg in hair of children less than 12 years in communities near mines in the municipality of Itaituba and in communities far from prospecting areas in the city of Abaetetuba. The communities of Itaituba (Barreiras and São Luiz do Tapajós) had THg mean levels of 5.64 ± 5.55 μg·g−1 (0.43–27.82) and 11.41 ± 7.16 μg.g−1 (1.08–28.17), respectively, and an average count of MeHg relative to THg of 92.20% and 90.27%, respectively. In the Maranhão community, the THg average concentrations results were 2.27 ± 2.11 μg·g−1 (0.13–9.54) and the average values were 93.17% for MeHg. Children of Itaituba had average levels of mercury above the limit established by the World Health Organization (10 μg·g−1) and the strong correlation coefficient between the communities (R = 0.968 and P = 0.0001) suggests the hair as an excellent biomarker of human exposure to organic mercury in riverside populations of the Tapajós, which has the intake of fish daily as main source of protein dietary. PMID:24734253

Analytical methodologies for aluminium speciation in environmental and biological samples--a review.

PubMed

Bi, S P; Yang, X D; Zhang, F P; Wang, X L; Zou, G W

2001-08-01

It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited.

Results Of Hg Speciation Testing On DWPF SMECT-1, SMECT-3, And SMECT-5 Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C.

2016-01-07

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team. The thirteenth shipment of samples was designated to include Defense Waste Processing Facility (DWPF) Slurry Mix Evaporator Condensate Tank (SMECT) from Sludge Receipt and Adjustment Tank (SRAT) Batch 736 and 738 samples. Triplicate samples of each material were prepared for this shipment. Each replicate was analyzed for seven Hg species: total Hg, total soluble (dissolved) Hg, elemental Hg [Hg(0)], ionic (inorganic) Hg [Hg(I) andmore » Hg(II)], methyl Hg [CH 3Hg-X, where X is a counter anion], ethyl Hg [CH 3CH 2-Hg-X, where X is a counter anion], and dimethyl Hg [(CH 3) 2Hg]. The difference between the total Hg and total soluble Hg measurements gives the particulate Hg concentration, i.e. Hg adsorbed to the surface of particulate matter in the sample but without resolution of the specific adsorbed species. The average concentrations of Hg species in the aqueous samples derived from Eurofins reported data corrected for dilutions performed by SRNL are tabulated.« less

Mercury Speciation and Bioaccumulation In Riparian and Upland Food Webs of the White Mountains Region, New Hampshire, USA

NASA Astrophysics Data System (ADS)

Rodenhouse, N.; Gebauer, R.; Lowe, W.; McFarland, K.; Bank, M. S.

2015-12-01

The soils and foods webs associated with mid to high elevation, forested, headwater streams are potential hotspots for mercury methylation and bioaccumulation but are not well studied. We tested the hypothesis that spatial variation in mercury bioaccumulation in upland taxa associated with headwater streams can be explained by variation in soil conditions promoting Hg methylation such as soil moisture, pH, and sulfur and organic matter content. We sampled at high (c. 700m) and mid elevation (c. 500m) in northern hardwood forest adjacent to and away from (75m) replicate headwater streams in the Hubbard Brook and Jeffers Brook watersheds of the White Mountains region, New Hampshire, USA. These forested watersheds differed primarily in soil calcium content and pH. We measured and assessed spatial variation in total Hg (THg) and methyl Hg (MeHg) concentrations in soils, insects, spiders, salamanders and birds. We also tested whether trophic position, as determined by nitrogen stable isotopes, was a major predictor of Hg bioaccumulation across these riparian and upland forest taxa. We found elevated levels of THg in all measured components of the food web, and conditions for methylation were better in the upland forest sites compared to the riparian sites located adjacent to headwater streams. Both THg and MeHg in biota were positively correlated with trophic position as indicated by 15N enrichment. In fact, trophic position was a better predictor of THg and MeHg content than spatial location, but the spatial patterning of bioaccumulation differed among taxa. Our data show that that significant Hg bioaccumulation and biomagnification can occur in soils and food webs of mid to high elevation temperate deciduous forests of the Northeast. They also suggest that mercury methylation in forested watersheds is a widespread phenomenon and not limited to areas with high soil moisture, such as lotic environments.

Total- and methyl-mercury concentrations and methylation rates across the freshwater to hypersaline continuum of the Great Salt Lake, Utah, USA.

PubMed

Johnson, William P; Swanson, Neil; Black, Brooks; Rudd, Abigail; Carling, Greg; Fernandez, Diego P; Luft, John; Van Leeuwen, Jim; Marvin-DiPasquale, Mark

2015-04-01

We examined mercury (Hg) speciation in water and sediment of the Great Salt Lake and surrounding wetlands, a locale spanning fresh to hypersaline and oxic to anoxic conditions, in order to test the hypothesis that spatial and temporal variations in Hg concentration and methylation rates correspond to observed spatial and temporal trends in Hg burdens previously reported in biota. Water column, sediment, and pore water concentrations of methylmercury (MeHg) and total mercury (THg), as well as related aquatic chemical parameters were examined. Inorganic Hg(II)-methylation rates were determined in selected water column and sediment subsamples spiked with inorganic divalent mercury (204Hg(II)). Net production of Me204Hg was expressed as apparent first-order rate constants for methylation (kmeth), which were also expanded to MeHg production potential (MPP) rates via combination with tin reducible 'reactive' Hg(II) (Hg(II)R) as a proxy for bioavailable Hg(II). Notable findings include: 1) elevated Hg concentrations previously reported in birds and brine flies were spatially proximal to the measured highest MeHg concentrations, the latter occurring in the anoxic deep brine layer (DBL) of the Great Salt Lake; 2) timing of reduced Hg(II)-methylation rates in the DBL (according to both kmeth and MPP) coincides with reduced Hg burdens among aquatic invertebrates (brine shrimp and brine flies) that act as potential vectors of Hg propagation to the terrestrial ecosystem; 3) values of kmeth were found to fall within the range reported by other studies; and 4) MPP rates were on the lower end of the range reported in methodologically comparable studies, suggesting the possibility that elevated MeHg in the anoxic deep brine layer results from its accumulation and persistence in this quasi-isolated environment, due to the absence of light (restricting abiotic photo demethylation) and/or minimal microbiological demethylation. Copyright © 2014 Elsevier B.V. All rights reserved.

Investigation of processes controlling summertime gaseous elemental mercury oxidation at midlatitudinal marine, coastal, and inland sites

NASA Astrophysics Data System (ADS)

Ye, Zhuyun; Mao, Huiting; Lin, Che-Jen; Kim, Su Youn

2016-07-01

A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate the oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (AI; marine), Thompson Farm (TF; coastal, rural), and Pack Monadnock (PM; inland, rural, elevated). The chemical mechanism in this box model included the most up-to-date Hg and halogen chemistry. As a result, the box model was able to simulate reasonably the observed diurnal cycles of gaseous oxidized mercury (GOM) and chemical speciation bearing distinct differences between the three sites. In agreement with observations, simulated GOM diurnal cycles at AI and TF showed significant daytime peaks in the afternoon and nighttime minimums compared to flat GOM diurnal cycles at PM. Moreover, significant differences in the magnitude of GOM diurnal amplitude (AI > TF > PM) were captured in modeled results. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80-99 % of total GOM production during daytime. H2O2-initiated GEM oxidation was significant (˜ 33 % of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL) atmosphere, Br and BrO became dominant GEM oxidants, with mixing ratios reaching 0.1 and 1 pptv, respectively, and contributing ˜ 70 % of the total GOM production during midday, while O3 dominated GEM oxidation (50-90 % of GOM production) over the remaining day when Br and BrO mixing ratios were diminished. The majority of HgBr produced from GEM+Br was oxidized by NO2 and HO2 to form brominated GOM species. Relative humidity and products of the CH3O2+BrO reaction possibly significantly affected the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas-particle partitioning could potentially be important in the production of GOM as well as Br and BrO at the marine site.

Total- and methyl-mercury concentrations and methylation rates across the freshwater to hypersaline continuum of the Great Salt Lake, Utah, USA

USGS Publications Warehouse

Johnson, William P.; Swanson, Neil; Black, Brooks; Rudd, Abigail; Carling, Gregory; Fernandez, Diego P.; Luft, John; Van Leeuwen, Jim; Marvin-DiPasquale, Mark C.

2015-01-01

We examined mercury (Hg) speciation in water and sediment of the Great Salt Lake and surrounding wetlands, a locale spanning fresh to hypersaline and oxic to anoxic conditions, in order to test the hypothesis that spatial and temporal variations in Hg concentration and methylation rates correspond to observed spatial and temporal trends in Hg burdens previously reported in biota. Water column, sediment, and pore water concentrations of methylmercury (MeHg) and total mercury (THg), as well as related aquatic chemical parameters were examined. Inorganic Hg(II)-methylation rates were determined in selected water column and sediment subsamples spiked with inorganic divalent mercury (204Hg(II)). Net production of Me204Hg was expressed as apparent first-order rate constants for methylation (kmeth), which were also expanded to MeHg production potential (MPP) rates via combination with tin reducible ‘reactive’ Hg(II) (Hg(II)R) as a proxy for bioavailable Hg(II). Notable findings include: 1) elevated Hg concentrations previously reported in birds and brine flies were spatially proximal to the measured highest MeHg concentrations, the latter occurring in the anoxic deep brine layer (DBL) of the Great Salt Lake; 2) timing of reduced Hg(II)-methylation rates in the DBL (according to both kmeth and MPP) coincides with reduced Hg burdens among aquatic invertebrates (brine shrimp and brine flies) that act as potential vectors of Hg propagation to the terrestrial ecosystem; 3) values ofkmeth were found to fall within the range reported by other studies; and 4) MPP rates were on the lower end of the range reported in methodologically comparable studies, suggesting the possibility that elevated MeHg in the anoxic deep brine layer results from its accumulation and persistence in this quasi-isolated environment, due to the absence of light (restricting abiotic photo demethylation) and/or minimal microbiological demethylation.

Mercury speciation and distribution in a glacierized mountain environment and their relevance to environmental risks in the inland Tibetan Plateau.

PubMed

Sun, Xuejun; Zhang, Qianggong; Kang, Shichang; Guo, Junming; Li, Xiaofei; Yu, Zhengliang; Zhang, Guoshuai; Qu, Dongmei; Huang, Jie; Cong, Zhiyuan; Wu, Guangjian

2018-08-01

Glacierized mountain environments can preserve and release mercury (Hg) and play an important role in regional Hg biogeochemical cycling. However, the behavior of Hg in glacierized mountain environments and its environmental risks remain poorly constrained. In this research, glacier meltwater, runoff and wetland water were sampled in Zhadang-Qugaqie basin (ZQB), a typical glacierized mountain environment in the inland Tibetan Plateau, to investigate Hg distribution and its relevance to environmental risks. The total mercury (THg) concentrations ranged from 0.82 to 6.98ng·L -1 , and non-parametric pairwise multiple comparisons of the THg concentrations among the three different water samples showed that the THg concentrations were comparable. The total methylmercury (TMeHg) concentrations ranged from 0.041 to 0.115ng·L -1 , and non-parametric pairwise multiple comparisons of the TMeHg concentrations showed a significant difference. Both the THg and MeHg concentrations of water samples from the ZQB were comparable to those of other remote areas, indicating that Hg concentrations in the ZQB watershed are equivalent to the global background level. Particulate Hg was the predominant form of Hg in all runoff samples, and was significantly correlated with the total suspended particle (TSP) and not correlated with the dissolved organic carbon (DOC) concentration. The distribution of mercury in the wetland water differed from that of the other water samples. THg exhibited a significant correlation with DOC as well as TMeHg, whereas neither THg nor TMeHg was associated with TSP. Based on the above findings and the results from previous work, we propose a conceptual model illustrating the four Hg distribution zones in glacierized environments. We highlight that wetlands may enhance the potential hazards of Hg released from melting glaciers, making them a vital zone for investigating the environmental effects of Hg in glacierized environments and beyond. Copyright © 2018 Elsevier B.V. All rights reserved.

Aircraft Observations of Mercury over the US: The Nomadss Experiment

NASA Astrophysics Data System (ADS)

Jaffe, D. A.; Ambrose, J. L., II; Gratz, L.; Jaegle, L.; Shah, V.; Selin, N. E.; Song, S.; Giang, A.

2014-12-01

The Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources and Sinks (NOMADSS) experiment took place in the summer of 2013. This is one of the first airborne experiments to focus on the sources and chemistry of Hg in the atmosphere. The experiment flew 19 research flights on the NCAR C-130 aircraft, based out of Smyrna, TN. The primary Hg goals for NOMADSS were to constrain emissions of Hg over the U.S. and quantify the distribution and chemistry of Gaseous Elemental Mercury (GEM) and Reactive Mercury (RM) in the troposphere. We measured speciated Hg on the C-130 using the UW-Detector of Oxidized HG species (UW-DOHGS). This instrument has been developed over several years and tested/calibrated with several HgX2 compounds and other compounds to examine possible interferences. In its current configuration, the instrument quantitatively measures HgX2 compounds (HgCl2 and HgBr2) with no interference from O3. During NOMADSS, flight planning was facilitated by use of the NASA GEOS-5 system, which provided forecasts for many relevant tracers. Post-mission analyses are being conducted using the GEOS-Chem Hg model. This provides a key tool to compare current estimates of Hg sources and distribution with aircraft observations. We are using the NOMADSS data for several types of analyses: GEM emissions and concentrations in power plant plumes and downwind of urban centers; Presence of RM in relatively high concentration in several free tropospheric locations; Evaluation and interpretation of the data using the GEOS-Chem Hg model. While there are a number of important results from NOMADSS, the most striking is the high concentrations of RM GOM in some regions of the upper troposphere, significantly higher than calculated by the standard GEOS-Chem simulation. We believe this is most likely due to halogen oxidation. These results suggest higher halogen concentrations or faster oxidation of GEM and thus a substantial rethinking of Hg oxidation in the global atmosphere.

A simulation study of inorganic sulfur cycling in the water level fluctuation zone of the Three Gorges Reservoir, China and the implications for mercury methylation.

PubMed

Liu, Jiang; Jiang, Tao; Huang, Rong; Wang, Dingyong; Zhang, Jinzhong; Qian, Sheng; Yin, Deliang; Chen, Hong

2017-01-01

The water level fluctuation zone (WLFZ) of the Three Gorges Reservoir (TGR) in China experiences a drying and wetting rotation every year, and the water level induced redox variation may influence inorganic sulfur speciation and mercury methylation. In this work, a simulative flooding and drying experiment and a sulfate added flooding experiment were conducted to study this topic. The results showed that sulfate was reduced from the 10th d during the flooding period based on the detected sulfide in water and the increased elemental sulfur (S 0 ) in sediment. Sulfate reduction and sulfide re-oxidation led to the increase of S 0 contents with the maximal values of 1.86 and 0.46 mg kg -1 during the flooding and drying period, respectively. Methylmercury (MeHg) content in sediment displayed a rising trend (0.16-0.28 μg kg -1 ) in the first 40 d during the flooding period, and then declined from 0.28 to 0.15 μg kg -1 . A positive correlation between MeHg content and S 0 content in soil (r = 0.53, p < 0.05) was found during the flooding period, and a positive but not significant correlation between the percent of MeHg in THg (%MeHg) and S 0 content (r = 0.85, p = 0.08). In sulfate added flooding simulation, MeHg content in sediment did not increase with the sulfate concentration increasing. The increased pyrite in high-sulfate treatment may fix mercury through adsorption process. This study demonstrated that inorganic sulfur species especially S 0 and chromium reducible sulfur (CRS) play an important role on mercury methylation in the WLFZ of the TGR. Copyright © 2016 Elsevier Ltd. All rights reserved.

A reactive transport model for mercury fate in soil--application to different anthropogenic pollution sources.

PubMed

Leterme, Bertrand; Blanc, Philippe; Jacques, Diederik

2014-11-01

Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg(2+) to Hg(0) was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg(2+) with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg(2+) sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of contaminated sites are discussed.

Development of a novel low-flow ion source/sampling cone geometry for inductively coupled plasma mass spectrometry and application in hyphenated techniques

NASA Astrophysics Data System (ADS)

Pfeifer, Thorben; Janzen, Rasmus; Steingrobe, Tobias; Sperling, Michael; Franze, Bastian; Engelhard, Carsten; Buscher, Wolfgang

2012-10-01

A novel ion source/sampling cone device for inductively coupled plasma mass spectrometry (ICP-MS) especially operated in the hyphenated mode as a detection system coupled with different separation modules is presented. Its technical setup is described in detail. Its main feature is the very low total argon consumption of less than 1.5 L min- 1, leading to significant reduction of operational costs especially when time-consuming speciation analysis is performed. The figures of merit of the new system with respect to sensitivity, detection power, long-term stability and working range were explored. Despite the profound differences of argon consumption of the new system in comparison to the conventional ICP-MS system, many of the characteristic features of the conventional ICP-MS could be maintained to a great extent. To demonstrate the ion source's capabilities, it was used as an element-selective detector for gas (GC) and high performance liquid chromatography (HPLC) where organic compounds of mercury and cobalt, respectively, were separated and detected with the new low-flow ICP-MS detection system. The corresponding chromatograms are shown. The applicability for trace element analysis has been validated with the certified reference material NIST 1643e.

Biosensor for metal analysis and speciation

DOEpatents

Aiken, Abigail M.; Peyton, Brent M.; Apel, William A.; Petersen, James N.

2007-01-30

A biosensor for metal analysis and speciation is disclosed. The biosensor comprises an electron carrier immobilized to a surface of an electrode and a layer of an immobilized enzyme adjacent to the electrode. The immobilized enzyme comprises an enzyme having biological activity inhibited by a metal to be detected by the biosensor.

Factors Controlling the Distribution of Atmospheric Mercury in the East Asian Free Troposphere

NASA Astrophysics Data System (ADS)

Sheu, G.; Lee, C.; Lin, N.; Wang, J.; Ouyang, C.

2008-12-01

Taiwan is located to the downwind side of both East and Southeast Asia, which are the major anthropogenic mercury (Hg) source region worldwide. Also, it has been suggested that mountain-top monitoring sites, which are frequently in the free troposphere, are essential to the understanding of the global Hg transport. Accordingly, continuous measurements of atmospheric Hg have been conducting at Lulin Atmospheric Background Station (LABS, 2862 m a.s.l.) in Taiwan since April 13, 2006 to study the trans-boundary transport and transformation of Hg in the free troposphere. Three types of atmospheric Hg, including gaseous elemental Hg (GEM), reactive gaseous Hg (RGM), and particulate Hg (PHg), are measured using the Tekran 2537A/1130/1135 speciation system. Diurnal variations in the concentrations of GEM, RGM, ozone, and water vapor (WV) mixing ratio indicated the influence of boundary layer air in daytime and the subsidence of free tropospheric air masses from higher altitudes at night. Seasonal variation in GEM concentrations was evident with elevated concentrations usually observed between fall and spring when air masses were more or less under the influence of Asian continent. Low summer GEM values were associated with marine air masses. Spikes of RGM were frequently detected between midnight and early morning with concurrent decreases in GEM and WV mixing ratio and increases in ozone concentrations, suggesting the oxidation of GEM and formation of RGM in free troposphere. Concentrations of PHg were usually low; however, elevated concentrations were detected in spring when the Southeast Asian biomass burning plumes affected the LABS. Analysis of the collected data indicate that at LABS the distribution of atmospheric Hg is dynamically controlled by background atmosphere, exchange and mixing of free troposphere/boundary layer air, chemical transformation, and long-range transport from East and Southeast Asia.

ECONOMIC AND ENVIRONMENTAL ANALYSIS OF TECHNOLOGIES TO TREAT MERCURY AND DISPOSE IN A WASTE CONTAINMENT FACILITY

EPA Science Inventory

The use of mercury in products and processes is decreasing. It is likely that in the future, the supply of mercury will far exceed the demand for mercury. In addition, the Department of Defense (DOD) has stockpiled more than 4,800 tons of mercury that are no longer needed, and th...

DIRECT MERCURY ANALYSIS IN ENVIRONMENTAL SOLIDS BY ICPMS WITH ON-LINE SAMPLE ASHING AND MERCURY PRE-CONCENTRATION USING THE DIRECT MERCURY ANALYZER

EPA Science Inventory

A Direct Mercury Analyzer based on sample combustion and mercury concentration by gold amalgamation, followed by atomic absorption determination, was interfaced with a quadrupole and a magnet sector ICPMS. In this paper, we discuss design and operating parameters and eval...

Mercury, methylmercury, and other constituents in sediment and water from seasonal and permanent wetlands in the Cache Creek settling basin and Yolo Bypass, Yolo County, California, 2005-06

USGS Publications Warehouse

Marvin-DiPasquale, Mark; Alpers, Charles N.; Fleck, Jacob A.

2009-01-01

This report presents surface water and surface (top 0-2 cm) sediment geochemical data collected during 2005-2006, as part of a larger study of mercury (Hg) dynamics in seasonal and permanently flooded wetland habitats within the lower Sacramento River basin, Yolo County, California. The study was conducted in two phases. Phase I represented reconnaissance sampling and included three locations within the Cache Creek drainage basin; two within the Cache Creek Nature Preserve (CCNP) and one in the Cache Creek Settling Basin (CCSB) within the creek's main channel near the southeast outlet to the Yolo Bypass. Two additional downstream sites within the Yolo Bypass Wildlife Area (YBWA) were also sampled during Phase I, including one permanently flooded wetland and one seasonally flooded wetland, which had began being flooded only 1–2 days before Phase I sampling.Results from Phase I include: (a) a negative correlation between total mercury (THg) and the percentage of methylmercury (MeHg) in unfiltered surface water; (b) a positive correlation between sediment THg concentration and sediment organic content; (c) surface water and sediment THg concentrations were highest at the CCSB site; (d) sediment inorganic reactive mercury (Hg(II)R) concentration was positively related to sediment oxidation-reduction potential and negatively related to sediment acid volatile sulfur (AVS) concentration; (e) sediment Hg(II)R concentrations were highest at the two YBWA sites; (f) unfiltered surface water MeHg concentration was highest at the seasonal wetland YBWA site, and sediment MeHg was highest at the permanently flooded YBWA site; (g) a 1,000-fold increase in sediment pore water sulfate concentration was observed in the downstream transect from the CCNP to the YBWA; (h) low sediment pore water sulfide concentrations (<1 µmol/L) across all sites; and (i) iron (Fe) speciation data suggest a higher potential for microbial Fe(III)-reduction in the YBWA compared to the CCSB.Phase II sampling did not include the original three Cache Creek sites, but instead focused on the original two sites within the YBWA and a similarly paired set of seasonally and permanently flooded wetland sites within the CCSB. Sediment sampling at the YBWA and CCSB occurred approximately 28 days and 52 days, respectively, after the initial flooding of the respective seasonal wetlands, and again towards the end of the seasonal flooding period (end of May 2006). Results from Phase II sampling include: (a) sediment MeHg concentration and the percentage of THg as MeHg (%MeHg) in unfiltered surface waters were generally higher in the YBWA compared to the CCSB; (b) suspended sediment concentration (SCC) in surface water was positively correlated with both THg and MeHg in unfiltered water across all sites, although the relationship between SCC and MeHg differed for the two regions, suggesting local MeHg sources; (c) MeHg concentration in unfiltered surface water was positively correlated to sediment MeHg concentrations across all sites, supporting the suggestion of unique local (sediment) sources of MeHg to the water column; (d) THg concentration in filtered water was positively correlated with both total Fe and dissolved organic carbon (DOC), offering additional support for the role of these constituents in the partitioning of THg between particulate and dissolved phases; (e) flooding of the YBWA seasonal wetland resulted in a rapid and significant (5-fold) rise in sediment MeHg concentration within 3–4 weeks following inundation; and (f) temporal changes in sediment S and Fe speciation suggest that rates of both microbial sulfate reduction and Fe(III)-reduction were significantly higher at YBWA, compared to CCSB, during the period between flooding and drying.The geochemical data presented in this report indicate that (a) strong spatial and temporal differences in Hg speciation and transformations can occur within the range of wetland habitats found in the lower Sacramento River basin; (b) flooding of seasonal wetlands can be accompanied by a rapid increase in benthic MeHg production and the release of previously formed MeHg (generated during or since the previous flooding season) to the overlying water column; (c) S and Fe chemistry, and associated microbial reduction pathways, play an important role in mediating the speciation and transformation of Hg in these wetland habitats; (d) hydroperiod is a primary forcing function in mediating MeHg production among various wetland types; and (e) MeHg production appears to be more active in the YBWA compared to the CCSB.

Determination of mercury in ayurvedic dietary supplements that are not rasa shastra using the hydra-C direct mercury analyzer.

PubMed

Abdalla, Amir A; Smith, Robert E

2013-01-01

Mercury has been determined in Ayurvedic dietary supplements (Trifala, Trifala Guggulu, Turmeric, Mahasudarshan, Yograj, Shatawari, Hingwastika, Shatavari, and Shilajit) by inductively coupled plasma-mass spectrometry (ICP-MS) and direct mercury analysis using the Hydra-C direct mercury analyzer (Teledyne Leeman Labs Hudson, NH, USA). Similar results were obtained from the two methods, but the direct mercury analysis method was much faster and safer and required no microwave digestion (unlike ICP-MS). Levels of mercury ranged from 0.002 to 56  μ g/g in samples of dietary supplements. Standard reference materials Ephedra 3240 and tomato leaves that were from the National Institute of Standard and Technology (NIST) and dogfish liver (DOLT3) that was from the Canadian Research Council were analyzed using Hydra-C method. Average mercury recoveries were 102% (RSD% 0.0018), 100% (RSD% 0.0009), and 101% (RSD% 0.0729), respectively. Hydra-C method Limit Of Quantitation was 0.5 ng.

Determination of Mercury in Ayurvedic Dietary Supplements That Are Not Rasa Shastra Using the Hydra-C Direct Mercury Analyzer

PubMed Central

Abdalla, Amir A.; Smith, Robert E.

2013-01-01

Mercury has been determined in Ayurvedic dietary supplements (Trifala, Trifala Guggulu, Turmeric, Mahasudarshan, Yograj, Shatawari, Hingwastika, Shatavari, and Shilajit) by inductively coupled plasma-mass spectrometry (ICP-MS) and direct mercury analysis using the Hydra-C direct mercury analyzer (Teledyne Leeman Labs Hudson, NH, USA). Similar results were obtained from the two methods, but the direct mercury analysis method was much faster and safer and required no microwave digestion (unlike ICP-MS). Levels of mercury ranged from 0.002 to 56 μg/g in samples of dietary supplements. Standard reference materials Ephedra 3240 and tomato leaves that were from the National Institute of Standard and Technology (NIST) and dogfish liver (DOLT3) that was from the Canadian Research Council were analyzed using Hydra-C method. Average mercury recoveries were 102% (RSD% 0.0018), 100% (RSD% 0.0009), and 101% (RSD% 0.0729), respectively. Hydra-C method Limit Of Quantitation was 0.5 ng. PMID:23710181

Quantitative proteomic analysis reveals proteins involved in the neurotoxicity of marine medaka Oryzias melastigma chronically exposed to inorganic mercury.

PubMed

Wang, Yuyu; Wang, Dazhi; Lin, Lin; Wang, Minghua

2015-01-01

Mercury is a ubiquitous environmental contaminant which exerts neurotoxicity upon animals. Nevertheless, the molecular mechanisms involved in inorganic mercury neurotoxicity are unknown. We investigated protein profiles of marine medaka, chronically exposed to mercuric chloride using two-dimensional difference gel electrophoresis (2D-DIGE) and matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometry (MALDI-TOF-TOF MS) analysis. The mercury accumulation and ultrastructure were also examined in the brain. The results showed that mercury was significantly accumulated in the treated brain, and subsequently caused a noticeable damage. The comparison of 2D-DIGE protein profiles between the control and treatment revealed that 16 protein spots were remarkably altered in abundance, which were further submitted for MALDI-TOF-TOF MS analysis. The identified proteins indicated that inorganic mercury may cause neurotoxicity through the induction of oxidative stress, cytoskeletal assembly dysfunction and metabolic disorders. Thus, this study provided a basis for a better understanding of the molecular mechanisms involved in mercury neurotoxicity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Selenium analysis in waters. Part 2: Speciation methods.

PubMed

LeBlanc, Kelly L; Kumkrong, Paramee; Mercier, Patrick H J; Mester, Zoltán

2018-06-21

In aquatic ecosystems, there is often no correlation between the total concentration of selenium present in the water column and the toxic effects observed in that environment. This is due, in part, to the variation in the bioavailability of different selenium species to organisms at the base of the aquatic food chain. The first part of this review (Kumkrong et al., 2018) discusses regulatory framework and standard methodologies for selenium analysis in waters. In this second article, we are reviewing the state of speciation analysis and importance of speciation data for decision makers in industry and regulators. We look in detail at fractionation methods for speciation, including the popular selective sequential hydride generation. We examine advantages and limitations of these methods, in terms of achievable detection limits and interferences from other matrix species, as well as the potential to over- or under-estimate operationally-defined fractions based on the various conversion steps involved in fractionation processes. Additionally, we discuss methods of discrete speciation (through separation methods), their importance in analyzing individual selenium species, difficulties associated with their implementation, as well as ways to overcome these difficulties. We also provide a brief overview of biological treatment methods for the remediation of selenium-contaminated waters. We discuss the importance of selenium speciation in the application of these methods and their potential to actually increase the bioavailability of selenium despite decreasing its total waterborne concentration. Copyright © 2018. Published by Elsevier B.V.

"Wave" signal-smoothing and mercury-removing device for laser ablation quadrupole and multiple collector ICPMS analysis: application to lead isotope analysis.

PubMed

Hu, Zhaochu; Zhang, Wen; Liu, Yongsheng; Gao, Shan; Li, Ming; Zong, Keqing; Chen, Haihong; Hu, Shenghong

2015-01-20

A novel "wave" signal-smoothing and mercury-removing device has been developed for laser ablation quadrupole and multiple collector ICPMS analysis. With the wave stabilizer that has been developed, the signal stability was improved by a factor of 6.6-10 and no oscillation of the signal intensity was observed at a repetition rate of 1 Hz. Another advantage of the wave stabilizer is that the signal decay time is similar to that without the signal-smoothing device (increased by only 1-2 s for a signal decay of approximately 4 orders of magnitude). Most of the normalized elemental signals (relative to those without the stabilizer) lie within the range of 0.95-1.0 with the wave stabilizer. Thus, the wave stabilizer device does not significantly affect the aerosol transport efficiency. These findings indicate that this device is well-suited for routine optimization of ICPMS, as well as low repetition rate laser ablation analysis, which provides smaller elemental fractionation and better spatial resolution. With the wave signal-smoothing and mercury-removing device, the mercury gas background is reduced by 1 order of magnitude. More importantly, the (202)Hg signal intensity produced in the sulfide standard MASS-1 by laser ablation is reduced from 256 to 0.7 mV by the use of the wave signal-smoothing and mercury-removing device. This result suggests that the mercury is almost completely removed from the sample aerosol particles produced by laser ablation with the operation of the wave mercury-removing device. The wave mercury-removing device that we have designed is very important for Pb isotope ratio and accessory mineral U-Pb dating analysis, where removal of the mercury from the background gas and sample aerosol particles is highly desired. The wave signal-smoothing and mercury-removing device was applied successfully to the determination of the (206)Pb/(204)Pb isotope ratio in samples with low Pb content and/or high Hg content.

Atmospheric mercury speciation dynamics at the high-altitude Pic du Midi Observatory, southern France

NASA Astrophysics Data System (ADS)

Fu, Xuewu; Marusczak, Nicolas; Heimbürger, Lars-Eric; Sauvage, Bastien; Gheusi, François; Prestbo, Eric M.; Sonke, Jeroen E.

2016-05-01

Continuous measurements of atmospheric gaseous elemental mercury (GEM), particulate bound mercury (PBM) and gaseous oxidized mercury (GOM) at the high-altitude Pic du Midi Observatory (PDM Observatory, 2877 m a.s.l.) in southern France were made from November 2011 to November 2012. The mean GEM, PBM and GOM concentrations were 1.86 ng m-3, 14 pg m-3 and 27 pg m-3, respectively and we observed 44 high PBM (peak PBM values of 33-98 pg m-3) and 61 high GOM (peak GOM values of 91-295 pg m-3) events. The high PBM events occurred mainly in cold seasons (winter and spring) whereas high GOM events were mainly observed in the warm seasons (summer and autumn). In cold seasons the maximum air mass residence times (ARTs) associated with high PBM events were observed in the upper troposphere over North America. The ratios of high PBM ARTs to total ARTs over North America, Europe, the Arctic region and Atlantic Ocean were all elevated in the cold season compared to the warm season, indicating that the middle and upper free troposphere of the Northern Hemisphere may be more enriched in PBM in cold seasons. PBM concentrations and PBM / GOM ratios during the high PBM events were significantly anti-correlated with atmospheric aerosol concentrations, air temperature and solar radiation, suggesting in situ formation of PBM in the middle and upper troposphere. We identified two distinct types of high GOM events with the GOM concentrations positively and negatively correlated with atmospheric ozone concentrations, respectively. High GOM events positively correlated with ozone were mainly related to air masses from the upper troposphere over the Arctic region and middle troposphere over the temperate North Atlantic Ocean, whereas high GOM events anti-correlated with ozone were mainly related to air masses from the lower free troposphere over the subtropical North Atlantic Ocean. The ARTs analysis demonstrates that the lower and middle free troposphere over the North Atlantic Ocean was the largest source region of atmospheric GOM at the PDM Observatory. The ratios of high GOM ARTs to total ARTs over the subtropical North Atlantic Ocean in summer were significantly higher than those over the temperate and sub-arctic North Atlantic Ocean as well as that over the North Atlantic Ocean in other seasons, indicating abundant in situ oxidation of GEM to GOM in the lower free troposphere over the subtropical North Atlantic Ocean in summer.

A comparative analysis of island floras challenges taxonomy-based biogeographical models of speciation.

PubMed

Igea, Javier; Bogarín, Diego; Papadopulos, Alexander S T; Savolainen, Vincent

2015-02-01

Speciation on islands, and particularly the divergence of species in situ, has long been debated. Here, we present one of the first, complete assessments of the geographic modes of speciation for the flora of a small oceanic island. Cocos Island (Costa Rica) is pristine; it is located 550 km off the Pacific coast of Central America. It harbors 189 native plant species, 33 of which are endemic. Using phylogenetic data from insular and mainland congeneric species, we show that all of the endemic species are derived from independent colonization events rather than in situ speciation. This is in sharp contrast to the results of a study carried out in a comparable system, Lord Howe Island (Australia), where as much as 8.2% of the plant species were the product of sympatric speciation. Differences in physiography and age between the islands may be responsible for the contrasting patterns of speciation observed. Importantly, comparing phylogenetic assessments of the modes of speciation with taxonomy-based measures shows that widely used island biogeography approaches overestimate rates of in situ speciation. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Multi-scale analysis of the occurrence of Pb, Cr and Mn in the NIST standards: Urban dust (SRM 1649a) and indoor dust (SRM 2584)

NASA Astrophysics Data System (ADS)

Jiang, Mingyu; Nakamatsu, Yuki; Jensen, Keld A.; Utsunomiya, Satoshi

2014-01-01

Adverse health effects of ambient particulate matters are closely related to the speciation of the constituting organic matters and toxic metals. To determine multi-parameters of the metal speciation in urban and indoor dusts, we have performed systematic bulk- to nano-scale (“multi-scale”) analysis on the speciation of Pb, Mn, and Cr in two National Institute of Standards and Technology (NIST) standard reference materials (SRMs): urban dust (SRM 1649a) and indoor dust (SRM 2584), utilizing X-ray absorption near-edge structure, powder X-ray diffraction analysis, electron microprobe analysis, scanning electron microscopy, and transmission electron microscopy. Major crystalline phases are quartz, gypsum, kaolinite, and muscovite in SRM 1649a, while quartz, gypsum, calcite, and possibly muscovite (or chabazite) in SRM 2584. A number of Pb sulfate nanoparticles (50-200 nm) occur in SRM 1649a, whereas micron-sized Pb carbonate is present containing various concentrations of Zn and Ti in the complex texture in SRM 2584. Relatively soluble Mn(II) sulfate is the bulk-averaged Mn speciation in SRM 1649a, although discrete Mn sulfate particles are not characterized by individual particle analysis, implying the diluted Mn distribution within other sulfate. In SRM 2584, Mn speciation includes a mixture of oxides and carbonates, and trace Mn in chromite. Chromite (FeCr2O4) is the major Cr speciation in SRM1694a, while unidentified Cr(III) phases with minor chromite and Pb chromate are present in SRM 2584, among which the Pb chromate is composed of Cr(VI). A significant number of the metal-bearing particles are distributed to the submicron-size fraction in the urban dust, SRM 1649a, suggesting that these metal nanoparticles can potentially penetrate into the deep respiratory system. This study demonstrates that multi-scale analysis combining nano and bulk analytical techniques is a powerful approach to investigate the multi-parameters of metal-bearing nanoparticles in heterogeneous PM samples.

Mercury study report to Congress. Volume 4. Health effects of mercury and mercury compounds. Sab review draft

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoeny, R.

1996-06-01

This volume of the draft Mercury Study Report to Congress summarizes the available information on human health effects and animal data for hazard identification and dose-response assessment for three forms of mercury: elemental mercury, mercury chloride (inorganic mercury), and methylmercury (organic mercury). Effects are summarized by endpoint. The risk assessment evaluates carcinogenicity, mutagenicity, developmental toxicity and general systemic toxicity of these chemical species of mercury. Toxicokinetics (absorption, distribution, metabolism and excretion) are described for each of the three mercury species. PBPK models are described, but not applied in risk assessment. Reference doses are calculated for inorganic and methylmercury; a referencemore » concentration for inhaled elemental mercury is provided. A quantitiative analysis of factors contributing to variability and uncertainty in the methylmercury RfD is provided in an appendix. Interations and sensitive populations are described.« less

Chronic atrophic gastritis in association with hair mercury level.

PubMed

Xue, Zeyun; Xue, Huiping; Jiang, Jianlan; Lin, Bing; Zeng, Si; Huang, Xiaoyun; An, Jianfu

2014-11-01

The objective of this study was to explore hair mercury level in association with chronic atrophic gastritis, a precancerous stage of gastric cancer (GC), and thus provide a brand new angle of view on the timely intervention of precancerous stage of GC. We recruited 149 healthy volunteers as controls and 152 patients suffering from chronic gastritis as cases. The controls denied upper gastrointestinal discomforts, and the cases were diagnosed as chronic superficial gastritis (n=68) or chronic atrophic gastritis (n=84). We utilized Mercury Automated Analyzer (NIC MA-3000) to detect hair mercury level of both healthy controls and cases of chronic gastritis. The statistic of measurement data was expressed as mean ± standard deviation, which was analyzed using Levene variance equality test and t test. Pearson correlation analysis was employed to determine associated factors affecting hair mercury levels, and multiple stepwise regression analysis was performed to deduce regression equations. Statistical significance is considered if p value is less than 0.05. The overall hair mercury level was 0.908949 ± 0.8844490 ng/g [mean ± standard deviation (SD)] in gastritis cases and 0.460198 ± 0.2712187 ng/g (mean±SD) in healthy controls; the former level was significantly higher than the latter one (p=0.000<0.01). The hair mercury level in chronic atrophic gastritis subgroup was 1.155220 ± 0.9470246 ng/g (mean ± SD) and that in chronic superficial gastritis subgroup was 0.604732 ± 0.6942509 ng/g (mean ± SD); the former level was significantly higher than the latter level (p<0.01). The hair mercury level in chronic superficial gastritis cases was significantly higher than that in healthy controls (p<0.05). The hair mercury level in chronic atrophic gastritis cases was significantly higher than that in healthy controls (p<0.01). Stratified analysis indicated that the hair mercury level in healthy controls with eating seafood was significantly higher than that in healthy controls without eating seafood (p<0.01) and that the hair mercury level in chronic atrophic gastritis cases was significantly higher than that in chronic superficial gastritis cases (p<0.01). Pearson correlation analysis indicated that eating seafood was most correlated with hair mercury level and positively correlated in the healthy controls and that the severity of gastritis was most correlated with hair mercury level and positively correlated in the gastritis cases. Multiple stepwise regression analysis indicated that the regression equation of hair mercury level in controls could be expressed as 0.262 multiplied the value of eating seafood plus 0.434, the model that was statistically significant (p<0.01). Multiple stepwise regression analysis also indicated that the regression equation of hair mercury level in gastritis cases could be expressed as 0.305 multiplied the severity of gastritis, the model that was also statistically significant (p<0.01). The graphs of regression standardized residual for both controls and cases conformed to normal distribution. The main positively correlated factor affecting the hair mercury level is eating seafood in healthy people whereas the predominant positively correlated factor affecting the hair mercury level is the severity of gastritis in chronic gastritis patients. That is to say, the severity of chronic gastritis is positively correlated with the level of hair mercury. The incessantly increased level of hair mercury possibly reflects the development of gastritis from normal stomach to superficial gastritis and to atrophic gastritis. The detection of hair mercury is potentially a means to predict the severity of chronic gastritis and possibly to insinuate the environmental mercury threat to human health in terms of gastritis or even carcinogenesis.

Atmospheric emissions estimation of Hg, As, and Se from coal-fired power plants in China, 2007.

PubMed

Tian, Hezhong; Wang, Yan; Xue, Zhigang; Qu, Yiping; Chai, Fahe; Hao, Jiming

2011-07-15

Over half of coal in China is burned directly by power plants, becoming an important source of hazardous trace element emissions, such as mercury (Hg), arsenic (As), and selenium (Se), etc. Based on coal consumption by each power plant, emission factors classified by different boiler patterns and air pollution control devices configuration, atmospheric emissions of Hg, As, and Se from coal-fired power plants in China are evaluated. The national total emissions of Hg, As, and Se from coal-fired power plants in 2007 are calculated at 132 t, 550 t, and 787 t, respectively. Furthermore, according to the percentage of coal consumed by units equipped with different types of PM devices and FGD systems, speciation of mercury is estimated as follows: 80.48 t of Hg, 49.98 t of Hg(2+), and 1.89 t of Hg(P), representing 60.81%, 37.76%, and 1.43% of the totals, respectively. The emissions of Hg, As, and Se in China's eastern and central provinces are much higher than those in the west, except for provinces involved in the program of electricity transmission from west to east China, such as Sichuan, Guizhou, Yunnan, Shaanxi, etc. Copyright © 2011 Elsevier B.V. All rights reserved.

Using organic matter gradients to predict mercury cycling following environmental changes

NASA Astrophysics Data System (ADS)

Bjorn, E.; Bravo, A. G.; Jonsson, S.; Seelen, E.; Skrobonja, A.; Skyllberg, U.; Soerensen, A.; Zhu, W.

2017-12-01

The biogeochemical cycling of mercury (Hg) includes redox and methylation transformation reactions, largely mediated by microorganisms. These reactions are decisive for mobility and bioavailability of Hg in ecosystems. Organic matter (OM) plays several critical roles in these important transformation reactions. In many aquatic systems, the composition of OM is naturally diverse and dynamic, and subject to further alternations due to ecosystem changes induced by climate, eutrophication, land use, and industrial activities. We will present recent findings on how changing characteristics of OM along natural salinity and carbon gradients control Hg methylation and reduction reactions, as well as bioaccumulation processes. We will further discuss potential changes to Hg cycling, primarily in coastal seas, following ecosystem perturbations which alter the amount and characteristics of OM. The presentation will focus on recent research advancements describing how: (i) the binding of Hg to thiol functional groups in OM controls the chemical speciation of Hg, and thereby its availability for chemical reactions and uptake in biota, (ii) the composition of OM is a primary controlling factor for methylation and reduction rates of divalent Hg by electron donation and shuttling processes, (iii) the amount and characteristics of dissolved OM affect the structure and productivity of the pelagic food web, and thereby the biomagnification of methylmercury.

Role of organic acids in promoting colloidal transport of mercury from mine tailings

USGS Publications Warehouse

Slowey, A.J.; Johnson, S.B.; Rytuba, J.J.; Brown, Gordon E.

2005-01-01

A number of factors affect the transport of dissolved and paniculate mercury (Hg) from inoperative Hg mines, including the presence of organic acids in the rooting zone of vegetated mine waste. We examined the role of the two most common organic acids in soils (oxalic and citric acid) on Hg transport from such waste by pumping a mixed organic acid solution (pH 5.7) at 1 mL/min through Hg mine tailings columns. For the two total organic acid concentrations investigated (20 ??M and 1 mM), particle-associated Hg was mobilized, with the onset of paniculate Hg transport occurring later for the lower organic acid concentration. Chemical analyses of column effluent indicate that 98 wt % of Hg mobilized from the column was paniculate. Hg speciation was determined using extended X-ray absorption fine structure spectroscopy and transmission electron microscopy, showing that HgS minerals are dominant in the mobilized particles. Hg adsorbed to colloids is another likely mode of transport due to the abundance of Fe-(oxyhydr)oxides, Fe-sulfides, alunite, and jarosite in the tailings to which Hg(II) adsorbs. Organic acids produced by plants are likely to enhance the transport of colloid-associated Hg from vegetated Hg mine tailings by dissolving cements to enable colloid release. ?? 2005 American Chemical Society.

Mercury methylation in mine wastes collected from abandoned mercury mines in the USA

USGS Publications Warehouse

Gray, J.E.; Hines, M.E.; Biester, H.; Lasorsa, B.K.; ,

2003-01-01

Speciation and transformation of Hg was studied in mine wastes collected from abandoned Hg mines at McDermitt, Nevada, and Terlingua, Texas, to evaluate formation of methyl-Hg, which is highly toxic. In these mine wastes, we measured total Hg and methyl-Hg contents, identified various Hg compounds using a pyrolysis technique, and determined rates of Hg methylation and methyl-Hg demethylation using isotopic-tracer methods. Mine wastes contain total Hg contents as high as 14000 ??g/g and methyl-Hg concentrations as high as 88 ng/g. Mine wastes were found to contain variable amounts of cinnabar, metacinnabar, Hg salts, Hg0, and Hg0 and Hg2+ sorbed onto matrix particulates. Samples with Hg0 and matrix-sorbed Hg generally contained significant methyl-Hg contents. Similarly, samples containing Hg0 compounds generally produced significant Hg methylation rates, as much as 26%/day. Samples containing mostly cinnabar showed little or no Hg methylation. Mine wastes with high methyl-Hg contents generally showed low methyl-Hg demethylation, suggesting that Hg methylation was dominant. Methyl-Hg demethylation was by both oxidative and microbial pathways. The correspondence of mine wastes containing Hg0 compounds and measured Hg methylation suggests that Hg0 oxidizes to Hg2+, which is subsequently bioavailable for microbial Hg methylation.

Long-term evolution of the Luteoviridae: time scale and mode of virus speciation.

PubMed

Pagán, Israel; Holmes, Edward C

2010-06-01

Despite their importance as agents of emerging disease, the time scale and evolutionary processes that shape the appearance of new viral species are largely unknown. To address these issues, we analyzed intra- and interspecific evolutionary processes in the Luteoviridae family of plant RNA viruses. Using the coat protein gene of 12 members of the family, we determined their phylogenetic relationships, rates of nucleotide substitution, times to common ancestry, and patterns of speciation. An associated multigene analysis enabled us to infer the nature of selection pressures and the genomic distribution of recombination events. Although rates of evolutionary change and selection pressures varied among genes and species and were lower in some overlapping gene regions, all fell within the range of those seen in animal RNA viruses. Recombination breakpoints were commonly observed at gene boundaries but less so within genes. Our molecular clock analysis suggested that the origin of the currently circulating Luteoviridae species occurred within the last 4 millennia, with intraspecific genetic diversity arising within the last few hundred years. Speciation within the Luteoviridae may therefore be associated with the expansion of agricultural systems. Finally, our phylogenetic analysis suggested that viral speciation events tended to occur within the same plant host species and country of origin, as expected if speciation is largely sympatric, rather than allopatric, in nature.

Monte Carlo treatment of resonance-radiation imprisonment in fluorescent lamps—revisited

NASA Astrophysics Data System (ADS)

Anderson, James B.

2016-12-01

We reported in 1985 a Monte Carlo treatment of the imprisonment of the 253.7 nm resonance radiation from mercury in the mercury-argon discharge of fluorescent lamps. The calculated spectra of the emitted radiation were found in good agreement with measured spectra. The addition of the isotope mercury-196 to natural mercury was found, also in agreement with experiments, to increase lamp efficiency. In this paper we report the extension of the earlier work with increased accuracy, analysis of photon exit-time distributions, recycling of energy released in quenching, analysis of dynamic similarity for different lamp sizes, variation of Mrozowski transfer rates, prediction and analysis of the hyperfine ultra-violet spectra, and optimization of tailored mercury isotope mixtures for increased lamp efficiency. The spectra were found insensitive to the extent of quenching and recycling. The optimized mixtures were found to increase efficiencies by as much as 5% for several lamp configurations. Optimization without increasing the mercury-196 fraction was found to increase efficiencies by nearly 1% for several configurations.

Direct analysis of environmental and biological samples for total mercury with comparison of sequential atomic absorption and fluorescence measurements from a single combustion event

NASA Astrophysics Data System (ADS)

Cizdziel, James V.; Tolbert, Candice; Brown, Garry

2010-02-01

A Direct Mercury Analyzer (DMA) based on sample combustion, concentration of mercury by amalgamation with gold, and cold vapor atomic absorption spectrometry (CVAAS) was coupled to a mercury-specific cold vapor atomic fluorescence spectrometer (CVAFS). The purpose was to evaluate combustion-AFS, a technique which is not commercially available, for low-level analysis of mercury in environmental and biological samples. The experimental setup allowed for comparison of dual measurements of mercury (AAS followed by AFS) for a single combustion event. The AFS instrument control program was modified to properly time capture of mercury from the DMA, avoiding deleterious combustion products from reaching its gold traps. Calibration was carried out using both aqueous solutions and solid reference materials. The absolute detection limits for mercury were 0.002 ng for AFS and 0.016 ng for AAS. Recoveries for reference materials ranged from 89% to 111%, and the precision was generally found to be <10% relative standard deviation (RSD). The two methods produced similar results for samples of hair, finger nails, coal, soil, leaves and food stuffs. However, for samples with mercury near the AAS detection limit (e.g., filter paper spotted with whole blood and segments of tree rings) the signal was still quantifiable with AFS, demonstrating the lower detection limit and greater sensitivity of AFS. This study shows that combustion-AFS is feasible for the direct analysis of low levels of mercury in solid samples that would otherwise require time-consuming and contamination-prone digestion.

DOE/NETL's phase II mercury control technology field testing program: preliminary economic analysis of activated carbon injection.

PubMed

Jones, Andrew P; Hoffmann, Jeffrey W; Smith, Dennis N; Feeley, Thomas J; Murphy, James T

2007-02-15

Based on results of field testing conducted by the U.S. Department of Energy's National Energy Technology Laboratory (DOE/NETL), this article provides preliminary costs for mercury control via conventional activated carbon injection (ACI), brominated ACI, and conventional ACI coupled with the application of a sorbent enhancement additive (SEA) to coal prior to combustion. The economic analyses are reported on a plant-specific basis in terms of the cost required to achieve low (50%), mid (70%), and high (90%) levels of mercury removal "above and beyond" the baseline mercury removal achieved by existing emission control equipment. In other words, the levels of mercury control are directly attributable to ACI. Mercury control costs via ACI have been amortized on a current dollar basis. Using a 20-year book life, levelized costs for the incremental increase in cost of electricity (COE), expressed in mills per kilowatt-hour (mills/kWh), and the incremental cost of mercury control, expressed in dollars per pound of mercury removed ($/lb Hg removed), have been calculated for each level of ACI mercury control. For this analysis, the increase in COE varied from 0.14 mills/kWh to 3.92 mills/kWh. Meanwhile, the incremental cost of mercury control ranged from $3810/lb Hg removed to $166000/lb Hg removed.

Investigating the Age of Mercury's Pyroclastic Deposits

NASA Astrophysics Data System (ADS)

Jozwiak, L. M.; Izenberg, N. R.; Olson, C. L.; Head, J. W.

2018-05-01

We use a combination of stratigraphic and comparative spectral analysis to investigate the ages of Mercury's pyroclastic deposits. We find that pyroclastic deposits have continued to form into Mercury's recent geologic history.

Mercury study report to Congress. Volume 5. Health effects of mercury and mercury compounds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hassett-Sipple, B.; Swartout, J.; Schoeny, R.

1997-12-01

This volume summarizes the available information on human health effects and animal data for hazard identification and dose-response assessment for three forms of mercury: elemental mercury, mercury chloride (inorganic mercury), and methylmercury (organic mercury). Effects are summarized by endpoint. The risk assessment evaluates carcinogenicity, mutagenicity, developmental toxicity and general systemic toxicity of these chemical species of mercury. Toxicokinetics (absorption, distribution, metabolism and excretion) are described for each of the three mercury species. Reference doses are calculated for inorganic and methylmercury; a reference concentrations for inhaled elemental mercury is provided. A quantitative analysis of factors contributing to variability and uncertainty inmore » the methylmercury RfD is provided in an appendix. Interactions and sensitive populations are described. the draft volume assesses ongoing research and research needs to reduce uncertainty surrounding adverse human health consequences of methylmercury exposure.« less

Dietary exposure to trace elements and health risk assessment in the 2nd French Total Diet Study.

PubMed

Arnich, Nathalie; Sirot, Véronique; Rivière, Gilles; Jean, Julien; Noël, Laurent; Guérin, Thierry; Leblanc, Jean-Charles

2012-07-01

Dietary exposure of the French population to trace elements has been assessed in the second national Total Diet Study (TDS). Food samples (n = 1319) were collected between 2007 and 2009 to be representative of the whole diet of the population, prepared as consumed, and analyzed. Occurrence data were combined with national individual consumption data to estimate dietary exposure for adults and children mean and high consumers. Compared to the 1st French TDS performed in 2000-2004, exposure is higher for cadmium, aluminium, antimony, nickel, cobalt and lower for lead, mercury and arsenic. For aluminium, methylmercury, cadmium, lead and inorganic arsenic risk cannot be ruled out for certain consumer groups. It still appears necessary to continue undertaking efforts to reduce exposure to these elements. Due to the lack of robust toxicological data and/or speciation analysis in food on chromium, tin, silver and vanadium to perform a risk assessment, data on occurrence and dietary exposure are provided as Supplementary material. In order to minimize nutritional and chemical risks, the French Agency for Food, Environmental and Occupational Health & Safety (ANSES) reiterates its recommendation for a diversified diet (food items and origins). Copyright © 2012 Elsevier Ltd. All rights reserved.

DIRECT MERCURY ANALYSIS IN ENVIRONMENTAL SOLIDS BY ICPMS WITH ON-LINE SAMPLE ASHING AND MERCURY PRECONCENTRATION USING A DIRECT MERCURY ANALYZER

EPA Science Inventory

Mercury is a persistent, mobile, and highly toxic pollutant. It's biogeochemistry is probably the most complex of any metal. For these reasons, the U.S. Environmental Protection Agency (EPA), through its Office of Research and Development (ORD), has developed a comprehensive res...

ANALYSIS OF MERCURY IN VERMONT AND NEW HAMPSHIRE LAKES: EVALUATION OF THE REGIONAL MERCURY CYCLING MODEL

EPA Science Inventory

An evaluation of the Regional Mercury Cycling Model (R-MCM, a steady-state fate and transport model used to simulate mercury concentrations in lakes) is presented based on its application to a series of 91 lakes in Vermont and New Hampshire. Visual and statistical analyses are pr...

AN OVERVIEW: DECISION-MAKING FRAMEWORK FOR THE ANALYSIS OF ALTERNATIVES FOR THE LONG TERM MANAGEMENT OF MERCURY

EPA Science Inventory

Over the past decade, the Environmental Protection Agency (EPA) has promoted the use of alternatives to mercury because it is a persistent, bio-accumulative, and toxic (PBT) chemical. The Agency's long-term goal for mercury is the elimination of mercury released to the air, wate...

Mechanisms of Hg(II) uptake and methylation in methylating bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morel, Francois M. M.

2016-10-14

The goal of this project was to understand the critical factors which control the availability and transport of Hg(II) into cells, a first step in the production of the neurotoxin, methylmercury. Specifically, this research focused on understanding the mechanism of bacterial mercury uptake and how mercury speciation affects the specificity and kinetics of mercury transport. Our research has shown that Hg(II) uptake in three different iron and sulfate-reducing proteobacteria occurs by the following mechanism (1) : Hg(II) uptake is an active transport process requiring energy, (2) it is dependent upon the structure of the Hg binding ligand, and (3) itmore » is mediated by a heavy metal transporter such as one which transports the essential metal, Zn(II). In order to determine whether this mechanism extends to more diverse phylogenetic groups, we have begun examining Hg(II) uptake and bioavailability in two representative Hg methylating strains within the Firmicutes. These organisms have remarkably different membrane structures distinct from the Proteobacteria. Our results show low uptake rates in these two species of Firmicutes relative to the previously characterized Proteobacteria. This may explain the low methylation rates and yields observed in these organisms. Most surprisingly, however, these organisms appear to take up Hg(II) passively, as the addition of a protonophore failed to reduce Hg(II) uptake in these organisms. This is quite different to what has been observed previously for the Proteobacteria and suggests a different mechanism for Hg(II) uptake in the Firmicutes. We are continuing to understand and describe Hg(II) uptake in these organisms. A manuscript is expected to be submitted on this research in June 2016.« less

Atmospheric mercury speciation in Yellowstone National Park

USGS Publications Warehouse

Hall, B.D.; Olson, M.L.; Rutter, A.P.; Frontiera, R.R.; Krabbenhoft, D.P.; Gross, D.S.; Yuen, M.; Rudolph, T.M.; Schauer, J.J.

2006-01-01

Atmospheric concentrations of elemental mercury (Hg0), reactive gaseous Hg (RGM), and particulate Hg (pHg) concentrations were measured in Yellowstone National Park (YNP), U.S.A. using high resolution, real time atmospheric mercury analyzers (Tekran 2537A, 1130, and 1135). A survey of Hg0 concentrations at various locations within YNP showed that concentrations generally reflect global background concentrations of 1.5-2.0 ng m- 3, but a few specific locations associated with concentrated geothermal activity showed distinctly elevated Hg0 concentrations (about 9.0 ng m- 3). At the site of intensive study located centrally in YNP (Canyon Village), Hg0 concentrations did not exceed 2.5 ng m- 3; concentrations of RGM were generally below detection limits of 0.88 pg m- 3 and never exceeded 5 pg m- 3. Concentrations of pHg ranged from below detection limits to close to 30 pg m-3. RGM and pHg concentrations were not correlated with any criteria gases (SO2, NOx, O3); however pHg was weakly correlated with the concentration of atmospheric particles. We investigated three likely sources of Hg at the intensive monitoring site: numerous geothermal features scattered throughout YNP, re-suspended soils, and wildfires near or in YNP. We examined relationships between the chemical properties of aerosols (as measured using real time, single particle mass spectrometry; aerosol time-of-flight mass spectrometer; ATOFMS) and concentrations of atmospheric pHg. Based on the presence of particles with distinct chemical signatures of the wildfires, and the absence of signatures associated with the other sources, we concluded that wildfires in the park were the main source of aerosols and associated pHg to our sampling site. ?? 2005 Elsevier B.V. All rights reserved.

The Role of Chloride Complexation on Anaerobic and Aerobic Mercury Bioavailability

NASA Astrophysics Data System (ADS)

Stenzler, B.; Ruuskanen, M.; Hinz, A.; Poulain, A.

2016-12-01

In the absence of dissolved organic matter, chloride and sulphide are the dominant complexing agents affecting mercury (Hg) speciation in the environment. Bioreporters are good tools in evaluating bioavailable species of Hg. However, signal production for current Hg bioreporters requires oxygen, namely for lux and gfp gene encoded proteins, resulting in a paucity of data in anaerobic bioavailability of Hg species where it is methylated to toxic CH3Hg+. We developed and optimized a whole-cell Hg bioreporter using Escherichia coli 5α capable of functioning in aerobic and anaerobic conditions by transforming a vector containing the gene fusion between the regulatory circuitry of the mer-operon and a flavin mononucleotide-based fluorescent protein. The bioreporter exhibited no physiological limitations with respect to signal production over a chloride gradient ranging from 0 to 0.7 M. The bioreporter had a detection limit of 1 nM Hg(II) however we used 5nM Hg(II) as the optimal working concentration for Hg speciation assays. We report that HgCl42- is highly bioavailable under anoxic conditions in contrast to what was observed under oxic conditions where Hg was not bioavailable. HgCl3- was not bioavailable regardless of the presence of oxygen which we attributed to either coordination polymers consisting of [HgCl3-]x chains on the cell surface or molecular mimicry of HgCl42- onto anaerobically expressed periplasmic binding proteins specific for divalent polyatomic anions shuttling Hg to the inner membrane. In the presence of HgCl42- in saline media and Hg(OH)2 in non-saline media the addition of 2.5 and 5 μM Zn, respectively, completely inhibited uptake of neutral and negatively charged Hg species regardless of the presence of oxygen. The presence of S2- inhibited Hg uptake regardless of the presence or absence of chloride. Our experiments also suggest that ligand exchange occurred faster between S2- and Cl- than between S2- and OH-. The unexpected bioavailability of HgCl42- indicates the possibility of a novel mechanism for Hg uptake in marine environments while the bioavailability of HgS species is dependent on equilibration time and salinity.

Minimal effects of latitude on present-day speciation rates in New World birds

PubMed Central

Rabosky, Daniel L.; Title, Pascal O.; Huang, Huateng

2015-01-01

The tropics contain far greater numbers of species than temperate regions, suggesting that rates of species formation might differ systematically between tropical and non-tropical areas. We tested this hypothesis by reconstructing the history of speciation in New World (NW) land birds using BAMM, a Bayesian framework for modelling complex evolutionary dynamics on phylogenetic trees. We estimated marginal distributions of present-day speciation rates for each of 2571 species of birds. The present-day rate of speciation varies approximately 30-fold across NW birds, but there is no difference in the rate distributions for tropical and temperate taxa. Using macroevolutionary cohort analysis, we demonstrate that clades with high tropical membership do not produce species more rapidly than temperate clades. For nearly any value of present-day speciation rate, there are far more species in the tropics than the temperate zone. Any effects of latitude on speciation rate are marginal in comparison to the dramatic variation in rates among clades. PMID:26019156

Detection of mercury in the 411-year-old beard hairs of the astronomer Tycho Brahe by elemental analysis in electron microscopy.

PubMed

Jonas, Ludwig; Jaksch, Heiner; Zellmann, Erhard; Klemm, Kerstin I; Andersen, Peter Hvilshøj

2012-10-01

Hairs more than 400 years old of the famous astronomer Tycho Brahe were studied by electron microscopy to evaluate the hypothesis that Johannes Kepler murdered his teacher Brahe by mercury intoxication. The beard hairs showed a well-preserved ultrastructure with typical hair scales and melanosomes. The authors detected an accumulation of electron-dense granules of about 10 nm inside the outer hair scales, but not in the hair shaft and roots. At the places of these heavy-metal-containing granules they detected mercury besides other elements by energy dispersive X-ray analysis (EDX, Oxford, UK) in a field cathode scanning electron microscope (SEM, Gemini, Zeiss). The mercury-containing granules were found over the whole length of hairs, but only in the outer hair scales. Nevertheless, surface coatings of hairs were free of mercury. This distribution of mercury does not support the murder hypothesis, but could be related to precipitation of mercury dust from the air during long-term alchemistic activities.

Mercury's Exosphere During MESSENGER's Second Flyby: Detection of Magnesium and Distinct Distributions of Neutral Species

NASA Technical Reports Server (NTRS)

McClintock, William E.; Vervack, Ronald J., Jr.; Bradley, E. Todd; Killen, Rosemary M.; Mouawad, Nelly; Sprague, Ann L.; Burger, Matthew H.; Solomon, Sean C.; Izenberg, Noam R.

2009-01-01

During MESSENGER's second Mercury flyby, the Mercury Atmospheric and Surface Composition Spectrometer observed emission from Mercury's neutral exosphere. These observations include the first detection of emission from magnesium. Differing spatial distributions for sodium, calcium, and magnesium were revealed by observations beginning in Mercury's tail region, approximately 8 Mercury radii anti-sunward of the planet, continuing past the nightside, and ending near the dawn terminator. Analysis of these observations, supplemented by observations during the first Mercury flyby as well as those by other MESSENGER instruments, suggests that the distinct spatial distributions arise from a combination of differences in source, transfer, and loss processes.

X exceptionalism in Caenorhabditis speciation.

PubMed

Cutter, Asher D

2017-11-13

Speciation genetics research in diverse organisms shows the X-chromosome to be exceptional in how it contributes to "rules" of speciation. Until recently, however, the nematode phylum has been nearly silent on this issue, despite the model organism Caenorhabditis elegans having touched most other topics in biology. Studies of speciation with Caenorhabditis accelerated with the recent discovery of species pairs showing partial interfertility. The resulting genetic analyses of reproductive isolation in nematodes demonstrate key roles for the X-chromosome in hybrid male sterility and inviability, opening up new understanding of the genetic causes of Haldane's rule, Darwin's corollary to Haldane's rule, and enabling tests of the large-X effect hypothesis. Studies to date implicate improper chromatin regulation of the X-chromosome by small RNA pathways as integral to hybrid male dysfunction. Sexual transitions in reproductive mode to self-fertilizing hermaphroditism inject distinctive molecular evolutionary features into the speciation process for some species. Caenorhabditis also provides unique opportunities for analysis in a system with XO sex determination that lacks a Y-chromosome, sex chromosome-dependent sperm competition differences and mechanisms of gametic isolation, exceptional accessibility to the development process and rapid experimental evolution. As genetic analysis of reproductive isolation matures with investigation of multiple pairs of Caenorhabditis species and new species discovery, nematodes will provide a powerful complement to more established study organisms for deciphering the genetic basis of and rules to speciation. © 2017 John Wiley & Sons Ltd.

Improved hopcalite procedure for the determination of mercury vapor in air by flameless atomic absorption.

PubMed

Rathje, A O; Marcero, D H

1976-05-01

Mercury vapor is efficiently trapped from air by passage through a small glass tube filled with hopcalite. The hopcalite and adsorbed mercury are dissolved in a mixture of nitric and hydrochloric acids. Solution is rapid and complete, with no loss of mercury. Analysis is completed by flameless atomic absorption.

Incorporating uncertainty in watershed management decision-making: A mercury TMDL case study

USGS Publications Warehouse

Labiosa, W.; Leckie, J.; Shachter, R.; Freyberg, D.; Rytuba, J.; ,

2005-01-01

Water quality impairment due to high mercury fish tissue concentrations and high mercury aqueous concentrations is a widespread problem in several sub-watersheds that are major sources of mercury to the San Francisco Bay. Several mercury Total Maximum Daily Load regulations are currently being developed to address this problem. Decisions about control strategies are being made despite very large uncertainties about current mercury loading behavior, relationships between total mercury loading and methyl mercury formation, and relationships between potential controls and mercury fish tissue levels. To deal with the issues of very large uncertainties, data limitations, knowledge gaps, and very limited State agency resources, this work proposes a decision analytical alternative for mercury TMDL decision support. The proposed probabilistic decision model is Bayesian in nature and is fully compatible with a "learning while doing" adaptive management approach. Strategy evaluation, sensitivity analysis, and information collection prioritization are examples of analyses that can be performed using this approach.

PM 2.5 ORGANIC SPECIATION INTERCOMPARISON RESULTS

EPA Science Inventory

This abstract describes a poster on results to a laboratory intercomparison of organic aerosol speciation analysis to be presented at the 2006 International Aerosol Conference sponsored by the American Association for Aerosol Research in St. Paul, Minnesota on September 10-15. T...

Exploring Space Weathering on Mercury Using Global UV-VIS Reflectance Spectroscopy

NASA Astrophysics Data System (ADS)

Izenberg, N. R.; Denevi, B. W.

2018-05-01

We apply UV analysis methods used on lunar LROC data to Mercury to explore space weathering maturity and possibly evidence of shocked minerals. What says the UV // about shock, maturity // on dear Mercury?

Chromosome breakage in humans exposed to methyl mercury through fish consumption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skerfving, S.; Hansson, K.; Lindsten, J.

1980-08-01

Chromosome analysis was performed on cells from lymphocyte cultures from nine subjects with increased levels of mercury in their red blood cells and in four healthy controls. The elevated mercury levels were likely to have originated from dietary fish with high levels of methyl mercury. A statistically significant rank correlation was found between the frequency of cells with chromosome breaks and mercury concentration. The biological significance of these findings is at present unknown.

Results of Hg speciation testing on DWPF SMECT-4, SMECT-6, and RCT-2 samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bannochie, C. J.

2016-02-04

The Savannah River National Laboratory (SRNL) was tasked with preparing and shipping samples for Hg speciation by Eurofins Frontier Global Sciences, Inc. in Seattle, WA on behalf of the Savannah River Remediation (SRR) Mercury Task Team.i,ii The fifteenth shipment of samples was designated to include Defense Waste Processing Facility (DWPF) Slurry Mix Evaporator Condensate Tank (SMECT) samples from Sludge Receipt and Adjustment Tank (SRAT) Batch 738 and a Recycle Condensate Tank (RCT) sample from SRAT Batch 736. The DWPF sample designations for the three samples analyzed are provided in Table 1. The Batch 738 ‘Baseline’ SMECT sample was taken priormore » to Precipitate Reactor Feed Tank (PRFT) addition and concentration and therefore, precedes the SMECT-5 sample reported previously. iii The Batch 738 ‘End of SRAT Cycle’ SMECT sample was taken at the conclusion of SRAT operations for this batch (PRFT addition/concentration, acid additions, initial concentration, MCU addition, and steam stripping). Batch 738 experienced a sludge slurry carryover event, which introduced sludge solids to the SMECT that were particularly evident in the SMECT-5 sample, but less evident in the ‘End of SRAT Cycle’ SMECT-6 sample. The Batch 736 ‘After SME’ RCT sample was taken after completion of SMECT transfers at the end of the SME cycle.« less

Speciation in Metal Toxicity and Metal-Based Therapeutics

PubMed Central

Templeton, Douglas M.

2015-01-01

Metallic elements, ions and compounds produce varying degrees of toxicity in organisms with which they come into contact. Metal speciation is critical to understanding these adverse effects; the adjectives “heavy” and “toxic” are not helpful in describing the biological properties of individual elements, but detailed chemical structures are. As a broad generalization, the metallic form of an element is inert, and the ionic salts are the species that show more significant bioavailability. Yet the salts and other chelates of a metal ion can give rise to quite different toxicities, as exemplified by a range of carcinogenic potential for various nickel species. Another important distinction comes when a metallic element is organified, increasing its lipophilicity and hence its ability to penetrate the blood brain barrier, as is seen, for example, with organic mercury and tin species. Some metallic elements, such as gold and platinum, are themselves useful therapeutic agents in some forms, while other species of the same element can be toxic, thus focusing attention on species interconversions in evaluating metal-based drugs. The therapeutic use of metal-chelating agents introduces new species of the target metal in vivo, and this can affect not only its desired detoxification, but also introduce a potential for further mechanisms of toxicity. Examples of therapeutic iron chelator species are discussed in this context, as well as the more recent aspects of development of chelation therapy for uranium exposure. PMID:29056656

Mercury in water and biomass of microbial communities in hot springs of Yellowstone National Park, USA

USGS Publications Warehouse

King, S.A.; Behnke, S.; Slack, K.; Krabbenhoft, D.P.; Nordstrom, D. Kirk; Burr, M.D.; Striegl, Robert G.

2006-01-01

Ultra-clean sampling methods and approaches typically used in pristine environments were applied to quantify concentrations of Hg species in water and microbial biomass from hot springs of Yellowstone National Park, features that are geologically enriched with Hg. Microbial populations of chemically-diverse hot springs were also characterized using modern methods in molecular biology as the initial step toward ongoing work linking Hg speciation with microbial processes. Molecular methods (amplification of environmental DNA using 16S rDNA primers, cloning, denatured gradient gel electrophoresis (DGGE) screening of clone libraries, and sequencing of representative clones) were used to examine the dominant members of microbial communities in hot springs. Total Hg (THg), monomethylated Hg (MeHg), pH, temperature, and other parameters influential to Hg speciation and microbial ecology are reported for hot springs water and associated microbial mats. Several hot springs indicate the presence of MeHg in microbial mats with concentrations ranging from 1 to 10 ng g-1 (dry weight). Concentrations of THg in mats ranged from 4.9 to 120,000 ng g-1 (dry weight). Combined data from surveys of geothermal water, lakes, and streams show that aqueous THg concentrations range from l to 600 ng L-1. Species and concentrations of THg in mats and water vary significantly between hot springs, as do the microorganisms found at each site. ?? 2006.

Speciation evolution of zinc and copper during pyrolysis and hydrothermal carbonization treatments of sewage sludges

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Rixiang; Zhang, Bei; Saad, Emily M.

Thermal and hydrothermal treatments are promising techniques for sewage sludge management that can potentially facilitate safe waste disposal, energy recovery, and nutrient recovery/recycling. Content and speciation of heavy metals in the treatment products affect the potential environmental risks upon sludge disposal and/or application of the treatment products. Therefore, it is important to study the speciation transformation of heavy metals and the effects of treatment conditions. By combining synchrotron X-ray spectroscopy/microscopy analysis and sequential chemical extraction, this study systematically characterized the speciation of Zn and Cu in municipal sewage sludges and their chars derived from pyrolysis (a representative thermal treatment technique)more » and hydrothermal carbonization (HTC; a representative hydrothermal treatment technique). Spectroscopy analysis revealed enhanced sulfidation of Zn and Cu by anaerobic digestion and HTC treatments, as compared to desulfidation by pyrolysis. Overall, changes in the chemical speciation and matrix properties led to reduced mobility of Zn and Cu in the treatment products. These results provide insights into the reaction mechanisms during pyrolysis and HTC treatments of sludges and can help evaluate the environmental/health risks associated with the metals in the treatment products.« less

Fate of heavy metals during municipal solid waste incineration.

PubMed

Abanades, S; Flamant, G; Gagnepain, B; Gauthier, D

2002-02-01

A thermodynamic analysis was performed to determine whether it is suitable to predict the heavy metal (HM) speciation during the Municipal Solid Waste Incineration process. The fate of several selected metals (Cd, Pb, Zn, Cr, Hg, As, Cu, Co, Ni) during incineration was theoretically investigated. The equilibrium analysis predicted the metal partitioning during incineration and determined the impact of operating conditions (temperature and gas composition) on their speciation. The study of the gas composition influence was based on the effects of the contents of oxygen (reducing or oxidising conditions) and chlorine on the HM partitioning. The theoretical HM speciation which was calculated in a complex system representing a burning sample of Municipal Solid Waste can explain the real partitioning (obtained from literature results) of all metals among the various ashes except for Pb. Then, the results of the thermodynamic study were compared with those of characterisation of real incinerator residues, using complementary techniques (chemical extraction series and X-ray micro-analyses). These analysis were performed to determine experimentally the speciation of the three representative metals Cr, Pb, and Zn. The agreement is good for Cr and Zn but not for Pb again, which mainly shows unleachable chemical speciations in the residues. Pb tends to remain in the bottom ash whereas thermodynamics often predicts its complete volatilisation under chlorides, and thus its presence exclusively in fly ash.

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

We have conducted aqueous speciation analyses of the Great Salt Lake (GSL) brine sample (Table 1) and a mock geo sample (Table 2) spiked with 1 ppb Tb and 100 ppb Tb. The GSL speciation (Figure 1) aligns with our basic speciation expectations that strong carbonate complexes would form at mid to higher pH's. Although we expected strong aqueous complexes with fluorides at neutral pH and with chlorides, and hydroxides at low pH, we observe that the dominant species in the low to mid pH range to be Tb3+ as a free ion. Still, we do see the presence of fluoride and chloride complexes within the expected low to mid pH range.

Evaluation of an offline method for the analysis of atmospheric reactive gaseous mercury and particulate mercury

USGS Publications Warehouse

Rutter, A.P.; Hanford, K.L.; Zwers, J.T.; Perillo-Nicholas, A. L.; Schauer, J.J.; Olson, M.L.

2008-01-01

Reactive gaseous mercury (RGM) and particulate mercury (PHg) were collected in Milwaukee, WI, between April 2004 and May 2005, and in Riverside, CA, between July 25 and August 7, 2005 using sorbent and filter substrates. The substrates were analyzed for mercury by thermal desorption analysis (TDA) using a purpose-built instrument. Results from this offline-TDA method were compared with measurements using a real-time atmospheric mercury analyzer. RGM measurements made with the offline-TDA agreed well with a commercial real-time method. However, the offline TDA reported PHg concentrations 2.7 times higher than the real-time method, indicating evaporative losses might be occurring from the real-time instrument during sample collection. TDA combined with reactive mercury collection on filter and absorbent substrates was cheap, relatively easy to use, did not introduce biases due to a semicontinuous sample collection strategy, and had a dynamic range appropriate for use in rural and urban locations. The results of this study demonstrate that offline-TDA is a feasible method for collecting reactive mercury concentrations in a large network of filter-based samplers. Copyright 2008 Air & Waste Management Association.

Public health benefits of hair-mercury analysis and dietary advice in lowering methylmercury exposure in pregnant women.

PubMed

Kirk, Line E; Jørgensen, Jan S; Nielsen, Flemming; Grandjean, Philippe

2017-06-01

To evaluate whether a public health intervention using focused dietary advice combined with a hair-mercury analysis can lower neurotoxic methylmercury exposure among pregnant women without decreasing their overall intake of seafood. A total of 146 pregnant women were consecutively recruited from the antenatal clinic at a Danish university hospital at their initial ultrasound scan. Dietary advice was provided on avoiding methylmercury exposure from large predatory fish and a hair sample from each participant was analysed for mercury, with the results being communicated shortly thereafter to the women. A dietary questionnaire was filled in. Follow-up three months later included a dietary questionnaire and a repeat hair-mercury analysis. In the follow-up group, 22% of the women had hair-mercury concentrations above a safe limit of 0.58 µg/g at enrolment, decreasing to 8% three months later. Average hair-mercury concentrations decreased by 21%. However, the total seafood intake remained at the same level after three months. Increased exposure to methylmercury among pregnant women is an important public health concern in Denmark. The observed lowering of hair-mercury concentrations associated with dietary advice corresponds to a substantial public health benefit that probably makes such an intervention highly profitable.

Mercury and methylmercury contamination related to artisanal gold mining, Suriname

USGS Publications Warehouse

Gray, J.E.; Labson, V.F.; Weaver, J.N.; Krabbenhoft, D.P.

2002-01-01

Elemental Hg-Au amalgamation mining practices are used widely in many developing countries resulting in significant Hg contamination of surrounding ecosystems. We have measured total Hg and methyl-Hg concentrations in sediment and water collected from artisanal Au mines and these are the first Hg speciation data from such mines in Suriname. Total Hg and methyl-Hg contents in mine-waste sediment and water are elevated over local uncontaminated baselines. Total Hg (10-930 ng/L) and methyl-Hg (0.02-3.8 ng/L) are highly elevated in mine waters. Increasing total Hg contents in discharged mine waters correlate with increasing water turbidity indicating that most Hg transport is on suspended particulates. Our Hg results are similar to those found in artisanal Au mines in the Amazon basin, where Hg contamination has led to adverse effects on tropical ecosystems.

Total and methyl mercury contents and distribution characteristics in cicada, Cryptotympana atrata (Fabricius).

PubMed

Zheng, Dongmei; Zhang, Zhongsheng; Wang, Qichao

2010-06-01

Total and methyl mercury concentrations of cicada bodies, wings, and exuviae were investigated to study the mercury distribution characteristics. Results indicated that total and methyl mercury concentrations of cicada bodies were 2.64 mg/kg and 123.93 ng/g on average, respectively. In cicada tissues, total mercury concentrations were found to increase in the order of exuviae (0.50 mg/kg on average) < wings (0.98 mg/kg on average) < cicada bodies (2.64 mg/kg on average) and methyl mercury concentrations of cicada bodies were 123.93 ng/g on average and were the highest. Methyl mercury concentrations accounted for about 4.69% of total mercury in cicada bodies and most mercury was in inorganic forms in cicada. Sex differences of total mercury concentrations were significantly great (F = 8.433, p < 0.01) and total mercury concentrations of the males, which were 3.38 mg/kg on average, were much higher. Correlation analysis showed that neither total nor methyl mercury concentrations of cicada bodies was significantly related to the corresponding contents of soil (r = 0.0598, p > 0.05).

Mercury: Next-gen Data Analysis and Annotation Pipeline (Seventh Annual Sequencing, Finishing, Analysis in the Future (SFAF) Meeting 2012)

ScienceCinema

Sexton, David

2018-01-22

David Sexton (Baylor) gives a talk titled "Mercury: Next-gen Data Analysis and Annotation Pipeline" at the 7th Annual Sequencing, Finishing, Analysis in the Future (SFAF) Meeting held in June, 2012 in Santa Fe, NM.

Mercury: Next-gen Data Analysis and Annotation Pipeline (Seventh Annual Sequencing, Finishing, Analysis in the Future (SFAF) Meeting 2012)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sexton, David

2012-06-01

David Sexton (Baylor) gives a talk titled "Mercury: Next-gen Data Analysis and Annotation Pipeline" at the 7th Annual Sequencing, Finishing, Analysis in the Future (SFAF) Meeting held in June, 2012 in Santa Fe, NM.

Mercury emissions from coal combustion in Silesia, analysis using geostatistics

NASA Astrophysics Data System (ADS)

Zasina, Damian; Zawadzki, Jaroslaw

2015-04-01

Data provided by the UNEP's report on mercury [1] shows that solid fuel combustion in significant source of mercury emission to air. Silesia, located in southwestern Poland, is notably affected by mercury emission due to being one of the most industrialized Polish regions: the place of coal mining, production of metals, stone mining, mineral quarrying and chemical industry. Moreover, Silesia is the region with high population density. People are exposed to severe risk of mercury emitted from both: industrial and domestic sources (i.e. small household furnaces). Small sources have significant contribution to total emission of mercury. Official and statistical analysis, including prepared for international purposes [2] did not provide data about spatial distribution of the mercury emitted to air, however number of analysis on Polish public power and energy sector had been prepared so far [3; 4]. The distribution of locations exposed for mercury emission from small domestic sources is interesting matter merging information from various sources: statistical, economical and environmental. This paper presents geostatistical approach to distibution of mercury emission from coal combustion. Analysed data organized in 2 independent levels: individual, bottom-up approach derived from national emission reporting system [5; 6] and top down - regional data calculated basing on official statistics [7]. Analysis, that will be presented, will include comparison of spatial distributions of mercury emission using data derived from sources mentioned above. Investigation will include three voivodeships of Poland: Lower Silesian, Opole (voivodeship) and Silesian using selected geostatistical methodologies including ordinary kriging [8]. References [1] UNEP. Global Mercury Assessment 2013: Sources, Emissions, Releases and Environmental Transport. UNEP Chemicals Branch, Geneva, Switzerland, 2013. [2] NCEM. Poland's Informative Inventory Report 2014. NCEM at the IEP-NRI, 2014. http://www.ceip.at/. [3] Zyśk J., Wyrwa A. and Pluta M. Emissions of mercury from the power sector in Poland. Atmospheric Environment, 45:605-610, 2011. http://dx.doi.org/10.1016/j.atmosenv.2010.10.041/. [4] Głodek A., Pacyna J. Mercury emission from coal-fired power plants in Poland. Atmospheric Environment, 43:5668-5673, 2009. http://dx.doi.org/10.1016/j.atmosenv.2009.07.041. [5] NCEM. National emission database, 2014. NCEM Management at the IEP-NRI. [6] Zasina D. and Zawadzki J. Disaggregation problems using data derived from polish air pollutant emission management system, Systems Supporting Production Engineering. Review of Problems and Solutions, ISBN 978-83-937845-9-2, pp. 128-137, 2014. [7] EUROSTAT. EUROSTAT Energy Database, 2014. [8] Wackernagel H. Basics in Geostatistics 3 Geostatistical Monte-Carlo methods: Conditional simulation, 2013.

Recent Approaches to Modeling Transport of Mercury in Surface Water and Groundwater - Case Study in Upper East Fork Poplar Creek, Oak Ridge, TN - 13349

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bostick, Kent; Daniel, Anamary; Tachiev, Georgio

2013-07-01

In this case study, groundwater/surface water modeling was used to determine efficacy of stabilization in place with hydrologic isolation for remediation of mercury contaminated areas in the Upper East Fork Poplar Creek (UEFPC) Watershed in Oak Ridge, TN. The modeling simulates the potential for mercury in soil to contaminate groundwater above industrial use risk standards and to contribute to surface water contamination. The modeling approach is unique in that it couples watershed hydrology with the total mercury transport and provides a tool for analysis of changes in mercury load related to daily precipitation, evaporation, and runoff from storms. The modelmore » also allows for simulation of colloidal transport of total mercury in surface water. Previous models for the watershed only simulated average yearly conditions and dissolved concentrations that are not sufficient for predicting mercury flux under variable flow conditions that control colloidal transport of mercury in the watershed. The transport of mercury from groundwater to surface water from mercury sources identified from information in the Oak Ridge Environmental Information System was simulated using a watershed scale model calibrated to match observed daily creek flow, total suspended solids and mercury fluxes. Mercury sources at the former Building 81-10 area, where mercury was previously retorted, were modeled using a telescopic refined mesh with boundary conditions extracted from the watershed model. Modeling on a watershed scale indicated that only source excavation for soils/sediment in the vicinity of UEFPC had any effect on mercury flux in surface water. The simulations showed that colloidal transport contributed 85 percent of the total mercury flux leaving the UEFPC watershed under high flow conditions. Simulation of dissolved mercury transport from liquid elemental mercury and adsorbed sources in soil at former Building 81-10 indicated that dissolved concentrations are orders of magnitude below a target industrial groundwater concentration beneath the source and would not influence concentrations in surface water at Station 17. This analysis addressed only shallow concentrations in soil and the shallow groundwater flow path in soil and unconsolidated sediments to UEFPC. Other mercury sources may occur in bedrock and transport though bedrock to UEFPC may contribute to the mercury flux at Station 17. Generally mercury in the source areas adjacent to the stream and in sediment that is eroding can contribute to the flux of mercury in surface water. Because colloidally adsorbed mercury can be transported in surface water, actions that trap colloids and or hydrologically isolate surface water runoff from source areas would reduce the flux of mercury in surface water. Mercury in soil is highly adsorbed and transport in the groundwater system is very limited under porous media conditions. (authors)« less

Cesium Speciation in Dust from Municipal Solid Waste and Sewage Sludge Incineration by Synchrotron Radiation Micro-X-ray Analysis.

PubMed

Shiota, Kenji; Takaoka, Masaki; Fujimori, Takashi; Oshita, Kazuyuki; Terada, Yasuko

2015-11-17

The chemical behavior of Cs in waste incineration processes is important to consider when disposing of radionuclide-contaminated waste from the Fukushima Daiichi nuclear power plant accident in Japan. To determine the speciation of Cs, we attempted the direct speciation of trace amounts of stable Cs in the dust from municipal solid waste incineration (MSWI) and sewage sludge incineration (SSI) by micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption fine structure (μ-XAFS) at the SPring-8 facility. The μ-XRF results revealed that locally produced Cs was present in MSWI and SSI dust within the cluster size range of 2-10 μm. The μ-XAFS analysis confirmed that the speciation of Cs in MSWI dust was similar to that of CsCl, while in SSI dusts it was similar to pollucite. The solubility of Cs was considered to be influenced by the exact Cs species present in incineration residue.

Sample preparation and storage can change arsenic speciation in human urine.

PubMed

Feldmann, J; Lai, V W; Cullen, W R; Ma, M; Lu, X; Le, X C

1999-11-01

Stability of chemical speciation during sample handling and storage is a prerequisite to obtaining reliable results of trace element speciation analysis. There is no comprehensive information on the stability of common arsenic species, such as inorganic arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine, in human urine. We compared the effects of the following storage conditions on the stability of these arsenic species: temperature (25, 4, and -20 degrees C), storage time (1, 2, 4, and 8 months), and the use of additives (HCl, sodium azide, benzoic acid, benzyltrimethylammonium chloride, and cetylpyridinium chloride). HPLC with both inductively coupled plasma mass spectrometry and hydride generation atomic fluorescence detection techniques were used for the speciation of arsenic. We found that all five of the arsenic species were stable for up to 2 months when urine samples were stored at 4 and -20 degrees C without any additives. For longer period of storage (4 and 8 months), the stability of arsenic species was dependent on urine matrices. Whereas the arsenic speciation in some urine samples was stable for the entire 8 months at both 4 and -20 degrees C, other urine samples stored under identical conditions showed substantial changes in the concentration of As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid. The use of additives did not improve the stability of arsenic speciation in urine. The addition of 0.1 mol/L HCl (final concentration) to urine samples produced relative changes in inorganic As(III) and As(V) concentrations. Low temperature (4 and -20 degrees C) conditions are suitable for the storage of urine samples for up to 2 months. Untreated samples maintain their concentration of arsenic species, and additives have no particular benefit. Strong acidification is not appropriate for speciation analysis.

Speciation distribution and mass balance of copper and zinc in urban rain, sediments, and road runoff.

PubMed

Zuo, Xiaojun; Fu, Dafang; Li, He

2012-11-01

Heavy metal pollution in road runoff had caused widespread concern since the last century. However, there are little references on metal speciation in multiple environmental media (e.g., rain, road sediments, and road runoff). Our research targeted the investigation of metal speciation in rain, road sediments, and runoff; the analysis of speciation variation and mass balance of metals among rain, road sediments, and runoff; the selection of main factors by principal component analysis (PCA); and the establishment of equation to evaluate the impact of rain and road sediments to metals in road runoff. Sequential extraction procedure contains five steps for the chemical fractionation of metals. Flame atomic absorption spectrometry (Shimadzu, AA-6800) was used to determine metal speciation concentration, as well as the total and dissolved fractions. The dissolved fractions for both Cu and Zn were dominant in rain. The speciation distribution of Zn was different from that of Cu in road sediments, while speciation distribution of Zn is similar to that of Cu in runoff. The bound to carbonates for both Cu and Zn in road sediments were prone to be dissolved by rain. The levels of Cu and Zn in runoff were not obviously influenced by rain, but significantly influenced by road sediments. The masses for both Cu and Zn among rain, road sediments, and road runoff approximately meet the mass balance equation for all rainfall patterns. Five principal factors were selected for metal regression equation based on PCA, including rainfall, average rainfall intensity, antecedent dry periods, total suspended particles, and temperature. The established regression equations could be used to predict the effect of road runoff on receiving environments.

Linear Combination Fitting (LCF)-XANES analysis of As speciation in selected mine-impacted materials

EPA Pesticide Factsheets

This table provides sample identification labels and classification of sample type (tailings, calcinated, grey slime). For each sample, total arsenic and iron concentrations determined by acid digestion and ICP analysis are provided along with arsenic in-vitro bioaccessibility (As IVBA) values to estimate arsenic risk. Lastly, the table provides linear combination fitting results from synchrotron XANES analysis showing the distribution of arsenic speciation phases present in each sample along with fitting error (R-factor).This dataset is associated with the following publication:Ollson, C., E. Smith, K. Scheckel, A. Betts, and A. Juhasz. Assessment of arsenic speciation and bioaccessibility in mine-impacted materials. Diana Aga, Wonyong Choi, Andrew Daugulis, Gianluca Li Puma, Gerasimos Lyberatos, and Joo Hwa Tay JOURNAL OF HAZARDOUS MATERIALS. Elsevier Science Ltd, New York, NY, USA, 313: 130-137, (2016).

Shedding Light on the Grey Zone of Speciation along a Continuum of Genomic Divergence.

PubMed

Roux, Camille; Fraïsse, Christelle; Romiguier, Jonathan; Anciaux, Yoann; Galtier, Nicolas; Bierne, Nicolas

2016-12-01

Speciation results from the progressive accumulation of mutations that decrease the probability of mating between parental populations or reduce the fitness of hybrids-the so-called species barriers. The speciation genomic literature, however, is mainly a collection of case studies, each with its own approach and specificities, such that a global view of the gradual process of evolution from one to two species is currently lacking. Of primary importance is the prevalence of gene flow between diverging entities, which is central in most species concepts and has been widely discussed in recent years. Here, we explore the continuum of speciation thanks to a comparative analysis of genomic data from 61 pairs of populations/species of animals with variable levels of divergence. Gene flow between diverging gene pools is assessed under an approximate Bayesian computation (ABC) framework. We show that the intermediate "grey zone" of speciation, in which taxonomy is often controversial, spans from 0.5% to 2% of net synonymous divergence, irrespective of species life history traits or ecology. Thanks to appropriate modeling of among-locus variation in genetic drift and introgression rate, we clarify the status of the majority of ambiguous cases and uncover a number of cryptic species. Our analysis also reveals the high incidence in animals of semi-isolated species (when some but not all loci are affected by barriers to gene flow) and highlights the intrinsic difficulty, both statistical and conceptual, of delineating species in the grey zone of speciation.

Atmospheric mercury distribution in Northern Europe and in the Mediterranean region

NASA Astrophysics Data System (ADS)

Wängberg, I.; Munthe, J.; Pirrone, N.; Iverfeldt, Å.; Bahlman, E.; Costa, P.; Ebinghaus, R.; Feng, X.; Ferrara, R.; Gårdfeldt, K.; Kock, H.; Lanzillotta, E.; Mamane, Y.; Mas, F.; Melamed, E.; Osnat, Y.; Prestbo, E.; Sommar, J.; Schmolke, S.; Spain, G.; Sprovieri, F.; Tuncel, G.

Mercury species in air have been measured at five sites in Northwest Europe and at five coastal sites in the Mediterranean region during measurements at four seasons. Observed concentrations of total gaseous mercury (TGM), total particulate mercury (TPM) and reactive gaseous mercury (RGM) were generally slightly higher in the Mediterranean region than in Northwest Europe. Incoming clean Atlantic air seems to be enriched in TGM in comparison to air in Scandinavia. Trajectory analysis of events where high concentrations of TPM simultaneously were observed at sites in North Europe indicate source areas in Central Europe and provide evidence of transport of mercury on particles on a regional scale.

[Evaluation and source analysis of the mercury pollution in soils and vegetables around a large-scale zinc smelting plant].

PubMed

Liu, Fang; Wang, Shu-Xiao; Wu, Qing-Ru; Lin, Hai

2013-02-01

The farming soil and vegetable samples around a large-scale zinc smelter were collected for mercury content analyses, and the single pollution index method with relevant regulations was used to evaluate the pollution status of sampled soils and vegetables. The results indicated that the surface soil and vegetables were polluted with mercury to different extent. Of the soil samples, 78% exceeded the national standard. The mercury concentration in the most severely contaminated area was 29 times higher than the background concentration, reaching the severe pollution degree. The mercury concentration in all vegetable samples exceeded the standard of non-pollution vegetables. Mercury concentration, in the most severely polluted vegetables were 64.5 times of the standard, and averagely the mercury concentration in the vegetable samples was 25.4 times of the standard. For 85% of the vegetable samples, the mercury concentration, of leaves were significantly higher than that of roots, which implies that the mercury in leaves mainly came from the atmosphere. The mercury concentrations in vegetable roots were significantly correlated with that in soils, indicating the mercury in roots was mainly from soil. The mercury emissions from the zinc smelter have obvious impacts on the surrounding soils and vegetables. Key words:zinc smelting; mercury pollution; soil; vegetable; mercury content

EPA Method 245.2: Mercury (Automated Cold Vapor Technique)

EPA Pesticide Factsheets

Method 245.2 describes procedures for preparation and analysis of drinking water samples for analysis of mercury using acid digestion and cold vapor atomic absorption. Samples are prepared using an acid digestion technique.

Biology and toxicology of tellurium explored by speciation analysis.

PubMed

Ogra, Yasumitsu

2017-05-24

Tellurium (Te) is widely used in industry because it has unique physicochemical properties. Although Te is a non-essential element in animals and plants, it is expected to be metabolized to organometallic compounds having a carbon-Te bond in living organisms exposed to inorganic Te compounds. Thus, the speciation and identification of tellurometabolites are expected to contribute to the depiction of the metabolic chart of Te. Speciation by elemental mass spectrometry and identification by molecular mass spectrometry coupled with separation techniques have significantly contributed to the discovery of tellurometabolites in animals and plants. The aim of this mini review is to present recent advances in the biology and toxicology of tellurium as revealed by speciation and identification by molecular mass spectrometry.

XAS Studies of Se Speciation in Selenite-Fed Rats

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Witting, Paul K.; Harris, Hugh H.

2014-01-01

The biological activity of selenium is dependent on its chemical form. Therefore, knowledge of Se chemistry in vivo is required for efficacious use of selenium compounds in disease prevention and treatment. Using X-ray absorption spectroscopy, Se speciation in the kidney, liver, heart, spleen, testis and red blood cells of rats fed control (~0.3 ppm Se) or selenite-supplemented (1 ppm or 5 ppm Se) diets for 3 or 6 weeks, was investigated. X-ray absorption spectroscopy revealed the presence of Se–Se and Se–C species in the kidney and liver, and Se–S species in the kidney, but not the liver. X-ray absorption near edge structure (XANES) spectra showed that there was variation in speciation in the liver and kidneys, but Se speciation was much more uniform in the remaining organs. Using principal component analysis (PCA) to interpret the Se K-edge X-ray absorption spectra, we were able to directly compare the speciation of Se in two different models of selenite metabolism – human lung cancer cells and rat tissues. The effects of Se dose, tissue type and duration of diet on selenium speciation in rat tissues were investigated, and a relationship between the duration of the diet (3 weeks versus 6 weeks) and selenium speciation was observed. PMID:25363824

Using Fur to Estimate Mercury Concentrations in Mink

EPA Science Inventory

Total mercury (Hg) concentrations in fur and muscle tissue from mink (Mustela vison) were compared to determine the utility of fur analysis as a non-lethal and convenient method for predicting mercury concentrations in tissues. Sixty nine wild-trapped mink were collected in Rhode...

Preparation and characterization of a novel graphene/biochar composite for aqueous phenanthrene and mercury removal.

PubMed

Tang, Jingchun; Lv, Honghong; Gong, Yanyan; Huang, Yao

2015-11-01

A graphene/biochar composite (G/BC) was synthesized via slow pyrolysis of graphene (G) pretreated wheat straw, and tested for the sorption characteristics and mechanisms of representative aqueous contaminants (phenanthrene and mercury). Structure and morphology analysis showed that G was coated on the surface of biochar (BC) mainly through π-π interactions, resulting in a larger surface area, more functional groups, greater thermal stability, and higher removal efficiency of phenanthrene and mercury compared to BC. Pseudo second-order model adequately simulated sorption kinetics, and sorption isotherms of phenanthrene and mercury were simulated well by dual-mode and BET models, respectively. FTIR and SEM analysis suggested that partitioning and surface sorption were dominant mechanisms for phenanthrene sorption, and that surface complexation between mercury and C-O, CC, -OH, and OC-O functional groups was responsible for mercury removal. The results suggested that the G/BC composite is an efficient, economic, and environmentally friendly multifunctional adsorbent for environmental remediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemical determination of inorganic mercury and arsenic--A review.

PubMed

Zaib, Maria; Athar, Muhammad Makshoof; Saeed, Asma; Farooq, Umar

2015-12-15

Inorganic mercury and arsenic encompasses a term which includes As(III), As(V) and Hg(II) species. These metal ions have been extensively studied due to their toxicity related issues. Different analytical methods are used to monitor inorganic mercury and arsenic in a variety of samples at trace level. The present study reviews various analytical techniques available for detection of inorganic mercury and arsenic with particular emphasis on electrochemical methods especially stripping voltammetry. A detailed critical evaluation of methods, advantages of electrochemical methods over other analytical methods, and various electrode materials available for mercury and arsenic analysis is presented in this review study. Modified carbon paste electrode provides better determination due to better deposition with linear and improved response under studied set of conditions. Biological materials may be the potent and economical alternative as compared to macro-electrodes and chemically modified carbon paste electrodes in stripping analysis of inorganic mercury and arsenic. Copyright © 2015 Elsevier B.V. All rights reserved.

Bio-metals imaging and speciation in cells using proton and synchrotron radiation X-ray microspectroscopy

PubMed Central

Ortega, Richard; Devès, Guillaume; Carmona, Asunción

2009-01-01

The direct detection of biologically relevant metals in single cells and of their speciation is a challenging task that requires sophisticated analytical developments. The aim of this article is to present the recent achievements in the field of cellular chemical element imaging, and direct speciation analysis, using proton and synchrotron radiation X-ray micro- and nano-analysis. The recent improvements in focusing optics for MeV-accelerated particles and keV X-rays allow application to chemical element analysis in subcellular compartments. The imaging and quantification of trace elements in single cells can be obtained using particle-induced X-ray emission (PIXE). The combination of PIXE with backscattering spectrometry and scanning transmission ion microscopy provides a high accuracy in elemental quantification of cellular organelles. On the other hand, synchrotron radiation X-ray fluorescence provides chemical element imaging with less than 100 nm spatial resolution. Moreover, synchrotron radiation offers the unique capability of spatially resolved chemical speciation using micro-X-ray absorption spectroscopy. The potential of these methods in biomedical investigations will be illustrated with examples of application in the fields of cellular toxicology, and pharmacology, bio-metals and metal-based nano-particles. PMID:19605403

Application of Hyphenated Techniques in Speciation Analysis of Arsenic, Antimony, and Thallium

PubMed Central

Michalski, Rajmund; Szopa, Sebastian; Jabłońska, Magdalena; Łyko, Aleksandra

2012-01-01

Due to the fact that metals and metalloids have a strong impact on the environment, the methods of their determination and speciation have received special attention in recent years. Arsenic, antimony, and thallium are important examples of such toxic elements. Their speciation is especially important in the environmental and biomedical fields because of their toxicity, bioavailability, and reactivity. Recently, speciation analytics has been playing a unique role in the studies of biogeochemical cycles of chemical compounds, determination of toxicity and ecotoxicity of selected elements, quality control of food products, control of medicines and pharmaceutical products, technological process control, research on the impact of technological installation on the environment, examination of occupational exposure, and clinical analysis. Conventional methods are usually labor intensive, time consuming, and susceptible to interferences. The hyphenated techniques, in which separation method is coupled with multidimensional detectors, have become useful alternatives. The main advantages of those techniques consist in extremely low detection and quantification limits, insignificant interference, influence as well as high precision and repeatability of the determinations. In view of their importance, the present work overviews and discusses different hyphenated techniques used for arsenic, antimony, and thallium species analysis, in different clinical, environmental and food matrices. PMID:22654649

Bioremediation potential of a highly mercury resistant bacterial strain Sphingobium SA2 isolated from contaminated soil.

PubMed

Mahbub, Khandaker Rayhan; Krishnan, Kannan; Megharaj, Mallavarapu; Naidu, Ravi

2016-02-01

A mercury resistant bacterial strain, SA2, was isolated from soil contaminated with mercury. The 16S rRNA gene sequence of this isolate showed 99% sequence similarity to the genera Sphingobium and Sphingomonas of α-proteobacteria group. However, the isolate formed a distinct phyletic line with the genus Sphingobium suggesting the strain belongs to Sphingobium sp. Toxicity studies indicated resistance to high levels of mercury with estimated EC50 values 4.5 mg L(-1) and 44.15 mg L(-1) and MIC values 5.1 mg L(-1) and 48.48 mg L(-1) in minimal and rich media, respectively. The strain SA2 was able to volatilize mercury by producing mercuric reductase enzyme which makes it potential candidate for remediating mercury. ICP-QQQ-MS analysis of Hg supplemented culture solutions confirmed that almost 79% mercury in the culture suspension was volatilized in 6 h. A very small amount of mercury was observed to accumulate in cell pellets which was also evident according to ESEM-EDX analysis. The mercuric reductase gene merA was amplified and sequenced. The deduced amino acid sequence demonstrated sequence homology with α-proteobacteria and Ascomycota group. Copyright © 2015 Elsevier Ltd. All rights reserved.

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 –4. Heteroatomic molecules, especially those containing multiple S and N atoms, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg-DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 -4. Heteroatomic molecules, especially those containing multiple S and N atoms, were found to bemore » among the most important in forming strong complexes with Hg. Major Hg-DOM complexes of C10H21N2S4Hg+ and C8H17N2S4Hg+ were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. These findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg-DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Influence of Reservoir Water Level Fluctuations on Sediment ...

EPA Pesticide Factsheets

Mercury (Hg) is a pollutant of global concern due to its ability to accumulate as methylmercury (MeHg) in biota. Mercury is methylated by anaerobic microorganisms such as sulfate reducing bacteria (SRB) in water and sediment. Throughout North America, reservoirs tend to have elevated methylmercury (MeHg) concentrations compared to natural lakes and rivers. This impact is most pronounced in newly created reservoirs where methylation is fueled by the decomposition of flooded organic material, which can release Hg and enhance microbial activity. Much less is known about the longer-term water-level management impacts on Hg cycling in older reservoirs. The objective of our study was to understand the role of on-going water-level fluctuations on sediment MeHg concentrations and sulfur speciation within a reservoir 75 years after initial impoundment. The study was performed at the Cottage Grove Reservoir located 15 km downstream of the historical Black Butte Hg mine. For 8 months each year, the water level is lowered resulting in roughly half of the reservoir’s sediment being exposed to the atmosphere. Water samples from the inflow, water-column, outflow, and sediment were collected seasonally over a year for total-Hg, MeHg, and several ancillary parameters. The results showed that conditions in the reservoir were favorable to methylation with a much higher %MeHg observed in the outflowing water (34%) compared to the inflow (7%) during the late-summer. An

Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

DOE PAGES

Chen, Hongmei; Johnston, Ryne C.; Mann, Benjamin F.; ...

2016-12-22

The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here in this paper, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg–DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 –4. Heteroatomic molecules, especially those containing multiple S and N atoms, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. Finally, these findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg–DOM complexes that affect biological uptake and transformation of Hg in the environment.« less

Mercury bioremediation by mercury accumulating Enterobacter sp. cells and its alginate immobilized application.

PubMed

Sinha, Arvind; Khare, Sunil Kumar

2012-02-01

The effective microbial remediation of the mercury necessitates the mercury to be trapped within the cells without being recycled back to the environment. The study describes a mercury bioaccumulating strain of Enterobacter sp., which remediated mercury from the medium simultaneous to its growth. The transmission electron micrographs and electron dispersive X-ray analysis revealed the accumulation of remediated mercury as nano-size particles in the cytoplasm as well as on the cell wall. The Enterobacter sp. in the present work was able to accumulate mercury, without being engineered in its native form. The possibility of recovering the accumulated mercury from the cells is also indicated. The applicability of the alginate immobilized cells in removing mercury from synthetic and complex industrial effluent in a batch mode was amply demonstrated. The initial load of 7.3 mg l(-1) mercury in the industrial effluent was completely removed in 72 h. The cells immobilized in calcium alginate were similarly effective in the complete removal of 5 mg l(-1) HgCl(2) of mercury from the synthetic effluent in less than 72 h. The immobilized cells could be reused for multiple cycles.

Prenatal mercury exposure, maternal seafood consumption and associations with child language at five years.

PubMed

Vejrup, Kristine; Brandlistuen, Ragnhild Eek; Brantsæter, Anne Lise; Knutsen, Helle Katrine; Caspersen, Ida Henriette; Alexander, Jan; Lundh, Thomas; Meltzer, Helle Margrete; Magnus, Per; Haugen, Margaretha

2018-01-01

Methyl mercury (MeHg) is a well-known neurotoxin and evidence suggests that also low level exposure may affect prenatal neurodevelopment. Uncertainty exists as to whether the maternal MeHg burden in Norway might affect child neurodevelopment. To evaluate the association between prenatal mercury exposure, maternal seafood consumption and child language and communication skills at age five. The study sample comprised 38,581 mother-child pairs in the Norwegian Mother and Child Cohort Study. Maternal mercury blood concentration in gestational week 17 was analysed in a sub-sample of 2239 women. Prenatal mercury exposure from maternal diet was calculated from a validated FFQ answered in mid-pregnancy. Mothers reported children's language and communications skills at age five by a questionnaire including questions from the Ages and Stages Questionnaire (ASQ), the Speech and Language Assessment Scale (SLAS) and the Twenty Statements about Language-Related Difficulties (language 20). We performed linear regression analyses adjusting for maternal characteristics, nutritional status and socioeconomic factors. Median maternal blood mercury concentration was 1.03μg/L, dietary mercury exposure was 0.15μg/kgbw/wk, and seafood intake was 217g/wk. Blood mercury concentrations were not associated with any language and communication scales. Increased dietary mercury exposure was significantly associated with improved SLAS scores when mothers had a seafood intake below 400g/wk in the adjusted analysis. Sibling matched analysis showed a small significant adverse association between those above the 90th percentile dietary mercury exposure and the SLAS scores. Maternal seafood intake during pregnancy was positively associated with the language and communication scales. Low levels of prenatal mercury exposure were positively associated with language and communication skills at five years. However, the matched sibling analyses suggested an adverse association between mercury and child language skills in the highest exposure group. This indicates that prenatal low level mercury exposure still needs our attention. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of Alternative Mercury Control Strategies

EIA Publications

2005-01-01

This analysis responds to a September 14, 2004, request from Chairmen James M. Inhofe and George V. Voinovich asking the Energy Information Administration (EIA) to analyze the impacts of different approaches for removing mercury from coal-fired power plants.

Instrumentation for Aerosol and Gas Speciation

NASA Technical Reports Server (NTRS)

Coggiola, Michael J.

1998-01-01

Using support from NASA Grant No. NAG 2-963, SRI International successfully completed the project, entitled, 'Instrumentation for Aerosol and Gas Speciation.' This effort (SRI Project 7383) covered the design, fabrication, testing, and deployment of a real-time aerosol speciation instrument in NASA's DC-8 aircraft during the Spring 1996 SUbsonic aircraft: Contrail and Cloud Effects Special Study (SUCCESS) mission. This final technical report describes the pertinent details of the instrument design, its abilities, its deployment during SUCCESS and the data acquired from the mission, and the post-mission calibration, data reduction, and analysis.

Selenium speciation analysis of Misgurnus anguillicaudatus selenoprotein by HPLC-ICP-MS and HPLC-ESI-MS/MS

USDA-ARS?s Scientific Manuscript database

Analytical methods for selenium (Se) speciation were developed using high performance liquid chromatography (HPLC) coupled to either inductively coupled plasma mass spectrometry (ICP-MS) or electrospray ionization tandem mass spectrometry (ESI-MS/MS). Separations of selenomethionine (Se-Met) and sel...

Speciation analysis of arsenic in biological matrices by automated hydride generation-cryotrapping-atomic absorption spectrometry with multiple microflame quartz tube atomizer (multiatomizer).

EPA Science Inventory

This paper describes an automated system for the oxidation state specific speciation of inorganic and methylated arsenicals by selective hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer. The corresponding arsines are ge...

Mercury and methylmercury stream concentrations in a Coastal Plain watershed: A multi-scale simulation analysis

EPA Science Inventory

Mercury is a ubiquitous global environmental toxicant responsible for most US fish advisories. Processes governing mercury concentrations in rivers and streams are not well understood, particularly at multiple spatial scales. We investigate how insights gained from reach-scale me...

SCIENTIFIC UNCERTAINTIES IN ATMOSPHERIC MERCURY MODELS II: SENSITIVITY ANALYSIS IN THE CONUS DOMAIN

EPA Science Inventory

In this study, we present the response of model results to different scientific treatments in an effort to quantify the uncertainties caused by the incomplete understanding of mercury science and by model assumptions in atmospheric mercury models. Two sets of sensitivity simulati...

MERCURY IN AND FLUXES TO LAKE MICHIGAN SURFICIAL SEDIMENTS

EPA Science Inventory

Sediment samples were collected from Lake Michigan between 1994 and 1996. One purpose of the coring was to define the horizontal distribution of mercury in the surficial 1 cm of sediment. When possible the sediments were box cored. Subcores for mercury analysis were sectioned at ...

ENVIRONMENTAL SCREENING MODELING OF MERCURY IN THE UPPER EVERGLADES OF SOUTH FLORIDA

EPA Science Inventory

This screening modeling analysis examines mercury sources and fate in the upper canals of the South Florida Everglades. Mass balance modeling techniques are applied along with available data to examine the relative importance of external sources and internal cycling of mercury an...

Virtual atmospheric mercury emission network in China.

PubMed

Liang, Sai; Zhang, Chao; Wang, Yafei; Xu, Ming; Liu, Weidong

2014-01-01

Top-down analysis of virtual atmospheric mercury emission networks can direct efficient demand-side policy making on mercury reductions. Taking China-the world's top atmospheric mercury emitter-as a case, we identify key contributors to China's atmospheric mercury emissions from both the producer and the consumer perspectives. China totally discharged 794.9 tonnes of atmospheric mercury emissions in 2007. China's production-side control policies should mainly focus on key direct mercury emitters such as Liaoning, Hebei, Shandong, Shanxi, Henan, Hunan, Guizhou, Yunnan, and Inner Mongolia provinces and sectors producing metals, nonmetallic mineral products, and electricity and heat power, while demand-side policies should mainly focus on key underlying drivers of mercury emissions such as Shandong, Jiangsu, Zhejiang, and Guangdong provinces and sectors of construction activities and equipment manufacturing. China's interregional embodied atmospheric mercury flows are generally moving from the inland to the east coast. Beijing-Tianjin (with 4.8 tonnes of net mercury inflows) and South Coast (with 3.3 tonnes of net mercury inflows) are two largest net-inflow regions, while North (with 5.3 tonnes of net mercury outflows) is the largest net-outflow region. We also identify primary supply chains contributing to China's virtual atmospheric mercury emission network, which can be used to trace the transfers of production-side and demand-side policy effects.

Marsh wrens as bioindicators of mercury in wetlands of Great Salt Lake: do blood and feathers reflect site-specific exposure risk to bird reproduction?

USGS Publications Warehouse

Hartman, C. Alex; Ackerman, Joshua T.; Herring, Garth; Isanhart, John; Herzog, Mark P.

2013-01-01

Nonlethal sampling of bird blood and feathers are among the more common ways of estimating the risk of mercury exposure to songbird reproduction. The implicit assumption is that mercury concentrations in blood or feathers of individuals captured in a given area are correlated with mercury concentrations in eggs from the same area. Yet, this assumption is rarely tested. We evaluated mercury concentrations in blood, feathers, and eggs of marsh wrens in wetlands of Great Salt Lake, Utah, and, at two spatial scales, specifically tested the assumption that mercury concentrations in blood and feather samples from birds captured in a defined area were predictive of mercury concentrations in eggs collected in the same area. Mercury concentrations in blood were not correlated with mercury concentrations in eggs collected within the same wetland unit, and were poorly correlated with mercury concentrations in eggs collected at the smaller home range spatial scale of analysis. Moreover, mercury exposure risk, as estimated via tissue concentrations, differed among wetland units depending upon whether blood or egg mercury concentrations were sampled. Mercury concentrations in feathers also were uncorrelated with mercury concentrations in eggs, and were poorly correlated with mercury concentrations in blood. These results demonstrate the potential for contrasting management actions that may be implemented based solely on the specific avian tissue that is sampled, and highlight the importance of developing avian tissues as biomonitoring tools for assessing local risk of mercury exposure to bird reproduction.

Mercury species and other selected constituent concentrations in water, sediment, and biota of Sinclair Inlet, Kitsap County, Washington, 2007-10

USGS Publications Warehouse

Huffman, R.L.; Wagner, R.J.; Toft, J.; Cordell, J.; DeWild, J.F.; Dinicola, R.S.; Aiken, G.R.; Krabbenhoft, D.P.; Marvin-DiPasquale, M.; Stewart, A.R.; Moran, P.W.; Paulson, A.J.

2012-01-01

The Methylation and Bioaccumulation Project included a comprehensive field study of mercury biogeochemistry in marine sediment, water, and zooplankton in Sinclair Inlet. Mercury, iron, and sulfur species in sediment porewater from six sites within and three sites outside of Sinclair Inlet were measured to provide insight into the processes that produce methylmercury in the sediments. Total mercury, methylmercury, dissolved organic carbon, and redox-sensitive species were measured in porewaters in the top 2 centimeters of sediment, and these data were paired with sedimentary flux measurements from core incubation experiments to connect sedimentary processes to the water column. A broad-scale study of mercury methylation potential and mercury species at 20-plus stations in Sinclair Inlet was conducted in February 2009 and 2010, June 2009, and August 2009. Sedimentary flux measurements and analysis of mercury and biogeochemicals in sediment porewater and bottom water were made at six of the broad-scale stations. Bioaccumulation processes in the water column in the context of the sedimentary flux of methylmercury were examined using monthly survey data collected between August 2008 and August 2009. The survey data included concentrations of methylmercury and isotope ratios of carbon and nitrogen in bulk zooplankton measured at four stations in Sinclair Inlet in the context of the population of bulk zooplankton ascertained by taxonomical identification. The analysis of filtered total mercury, total particulate mercury, filtered methylmercury, particulate methylmercury, chlorophyll a, isotopes of carbon and nitrogen in suspended matter, and other biogeochemical data will facilitate the examination of the biogeochemistry of mercury in Sinclair Inlet.

Essential Indicators Identifying Chronic Inorganic Mercury Intoxication: Pooled Analysis across Multiple Cross-Sectional Studies.

PubMed

Doering, Stefan; Bose-O'Reilly, Stephan; Berger, Ursula

2016-01-01

The continuous exposure to inorganic mercury vapour in artisanal small-scale gold mining (ASGM) areas leads to chronic health problems. It is therefore essential to have a quick, but reliable risk assessing tool to diagnose chronic inorganic mercury intoxication. This study re-evaluates the state-of-the-art toolkit to diagnose chronic inorganic mercury intoxication by analysing data from multiple pooled cross-sectional studies. The primary research question aims to reduce the currently used set of indicators without affecting essentially the capability to diagnose chronic inorganic mercury intoxication. In addition, a sensitivity analysis is performed on established biomonitoring exposure limits for mercury in blood, hair, urine and urine adjusted by creatinine, where the biomonitoring exposure limits are compared to thresholds most associated with chronic inorganic mercury intoxication in artisanal small-scale gold mining. Health data from miners and community members in Indonesia, Tanzania and Zimbabwe were obtained as part of the Global Mercury Project and pooled into one dataset together with their biomarkers mercury in urine, blood and hair. The individual prognostic impact of the indicators on the diagnosis of mercury intoxication is quantified using logistic regression models. The selection is performed by a stepwise forward/backward selection. Different models are compared based on the Bayesian information criterion (BIC) and Cohen`s kappa is used to evaluate the level of agreement between the diagnosis of mercury intoxication based on the currently used set of indicators and the result based on our reduced set of indicators. The sensitivity analysis of biomarker exposure limits of mercury is based on a sequence of chi square tests. The variable selection in logistic regression reduced the number of medical indicators from thirteen to ten in addition to the biomarkers. The estimated level of agreement using ten of thirteen medical indicators and all four biomarkers to diagnose chronic inorganic mercury intoxication yields a Cohen`s Kappa of 0.87. While in an additional stepwise selection the biomarker blood was not selected, the level of agreement based on ten medical indicators and only the three biomarkers urine, urine/creatinine and hair reduced Cohen`s Kappa to 0.46. The optimal cut-point for the biomarkers blood, hair, urine and urine/creatinine were estimated at 11. 6 μg/l, 3.84 μg/g, 24.4 μg/l and 4.26 μg/g, respectively. The results show that a reduction down to only ten indicators still allows a reliable diagnosis of chronic inorganic mercury intoxication. This reduction of indicators will simplify health assessments in artisanal small-scale gold mining areas.

117.6-kilobit telemetry from Mercury in-flight system analysis

NASA Technical Reports Server (NTRS)

Evanchuk, V. L.

1974-01-01

This paper discusses very specifically the mode of the Mariner Venus/Mercury 1973 (MVM'73) telecommunications system in the interplexed dual channel 117.6 kilobits per second (kbps) and 2.45 kbps telemetry. This mode, originally designed for only Venus encounter, was also used at Mercury despite significantly less performance margin. Detailed analysis and careful measurement of system performance before and during flight operations allowed critical operational decisions, which made maximum use of the system capabilities.

Non-Thermal, On-Site Decontamination and Destruction of Practice Bombs

DTIC Science & Technology

2006-06-12

extraction (SW1311) followed by analysis (SW6010B with analysis for Mercury SW7470). The samples taken from the process tanks indicated in Table 3...A: Analytical Methods Supporting Project CD-ROM 7471A - 1 Revision 1 September 1994 METHOD 7471A MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL...COLD-VAPOR TECHNIQUE) 1.0 SCOPE AND APPLICATION 1.1 Method 7471 is approved for measuring total mercury (organic and inorganic) in soils, sediments

Ultrasensitive quantum dot fluorescence quenching assay for selective detection of mercury ions in drinking water.

PubMed

Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

2014-07-09

Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg(2+) ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples.

Mercury mass measurement in fluorescent lamps via neutron activation analysis

NASA Astrophysics Data System (ADS)

Viererbl, L.; Vinš, M.; Lahodová, Z.; Fuksa, A.; Kučera, J.; Koleška, M.; Voljanskij, A.

2015-11-01

Mercury is an essential component of fluorescent lamps. Not all fluorescent lamps are recycled, resulting in contamination of the environment with toxic mercury, making measurement of the mercury mass used in fluorescent lamps important. Mercury mass measurement of lamps via instrumental neutron activation analysis (NAA) was tested under various conditions in the LVR-15 research reactor. Fluorescent lamps were irradiated in different positions in vertical irradiation channels and a horizontal channel in neutron fields with total fluence rates from 3×108 cm-2 s-1 to 1014 cm-2 s-1. The 202Hg(n,γ)203Hg nuclear reaction was used for mercury mass evaluation. Activities of 203Hg and others induced radionuclides were measured via gamma spectrometry with an HPGe detector at various times after irradiation. Standards containing an Hg2Cl2 compound were used to determine mercury mass. Problems arise from the presence of elements with a large effective cross section in luminescent material (europium, antimony and gadolinium) and glass (boron). The paper describes optimization of the NAA procedure in the LVR-15 research reactor with particular attention to influence of neutron self-absorption in fluorescent lamps.

Ultrasensitive Quantum Dot Fluorescence quenching Assay for Selective Detection of Mercury Ions in Drinking Water

PubMed Central

Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

2014-01-01

Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg2+ ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples. PMID:25005836

[Cognitive disorders in patients with chronic mercury intoxication].

PubMed

Katamanova, E V; Shevchenko, O I; Lakhman, O L; Denisova, I A

2014-01-01

To assess severity of cognitive disorders in chronic mercury intoxication, the authors performed claster and discrimination analysis of neuropsychologic and neurophysiologic research data from workers exposed to mercury during long length of service, from patients with early and marked stages of chronic mercurial intoxication. Cognitive disorders in chronic mercurial intoxication have three severity degrees, in the light degree disorders patients demonstrate lower amplitude of cognitive evoked potentials, poor long-term memory and associative thinking. Moderate cognitive disorders are characterized by decreased visual, long-term memory, concentration of attention, poor optic and spatial gnosis. Marked cognitive disorders with chronic mercurial intoxication present with more decreased long-term, short-term, picturesque memory, poor intellect, optic and spatial gnosis and associative thinking.

Selenium Speciation in the Fountain Creek Watershed (Colorado, USA) Correlates with Water Hardness, Ca and Mg Levels.

PubMed

Carsella, James S; Sánchez-Lombardo, Irma; Bonetti, Sandra J; Crans, Debbie C

2017-04-30

The environmental levels of selenium (Se) are regulated and strictly enforced by the Environmental Protection Agency (EPA) because of the toxicity that Se can exert at high levels. However, speciation plays an important role in the overall toxicity of Se, and only when speciation analysis has been conducted will a detailed understanding of the system be possible. In the following, we carried out the speciation analysis of the creek waters in three of the main tributaries-Upper Fountain Creek, Monument Creek and Lower Fountain Creek-located in the Fountain Creek Watershed (Colorado, USA). There are statistically significant differences between the Se, Ca and Mg, levels in each of the tributaries and seasonal swings in Se, Ca and Mg levels have been observed. There are also statistically significant differences between the Se levels when grouped by Pierre Shale type. These factors are considered when determining the forms of Se present and analyzing their chemistry using the reported thermodynamic relationships considering Ca 2+ , Mg 2+ , SeO₄ 2- , SeO₃ 2- and carbonates. This analysis demonstrated that the correlation between Se and water hardness can be explained in terms of formation of soluble CaSeO₄. The speciation analysis demonstrated that for the Fountain Creek waters, the Ca 2+ ion may be mainly responsible for the observed correlation with the Se level. Considering that the Mg 2+ level is also correlating linearly with the Se levels it is important to recognize that without Mg 2+ the Ca 2+ would be significantly reduced. The major role of Mg 2+ is thus to raise the Ca 2+ levels despite the equilibria with carbonate and other anions that would otherwise decrease Ca 2+ levels.

Electrochemical sensors and devices for heavy metals assay in water: the French groups' contribution

PubMed Central

Pujol, Luca; Evrard, David; Groenen-Serrano, Karine; Freyssinier, Mathilde; Ruffien-Cizsak, Audrey; Gros, Pierre

2014-01-01

A great challenge in the area of heavy metal trace detection is the development of electrochemical techniques and devices which are user-friendly, robust, selective, with low detection limits and allowing fast analyses. This review presents the major contribution of the French scientific academic community in the field of electrochemical sensors and electroanalytical methods within the last 20 years. From the well-known polarography to the up-to-date generation of functionalized interfaces, the different strategies dedicated to analytical performances improvement are exposed: stripping voltammetry, solid mercury-free electrode, ion selective sensor, carbon based materials, chemically modified electrodes, nano-structured surfaces. The paper particularly emphasizes their advantages and limits face to the last Water Frame Directive devoted to the Environmental Quality Standards for heavy metals. Recent trends on trace metal speciation as well as on automatic “on line” monitoring devices are also evoked. PMID:24818124

Understanding the paradox of selenium contamination in mercury mining areas: high soil content and low accumulation in rice.

PubMed

Zhang, Hua; Feng, Xinbin; Jiang, Chengxin; Li, Qiuhua; Liu, Yi; Gu, Chunhao; Shang, Lihai; Li, Ping; Lin, Yan; Larssen, Thorjørn

2014-05-01

Rice is an important source of Se for billions of people throughout the world. The Wanshan area can be categorized as a seleniferous region due to its high soil Se content, but the Se content in the rice in Wanshan is much lower than that from typical seleniferous regions with an equivalent soil Se level. To investigate why the Se bioaccumulation in Wanshan is low, we measured the soil Se speciation using a sequential partial dissolution technique. The results demonstrated that the bioavailable species only accounted for a small proportion of the total Se in the soils from Wanshan, a much lower quantity than that found in the seleniferous regions. The potential mechanisms may be associated with the existence of Hg contamination, which is likely related to the formation of an inert Hg-Se insoluble precipitate in soils in Wanshan. Copyright © 2014 Elsevier Ltd. All rights reserved.

Heavy metals in marine fish meat and consumer health: a review.

PubMed

Bosch, Adina C; O'Neill, Bernadette; Sigge, Gunnar O; Kerwath, Sven E; Hoffman, Louwrens C

2016-01-15

The numerous health benefits provided by fish consumption may be compromised by the presence of toxic metals and metalloids such as lead, cadmium, arsenic and mercury, which can have harmful effects on the human body if consumed in toxic quantities. The monitoring of metal concentrations in fish meat is therefore important to ensure compliance with food safety regulations and consequent consumer protection. The toxicity of these metals may be dependent on their chemical forms, which requires metal speciation processes for direct measurement of toxic metal species or the identification of prediction models in order to determine toxic metal forms from measured total metal concentrations. This review addresses various shortcomings in current knowledge and research on the accumulation of metal contaminants in commercially consumed marine fish globally and particularly in South Africa, affecting both the fishing industry as well as fish consumers. © 2015 Society of Chemical Industry.

Is there a relationship between tea intake and maternal whole blood heavy metal concentrations?

PubMed

Colapinto, Cynthia K; Arbuckle, Tye E; Dubois, Lise; Fraser, William

2016-09-01

The aim of this analysis was to examine the association between tea intake during pregnancy and maternal and infant metal exposures. Data from the Maternal-Infant Research on Environmental Chemicals (MIREC) Study, a pan-Canadian pregnancy cohort, were used. All participants with a gestational age of ⩾20 weeks (n=1954) with available biomarkers were included. Geometric means (GMs) for lead, arsenic, mercury, cadmium and manganese in maternal (first and third trimesters) and cord blood, as well as speciated arsenic in maternal urine in the first trimester, were calculated for participants who drank regular, green or herbal tea and for those who did not. Differences between groups were examined using chi-square tests. Adjusted least squares geometric means (LSGMs) were estimated by tea intake, controlling for factors such as country of birth, coffee intake and maternal smoking. Concentrations of all metals were above the limits of detection in most participants in the first trimester: lead (GM): 0.62 μg/dl), mercury (GM: 2.99 nmol/l); cadmium (GM 1.93 nmol/l), arsenic (GM 9.75 nmol/l) and manganese (GM 160.1 nmol/l). Adjusted LSGMs for lead in the first trimester were higher for tea drinkers than for those who were non-tea drinkers (LSGM 0.65 μg/dl, 95%CI: 0.62, 0.69 and 0.61 μg/dl, 95%CI: 0.59, 0.62), and there was evidence of a dose-response relationship for green and herbal tea. Those who consumed herbal tea in the third trimester had significantly higher third trimester maternal and cord blood lead concentrations than non-herbal tea drinkers. This study provides evidence of an association between blood lead concentrations and green or herbal tea consumption. However, the GM blood lead concentrations of the highest tea consumers were still less than 1 μg/dl and within the normal range of blood lead concentrations in the Canadian population.

A COMPARISON OF URINARY ARSENIC SPECIATION VIA DIRECT NEBULIZATION AND ON-LINE PHOTOOXIDATION-HYDRIDE GENERATION WITH DETECTION BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY

EPA Science Inventory

Arsenic speciation continues to be important in assessing human and environmental exposure risk. Urinary arsenic analysis provides information on recent arsenic exposure. In this study, two sample introduction pathways: direct nebulization (DN) and hydride generation (HG) were ut...