Mercury Fractions Research Articles

Mode of Occurrence and Thermal Stability of Mercury in Coal†

Mode of occurrence of mercury in three coals was studied using sequential selective extraction, physical separation, and thermal treatment methods. Mercury speciation in the selected coals was determined using a five step sequential selective extraction method showing associations of mercury fractions with the organic and mineral structure in the analyzed coals. One of the coals was further subjected to thermal treatment with results revealing release of the organo-complexed mercury from coal at temperatures below 400 °C, while the mercury fraction associated with the coal mineral lattice was found to be the more stable form, released at temperatures of 600 °C. The mercury content was also determined for a selected range of coal density fractions showing strong correlation between mercury concentration in coal and the coal density fractions. The heaviest density fraction of the coal exhibited the largest ash as well as the highest pyritic sulfur content. Previous studies have established a strong relationship between mercury and the pyritic sulfur in coal, which was also confirmed in this work.

Experimental study of mass-independence of Hg isotope fractionation during photodecomposition of dissolved methylmercury

Experiments modelling photolytic decomposition of methylmercury chloride in aqueous solutions of different chemical composition have been performed. Ion-exchange chromatographic separation using Chelex® 100 resin was used in order to separate methylmercury from inorganic mercury prior to the isotope ratio measurements by solution nebulization multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The performance of the chromatographic separation has been evaluated in terms of recovery of both methylmercury and inorganic Hg using synthetic solutions. Both mass-dependent and mass-independent fractionation of Hg isotopes concomitant with the decomposition process have been observed. Mass-independent Hg isotope fractionation (MIF) resulted in selective enrichment of 199Hg and 201Hg relative to the other isotopes in the methylmercury molecules and has been attributed to the magnetic isotope effect. The highest extent of MIF of Hg isotopes, expressed as Δ199Hg and Δ201Hg values, has been observed in acidified solution with low concentration of total dissolved solids (TDS). Progressive decrease in Δ199Hg and Δ201Hg values in acidified solution with higher concentration of TDS, alkaline solutions of both low and high concentration of TDS, and in a solution of ascorbic acid has been attributed to suppression of the radical pair reaction mechanism, responsible for the occurrence of the magnetic isotope effect, by substances acting as radical scavengers, such as OH− or ascorbic acid. The data obtained in this study demonstrate the significance of spin chemistry effects in the isotope fractionation of mercury.

Species-Specific Stable Isotope Fractionation of Mercury during Hg(II) Methylation by an Anaerobic Bacteria (Desulfobulbus propionicus) under Dark Conditions

This work reports the first results on the stable isotope fractionation of Hg during methylation by anaerobic bacteria under dark conditions. The GC-MC-ICPMS methodology employed is capable of simultaneously measuring the species-specific isotopic composition of different Hg species within the same sample. We have studied Hg isotopic fractionation caused by methylation of Hg(II) standard reference material NIST-3133 in the presence of the pure bacterial strain Desulfobulbus propionicus MUD10 (DSM 6523) under fermentative conditions. We have measured the isotopic composition of Hg(II) and monomethyl mercury (MMHg) in these cultures as a function of time and calculated delta-values for both species versus the starting material (NIST-3133) as a delta-zero standard. Two different strategies for the incubation were applied: single sampling cultures and a continuous sampling culture. The results obtained have shown that under the conditions employed in this work the methylation of Hg(II) causes mass-dependent fractionation of the Hg isotopes for both Hg(II) substrate and produced MMHg. Such a process occurred under the exponential growth of the bacteria which preferentially methylate the lighter isotopes of Hg. After 96 h for the continuous culture and 140 h for the single sampling cultures, we observed a change in the fractionation trend in the samples at a similar cell density value (ca. 6.0 x 10(7) cells mL(-1)) which suggests the increasing contribution of a simultaneous process balancing methylation extent such as demethylation. Assuming that Rayleigh type fractionation conditions are met before such suppression, we have obtained a alpha(202/198) fractionation factor of 1.0026 +/- 0.0004 for the single sampling cultures.

Variations in Stable Isotope Fractionation of Hg in Food Webs of Arctic Lakes

Biotic and abiotic fractionation of mercury (Hg) isotopes has recently been shown to occur in aquatic environments. We determined isotope ratios (IRs) of Hg in food webs (zooplankton, chironomids, Arctic char) and sediments of 10 Arctic lakes from four regions and investigated the extent of Hg isotope fractionation. Hg IRs were analyzed by multicollector inductively coupled plasma mass spectrometry (MC-ICP/MS). Hg mass independent fractionation (MIF; Delta(199)Hg) and mass dependent fractionation (MDF; delta(202)Hg) were calculated and compared among samples. IRs of Hg in sediment were characterized mainly by MDF and low MIF (Delta(199)Hg -0.37 to 0.74 per thousand). However, all biota showed evidence of MIF, most pronounced in zooplankton (Delta(199)Hg up to 3.40 per thousand) and char (Delta(199)Hg up to 4.87 per thousand). Zooplankton takes up highly fractionated MeHg directly from the water column, while benthic organisms are exposed to sedimentary Hg, which contains less fractionated Hg. As evidenced by delta(13)C measurements, benthic chironomids make up a large proportion of char diet, explaining in part why MIF(char) < MIF(zooplankton) in lakes, where both samples were measured. Hg IRs in char varied among regions, while char from lakes from each region showed similar degrees of MIF. A MIF-offset was derived representing the mean MIF difference between sediment and fish, and indicated that fish in two regions retain sediment signatures altered by a consistent offset. Due to its minimal lake-to-catchment area and very high water retention time ( approximately 330 years), the meteor impact crater lake (Pingualuk) reflects a "pure" atmospheric Hg signature, which is modified only by aqueous in-lake processes. All other lakes are also affected by terrestrial Hg inputs and sediment processes.

A case for in vivo mass‐independent fractionation of mercury isotopes in fish

The recent discovery of mass‐independent fractionation of mercury isotopes allows new constraints to be placed on the mercury cycle. Here we report new Hg isotopic analyses of zooplankton and fish from different trophic levels of a freshwater lake (Lake Jackson, Florida) bearing systematic mass‐independent fractionation of mercury isotopes. Fish muscle tissues show a progressive enrichment in the odd‐mass mercury isotopes having odd atomic mass numbers (199 and 201) with increasing trophic level. Trophic level was determined based on nitrogen isotopic composition as well as fish stomach content. Zooplankton in the lake contain mercury with Δ199Hg and Δ201Hg values of +0.43 (±0.07)‰ and +0.44 (±0.07)‰, respectively. The Δ199Hg values increase by ∼1‰ from ∼+0.4‰ in zooplankton, juvenile bluegill, and several other small fishes to Δ199Hg = +1.36‰ for the Florida gar, which is the top predator fish in the lake. Previous observations of odd‐mass‐number isotope enrichment of mercury have been explained by photoreduction and demethylation of methyl mercury in the water column or as isotope effects related to microbial methylation. However, our data and the data of Jackson et al. (2008) are also consistent with in vivo production of mass‐independent fractionation. Considering the alternatives, mass‐independent fractionation by metabolic processes is the most straightforward explanation for the mercury isotope data. There are two known mechanisms for mass‐independent fractionation of mercury, i.e., the nuclear volume effect and the magnetic isotope effect. While the data are insufficient to serve as proof, the magnitude of the mass‐independent effect and the nearly equal enrichment of 199Hg and 201Hg seem most suggestive of a magnetic isotope effect.

Evaluation of Two In Vitro Protocols for Determination of Mercury Bioaccessibility: Influence of Mercury Fractionation and Soil Properties

Soil ingestion by children can be a significant exposure pathway to mercury (Hg). Unfortunately, no reliable in vivo results for Hg oral bioavailability determination in soils have been published. In vitro extractions enable the assessment of metals' bioaccessibility, which is an estimate of oral bioavailability. Therefore, the goal of this study was to evaluate two in vitro protocols (CDM (Camp Dresser and Mc Kee Inc.) and IVG (In Vitro Gastrointestinal)) for determination of Hg bioaccessibility in soils using pure Hg-compounds, reference materials (CRM 025-050 and ERM-CC580), and field-collected soils with elevated Hg concentrations. The influence of Hg fractionation and soil properties on Hg bioaccessibility was also investigated. In the field-collected soils, IVG bioaccessibility ranged from 1.5 to 7.5%, and was always below 3.15%, using the CDM method. Mercury bioaccessibility in CRM 025-050 was 61.5 and 34.7%, using IVG and CDM protocols, respectively, whereas Hg bioaccessibility was much lower in the certified sediment sample ERM-CC580 (<7%). Overall, the CDM protocol resulted in lower Hg bioaccessibility values. The water-soluble and exchangeable Hg fraction was highly correlated with gastrointestinal bioaccessibility (r=0.99, p<0.001 for both methods) and this fraction could be a potentially good indicator of Hg bioaccessibility. Because the IVG method is less time-consuming than the CDM protocol and includes organic physiological components which seem to increase Hg bioaccessibility, it might be preferred for determination of Hg bioaccessibility.

Simple mercury fractionation in biological samples by CV AAS following microwave-assisted acid digestion or TMAH pre-treatment

A simple and reliable method to determine total and inorganic mercury in biological certified reference material (CRM) by cold vapor atomic absorption spectrometry (CV AAS) is proposed. After the CRM treatment at room temperature with tetramethylammonium hydroxide (TMAH), inorganic mercury is determined by CV AAS. Total mercury is measured by the same technique, after sample acid digestion in a microwave oven. Organic mercury, basically methylmercury, is obtained by difference. In both procedures, the quartz tube is kept at room temperature. By means of analysis of the following reference materials: pig kidney, lobster hepatopancreas, dogfish liver and mussel tissue, it was clear that the difference between the total and inorganic mercury concentrations agrees with the methylmercury concentration. Only one calibration curve against aqueous standards in acidic medium was carried out for both procedures. The concentrations obtained by both procedures are in agreement with the certified values according to the t-test at a 95% confidence level. The relative standard deviations were lower than 3.0% for digested CRM and 6.0% for CRM treated with TMAH for most of the samples. The limits of detection in the samples were 0.02 µg g − 1 and 0.04 µg g − 1 for inorganic and total Hg, respectively, since the sample mass for total mercury was half of that for inorganic mercury determination. Simplicity and high efficiency without using chromatographic techniques are some of the qualities of the proposed method, being adequate for fractionation analysis of mercury in biological samples.

Mass dependent stable isotope fractionation of mercury during mer mediated microbial degradation of monomethylmercury

Controlling bioaccumulation of toxic monomethylmercury (MMHg) in aquatic food chains requires differentiation between biotic and abiotic pathways that lead to its production and degradation. Recent mercury (Hg) stable isotope measurements of natural samples suggest that Hg isotope ratios can be a powerful proxy for tracing dominant Hg transforming pathways in aquatic ecosystems. Specifically, it has been shown that photo-degradation of MMHg causes both mass dependent (MDF) and mass independent fractionation (MIF) of Hg isotopes. Because the extent of MDF and MIF observed in natural samples (e.g., fish, soil and sediments) can potentially be used to determine the relative importance of pathways leading to MMHg accumulation, it is important to determine the potential role of microbial pathways in contributing to the fractionation, especially MIF, observed in these samples. This study reports the extent of fractionation of Hg stable isotopes during degradation of MMHg to volatile elemental Hg and methane via the microbial Hg resistance ( mer) pathway in Escherichia coli carrying a mercury resistance ( mer) genetic system on a multi-copy plasmid. During experimental microbial degradation of MMHg, MMHg remaining in reactors became progressively heavier (increasing δ 202Hg) with time and underwent mass dependent Rayleigh fractionation with a fractionation factor α 202/198 = 1.0004 ± 0.0002 (2SD). However, MIF was not observed in any of the microbial MMHg degradation experiments indicating that the isotopic signature left by mer mediated MMHg degradation is significantly different from fractionation observed during DOC mediated photo-degradation of MMHg. Additionally, a clear suppression of Hg isotope fractionation, both during reduction of Hg(II) and degradation of MMHg, was observed when the cell densities increased, possibly due to a reduction in substrate bioavailability. We propose a multi-step framework for understanding the extent of fractionation seen in our MMHg degradation experiments and, based on estimates of the rates of the various steps involved in this mer mediated pathway, suggest which steps in the process could contribute towards the observed extent of fractionation. This framework suggests that at lower cell densities catalysis by MerB was the rate limiting step while at higher cell densities transport into the cell, which does not cause fractionation, became the rate limiting step. In addition to presenting evidence for absence of MIF during mer mediated Hg transformations, based on the nature of Hg compounds and microbe–Hg interactions, we suggest that the nuclear spin dependent MIF (i.e., the magnetic isotope effect) is also unlikely to occur during other non mer mediated ‘dark’ microbial Hg transformations (e.g., formation of MMHg and oxidative degradation of MMHg). Because of the important implications of the absence of MIF during biological processes on Hg isotope systematics, we discuss theoretical considerations and experimental strategies that could be used to confirm this suggestion.

Quantification and fractionation of mercury in soils from the Chatian mercury mining deposit, southwestern China

Contents of total Hg and Hg fraction, organic matter, pH, grain size and chemical composition were measured to investigate the pollution characteristics and binding behavior of Hg in soils collected from the Chatian Hg mining deposit (CMD), southwestern China. The average concentration of Hg concentration in the CMD soils was 155 and 1,315 times higher than that in control soils and Chinese soils, respectively, suggesting that the CMD soils were heavily contaminated by the element. The finding was confirmed by Müller geoaccumulation index assessment with 75% very seriously polluted, 6.25% highly to very highly polluted and 18.75% moderately to highly polluted. Hg sources in the region were natural and anthropogenic: in addition to the pedogenic process and original geochemical situation, human mining-refining activities have also seriously impacted the redistribution of Hg in soils, especially in paddy soils. Based on the BCR protocol, soil Hg was divided into exchangeable (EXC), amorphous Fe-Mn oxides (AFe-MnOX), organic-crystalline iron oxides (OM-CFe) and residual (RES) fraction. The average percentage of the four fractions in the CMD followed the trend: RES (85.77%) > OM-CFe (12.44%) > AFe-MnOX (0.93%) ≥ EXC (0.86%), suggesting that the majority proportion of soil Hg in the study area remained of residual form inside the soil mineral matrix. However, their concentrations and percentages significantly varied among different locations and land use types. Soil physico-chemical parameters were key factors affecting the presence of Hg fraction. Generally, Hg fraction concentrations were positively correlated with the sand contents and soil pH values, which was presumably due to the basic anthropogenic input of Hg-containing materials and their similarity to sand in physical characteristics. However, organic matter caused adsorption-fixation and reduction-volatilization to coexist, which had opposite effects on Hg concentrations in soil, consequently exhibiting its dual nature.

Natural Mercury Isotope Variation in Coal Deposits and Organic Soils

There is a need to distinguish among sources of Hg to the atmosphere in order to more fully understand global Hg pollution. In this study we investigate whether coal deposits within the United States, China, and Russia-Kazakhstan, which are three of the five greatest coal-producing regions, have diagnostic Hg isotopic fingerprints that can be used to discriminate among Hg sources. We also investigate the Hg isotopic composition of modern organic soil horizons developed in areas distant from point sources of Hg in North America. Mercury stored in coal deposits displays a wide range of both mass dependent fractionation (MDF, delta202Hg) and mass independent fractionation (MIF, delta201Hg). delta202Hg varies in coals by 3 per thousand and delta201Hg varies by 0.9 per thousand. Combining these two Hg isotope signals results in what may be a unique isotopic "fingerprint" for many coal deposits. Mass independent fractionation of mercury has been demonstrated to occur during photochemical reactions of mercury. This suggests that Hg found in most coal deposits was subjected to photochemical reduction near the Earth's surface prior to deposition. The similarity in MDF and MIF of modern organic soils and coals from North America suggests that Hg deposition from coal may have imprinted an isotopic signature on soils. This research offers a new tool for characterizing mercury inputs from natural and anthropogenic sources to the atmosphere and provides new insights into the geochemistry of mercury in coal and soils.

Mercury fractionation in stream sediments from the Quadrilátero Ferrífero gold mining region, Minas Gerais State, Brazil

The Iron Quadrangle (IQ) region, located in the state of Minas Gerais, has been the most important gold producing area in Brazil since the end of seventeenth century. The use of mercury for gold amalgamation in small scale mines has been responsible for large release of Hg to aquatic and terrestrial environments during 300 years of mining. The present work sought to evaluate the fractionation of Hg in stream sediments is the southern region of the IQ by utilizing sequential extraction. Since mobility and availability of Hg are related to its distribution among sediment partitions, fractionation methods provide detailed information on the ecotoxicological impact and risks associated to the presence of Hg in sediments. The total Hg concentration varied from 179.3 to 690.1 microg kg( - 1) and Hg(0) accounted for the majority at all sample sites, ranging from 42% to 56% of the total.

Isotopic fractionation of mercury induced by reduction and ethylation

Isotope ratio measurements characterizing (202)Hg/(200)Hg in NIST SRM 3133 Mercury Standard Solution were undertaken by multicollector inductively coupled plasma mass spectrometry employing NIST SRM 997 Tl for mass bias correction by use of the slope and the intercept obtained from a natural logarithmic plot of each session of measurements of (202)Hg/(200)Hg against (205)Tl/(203)Tl. The calculated value of 1.285333 +/- 0.000192 (mean and one standard deviation, n = 40) for the mass bias corrected (202)Hg/(200)Hg was then used for mass bias correction of other Hg isotope pairs. Ratios of 0.015337 +/- 0.000011, 1.68770 +/- 0.00054, 2.3056 +/- 0.0015, 1.3129 +/- 0.0013, 2.9634 +/- 0.0038, and 0.67937 +/- 0.0013 (expanded uncertainty, k = 2) were obtained for (196)Hg/(198)Hg, (199)Hg/(198)Hg, (200)Hg/(198)Hg, (201)Hg/(198)Hg, (202)Hg/(198)Hg, and (204)Hg/(198)Hg, respectively. Reduction of Hg(II) to Hg(0) in solutions of SRM 3133 was then undertaken using SnCl(2), NaBH(4), UV photolysis in the presence of formic acid, and ethylation of Hg(II) using NaBEt(4.) These reactions induced significant isotope fractionation with maximum values of 1.17 +/- 0.07, 1.08 +/- 0.09, 1.34 +/- 0.07, and 3.59 +/- 0.09 per thousand (one standard deviation, 1SD, n = 5) for delta (202/198)Hg relative to the initial isotopic composition in the solution following 85-90% reduction of the Hg by SnCl(2), NaBH(4), UV photolysis, and ethylation with NaBEt(4), respectively. Mass-dependent fractionation was found to be dominant for all reduction processes.

Pattern and pathways for mercury lifespan bioaccumulation in Carcinus maenas

Carcinus maenas is an important and exploited natural resource in temperate estuaries, being consumed by local populations and also used as fish bait. Through bioaccumulation and bioamplification processes occurring in polluted estuarine ecosystems, this species may directly or indirectly represent a major pathway for Human contamination. No information is available on the overall lifespan bioaccumulation pattern of mercury for this species, which would be an invaluable tool for assessing the risks associated with C. maenas harvest in contaminated areas. Taking that in mind, the main objectives of this work were to clarify the lifespan bioaccumulation pattern of mercury for this species. A consistent lifespan accumulation pattern was found for this species, both for total and organic mercury, and coherent differences were found between genders, suggesting different physiological responses to contamination. From our results two scenarios emerge: (a) for low mercury contamination areas where the diet is the major pathway for metal uptake, with higher levels in muscle and hepatopancreas (twice as high as in gills) and higher organic mercury fractions (as high as 80–90% in muscle), crabs bioaccumulate with age and (b) on high contaminated areas, environmental exposure is predominant, with higher levels found in gills (reaching 0.8 mg kg −1), lower organic fractions and no mercury increment with age. Detoxification strategies, dietary differences and species mobility may account for these two accumulation patterns.

The role of two sediment-dwelling invertebrates on the mercury transfer from sediments to the estuarine trophic web

The annual total and organic mercury bioaccumulation pattern of Scrobicularia plana and Hediste diversicolor was assessed to evaluate the potential mercury transfer from contaminated sediments to estuarine food webs. S. plana was found to accumulate more total and organic mercury than H. diversicolor, up to 0.79 mg kg −1 and 0.15 mg kg −1 (wet weight) respectively, with a maximum annual uptake of 0.21 mg kg −1 y −1, while for methylmercury the annual accumulation was similar between species and never exceeded 0.045 mg kg −1 y −1. The higher organic mercury fraction in H. diversicolor is related to the omnivorous diet of this species. Both species increase methylmercury exposure by burrowing activities and uptake in anoxic, methylmercury rich sediment layers. Integration with the annual biological production of each species revealed mercury incorporation rates that reached 28 μg m −2 y −1, and to extract as much as 11.5 g Hg y −1 (of which 95% associated with S. plana) in the 0.4 km 2 of the most contaminated area, that can be transferred to higher trophic levels. S. plana is therefore an essential vector in the mercury biomagnification processes, through uptake from contaminated sediments and, by predation, to transfer it to economically important and exploited estuarine species.

Assembly and Study of Different Mercury Cells with Known Impurity Content and Isotopic Composition

The “Centro Espanol de Metrologia” is carrying out a project to improve the knowledge of the influence of impurities and isotopic composition on the temperature of the mercury triple point. High-purity mercury from the Almaden mine (stated purity of 99.9998%) was further purified by vacuum distillation. Three mercury fractions, the original mercury from Almaden and two distilled fractions, were characterized in terms of both impurities and isotopic composition and used to measure the mercury triple point. The original mercury sample contained silver at 560 ng · g−1 as the main impurity while the impurity levels were much lower (silver < 1 ng · g−1) in the two distilled fractions. The isotopic composition of the distilled fractions showed delta values, expressed as \(1,000\times(^{198/202}{\rm Hg}_{\rm sample}-^{198/202}\,{\rm Hg}_{\rm reference})/^{198/202}{\rm Hg}_{\rm reference}\), of 1.37±0.07 (1σ) for the first distilled sample and −1.55±0.03 (1σ) for the second distilled sample with reference to the original Almaden mercury. For the measurement of the mercury triple point, an alcohol stirred bath was used that allowed two cells to be compared nearly simultaneously. It was observed that the presence of the silver impurities in the high-purity mercury modified slightly the mercury triple point while the effect of variations in the isotopic composition can be considered negligible.

Determination of monomethylmercury in low- and high-polluted sediments by microwave extraction and gas chromatography with atomic fluorescence detection

The analysis of monomethylmercury (MMHg) in sediments is a difficult task because both very low concentrations and interconversion between species especially in highly polluted samples are frequent. This work features a general strategy for real sediment analysis with preconcentration and/or clean-up steps for both low- and high-polluted sediments to control these specific problems. The extraction conditions have been optimized using closed-vessel microwave-assisted heating with acidic extractants. The analysis has been carried out by the injection of ethylated derivatives of the analytes into a capillary gas chromatographic system coupled to fluorescence spectrometry. When using 6 M HNO 3, the most labile inorganic mercury fraction as well as MMHg were extracted from the sediment but there was still some inorganic mercury that remained un-extracted. MMHg was stable and quantitatively recovered by applying this procedure. The role of the labile inorganic fraction on artifact MMHg generation has been evaluated and it has been found to be highly variable depending on the sediments’ geochemical characteristics. Therefore, for high-polluted sediments (inorganic mercury concentration above 500 ng g −1) a clean-up step with dichloromethane has been used before ethylation, whereas for low content samples, preconcentration under nitrogen stream at room temperature has been optimized. Both steps can be combined if necessary. MMHg content has been found in good agreement with the certified value for the reference materials (IAEA-405 and ERM-CC580).

Mercury mobility and bioavailability in soil from contaminated area

The mobility and bioavailability of mercury in the soil from the area near a plant using elemental mercury for manufacturing thermometers, areometers, glass energy switches and other articles made of technical glass has been evaluated. Mercury has been determined by sequential extraction method and with additional thermo desorption stage to determine elemental mercury. The procedure of sequential extraction involves five subsequent stages performed with the solutions of chloroform, deionized water, 0.5 M HCl, 0.2 M NaOH and aqua regia. The mean concentration of total mercury in soil was 147 ± 107 μg g−1 dry mass (range 62–393), and the fractionation revealed that mercury was mainly bound to sulfides 56 ± 8% (range 45–66), one of the most biounavailable and immobile species of mercury in the environment. The fractions that brought lower contribution to the total mercury content were semi-mobile humic matter 22 ± 9% (range 11–34) and elemental mercury 17 ± 5% (range 8–23). The contributions brought by the highly mobile and toxic organomercury compounds were still lower 2.3 ± 2.7% (range 0.01–6.5). The lowest contributions brought the acid-soluble mercury 1.5 ± 1.3% (range 0.1–3.5) and water-soluble mercury 1.0 ± 0.3% (range 0.6–1.7). The surface layer of soil (0–20 cm) was characterized by higher mercury concentrations than that of the subsurface soil (60–80 cm), but the fractional contributions were comparable. The comparison of mercury fractionation results obtained in this study for highly polluted soils with results of fractionation of uncontaminated or moderately contaminated samples of soil and sediments had not shown significant statistical differences; however, in the last samples elemental mercury is usually present at very low concentrations. On the basis of obtained correlation coefficients it seems that elemental mercury soils from “Areometer” plant are contaminated; the main transformation is its vaporization to atmosphere and oxidation to divalent mercury, probably mainly mediated by organic matter, and next bound to humic matter and sulfides.

Mercury fluxes between an impacted coastal lagoon and the Atlantic Ocean

The objective was to estimate the seasonal and inter-tidal variability of dissolved and particulate mercury fluxes between the Ria de Aveiro (Portugal) and the Atlantic Ocean. The mercury fluxes were estimated by means of a two-dimensional vertically integrated hydrodynamic model. Results showed that the particulate fraction plays an important role in the transport of mercury while the contribution of the seston fraction to the transport of mercury was always <0.5%. During spring tides, in summer, about 2% of mercury transported in seston was present in an organic form. The mass balance for the mercury fractions revealed that the mercury export to the Atlantic Ocean varied with season and tidal regime, mainly in terms of the relative importance of the dissolved and particulate fractions. An approximate range of values for the annual mass balance between 42 and 77 kg shows that the export of dissolved and particulate mercury makes little impact on the near shore region of the Atlantic Ocean and that the recovery of the lagoon from mercury contamination is likely to remain a long-term issue.

3557 POSTER Phase I study of docetaxel, oxaliplatin and S-1 (DOS) for patients with advanced gastric cancer

Content of heavy metals, including mercury, determines the method of management and disposal of sewage sludge. Excessive concentration of mercury in composts used as organic fertilizer may lead to accumulation of this element in soil and plant material. Fractionation of mercury in sewage sludge and composts provides a better understanding of the extent of mobility and bioavailability of the different mercury species and helps in more informed decision making on the application of sludge for agricultural purposes. The experimental setup comprises the composing process of the sewage sludge containing 13.1 mg kg−1 of the total mercury, performed in static reactors with forced aeration. In order to evaluate the bioavailability of mercury, its fractionation was performed in sewage sludge and composts during the process. An analytical procedure based on four-stage sequential extraction was applied to determine the mercury content in the ion exchange (water soluble and exchangeable Hg), base soluble (Hg bound to humic and fulvic acid), acid soluble (Hg bound to Fe/Mn oxides and carbonates) and oxidizable (Hg bound to organic matter and sulphide) fractions. The results showed that from 50.09% to 64.55% of the total mercury was strongly bound to organo-sulphur and inorganic sulphide; that during composting, increase of concentrations of mercury compounds strongly bound with organic matter and sulphides; and that mercury content in the base soluble and oxidizable fractions was strongly correlated with concentration of dissolved organic carbon in those fractions.

Mercury fractionation in sediments of the Lower Vistula River (Poland)

Abstract The Vistula is the second largest river in the Baltic Sea catchment area and provides one of the main inputs to the Baltic. The river and its tributaries flow through some of the major industrialized and urbanised regions of Poland, making it one of the most highly human-impacted rivers in Europe. Although the river status is monitored routinely, little is known about mercury forms in the sediments. This study examines mercury fractionation in the sediments of the lower part of the Vistula River. The results show that the cities along this stretch of river have a relatively low impact on both the mercury forms found in the sediment and its bioavailability in the floodplain soils. The mean concentration of total mercury in the sediments was 65 ± 14 ng g-1 dry mass (range 54-92), calculated as the sum of mercury concentrations in the individual fractions. The most abundantly represented of these fractions were mercury bound to sulphides (68 ± 11%, range 55-82%) and humic matter (19 ± 10%, range 10-35%), with lower fractions of water-soluble mercury (6.9 ± 2.9%, range 5.1-13%) and organomercury compounds (6.4 ± 5.3%, range 0.6-13%). The least abundant fraction observed was acid-soluble mercury (0.3 ± 0.2%, range 0.1-0.6%). Similar concentrations and fractionation were observed in floodplain soils from Kiezmark, collected 1, 10 and 50 meters from the riverbed.