Chemical availability of mercury in stream sediments from the Almadén area, Spain

The chemical speciation, fractionation and availability of mercury in sediments from a cinnabar mining area (Almadén, Spain) was studied with different extraction and analytical procedures, in order to determine the degree to which the ecosystem is harmed by this pollutant. Three total extraction procedures, a sequential extraction and the speciation of organo-mercury compounds were performed in nine sediment samples. In the study area, although concentrations of mercury can be extremely high (up to 1,000 mg kg(-1)), no organomercury compounds were detected (< 2 microg kg(-1) and the availability of this element seems restricted. One of the methods for total extraction presented considerably lower recovery in Almadén's sediments, yet the results were controlled with certified reference materials. This disagreement was attributed to the fact that the mercury is in a refractory form. Sequential extraction was able to show that most of the mercury is associated with sulfides (probably as metacinnabar) or in the residual refractory phase (probably as red cinnabar).     

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.     

Distribution of mercury in chemical fractions of contaminated urban soils of Middle Amur,Russia

The distribution of mercury (Hg) in fractions of urban soils from two industrial cities in the Russian Far East which are subject to varying degrees of Hg contamination was examined. The speciation scheme applied was based on routine chemical extraction methods used in soil investigations. Such an approach enables the Hg data to be brought into correlation with soil basic fractions and the fate of Hg bound to different soil components to be followed. Humic acids and a non-hydrolysable residue (humin), i.e. the soil fractions most refractory to microbiotic and chemical attack, were found to be principal Hg repositories in the soils studied. This pattern was equally observed for slightly, moderately and heavily contaminated soils. Hymatomelanic acids do not appear to be an efficient Hg concentrator. In heavily contaminated soils, Hg concentrations were evident in mobile fractions of fulvic acids as well as in those fractions extracted by H2O and 0.05 M Na2-EDTA pH 3. A portion of Hg extracted by 1 M HCl increased in lower horizons, reflecting relatively weakly bound Hg.     

Fractions and leaching characteristics of mercury in coal

A huge amount of coal is always stored in open spaces in coal-fired power plants before combustion. Mercury released from coal by rain or flowing water is an environmental risk and can cause contamination of the soil around the storage area. To better understand mercury pollution and to control mercury emission before combustion, it is necessary to determine the mobility and leaching characteristics of mercury from coal. In this study, we collected ten coal samples from one coal-fired power plant and proposed a sequential extraction procedure to get five fractions of mercury for evaluation. Elemental Hg was found as the most dominant fraction, and sulfate Hg was shown to be the second largest fraction. The mercury in the organic and the soluble fractions were not the major fractions, but they should still be considered because of their high mobility.     

Mercury emission and dispersion models from soils contaminated by cinnabar mining and metallurgy

The laboratory flux measurement system (LFMS) and dispersion models were used to investigate the kinetics of mercury emission flux (MEF) from contaminated soils. Representative soil samples with respect to total Hg concentration (26-9770 μg g(-1)) surrounding a decommissioned mercury-mining area (Las Cuevas Mine), and a former mercury smelter (Cerco Metalúrgico de Almadenejos), in the Almadén mercury mining district (South Central Spain), were collected. Altogether, 14 samples were analyzed to determine the variation in mercury emission flux (MEF) versus distance from the sources, regulating two major environmental parameters comprising soil temperature and solar radiation. In addition, the fraction of the water-soluble mercury in these samples was determined in order to assess how MEF from soil is related to the mercury in the aqueous soil phase. Measured MEFs ranged from less than 140 to over 10,000 ng m(-2) h(-1), with the highest emissions from contaminated soils adjacent to point sources. A significant decrease of MEF was then observed with increasing distance from these sites. Strong positive effects of both temperature and solar radiation on MEF was observed. Moreover, MEF was found to occur more easily in soils with higher proportions of soluble mercury compared to soils where cinnabar prevails. Based on the calculated Hg emission rates and with the support of geographical information system (GIS) tools and ISC AERMOD software, dispersion models for atmospheric mercury were implemented. In this way, the gaseous mercury plume generated by the soil-originated emissions at different seasons was modeled. Modeling efforts revealed that much higher emissions and larger mercury plumes are generated in dry and warm periods (summer), while the plume is smaller and associated with lower concentrations of atmospheric mercury during colder periods with higher wind activity (fall). Based on the calculated emissions and the model implementation, yearly emissions from the "Cerco Metalúrgico de Almadenejos" decommissioned metallurgical precinct were estimated at 16.4 kg Hg y(-1), with significant differences between seasons.     

Total mercury determination in sand boxes from Montreal

Direct mercury analysis was successfully applied to determine trace levels of total mercury in samples from sand boxes in Montréal (Québec, Canada). Twenty sand boxes were sampled from across the city and divided into two size fractions, a fine fraction (<100 microm) and a whole fraction. The concentrations of mercury ranged from 1.6 to 35 microg Hg kg(-1) dry soil for the fine fraction and from 0.7 to 6 microg Hg kg(-1) dry soil for the whole fraction. The mercury concentrations correlated with the soil organic carbon content (R2= 0.67) in the sand. The ratio of the concentration of mercury in the fine over the whole fraction varied from 2.2 to 18. Using published soil ingestion rates for children, the calculated daily intake values varied from 0 to 0.5 ng Hg kg(-1) bw d(-1) with an estimated oral ingestion of 200 mg of sand and from 0.2 to 4.7 ng Hg kg(-1) bw d(-1) with an ingestion of 1750 mg of sand. None of the sand boxes contain sufficient amounts of mercury so as to exceed the currently accepted daily intake threshold of 0.105 microg Hg kg(-1) bw d(-1) established by Health Canada.     

Fractionation and ecotoxicological implication of potentially toxic metals in sediments of three urban rivers and the Lagos Lagoon,Nigeria, West Africa

The potential environmental impact of sediment-bound Cd, Cr, Cu, Pb and Zn in three trans-urban rivers in Lagos state and in the Lagos Lagoon was assessed by use of the modified Community Bureau of Reference (BCR) sequential extraction. The quality of the data was checked using BCR CRM 143R and BCR CRM 701. Good agreement was obtained between found and certified/indicative values. Of the rivers, the Odo-Iyaalaro, was generally the most contaminated and the Ibeshe the least. Higher concentrations of metals were generally found in the dry season compared to the wet season. Cadmium and Zn were released mostly in the acid exchangeable step of the sequential extraction, indicating that they have the greatest potential mobility and bioavailability of the analytes studied. Chromium and Cu were associated mainly with the reducible and oxidisable fractions, and Pb predominantly with the reducible and residual fractions. Sediments with the highest pseudototal analyte concentrations also released higher proportions of analytes earlier in the sequential extraction procedure. The study suggests that, during the dry season, potentially toxic metals (PTM) may accumulate in sediments in relatively labile forms that are released and can potentially be transported or bioaccumulate in the rainy season. Application of risk assessment codes and Hankanson potential risk indices indicated that Cd was the element of greatest concern in the Lagos Lagoon system. The study indicated that there is a need to strengthen environmental management and pollution control measures to reduce risk from PTM, but that even relatively simple strategies, such as seasonal restrictions on dredging and fishing, could be beneficial.     

Mercury in chemical fractions of recent pelagic sediments of the sea of Japan

The distribution of mercury (Hg) in chemical fractions (H2O, 0.05 M Na2-EDTA pH 3, 1 M HCl, humic and fulvic acids, and non-hydrolysing residue) of recent pelagic sediment cores of the Sea of Japan (East Sea) was studied. Total Hg content in the sediments was rather low: 83 +/- 30 (21-173) etag g(-1), indicating the absence of substantial specific sources of the element in the deep part of the sea. Hg content within the sediment core varied by a factor of 1.3-1.8, showing peaks that coincide with the near-surface and buried sediment slices of light brown and brown "oxidized" colours and evidencing Hg redox-sensitive diagenetic redistribution. Hg exerted its maximum mobility in the near-surface sediment strata as a component of water-soluble organic matter. Despite the predominance of fulvic acids in extracted humus fractions, humic acids were a much more efficient concentrator for Hg (0-79 vs. 188-233 microg Hg g(-1) C(org), respectively). Nevertheless, the most refractory non-hydrolyzing residue (humin) fraction contained the principal Hg pool in the sediments. Hg content in all the extracted fractions decreased with core depth, thus indicating Hg immobilization as a principal tendency in Hg fate during post-depositional diagenesis.     

Controls on Mercury and Methylmercury Deposition for Two Watersheds in Acadia National Park, Maine

Throughfall and bulk precipitation samples were collected for two watersheds at Acadia National Park, Maine, from 3 May to 16 November 2000, to determine which landscape factors affected mercury (Hg) deposition. One of these watersheds, Cadillac Brook, burned in 1947, providing a natural experimental design to study the effects of forest type on deposition to forested watersheds. Sites that face southwest received the highest Hg deposition, which may be due to the interception of cross-continental movement of contaminated air masses. Sites covered with softwood vegetation also received higher Hg deposition than other vegetation types because of the higher scavenging efficiency of the canopy structure. Methyl mercury (MeHg) deposition was not affected by these factors. Hg deposition, as bulk precipitation and throughfall was lower in Cadillac Brook watershed (burned) than in Hadlock Brook watershed (unburned) because of vegetation type and watershed aspect. Hg and MeHg inputs were weighted by season and vegetation type because these two factors had the most influence on deposition. Hg volatilization was not determined. The total Hg deposition via throughfall and bulk precipitation was 9.4 μg/m²/year in Cadillac Brook watershed and 10.2 μg/m²/year in Hadlock Brook watershed. The total MeHg deposition via throughfall and bulk precipitation was 0.05 μg/m²/year in Cadillac Brook watershed and 0.10 μg/m²/year in Hadlock Brook watershed.     

Ambient elemental, reactive gaseous, and particle-bound mercury concentrations in New Jersey, U.S.: measurements and associations with wind direction

Two and a half years of data of ambient concentrations of elemental mercury (Hg(0)), reactive gaseous mercury (RGM), and particle-bound mercury (Hg(p)) were collected at measurement sites at Elizabeth, New Jersey and New Brunswick, New Jersey with Tekran sampling units. The data were processed, summarized, and analyzed from a variety of perspectives. Data quality control and quality assurance procedures are described. Wind direction and wind speed data for each of the sites were also collected. Significant temporal variations in concentrations of all three species were observed. Some significant directional variations were also seen. The sporadic nature of many of the temporal variations is consistent with and could reflect highly variable emissions patterns from anthropogenic mercury sources. Overall mean concentrations of all species were determined. These were, for Hg(0), Hg(p), and RGM respectively; 2.25 +/- 0.04 nanograms per cubic meter (ng/m(3)), 8.21 +/- 0.39 picograms per cubic meter (pg/m(3)), and 8.93 +/- 0.31 pg/m(3) (arithmetic means and 95% confidence intervals) at Elizabeth, and 2.15 +/- 0.02 ng/m(3), 10.73 +/- 0.45 pg/m(3), and 6.04 +/- 0.30 pg/m(3) at New Brunswick. Mean concentrations were determined for 16 different sectors representing wind directions. The impact of one known large source is suggested by these data. Reasons for some directional variations are not apparent and suggest a need for further investigation.     

Speciation of Trace Metals in Coastal Sediments of El-Mex Bay South Mediterranean Sea–West of Alexandria (Egypt)

Sediments of El-Mex Bay estuary on the southern Mediterranean Sea have been analyzed for trace metals after sediment fractionation by sequential leaching. A sequential extraction procedure was applied to identify forms of Mn, Cu, Cd, Cr, Zn and Fe. The five steps of the sequential extraction procedure partitioned metals into: CH₃COONH₄ extractable (F1); NaOAC carbonate extractable (F2); NH₂OH.HCl/CH₃COOH reducible extractable (F3); H₂O₂–HNO₃ organic extractable (F4) and NHO₃/HClO₄/HF acid soluble residue (F5). Extracted concentrations of trace metals analyzed after all five steps, were found to be (μg/g) for Mn: 1930.2, Cu: 165.3, Cd: 60.9, Cr: 386.3, Zn: 2351.3 and Fe: 10895. Most of elements were found in reducible fraction except Fe found in acid soluble residue, characterizing stable compounds in sediments. Labile (non-residual) fractions of trace elements (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis was used to understand and visualize the associations between the labile fractions of trace metals and certain forms, since Fe-and Mn-oxides play an important role in trace metals sorption within aquatic systems, especially within El-Mex Bay sediments that characterized by varying metal bioavailability.     

Fractionation and ecological risk of metals in urban river sediments in Zhongshan City, Pearl River Delta

Surface sediments collected from nine urban rivers located in Zhongshan City, Pearl River Delta, were analyzed for total concentration of metals with digestion and chemical fractionation adopting the modified European Community Bureau of Reference (BCR) sequential extraction procedure. The results showed that concentration and fractionation of metals varied significantly among the rivers. The total concentration of eight metals in most rivers did not exceed the China Environmental Quality Standard for Soil, Grade III. The potential ecological risk of metals to rivers were related to the land use patterns, in the order of manufacturing areas > residential areas > agriculture areas. The concentration of Pb in the reducible fraction was relatively high (60.0-84.3%). The dominant proportions of Cd, Zn and Cu were primary in the non-residual fraction (67.0%, 71.8% and 81.4% on average respectively), while the percentages of the residual fractions of Cr and Ni varied over a wide range (43-85% and 24-71% respectively). The approaches of the H?kanson ecological risk index and Secondary Phase Enrichment Factor were applied for ecological risk assessment and metal enrichment calculation. The results indicated Hg and Cd had posed high potential ecological risk to urban rivers in this region. Meanwhile, there was widespread pollution and high enrichment of Cu in river sediments in this region. Multiple regression analysis showed that five water quality parameters (pH, DO, COD(Mn), NH(4)(+)-N, TP) had little influence on the distribution of metal fractionation. This result revealed that the ecological risk of metals was not eliminated along with the improvement in water quality. Correlation studies showed that among the metals, Group A (Cd, As, Pb, Zn Hg, r = 0.730-0.924) and Group B (Cr, Cu, Ni, r = 0.815-0.948) were obtained, and the metal contaminations were from industrial activities rather than residential.     

Distribution of mercury and organic matter in particle-size classes in sediments contaminated by a waste water treatment plant: Vidy Bay, Lake Geneva, Switzerland

In Lake Geneva, Switzerland, the most Hg-contaminated sediments have been found in the Vidy Bay where high Hg contents largely exceeds the background levels of Lake Geneva sediments. This contamination has been attributed to the discharge of a waste water treatment plant (WWTP). Total Hg (THg) and monomethylmercury (MMHg) were determined in bulk sediment and in three different grain size fractions (i: clay and silt, ii: fine-coarse sand, iii: and very coarse sand and gravel) collected close to the outlet pipe of a WWTP in order to verify whether the standardized procedures of sediment treatment is adequate for this setting and, by extension, for similar contaminated sites. THg was homogeneously distributed in the different grain size fractions and was correlated to organic matter content (R(2) = 0.6). MMHg was homogeneously distributed in the two finer grain fractions (Φ < 0.063 mm; 0.063 mm < Φ <1 mm). The results of this study suggested that the analysis of the bulk sediment seems to be more appropriate for the assessment of the content and spatial distribution of Hg in freshwater sediments contaminated by WWTPs.     

Rapid,ultra-sensitive detection of gas phase elemental mercury under atmospheric conditions using sequential two-photon laser induced fluorescence

We have examined the sensitivity of sequential two photon laser induced fluorescence (LIF) detection of elemental mercury, Hg(0) in the gas phase. The most sensitive approach involves an initial laser excitation of the 6(3)P1-6(1)S0 transition at 253.7 nm, followed by excitation with a second laser to the 7(1)S0 level. Blue shifted fluorescence is observed on the 6(1)P1-6(1)S0 transition at 184.9 nm. The excitation scheme, involving sequential excitation of two atomic transitions, followed by detection of the emission from a third is extremely specific and precludes detection of anything other than atomic mercury. Using our 10 Hz laser system we have achieved a detection sensitivity of 0.1 ng m(-3) at a sampling rate of 0.1 Hz, i.e. averaging 100 laser shots at a pressure of one atmosphere in air. At low concentrations we sampled simultaneously with an automated mercury analyzer (Tekran 2537A), to ensure accuracy. We have examined the linearity of the technique, generating flows containing mercury concentrations between 1 and 10,000 ng m(-3) using a permeation tube and dynamic dilution, but relying on the concentrations given by the Tekran at low levels and the concentration calculated from dilution at high levels. We find that the detection is linear over the five orders of magnitude that we were able to vary the concentration. Our measured detection limits in He and Ar are much lower as these gases are inefficient fluorescence quenchers.     

Assessment of carcinogenic heavy metal levels in Brazilian cigarettes

Total mercury (Hg(T)) and bioavailability Hg (Hg(HCl)) concentrations in soil were determined in five districts in Wuhu urban area. Spatial pattern of soil Hg concentration was generated through kriging technology. Results showed that Hg concentration in soil ranged from 0.024 to 2.844 mg kg(?-1) with an average of 0.207 mg kg(?-1). Hg concentration in soil appeared to have a block distribution and decreased from downtown to surrounding district. And Hg concentrations appeared to have a medium scale spatial auto correlation, strongly affected by human activity. The maximal Hg average concentration (0.332 mg kg(?-1)) in soil appeared in Jinghu district, where the high intensity of human activities is. Second highest Hg average concentration (0.263 mg kg(?-1)) in soil appeared in development district, where the intensive industrial activities are. Bioavailability Hg concentration in soil ranged from 2.6 to 4.9 μg kg(?-1) with an average of 3.8 μg kg(?-1), which had a ratio of 0.28~6.44% to total Hg. The ratios of bioavailability Hg to total Hg in vegetable soil were bigger than those of park soil. Correlation analysis showed that total Hg, organic matter, total phosphorus, and bioavailability Hg concentrations in soil were significantly positively correlated. Hg concentration in vegetable ranged from 2.7 to 15.2 μg kg(?-1) with an average of 6.5 μg kg(?-1). Hg concentration in vegetable was positively correlated with Hg(HCl) concentration in soil. According to the calculation on hazard quotient (HQ) for children, inhalation of Hg vapor from soil is the main exposure pathway, in which HQ is 2.517 × 10(?-2), accounting for 80.3% of the four exposure pathways. Hazard index (HI) of the four exposure pathways is lower than the "safe" level of HI = 1; therefore, exposure of soil Hg exhibited little potential health risk to children in Wuhu urban area.     

Aquatic humus from an unpolluted Brazilian dark-brown stream: general characterization and size fractionation of bound heavy metals

The main pool of dissolved organic carbon in tropical aquatic environments, notably in dark-coloured streams, is concentrated in humic substances (HS). Aquatic HS are large organic molecules formed by micro-biotic degradation of biopolymers and polymerization of smaller organic molecules. From an environmental point of view, the study of metal humic interactions is often aimed at predicting the effect of aquatic HS on the bioavailability of heavy metal ions in the environment. In the present work the aquatic humic substances (HS) isolated from a dark-brown stream (located in an environmental protection area near Cubat?o city in S?o Paulo-State, Brazil) by means of the collector XAD-8 were investigated. FTIR studies showed that the carboxylic carbons are probably the most important binding sites for Hg(II) ions within humic molecules. 13C-NMR and 1H-NMR studies of aquatic HS showed the presence of constituents with a high degree of aromaticity (40% of carbons) and small substitution. A special five-stage tangential-flow ultrafiltration device (UF) was used for size fractionation of the aquatic HS under study and for their metal species in the molecular size range 1-100 kDa (six fractions). The fractionation patterns showed that metal traces remaining in aquatic HS after their XAD-8 isolation have different distributions. Generally, the major percentage of traces of Mn, Cd and Ni (determined by ICP-AES) was preferably complexed by molecules with relatively high molecular size. Cu was bound by fractions with low molecular size and Co showed no preferential binding site in the various humic fractions. Moreover, the species formed between aquatic HS and Hg(II), prepared by spiking (determined by CVAAS), appeared to be concentrated in the relatively high molecular size fraction F1 (> 100 kDa).     

Speciation and mass-balance of mercury from pulverized coal fired power plants burning western Canadian subbituminous coals

This report summarizes the results of a study carried out on six pulverized coal-fired power plants in western Canada burning subbituminous coal for the mass-balance and speciation of mercury. The main objectives of this study were to: determine the total gaseous mercury (TGM) emitted from stacks of power plants using the Ontario Hydro method; identify the speciation of emitted mercury such as metallic (Hg(0)) and gaseous elemental (GEM) mercury; and perform mass-balance calculations of mercury for milled-coal, bottom ash, electrostatic precipitators (ESP) fly ash and stack-emitted mercury based on three tests. Sampling of mercury was carried out using the Ontario Hydro method and mercury was determined using the USEPA method 7473 by cold vapor atomic absorption (CVAAS). The sample collection efficiencies confirmed that both oxidized and the elemental mercury had been successfully sampled at all power plants. The total gaseous mercury emitted (TGM) is 6.95-15.66 g h(-1) and is mostly in gaseous elemental mercury (GEM, Hg(0)) form. The gaseous elemental mercury is emitted at a rate of 6.59-12.62 g h(-1). Reactive gaseous mercury (RGM, Hg(2+)) is emitted at a rate of 0.34-3.68 g h(-1). The rate of emission of particulate mercury (Hg(p)) is low and is in the range 0.005-0.076 g h(-1). The range of mass-balances for each power plant is more similar to the variability in measured mercury emissions, than to the coal and ash analyses or process data. The mass-balance calculations for the six power plants, performed on results of the three tests at each power plant, are between 86% and 123%, which is acceptable and within the range 70-130%. The variation in mass-balance of mercury for the six power plants is mostly related to the variability of coal feed rate.     

Association of metals (mercury, cadmium and zinc) with metallothionein-like proteins in storage organs of stranded dolphins from the Mediterranean sea (Southern Italy)

Selected toxic and essential metals (mercury, Hg; cadmium, Cd; and zinc, Zn) were determined in the liver and in the kidney collected from 13 dolphins (Stenella coeruleoalba and Tursiops truncatus) stranded along the southern coasts of Italy from 1991 to 1999. Liver samples were also analysed for their methyl mercury (MeHg) and selenium (Se) contents. For subcellular fractionation, liver and kidney samples were homogenized in Tris-HCl buffer; after centrifugation, the supernatant (cytosol) was separated from pellets (insoluble fraction), heated at 80 degrees C for 10 min and centrifuged in order to separate the precipitate containing the thermolabile high molecular weight proteins. The cytosol heat-stable fraction, including metallothionein-like proteins (MTLPs), was then purified by gel filtration chromatography on Sephadex G-75 column. The three subcellular fractions collected (insoluble fraction, thermolabile fraction and purified heat-stable fraction) were analysed for their Hg, Cd and Zn contents. The analytical results confirm previous similar studies on toothed whales in showing that: (1) in the liver, as well as in the kidney, Hg was mainly found in the insoluble fraction, therefore, metallothioneins seem to have no role in the Hg detoxification; (2) in the liver, the molar ratio between Se and inorganic Hg was very close to 1; this suggests that the final compound of MeHg detoxification could be HgSe (tiemannite); (3) in almost all the samples, Cd and Zn were detected in the purified heat-stable fraction (including MTLPs). The mechanism of Cd detoxification and Zn homeostasis is also discussed.     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

Colloidal mercury (Hg) distribution in soil samples by sedimentation field-flow fractionation coupled to mercury cold vapour generation atomic absorption spectroscopy

Diverse analytical techniques are available to determine the particle size distribution of potentially toxic elements in matrices of environmental interest such as soil, sediments, freshwater and groundwater. However, a single technique is often not exhaustive enough to determine both particle size distribution and element concentration. In the present work, the investigation of mercury in soil samples collected from a polluted industrial site was performed by using a new analytical approach which makes use of sedimentation field-flow fractionation (SdFFF) coupled to cold vapour generation electrothermal atomic absorption spectroscopy (CV-ETAAS). The Hg concentration in the SdFFF fractions revealed a broad distribution from about 0.1 to 1 μm, roughly following the particle size distributions, presenting a maximum at about 400-700 nm in diameter. A correlation between the concentration of Hg in the colloidal fraction and organic matter (O.M.) content in the soil samples was also found. However, this correlation is less likely to be related to Hg sorption to soil O.M. but rather to the presence of colloidal mercuric sulfide particles whose size is probably controlled by the occurrence of dissolved O.M. The presence of O.M. could have prevented the aggregation of smaller particles, leading to an accumulation of mercuric sulfides in the colloidal fraction. In this respect, particle size distribution of soil samples can help to understand the role played by colloidal particles in mobilising mercury (also as insoluble compounds) and provide a significant contribution in determining the environmental impact of this toxic element.