Distribution and mobility of mercury in soils from an old mining area in Mieres, Asturias (Spain)

Mercury content in soils near abandoned mine wastes in the mercury mining area of Mieres (Asturias, Spain) is highly elevated as a result of the long period of mining and abundant Hg production. In this work, an evaluation of Hg concentration, distribution, and mobility in three soil samples from the immediate vicinity of a chimney used for vapour evacuation during pyrometallurgical treatment of the ore was carried out. For that purpose, total Hg contents were determined for the original samples and their grain-size subsamples. The study of mercury mobility in the original samples and in the different particle-size subsamples was made by the application of a sequential extraction method. Results showed that Hg concentration in soils decreases directly with the distance from the chimney and the dispersion of Hg is not influenced by the topographic height of the site tested. The sample collected in the base of the chimney exhibited appreciable amounts of mobile Hg. In general, a higher Hg concentration was found for the finest particle-size subsamples. Hg mobility was found to be higher for quite developed soils. The sample collected downstream from the chimney showed a significant Hg mobile content as a result of a more intensive weathering. An increase of Hg mobility at decreasing particle size was found in all three analysed samples.     

Alteration to lake trophic status as a means to control arsenic mobility in a mine-impacted lake

The relationship between lake trophic status, sedimentary redox conditions and As mobility was examined in mine-impacted Balmer Lake, Canada. Under the current redox regime, the reductive dissolution of As-bearing Fe(III) oxyhydroxides occurs in close proximity to the sediment–water interface, resulting in the remobilization of dissolved As in the shallow porewaters to values as high as 8.5 mg L⁻¹. The shallow depth of the oxic zone limits the extent to which As can be re-sorbed in the interfacial horizons, and as a result, a proportion of the remobilized As escapes into the water column where it poses a water quality concern. Examination of the relationship between summer average chlorophyll a and total P at spring overturn in the lake water column demonstrates that Balmer Lake is currently eutrophic as a result of mining-derived inputs of P (domestic waters) and N (blasting residues and cyanide breakdown products). The results suggest that actively pushing the system towards oligotrophy by reducing non-natural P loadings to the system will decrease rates of in situ production and associated sediment oxygen demand, which will in turn result in increased thickness of the aerobic zone and enhanced As scavenging. Such conclusions are supported by porewater data which indicate that the flux of As to the water column is significantly reduced when the Fe(III) redox cline is situated at deeper sediment depths. In the absence of detailed P-loading data, it is recommended that P inputs be reduced to 10% of the estimated pre-mining P loading of 200 kg yr⁻¹. This implies reducing the collective P-loadings from the two mine sites adjacent to the lake from the approximate current value (150 kg yr⁻¹) to 20 kg yr⁻¹. It is proposed that establishment of oligotrophy in the lake should significantly mitigate the current level of dissolved As in lake waters.     

Antimony, arsenic and mercury in the aquatic environment and fish in a large antimony mining area in Hunan, China

Antimony (Sb) has received increasing attention recently due to its toxicity and potential human carcinogenicity. In the present work, drinking water, fish and algae samples were collected from the Xikuangshan (XKS) Sb mine area in Hunan, China. Results show that serious Sb and moderate arsenic (As) contamination is present in the aquatic environment. The average Sb concentrations in water and fish were 53.6 ± 46.7 μg L^− 1 and 218 ± 113 μg kg^− 1 dry weight, respectively. The Sb concentration in drinking water exceeded both Chinese and WHO drinking water guidelines by 13 and 3 times, respectively. Antimony and As concentrations in water varied with seasons. Fish gills exhibited the highest Sb concentrations but the extent of accumulation varied with habitat. Antimony enrichment in fish was significantly lower than that of As and Hg.     

Release of toxic metals and metalloids from Los Rueldos mercury mine (Asturias, Spain)

The abandoned mercury mining works of "Los Rueldos" are located 20 km from Oviedo, along the northwestern border of the Asturian Central Coal Basin, in an area with intense tectonization. Hg mainly appears as cinnabar, but occasionally metacinnabar and native Hg are present; associated with Hg ore appear As-rich minerals (arsenopyrite, As-rich pyrite, realgar and scorodite). In the spoil heap, Hg content ranges from 14 to 2224 mg kg(-1), and As from 4746 to 62,196 mg kg(-1). Mine drainage and spoil heap leachates show acidic conditions (pH: 2.43-2.50), 2900-4600 mg l(-1) sulphate, 1.4-9.2 mg l(-1) As, 0.03-0.48 mg l(-1) Pb, and 3.6-14 microg l(-1) Hg. According to the analytical data and characteristics of the site, the application of corrective measurements to avoid the dispersion of contaminants in the environment must be considered.     

Urinary arsenic concentrations and speciation in residents living in an area with naturally contaminated soils

A cross sectional study was carried out to evaluate arsenic exposure of residents living in an area with a soil naturally rich in arsenic (As), through urinary measurements. During the summer of 2007, 322 people aged over 7 years and resident in the study area for at least 4 days prior to the investigation were recruited. The sum of urinary inorganic arsenic and metabolites (iAs + MMA + DMA) and speciation were determined by graphite furnace atomic absorption spectrometry and high performance liquid chromatography coupled to inductively coupled plasma mass spectrometry, respectively. Geometric means levels of iAs + MMA + DMA were 3.6 µg/L or 4.4 µg/g creatinine. The percent of DMA, As(III) and MMA contribution to urinary arsenic concentrations was respectively 84.2%, 12% and 3.7%. We found significant associations between urinary arsenic concentrations and the consumption of seafood (p = 0.03), the consumption of wine (p = 0.03) and beer (p = 0.001), respectively 3 and 4 days before the investigation. When we focus on the various species, As(V) was rarely detected and DMA is the predominant metabolite composing the majority of measurable inorganic-related As in the urine. Considering the percent of DMA contribution to iAs + MMA + DMA urinary concentrations, almost half of the subjects had 100% of DMA contribution whatever the concentration of urinary As whereas the others had a lower DMA contribution, between 39 and 90%.Arsenic levels reported in this original study in France were between 2 and 4 times lower than in other studies dealing with iAs + MMA + DMA levels associated with soil arsenic exposure. Arsenic levels were similar to those observed in unexposed individuals in European countries, although 10% were above the French guideline values for the general population.     

Mobilisation of arsenic from a mining soil in batch slurry experiments under bio-oxidative conditions

Laboratory investigations were performed to estimate the potential mobility of arsenic (As) from a highly contaminated gold-mining soil under bio-oxidative aerobic conditions as a potential remediation process. The selected soil was sampled from a gold-mining site in the South of France. It contained 27700 mg kg(-1) total As, with only 0.01% present under water-soluble forms. The nature of the immobilization mechanisms was identified by using complementary physical and chemical techniques. As was found to be strongly associated to iron (oxy)hydroxide solid phase by adsorption and/or co-precipitation. Determination of iron (Fe) and As mobility as a function of pH showed that the release of As was related with the dissolution of Fe (oxy)hydroxide at very low pH values. Bioleaching experiments were conducted with the objective to enhance the mobilization of As from the source material via biological oxidation of elemental sulfur (S degree) into sulfuric acid by autotrophic exogenous or indigenous bacteria naturally located in the soil (i.e. Acidithiobacillus species). Tests conducted at 30 degrees C in shaker flasks supplemented with S degree resulted in very acidic (pH < 1) and oxidative conditions (oxidation/reduction potential (ORP) around +800 mV vs. NHE) and induced the extraction of up to 35% of As over 84 days of incubation. Under the experimental conditions of the study (batch experiments), As mobilization was strongly correlated to the dissolution of Fe solid phases. As mobilization was probably limited by the saturation of the liquid phase. Chimiolithotrophic exogenous population appeared to have a minor effect on As bioleaching. Endogenous populations were shown to rapidly develop their capacity to oxidize S degree and mobilize As from the mining soil in the form of arsenate when elemental S degree was supplemented. The use of microbial population adapted to high As concentrations reduced significantly the lag period to reach optimal pH/ORP conditions, and increased As extraction rate to a maximum of 41% within 70 days of incubation. However, As reprecipitation was subsequently observed, suggesting that the solution should be periodically replaced in order to optimize the process.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.     

Alteration of arsenopyrite in soils under different vegetation covers

The weathering of arsenopyrite (FeAsS) has been monitored in soils using an in situ experimental approach. Arsenopyrite in nylon experimental bags was placed in individual horizons in soils in spruce (litter, horizons A, B, and C), beech (litter, horizons A, B, and C) and unforested (horizons A, B, and C) areas and left in contact with the soil for a period of 1 year. The individual areas on the ridge of the Krušné hory Mts., Czech Republic, had the same lithology, climatic and environmental conditions. Scorodite (FeAsO₄·2H₂O) was identified as a principal secondary mineral of arsenic (As) formed directly on the surface of the arsenopyrite. Scorodite was formed in all the areas in all soil horizons. The amount of scorodite formed decreased in the series beech, spruce and unforested areas. In forested areas, there was a larger amount of scorodite on arsenopyrites exposed in organic horizons (litter, A horizon). The greater rate of arsenopyrite alteration in organic horizons in the beech stand compared to spruce stand is probably a result of faster mineralization of organic material with resulting production of nitrate and better seepage conditions of soil in this area. Speciation of As determined using the sequential extraction technique demonstrated that As was bonded in the soils primarily in the residual fractions prior to the experiment. The As content in the mobile fractions increased in the organic horizon in the forested areas after the experiments.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Speciation analysis of arsenic in terrestrial plants from arsenic contaminated area

Arsenic speciation analysis was carried out in plants collected from arsenic contaminated area. Two plant species were chosen for the investigation: Reed Grass (Calamagrostis arundinacea) and Lady Fern (Athyrium filix-femina). To characterize arsenic species several different extraction procedures were applied including enzymatic extraction and extraction using surfactant solution (SDS). Two-step sequential extraction (water + SDS) that assures the highest extraction efficiency was applied to extract arsenic species from plant material. HPLC with anion-exchange column was used to separate extracted arsenic compounds and ICP-MS was applied for quantitative arsenic determination after species separation.     

Immobilization of arsenic in a tailings material by ferrous iron treatment

Weathering and internal dissolution processes in mining waste materials may mobilize elevated levels of arsenic (As), contaminating ground and surface waters. Treating the polluted waters with iron oxyhydroxides is an established remediation method. By contrast, little knowledge is available to stabilize As in source materials by treating it with Fe precipitates and, on this way, to prevent the generation of polluted waters. In the present work the efficiency of Fe(II) treatment on As immobilization in a tailings material (TM) was studied with regard to the Fe:As molar ratio, the influence of CaCO3 amendment, and the As desorption at continued intensive leaching of Fe-treated TM. Fe precipitates were created by aerobic treatment of TM with Fe(II)sulfate at several Fe:As molar ratios with or without adding CaCO3, followed by aging the Fe-treated TM. The As retention in the treated tailings was studied by 4-fold elution with water, and the As desorption kinetics was examined by suspension leaching in laboratory microcosms over 3 weeks. Fe(II) treatment of TM reduced the water-extractable total As to <10 microg/L as the Fe:As molar ratio increased from 0 to 8. The water-soluble As of Fe-treated tailings could be reduced to 10-30 microg/L also under conditions of intensive leaching. Stabilizing the pH with CaCO3 resulted in consistently higher As release. The As desorption data followed the first-order kinetics in the early time stages of the desorption whereas at longer times the parabolic diffusion model was valid.     

Distribution and mobility of chromium, copper, and arsenic in soils collected near CCA-treated wood structures in Korea

Chromated copper arsenate (CCA) is currently the most commonly used wood preservative in Korea. Questions, however, have been raised regarding the potential environmental impacts of metal leaching from CCA-treated wood to soil. Although a number of researchers from other countries have reported that chromium, copper, and arsenic do leach from CCA-treated wood over time, to date few field studies have been performed on those metals in soils adjacent to CCA-treated wood structures in Korea. The present study was conducted to determine the lateral and vertical distributions and accumulation of chromium, copper, and arsenic in soils collected from CCA-treated wood structures. A total of fifty-five composite soil samples were collected from four CCA-treated wood structures of approximately one year in age. The samples were analyzed for physicochemical properties as well as for the total chromium, copper, and arsenic concentrations. The chromium, copper, and arsenic concentrations in soil samples adjacent to the structures were as high as 79.0, 98.9, and 128 mg/kg, respectively, compared to background soil samples (48.2, 26.9, and 6.27 mg/kg, respectively). Arsenic was more mobile in soil than chromium and copper. The concentration gradient of arsenic in soil was observed only to the depth of approximately 5 cm in one year of outdoor exposure, whereas chromium and copper apparently remained near the surface (approximately less than 1 cm) after their release. Future efforts should be made to observe seasonal impacts on the release of metals and incorporate metal speciation into determining more detailed mobility and distribution.     

Sources and temporal dynamics of arsenic in a New Jersey watershed, USA

We examined potential sources and the temporal dynamics of arsenic (As) in the slightly alkaline waters of the Wallkill River, northwestern New Jersey, where violations of water-quality standards have occurred. The study design included synoptic sampling of stream water and bed sediments in tributaries and the mainstem, hyporheic-zone/ground water on the mainstem, and seasonal and diurnal sampling of water at selected mainstem sites. The river valley is bordered by gneiss and granite highlands and shale lowlands and underlain by glacial deposits over faulted dolomites and the Franklin Marble. Ore bodies in the Marble, which have been mined for rare Zn ore minerals, also contain As minerals. Tributaries, which drain predominantly forested and agricultural land, contributed relatively little As to the river. The highest concentrations of As (up to 34 mug/L) emanated from the outlet of man-made Lake Mohawk at the river's headwaters; these inputs varied substantially with season--high during warm months, low during cold months, apparently because of biological activity in the lake. Dissolved As concentrations were lower (3.3 microg/L) in river water than those in ground water discharging into the riverbed (22 microg/L) near the now-closed Franklin Mine. High total As concentrations (100-190 mg/kg) on the <0.63 microm fraction of bed sediments near the mine apparently result from sorption of the As in the ground-water discharge as well as from the As minerals in the streambed. As concentrations in river water were diluted during high stream flow in fall, winter and spring, and concentrated during low flow in summer. In unfiltered samples from a wetlands site, diurnal cycles in trace-element concentrations occurred; As concentrations appeared to peak during late afternoon as pH increased, but Fe, Mn, and Zn concentrations peaked shortly after midnight. The temporal variability of As and its presence at elevated concentrations in ground water and sediments as well as streamwater demonstrate the importance of (1) sampling a variety of media and (2) determining the time scales of As variability to fully characterize its passage through a river system.     

Biomonitoring of Cd, Cr, Hg and Pb in the Baluarte River basin associated to a mining area (NW Mexico)

With the purpose of knowing seasonal variations of Cd, Cr, Hg and Pb in a river basin with past and present mining activities, elemental concentrations were measured in six fish species and four crustacean species in Baluarte River, from some of the mining sites to the mouth of the river in the Pacific Ocean between May 2005 and March 2006. In fish, highest levels of Cd (0.06 μg g^− 1 dry weight) and Cr (0.01 μg g^− 1) were detected during the dry season in Gobiesox fluviatilis and Agonostomus monticola, respectively; the highest levels of Hg (0.56 μg g^− 1) were detected during the dry season in Guavina guavina and Mugil curema. In relation to Pb, the highest level (1.65 μg g^− 1) was detected in A. monticola during the dry season. In crustaceans, highest levels of Cd (0.05 μg g^− 1) occurred in Macrobrachium occidentale during both seasons; highest concentration of Cr (0.09 μg g^− 1) was also detected in M. occidentale during the dry season. With respect to Hg, highest level (0.20 μg g^− 1) was detected during the rainy season in Macrobrachium americanum; for Pb, the highest concentration (2.4 μg g^− 1) corresponded to Macrobrachium digueti collected in the dry season. Considering average concentrations of trace metals in surficial sediments from all sites, Cd (p < 0.025), Cr (p < 0.10) and Hg (p < 0.15) were significantly higher during the rainy season. Biota sediment accumulation factors above unity were detected mostly in the case of Hg in fish during both seasons. On the basis of the metal levels in fish and crustacean and the provisional tolerable weekly intake of studied elements, people can eat up to 13.99, 0.79 and 2.34 kg of fish in relation to Cd, Hg and Pb, respectively; regarding crustaceans, maximum amounts were 11.33, 2.49 and 2.68 kg of prawns relative to levels of Cd, Hg and Pb, respectively.     

Arsenic microdistribution and speciation in toenail clippings of children living in a historic gold mining area

Arsenic is naturally associated with gold mineralisation and elevated in some soils and mine waste around historical gold mining activity in Victoria, Australia. To explore uptake, arsenic concentrations in children's toenail clippings and household soils were measured, and the microdistribution and speciation of arsenic in situ in toenail clipping thin sections investigated using synchrotron-based X-ray microprobe techniques. The ability to differentiate exogenous arsenic was explored by investigating surface contamination on cleaned clippings using depth profiling, and direct diffusion of arsenic into incubated clippings. Total arsenic concentrations ranged from 0.15 to 2.1 µg/g (n = 29) in clipping samples and from 3.3 to 130 µg/g (n = 22) in household soils, with significant correlation between transformed arsenic concentrations (Pearson's r = 0.42, P = 0.023) when household soil was treated as independent. In clipping thin sections (n = 2), X-ray fluorescence (XRF) mapping showed discrete layering of arsenic consistent with nail structure, and irregular arsenic incorporation along the nail growth axis. Arsenic concentrations were heterogeneous at 10 × 10 µm microprobe spot locations investigated (< 0.1 to 13.3 µg/g). X-ray absorption near-edge structure (XANES) spectra suggested the presence of two distinct arsenic species: a lower oxidation state species, possibly with mixed sulphur and methyl coordination (denoted As^≈ III_{(-S, -CH3)}); and a higher oxidation state species (denoted As^≈ V_(-O)). Depth profiling suggested that surface contamination was unlikely (n = 4), and XRF and XANES analyses of thin sections of clippings incubated in dry or wet mine waste, or untreated, suggested direct diffusion of arsenic occurred under moist conditions. These findings suggest that arsenic in soil contributes to some systemic absorption associated with periodic exposures among children resident in areas of historic gold mining activity in Victoria, Australia. Future studies are required to ascertain if adverse health effects are associated with current levels of arsenic uptake.     

Evaluation of distribution, mobility and binding behaviour of heavy metals in surficial sediments of Louro River (Galicia, Spain) using chemometric analysis: a case study

Contents of total and extractable heavy metals, carbonates, MnO and Fe₂O₃, organic matter, and matrix components such as SiO₂, Al₂O₃, CaO, Na₂O, MgO, TiO₂, K₂O and P₂O₅ are used along with principal component analysis (PCA) for studying distribution, mobility and binding behaviour of Cd, Cr, Cu, Ni and Pb in the Louro River (Galicia, Spain). Eleven surficial sediment samples were taken along the beds of the river course. Total metal concentrations were obtained after microwave-assisted digestion whilst extractable metal contents were obtained following a three-stage sequential extraction scheme (i.e. soluble, reducible and oxidisable fractions). Loading plots of heavy metals bound to carbonates, Fe–Mn oxides, organic matter and aluminosilicates allowed determination of binding behaviour. Correlations found indicate that Pb and Cu are mainly discharged from urban wastes, whereas Cr and Ni are from electroplating and galvanizing industries. The occurrence of diffuse pollution sources along the river can account for the binding behaviour of Cd. Metal mobility decreased in the order: Cd>Pb>Cu>Ni>Cr. Despite total contents indicating moderate-to-high heavy metal pollution in this river, metals are mostly distributed in the residual fraction, hence showing a low risk of mobility.     

Microbes influence the fractionation of arsenic in paddy soils with different fertilization regimes

Sequential extraction procedures were used to investigate the influence of the microbes on the distribution of arsenic in a Chinese paddy soil under different long-term fertilization treatments. The paddy soil with four long-term fertilization treatments (CK, M, NPK and NPK + M) and three levels of arsenate addition (0, 50, 100 mg As kg^− 1 dry soil), were selected to construct microcosms for laboratory incubation. After the incubation, soil samples were sequentially extracted to determine As in various fractions, i.e. water soluble (F0), exchangeable (F1), bound to carbonates (F2), bound to Fe and Mn oxides (F3), bound to organic matter and sulfides (F4), and residual (F5, mineral matrix). Results showed that most of the As was fixed by mineral matrix (F5, ratios ranging from 46.22% to 96.37%), followed by As bound to Fe and Mn oxides (F3, ratios ranging from 3.14% to 28.18%), and the ratios of the other four fractions (F0, F1, F2 and F4) were mostly less than 10%. The microbes in the paddy soil could make As transform from inactive fraction (F5) to relatively active fractions (F0, F1, F2 and F3) and thus increase its environmental risk. With the increase of the As addition levels and with the application of manure or chemical NPK fertilizers, As was distributed more in the relatively active fractions (F0, F1, F2, F3 and F4) in the paddy soil mediated by the microbes. In addition, Fe and Mn oxides could play an important role in decreasing the As leaching potential from the mineral matrix to soil solution and thus abate the As risk to human health.     

Partitioning and speciation of chromium, copper, and arsenic in CCA-contaminated soils: influence of soil composition

This study focused on the influence of soil composition and physicochemical characteristics on the retention and partitioning of Cu, Cr and As in nine chromated copper arsenate (CCA) artificially contaminated soils. A statistical mixture design was used to set up the number of soils and their respective composition. Sequential extraction and modified solvent extraction were used to assess Cu and Cr partitioning and As speciation [As(III) or As(V)]. It was found that peat had a strong influence on CEC (232 meq/100 g), on buffer capacity and on Cu and Cr retention, whereas kaolinite's contribution to the CEC was minor (38 meq/100 g). Average metal retention in mineral soils was low (58% for Cu and 23% for Cr) but increased dramatically in highly organic soils (96% for Cu and 78% for Cr). However, both organic and mineral soils demonstrated a very high sorption of added As (71-81%). Levels of Cu and Cr in a soluble or exchangeable form (F1) in highly organic soils were very low, whereas the levels strongly bound to organic matter were much higher. Conversely, in mineral soils, 47% of Cu and 18% of Cr were found in F1. As a result, Cr and Cu in moderately and highly organic contaminated soils were present in less mobile and less bioavailable forms, whereas in mineral soils, the labile fraction was higher. The modified method used for selective determination of mineral As species in CCA-contaminated soils was found to be quantitative and reliable. Results revealed that arsenic was principally in the pentavalent state. Nevertheless, in organic soils, arsenite was found in significant proportions (average value of 29% in highly organic soils). This indicates that some reduction of arsenate to arsenite occurred since the original species in CCA is As(V).     

Remediation of arsenic contaminated soils by iron-oxide application, evaluated in terms of plant productivity, arsenic and phytotoxic metal uptake

Four iron-bearing additives, selected for known or potential ability to adsorb anions, were evaluated for their effectiveness in attenuation of arsenic (As) in three soils with different sources of contamination (canal dredgings, coal fly ash deposits, and low-level alkali waste). Amendments used were lime, goethite (alpha-FeOOH) (crystallised iron oxide) and three iron-bearing additives, iron grit and iron (II) and (III) sulphates plus lime, which result in 'de novo' iron oxide formation in soils. Each was applied to the test soils at a rate of 1% w/w. A series of plant growth trials were conducted on the equilibrated, amended soils using spinach (Spinacia oleracea) and tomato (Lycopersicon esculentum) as test crops. These were grown in the contaminated soils for a period of three months in controlled glasshouse conditions. Evaluation of the potential of the amendments as immobilising agents was determined by plant growth (biomass) and elemental accumulation in plant tissues, indicating the bioavailability of As and other heavy metals following amendment. Goethite produced the most promising results in terms of reduction of plant shoot As content. It was concluded that, whilst Fe-oxides may be used as effective in situ amendments to attenuate As in soils by reducing its bioavailability, their effects on plant growth require careful consideration. In addition, soil-plant transfer of As was not completely halted by any amendment.     

Enrichment processes of arsenic in oxidic sedimentary rocks - From geochemical and genetic characterization to potential mobility

Sedimentary marine iron ores of Jurassic age and Tertiary marine sandy sediments containing iron hydroxides concretions have been sampled from boreholes and outcrops in two study areas in Germany to examine iron and arsenic accumulation processes. Samples were analyzed for bulk rock geochemistry (INAA/ICP-OES), quantitative mineralogy (XRD with Rietveld analysis), element distribution (electron microprobe) and arsenic fractionation (sequential extraction). Bulk Jurassic ores contain an average arsenic content of 123 μg g⁻¹ hosted in mainly goethite ooids which slowly formed in times of condensed sedimentation. Enrichment occurred syndepositionally and is therefore characterized as primary. Iron concretions in Tertiary sediments mainly consist of goethite and yield arsenic up to 1860 μg g⁻¹. The accumulation process is secondary as it took place in the course of oxidation of the originally reduced marine sediments under terrestrial conditions, leading to element redistribution and local enrichment in the near-surface part. The scale of enrichment was assessed calculating Enrichment Factors, indicating that arsenic accumulation was favoured over other potential contaminants. In spite of higher bulk arsenic contents in the oxidic rocks, the mainly pyrite-hosted As pool within the reduced deeper part of the Tertiary sediments is shown to have a higher potential for remobilization and creation of elevated arsenic concentrations in groundwater.