Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Transport and attenuation of metal(loid)s in mine tailings amended with organic carbon: Column experiments

A laboratory-scale column experiment was conducted to evaluate the effect of organic carbon amendments on the mobility of As, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Tl and Zn in mine tailings. Three columns were packed with sulfide- and carbonate-rich tailings, which were amended with a 1:1 (vol.) mixture of peat and spent brewing grain at proportions of 0, 2 and 5vol.%. A simulated input solution characterized by circumneutral pH and elevated concentrations of SO(4) and S(2)O(3) was passed through the columns for 540 days. The input solution contained low concentrations of metal(loid)s during the initial 300 days and elevated concentrations thereafter. Decreases in mass transport of S(2)O(3) were observed in all columns; with increased attenuation observed at 5 vol. % organic carbon content. Removal of Mn, Ni, Cu, Sb and Mo was observed in all columns during the initial 300 days. However, during this time, mobilization of Fe, As, Zn and Pb was observed, with the greatest increases in concentration observed at the higher organic carbon content. During the final 240 days, S(2)O(3) removal was enhanced in columns containing organic carbon, and Fe, Mn, Ni, Tl, As and Sb removal also was observed. This study demonstrates the influence of organic carbon amendments on metal(loid) mobility in mine tailings. Decreases in mass discharge of metal(loid)s may be achieved using this technique; however, site-specific geochemical conditions must be considered before field-scale implementation.     

As(V) and Sb(V) co-adsorption onto ferrihydrite: synergistic effect of Sb(V) on As(V) under competitive conditions

Competitive adsorption of As(V) and Sb(V) at environmentally relevant concentrations onto ferrihydrite was investigated. Batch experiments and XPS analyses confirmed that in a binary system, the presence of Sb(V) exhibited a slight synergistic effect on As(V) adsorption. XPS analyses showed that As(V) and Sb(V) adsorption led to obvious diminishment of Fe–O–Fe and Fe–O–H bonds respectively. At pH of 9, a more significant decrease of Fe–O–Fe was observed in the binary system than that in a single system, indicating that As(V) displayed an even stronger interaction with lattice oxygen atoms under competitive conditions. Basically, ionic strength demonstrated a negligible or positive influence on As(V) and Sb(V) adsorption in binary system. Study of adsorption sequence also indicated that the presence of Sb(V) showed a promotion effect on As(V) adsorption at neutral pHs. Considering that co-contamination of As and Sb in waters has been of great concern throughout the world, our findings contributed to a better understanding of their distribution, mobility, and fate in environment.

     

Distribution, speciation and availability of antimony (Sb) in soils and terrestrial plants from an active Sb mining area

Here, we present one of the first studies investigating the mobility, solubility and the speciation-dependent in-situ bioaccumulation of antimony (Sb) in an active Sb mining area (Xikuangshan, China). Total Sb concentrations in soils are high (527-11,798 mg kg⁻¹), and all soils, including those taken from a paddy field and a vegetable garden, show a high bioavailable Sb fraction (6.3-748 mg kg⁻¹), dominated by Sb(V). Elevated concentrations in native plant species (109-4029 mg kg⁻¹) underpin this. Both chemical equilibrium studies and XANES data suggest the presence of Ca[Sb(OH)₆]₂, controlling Sb solubility. A very close relationship was found between the citric acid extractable Sb in plants and water or sulfate extractable Sb in soil, indicating that citric acid extractable Sb content in plants may be a better predictor for bioavailable Sb in soil than total acid digestible Sb plant content.     

Arsenic and mercury bioaccumulation in the aquatic plant, Vallisneria neotropicalis

Arsenic (As) and mercury (Hg) are among the most toxic metals/metalloids. The overall goal of this study was to investigate the bioaccumulation of these trace elements in Vallisneria neotropicalis, a key trophic species in aquatic environments. For this purpose, As and Hg concentrations were determined in sediments and natural populations of V. neotropicalis in sub-estuaries of Mobile Bay (Alabama, USA), differing with respect to past and present anthropogenic impact. Analyses indicate that the Fish River is the most contaminated among the sub-estuaries investigated; levels of As found in Fish River sediments fall within a range that could potentially cause adverse effects in biota. Sediment As concentrations were only moderately correlated with those in V. neotropicalis; no correlation was found between sediment and plant Hg levels. However, several parameters could have masked such potential relationships (e.g., differences in sediment characteristics and “biological dilution” phenomena). Results presented herein highlight the numerous parameters that can influence metal/metalloids accumulation in aquatic plants as well as species-specific responses to trace element contamination. Finally, this study underscores the need for further investigation into contaminant bioaccumulation in ecologically and economically important coastal environments.     

Diffusive gradients in thin films,Rhizon soil moisture samplers,and indicator plants to predict the bioavailabilities of potentially toxic elements in contaminated technosols

The phytoavailabilities and potential remobilization of potentially toxic elements (PTEs) such as Zn, Pb, Cd, As, and Sb were assessed in contaminated technosols from former mining and smelting sites. The PTE concentrations in soil pore water (SPW) and diffusive gradients in thin films (DGT)-measured concentration (C _DGT) methods were used to assess the bioavailabilities of PTE and their remobilization in this study. Together with classical Chelex-100 DGT probes to measure Zn, Cd, and Pb, novel ferrihydrite-backed DGT were used for As and Sb measurements alongside with Rhizon soil moisture sampler method for SPW sampling. To assess the phytoavailabilities of PTE, a germination test with dwarf beans as a plant indicator was used for this purpose. Dwarf bean primary leaves showed high Zn concentrations in contrast to Pb and Cd which showed low phytoavailabilities. Despite As and Sb are present in high concentrations in the mine tailings, their phytoavailabilities indicate very low bioavailabilities. The amounts of Zn, Pb, Cd, As, and Sb extracted with DGT devices correlated well with the total dissolved PTE concentrations in the SPW. The highest R values were observed for Zn, followed by Cd and Pb, indicating the ability of the soil to sustain SPW concentrations, which decreased in that order. Good correlations were also observed between each of dissolved PTE concentrations in SPW, DGT-measured PTE concentrations (C _DGT), and the accumulation of PTE in dwarf bean primary leaves. It could be concluded that the use of Rhizon soil moisture samplers and DGT methods may be considered to be a good methods to predict the PTE bioavailabilities in contaminated technosols.     

Food crop accumulation and bioavailability assessment for antimony (Sb) compared with arsenic (As) in contaminated soils

Field samples and a 9-week glasshouse growth trial were used to investigate the accumulation of mining derived arsenic (As) and antimony (Sb) in vegetable crops growing on the Macleay River Floodplain in Northern New South Wales, Australia. The soils were also extracted using EDTA to assess the potential for this extractant to be used as a predictor of As and Sb uptake in vegetables, and a simplified bioaccessibility extraction test (SBET) to understand potential for uptake in the human gut with soil ingestion. Metalloids were not detected in any field vegetables sampled. Antimony was not detected in the growth trial vegetable crops over the 9-week greenhouse trial. Arsenic accumulation in edible vegetable parts was <10 % total soil-borne As with concentrations less than the current Australian maximum residue concentration for cereals. The results indicate that risk of exposure through short-term vegetable crops is low. The data also demonstrate that uptake pathways for Sb and As in the vegetables were different with uptake strongly impacted by soil properties. A fraction of soil-borne metalloid was soluble in the different soils resulting in Sb soil solution concentration (10.75?±?0.52 μg L^–1) that could present concern for contamination of water resources. EDTA proved a poor predictor of As and Sb phytoavailability. Oral bioaccessibility, as measured by SBET, was <7 % for total As and <3 % total Sb which is important to consider when estimating the real risk from soil borne As and Sb in the floodplain environment.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.     

Speciation and quantification of mercury in Oxisol, Ultisol, and Spodosol from Amazon (Manaus, Brazil)

In order to investigate the content and distribution of Hg in soils from Amazon areas not impacted by gold mining activities, the concentration and granulometric distribution of Hg were determined in three different types of soils. Hg speciation data were obtained by a thermodesorption atomic spectrometry system and the role of physico-chemical and mineralogical characteristics on Hg content were also studied. Hg concentrations found in the soil fraction <2000 microm were similar to values found in other Amazon areas without anthropogenic sources. The fine fraction (<53 microm) of podzolized soils had a higher Hg content than clayey soils. Multivariate analysis shows that there are marking differences between Spodosols of two distinct areas (fine fraction Hg contents up to 10-fold as high) indicating the importance of pedogenic processes. All statistical data analysis indicated that organic matter plays an important role in Hg accumulation in the types of soils studied. Thermodesorption analysis revealed the presence of only Hg2+, and the predominance of organically bound Hg in the majority of the studied samples.     

Cytotoxicity to alveolar macrophages of airborne particles and waste incinerator fly-ash fractions

A waste incinerator fly ash was separated into different grain-size fractions by sieving and sedimentation in butanol. The element content of each fraction was determined by atomic absorption and emission spectrometry. The fly-ash fractions, an eluted fine fly-ash fraction and an eluted airborne dust were analysed microscopically for particle size and numbers, together with standard quartz DQ 12 and three element-analysed airborne dusts. Rabbit alveolar macrophages, isolated by lung lavage, were incubated for 24 h with the particulates, the two eluates and a mixed element compound solution corresponding to the element concentrations of one airborne dust. At the end of incubation, the activities of lactate dehydrogenase, N-acetyl-beta-glucosaminidase, beta-galactosidase and acid phosphatase were determined in medium and cell lysates. Cytotoxicity was expressed as ratio of extracellular to total LDH (lactate dehydrogenase) activity. Release of N-acetyl-beta-glucosaminidase and beta-galactosidase was correlated positively with LDH release, whereas the total activity of acid phosphatase decreased with increasing LDH release. Cytotoxicity of the dusts was correlated with particle numbers, and As, Sb and Pb contents. The contribution of As to particle toxicity is discussed. Eluates of dusts did not affect rabbit alveolar macrophage viability.     

Soil contamination in Colombian playgrounds: effects of vehicles,construction, and traffic

The presence of potentially hazardous elements (PHEs) in playground soils is generally associated with anthropogenic sources such as vehicle traffic, industries, construction sites, and biomass burning. Studies indicate that PHEs are harmful to human health and may even be carcinogenic. Therefore, the aim of this study was to evaluate the physicochemical, morphological, and mineralogical properties of soil samples from three public playgrounds located in the cities of Bogota, Medellin, and Barranquilla. Besides, the possible impacts caused by the aerodynamics of particles in Colombian cities were verified. The morphology, composition, and structure of the nanoparticles (NPs) (< 100 nm) present in these soils were evaluated by field emission scanning electron microscopy (FE-SEM) equipped with high-precision field emission (FE) and high-resolution transmission electron microscopy (HR-TEM). Soil samples were predominantly feldspar, quartz, and, to a lesser extent, clay minerals, carbonates, and hematites. The average content of PHEs was anthropogenically enriched in relation to the upper continental crust. As and Sn showed a large spatial variation, indicating the influence of local sources, such as vehicle traffic and industries. There is an inverse relationship between the total concentrations of some elements and their leachable fractions. The accumulation of traffic-derived PHEs has a negative impact on human health and the environment, which is alarming, especially for elements such as Pb, Sb, or As. Therefore, the presence of PHEs should receive greater attention from public health professionals, and limits should be set and exposures controlled. This study includes the construction of a baseline that provides basic information on pollution, its sources, and exposure routes for humans in the vicinity of Colombia’s major cities, characterized by their increasing urbanization and industrialization.

     

Source identification of inorganic airborne particle fraction (PM10) at ultratrace levels by means of INAA short irradiation

Many studies have focused their attention on the determination of elements of toxicological and environmental interest in atmospheric particulate matter using analytical techniques requiring chemical treatments. The instrumental nuclear activation analysis technique allows achieving high sensitivity, good precision, and excellent limit of detection without pretreatment, also considering the problems related to the radioisotope characteristics (e.g., half-life time, interfering reactions, spectral interferences). In this paper, elements such as Al, As, Br, Cl, Cu, I, La, Mg, Mn, Na, Sb, Si, Ti, and V are studied in atmospheric PM₁₀ sampled in downtown Rome: The relative radionuclides after activation of the sample are characterized by very short (ranging from 2.24 to 37.2 min) and short (ranging from 2.58 h to 2.70 days) half-lives. Furthermore, As, Br, La, Mn, and Sb were also determined for evaluating the aerosol characteristics. The results, elaborated considering the matrix effects and the interfering reaction contribution to the radioisotope formation (e.g., ²⁸Al generated by both (n,γ) reaction from ²⁷Al and (n,p) reaction from ²⁸Si), show interesting values of As (0.3–6.1 ng m^?3), Cu (22–313 ng m^?3), Mn (17–125 ng m^?3), V (7–63 ng m^?3), higher than those determined in an area not influenced by autovehicular traffic, and significant levels of I (1–11 ng m^?3) and Ti (25–659 ng m^?3) in Rome PM₁₀. The other elements show a pattern similar to the very few data present in the literature. It should be underlined the good correlation (r ²) of Al vs. Mg (0.915) and Al vs. La (0.726), indicating a same sources for these species as well as Br–Sb showing a little lower correlation (0.623). This last hypothesis is confirmed by the study of the enrichment factors: Sb and Br may be attributed to anthropogenic sources; Cu, Cl, and I show a mixed origin (natural and anthropogenic), whereas Al, Si, Ti, Mn, Na, Mg, and As are of crustal origin. For having more information, a statistical approach based on the principal component analysis and the canonical discriminant analysis has been performed: All the samples (except one) are grouped in a cluster, and elements such as As, Br, Cu, I, La, Mn, Sb, Ti, and V are highly correlated, whereas Na and Cl and Mg and Al assemble in two different clusters. Finally, a comparison with other similar studies is reported showing interesting values for Al, As, Mg, Mn, and Ti.     

PAH Metabolites in Bile Fluids of Dab (Limanda limanda) and Flounder (Platichthys flesus): Spatial Distribution and Seasonal Changes (7 pp)

Background, Aim and Scope Polycyclic aromatic hydrocarbons (PAH) are important environmental contaminants which may lead to increased levels of neoplastic aberrations or tumours in fish liver. Therefore, monitoring of PAH and their effects are part of several international environmental programmes. The aim of the present field study was to investigate the concentrations of the PAH metabolites in fish bile, to elucidate spatial, seasonal and species differences as well as to discuss different strategies of normalisation with regard to environmental monitoring. Materials and Methods: PAH metabolites were determined in the bile fluid of dab (Limanda limanda) and flounder (Platichthys flesus) caught in the North Sea and Baltic Sea between 1997 and 2004. After enzymatic deconjugation, two metabolites were determined by means of HPLC. The limit of detection and the limit of quantification were calculated. The accuracy of the method was tested with a standard reference material. Results were referred to bile volume as well as to biliverdin. Results: The main metabolite, 1-hydroxypyrene, was determined in concentrations from <0.7 to 838 ng/ml in bile of dab (Limanda limanda) and flounder (Platichthys flesus) caught between 1997 and 2004. The values for 1-hydroxyphenanthrene in fish bile were considerably lower (<0.4 – 87 ng/ml). Significant differences in the 1-hydroxypyrene levels were found between summer and winter surveys as well as between the sampling sites in the data set from 2004 (383 dabs and 62 flounders): Highest levels of PAH contamination were found in dab from the German Bight and in flounder from the Baltic Sea. Discussion: Spatial differences in 1-hydroxypyrene concentrations between North Sea and Baltic Sea were discussed, as well as differences in relation to season, sex and species. Three parameters of normalisation (biliary protein, biliverdin and bile pigments) were discussed. Biliverdin was identified as a suitable parameter for the normalisation of PAH metabolites in field samples. Conclusions: Spatial differences in 1-hydroxypyrene concentrations of dab demonstrate the usefulness of PAH metabolites in fish bile as a monitoring parameter in marine regions. Significant differences in 1-hydroxypyrene concentrations were found between summer and winter sampling campaigns. This may be linked to an annual cycle of 1-hydroxyprene in dab. It is also possible that bile synthesis/release in dab differs between the seasons. There is no indication for a time trend from 1997 to 2004. Recommendations and Perspectives: It is recommended to relate PAH metabolites in fish bile to biliverdin concentrations. Although the concentrations are low in offshore regions and bile volumes are small, the method presented here allows one to measure PAH metabolites on an individual level which is a crucial prerequisite for meaningful monitoring studies.     

Correlation and toxicological inference of trace elements in tissues from stranded and free-ranging bottlenose dolphins (Tursiops truncatus)

The significance of metal concentrations in marine mammals is not well understood and relating concentrations between stranded and free-ranging populations has been difficult. In order to predict liver concentrations in free-ranging dolphins, we examined concentrations of trace elements (Al, As, Ba, Be, Cd, Co, Cu, Fe, Li, Mn, Ni, Pb, Sb, Se, Sn, total Hg (THg), V, Zn) in skin and liver of stranded bottlenose dolphins (Tursiops truncatus) from the South Carolina (SC) coast and the Indian River Lagoon, Florida (FL) during 2000-2008. Significantly higher concentrations of Zn, Fe, Se, Al, Cu and THg were found in skin while liver exhibited significantly higher Cu, Fe, Mn and THg concentrations for both study sites. Mean skin concentrations of Cu and Mn were significantly higher in SC dolphins while higher concentrations of THg and V were found in FL dolphins. In addition, liver tissues in SC dolphins exhibited significantly higher As concentrations while higher Fe, Pb, Se, THg, and V levels were found in FL dolphins. Two elements (Cu and THg) showed significant age-related correlations with skin concentration while five elements (Cu, Se, THg, Zn and V) showed age-related correlations with liver concentrations. Geographic location influenced age-related accumulation of several trace elements and age-related accumulation of THg in hepatic tissue was observed for both sites to have the highest correlations (r² = 0.90SC; r² = 0.69FL). Mean THg concentration in liver was about 10 times higher in FL dolphins (330 μg g⁻¹ dw) than those samples from SC dolphins (34.3 μg g⁻¹ dw). The mean molar ratio of Hg to Se was 0.93 ± 0.32 and 1.08 ± 0.38 for SC and FL dolphins, respectively. However, the Hg:Se ratio varied with age as much lower ratios (0.2-0.4) were found in younger animals. Of the 18 measured elements, only THg was significantly correlated in skin and liver of stranded dolphins and skin of free-ranging dolphins from both sites suggesting that skin may be useful in predicting Hg concentrations in liver tissue of free-ranging dolphins. Results indicate that 33% of the stranded and 15% of the free-ranging dolphins from FL exceed the minimum 100 μg g⁻¹ wet weight (ww) (∼400 dw) Hg threshold for hepatic damage while none from SC reached this level. Hepatic concentrations of As in SC dolphins and V in FL dolphins were also highly correlated with skin concentrations which may have some regional specificity predictive value. The present study provides the first application of trace element concentrations derived from stranded bottlenose dolphins to predict liver concentrations in free-ranging populations.     

Accumulation and fraction distribution of Ni(II) in activated sludge treating Ni-laden wastewater

The accumulation and fraction distribution of Ni(II) in sludge was determined, and their effect on the performance of sequencing batch reactor (SBR) systems was evaluated at laboratory scale. The results showed that the removal efficiencies of substrates decreased significantly with increasing feeding concentration of Ni(II) into SBRs. The concentration of Ni(II) fed into the SBRs was significantly positively correlated with the Ni(II) contents accumulated in the sludge, while it was negatively correlated with the biomass in the SBRs. The accumulated Ni(II) in the sludge was distributed mainly in the available fraction, accounting for 75.8–90.0 % of the total Ni(II) content. The accumulated content of Ni(II) in each sludge fraction could be predicted satisfactorily by the feeding Ni(II) concentrations in the solutions. As compared with the total contents and other chemical fractions, Ni(II) in the oxidizable fraction in sludge exhibited more important inhibition effects on sludge microorganisms in the SBRs.     

Arsenic and Mn levels in Isaza (Gymnogobius isaza) during the mass mortality event in Lake Biwa, Japan

The present study measured the concentrations of 25 elements (Li, Mg, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, Hg, Tl, Pb and Bi) in the whole body of Isaza which is an endemic fish species to Lake Biwa, Japan, and compared the values in the specimens from the mass mortality Isaza (MMI) and normal fresh Isaza (NFI). The mean levels of Mn and total As (T-As) were relatively higher in MMI than in NFI. In the T-As, highly toxic inorganic As was detected in MMI. Moreover we found Mn and As concentrations in surface sediment were extremely high and temporally increased. From all these results, we could infer that the dissolution of Mn and As from surface sediment of Lake Biwa might have been one of the cause for the mass mortality of Isaza.     

Lead, cadmium and arsenic bioavailability in the abandoned mine site of Cabezo Rajao (Murcia, SE Spain)

An in vitro method that simulated the physiological conditions of the digestive process was applied to samples taken from an old mining site, providing information on the levels of metals (Cd, Pb and As) that can be ingested and assimilated by humans. Samples were first characterized by determining pH, texture, mineralogical composition and total metal contents. The mean pH value was 5.4, ranging from 3.1 to 8.4. The mean total metal content for Pb was 2,632+/-59 mg kg(-1), 65+/-1.5 mg kg(-1) for Cd and 279.9+/-9.9 mg kg(-1) for As. Cadmium was the most bioavailable metal both in the stomach and intestinal phases (mean value of 47% and 27.8%, respectively), followed by lead (25.3% and 11.5%) and arsenic (4.9% and 0.5%). A Pearson correlation matrix suggested that pH and mineralogical composition were important factors controlling metal bioavailability from materials in abandoned mining sites.     

Biosorption of antimony(V) by freshwater cyanobacteria Microcystis from Lake Taihu,China: effects of pH and competitive ions

There is limited knowledge available on metalloid biosorption by freshwater algae. In this study, biosorption properties of anionic Sb(OH) ₆ ^? by naturally occurring cyanobacteria Microcystis were investigated as a function of initial pH, biosorbent dosage, contact time, and addition sequences of competitive ions, and their binding mechanisms were discussed. The biosorption process was fast and equilibrium was reached at 2 h. Sb(V) biosorption decreased with the increase of pH and the optimum pH range was 2.5–3.0, which corresponded with the changes of surface charges of the cell wall of Microcystis. The biosorption data satisfactorily followed the Freundlich model. The simultaneous addition of H₂PO₄ ^? and Ca²⁺ enhanced Sb(V) biosorption, while NO₃ ^? greatly inhibited the biosorption, compared with single Sb(V) addition. The initial addition of the competitive ions reduced Sb(V) biosorption at higher Sb(V) concentrations, compared with simultaneous addition. A fraction of biosorbed Sb(V) was replaced by the competitive ions which were added subsequently, and the exchange only occurred at higher concentrations of Sb(V). 1.0 mol/L HCl demonstrated the highest desorption efficiency. Speciation analyses indicated that no reduction of Sb(V) into Sb(III) occurred. Based on the results of zeta potential and attenuated total reflection infrared spectroscopy spectra, Sb(OH) ₆ ^? bound to the biomass through electrostatic attraction and surface complexation, and amino, carboxyl, and hydroxyl groups were involved in the biosorption process. The study suggest that Microcystis from cyanobacteria blooms could be used as a potential biosorbent to remove Sb(V) from effluents at environmentally relevant concentrations (≤10.0 mg/L).     

Determination of soil content in chlordecone (organochlorine pesticide) using near infrared reflectance spectroscopy (NIRS)

Chlordecone is a toxic organochlorine insecticide that was used in banana plantations until 1993 in the French West Indies. This study aimed at assessing the potential of near infrared reflectance spectroscopy (NIRS) for determining chlordecone content in Andosols, Nitisols and Ferralsols from Martinique. Using partial least square regression, chlordecone content conventionally determined through gas chromatography–mass spectrometry could be correctly predicted by NIRS (Q² = 0.75, R² = 0.82 for the total set), especially for samples with chlordecone content <12 mg kg⁻¹ or when the sample set was rather homogeneous (Q² = 0.91, R² = 0.82 for the Andosols). Conventional measures and NIRS predictions were poorly correlated for chlordecone content >12 mg kg⁻¹, nevertheless ca. 80% samples were correctly predicted when the set was divided into three or four classes of chlordecone content. Thus NIRS could be considered a time- and cost-effective method for characterising soil contamination by chlordecone.     

Fate and transport of carbamazepine in soil aquifer treatment (SAT) infiltration basin soils

The transport and fate of the pharmaceutical carbamazepine (CBZ) were investigated in the Dan Region Reclamation Project (SHAFDAN), Tel-Aviv, Israel. Soil samples were taken from seven subsections of soil profiles (150 cm) in infiltration basins of a soil aquifer treatment (SAT) system. The transport characteristics were studied from the release dynamics of soil-resident CBZ and, subsequently, from applying a pulse input of wastewater containing CBZ. In addition, a monitoring study was performed to evaluate the fate of CBZ after the SAT. Results of this study indicate adsorption, and consequently retardation, in CBZ transport through the top soil layer (0-5 cm) and to a lesser extent in the second layer (5-25 cm), but not in deeper soil layers (25-150 cm). The soluble and adsorbed fractions of CBZ obtained from the two upper soil layers comprised 45% of the total CBZ content in the entire soil profile. This behavior correlated to the higher organic matter content observed in the upper soil layers (0-25 cm). It is therefore deduced that when accounting for the full flow path of CBZ through the vadose zone to the groundwater region, the overall transport of CBZ in the SAT system is essentially conservative. The monitoring study revealed that the average concentration of CBZ decreased from 1094 ± 166 ng L⁻¹ in the recharged wastewater to 560 ± 175 ng L⁻¹ after the SAT. This reduction is explained by dilution of the recharged wastewater with resident groundwater, which may occur as it flows to active reclamation wells.