Model for the formation of arsenic contamination in groundwater: 2. Influence of sorption

Arsenic is accumulated in groundwater in response to As desorption at an increase in the alkalinity of aqueous solution owing to (a) a decrease in the equilibrium concentration of the sorbed H₃AsO₃⁰ and H₃AsO₄⁰ species and (b) sorbent (iron hydroxide) decomposition, when Eh decreases below the line of the iron hydroxide-siderite equilibrium.     

Arsenic mobilization in alluvial soils of Punjab, North–West India under flood irrigation practices

A laboratory investigation was carried out to examine the mechanism of arsenic (As) mobilization under flooded conditions (24 and 240 h) in 18 alluvial soils of Punjab, North–West India. Total dissolved As increased from a range of 3–16 μg L^?1 (mean 9 μg L^?1) to a range of 33–1,761 μg L^?1 (mean 392 μg L^?1) with the increase in flooding period from 24 to 240 h. The amount of As mobilization varied depending upon redox potential (pe) created by flooding conditions. After 24 h of flooded conditions, pe of soil water suspension ranged from ?1.75 to 0.77 (mean ?0.24). Increasing the flooding period to 240 h, pe of soil water suspension decreased in the range of ?4.49 to ?2.74 (mean ?3.29). Pourbaix diagram identified arsenate (HAsO₄ ^2?) as predominant species in most of the alluvial soil–water suspensions under oxidized conditions, after 24 h of equilibration period, which ultimately transformed to arsenite (H₃AsO₃ ⁰) after 240 h of anaerobic condition due to more reduced status. The solid phase identified was orpiment (As₂S₃). Identification of iron and manganese species in alluvial soil water suspension by Pourbaix diagram indicated decline in both soluble Fe²⁺ and SO₄ ^2? concentration due to the formation of iron sulfide mineral phase after 240 h under anaerobic conditions. In these soils, decline in soluble Fe was also due to the precipitation of vivianite [Fe₃(PO₄)₂·8H₂O]. Elevated arsenic content and low pe value were measured in aquifers located in paddy growing fields comparative to aquifers of other sites. Large degree of variability in As concentrations was recorded in aquifers located at same sites. Thus, it is better to analyze each aquifer for their As content rather than to depends on the prediction on As content of neighbouring wells. The present investigation elucidates that flood irrigation practices in Punjab for growing paddy crop could induce the geochemical conditions favorable to mobilize arsenic from surface soils which could eventually elevate its content in the underlying shallow aquifers. Water abstracted from these aquifers by hand pumps or tube wells for drinking purposes could create hazards for local population due to loading with arsenic concentration above the safe limits. Thus, to avoid further contamination of shallow aquifers with arsenic, it is advisable to shift the flooded rice cultivation to other upland crops having lesser water requirement.     

Speciation and colloid transport of arsenic from mine tailings

In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d⁻¹ through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe₃(SO₄, AsO₄)₂(OH)₆] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.     

Investigating water quality and arsenic contamination in drinking water resources in the Tavşanlı District (Kütahya,Western Turkey)

Arsenic is a natural component of the earth’s crust, and it is transported into surface water and groundwater through the dissolution of rocks, minerals and ores. In addition, arsenic leaching processes contaminate water sources and this geogenic arsenic contamination causes significant water quality problems in many parts of the world. In this study, water quality, arsenic contamination and human health risks of drinking water resources in the Tav?anl? District were determined and the origins were discussed. For this purpose, geological and hydrogeological properties were investigated. In situ measurements and chemical analyses were carried out on water samples taken from drinking water sources such as wells, springs and surface waters for hydrogeochemical studies. According to the obtained results, water resources are Ca–Mg–HCO₃, Mg–HCO₃ and Na–HCO₃ type. Total As (As_T) concentration of the water samples sometimes exceeds the permissible limit given by the TSI-266 (Standards for drinking waters, Turkish Standards Institution, Ankara, 2005) and WHO (Guidelines for drinking-water quality, World Health Organization, Geneva, 2008) for drinking water. H₃AsO ₃ ⁰ and HAsO₄ ^2? are dominant arsenic species in groundwater and surface water, respectively. Typically high total arsenic concentrations can be found in regions characterized by magmatic rocks. In addition, As concentrations in surface waters were found to be higher than in groundwater in the region, due to the anthropogenic influence of mining activities in the region.     

A laboratory batch study on arsenic sorption and desorption on guava orchard soils of Baruipur,West Bengal,India

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the sorption and desorption behavior of As in surface soils is of high importance, because these processes regulate the bioavailability of As in the soil environment. In this study, we have collected soils from guava orchards of Baruipur, West Bengal, and characterized soil chemistry and batch sorption and desorption behavior in the laboratory. The sorption and desorption behavior of As in the soils were examined using the Langmuir and Freundlich sorption equation. Regression analysis of the soil chemical characteristics and sorption equation parameters were also performed. The results suggest that the sorption behavior of arsenate is highly dependent on soil characteristics, specifically organic carbon, clay and Al₂O₃ content of the soils. Whereas desorption behavior is critically influenced by the presence of high concentrations of amorphous and/or crystalline Fe₂O₃ in the soils. Retention of the significant portion of As in the soils (~ 84% of the total) suggests that As in the orchard soils may not be highly bioavailable to plants for uptake. However, more detailed studies will be required to ascertain the role of individual soil components on the As sorption and desorption processes.     

Arsenic in surface- and up to 90°C ground waters in a basalt area,N-Iceland: processes controlling its mobility

The concentrations of As in surface- and up to 90 °C ground waters in a tholeiite flood basalt area in N-Iceland lie in the range <0.03–10 μg/kg. With few exceptions surface waters contain <0.5 μg/kg As whereas ground waters generally contain >0.5 μg/kg As. The As content of ground waters increases on the whole with rising temperature. Arsenic is highly mobile in the basalt-water environment of the study area. An insignificant fraction of the As dissolved from the rock is taken up into secondary minerals. Arsenic is less mobile than B but considerably more mobile than Na which has the highest mobility among the major aqueous components. A significant fraction of the As in the basalt occurs in an easily soluble form. The As hosted in the primary minerals is expected to be concentrated in the titano-magnetite. This mineral is stable in contact with both surface- and ground waters and does not, therefore, supply As to the water, explaining the difference in mobility between As and B. Aqueous As concentrations are a reflection of water/rock ratios, i.e. how much rock a given quantity of water has dissolved. This ratio increases with increasing temperature and increasing residence time of the water in contact with the rock. The distribution of As species has been calculated on the assumption of equilibrium at the redox potential retrieved from measurement of aqueous Fe(II) and Fe(III) concentrations. These calculations indicate that pentavalent As is stable in surface waters and in ground waters with an in situ pH of <10 and would occur mostly as H₂AsO₄⁻ and HAsO₄⁻². In higher pH ground waters the concentrations of the arsenite species H₂AsO₃⁻ is significant at equilibrium, up to 65% of the total dissolved As.     

Bioavailability of arsenic in the soil horizon: a laboratory column study

Groundwater contaminated with arsenic (As), when extensively used for irrigation, causes potentially long-term detrimental effects to surface soils. Such contamination can also directly affect human health when irrigated crops, such as rice, vegetable and fruits, are used for human consumption. Therefore, an understanding of the leaching behavior of As in surface soils is of high importance, because such behavior may increase the bioavailability of As in the soil horizon. In this study, we have investigated the role of phosphate ions in leaching and bioavailability of As in the soil horizon, where drinking groundwater contains elevated levels of As (≥50 μg/L). Soil and groundwater samples were characterized in the laboratory and measured for physical and chemical constituents. The soils are generally neutral to slightly alkaline in character (pH range 7.5–8.1) with low to moderate levels of free Fe₂O₃, Al₂O₃, CaCO₃, organic carbon, and clay content. The measured electrical conductivity (mean 599 μS/cm) of the soils demonstrates their non-saline nature. The Eh values (range −37 to −151 mV) of the groundwater indicate anoxic condition with low to moderate levels of bicarbonate (range 100–630 mg/L) and phosphate (range 0.002–4.0 mg/L). The arsenic content (range 50–690 μg/L; mean 321 μg/L) in groundwater has exceeded both WHO recommended guideline values (10 μg/L) and the National safe drinking water limit (50 μg/L). Regression analyses demonstrate that the bioavailability of As in the soil horizon is mainly controlled by the composition of free Fe₂O₃ and CaCO₃ content of the soils. However, application of P could increase bioavailability of As in the soil horizon and become available to plants for uptake.     

Arsenic in the Muteh gold mining district, Isfahan, Iran

Following the appearance of symptoms of arsenic toxicity in the inhabitants of villages in the Muteh gold mining region, central Iran, the concentration of this element in various parts of biogeochemical cycle is investigated. For this purpose, rock, groundwater, soil, plant, livestock hair and wool, and human hair samples are collected and analysed. Total arsenic content ranges from 23 to 2,500?mg/kg in rock samples, 7?C1,061???g/l in water, 12?C232?mg/kg in soil, 0.5?C16?mg/kg in plant samples, 4.10?C5.69?mg/kg in livestock hair and wool, and 0.64?C5.82?mg/kg in human hair. Arsenic concentration in various parts of biogeochemical cycle near the gold deposit in a metamorphic complex, and also close to the gold-processing plant, is very high and decreases exponentially with increasing distance from them. Arsenic concentration in water from a well close to the Muteh gold mine is above 1?mg/L. Arsenic in hair samples taken from local inhabitants is above the recommended levels, and the control samples in Shahre-Kord city. Arsenic concentration is higher in male population and correlates positively with age. It is suggested that arsenic resulting from the decomposition of ore mineral such as orpiment (As₂S₃), realgar (As₂S₂) and arsenopyrite (FeAsS) is responsible for polluting natural resources and the human intake via drinking water and the food chain. Gold mining and processing has undoubtedly enhanced the release of arsenic and intensified the observed adverse effects in Muteh area.     

Assessing redox properties of standard humic substances

Redox properties of humic substances (HS) control important biogeochemical processes. Thus, accurate estimation of redox properties of HS is essential. However, there is no general consensus regarding the best available measurement method of HS redox properties. In this study, we compared several common HS redox property measurement methods using anthraquinone-2,6-disulfonate (AQDS) as model compound, and standard Elliot soil humic acid (1S102H, ESHA), reference Pahokee peat (1R103H, PPHA), and Suwannee River natural organic matter (1R101N, SRNOM) as representative HS. We found that the H₂/Pd reduction method followed by incubation with ferric citrate (FeCit) reagent was incomplete, and the H₂/Pd reduction method followed by incubation with potassium ferricyanide (K₃Fe(CN)₆) was insensitive. Stannous chloride (SnCl₂) reduction followed by titration of excess stannous (Sn²⁺) by potassium dichromate (K₂Cr₂O₇) was found to be most accurate. These findings will help in future investigations on detailed characterizations of functional groups of HS responsible for oxidation/reduction reactions.     

Minerals of the beudantite–segnitite series from the oxidation zone of the Berezovskoe gold deposit,middle Urals: Chemical variations,behavior of admixtures,and antimonian varieties

In the oxidation zone of the Berezovskoe gold deposit in the middle Urals, Russia, minerals of the beudantite–segnitite series (idealized formulas PbFe₃ ³⁺ AsO₄)(SO₄)(OH)₆ and PbFe₃ ³⁺ AsO₄)(AsO₃OH)(OH)₆, respectively) form a multicomponent solid solution system with wide variations in the As, S, Fe, Cu, and Sb contents and less variable P, Cr, Zn, Pb, and contents K. The found minerals of this system correspond to series from beudantite with 1.25 S apfu to S-free segnitite, with segnitite lacking between 1.57 and 1.79 As apfu. Segnitite at the Berezovskoe deposit contains presumably pentavalent Sb (up to 15.2 wt % Sb₂O₅ = 0.76 Sb apfu, the highest Sb content in the alunite supergroup minerals), which replaces Fe³⁺. The Sb content increases with increasing As/S value. On the contrary, beudantite is free of or very poor in Sb (0.00–0.03 Sb apfu). Many samples of segnitite are enriched in Cu (up to 8.2 wt% CuO = 0.83 Cu apfu, uncommonly high Cu content for this mineral) and/or in Zn (up to 2.0 wt% ZnO = 0.19 Zn apfu). Both Cu and Zn replace Fe. The generalized formula of a hypothetic end member of the segnitite series with 1 Sb apfu is Pb(Fe³⁺ M ²⁺Sb⁵⁺)(AsO₄)₂(OH)₆, where M = Cu, Zn, Fe²⁺. The chemical evolution of beudantite–segnitite series minerals at the Berezovskoe deposit is characterized by an increase in the S/As value with a decrease in the Sb content from early to late generations.     

Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil – pH as the master variable

Chromium (Cr) is a heavy metal that exists in soils in two stable oxidation states, +III and +VI. The trivalent species is an essential nutrient, whereas the hexavalent species is highly toxic. This study investigated the environmental impact of Cr^III potentially released into soil from wastes and various materials by determining the risk of oxidation of initially soluble inorganic Cr^III into hazardous Cr^VI. The principal aim was to describe the pH-dependent mechanisms that regulate 1) the formation of Cr^VI from the easily soluble Cr^III and 2) the potential bioavailability of Cr^III and that of Cr^VI species produced in the oxidation of Cr^III in agricultural soil (fine sand, organic carbon 3.2%). The amount of Cr^VI formed in oxic soil conditions was regulated by two counteracting reactions: 1) oxidation of Cr^III into Cr^VI by manganese oxide (Mn^IVO₂) and 2) the subsequent reduction of Cr^VI by organic matter back to Cr^III. The effect of pH on this net-oxidation of Cr^III and on the chemical availability of both Cr^III and Cr^VI species was investigated in soil samples incubated with or without excessive amounts of synthetic MnO₂, over the chemically adjusted pH range of 3.9–6.3 (+22 °C, 47 d). In soil subsamples without added MnO₂, the net-oxidation of Cr^III into Cr^VI (1 mM CrCl₃ in soil suspensions, 1:10 w/V) was negligible. As for the MnO₂-treated soils, at maximum only 4.7% of added Cr^III was oxidized – regardless of the high oxidation potential of these subsamples. The lowest production of Cr^VI was observed under acidic soil conditions at pH ∼4. At low pH, the net-oxidation diminished as result of enhanced reduction of Cr^VI back to Cr^III. At higher pHs, the oxidation was limited by enhanced precipitation (or adsorption) of Cr^III, which lowered the overall amount of Cr^III susceptible for oxidation. Moreover, the oxidation reactions by MnO₂ were inhibited by formation of Cr(OH)₃ coverage on its surface. The pH-dependent chemical bioavailability of added Cr^III differed from that of the Cr^VI formed. At elevated pHs the chemical availability of Cr^III decreased, whereas that of Cr^VI produced increased. However, the risk of Cr^VI formation through oxidation of the easily soluble inorganic Cr^III was considered to be low in agricultural soils high in organic matter and low in innate MnO₂.     

Rhizosphere: A new frontier for soil biogeochemistry

A range of key biological functions of plant roots such as uptake, respiration and exudation can considerably alter biogeochemical parameters of the soil in the vicinity of the roots, i.e., the rhizosphere: concentrations of nutrients, toxic elements (e.g., aluminium) and pollutants, concentrations of complexing or chelating compounds, pH and redox potential, partial pressures of gases such as O₂ and CO₂, etc. Such parameters can also be directly influenced by the activities of soil microorganisms that are known to be stimulated by root exudation in the rhizosphere. Changes of biogeochemical parameters of the soil solution occurring in the rhizosphere influence a whole range of reactions at the soil solid/soil solution interface. Higher plants thereby play a key role in (i) the weathering of soil minerals, (ii) soil formation processes (pedogenesis) and (iii) the biogeochemistry of elements that are either beneficial or toxic to themselves and other soil biota.     

Distribution and speciation of arsenic around roots in a contaminated riparian floodplain soil: Micro-XRF element mapping and EXAFS spectroscopy

Riparian soils are periodically flooded, leading to temporarily reducing conditions. Diffusion of O₂ through plants into the rhizosphere maintains oxic conditions around roots, thereby promoting trace element fractionation along a redox gradient from the reduced soil matrix towards the oxic rhizosphere. The aim of this study was to determine the distribution and speciation of arsenic around plant roots in a contaminated (170-280 mg/kg As) riparian floodplain soil (gleyic Fluvisol). The analysis of soil thin sections by synchrotron micro-X-ray fluorescence (μ-XRF) spectrometry showed that As and Fe were enriched around roots and that As was closely correlated with Fe. Arsenic contents of three manually separated rhizosphere soil samples from the subsoil were 5-9 times higher than respective bulk As contents. This corresponds to the accumulation of about half of the total As in the subsoil in Fe-enrichments around roots. The speciation of As in the soil was assessed by oxalate extractions at pH 3.0 as well as by X-ray absorption near edge structure (XANES) and extended X-ray fine structure (EXAFS) spectroscopy. More than 77% of the total As was oxalate extractable in all samples. XANES and EXAFS spectra demonstrated that As was predominantly As(V). For the accurate analysis of the EXAFS data with respect to the bonding of As(V) to the Fe- or Al-octahedra of (hydr)oxides and clays, all 3-leg and 4-leg multiple scattering paths within the As^(V)O₄-tetrahedron were considered in a fully constrained fitting scheme. We found that As(V) was predominantly associated with Fe-(hydr)oxides, and that sorption to Al- and Mn-hydroxides was negligible. The accumulation of As in the rhizosphere may affect As uptake by plants. Regarding the mobility of As, our results suggest that by oxygenation of the rhizosphere, plants attenuate the leaching of As from riparian floodplain soils during periods of high groundwater levels or flooding.     

Heavy metal concentrations in sultana-cultivation soils and sultana raisins from Manisa (Turkey)

This paper describes the concentrations of heavy metals in soils and in raisins (sultanas) cultivated upon the Gediz Plain (Manisa), western Turkey, which is cut by major roads from ?zmir to ?stanbul and ?zmir to Ankara. A total of 212 samples of surface soil and 82 raisin samples were analysed. Soil samples have nearly same mineralogy, quartz, calcite, magnetite, pseudo-rutile and clay minerals. Dolomite is seen especially in areas close to Neogene sediments. Clay minerals are mainly mica (illite?Cmuscovite), chlorite/kaolinite, smectite and mixed layers (Sm-Il). The concentrations of 21 elements (Ba, Ni, Mo, Cu, Pb, Zn, Co, Mn, As, U, Sr, Cd, Sb, Bi, Cr, B, W, Hg, Sn, Li and organic C) were determined in the surface soils. The degree of element enrichment in soil can be measured in many ways, the most common of which are the geoaccumulation index (Igeo), enrichment factor and the pollution index. Arsenic and Sb showed the highest Igeo values, corresponding to Igeo classes 3?C4. Hence, the area is characterised as ??being heavily contaminated to polluted?? by As and Sb. Arsenic contamination has been reported from all over world. Arsenic-related pollutants enter the groundwater system by gradually moving with the flow of groundwater from rains and irrigation. Gediz Plain forms the main groundwater supply of ?zmir city. The enrichment factor (EF_arsenic) of the analysed soil samples is around 76, which corresponds to ??extremely high enrichment??. The concentrations of 33 elements (Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cu, Fe, Pb, Li, Mg, Mn, Hg, Mo, Ni, K, Se, Ag, Na, Sr, Ta, Th, Sn, Ti, U, V, Zn and Zr) were determined in the raisin samples. The Pb and Cd contents of raisins are of great concern due to their toxicity. Pb contents ranged between 0.05 and 0.46?mg?kg^?1, and average Cd content was 0.04?mg?kg^?1. Only one sample contained high level of Cd, 0.23?mg?kg^?1. After cleaning the raisins, the heavy metal concentrations were low as in the European Community (EC) regulation No: 466/2001 for allowable levels of Pb (0.2?mg?kg^?1) and Cd (0.05?mg?kg^?1).     

Arsenic adsorption on nanocrystalline goethite: the natural example of bolar earths from Mt Amiata (Central Italy)

Bolar earths deposits from Mt Amiata (Central Italy) consist of nanosized pseudo-spherical goethite, with average crystal size of 10–15 nm (as determined by X-ray powder diffraction and transmission electron microscopy observations), possibly associated to amorphous silica and minor sheet silicates, quartz and feldspars. Chemical analyses revealed high As contents (up to 7.4 wt% As₂O₅), thus indicating the occurrence of a potentially dangerous contaminant. Arsenic doesn’t occur as a specific As phase, but it is strictly associated with goethite nanocrystals. Eh and pH measurements suggest that As occurs as arsenate anions (H₂AsO₄⁻ and HAsO₄²⁻), which are easily and strongly adsorbed to goethite surfaces. The high specific surface area, resulting from goethite nanosize, and the absence of competitive anions explain the extremely efficient adsorption of arsenate and the anomalously high As content in bolar earths. Overall physical/chemical data suggest stable arsenate adsorption, with very limited risk for As release to the environment.     

Composition and solubility of precipitated copper(II) arsenates

Equilibrium reactions involving Cu(II) and As(V) have been studied with respect to formation of complexes in aqueous solutions as well as formation of solid phases. Potentiometric titrations performed at 25 °C (I = 0.1 M Na(Cl)) and at different Cu to As ratios gave no evidence for the existence of Cu(II) arsenate complexes in solution below the pH of the precipitation boundaries (pH ≈ 4), irrespective of the Cu to As ratio and pH. Mixing of solutions of Cu(II) and As(V) at different proportions and adjusting pH to values ranging from 4 to 9 resulted in precipitation of five different solid phases. The elemental composition of the solids was determined using X-ray Photoelectron Spectroscopy, and Environmental Scanning Microscopy-Field Emission Gun equipped with an energy dispersive spectroscopy detector. The average Cu/As ratio was determined by dissolving the solids. Total soluble concentrations of the components Cu(II) and As(V), as well as the basicity of the solid phases were determined by analysis of aqueous solutions. Based upon these experimental data the stoichiometric composition of the solid phases and their stability were determined. The resulting equilibrium model includes the solid phases Cu₃(AsO₄)₂, Cu₃(AsO₄)(OH)₃, Cu₂(AsO₄)(OH), Cu₅Na(HAsO₄)(AsO₄)₃ and Cu₅Na₂AsO₄)₄, where Cu₅Na(HAsO₄)(AsO₄)₃ and Cu₅Na₂(AsO₄)₄ have not been reported previously. In 0.1 M Na(Cl), Na⁺ was found to be a significant component in two of the solid phases. The Cu₅Na₂(AsO₄)₄ was formed in weakly alkaline conditions with pNa < 2.5. Stability constants for all solid phases have been determined. Distribution diagrams as well as predominance area (pNa-pH) diagrams are presented to illustrate stability fields of the different solid phases.     

Distribution of arsenic and its mobility in shallow aquifer sediments from Ambikanagar, West Bengal, India

Sediments from a core retrieved during installation of a shallow drinking water well in Ambikanagar (West Bengal, India) were analyzed for various physical and chemical parameters. The geochemical analyses included: (1) a 4-step sequential extraction scheme to determine the distribution of As between different fractions, (2) As speciation (As³⁺ vs. As⁵⁺), and (3) C, N and S isotopes. The sediments have a low percentage of organic C and N (0.10-0.56% and 0.01-0.05%, respectively). Arsenic concentration is between 2 and 7 mg kg⁻¹, and it is mainly associated with the residual fraction, less susceptible to chemical weathering. The proportion of As³⁺ in these sediments is high and ranges from 24% to 74%. Arsenic in the second fraction (reducible) correlates well with Mn, and in the residual fraction As correlates well with several transition elements. The stable isotope results indicate microbial oxidation of organic matter involving SO₄ reduction. Oxidation of primary sulfide minerals and release of As from reduction of Fe-(oxy)hydroxides do not seem important mechanisms in As mobilization. Instead, the dominance of As³⁺ and presence of As⁵⁺ reducing microorganisms in this shallow aquifer imply As remobilization involving microbial processes that needs further investigations.     

Chemical Dynamics and Evaluation of Biogeochemical Processes in Alpine River Kamniška Bistrica, North Slovenia

Biogeochemical processes were investigated in alpine river—Kamni?ka Bistrica River (North Slovenia), which represents an ideal natural laboratory for studying anthropogenic impacts in catchments with high weathering capacity. The Kamni?ka Bistrica River water chemistry is dominated by HCO₃ ^?, Ca²⁺ and Mg²⁺, and Ca²⁺/Mg²⁺ molar ratios indicate that calcite weathering is the major source of solutes to the river system. The Kamni?ka Bistrica River and its tributaries are oversaturated with respect to calcite and dolomite. pCO₂ concentrations were on average up to 25 times over atmospheric values. δ¹³C_DIC values ranged from ?12.7 to ?2.7 ‰, controlled by biogeochemical processes in the catchment and within the stream; carbonate dissolution is the most important biogeochemical process affecting carbon isotopes in the upstream portions of the catchment, while carbonate dissolution and organic matter degradation control carbon isotope signatures downstream. Contributions of DIC from various biogeochemical processes were determined using steady state equations for different sampling seasons at the mouth of the Kamni?ka Bistrica River; results indicate that: (1) 1.9–2.2 % of DIC came from exchange with atmospheric CO₂, (2) 0–27.5 % of DIC came from degradation of organic matter, (3) 25.4–41.5 % of DIC came from dissolution of carbonates and (4) 33–85 % of DIC came from tributaries. δ¹⁵N values of nitrate ranged from ?5.2 ‰ at the headwater spring to 9.8 ‰ in the lower reaches. Higher δ¹⁵N values in the lower reaches of the river suggest anthropogenic pollution from agricultural activity. Based on seasonal and longitudinal changes of chemical and isotopic indicators of carbon and nitrogen in Kamni?ka Bistrica River, it can be concluded that seasonal changes are observed (higher concentrations are detected at low discharge conditions) and it turns from pristine alpine river to anthropogenic influenced river in central flow.     

Migration of Cu, Zn, Cd and As in epikarst water affected by acid mine drainage at a coalfield basin, Xingren, Southwest China

Epikarst water, which is one of the most important water resources in karst mountain areas, is extremely sensitive to mining activities. Acid mine drainage (AMD) with high levels of heavy metals can degrade the water quality. A typical coalfield basin was chosen to research the migration process of heavy metals. It was found that the chemical compositions of the stream water in the research field were controlled by the dissolution of carbonate rocks or/and the weathering and oxidation of pyrite in the mining area. Excluding a few sites in the mining area, As(V) was dominant species of arsenic in the form of H₂AsO₄ ^? or HAsO₄ ^2? in the research field. Based on the mass balance concept, it was found that fluxes of As, Zn, Cu and Cd in water from the mining area (site 17) affected by AMD were 18, 871, 281 and 12 kg year^?1, respectively. Also, concentrations of Cd, Zn, As and Cu in the stream water decreased along the flow, because these ions deposited from the water to the stream bed as the redistribution processes in environment.     

Nitric oxide emissions from soils: a case study with temperate soils from Saxony, Germany

Nitrogen oxides (NO _x ) are involved in acid rain and ozone formation, as well as destruction. NO _x are climate-relevant trace gases in the atmosphere. Atmospheric NO _x originate from anthropogenic emissions (mainly combustion processes). NO from natural processes derives from thunderstorms and soil microbial processes. They may play a crucial role in soil?Catmosphere feedback processes. This study aims to investigate NO _x -emissions from soils under different land use, geographical and meteorological conditions. NO _x -emissions were quantified in both field and laboratory experiments with a closed static chamber. Disturbed soil samples have been used for laboratory experiments. A climate chamber was used to regulate soil temperature of the samples. Field experiments showed that NO-soil emissions strongly depend on soil temperature. NO-emissions from a soil under meadow showed significant daily variations, unlike soil below spruce forest. Peak emission values were 18???g NO?CN?m^?2?h^?1 above meadow and 1.3???g NO?CN?m^?2?h^?1 under forest canopy. In addition, NO-emissions of meadow and forest soil were studied in a climate chamber, enhanced by an additional experiment with agricultural soil. These experiments revealed strong exponential correlations of NO-emissions and soil temperature. Maximum values reached above 400???g NO?CN?m^?2?h^?1 from agricultural soils at soil temperatures above 50°C. This study shows that soil NO-emissions strongly depend on temperature, vegetation type and geographical position. Consequently, NO-emissions may have a positive feedback effect on climate change.