Arsenic associations in sediments from shallow aquifers of northwestern Hetao Basin,Inner Mongolia

Understanding the mechanism of arsenic mobilization from sediments to groundwater is important for water quality management in areas of endemic arsenic poisoning, such as the Hetao Basin in Inner Mongolia, northern China. Aquifer geochemistry was characterized at three field sites (SH, HF, TYS) in Hangjinhouqi County of northwestern Hetao Basin. The results of bulk geochemistry analysis of sediment samples indicated that total As concentrations have a range of 6.8–58.5 mg/kg, with a median of 14.4 mg/kg. The highest As concentrations were found at 15–25 m depth. In the meanwhile, the range of As concentration in the sediments from background borehole is 3–21.8 mg/kg, with a median value of 9 mg/kg. The As sediments concentrations with depth from the SH borehole were correlated with the contents of Fe, Sb, B, V, total C and total S. Generally, the abundance of elements varied with grain size, with higher concentrations in finer fractions of the sediments. Distinct lithology profile and different geochemical characteristics of aquifer sediments indicate the sediments are associated with different sources and diverse sedimentary environments. Up to one third of arsenic in the sediments could be extracted by ammonium oxalate, suggesting that Fe oxyhydroxides may be the major sink of As in the aquifer. Sequential extraction results indicate that arsenic occurs as strongly adsorbed on and/or co-precipitated with amorphous Fe oxyhydroxides in sediments accounting for 35 and 20%, respectively, of the total contents of arsenic. The release of As into groundwater may occur by desorption from the mineral surface driven by reductive dissolution of the Fe oxide minerals. Furthermore, small proportions of As associated with iron sulfides occur in the reductive sediments.     

Environmental and health risk assessment in abandoned mining area, Zlata Idka, Slovakia

The Zlata Idka village is a typical mountainous settlement. As a consequence of more than 500 years of mining activity, its environment has been extensively affected by pollution from potentially toxic elements. This paper presents the results of an environmental-geochemical and health research in the Zlata Idka village, Slovakia. Geochemical analysis indicates that arsenic (As) and antimony (Sb) are enriched in soils, groundwater, surface water and stream sediments. The average As and Sb contents are 892 mg/kg and 818 mg/kg in soils, 195 mg/kg and 249 mg/kg in stream sediments, 0.028 mg/l and 0.021 mg/l in groundwater and 0.024 mg/l and 0.034 mg/l in surface water. Arsenic and Sb concentrations exceed upper permissible limits in locally grown vegetables. Within the epidemiological research the As and Sb contents in human tissues and fluids have been observed (blood, urine, nails and hair) in approximately one third of the village’s population (120 respondents). The average As and Sb concentrations were 16.3 μg/l and 3.8 μg/l in blood, 15.8 μg/l and 18.8 μg/l in urine, 3,179 μg/kg and 1,140 μg/kg in nails and 379 μg/kg and 357 μg/kg in hair. These concentrations are comparatively much higher than the average population. Health risk calculations for the ingestion of soil, water, and vegetables indicates a very high carcinogenic risk (>1/1,000) for as content in soil and water. The hazard quotient [HQ=average daily dose (ADD)/reference dose (RfD)] calculation method indicates a HQ>1 for groundwater As and Sb concentrations.     

Naturally occurring arsenic in groundwater and identification of the geochemical sources in the Duero Cenozoic Basin, Spain

Arsenic concentrations surpassing potability limit of 10 μg/L in the groundwater supplies of an extensive area in the Duero Cenozoic Basin (central Spain) have been detected and the main sources of arsenic identified. Arsenic in 514 samples of groundwater, having mean values of 40.8 μg/L, is natural in origin. Geochemical analysis of 553 rock samples, assaying arsenic mean values of 23 mg/kg, was performed. Spatial coincidence between the arsenic anomaly in groundwater and the arsenic lithogeochemical distribution recorded in the Middle Miocene clayey organic-rich Zaratan facies illustrates that the rocks of this unit are the main source of arsenic in groundwater. The ferricretes associated to the Late Cretaceous–Middle Miocene siliciclastics also constitute a potential arsenic source. Mineralogical study has identified the presence of arsenic in iron oxides, authigenic pyrite, manganese oxides, inherited titanium–iron oxides, phyllosilicates and organomineral compounds. Arsenic mobilization to groundwater corresponds to arsenic desorption from iron and manganese oxides and from organic matter.     

Exposure and bioavailability of arsenic in contaminated soils from the La Parrilla mine, Spain

Arsenic derived from mining activity may contaminate water, soil and plant ecosystems resulting in human health and ecotoxicological risks. In this study, exposure assessment of arsenic (As) in soil, spoil, pondwater and plants collected from the areas contaminated by mine tailings and spoils in and around the La Parrilla mine, Caceres province, Spain, was carried out using AAS method. Water solubility, bioavailability and soil–plant transfer coefficients of As and phytoremediation potential of plants were determined. Arsenic concentrations varied from 148 to 2,540 mg/kg in soils of site 1 and from 610 to 1,285 mg/kg in site 2 exceeding the guideline limit for agricultural soil (50 mg/kg). Arsenic concentrations in pond waters varied from 8.8 to 101.4 μg/l. High concentrations of water-soluble As in the soils that ranged from 0.10 to 4.71 mg/kg in site 1 and from 0.46 to 4.75 mg/kg in site 2 exceeded the maximum permitted level of water-soluble As (0.04 mg/kg) in agricultural soils. Arsenic concentrations varied from 0.8 to 149.5 mg/kg dry wt in the plants of site 1 and from 2.0 to 10.0 mg/kg in the plants of site 2. Arsenic concentrations in plants increased in the approximate order: Retama sphaerocarpa < Pteridium aquilinum < Erica australis < Juncus effusus < Phalaris caerulescens < Spergula arvensis in site 1. The soil–plant transfer coefficients for As ranged from 0.001 to 0.21 in site 1 and from 0.004 to 0.016 in site 2. The bioconcentration factor based on water-soluble As of soil varied from 3.2 to 593.9 in the plants of site 1 whereas it varied from 2.1 to 20.7 in the plants of site 2. To our knowledge, this is the first study in Europe to report that the fern species P. aquilinum accumulates extremely low contents of As in its fronds despite high As levels in the soils. Therefore, the S. arvensis, P. caerulescens and J. effusus plant species grown in this area might be used to partly remove the bioavailable toxic As for the purpose of minimization of mining impacts until hypothetical hyperaccumulating and/or transgenic plants could be transplanted for the phytoremediation of As contaminated soils.     

Arsenic and fluoride in a loess aquifer in the central area of Argentina

The objective of this study is to analyze the geochemical conditions associated with the presence of arsenic (As) and fluoride (F) in the phreatic aquifer of Coronel Moldes, in the central sector of the Argentine Chacopampean plain. The studied aquifer is composed of silty sand sediments of aeolian origin, typically loess-like sediments. The geochemical composition of water varies from sodium bicarbonate to sodium sulfate-chloride water. As contents range from low concentrations, below detection level, to 250 μg/l. High values of F (up to 12 mg/l) were recorded. A high As–F correlation was found (R ² = 0.84). The pH varied from 7.31 to 8.85 and the nitrates reached concentrations up to 200 mg/l, indicating an oxidant environment. The highest values of As and F agreed with sodium bicarbonate waters as well as with the highest values of pH recorded. There was a high correlation between As and F⁻ as well as between As and the Na/Ca ratio. The composition and texture of loess, low permeability and hydraulic gradients together with the geochemical features of sodium bicarbonate waters are proper conditions for the mobilization of As and F in groundwater in the central area of Argentina.     

Granitoid zircon forms the nucleus for minerals precipitated by carbonatite-derived metasomatic fluids at Chilwa Island,Malawi

Mineralogical assemblages are fundamental to the interpretation of geological processes. Zircon is an integral petrographic component of the mineral assemblages present in fenites (rocks formed by alkaline metasomatism) associated with the 136 Ma-aged Chilwa Island carbonatite complex, Malawi. Zircon exhibits contrasting characteristics and properties across the fenite aureole that surrounds the carbonatite stock. It shows intense grain dissolution and subsequent replacement by pyrochlore in the more intensely metasomatised ‘high-grade’ fenite of the innermost part of the aureole. By contrast, relict zircon crystals form the nucleus for the development of apatite-ilmenite-REE mineral assemblages in less altered zones. These changes in zircon properties are considered to be evidence of the diverse nature of fluids that metasomatised the Chilwa Islands fenite aureole. Although zircon is a principal component of the fenite mineral assemblages, when dated by LA-ICP-MS techniques it was found to predate the other minerals present in the mineral assemblages and thus, the age of carbonatite intrusion, by over 380 Ma. Instead of co-crystallising with the assemblage, zircon is therefore interpreted as providing a focus around which the minerals in the fenite assemblage formed. This implies that caution is needed both in the interpretation of Zr mobility in metasomatic assemblages, and also in attributing a zircon age to the assemblage as a whole in such sequences.     

Fluorine speciation in topsoils of three active volcanoes of Sicily (Italy)

Fluorine is one of the many environmental harmful elements released by volcanic activity. The content of total oxalate-extractable and water-extractable fluorine was determined in 96 topsoils of three active volcanic systems of southern Italy (Mt Etna, Stromboli and Vulcano). Total fluorine (F) content (F _TOT) ranges from 112 to 7,430 mg kg⁻¹, F extracted with oxalate (F _OX) ranges from 16 to 2,320 mg kg⁻¹ (2–93% of F _TOT) and F extracted with distilled water ( ) ranges from 1.7 to 159 mg kg⁻¹ (0.2–40 % of F _TOT). Fluorine in the sampled topsoils derives both from the weathering of volcanic rocks and ashes and from the enhanced deposition due to volcanic gas emissions either from open-conduit passive degassing (Mt Etna and Stromboli) or from a fumarolic field (Vulcano). Fluorine accumulation in the studied soils does not generally present particular environmental issues except for a few anomalous sites at Vulcano, where measured contents could be dangerous both for vegetation and for grazing animals.     

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.     

Geochemistry and mineralogy of shallow alluvial aquifers in Daudkandi upazila in the Meghna flood plain, Bangladesh

The shallow alluvial aquifers of the delta plains and flood plains of Bangladesh, comprises about 70% of total land area are mostly affected by elevated concentrations of arsenic (As) in groundwater exposing a population of more than 35 million to As toxicity. Geochemical studies of shallow alluvial aquifer in the Meghna flood plain show that the uppermost yellowish grey sediment is low in As (1.03 mg/kg) compared to the lower dark grey to black sediment (5.24 mg/kg) rich in mica and organic matter. Sequential extraction data show that solid phase As bound to poorly crystalline and amorphous metal (Fe, Mn, Al)-oxyhydroxides is dominant in the grey to dark grey sediment and reaches its maximum level (3.05 mg/kg) in the mica rich layers. Amount of As bound to sulphides and organic matter also peaks in the dark grey to black sediment. Vertical distributions of major elements determined by X-ray fluorescence (XRF) show that iron (Fe₂O₃), aluminum (Al₂O₃) and manganese (MnO) follow the general trend of distribution of As in the sediments. Concentrations of As, Mn, Fe, HCO₃ ⁻, SO₄ ²⁻ and NO₃ ⁻ in groundwater reflect the redox status of the aquifer and are consistent with solid phase geochemistry. Mineralogical analysis by X-ray diffraction (XRD) and scanning electron microscopy (SEM) fitted with energy dispersive X-ray spectrometer (EDS) revealed dominance of crystalline iron oxides and hydroxides like magnetite, hematite and goethite in the oxidised yellowish grey sediment. Amorphous Fe-oxyhydroxides identified as grain coating in the mica and organic matter rich sediment suggests weathering of biotite is playing a critical role as the source of Fe(III)-oxyhydroxides which in turn act as sink for As. Presence of authigenic pyrite in the dark grey sediment indicates active reduction in the aquifer.     

晋南临汾-运城盆地土壤氟含量及其影响因素

通过对临汾-运城盆地表层土壤F含量的空间变化规律和影响因素的研究,发现土壤平均含F量为520mg/kg,高于全国土壤背景值。表层土壤中F的空间分布不均匀,呈现出由盆地四周向盆地中心递增的趋势。研究表明,土壤F含量的分布主要受控于粉粒和有机质等土壤理化性质、元素间的相互作用、F的吸附特性等因素,人为因素对其也有一定影响。有机质和粉粒等土壤理化性质对土壤F含量的影响较大,说明研究区土壤F含量与F的特殊化学性质和母岩类型有关。因子分析发现,研究区表层土壤F的分布可能受自然地质作用和人为作用2种因素的影响,N、Cd、Se、Cu、Zn、Mo可能代表了F的原始共生元素;土壤F的含量随Mo、Zn、Fe、Mg等元素含量的增加而增加,可能与Fe3 离子在土壤中的吸附作用有关;而F-与OH-的配位置换作用可能是造成土壤中F-吸附的主导因素。     

Geological sources of boron and fluoride anomalies in Silurian–Ordovician aquifer system,Estonia

The objective of this study was to examine the possible natural sources of fluorides and boron in Silurian–Ordovician (S–O) aquifer system, as the anomaly of these elements has been distinguished in groundwater of western Estonia. Water–rock interactions, such as dissolution and leaching of the host rock, are considered to be the main source of high fluoride and boron concentrations in groundwater. Altogether 91 rock samples were analysed to determine if high F⁻ and B levels in groundwater could be attributed to certain aquifer forming rock types. Fluorine and boron contents in limestones and dolomites vary from 100 to 500 mg/kg and 5 to 20 mg/kg, reaching up to 1,000 and 150 mg/kg in marlstones, respectively. K-bentonites, altered volcanic ash beds, are rich in fluorine (400–4,500 mg/kg) and boron (50–1,000 mg/kg). Thus, clay-rich sediments, providing ion-exchange and adsorption sites for F⁻ and B, are the probable sources of both elements in S–O aquifer system in western Estonia.     

Assessment of heavy metal contamination in soils around Balanagar industrial area,Hyderabad, India

The concentration of heavy metals such as Ba, Co, Cr, Cu, Ni, Pb, Rb, Sr, V, Y, Zn, Zr were studied in soils of Balanagar industrial area, Hyderabad to understand heavy metal contamination due to industrialization and urbanization. This area is affected by the industrial activities like steel, petrochemicals, automobiles, refineries, and battery manufacturing generating hazardous wastes. The assessment of the contamination of the soils was based on the geoaccumulation index, enrichment factor (EF), contamination factor, and degree of contamination. Soil samples were collected from Balanagar industrial area from top 10–50 cm layer of soil. The samples were analyzed using X-ray fluorescence spectrometer for heavy metals. The data revealed that the soils in the study area are significantly contaminated, showing high level of toxic elements than normal distribution. The ranges of concentration of Cr (82.2–2,264 mg/kg), Cu (31.3–1,040 mg/kg), Ni (34.3–289.4 mg/kg), Pb (57.5–1,274 mg/kg), Zn (67.5–5819.5 mg/kg), Co (8.6–54.8 mg/kg), and V (66.6–297 mg/kg). The concentration of above-mentioned other elements was similar to the levels in the earth’s crust pointed to metal depletion in the soil as the EF was <1. Some heavy metals showed high EF in the soil samples indicating that there is a considerable heavy metal pollution, which could be correlated with the industries in the area. A contamination site poses significant environmental hazards for terrestrial and aquatic ecosystems. They are important sources of pollution and may results in ecotoxicological effects on terrestrial, groundwater and aquatic ecosystems.     

Biotites as Indicators of Fluorine Fugacities in Late-Stage Magmatic Fluids: the Gardar Province of South Greenland

The major element chemistry and fluorine contents of biotitesfrom the Gardar alkaline province of South Greenland providean insight into the F contents of late-stage fluids associatedwith the magmatism. Biotites were taken from composite intrusionsranging from alkali gabbro to syenites, nepheline syenites andalkali granites. In each complex they show a large range ofFe/(Fe+Mg) (from 0•2 to 1) and exhibit strong Fe-F avoidance.There is considerable variation in F for any value of Fe/(Fe+Mg)but for each centre maximum F values plotted against Fe/(Fe+Mg)define a nearly straight line of characteristic slope towardslow or zero F at pure annite. Micas in the SiO₂ undersaturatedcentres have higher F contents than those from oversaturatedcentres. Cl is low (0•69 wt%) except in the Kûngnâtintrusion, where it reaches 1•4 wt%. Phase equilibriumand textural considerations suggest that most or all biotitesgrew subsolidus in a pervasive deuteric fluid. ¹⁸O values suggestthat these fluids were largely magmatic in character and thatextensive reactions with envelope fluids did not occur. Metasomaticresetting of F in biotites in early intrusive units in the aureoleof later units can be demonstrated. Experimental data of Munoz (Mineralogical Society of America,Reviews in Mineralogy 13, 469–494, 1984) were used tocalculate families of curves showing variation in F with Fe/(Fe+Mg)for biotites in equilibrium with fluids of fixed fugacity ratio,f(HF)/f(H₂O), at fixed P and T. The resulting curves cut sharplyacross the maximum fluorine lines observed in the natural examples.As it seems highly unlikely that changes in fluid compositionand T, acting together, could produce the observed linear relationship,we conclude that the partitioning of F between fluid and micain the plutonic environment is not well modelled by the experiments.Possible explanations are short-range order (SRO) of Fe andMg on octahedral sites in biotite (Mason, Canadian Mineralogist30, 343–354, 1992) or effects resulting from differentF speciation in alkaline fluids. If perfect Fe-F avoidance isassumed, Fe-Mg SRO can increase maximum F content. The F levelsseen in the silica-saturated centres are broadly consistentwith a cooling-rate related control. It is possible that thehigher F in biotites in the undersaturated centres reflectsdifferent speciation in the fluid rather than higher F contents,with strongly bound SiF₄° complexes more common. KEY WORDS: biotites; Gardar; fluorine; alkaline rocks; fluids     

Fluorine distribution in waters of Nalgonda District, Andhra Pradesh, India

Geochemical and hydrochemical studies were conducted in Nalgonda District (A.P.), to explore the causes of high fluorine in waters, causing a widespread incidence of fluorosis in the local population. Samples of granitic rocks, soils, stream sediments, and waters were analyzed for F and other salient chemical parameters. Samples from the area of Hyderabad city were analyzed for comparison. The F content of waters in areas with endemic fluorosis ranges from 0.4 to 20 mg/l. The low calcium content of rocks and soils, and the presence of high levels of sodium bicarbonate in soils and waters are important factors favoring high levels of F in waters.     

Appraisal of highly fluoride zones in groundwater of Kurmapalli watershed,Nalgonda district,Andhra Pradesh (India)

Fluoride (F) contamination study had been carried out to see its allocation in Kurmapalli watershed, Nalgonda district, Andhra Pradesh, India. The study area is located about 60 km SE of Hyderabad city. The groundwater is the main source of water for their living. The groundwater in villages and its surrounding are affected by fluoride contamination and consequently the majority of the people living in these villages has health hazards and is facing fluorosis. The purpose of this study is to identify the wells with high F, raise awareness in people, study the water chemistry, and also find out the source of F in groundwater. A total of 32 groundwater samples were collected from different wells in both shallow aquifers and deeper fractures zones during October 2004. The chemical analysis of groundwater has been done. Fluoride values vary from 0.7 to 19.0 mg/l. It is noted that the maximum value (19.0 mg/l) is one of the highest values found in groundwater in India and 78% of the total samples show F concentrations that exceeds the permissible limit value (1.5 mg/l). The highest value of F is found at Madanapur bore well which is located at central part of the watershed. The F value of this bore well was monitored from October 2004 to October 2006. During this period the F concentration varies from 17.8 to 21.0 mg/l with mean 19.3 mg/l. There is no correlation of F with chemical parameters except calcium. The Ca has shown inverse proportional with F. Water–rock interaction studies were also carried out to understand the behavior of F in groundwater at prominent F affected areas. Rock samples were collected and analyzed, and found their enrichment of F. The anthropogenic possibility of F is almost negligible. The rocks of this area are enriched in F from 460 to 1,706 mg/kg. It is indicated that the rock–water interaction is the main source of F in groundwater. The highest values of F are found in middle part of the region and are related to the occurrence of fluoride rich rocks and their chemical kinetic behavior with groundwater.     

A regional-scale study of chromium and nickel in soils of northern California, USA

A soil geochemical survey was conducted in a 27,000-km² study area of northern California that includes the Sierra Nevada Mountains, the Sacramento Valley, and the northern Coast Range. The results show that soil geochemistry in the Sacramento Valley is controlled primarily by the transport and weathering of parent material from the Coast Range to the west and the Sierra Nevada to the east. Chemically and mineralogically distinctive ultramafic (UM) rocks (e.g. serpentinite) outcrop extensively in the Coast Range and Sierra Nevada. These rocks and the soils derived from them have elevated concentrations of Cr and Ni. Surface soil samples derived from UM rocks of the Sierra Nevada and Coast Range contain 1700–10,000 mg/kg Cr and 1300–3900 mg/kg Ni. Valley soils west of the Sacramento River contain 80–1420 mg/kg Cr and 65–224 mg/kg Ni, reflecting significant contributions from UM sources in the Coast Range. Valley soils on the east side contain 30–370 mg/kg Cr and 16–110 mg/kg Ni. Lower Cr and Ni concentrations on the east side of the valley are the result of greater dilution by granitic sources of the Sierra Nevada.Chromium occurs naturally in the Cr(III) and Cr(VI) oxidation states. Trivalent Cr is a non-toxic micronutrient, but Cr(VI) is a highly soluble toxin and carcinogen. X-ray diffraction and scanning electron microscopy of soils with an UM parent show Cr primarily occurs within chromite and other mixed-composition spinels (Al, Mg, Fe, Cr). Chromite contains Cr(III) and is highly refractory with respect to weathering. Comparison of a 4-acid digestion (HNO₃, HCl, HF, HClO₄), which only partially dissolves chromite, and total digestion by lithium metaborate (LiBO₃) fusion, indicates a lower proportion of chromite-bound Cr in valley soils relative to UM source soils. Groundwater on the west side of the Sacramento Valley has particularly high concentrations of dissolved Cr ranging up to 50 μg L⁻¹ and averaging 16.4 μg L⁻¹. This suggests redistribution of Cr during weathering and oxidation of Cr(III)-bearing minerals. It is concluded that regional-scale transport and weathering of ultramafic-derived constituents have resulted in enrichment of Cr and Ni in the Sacramento Valley and a partial change in the residence of Cr.     

Magma degassing during 7600 14C Kurile Lake caldera-forming eruption and its climatic impact

The main goal of this investigation is estimating volume of volatile emission, atmospheric and climatic impact of the Kurile Lake caldera-forming eruption, one of the Earth’s largest Holocene explosive eruptions. The volatile content of magma before the eruption was estimated by comparing H₂O, S, Cl and F contents in natural quenched glassy melt inclusions trapped by plagioclase phenocrysts. The volatile content of igneous rocks after eruption was estimated by comparing concentrations of degassed matrix glasses. As a result of KO-eruption not more than (3.7–4.2) × 10¹² kg of water, (4.3–4.9) × 10¹⁰ kg of chlorine, (8.6–9.8) × 10⁹ kg of fluorine and (2.6–2.9) × 10¹⁰ kg of sulphur were injected into the atmosphere. This eruption had to produce an important climatic impact.     

Natural Arsenic Attenuation via Metal Arsenate Precipitation in Soils Contaminated with Metallurgical Wastes: I. Wet Chemical and Thermodynamic Evidences

Arsenic from natural and anthropogenic sources is a worldwide contaminant of aqueous environments, such as groundwater and soils. The present investigation was performed on Mexican soils contaminated with residues from metallurgical processes that have shown a natural As attenuation. Experimental aqueous arsenic extractions in these were successfully simulated for almost half of the soil samples using a database updated for all known metal arsenate formation constants, revealing the predominance of solubility-controlled As mobility via Pb, mixed Pb–Cu, and Ca arsenate solid formation. The relatively low total Fe/As ratios (2–13 w/w) present in the soils studied, together with the high and equivalent contents of As, Pb, and Cu in these, favor the precipitation process over As(V) adsorption to Fe oxides, despite a 2% average Fe content in the soils studied. Under these conditions bicarbonate was found to be a highly unsuitable extractant due to its indirect As release from the solid arsenates, via heavy metal carbonate precipitation processes.     

Effects of pH on arsenic mineralogy and stability in Poldice Valley,Cornwall, United Kingdom

Many abandoned mine sites in Cornwall, UK, are characterised by elevated concentrations of arsenic (As), which can cause contamination of surrounding soil and water resources. These sites have important historical value that requires access to be maintained, despite exposure of humans to toxins that may lead to health issues including hyperpigmentation keratosis (including skin cancers) and liver fibrosis. The abandoned mine tailings at Wheal Maid has been assessed for As-bearing mineralogy and stability taking into account the public footpaths made by the local council to areas of potential contamination.To assess the potential risk associated with these mine sites, the As concentration in waters along the tailings dam and Carnon River have been measured and range up to 3.6 ppm, which is 2 orders of magnitude above the WHO guideline value of 0.01 ppm for drinking water. Samples of water, rocks and soils from the mine tailings ponds and the Carnon River were analysed using Inductively Coupled Plasma – Optical Emission Spectrometry (ICP-OES) and Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) to determine the concentration of individual elements in each sample followed by mineral identification using X-Ray Diffraction (XRD). Mineralogical evaluation indicated that the majority of mine tailings consist of clay-rich rocks, with few associated As-bearing minerals. Scorodite (FeAsO₄·2H₂O) is observed in the mine tailings pond and appears critical to the As distribution and storage in this surface environment. Using the analysed water chemistry, a modified version of PHREEQC is used to calculate the saturation index of scorodite as a function of pH conditions. The strong variation of the solubility of this mineral with pH and oxidation state highlights potential risks for using scorodite for As fixation and storage.     

Geochemical study of arsenic and other trace elements in groundwater and sediments of the Old Brahmaputra River Plain,Bangladesh

The geochemical study of groundwaters and core sediments from the Old Brahmaputra plain of Bangladesh was conducted to investigate the distribution of arsenic and related trace elements. Groundwaters from tube wells are characterized by pH of 6.4–7.4, dissolved oxygen (DO) of 0.8–1.8 mg/l, Ca contents of 5–50 mg/l, and Fe contents of 0.2–12.9 mg/l. Arsenic concentrations ranged from 8 to 251 μg/l, with an average value of 63 μg/l. A strong positive correlation exists between As and Fe (r ² = 0.802; p = 0.001) concentrations in groundwater. The stratigraphic sequences in the cores consist of yellowish silty clays at top, passing downward into grayish to yellowish clays and sands. The uppermost 3 m and lower parts (from 13 to 31 m) of the core sediments are oxidized (average oxidation reduction potential (ORP) +170 and +220 mV, respectively), and the ORP values gradually become negative from 3 to 13 m depths (−35 to −180 mV), indicating that anoxic conditions prevail in the shallow aquifers of the Brahmaputra plain. Age determinations suggest that clay horizons at ~10 m depth were deposited at around 2,000 and 5,000 years BP (¹⁴C ages) during the transgressive phase of sea-level change. Elevated concentrations of As, Pb, Zn, Cu, Ni, Cr, and V are present in the silts and clays, probably due to adsorption onto clay particles. Significant concentrations of As occur in black peat and peaty sediments at depths between 9 and 13 m. A strong positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed onto Fe oxides in aquifer sediments.