Vertical distribution and mobilization of arsenic in shallow alluvial aquifers of Chapai-Nawabganj district, Northwestern Bangladesh

Core sediments from two boreholes and groundwater from fifty four As-contaminated well waters were collected in the Chapai-Nawabganj area of northwestern Bangladesh for geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10 to 40 m of depth) range from 2.76?C315.15 mg/l (average 48.81 mg/l). Arsenic concentration in sediments ranges from 3.26?C10 mg/kg. Vertical distribution of arsenic in both groundwater and sediments shows that maximum As concentration (462 mg/l in groundwater and 10 mg/kg in sediments) occurs at a depth of 24 m. In January 2008, 2009 and 2010, maximum As concentration occurs at the same depth. Environmental scanning electron microscope (ESEM) with EDAX was used to investigate the presence of major and trace elements in the sediments. The dominant groundwater type is Ca-HCO₃ with high concentrations of As and Fe, but with low levels of NO₃ ^? and SO₃ ^?2. Statistical analysis clearly shows that As is closely associated with Fe (R² = 0.64) and Mn (R² = 0.91) in sediments while As is not correlated with Fe and Mn in groundwater samples. Comparatively low Fe and Mn concentrations in some groundwater, suggest that probably siderite and/or rhodochrosite precipitated as secondary mineral on the surface of the sediment particles. The correlations along with results of sequential leaching experiments suggest that reductive dissolution of FeOOH and MnOOH mediated by anaerobic bacteria represents mechanism for releasing arsenic into the groundwater.     

Environmental geochemistry of high arsenic groundwater at western Hetao plain, Inner Mongolia

Environmental geochemistry of high arsenic groundwater at Hetao plain was studied on the basis of geochemical survey of the groundwater and a core sediment. Arsenic concentration in groundwater samples varies from 76 to 1093 μg/L. The high arsenic groundwater mostly appears to be weakly alkaline. The concentrations of NO₃⁻ and SO₄²⁻ are relatively low, while the concentrations of DOC, NH₄⁺, dissolved Fe and sulfide are relatively great. Analysis of arsenic speciation in 21 samples shows that arsenic is present in the solution predominantly as As(III), while particulate arsenic constitutes about 10% of the total arsenic. Methane is detected in five samples with the greatest content being 5107 μg/L. The shallow aquifer in Hangjinhouqi of western Hetao plain is of strongly reducing condition. The arsenic content in 23 core sediment samples varies from 7.7 to 34.6 mg/kg, with great value in clay and mild clay layer. The obvious positive relationship in content between Fe₂O₃, Mn, Sb, B, V and As indicates that the distribution of arsenic in the sediments may be related to Fe and Mn oxides, and the mobilization of Sb, B and V may be affected by similar geochemical processes as that of As.     

Geochemical features of rocks,stream sediments,and soils of the Fiume Grande Valley (Calabria,Italy)

The role of both natural weathering and anthropogenic pollution in controlling the distribution of major oxides and several trace elements in soils, stream sediments, and rocks of the Fiume Grande catchment was evaluated. The contents of major oxides and trace elements in soils appear to be governed by weathering and pedogenetic processes, although the use of fertilizers in agriculture could also partly affect K₂O and P₂O₅ contents. Stream sediments have concentrations of major oxides (except CaO) very similar to soils, as relevant amounts of soil materials are supplied to the stream channels by erosive phenomena. In contrast, stream sediments have concentrations of Cr, Co, Ni, Zn, As, and Pb significantly higher than those of soils, probably due to different conditions and rates of mobility of these elements within the three considered matrices and/or disposal of wastes in the drainage network. Comparison of the concentrations of PHEs in soils with the maximum admissible contents established by the Italian law shows that these limits are too restrictive in some cases and too permissive in other ones. The approach of setting these limits with no consideration for the local geological–geochemical framework may lead to improper management of the territory and its resources. Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users.     

Arsenic mobilization in shallow aquifers of Datong Basin: Hydrochemical and mineralogical evidences

To better understand the sources and mobilization processes responsible for arsenic enrichment in groundwater in the central part of Datong Basin where serious arsenic poisoning cases have been reported, hydrochemical characteristics of the groundwater and the geochemical and mineralogical features of the aquifer sediments were studied. The aqueous arsenic levels are strongly depth-dependent in the study area and the high arsenic concentrations are found at depths between 15 m and 60 m, with a maximum up to 1820 μg/L. The hydrochemical characteristics of high arsenic groundwater from the Datong Basin indicate that the mobilization of arsenic is related to reductive dissolution of Fe oxides/oxyhydroxides and/or desorption from the Fe oxides/oxyhydroxides at high pH (above 8.0). The bulk chemical results of sediments show the arsenic and iron are moderately correlated, suggesting that arsenic is associated with iron-bearing minerals. Results of sequential-extraction experiment show that solid-phase arsenic is similarly distributed among the different pools of reservoir in the aquifer sediments. Strongly adsorbed arsenic and co-precipitated arsenic are its dominant species in the solid-phase. Geochemical studies using chemical analysis, X-ray diffraction and scanning electron microscopy on magnetically separated fractions demonstrate that iron oxides/oxyhydroxides with residual magnetite and chlorite, illite, iron oxides/oxyhydroxides-coated quartz and feldspar, and ankerite are the dominant carriers of arsenic in the sediments. The major processes of arsenic mobilization are probably linked to desorption of As from Fe oxides/oxyhydroxides and reductive dissolution of Fe-rich phases in the aquifer sediments under reducing and alkaline conditions.     

Origin of arsenic in the groundwater of the Rioverde basin, Mexico

Groundwater in the semiarid Rioverde basin in the northern part of Mexico was investigated with respect to major and minor elements including arsenic, as well as As(III) and As(V). The total arsenic concentrations varied from less than 5 to 50 g/L. The in situ arsenic determination method produced reliable results with deviations from -5.6 to 2.2 g/L compared to laboratory HGAAS. Since arsenic and barium were found to be inversely correlated, it was suspected that precipitation of barium arsenate controlled arsenic solubility. Thermodynamically modeling by means of PHREEQC indicated that BaHAsO₄·H₂O (not BaAsO₄) might be a limiting phase, however only at higher concentrations than those determined in this study. Increased arsenic groundwater concentrations were found with lacustrine sediments and decreased concentrations with fluvial Quaternary sediments. Increased total arsenic concentrations correlate with increased As(III) concentrations in the groundwater of the lacustrine sediments.     

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.     

Distribution of arsenic and other trace elements in the Holocene sediments of the Meghna River Delta, Bangladesh

Geochemical study of the Holocene sediments of the Meghna River Delta, Chandpur, Bangladesh was conducted to investigate the distribution of arsenic and related trace and major elements. The work carried out includes analyses of core sediments and provenance study by rare earth element (REE) analysis. Results showed that the cores pass downward from silty clays and clays into fine to medium sands. The uppermost 3 m of the core sediments are oxidized [average oxidation reduction potential (ORP) + 230 mV], and the ORP values gradually become negative with depths (−45 to −170 mV), indicating anoxic conditions prevail in the Meghna sediments. The REE patterns of all lithotypes in the study areas are similar and are comparable to the average upper continental crust. Arsenic and other trace elements (Pb, Zn, Cu, Ni, and Cr) have greater concentrations in the silts and clays compared to those in the sands. Positive correlation between As and Fe was found in the sediments, indicating As may be adsorbed on Fe oxides in aquifer sediments.     

Vertical geochemical variations and arsenic mobilization in the shallow alluvial aquifers of the Chapai-Nawabganj District, northwestern Bangladesh: implication of siderite precipitation

Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO₃ type with high concentrations of As, but low levels of Fe, Mn, NO₃ ^? and SO ₄ ^?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.     

High arsenic contents in groundwater of central Spain

The chemical and microbiological characteristics of groundwater from two provinces of central Spain were studied. In some zones of this area, the concentrations of As in groundwater exceed the guideline concentrations, set internationally between 10 g/l and 50 g/l, reaching levels over 100 g/l. A narrow correlation between the contents of arsenic and HCO₃^– was observed. These data suggest a possible mechanism of the As mobilization from aquifer sediments to groundwater: the bicarbonate ions could displace HAsO₄^2– adsorbed on aquifer oxyhydroxides. Sediments containing relatively high contents of adsorbed arsenic are deposited in surface water environments with low carbonate concentrations. Subsequently, the sediments become exposed to groundwater with highly dissolved carbonate content, and arsenic can be mobilized by displacement from mineral surfaces. In addition, the presence of Pseudomonas genera bacteria, which secrete siderophores (Fe chelating agents) could mobilize As adsorbed on Fe oxides through their dissolution. These combined microbiological and chemical processes might have increased the natural mobility of As.     

Irrigation produces elevated arsenic in the underlying groundwater of a semi-arid basin in Southwestern Idaho

The shallow aquifer beneath the Western Snake River Plain (Idaho, USA) exhibits widespread elevated arsenic concentrations (up to 120 μg L⁻¹). While semi-arid, crop irrigation has increased annual recharge to the aquifer from approximately 1 cm prior to a current rate of >50 cm year⁻¹. The highest aqueous arsenic concentrations are found in proximity to the water table (all values >50 μg L⁻¹ within 50 m) and concentrations decline with depth. Despite strong vertical redox stratification within the aquifer, spatial distribution of aqueous species indicates that redox processes are not primary drivers of arsenic mobilization. Arsenic release and transport occur under oxidizing conditions; groundwater wells containing dissolved arsenic at >50 μg L⁻¹ exhibit elevated concentrations of O₂ (average 4 mg L⁻¹) and NO₃ (average 8 mg L⁻¹) and low concentrations of dissolved Fe (<20 μg L⁻¹). Sequential extractions and spectroscopic analysis of surficial soils and sediments indicate solid phase arsenic is primarily arsenate and is present at elevated concentrations (4–45 mg kg⁻¹, average: 17 mg kg⁻¹) relative to global sedimentary abundances. The highest concentrations of easily mobilized arsenic (up to 7 mg kg⁻¹) are associated with surficial soils and sediments visibly stained with iron oxides. Batch leaching experiments on these materials using irrigation waters produce pore water arsenic concentrations approximating those observed in the shallow aquifer (up to 152 μg L⁻¹). While As:Cl aqueous phase relationships suggest minor evaporative enrichment, this appears to be a relic of the pre-irrigation environment. Collectively, these data indicate that infiltrating irrigation waters leach arsenic from surficial sediments to the underlying aquifer.     

Geological and geochemical examination of arsenic contamination in groundwater in the Holocene Terai Basin, Nepal

Geological and geochemical study has been carried out to investigate arsenic contamination in groundwater in Nawalparasi, the western Terai district of Nepal. The work carried out includes analyses of core sediments, provenance study by rare earth elements analyses, ¹⁴C dating, and water analyses. Results showed that distribution of the major and trace elements are not homogeneous in different grain size sediments. Geochemical characteristics and sediment assemblages of the arsenic contaminated (Nawalparasi) and uncontaminated (Bhairahawa) area have been compared. Geochemical compositions of sediments from both the areas are similar; however, water chemistry and sedimentary facies vary significantly. Extraction test of sediment samples showed significant leaching of arsenic and iron. Chemical reduction and contribution from organic matter could be a plausible explanation for the arsenic release in groundwater from the Terai sediments.     

Arsenic associations in sediments from the loess aquifer of La Pampa,Argentina

Groundwater from the Quaternary loess aquifer of La Pampa, central Argentina, has significant problems with high concentrations of As (up to 5300 μg L⁻¹) as well as other potentially toxic trace elements such as F, B, Mo, U, Se and V. Total As concentrations in 45 loess samples collected from the aquifer have a range of 3–18 mg kg⁻¹ with a mean of 8 mg kg⁻¹. These values are comparable to world-average sediment As concentrations. Five samples of rhyolitic ash from the area have As concentrations of 7–12 mg kg⁻¹. Chemical analysis included loess sediments and extracted porewaters from two specially cored boreholes. Results reveal a large range of porewater As concentrations, being generally higher in the horizons with highest sediment As concentrations. The displaced porewaters have As concentrations ranging up to 7500 μg L⁻¹ as well as exceptionally high concentrations of some other oxyanion species, including V up to 12 mg L⁻¹. The highest concentrations are found in a borehole located in a topographic depression, which is a zone of likely groundwater discharge and enhanced residence time. Comparison of sediment and porewater data does not reveal unequivocally the sources of the As, but selective extract data (acid-ammonium oxalate and hydroxylamine hydrochloride) suggest that much of the As (and V) is associated with Fe oxides. Primary oxides such as magnetite and ilmenite may be partial sources but given the weathered nature of many of the sediments, secondary oxide minerals are probably more important. Extract compositions also suggest that Mn oxide may be an As source. The groundwaters of the region are oxidising, with dissolved O₂, NO₃ and SO₄ normally present and As(V) usually the dominant dissolved As species. Under such conditions, the solubility of Fe and Mn oxides is low and As mobilisation is strongly controlled by sorption–desorption reactions. Desorption may be facilitated by the relatively high-pH conditions of the groundwaters in the region (7.0–8.8) and high concentrations of potential competitors (e.g. V, P, HCO₃). PHREEQC modelling suggests that the presence of V at the concentrations observed in the Pampean porewaters can suppress the sorption of As to hydrous Fe(III) oxide (HFO) by up to an order of magnitude. Bicarbonate had a comparatively small competitive effect. Oxalate extract concentrations have been used to provide an upper estimate of the amount of labile As in the sediments. A near-linear correlation between oxalate-extractable and porewater As in one of the cored boreholes investigated has been used to estimate an approximate K_d value for the sediments of 0.94 L kg⁻¹. This low value indicates that the sediments have an unusually low affinity for As.     

Investigation of the hydrogeochemical processes in an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa

An investigation was conducted to assess the hydrogeochemical processes of an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa. The investigation was aimed at identifying and describing the groundwater chemistry evolution and its contribution to the overall groundwater quality. X-ray fluorescent spectrometry (XRF) and X-ray diffractometry (XRD) analyses were performed on geological samples to identify and quantify the major element oxides and minerals. The study utilises the conventional Piper diagram, bivariate plots and PHREEQC hydrogeochemical model to analyse groundwater chemistry data obtained during the wet (February and May) and dry seasons (August and December) of 2011. The XRF and XRD results show that the channel deposits are dominated by SiO₂ element oxides and quartz minerals, thus elevated concentrations of silicon (Si⁴⁺) were found in the groundwater. Dolomite and calcite minerals were also detected in the unconsolidated aquifer sediments. The detailed study of the alluvial aquifer system has shown that dissolution of dolomite and calcite minerals and ion exchange are the dominant hydrogeochemical processes influencing the groundwater quality. The groundwater evolves from Ca²⁺–Mg²⁺–HCO₃ ^? recharge water that goes through ion exchange with Na⁺ in the clay-silt sediment to give a Na⁺–HCO₃ ^? water type. The groundwater is supersaturated with respect to quartz, dolomite and calcite minerals. The study shows the potential usefulness of simple bivariate plots as a complimentary tool to the conventional methods for analyzing groundwater hydrogeochemical processes.     

Arsenic enrichment in unconfined sections of the southern Gulf Coast aquifer system, Texas

Groundwater arsenic concentrations exceeding the federal drinking water standard are common in the southern Gulf Coast aquifer system in Texas, including in aerobic, unconfined groundwater which provides much of the municipal and domestic water supplies for the region. The objective of this study was to determine geochemical factors affecting the occurrence and distribution of groundwater As in unconfined portions of the southern Gulf Coast aquifer system through a comparative transect study of groundwater across three major hydrostratigraphic units (the Catahoula Formation, Jasper aquifer and Evangeline aquifer) and analysis of regional water quality data. Results show that As concentrations decrease with increasing distance from the Catahoula Formation, which is consistent with Miocene volcanic ash as the main source of As to groundwater in the region. Arsenic concentrations correlate with V, SiO₂ and K, all of which were released during weathering of volcanic sediments and their degradation products. In all three units, carbonate weathering and active recharge in the unconfined zones result in circum-neutral pH and oxidizing groundwater, which are typically amenable to As immobilization by adsorption of arsenate onto mineral oxides and clays. However, As concentrations exceed 10 μg/L in approximately 30% of wells. Silica that was co-released with As may compete for sorption sites and reduce the capacity for arsenate adsorption.     

Assessment of metal concentrations in lake sediments of southwest Japan based on sediment quality guidelines

Geochemical analysis of the bottom sediments of Lakes Banryoko, Onbe, Hamahara and Kijima in Shimane prefecture of southwest Japan was carried out to determine their metal concentrations, and to assess the potential for ecological harm by comparison with sediment quality guidelines. The work conducted includes water quality measurement, and analyses of trace and major elements and rare earth element (REE) of sediments. Results showed that water quality of the lakes contrasts slightly between their upper and lower parts. Average abundances of As, Pb, Zn, Cu, Ni, and Cr in Banryoko sediments were 27, 33, 90, 27, 25, and 46 ppm, respectively, compared to 31, 52, 175, 44, 44, and 75 ppm at Onbe, 11, 26, 96, 13, 13, and 35 ppm at Hamahara, and 24, 43, 193, 31, 12, and 30 ppm at Kijima. These concentrations exceeded the lowest effect level that has moderate impact on aquatic organisms as proposed by the New York State Department of Environmental conservation. Pb and Cu abundances are comparable to the Coastal Ocean Sediment Database threshold, while As and Zn exceed this value, indicating the concentrations of these metals are potentially toxic. Increases in the abundances of these metals in lake sediments are probably related to the reducing condition of the sediments, anthropogenic sources and surface soil erosion. The REE patterns of sediments in the study areas are broadly comparable to the average upper continental crust, but show some contrast between lakes due to differing source litho type. Significant positive correlations between Fe₂O₃ and As, Pb, Zn, and Cu were found in the sediments, suggesting these metals may be adsorbed on Fe oxides in the lake sediments.     

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.     

Potential contaminants at a dredged spoil placement site,Charles City County,Virginia, as revealed by sequential extraction

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.     

Improved methods for selective dissolution of Mn oxides: applications for studying trace element associations

The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl₂(Mn^IV₂Mn^III)O₆(OH)₆ was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn₈O₁₆) and/or coronadite (PbMn₈O₁₆) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.     

Assessment of naturally occurring arsenic contamination in the groundwater of Sarkisla Plain (Sivas/Turkey)

High arsenic levels in groundwater of the aquifers, belonging to the Pliocene terrestrial layers and Quaternary alluvial sediments, have become a significant problem for the inhabitants living in Sarkisla (Turkey). The main objective of this study was to determine the origin and arsenic contamination mechanisms of the Sarkisla drinking water aquifer systems. The highest arsenic concentrations were found in Pliocene layers and alluvial sediments with concentrations ranging from 2.1 to 155 mg/kg. These rocks are the main aquifers in the study area, and most of the drinking groundwater demand is met by these aquifers. Groundwater from the Pliocene aquifer is mainly Ca-HCO₃ and Ca-SO₄ water type with high EC values reaching up to 3,270 μS/cm, which is due to the sulfate dissolution in some parts of the alluvial aquifer. Stable isotope values showed that the groundwater was of meteoric origin. Tritium values for the groundwater were between 8.31 and 14.06 TU, representing a fast circulation in the aquifer. Arsenic concentrations in the aquifers were between 0.5 and 345 μg/L. The highest arsenic concentrations detected in the Pliocene aquifer system reached up to 345 μg/L with an average value of 60.38 μg/L. The arsenic concentrations of the wells were high, while the springs had lower arsenic concentrations. These springs are located in the upper parts of the study area where the rocks are less weathered. The hydrogeochemical properties demonstrated that the water–rock interaction processes in sulfide-bearing rocks were responsible for the remarkably high groundwater arsenic contamination in the study area. In the study area, the arsenic levels determined in groundwater exceeded the levels recommended by the WHO. Therefore, it is suggested that this water should not be used for drinking purposes and new water sources should be investigated.     

Transportation and evolution of trace element bearing phases in stream sediments in a mining – Influenced basin (Upper Isle River,France)

Arsenic-bearing stream sediments enter the Upper Isle River, an Au mining-influenced basin (France), by the discharge of mining sites, tailings runoff and weathering of mineralized veins in granites and gneiss. Some fresh ochreous As-rich deposits on the river banks and in floodplains are identified as additional As-rich point sources (As between 0.07 and 6.5 wt.%). The <63 μm fraction of stream sediments contains elevated As bulk concentrations, ranging from 160 to 890 mg/kg, compared to the geochemical background (70 mg/kg on average). It is also enriched in Cd, Hg and W. Spatial variations of these trace elements show 3 significant increases corresponding to the 3 drained mining districts. They decrease down river but are still enriched 30 km downstream of the mining districts due to downstream transportation. Three types of trace element-bearing phases have been identified as: (i) detrital primary sulfides, with high in situ As percentages (up to 43.7 wt.%). They also carry significant amounts of W according to the differences in chemical compositions of the total and light <63 μm fractions. These sulfide particles do not show any sign of alteration in the oxygenated stream sediments; (ii) Secondary Fe–Mn oxyhydroxides,some with very high in situ As₂O₅ concentrations (up to 59.8 wt.%) and with about 40% of the total Cd composition. They occur as fresh precipitates in the river banks and floodplains and as discrete particles in stream sediments and (iii) Al–Si fine-grained phases. Their major element composition is highly variable with in situ As₂O₅ concentrations ranging between 430 and 5020 mg/kg. This type of solid phase is also the major carrier of Hg.