Factors responsible for high arsenic concentrations in two groundwater catchments in Taiwan

High As contents in groundwater were found in two neighboring catchments – the Chianan plain and the southern Choushui river alluvial fan in Taiwan. The groundwater quality, the redox potential and the As distribution of the Chianan plain were characterized using factor analysis, redox zoning and a geochemical program. The results were compared with those of the southern Choushui river alluvial fan. Possible As release mechanisms are also elucidated. Factors 1 and 2 of the groundwater in the Chianan plain – the salinization factor and the As enrichment factor – are similar to those in the southern Choushui river alluvial fan. However, the spatial distribution of reductive tendency in the Chianan plain is different to that in the Choushui river alluvial fan, and yields spatially distinct hydrogeochemical environments in these two neighboring areas. The reduction potential in the Chianan plain is stronger than that in the Choushui river alluvial fan. The difference between the reduction potentials in these two vicinal areas influences the concentrations of As in groundwater. The reductive dissolution of As-rich Fe oxyhydroxide is suggested to be the major mechanism for release of As to the groundwater in the Chianan plain and the Choushui river alluvial fan of Taiwan.     

Geochemical characterization of arsenic-affected alluvial aquifers of the Bengal Delta (West Bengal and Bangladesh) and Chianan Plains (SW Taiwan): Implications for human health

Major ion and trace element analyses were performed on groundwater samples collected from the Bengal Delta (Chakdaha municipality, West Bengal and Manikgonj town, Bangladesh) and Chianan Plains (SW Taiwan) to compare geochemical characteristics. Results showed that concentrations of Na, K, Mg, Cl and SO₄ were generally higher in Chianan Plain (CNP) groundwaters, while high Ca was observed in Bengal Delta Plain (BDP) groundwater. Measured As concentrations in groundwaters of BDP and CNP showed large variations, with mean As concentrations of 221 μg/L (range: 1.1-476 μg/L) in Chakdaha, 60 μg/L (range: 0.30-202 μg/L) in Manikgonj, and 208 μg/L (range: 1.3-575 μg/L) in CNP groundwater. The Fe-reduction mechanism was found to be the dominant geochemical process in releasing As from sediment to groundwater in Chakdaha, West Bengal, however the Mn-reduction process was dominant in groundwaters of Manikgonj, Bangladesh. In Chianan Plain groundwater, a combination of geochemical processes (e.g., bacterial Fe-reduction, mineral precipitation and dissolution reactions) controlled release of As. Fluorescence spectral patterns of the groundwater showed low relative fluorescence intensity (RFI) of dissolved humic substances in BDP groundwater (mean: 63 and 72 QSU, Chakdaha and Manikgonj, respectively), while high RFI was observed in CNP groundwater (mean: 393 QSU). The FT-IR spectra of the extracted humic acid fractions from sediments of Chianan Plain showed a stronger aliphatic band at 2850-3000 cm⁻¹ and a higher resolved fingerprint area (from 1700 to 900 cm⁻¹) compared with BDP sediments. The geochemical differences between the study areas may play a crucial role in the clinical manifestation of Blackfoot disease observed only in Chianan Plain, SW Taiwan.     

The origin of groundwater arsenic and fluorine in a volcanic sedimentary basin in central Mexico: a hydrochemistry hypothesis

A groundwater sampling campaign was carried out in the summer of 2013 in a low-temperature geothermal system located in Juventino Rosas (JR) municipality, Guanajuato State, Mexico. This groundwater presents high concentrations of As and F^? and high Rn counts, mainly in wells with relatively higher temperature. The chemistry of major elements was interpreted with different methods, like Piper and D’Amore diagrams. These diagrams allowed for classification of four groundwater types located in three hydrogeological environments. The aquifers are hosted mainly in alluvial-lacustrine sediments and volcanic rocks in interaction with fault and fracture systems. The subsidence, faults and fractures observed in the study area can act as preferential channels for recharge and also for the transport of deep fluids to the surface, especially in the basin plain. The formation of a piezometric dome and the observed hydrochemical behavior of groundwater suggest a possible origin of the As and F^?. Geochemical processes occurring during water–rock interaction are related to high concentrations of As and F^?. High temperatures and alteration processes (like rock weathering) induce dissolution of As and F^?-bearing minerals, increasing the content of these elements in groundwater.     

Identification of hydrogeochemical processes and pollution sources of groundwater resources in the Marand plain,northwest of Iran

The main aims of the present study are to identify the major factors affecting hydrogeochemistry of groundwater resources in the Marand plain, NW Iran and to evaluate the potential sources of major and trace elements using multivariate statistical analysis such as hierarchical clustering analysis (HCA) and factor analysis (FA). To achieve these goals, groundwater samples were collected in three sampling periods in September 2013, May 2014 and September 2014 and analyzed with regard to ions (e.g., Ca²⁺, Mg²⁺, Na⁺ and K⁺, HCO₃ ^?, SO₄ ^2?, Cl^?, F^? and NO₃ ^?) and trace metals (e.g., Cr, Pb, Cd, Mn, Fe, Al and As). The piper diagrams show that the majority of samples belong to Na–Cl water type and are followed by Ca–HCO₃ and mixed Ca–Na–HCO₃. Cross-plots show that weathering and dissolution of different rocks and minerals, ion exchange, reverse ion exchange and anthropogenic activities, especially agricultural activities, influence the hydrogeochemistry of the study area. The results of the FA demonstrate that 6 factors with 81.7% of total variance are effective in the overall hydrogeochemistry, which are attributed to geogenic and anthropogenic impacts. The HCA categorizes the samples into two clusters. Samples of cluster C1, which appear to have higher values of some trace metals like Pb and As, are spatially located at the eastern and central parts of the plain, while samples of cluster C2, which express the salinization of the groundwater, are situated mainly westward with few local exceptions.     

Assessing the hydrogeochemistry and water quality of the Aji-Chay River,northwest of Iran

Aji-Chay River is one of the most important surface reservoirs of northwest of Iran, because it passes through Tabriz city and discharges to Urmia Lake, one of the largest permanent salty lakes in the world. The main objectives of the present study are to evaluate its overall water quality and to explore its hydrogeochemical characteristics, including the potential contamination from heavy metals and metalloids such as Co, Pb, Zn, Cd, Cu, Cr, Al and As. For this purpose, 12 water samples were collected from the main river body and its tributaries within Tabriz plain. The Piper diagram classified water samples mainly into Na–Cl and secondary into Ca–HCO₃ and mixed Ca–Mg–Cl types, denoting a profound salinization effect. The cross-plots showed that natural geochemical processes including dissolution of minerals (e.g., carbonates, evaporites and silicates), as well as ion exchange, are the predominant factors that contribute to fluvial hydrogeochemistry, while anthropogenic activities (industrial and agricultural) impose supplementary effects. Cluster analysis classified samples into two distinct clusters; samples of cluster B appear to have elevated electrical conductivity (EC) values and trace metals concentrations such as Co, Pb and Cd, while SiO₂ and Zn are low in comparison with the samples of the cluster A. The main processes controlling Aji-Chay River hydrogeochemistry and water quality were identified to be salinization and rock weathering. Both are related with geogenic sources which enrich river system with elevated values of Na⁺, Cl^?, Ca²⁺, Mg²⁺, K⁺, SO₄ ^2? and EC as a direct effect of evaporites leaching and elevated values of Pb and Cd as an impact from the weathering process of volcanic formations. According to the US salinity diagram, all of the water samples are unsuitable for irrigation as having moderate to bad quality.     

Geochemical techniques to identify fluid sources in highly pressured casing-casing annuli (CCA)

The buildup of high pressure in the casing-casing annulus (CCA) threatens well integrity and can cause serious incidents in case of left untreated. Either, trapped water in the cement column or a dynamic water inflow represent potential fluid sources for the elevated CCA pressure. This study presents a sequential methodology to determine the provenance of CCA effluent as trigger for high pressure in newly drilled wells. Single fluid types, multicomponent mixing, and secondary fluid alteration processes were identified through inorganic geochemical techniques; in detail by monitoring the hydrochemical (major, minor, and trace elements) and stable isotopic (δ²H, δ¹⁸O) relationship between fluid candidates. As a proof-of-concept, geochemical signatures of CCA effluent from three wells were linked with potential source candidates, i.e., utilized drilling fluids (mud filtrate, supply water) from the prospect well site, groundwater from Lower - Upper Cretaceous aquifers, and Upper Jurassic - Upper Triassic formation waters from adjacent wells and fields. The detection of geochemical affinities of CCA water with groundwater from a Lower Cretaceous aquifer postulates one single lithological unit as source for active groundwater inflow. Nonreactive elements (Na⁺, Cl⁻) and environmental isotopes (δ²H, δ¹⁸O) were found to be most suited tools for primary fluid identification. The ²H/¹H and ¹⁸O/¹⁶O ratios of supply water and mud filtrate are generally close to global meteoric water and Tertiary groundwater composition, while formation water from Mesozoic units (Cretaceous, Jurassic, and Triassic) can individually be distinguished through increasing ratios in δ¹⁸O and δ²H. Compositional anomalies in SO₄²⁻ and K⁺, and extreme alkaline conditions for CCA water indicate the occurrence of secondary fluid alteration processes, likely caused by the contact of inflowing groundwater with alkaline minerals in the cement column or by fluid mixing with residuals of potassium chloride (KCl) additives from the drilling process. The geochemical techniques from this study facilitate the detection of high CCA pressure and fluid leakages sources. As a practical benefit, workover engineers are enabled to plan for potential remedial actions prior to moving the rig to affected well sites; thereby significantly reducing operational costs. Appropriate remedial solutions can be induced for safe well abandonment, plus to resume operation at the earliest time.     

Interrelationship of TOC,As, Fe,Mn, Al and Si in shallow alluvial aquifers in Chapai-Nawabganj,Northwestern Bangladesh: implication for potential source of organic carbon

Two boreholes and ten piezometers in the Ganges flood plain were drilled and installed for collecting As-rich sediments and groundwater. Groundwater samples from the Ganges flood plain were collected for the analysis of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃ ⁻, SO₄ ²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction was performed to characterize the major mineral contents of aquifer sediments and X-ray fluorescence (XRF) to analyze the major chemical composition of alluvial sediments. Results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescence index (15–38 QSU) of humic substance in groundwater was measured using spectrofluorometer, the results revealed that groundwater in the Ganges flood plain contains less organic matter (OM). Arsenic concentration in water ranges from 2.8 to 170 μg/L (mean 50 μg/L) in the Ganges flood plain. Arsenic content in sediments ranges from 2.1 to 14 mg/kg (mean 4.58 mg/kg) in the flood plains. TOC ranges from 0.49 to 3.53 g/kg (mean 1.64 g/kg) in the Ganges flood plain. Arsenic is positively correlated with TOC (R ² = 0.55) in sediments of this plain. Humic substances were extracted from the sediments from the Ganges flood plain. Fourier transform infrared analysis of the sediments revealed that the plain contains less humic substances. The source of organic carbon was assigned from δ¹³C values obtained using elemental analysis-isotope ratio mass spectrometry (EA-IRMS); the values (−10 to −29.44‰) strongly support the hypothesis that the OM of the Ganges flood plain is of terrestrial origin.     

Hydrogeochemical processes affecting groundwater in an irrigated land in Central Tunisia

Detailed hydrogeochemical investigation has provided new information concerning the major factors and mechanisms controlling the groundwater chemistry of Chougafiya basin. The hydrogeochemical characteristics of groundwaters comprise three main types: Cl–SO₄–Ca, Cl–SO₄–Na and Cl–Na. Hydrochemical characteristics based on the bivariate diagrams of major (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Na⁺, Mg²⁺, K⁺ and Ca²⁺) and some trace (Br^? and Sr²⁺) ions, mineral saturation indices and hierarchical cluster analysis indicate different origins of groundwater mineralization. The water–rock interaction (dissolution of evaporitic minerals), followed by cation exchange reactions with clay minerals, constitute the main processes that control groundwater salinization. However, the chemical composition of brackish groundwater in the central and southern parts of the study area is influenced by a mixing process with Sabkhas salt groundwater. The mixing proportions inferred from chloride mass balance prove that the contribution of Sabkhas groundwater to Quaternary aquifer ranges between 2.7 and 9.1 %. These intrusion rates reflect the progress of the saltwater–freshwater interface, which is mainly controlled by the piezometric level variation and the distance to the Sabkhas.     

Influence of hydrostratigraphy and structural setting on the arsenic occurrence in groundwater of the Cimino-Vico volcanic area (central Italy)

Arsenic occurrence in groundwater near the Cimino-Vico volcanoes (central Italy) was analysed considering the hydrostratigraphy and structural setting and the shallow and deep flows interacting within the Quaternary volcanics. Groundwater is the local source of drinking water. As documented in the past, arsenic in the groundwater has become a problem, and the European maximum allowable contaminant level was recently lowered to 10 μg/L. Chemical analyses of groundwater were conducted, sampled over an area of about 900 km², from 65 wells and springs representative of the volcanic aquifer and thermal waters. Considering the type of aquifer, the nature of the aquifer formation and its substratum, the hydrochemical data highlight that the arsenic content of the groundwater is mainly connected with the hydrothermal processes in the volcanic area. Thermal waters (54–60°C) fed from deep-rising fluids show higher arsenic concentrations (176–371 μg/L). Cold waters sampled from the volcanic aquifer are characterized by a wide variability in their arsenic concentration (1.6–195 μg/L), and about 62% exceed the limit of 10 μg/L. Where the shallow volcanic aquifer is open to deep-rising thermal fluids, relatively high arsenic concentrations (20–100 μg/L) are found. This occurs close to areas of the more recent volcano-tectonic structures.     

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.     

Uranium and arsenic dynamics in volcano-sedimentary basins – An exemplary study in North-Central Mexico

Uranium and As in deep groundwater of the volcano-sedimentary Villa de Reyes Graben around the city of San Luis Potosí in semi-arid North-Central Mexico (mean U: 7.6 μg L⁻¹, max. 138 μg L⁻¹; mean As: 11.4 μg L⁻¹, max. 25.8 μg L⁻¹) partly exhibit concentrations in excess of the WHO guideline values and thus endanger the quality of the most important drinking water source. To unravel the mechanisms for their enrichment in groundwater, the potential trace element sources, volcanic rocks and basin fill sediments, were characterized. A total of 131 solid and liquid samples were analyzed for major and trace element composition. The As/U hydrogeochemical signatures, their behavior during rock alteration and evidence from other major and trace element distributions, especially rare earth elements, strongly argue for dissolution of acid volcanic glass to be the dominating process of U and As release into groundwater. This natural baseline quality representing water–acid volcanic rock interaction is modified by additional trace element (preferentially As) mobilization from the sedimentary basin fill, representing a secondary source, in the course of decarbonatization of playa lake sediments and desorption from Fe-(hydr)oxide coated clastic material. The common behavior of both elements during magmatic differentiation and growing drift apart in sedimentary environments are important findings of this work. Comparison with recent findings in a similar environment suggests a common primary trace element source identification but significant differences in the evolution of As and U distribution. Geological and climatic similarity to numerous volcano-sedimentary basins makes the findings useful for water management purposes and transferable to other semi-arid regions facing challenges of geogenically impacted drinking water quality.     

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.     

Origin of methane in high-arsenic groundwater of Taiwan – Evidence from stable isotope analyses and radiocarbon dating

Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH₄). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH₄ and its hydrological implications, stable carbon isotope ratios (δ¹³C) and radiocarbon (¹⁴C) ages of exsolved CH₄, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ¹³C_CH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ¹³C_CH4=38.2‰) from the Ilan plain, all CH₄ samples analyzed were produced via microbially mediated CO₂ reduction. Many δ¹³C_DIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO₂ reduction. (2) Almost all the ¹⁴C ages of CH₄ samples from the shallow aquifer (I) (<60 m depth) are greater than the ¹⁴C ages of coexisting DIC and sediments, suggesting the presence of CH₄ from underlying aquifers. (3) The ¹⁴C ages of coexisting CH₄, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH₄ and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH₄ and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH₄ sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO₂ and CH₄ from underlying strata.     

Understanding groundwater chemistry in Mediterranean semi-arid system using multivariate statistics techniques and GIS methods: case of Manouba aquifer (Northeastern Tunisia)

The rapid urbanization and industrialization of the Manouba plain (Northeastern Tunisia), the extensive agricultural expansion and the succession of dry years during recent decades have exerted greatly load on the water needs and lead to groundwater quality degradation. The aim of this study is to evaluate the processes controlling the groundwater mineralization of the shallow aquifer for determining its suitability for drinking and agricultural purposes. For establishing that, we combine several geological, hydrological and hydrochemical data with geostatistical techniques. The samples were collected at 17 sites covering 230 km² of the study area and analyzed for major and trace components. The total dissolved solid (TDS) content ranges from 1372 to 3999 mg/l. The results of Piper diagram indicate that Na⁺/Cl^? and Ca²⁺?>?Na⁺/SO₄ ^2? were the main dominant water types localized in the sloping sides of the watershed and near the saline depression; the suitability for irrigation use was also evaluated. The high concentrations of nitrates and chlorides are indicators of anthropogenic pollution, like the agricultural over application of nitrogen fertilizers and the discharge of domestic and industrial wastewater. Saturation indexes calculated by using PHREEQC (USGS) program show that groundwaters are undersaturated with evaporitic minerals (halite, gypsum) and saturated with carbonates (calcite, aragonite). The use of principal component analysis and hierarchical cluster analysis has shown that two main factors accounting 67.13% of the information of variability within the dataset confirm the existence of dissolution of evaporitic minerals and the mechanisms of nitrate increasing the salinity of the Manouba groundwater.     

Assessment of an arid region soil capacity on natural attenuation of municipal treated wastewater: a column experiment using soil of Varamin area,Iran

Soil aquifer treatment (SAT) is an effective indirect technique for wastewater reuse. The present study aims at assessing the soil capacity in arid region of Varamin on natural attenuation of inorganic constituents of municipal treated wastewater of Tehran City. In order to simulate SAT pond, four columns of 30 cm in height and 4 cm in diameter were filled with sandy loam soil taken from artificial recharge pond in Varamin plain. These columns were recharged by secondary treated wastewater from Shahre-Rey treatment plant under the plan of 12-h wetting and drying cycles. During the experiment, 50 pore volume passed through each column. The pH, EC, TDS, SAL, SAR, major ions, nitrate, phosphate and trace elements were measured in influent and effluent samples. The concentration of Na⁺, Ca²⁺, Mg²⁺, Cl^? and SO₄^2? increased in effluent samples due to a washout process and dissolution of minerals. The soil could only attenuate NO₃^?, K⁺, Rb and PO₄^3? with the percentage of 18.4, 24.6, 67.7 and 83.6, respectively. The soil of studied area is rich in Cr, Ni, Sr, Pb, Cu, Zn, Ba and Rb. The concentrations of all mentioned trace elements, with the exception of Rb, have increased in the effluent samples with respect to influent. Also, the quality indices of TDS, SAL and SAR have increased 10.6, 25.2 and 8.7%, respectively, in effluent. Soil column samples, at the end of experiment, contain high amounts of major and trace elements. Consequently, there is a potential risk for groundwater contamination in long-term recharge.     

Surface and groundwater quality characterization of Deoria District,Ganga Plain,India

A water quality investigation was carried out in the Deoria district, Ganga plain, to assess the suitability of surface and groundwaters for domestic, agricultural, and industrial purposes. As much as 50 representative samples from river and groundwater were collected from various stations to monitor the water chemistry of various ions, comprising Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ⁻, SO₄ ²⁻, NO₃ ⁻, Cl⁻, F⁻, and trace metals, such as Fe, Cu, Mn, Zn, Cd, and Pb. The results showed that electrical conductance (EC), total dissolved solids (TDS), HCO₃ ⁻, Mg²⁺, Na⁺, and total hardness (TH) are above the maximum desirable limit, and apart from Fe and Mn all other trace metals are within the maximum permissible limit for drinking water. The calculated values for sodium absorption ratio (SAR), salinity, residual sodium carbonate (RSC), and permeability index (PI) indicate well to permissible use of water for irrigation. High values of Na%, RSC, and Mg-hazard (MH) at some stations restrict its use for agricultural purpose. Anthropogenic activities affect the spatial variation of water quality. Economic and social developments of the study area is closely associated with the characteristics of the hydrological network.