Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Hydrogeochemical comparison and effects of overlapping redox zones on groundwater arsenic near the Western (Bhagirathi sub-basin, India) and Eastern (Meghna sub-basin, Bangladesh) margins of the Bengal Basin

Although arsenic (As) contamination of groundwater in the Bengal Basin has received wide attention over the past decade, comparative studies of hydrogeochemistry in geologically different sub-basins within the basin have been lacking. Groundwater samples were collected from sub-basins in the western margin (River Bhagirathi sub-basin, Nadia, India; 90 samples) and eastern margin (River Meghna sub-basin; Brahmanbaria, Bangladesh; 35 samples) of the Bengal Basin. Groundwater in the western site (Nadia) has mostly Ca-HCO(3) water while that in the eastern site (Brahmanbaria) is much more variable consisting of at least six different facies. The two sites show differences in major and minor solute trends indicating varying pathways of hydrogeochemical evolution However, both sites have similar reducing, postoxic environments (p(e): +5 to -2) with high concentrations of dissolved organic carbon, indicating dominantly metal-reducing processes and similarity in As mobilization mechanism. The trends of various redox-sensitive solutes (e.g. As, CH(4), Fe, Mn, NO(3)(-), NH(4)(+), SO(4)(2-)) indicate overlapping redox zones, leading to partial redox equilibrium conditions where As, once liberated from source minerals, would tend to remain in solution because of the complex interplay among the electron acceptors.     

Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia

Little is known about the importance of drainage/irrigation channels and biogeochemical processes in arsenic distribution of shallow groundwaters from the Hetao basin. This investigation shows that although As concentrations are primarily dependent on reducing conditions, evaporation increases As concentration in the centre of palaeo-lake sedimentation. Near drainage channels, groundwater As concentrations are the lowest in suboxic-weakly reducing conditions. Results demonstrate that both drainage and irrigation channels produce oxygen-rich water that recharges shallow groundwaters and therefore immobilize As. Groundwater As concentration increases with a progressive decrease in redox potential along the flow path in an alluvial fan. A negative correlation between SO₄²⁻ concentrations and δ³⁴S values indicates that bacterial reduction of SO₄²⁻ occurs in reducing aquifers. Due to high concentrations of Fe (>0.5 mg L⁻¹), reductive dissolution of Fe oxides is believed to cause As release from aquifer sediments. Target aquifers for safe drinking water resources are available in alluvial fans and near irrigation channels.     

Evaluating mobilization and transport of arsenic in sediments and groundwaters of Aquia aquifer, Maryland, USA

Groundwater and sediment samples were collected along a flow path in the Aquia aquifer (Paleocene), Maryland in order to examine and study the factors influencing "evolution" of arsenic (As) in these groundwaters. The Aquia crops out near Washington, DC, where it is unconfined, and extends approximately 90 km down dip to the south and east towards and beneath the Chesapeake Bay. The studied flow path was chosen owing to (i) the number of accessible wells, (ii) differences in total dissolved As concentrations in groundwaters from some of the sampled wells, which reach values >/=667 nmol kg(-1) or >/=50 ppb, and (iii) the distinct difference in total dissolved As concentrations in Aquia groundwaters between the northern and southern portions of the study area. In groundwater samples, in situ separation of inorganic As species [As(III) and As(V)] were performed by using anion exchange chromatography. Subsequently, As concentrations were determined by inductively coupled plasma mass spectrometry. In situ measurements of Fe concentrations and speciation, dissolved S(-II) concentrations, pH, alkalinity, and oxidation-reduction potential (Eh) were determined to establish the oxidation-reduction conditions and solution chemistry along the flow path. Concentrations of As in 12 analyzed groundwater samples range from approximately 0.75 to 1 072 nmol kg(-1), and As(III) concentrations ranging from 0.24 to 980 nmol kg(-1) appears to be the dominant form of As in solution. 50% of the studied wells yielded groundwaters with concentrations that exceed the US EPA's Maximum Contaminant Level for As in drinking water of 133 nmol kg(-1) or 10 ppb. In order to examine the solid phase speciation of As within the aquifer sediments, we collected a number of Aquia sediment samples from a drill core that was archived at the Maryland Geological Survey. These sediment samples were evaluated using a previously established sequential extractions procedure. Solid phase As concentrations range between 973 and 2,012 nmol kg(-1). Additionally, petrographic, X-Ray diffraction and diffuse reflectance spectroscopy analyses of the Aquia sediments reveal presence of glauconite, and smectite along with goethite and hematite within the samples. Here, we present the possible mechanisms responsible for the elevated As concentrations in the studied groundwaters of the Aquia aquifer.     

Quaternary stratigraphy, sediment characteristics and geochemistry of arsenic-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in central Bangladesh

This study focuses on the Quaternary stratigraphy, sediment composition, mineralogy, and geochemistry of arsenic (As)-contaminated alluvial aquifers in the Ganges–Brahmaputra floodplain in the central Bangladesh. Arsenic concentrations in 85 tubewells in Manikganj area, 70 km northwest of Dhaka City, range from 0.25 µg/L to 191 µg/L with a mean concentration of 33 µg/L. Groundwater is mainly Ca–HCO₃ type with high concentrations of dissolved As, Fe, and Mn, but low level of SO₄. The uppermost aquifer occurs between 10 m and 80 m below the surface that has a mean arsenic concentration of 35 µg/L. Deeper aquifer (> 100 m depth) has a mean arsenic concentration of 18 µg/L. Sediments in the upper aquifer are mostly gray to dark-gray, whereas sediments in the deep aquifer are mostly yellowing-gray to brown. Quartz, feldspar, mica, hornblende, garnet, kyanite, tourmaline, magnetite, ilmenite are the major minerals in sediments from both aquifers. Biotite and potassium feldspar are dominant in shallow aquifer, although plagioclase feldspar and garnet are abundant in deep aquifer sediments. Sediment composition suggests a mixed provenance with sediment supplies from both orogenic belts and cratons. High arsenic concentrations in sediments are found within the upper 50 m in drilled core samples. Statistical analysis shows that As, Fe, Mn, Ca, and P are strongly correlated in sediments. Concentrations of Cd, Cu, Ni, Zn, and Bi also show strong correlations with arsenic in the Manikganj sediment cores. Authigenic goethite concretions, possibly formed by bacteria, are found in the shallow sediments, which contain arsenic of a concentration as high as 8.8 mg/kg. High arsenic concentrations in aquifers are associated with fine-grained sediments that were derived mostly from the recycled orogens and relatively rapidly deposited mainly by meandering channels during the Early to Middle Holocene rising sea-level conditions.     

Hydrochemical and multivariate statistical interpretations of spatial controls of nitrate concentrations in a shallow alluvial aquifer around oxbow lakes (Osong area, central Korea)

Hydrochemical and multivariate statistical interpretations of 16 physicochemical parameters of 45 groundwater samples from a riverside alluvial aquifer underneath an agricultural area in Osong, central Korea, were performed in this study to understand the spatial controls of nitrate concentrations in terms of biogeochemical processes occurring near oxbow lakes within a fluvial plain. Nitrate concentrations in groundwater showed a large variability from 0.1 to 190.6 mg/L (mean = 35.0 mg/L) with significantly lower values near oxbow lakes. The evaluation of hydrochemical data indicated that the groundwater chemistry (especially, degree of nitrate contamination) is mainly controlled by two competing processes: 1) agricultural contamination and 2) redox processes. In addition, results of factorial kriging, consisting of two steps (i.e., co-regionalization and factor analysis), reliably showed a spatial control of the concentrations of nitrate and other redox-sensitive species; in particular, significant denitrification was observed restrictedly near oxbow lakes. The results of this study indicate that sub-oxic conditions in an alluvial groundwater system are developed geologically and geochemically in and near oxbow lakes, which can effectively enhance the natural attenuation of nitrate before the groundwater discharges to nearby streams. This study also demonstrates the usefulness of multivariate statistical analysis in groundwater study as a supplementary tool for interpretation of complex hydrochemical data sets.