Harald Neidhardt

Influences of groundwater extraction on the distribution of dissolved As in shallow aquifers of West Bengal, India

Here we report temporal changes of As concentrations in shallow groundwater of the Bengal Delta Plain (BDP). Observed fluctuations are primarily induced by seasonally occurring groundwater movement, but can also be connected to anthropogenic groundwater extraction. Between December 2009 and July 2010, pronounced variations in the groundwater hydrochemistry were recorded in groundwater samples of a shallow monitoring well tapping the aquifer in 22-25 m depth, where Astot concentrations increased within weeks from 100 to 315 μg L(-1). These trends are attributed to a vertically shift of the hydrochemically stratified water column at the beginning of the monsoon season. This naturally occurring effect can be additionally superimposed by groundwater extraction, as demonstrated on a local scale by an in situ experiment simulating extensive groundwater withdrawal during the dry post-monsoon season. Results of this experiment suggest that groundwater extraction promoted an enduring change within the distribution of dissolved As in the local aquifer. Presented outcomes contribute to the discussion of anthropogenic pumping influences that endanger the limited and yet arsenic-free groundwater resources of the BDP.

Effect of carbon sources and of sulfate on microbial arsenic mobilization in sediments of West Bengal, India.

Arsenic (As) dissolution from sediments into groundwater in the Bengal Delta/West India was investigated. Two experimental sites were choosen with contrasting As concentrations in shallow groundwater. Apparently patches of high-As and low-As sediments occured in close neigbourhood. A fast As mobilization with lactate or ethanol as carbon sources and sulfate as an electron acceptor and a possible influence of indigenous flora because of higher As amounts and an increasing total cell count was observed over a peroid of 110 days. Sucrose was a less suitable carbon source. Inoculation of an arsenate-reducing Pseudomonas putida WB, that was isolated from the sediments did not improve arsenic mobilization. Maximal arsenic concentrations up to 160μg/l were leached out from sediment columns with lactate or ethanol+sulfate in the water at natural groundwater flow, but the majority of the As remained in the sandy sediments. Some correlation of arsenic with Fe, but not with Mn dissolution seems to exist.

Quantifying Reactive Transport Processes Governing Arsenic Mobility after Injection of Reactive Organic Carbon into a Bengal Delta Aquifer

Over the last few decades, significant progress has been made to characterize the extent, severity, and underlying geochemical processes of groundwater arsenic (As) pollution in S/SE Asia. However, comparably little effort has been made to merge the findings into frameworks that allow for a process-based quantitative analysis of observed As behavior and for predictions of its long-term fate. This study developed field-scale numerical modeling approaches to represent the hydrochemical processes associated with an in situ field injection of reactive organic carbon, including the reductive dissolution and transformation of ferric iron (Fe) oxides and the concomitant release of sorbed As. We employed data from a sucrose injection experiment in the Bengal Delta Plain to guide our model development and to constrain the model parametrization. Our modeling results illustrate that the temporary pH decrease associated with the sucrose transformation and mineralization caused pronounced, temporary shifts in the As partitioning between aqueous and sorbed phases. The results also suggest that while the reductive dissolution of Fe(III) oxides reduced the number of sorption sites, a significant fraction of the released As was rapidly scavenged through coprecipitation with neo-formed magnetite. These secondary reactions can explain the disparity between the observed Fe and As behavior.

Processes governing arsenic retardation on Pleistocene sediments: adsorption experiments and model-based analysis

In many countries of south/south-east Asia, reliance on Pleistocene aquifers for the supply of low-arsenic groundwater has created the risk of inducing migration of high-arsenic groundwater from adjacent Holocene aquifers. Adsorption of arsenic onto mineral surfaces of Pleistocene sediments is an effective attenuation mechanism. However, little is known about the sorption under anoxic conditions, in particular the behavior of arsenite. We report the results of anoxic batch experiments investigating arsenite (1–25 µmol/L) adsorption onto Pleistocene sediments under a range of field-relevant conditions. The sorption of arsenite was non-linear and decreased with increasing phosphate concentrations (3–60 µmol/L) while pH (range 6–8) had no effect on total arsenic sorption. To simulate the sorption experiments, we developed surface complexation models of varying complexity. The simulated concentrations of arsenite, arsenate and phosphate were in good agreement for the isotherm and phosphate experiments while secondary geochemical processes affected the pH experiments. For the latter, the model-based analysis suggests that the formation of solution complexes between organic buffers and Mn(II) ions promoted the oxidation of arsenite involving naturally-occurring Mn-oxides. Upscaling the batch experiment model to a reactive transport model for Pleistocene aquifers demonstrates strong arsenic retardation and could have useful implications in the management of arsenic-free Pleistocene aquifers.

An Insight into the Spatio-vertical Heterogeneity of Dissolved Arsenic in Part of the Bengal Delta Plain Aquifer in West Bengal (India)

Naturally occurring, carcinogenic, arsenic (As) is omnipresent in hydrological systems, and is considered as the most serious abiotic contaminant of groundwater in several parts of the world (Smedley and Kinniburgh, Appl Geochem 17:517–56, 2002; Chatterjee et al., Environ Geol 49:188–206, 2005; Charlet et al., Appl Geochem 22:1273–1292, 2007; Mukherjee et al., J Contam Hydrol 99:1–7, 2008a; Neumann et al., Nat Geosci 3:46–52, 2010 and references therein). Holocene aquifers of south-east Asia (mostly shallow, <50 m) often contain high As groundwater. The groundwater is predominantly used for irrigation and domestic purposes, e.g., cooking, drinking and bathing (Bhattacharya et al., J Water Resour Dev 13:79–92, 1997; Bhattacharyya et al., Mol Cell Biochem 253:347–355, 2003a; Charlet et al., Appl Geochem 22:1273–1292, 2007). In south-east Asia, As-rich groundwaters are often found in alluvial plains of regional rivers (Fendorf et al., Science 328:1123–1127, 2010). Prolonged consumption of groundwater with elevated levels of As may cause a formidable threat to human health and millions of people are now at risk (Bhattacharyya et al. Mol Cell Biochem 253:347–355, 2003a; Chatterjee et al., Water Res 44:5803–5812, 2010; Nath et al., Water Air Soil Pollut 190:95–113, 2008a). Arsenic contamination in groundwater and related health issues is considered as the greatest mass poisoning in human history (Smith et al., Bull World Health Organ 78:1093–1103, 2000).

Biogeochemical phosphorus cycling in groundwater ecosystems – Insights from South and Southeast Asian floodplain and delta aquifers

The biogeochemical cycling of phosphorus (P) in South and Southeast Asian floodplain and delta aquifers has received insufficient attention in research studies, even though dissolved orthophosphate (PO43-) in this region is closely linked with the widespread contamination of groundwater with toxic arsenic (As). The overarching aim of this study was to characterize the enrichment of P in anoxic groundwater and to provide insight into the biogeochemical mechanisms underlying its mobilization, subsurface transport, and microbial cycling. Detailed groundwater analyses and in situ experiments were conducted that focused on three representative field sites located in the Red River Delta (RRD) of Vietnam and the Bengal Delta Plain (BDP) in West Bengal, India. The results showed that the total concentrations of dissolved P (TDP) ranged from 0.03 to 1.50 mg L-1 in groundwater, with PO43- being the dominant P species. The highest concentrations occurred in anoxic sandy Holocene aquifers where PO43- was released into groundwater through the microbial degradation of organic carbon and the concomitant reductive dissolution of Fe(III)-(hydr)oxides. The mobilization of PO43- may still constitute an active process within shallow Holocene sediments. Furthermore, a sudden supply of organic carbon may rapidly decrease the redox potential, which causes an increase in TDP concentrations in groundwater, as demonstrated by a field experiment. Considering the subsurface transport of PO43-, Pleistocene aquifer sediments represented effective sinks; however, the enduring contact between oxic Pleistocene sediments and anoxic groundwater also changed the sediments PO43--sorption capacity over time. A stable isotope analysis of PO43--bound oxygen indicated the influences of intracellular microbial cycling as well as a specific PO43- source with a distinct isotopically heavy signal. Consequently, porous aquifers in Asian floodplain and delta regions proved to be ideal natural laboratories to study the biogeochemical cycling of P and its behavior in groundwater environments.

Organic layers favor phosphorus storage and uptake by young beech trees (Fagus sylvatica L.) at nutrient poor ecosystems

AimsThe accumulation of organic layers in forests is linked to decreasing nutrient availability. Organic layers might represent a source of phosphorus (P) nutrition of trees in forests. Our aims were i) to test if the fate of P in a tree sapling-soil system differs between nutrient-poor and nutrient-rich sites, and ii) to assess the influence of organic layers on the fate of P in a tree sapling-soil system at either site.MethodsWe conducted a 33P labeling experiment of mesocosms of beech (Fagus sylvatica) saplings.ResultsRecovery of 33P in the organic layer was greater under nutrient-poor than under nutrient-rich conditions likely caused by the abundance of microorganisms and roots. Under nutrient-poor conditions, we found that the mobilization of P followed by efficient uptake promoted tree sapling growth if the organic layer was present. The presence of organic layers did not significantly influence P uptake by beech saplings under nutrient-rich conditions suggesting mechanisms of P mobilization in addition to organic matter mineralization.ConclusionsOur results highlight the importance of organic layers for P nutrition of young beech trees growing on nutrient-poor soils in temperate forest ecosystems. The role of organic layers should be considered for sustainable forest management.