Lenny H. E. Winkel

Contamination of drinking water resources in the Mekong delta floodplains: Arsenic and other trace metals pose serious health risks to population

This study presents a transnational groundwater survey of the 62,000 km(2) Mekong delta floodplain (Southern Vietnam and bordering Cambodia) and assesses human health risks associated with elevated concentrations of dissolved toxic elements. The lower Mekong delta generally features saline groundwater. However, where groundwater salinity is <1 g L(-)(1) Total Dissolved Solids (TDS), the rural population started exploiting shallow groundwater as drinking water in replacement of microbially contaminated surface water. In groundwater used as drinking water, arsenic concentrations ranged from 0.1-1340 microg L(-)(1), with 37% of the studied wells exceeding the WHO guidelines of 10 microg L(-)(1) arsenic. In addition, 50% exceeded the manganese WHO guideline of 0.4 mg L(-)(1), with concentrations being particularly high in Vietnam (range 1.0-34 mg L(-)(1)). Other elements of (minor) concern are Ba, Cd, Ni, Se, Pb and U. Our measurements imply that groundwater contamination is of geogenic origin and caused by natural anoxic conditions in the aquifers. Chronic arsenic poisoning is the most serious health risk for the ~2 million people drinking this groundwater without treatment, followed by malfunction in childrens development through excessive manganese uptake. Government agencies, water specialists and scientists must get aware of the serious situation. Mitigation measures are urgently needed to protect the unaware people from such health problems.

Arsenic pollution of groundwater in Vietnam exacerbated by deep aquifer exploitation for more than a century

Arsenic contamination of shallow groundwater is among the biggest health threats in the developing world. Targeting uncontaminated deep aquifers is a popular mitigation option although its long-term impact remains unknown. Here we present the alarming results of a large-scale groundwater survey covering the entire Red River Delta and a unique probability model based on three-dimensional Quaternary geology. Our unprecedented dataset reveals that ∼7 million delta inhabitants use groundwater contaminated with toxic elements, including manganese, selenium, and barium. Depth-resolved probabilities and arsenic concentrations indicate drawdown of arsenic-enriched waters from Holocene aquifers to naturally uncontaminated Pleistocene aquifers as a result of > 100 years of groundwater abstraction. Vertical arsenic migration induced by large-scale pumping from deep aquifers has been discussed to occur elsewhere, but has never been shown to occur at the scale seen here. The present situation in the Red River Delta is a warning for other As-affected regions where groundwater is extensively pumped from uncontaminated aquifers underlying high arsenic aquifers or zones.

Environmental Selenium Research: From Microscopic Processes to Global Understanding

Selenium is a natural trace element that is of fundamental importance to human health. The extreme geographical variation in selenium concentrations in soils and food crops has resulted in significant health problems related to deficient or excess levels of selenium in the environment. To deal with these kinds of problems in the future it is essential to get a better understanding of the processes that control the global distribution of selenium. The recent development of analytical techniques and methods enables accurate selenium measurements of environmental concentrations, which will lead to a better understanding of biogeochemical processes. This improved understanding may enable us to predict the distribution of selenium in areas where this is currently unknown. These predictions are essential to prevent future Se health hazards in a world that is increasingly affected by human activities.

Modelling arsenic hazard in Cambodia : A geostatistical approach using ancillary data

Arsenic in shallow groundwaters extensively utilized for drinking, irrigation and/cooking in many parts of the world, including Cambodia, represents a major environmental hazard (Charlet and Polya, 2006). The goal of this work is to develop a spatial model to estimate As concentration in groundwater in Cambodia and hence predict areas of high As hazard as tool to inform the development of adequate measurements to reduce risks to human health. Geostatistical mapping

Natural wetland emissions of methylated trace elements

Natural wetlands are well known for their significant methane emissions. However, trace element emissions via biomethylation and subsequent volatilization from pristine wetlands are virtually unstudied, even though wetlands constitute large reservoirs for trace elements. Here we show that the average volatile fluxes of selenium (<0.12 μg m(-2) day(-1)), sulphur (<37 μg m(-2) day(-1)) and arsenic (<0.54 μg m(-2) day(-1)) from a pristine peatland are considerable and consistent over two summers. We compare these fluxes with the total concentrations in the peat and show that selenium is up to 40 times more efficiently volatilized than arsenic, and over 100 times more efficiently volatilized than sulphur. We further show that the volatilization of selenium and arsenic increases with temperature, implying that emissions of these health-relevant trace elements will increase with global warming. We suggest that biomethylation and volatilization in wetlands play a crucial role in the mobilization and global biogeochemical cycling of trace elements.

Quantitative and qualitative trapping of volatile methylated selenium species entrained through nitric acid.

Quantification and speciation of volatile selenium (Se) fluxes in remote areas has not been feasible previously, due to the absence of a simple and easily transportable trapping technique that preserves speciation. This paper presents a chemo-trapping method with nitric acid (HNO3) for volatile Se species, which preserves speciation of trapped compounds. The recovery and speciation of dimethylselenide (DMSe) and dimethyl diselenide (DMDSe) entrained through both concentrated nitric acid and hydrogen peroxide (H2O2) were compared by HPLC-ICP-MS and HPLC-HG-AFS analyses. It was demonstrated that trap reproducibility was better for nitric acid and a recovery of 65.2 +/- 1.9% for DMSe and 81.3 +/- 3.9% for DMDSe was found in nitric acid traps. HPLC-ES-MS identified dimethyl selenoxide (DMSeO) as the trapped product of DMSe. Methylseleninic acid (MSA) was identified to be the single product of DMDSe trapping. These oxidized derivatives have a high stability and low volatility, which makes nitric acid a highly attractive trapping liquid for volatile Se species and enables reconstruction of the speciation of those species. The presented trapping method is simple, quantifiable, reproducible, and robust and can potentially be applied to qualitatively and quantitatively study Se volatilization in a wide range of natural environments.

Terrestrial selenium distribution in China is potentially linked to monsoonal climate

The prevalence of terrestrial environments low in the essential trace element selenium (Se) results in large-scale Se deficiency worldwide. However, the underlying processes leading to Se-depleted environments have remained elusive. Here we show that over the last 6.8 million years (Ma) climatic factors have played a key role in the Se distribution in loess-paleosol sequences in the Chinese Loess Plateau (CLP), which lies in a severely Se-depleted region with a history of Se deficiency-related diseases. We use a combination of geochemical and paleoclimate data to demonstrate that during interglacial periods between 2.30 and 0.16 Ma, variations in the Se concentration in the CLP are potentially related to variability in Se input via East Asian monsoon-derived precipitation. Our results identify precipitation as an important controlling factor of Se distribution in monsoonal China. We suggest that atmospheric Se inputs via precipitation could also play an important role in other regions worldwide.

Selenium deficiency risk predicted to increase under future climate change

Significance The trace element selenium is essential for human health and is required in a narrow dietary concentration range. Insufficient selenium intake has been estimated to affect up to 1 billion people worldwide. Dietary selenium availability is controlled by soil–plant interactions, but the mechanisms governing its broad-scale soil distributions are largely unknown. Using data-mining techniques, we modeled recent (1980–1999) distributions and identified climate–soil interactions as main controlling factors. Furthermore, using moderate climate change projections, we predicted future (2080–2099) soil selenium losses from 58% of modeled areas (mean loss = 8.4%). Predicted losses from croplands were even higher, with 66% of croplands predicted to lose 8.7% selenium. These losses could increase the worldwide prevalence of selenium deficiency. Deficiencies of micronutrients, including essential trace elements, affect up to 3 billion people worldwide. The dietary availability of trace elements is determined largely by their soil concentrations. Until now, the mechanisms governing soil concentrations have been evaluated in small-scale studies, which identify soil physicochemical properties as governing variables. However, global concentrations of trace elements and the factors controlling their distributions are virtually unknown. We used 33,241 soil data points to model recent (1980–1999) global distributions of Selenium (Se), an essential trace element that is required for humans. Worldwide, up to one in seven people have been estimated to have low dietary Se intake. Contrary to small-scale studies, soil Se concentrations were dominated by climate–soil interactions. Using moderate climate-change scenarios for 2080–2099, we predicted that changes in climate and soil organic carbon content will lead to overall decreased soil Se concentrations, particularly in agricultural areas; these decreases could increase the prevalence of Se deficiency. The importance of climate–soil interactions to Se distributions suggests that other trace elements with similar retention mechanisms will be similarly affected by climate change.

Online preconcentration-IC-ICP-MS for selenium quantification and speciation at ultratraces.

Selenium (Se) is of key importance to human health with a very narrow concentration range of optimal dietary intake. Due to the inherent analytical challenge linked with the low natural abundance, information on precise and accurate Se speciation in deficient environments is hardly existent. This study presents a novel approach to determine Se species-specifically at ultratraces, by online coupling of a preconcentration (trap) column to an ion chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS) system. It is demonstrated that with this robust and work/time efficient method, the predominant selenium oxyanions, selenite (Se(IV)) and selenate (Se(VI)), can be quantified down to 7.3 and 8.3 picogram total Se, respectively, in an overall analytical time of 420 s, only. The applicability for environmental samples was proven on pristine volcanic ashes collected from seven different volcanoes. The high sensitivity of the novel approach allowed to determine speciation in samples that were strongly depleted in total selenium (<0.05 mg kg(-1) Se) with only minor fractions of Se mobilized (i.e., less than 10% of the total selenium was leached in 10 out of 12 samples). The studied samples showed considerate differences in selenium speciation, with selenite and selenate co-occurring in most samples. The fact that the studied sample leachates had a wide range of pH (3.78-9.55) and major anion/cation composition underlines the versatility and wide potential application range of the method presented.

Predicting geogenic arsenic contamination in shallow groundwater of south Louisiana, United States.

Groundwater contaminated with arsenic (As) threatens the health of more than 140 million people worldwide. Previous studies indicate that geology and sedimentary depositional environments are important factors controlling groundwater As contamination. The Mississippi River delta has broadly similar geology and sedimentary depositional environments to the large deltas in South and Southeast Asia, which are severely affected by geogenic As contamination and therefore may also be vulnerable to groundwater As contamination. In this study, logistic regression is used to develop a probability model based on surface hydrology, soil properties, geology, and sedimentary depositional environments. The model is calibrated using 3286 aggregated and binary-coded groundwater As concentration measurements from Bangladesh and verified using 78 As measurements from south Louisiana. The models predictions are in good agreement with the known spatial distribution of groundwater As contamination of Bangladesh, and the predictions also indicate high risk of As contamination in shallow groundwater from Holocene sediments of south Louisiana. Furthermore, the model correctly predicted 79% of the existing shallow groundwater As measurements in the study region, indicating good performance of the model in predicting groundwater As contamination in shallow aquifers of south Louisiana.