Michael V. Schaefer

Spectroscopic Evidence for Interfacial Fe(II)−Fe(III) Electron Transfer in a Clay Mineral

Interfacial electron transfer has been shown to occur between sorbed Fe(II) and structural Fe(III) in Fe oxides, but it is unknown whether a similar reaction occurs between sorbed Fe(II) and Fe(III)-bearing clay minerals. Here, we used the isotopic specificity of (57)Fe Mössbauer spectroscopy to demonstrate electron transfer between sorbed Fe(II) and structural Fe(III) in an Fe-bearing smectite clay mineral (NAu-2, nontronite). Mössbauer spectra of NAu-2 reacted with aqueous (56)Fe(II) (which is invisible to (57)Fe Mössbauer spectroscopy) showed direct evidence for reduction of NAu-2 by sorbed Fe(II). Mössbauer spectra using aqueous (57)Fe(II) showed that sorbed Fe(II) is oxidized upon sorption to the clay and pXRD patterns indicate that the oxidation product is lepidocrocite. Spectra collected at different temperatures indicate that reduction of structural Fe(III) by sorbed Fe(II) induces electron delocalization in the clay structure. Our results also imply that interpretation of room temperature and 77 K Mössbauer spectra may significantly underestimate the amount of Fe(II) in Fe-bearing clays. These findings provide compelling evidence for abiotic reduction of Fe-bearing clay minerals by sorbed Fe(II), and require us to reframe our conceptual model for interpreting biological reduction of clay minerals, as well as contaminant reduction by reduced clays.

Aquifer Arsenic Cycling Induced by Seasonal Hydrologic Changes within the Yangtze River Basin

Consumption of groundwater containing >10 μg L(-1) arsenic (As) adversely impacts more than 100 million people worldwide. Multiyear trends in aquifer As concentrations have been documented, but strong seasonal variations are not commonly observed. Here we report dramatic seasonal changes in As concentrations and aquifer chemistry within the Jianghan Plain of the Yangtze River, China. At some wells, concentrations fluctuate by more than an order of magnitude within a single year (100-1200 μg L(-1)). Groundwater extraction and sustained water levels of surface channels during the dry season induces a strong downward hydraulic gradient, seasonally supplying oxidizing (oxygen, nitrate) water to the otherwise anoxic aquifer. Oxygen and/or nitrate addition promotes a transient drop in As concentrations for 1-3 months. When recharge ceases, reducing, low-arsenic conditions are reestablished by reactive, endogenous organic carbon. Temporal variability in As concentrations is especially problematic because it increases the probability of false-negative well testing during low-arsenic seasons. However, periods of low As may also provide a source of less toxic water for irrigation or other uses. Our results highlight the vulnerability and variability of groundwater resources in the Jianghan Plain and other inland basins within Asia to changing geochemical conditions, both natural and anthropogenic, and reinforce that continued monitoring of wells in high-risk regions is essential.

Depth Stratification Leads to Distinct Zones of Manganese and Arsenic Contaminated Groundwater

Providing access to safe drinking water is a global challenge, for which groundwater is increasingly being used throughout the world. However, geogenic contaminants limit the suitability of groundwater for domestic purposes over large geographic areas across most continents. Geogenic contaminants in groundwater are often evaluated individually, but here we demonstrate the need to evaluate multiple contaminants to ensure that groundwater is safe for human consumption and agricultural usage. We compiled groundwater chemical data from three aquifer regions across the world that have been reported to have widespread As and Mn contamination including the Glacial Aquifer in the U.S., the Ganges-Brahmaputra-Mehta Basin within Bangladesh, and the Mekong Delta in Cambodia, along with newly sampled wells in the Yangtze River Basin of China. The proportion of contaminated wells increase by up to 40% in some cases when both As and Mn contaminants are considered. Wilcoxon rank-sum analysis indicates that Mn contamination consistently occurs at significantly shallower depths than As contaminated wells in all regions. Arsenic concentrations in groundwater are well predicted by redox indicators (Eh and dissolved oxygen) whereas Mn shows no significant relationship with either parameter. These findings illustrate that the number of safe wells may be drastically overestimated in some regions when Mn contamination is not taken into account and that depth may be used as a distinguishing variable in efforts to predict the presence of groundwater contaminants regionally.

Experimental constraints on redox-induced arsenic release and retention from aquifer sediments in the central Yangtze River Basin

The consumption of arsenic (As) contaminated groundwater affects the health of almost 20 million people in China. Unlike the preponderance of observations within the deltas of South and Southeast Asia, groundwater As concentrations in the central Yangtze River Basin, China, vary by up to an order of magnitude seasonally. In order to decipher the cause of seasonal release and retention of As between sediments and groundwater, we conducted batch sediment incubations under varying (imposed) redox conditions. Incubations were conducted under both N2 and O2 gas purges to simulate conditions observed within the field. In all cases, anoxic conditions resulted in As release to solution while As was removed from solution under oxic conditions. These experiments confirm that anoxia is a prerequisite for As mobilization into groundwater from Yangtze River Basin sediments. Alternating redox conditions resulted in Fe minerals dissolution, transformation, crystallization, and precipitation, and subsequent As release and retention in the system. More importantly, aquifer sediments at depths >15 m release As through multiple redox cycles without an exogenous electron donor (carbon source), organic matter in the sediments is sufficiently reactive to support microbial reduction of As(V) and Fe(III). These results provide direct evidence for previously described mechanisms explaining the observed seasonal variation of groundwater As concentrations in the central Yangtze River Basin, where seasonal changes in surface and groundwater levels drive changes in redox conditions and thus As concentrations.

Discerning Microbially Mediated Processes During Redox Transitions in Flooded Soils Using Carbon and Energy Balances

Recurring dry-wet cycles of soils, such as in rice paddies and on floodplains, have a dramatic impact on biogeochemical processes. The rates and trajectories of microbial metabolic functions during transition periods from drained to flooded conditions affect the transformation rates and phase partitioning of carbon, nutrients, and contaminants. However, the regulating mechanisms responsible for diverging functional metabolisms during such transitions are poorly resolved. The chemistry of organic carbon within the microbially available pool likely holds key information regarding carbon cycling and redox transformation rates. In this study, we used mesocosms to examine the influence of different carbon sources (glucose, straw, manure, char) on microbial energetics, respiration rates, and carbon balances in rice paddy soils during the transition from drained to flooded conditions following inundation. We found that variability in carbon solubility (1.6-400 mg g-1) and chemical composition of the amendments led to non-uniform stimulation of carbon dioxide production per unit carbon added (0.4-32.9 mmol CO2 mol-1 added C). However, there was a clear linear correlation between energy release and net CO2 production rate (R2=0.85), between CO2 and initial soluble C (R2=0.91, excluding glucose treatment) and between heat output and Gibbs free energy of initial soluble C (R2=0.78 and 0.69, with/without glucose respectively). Our results further indicated that the chemical composition of the soluble C from amendments initiated divergent anaerobic respiration behavior, impacting methane production and the partitioning of elements between soil solid phase and solution. This study shows the benefit of monitoring energy and element mass balances for elucidating the contribution of various microbial metabolic functions in complex systems. Further, our results highlight the importance of organic carbon composition within the water soluble pool as a key driver of microbially mediated redox transformations with major impacts on greenhouse gas emissions, contaminant fate, and nutrient cycling in paddy soils and similar ecosystems.

Arsenic leaching from ceramic water filters

Ceramic water filters (CWFs) provide a low-cost and effective means of pathogen removal for drinking water and are an attractive water treatment option because they can usually be manufactured without the need for imported materials. However, variation in the chemical composition of materials used for CWF production, especially in source clay, provides a potential hazard to CWF users through leaching of arsenic into filtered water. We determined the chemical composition of source clay material, and then evaluated the extent of arsenic leaching from CWFs manufactured in Kandal Province, Cambodia. Arsenic leaching from CWFs is rapid and non-linear, resulting in initial filtrate arsenic concentrations more than 100 times the World Health Organization recommended limit for safe drinking water (10 μg L−1). Under typical operating conditions in Cambodia, we determined that each CWF will leach approximately 43.5 mg of As, but that 80% of the As is released in the first 100 L of water. Arsenic desorption tests performed on source clay indicated that the ceramic firing process drastically increases the leachability of arsenic compared to unfired clay in the region. Testing of fired CWF material, not only source materials, is essential to predict arsenic leaching. Competitive desorption did not increase the release of arsenic from fired CWF materials as phosphate-dosed water in contact with CWF material showed no significant effect on arsenic release. We conclude that CWF arsenic leaching poses a potential exposure to end-users but because leaching occurs rapidly, design of controlled leaching systems prior to product distribution can mitigate arsenic exposure.