Overpumping Leads to California Groundwater Arsenic Threat

Water resources are being challenged to meet domestic, agricultural, and industrial needs. To complement finite surface water supplies that are being stressed by changes in precipitation and increased demand, groundwater is increasingly being used. Sustaining groundwater use requires considering both water quantity and quality. A unique challenge for groundwater use, as compared with surface water, is the presence of naturally occurring contaminants within aquifer sediments, which can enter the water supply. Here we find that recent groundwater pumping, observed through land subsidence, results in an increase in aquifer arsenic concentrations in the San Joaquin Valley of California. By comparison, historic groundwater pumping shows no link to current groundwater arsenic concentrations. Our results support the premise that arsenic can reside within pore water of clay strata within aquifers and is released due to overpumping. We provide a quantitative model for using subsidence as an indicator of arsenic concentrations correlated with groundwater pumping

Deciphering and Predicting Spatial and Temporal Concentrations of Arsenic Within the Mekong Delta Aquifer

Unravelling the complex, coupled processes responsible for the spatial distribution of arsenic within groundwaters of South and South-East Asia remains challenging, limiting the ability to predict the subsurface spatial distribution of arsenic. Previous work illustrates that Himalayan-derived, near-surface (0 to 12 m) sediments contribute a substantial quantity of arsenic to groundwater, and that desorption from the soils and sediments is driven by the reduction of AsV and arsenic-bearing iron (hydr)oxides. However, the complexities of groundwater flow will ultimately dictate the distribution of arsenic within the aquifer, and these patterns will be influenced by inherent physical heterogeneity along with human alterations of the aquifer system. Accordingly, we present a unified biogeochemical and hydrologic description of arsenic release to the subsurface environment of an arsenic-afflicted aquifer in the Mekong Delta, Kandal Province, Cambodia, constructed from measured geochemical profiles and hydrologic parameters. Based on these measurements, we developed a simple yet dynamic reactive transport model to simulate one- and two-dimensional geochemical profiles of the near surface and aquifer environment to examine the effects of subsurface physical variation on the distribution of arsenic. Our results show that near-surface release (0–12 m) contributes enough arsenic to the aquifer to account for observed field values and that the spatial distribution of arsenic within the aquifer is strongly affected by variations in biogeochemical and physical parameters. Furthermore, infiltrating dissolved organic carbon and ample buried particulate organic carbon ensures arsenic release from iron (hydr)oxides will occur for hundreds to thousands of years

Facters Affecting Arsenic Retetion Under Anaerobic Conditions

Stanford UniversityColorado State UniversityPromoting Environmental Pesearch in Pan-Japan Sea Area : Young Researchers\u27 Network, Schedule: March 8-10,2006,Kanazawa Excel Hotel Tokyu, Japan, Organized by: Kanazawa University 21st-Century COE Program, Environmental Monitoring and Prediction of Long- & Short- Term Dynamics of Pan-Japan Sea Area ; IICRC(Ishikawa International Cooperation Research Centre), Sponsors : Japan Sea Research ; UNU-IAS(United Nations University Institute of Advanced Studies)+Ishikawa Prefecture Government ; City of Kanazaw

Characterization of Organic Carbon in Sediments from Old Rifle, CO, a Former Uranium Mill

Characterization of sediments from Old Rifle, CO, a former uranium mill More than 34 million gallons (~129 million liters) of groundwater are contaminated with uranium at Old Rifle, Colorado – a former uranium-processing site that operated until 1958. The original Department of Energy strategy for remediation, involving natural flushing of U from the groundwater through mixing with surface water, has not been as successful as predicted. The uranium plume is replenished when insoluble U(IV) is oxidized to the more mobile U(VI). Relatively thin pockets of silt-, clay-, and organic-rich sediments contain reduced uranium, iron and sulfur and are referred to as naturally reduced zones (NRZs). There is a correlation between organic carbon (OC) and U concentrations; thus it can be inferred that OC is controlling U distribution and speciation. Sediment samples representing five different depths from the JB-02 well at Old Rifle were collected; two depths are above the NRZ, two are within the NRZ and one is below the NRZ. Sub-samples were then extracted using deionized water, NaCl and NaOH. The extractions were analyzed for non-purgeable organic carbon (NPOC) concentrations. Base extractions produced the highest concentrations of dissolved organic carbon (DOC) at all depths. Sediments within the NRZ produced more DOC than sediments above or below the NRZ. Further analysis by X-ray absorption spectroscopy (XAS) is expected to give key information on which organic functional groups are present within the sediments and their extractable carbon fractions, which will inform uranium management strategies. Additionally the amount of permanganate oxidizable carbon will be determined to further compare the carbon pools in and out of the NRZ

Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow

Iron (hydr)oxides not only serve as potent sorbents and repositories for nutrients and contaminants but also provide a terminal electron acceptor for microbial respiration. The microbial reduction of Fe (hydr)oxides and the subsequent secondary solid-phase transformations will, therefore, have a profound influence on the biogeochemical cycling of Fe as well as associated metals. Here we elucidate the pathways and mechanisms of secondary mineralization during dissimilatory iron reduction by a common iron-reducing bacterium, Shewanella putrefaciens (strain CN32), of 2-line ferrihydrite under advective flow conditions. Secondary mineralization of ferrihydrite occurs via a coupled, biotic-abiotic pathway primarily resulting in the production of magnetite and goethite with minor amounts of green rust. Operating mineralization pathways are driven by competing abiotic reactions of bacterially generated ferrous iron with the ferrihydrite surface. Subsequent to the initial sorption of ferrous iron on ferrihydrite, goethite (via dissolution/reprecipitation) and/or magnetite (via solid-state conversion) precipitation ensues resulting in the spatial coupling of both goethite and magnetite with the ferrihydrite surface. The distribution of goethite and magnetite within the column is dictated, in large part, by flow-induced ferrous Fe profiles. While goethite precipitation occurs over a large Fe(II) concentration range, magnetite accumulation is only observed at concentrations exceeding 0.3 mmol/L (equivalent to 0.5 mmol Fe[II]/g ferrihydrite) following 16 d of reaction. Consequently, transportregulated ferrous Fe profiles result in a progression of magnetite levels downgradient within the column. Declining microbial reduction over time results in lower Fe(II) concentrations and a subsequent shift in magnetite precipitation mechanisms from nucleation to crystal growth. While the initial precipitation rate of goethite exceeds that of magnetite, continued growth is inhibited by magnetite formation, potentially a result of lower Fe(III) activity. Conversely, the presence of lower initial Fe(II) concentrations followed by higher concentrations promotes goethite accumulation and inhibits magnetite precipitation even when Fe(II) concentrations later increase, thus revealing the importance of both the rate of Fe(II) generation and flow-induced Fe(II) profiles. As such, the operating secondary mineralization pathways following reductive dissolution of ferrihydrite at a given pH are governed principally by flow-regulated Fe(II) concentration, which drives mineral precipitation kinetics and selection of competing mineral pathways

The Ability of Soil Pore Network Metrics to Predict Redox Dynamics Is Scale Dependent

Variations in microbial community structure and metabolic efficiency are governed in part by oxygen availability, which is a function of water content, diffusion distance, and oxygen demand; for this reason, the volume, connectivity, and geometry of soil pores may exert primary controls on spatial metabolic diversity in soil. Here, we combine quantitative pore network metrics derived from X-ray computed tomography (XCT) with measurements of electromotive potentials to assess how the metabolic status of soil depends on variations of the overall pore network architecture. Contrasting pore network architectures were generated using a Mollisol—A horizon, and compared to intact control samples from the same soil. Mesocosms from each structural treatment were instrumented with Pt-electrodes to record available energy dynamics during a regimen of varying moisture conditions. We found that volume-based XCT-metrics were more frequently correlated with metrics describing changes in available energy than medial-axis XCT-metrics. An abundance of significant correlations between pore network metrics and available energy parameters was not only a function of pore architecture, but also of the dimensions of the sub-sample chosen for XCT analysis. Pore network metrics had the greatest power to statistically explain changes in available energy in the smallest volumes analyzed. Our work underscores the importance of scale in observations of natural systems

Peat Formation Concentrates Arsenic Within Sediment Deposits of the Mekong Delta

Mekong River Delta sediment bears arsenic that is released to groundwater under anaerobic conditions over the past several thousand years. The oxidation state, speciation, and distribution of arsenic and the associated iron bearing phases are crucial determinants of As reactivity in sediments. Peat from buried mangrove swamps in particular may be an important host, source, or sink of arsenic in the Mekong Delta. The total concentration, speciation, and reactivity of arsenic and iron were examined in sediments in a Mekong Delta wetland by X-ray fluorescence spectrometry (XRF), X-ray absorption spectroscopy (XAS), and selective chemical extractions. Total solid-phase arsenic concentrations in a peat layer at a depth of 6 m below ground increased 10-fold relative to the overlying sediment. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that arsenic in the peat was predominantly in the form of arsenian pyrite. Arsenic speciation in the peat was examined further at the micron-scale using μXRF and μX-ray absorption near-edge structure (XANES) spectroscopy coupled with principal component analysis. The multiple energy μXRF mapping and μXANES routine was repeated for both iron and sulfur phase analyses. Our μXRF/μXANES analyses confirm arsenic association with pyrite – a less reactive host phase than iron (hydr)oxides under anaerobic conditions. The arsenian pyrite likely formed upon deposition/formation of the peat in a past estuarine environment (∼ 5.5 ka BP), a process that is not expected under current geochemical conditions. Presently, arsenian pyrite is neither a source nor a sink for aqueous arsenic in our sediment profile, and under present geochemical conditions represents a stable host of As under the reducing aquifer conditions of the Mekong Delta. Furthermore, organic carbon within the peat is unable to fuel Fe(III) reduction, as noted by the persistence of goethite which can be reduced microbially with the addition of glucose

Are oxygen limitations under recognized regulators of organic carbon turnover in upland soils?

Understanding the processes controlling organic matter (OM) stocks in upland soils, and the ability to management them, is crucial for maintaining soil fertility and carbon (C) storage as well as projecting change with time. OM inputs are balanced by the mineralization (oxidation) rate, with the difference determining whether the system is aggrading, degrading or at equilibrium with reference to its C storage. In upland soils, it is well recognized that the rate and extent of OM mineralization is affected by climatic factors (particularly temperature and rainfall) in combination with OM chemistry, mineral–organic associations, and physical protection. Here we examine evidence for the existence of persistent anaerobic microsites in upland soils and their effect on microbially mediated OM mineralization rates. We corroborate long-standing assumptions that residence times of OM tend to be greater in soil domains with limited oxygen supply (aggregates or peds). Moreover, the particularly long residence times of reduced organic compounds (e.g., aliphatics) are consistent with thermodynamic constraints on their oxidation under anaerobic conditions. Incorporating (i) pore length and connectivity governing oxygen diffusion rates (and thus oxygen supply) with (ii) ‘hot spots’ of microbial OM decomposition (and thus oxygen consumption), and (iii) kinetic and thermodynamic constraints on OM metabolism under anaerobic conditions will thus improve conceptual and numerical models of C cycling in upland soils. We conclude that constraints on microbial metabolism induced by oxygen limitations act as a largely unrecognized and greatly underestimated control on overall rates of C oxidation in upland soils.Keywords: Anaerobic metabolism, Soil carbon, Soils, Organic matter, Oxygen limitationsKeywords: Anaerobic metabolism, Soil carbon, Soils, Organic matter, Oxygen limitation