Removal of hexavalent chromium by hyporheic zone sediments in an urbanized estuary.

More than 2 million tons of chromium ore processing residue (COPR) waste was disposed of in Hudson County of New Jersey, which was known as the center of the production of chromate in the 20th century. The Cr(VI) removal experiments were conducted with the hyporheic zone (HZ) sediments collected along the shore of an urbanized estuary located in and near Hudson County to investigate the natural remediation of Cr(VI). Fine-grained and organic-rich Passaic River sediments showed the highest removal capacity for Cr(VI), whereas the lowest removal of Cr(VI) occurred in coarse-grained and organic-poor sediments from Newark Bay. In general, Cr(VI) removal increased with higher amounts of sediment organic matter, sulfur, and silt and clay fractions, as well as lower pH conditions. The removal of hexavalent chromium in organic-rich sediments is attributed mainly to the reduction of Cr(VI) to Cr(III), resulting in less reversible immobilization of Cr(VI), while reversible adsorption could also remove Cr(VI). The results suggest that the organic-rich, fine-grained HZ sediments can act as a natural reactive barrier for the remediation of Cr(VI) transport from subsurface to surface water in the estuary. Further research is needed to understand the long-term mobility of Cr along the urban estuary.

Numerical Simulation of Permeability Change in Wellbore Cement Fractures after Geomechanical Stress and Geochemical Reactions Using X-ray Computed Tomography Imaging.

X-ray microtomography (XMT) imaging combined with three-dimensional (3D) computational fluid dynamics (CFD) modeling technique was used to study the effect of geochemical and geomechanical processes on fracture permeability in composite Portland cement-basalt caprock core samples. The effect of fluid density and viscosity and two different pressure gradient conditions on fracture permeability was numerically studied by using fluids with varying density and viscosity and simulating two different pressure gradient conditions. After the application of geomechanical stress but before CO2-reaction, CFD revealed fluid flow increase, which resulted in increased fracture permeability. After CO2-reaction, XMT images displayed preferential precipitation of calcium carbonate within the fractures in the cement matrix and less precipitation in fractures located at the cement-basalt interface. CFD estimated changes in flow profile and differences in absolute values of flow velocity due to different pressure gradients. CFD was able to highlight the profound effect of fluid viscosity on velocity profile and fracture permeability. This study demonstrates the applicability of XMT imaging and CFD as powerful tools for characterizing the hydraulic properties of fractures in a number of applications like geologic carbon sequestration and storage, hydraulic fracturing for shale gas production, and enhanced geothermal systems.

Redox Zonation and Oscillation in the Hyporheic Zone of the Ganges-Brahmaputra-Meghna Delta: Implications for the Fate of Groundwater Arsenic during Discharge.

Riverbank sediment cores and pore waters, shallow well waters, seepage waters and river waters were collected along the Meghna Riverbank in Gazaria Upazila, Bangladesh in Jan. 2006 and Oct.-Nov. 2007 to investigate hydrogeochemical processes controlling the fate of groundwater As during discharge. Redox transition zones from suboxic (0-2 m depth) to reducing (2-5 m depth) then suboxic conditions (5-7 m depth) exist at sites with sandy surficial deposits, as evidenced by depth profiles of pore water (n=7) and sediment (n=11; diffuse reflectance, Fe(III)/Fe ratios and Fe(III) concentrations). The sediment As enrichment zone (up to ~700 mg kg-1) is associated with the suboxic zones mostly between 0-2 m depth and less frequently between 5-7 m depth. The As enriched zones consist of several 5 to 10 cm-thick dispersed layers and span a length of ~5-15 m horizontally from the river shore. Depth profiles of riverbank pore water deployed along a 32 m transect perpendicular to the river shore show elevated levels of dissolved Fe (11.6±11.7 mg L-1) and As (118±91 µg L-1, mostly as arsenite) between 2-5 m depth, but lower concentrations between 0-2 m depth (0.13±0.19 mg L-1 Fe, 1±1 µg L-1 As) and between 5-6 m depth (1.14±0.45 mg L-1 Fe, 28±17 µg L-1 As). Because it would take more than a few hundred years of steady groundwater discharge (~10 m yr-1) to accumulate hundreds of mg kg-1 of As in the riverbank sediment, it is concluded that groundwater As must have been naturally elevated prior to anthropogenic pumping of the aquifer since the 1970s. Not only does this lend unequivocal support to the argument that As occurrence in the Ganges-Brahmaputra-Meghna Delta groundwater is of geogenic origin, it also calls attention to the fate of this As enriched sediment as it may recycle As into the aquifer.

Imaging wellbore cement degradation by carbon dioxide under geologic sequestration conditions using X-ray computed microtomography.

X-ray microtomography (XMT), a nondestructive three-dimensional imaging technique, was applied to demonstrate its capability to visualize the mineralogical alteration and microstructure changes in hydrated Portland cement exposed to carbon dioxide under geologic sequestration conditions. Steel coupons and basalt fragments were added to the cement paste in order to simulate cement-steel and cement-rock interfaces. XMT image analysis showed the changes of material density and porosity in the degradation front (density: 1.98 g/cm(3), porosity: 40%) and the carbonated zone (density: 2.27 g/cm(3), porosity: 23%) after reaction with CO(2)-saturated water for 5 months compared to unaltered cement (density: 2.15 g/cm(3), porosity: 30%). Three-dimensional XMT imaging was capable of displaying spatially heterogeneous alteration in cement pores, calcium carbonate precipitation in cement cracks, and preferential cement alteration along the cement-steel and cement-rock interfaces. This result also indicates that the interface between cement and host rock or steel casing is likely more vulnerable to a CO(2) attack than the cement matrix in a wellbore environment. It is shown here that XMT imaging can potentially provide a new insight into the physical and chemical degradation of wellbore cement by CO(2) leakage.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Can arsenic occurrence rates in bedrock aquifers be predicted?

A high percentage (31%) of groundwater samples from bedrock aquifers in the greater Augusta area, Maine was found to contain greater than 10 µg L(-1) of arsenic. Elevated arsenic concentrations are associated with bedrock geology, and more frequently observed in samples with high pH, low dissolved oxygen, and low nitrate. These associations were quantitatively compared by statistical analysis. Stepwise logistic regression models using bedrock geology and/or water chemistry parameters are developed and tested with external data sets to explore the feasibility of predicting groundwater arsenic occurrence rates (the percentages of arsenic concentrations higher than 10 µg L(-1)) in bedrock aquifers. Despite the under-prediction of high arsenic occurrence rates, models including groundwater geochemistry parameters predict arsenic occurrence rates better than those with bedrock geology only. Such simple models with very few parameters can be applied to obtain a preliminary arsenic risk assessment in bedrock aquifers at local to intermediate scales at other localities with similar geology.

Field, experimental, and modeling study of arsenic partitioning across a redox transition in a Bangladesh aquifer.

To understand redox-dependent arsenic partitioning, we performed batch sorption and desorption experiments using aquifer sands subjected to chemical and mineralogical characterization. Sands collected from the redox transition zone between reducing groundwater and oxic river water at the Meghna riverbank with HCl extractable Fe(III)/Fe ratio ranging from 0.32 to 0.74 are representative of the redox conditions of aquifers common in nature. One brown suboxic sediment displayed a partitioning coefficient (K(d)) of 7-8 L kg(-1) at equilibrium with 100 µg L(-1) As(III), while two gray reducing sediments showed K(d) of 1-2 L kg(-1). Lactate amendment to aquifer sands containing 91 mg kg(-1) P-extractable As resulted in the reduction of As and Fe with sediment Fe(III)/Fe decreasing from 0.54 to 0.44, and mobilized an equivalent of 64 mg kg(-1) As over a month. Desorption of As from nonlactate-amended sediment was negligible with little change in sediment Fe(III)/Fe. This release of As is consistent with microbial reduction of Fe(III) oxyhydroxides and the resulting decrease in the number of surface sites on Fe(III) oxyhydroxides. Arsenic partitioning (K(d)) in iron-rich, sulfur-poor aquifers with circumneutral pH is redox-dependent and can be estimated by HCl leachable sediment Fe(III)/Fe ratio with typical Fe concentrations.

Field, laboratory, and modeling study of reactive transport of groundwater arsenic in a coastal aquifer.

A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(III) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows toward the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80-90% Fe(III)) are 734 +/- 232 mg kg(-1) and sedimentary phosphate-extractable As (90-100% As(VI) are 316 +/- 111 microg kg(-1) and are linearly correlated. Batch adsorption of As(III) onto orange, brown, and gray sediments follows Langmuir isotherms and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site-specific isotherms should be established for Kd- or SCM-based models.

Spatial pattern of groundwater arsenic occurrence and association with bedrock geology in greater Augusta, Maine.

In New England, groundwater arsenic occurrence has been linked to bedrock geology on regional scales. To ascertain and quantify this linkage at intermediate (10(0)-10(1) km) scales, 790 groundwater samples from fractured bedrock aquifers in the greater Augusta, Maine area are analyzed, and 31% of the sampled wells have arsenic concentrations >10 microg/L. The probability of [As] exceeding 10 microg/L mapped by indicator kriging is highest in Silurian pelite-sandstone and pelite-limestone units (approximately 40%). This probability differs significantly (p < 0.001) from those in the Silurian-Ordovician sandstone (24%),the Devonian granite (15%), and the Ordovician-Cambrian volcanic rocks (9%). The spatial pattern of groundwater arsenic distribution resembles the bedrock map. Thus, bedrock geology is associated with arsenic occurrence in fractured bedrock aquifers of the study area at intermediate scales relevant to water resources planning. The arsenic exceedance rate for each rock unit is considered robust because low, medium, and high arsenic occurrences in four cluster areas (3-20 km2) with a low sampling density of 1-6 wells per km2 are comparable to those with a greater density of 5-42 wells per km2. About 12,000 people (21% of the population) in the greater Augusta area (approximately 1135 km2) are at risk of exposure to >10 microg/L arsenic in groundwater.

In-situ electrochemical measurements of total concentration and speciation of heavy metals in acid mine drainage (AMD): assessment of the use of anodic stripping voltammetry.

We assessed the use of anodic stripping voltammetry (ASV) for in-situ determinations of both total concentration and speciation of dissolved heavy metals (Cd, Cu, Pb and Zn) in acid mine drainage (AMD). In the Kwangyang Au-Ag mine area of South Korea, different sites with varying water chemistry within an AMD were studied with a field portable anodic stripping voltammeter. Anodic stripping voltammetry after wet oxidation (acidification) was very sensitive enough to determine total concentration of dissolved Cd because Cd was dominantly present as 'labile' species, whilst the technique was not so effective for determining total Cu especially in the downstream sites from the retention pond, due to its complexation with organic matter. For dissolved Pb, the concentrations determined by ASV after wet oxidation generally agreed with those by ICP-AES. In the downstream samples (pH>5), however, ASV data after wet oxidation were lower than ICP-AES data because a significant fraction of dissolved Pb was present in those samples as 'inert' species associated with colloidal iron oxide particles. The determination of total dissolved Zn by ASV after wet oxidation appeared to be unsatisfactory for the samples with high Cu content, possibly due to the interference by the formation of Zn-Cu intermetallic compounds on the mercury coated electrode. In AMD samples with high dissolved iron, use of ultraviolet irradiation was not effective for determining total concentrations because humate destruction by UV irradiation possibly resulted in the removal of a part of dissolved heavy metals from waters through the precipitation of iron hydroxides.

Arsenic redistribution between sediments and water near a highly contaminated source.

Mechanisms controlling arsenic partitioning between sediment, groundwater, porewaters, and surface waters were investigated at the Vineland Chemical Company Superfund site in southern New Jersey. Extensive inorganic and organic arsenic contamination at this site (historical total arsenic > 10 000 microg L(-1) or > 130 microM in groundwater) has spread downstream to the Blackwater Branch, Maurice River, and Union Lake. Stream discharge was measured in the Blackwater Branch, and water samples and sediment cores were obtained from both the stream and the lake. Porewaters and sediments were analyzed for arsenic speciation as well as total arsenic, iron, manganese, and sulfur, and they indicate that geochemical processes controlling mobility of arsenic were different in these two locations. Arsenic partitioning in the Blackwater Branch was consistent with arsenic primarily being controlled by sulfur, whereas in Union Lake, the data were consistent with arsenic being controlled largely by iron. Stream discharge and arsenic concentrations indicate that despite large-scale groundwater extraction and treatment, > 99% of arsenic transport away from the site results from continued discharge of high arsenic groundwater to the stream, rather than remobilization of arsenic in stream sediments. Changing redox conditions would be expected to change arsenic retention on sediments. In sulfur-controlled stream sediments, more oxic conditions could oxidize arsenic-bearing sulfide minerals, thereby releasing arsenic to porewaters and streamwaters; in iron-controlled lake sediments, more reducing conditions could release arsenic from sediments via reductive dissolution of arsenic-bearing iron oxides.