Evaluation of filter pack dewatering on Voc concentrations in a simulated low-yield monitoring well

A physical model was constructed to investigate the physical process of dewatering the filter-pack of a low-yield ground-water monitoring well and determine if this process effects the concentration of dissolved volatile organic compounds (VOCs). It was hypothesized that losses of VOCs would be observed as a result of an increased air-water interface and possibly turbulent flow through the filter pack during water-level recovery; Little or no measurable losses of 1,1,1-TCA, MCB, or 1,1,2,2-TET were detected during water-level recovery while simulating non-stagnant well conditions. These data imply that losses of VOCs due to volatilization resulting from the physical action of water reinfiltrating a dewatered monitoring well will be minimal; Stagnant well simulations resulted in a trend of increasing concentration with time during water-level recovery, reflecting the mixing of residual stagnant water in the filter pack and incoming fresh water. These results indicate that similar trends observed in field studies may have resulted from mixing stagnant water with incoming formation water

Influence of riboflavin on the reduction of radionuclides by Shewanella oneidenis MR-1

Uranium (as UO22+), technetium (as TcO4−) and neptunium (as NpO2+) are highly mobile radionuclides that can be reduced enzymatically by a range of anaerobic and facultatively anaerobic microorganisms, including Shewanella oneidensis MR-1, to poorly soluble species. The redox chemistry of Pu is more complicated, but the dominant oxidation state in most environments is highly insoluble Pu(IV), which can be reduced to Pu(III) which has a potentially increased solubility which could enhance migration of Pu in the environment. Recently it was shown that flavins (riboflavin and flavin mononucleotide (FMN)) secreted by Shewanella oneidensis MR-1 can act as electron shuttles, promoting anoxic growth coupled to the accelerated reduction of poorly-crystalline Fe(III) oxides. Here, we studied the role of riboflavin in mediating the reduction of radionuclides in cultures of Shewanella oneidensis MR-1. Our results demonstrate that the addition of 10 μM riboflavin enhances the reduction rate of Tc(VII) to Tc(IV), Pu(IV) to Pu(III) and to a lesser extent, Np(V) to Np(IV), but has no significant influence on the reduction rate of U(VI) by Shewanella oneidensis MR-1. Thus riboflavin can act as an extracellular electron shuttle to enhance rates of Tc(VII), Np(V) and Pu(IV) reduction, and may therefore play a role in controlling the oxidation state of key redox active actinides and fission products in natural and engineered environments. These results also suggest that the addition of riboflavin could be used to accelerate the bioremediation of radionuclide-contaminated environments

Stabilization of Plutonium in Subsurface Environments via Microbial Reduction and Biofilm Formation

Plutonium has a long half-life (2.4 x 104 years) and is of concern because of its chemical and radiological toxicity, high-energy alpha radioactive decay. A full understanding of its speciation and interactions with environmental processes is required in order to predict, contain, or remediate contaminated sites. Under aerobic conditions Pu is sparingly soluble, existing primarily in its tetravalent oxidation state. To the extent that pentavalent and hexavalent complexes and small colloidal species form they will increase the solubility and resultant mobility from contamination sources. There is evidence that in both marine environments and brines substantial fractions of the plutonium in solution is present as hexavalent plutonyl, PuO2 2+

Bacterial Biotransformations for the In situ Stabilization of Plutonium

Plutonium contamination in the environment is generally low-level and may be present and transported in a range of forms (IV, V, VI). Current remediation strategies are costly, financially and in terms of increased exposure risk to people and the environment. In situ bacterial biostabilization is a promising alternative

Iron isotope fractionation in subterranean estuaries

Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 72 (2008): 3413-3430, doi:10.1016/j.gca.2008.05.001.Dissolved Fe concentrations in subterranean estuaries, like their river-seawater counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redoxstratified environments and determine potential Fe-isotope signatures of groundwater sources to coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration consistent with anoxic conditions and yield δ56Fe values between 0.3 and –1.3‰. In contrast, sediment porewaters occurring in the mixing zone of the subterranean estuary have very low δ56Fe values down to –5‰. These low δ56Fe values reflect Fe-redox cycling and result from the preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Feoxides precipitated onto subsurface sands in two cores from the subterranean estuary revealed strong δ56Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ56Fe values between –2 and 1.5‰. The relationship between Fe concentration and δ56Fe of Fe-rich sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to 5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by very low δ56Fe values relative to river values.This study was supported by the National Science Foundation (OCE 0550066) to OR and ES , (OCE 0095384) to MC and ES and NASA Astrobiology Institute - Cycle 3 CAN-02-OSS-02 to KJE

Iron isotope systematics in estuaries : the case of North River, Massachusetts (USA)

Author Posting. © The Author(s), 2009. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 73 (2009): 4045-4059, doi:10.1016/j.gca.2009.04.026.Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22 μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ56Fe values (with an average of 0.43 ± 0.04 ‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ56Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ56Fe values vary from -0.09‰ at no flocculation to ~ 0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ56Fe composition of rivers can also be characterized by more positive δ56Fe values (up to 0.3 per mil) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe isotopes during continental run-off.This study was supported by the National Science Foundation (OCE 0550066) to O. Rouxel and Edward Sholkovitz

Pre-nucleation clusters as solute precursors in crystallisation

Crystallisation is at the heart of various scientific disciplines, but still the understanding of the molecular mechanisms underlying phase separation and the formation of the first solid particles in aqueous solution is rather limited. In this review, classical nucleation theory, as well as established concepts of spinodal decomposition and liquid–liquid demixing, is introduced together with a description of the recently proposed pre-nucleation cluster pathway. The features of pre-nucleation clusters are presented and discussed in relation to recent modifications of the classical and established models for phase separation, together with a review of experimental work and computer simulations on the characteristics of pre-nucleation clusters of calcium phosphate, calcium carbonate, iron(oxy)(hydr)oxide, silica, and also amino acids as an example of small organic molecules. The role of pre-nucleation clusters as solute precursors in the emergence of a new phase is summarized, and the link between the chemical speciation of homogeneous solutions and the process of phase separation via pre-nucleation clusters is highlighted

Chromium speciation and mobility in contaminated soils, Sault Ste. Marie, MI

Thesis (Ph. D.)--Michigan State University. Department of Geological Sciences, 2000Includes bibliographical references (pages 89-98

Improvements to the Water Quality of the Acidic Berkeley Pit Lake due to Copper Recovery and Sludge Disposal

AbstractThe chemistry and limnology of the Berkeley Pit lake, located in Butte, Montana, have substantially changed during the past 15 years. These changes are due to: (1) a large-scale Cu recovery project in which deep water was pumped to a Cu precipitation plant and returned to the surface of the lake; and (2) in-pit disposal of lime-treatment sludge. As a consequence, the lake has shifted from a meromictic to a holomictic state, over 99% of the dissolved Fe has precipitated as schwertmannite and other ferric solids, the total acidity of the water column has dropped by roughly 35%, and the pH has risen from about 2.5 to near 4.1. Whereas most of the lake was anoxic prior to 2013, the water column now contains &gt; 6 mg/L dissolved oxygen from the lake surface to the deepest levels sampled (&gt; 150 m). Concentrations of several other solutes, including As, P, Cr, and V, have fallen sharply due to adsorption or co-precipitation with Fe, while other species, such as Al, Mg, and Mn, have increased due to dissolution of solids in the sludge. Although the Cu recovery circuit was discontinued in 2013, in-pit disposal of sludge is expected to continue. The pit water is now close to saturation with basaluminite, and the pH should remain poised in the range of 4.1–4.5 for many years as Al precipitates out of the water column. Pumping and treating of pit water is set to commence in 2019, and will continue for the foreseeable future. Continued in-pit disposal of sludge should translate into long term water-quality improvement and a decrease in annual lime-consumption costs. Although the Berkeley Pit still has a long ways to go before it will meet water quality standards, it is heartening to mine-water specialists that the pit lake may not be a problem that is “too big to fix”.</jats:p