Solid Phase Partitioning Research Articles

Distribution of REEs and yttrium among major geochemical phases of marine Fe–Mn-oxides: Comparative study between hydrogenous and hydrothermal deposits

Mineralogy and geochemistry of the ferromanganese oxides collected from two seamounts in the Andaman Sea have been investigated with special reference to the solid phase partitioning behavior of rare earth elements (REEs). Bulk elemental compositions indicate that the oxides from a volcanic cratered seamount, CSM, are hydrothermal while those from another seamount, SM2, are hydrogenous in origin. The distributions of REEs and yttrium in four geochemical phases (viz. easily exchangeable, Mn-oxide, Fe-oxyhydroxide and residual) of CSM-oxides were distinctly different from that of SM2-oxides. In CSM-oxides, the REEs and yttrium are mainly associated with Fe-oxyhydroxide phase while in SM2-oxides, both Mn-oxide and Fe-oxyhydroxide phases contain the major fraction of these elements. The exchangeable and residual phases of both hydrothermal and hydrogenous oxides have extremely low REE-content. The shale normalized negative Ce-anomalies and relative enrichment of heavy REE, characteristic of hydrothermal oxides, are retained in Fe-oxyhydroxide phase. In hydrogenous oxides, the positive Ce-anomalies occurred in both Fe and Mn-oxide phases while negative Y-anomalies were found only in Fe-oxyhydroxide phase. The phase distribution of REEs and yttrium in hydrothermal oxides is described in terms of co-precipitation and adsorption of their halide complexes and available free ions in hydrothermal solutions. Instead, adsorption of major carbonate species from seawater primarily regulates the partitioning of REEs among the co-existing phases of hydrogenous oxides.

Evaluation of Cu potential bioavailability changes upon coastal sediment resuspension: an example on how to improve the assessment of sediment dredging environmental risks

Metal bioavailability-based sediment quality analysis, inferred from geochemical partitioning data, may contribute to improve sediment management policies. This is important because decision-making processes should not give similar priorities to sediments offering contrasting environmental risks associated to metal bioavailability. However, current uses of Sediment Quality Guidelines (SQGs) as interpretive tools to support decisions about dredging-related activities have not considered the changes in metal bioavailability upon sediment resuspension. Sediments from a Cu-contaminated site in Guanabara Bay (Brazil) were submitted to 16-h resuspension experiments in estuarine water to assess the susceptibility of Cu mobilization to the dissolved phase and alteration in the solid phase partitioning between a potentially bioavailable (1mol/l HCl-extractable) phase and concentrated HNO(3)-extractable phase. After sediment resuspensions, dissolved Cu levels became slightly lower (in a surface water-resuspension treatment) or slightly higher (in a bottom water-resuspension treatment). In both treatments, the 1mol/l HCl-extractable solid phase concentrations changed from seven times lower to two times higher values than an SQG adopted in Brazilian legislation. This change was explained by a transition from concentrated HNO(3)-extractable phases to reactive HCl-extractable phases upon resuspension. An evaluation of metal susceptibility to present geochemical partitioning changes, as can be inferred from HCl-extractable fraction analyses before and after resuspension experiments, is recommended as an additional criterion to assess environmental risks of sediment dredging in relation to resuspension-sensitive metals, such as Cu.

Effect of Density‐Driven Advection on Trichloroethylene Vapor Diffusion in a Porous Medium

To quantify the vertical diffusive mass transfer of trichloroethylene (TCE) in a low water‐saturated porous medium, diffusion experiments were conducted in soil columns using a medium‐size quartz sand at two different water saturations; namely, completely dry and at irreducible water saturation. Advective transport of TCE vapors was mainly generated by density gradients in the soil gas during diffusion of TCE vapors in the vertical direction. The maximum stationary TCE vapor concentrations measured at the column outlet attained only 70 to 75% of the prescribed inlet vapor concentration, indicating a strong influence of density‐driven advective mass transport on vertical diffusion of TCE. Without taking into account the density of the vapors, the measured apparent TCE diffusion coefficient was about seven and five times smaller than the coefficients predicted by the model for dry sand and sand at irreducible water saturation, respectively. A numerical transport model was used to interpret the experimental results. The numerical results fit the experimentally measured TCE breakthrough curves well. A sensitivity study demonstrated that the simulated vapor breakthrough curves were not very sensitive to variations in the dimensionless Henry's constant, the gas–solid or water–solid phase partitioning coefficients but were sensitive to modification of the intrinsic permeability and the gas tortuosity–connectivity parameter. Two series of numerical simulations were also conducted to analyze the steady‐state conditions of vertical vapor transport. The results highlighted how both the relative density of TCE vapors and the height of the soil column, expressed as a dimensionless Rayleigh number, might reduce the vertical diffusive mass flux.

Kinetic Controls on the Complexation between Mercury and Dissolved Organic Matter in a Contaminated Environment

The interaction of mercury (Hg) with dissolved natural organic matter (NOM) under equilibrium conditions is the focus of many studies but the kinetic controls on Hg-NOM complexation in aquatic systems have often been overlooked. We examined the rates of Hg-NOM complexation both in a contaminated Upper East Fork Poplar Creek (UEFPC) in Oak Ridge, Tennessee, and in controlled laboratory experiments using reducible Hg (Hg(R)) measurements and C(18) solid phase extraction techniques. Of the filterable Hg at the headwaters of UEFPC, >90% was present as Hg(R) and this fraction decreased downstream but remained >29% of the filterable Hg at all sites. The presence of higher Hg(R) concentrations than would be predicted under equilibrium conditions in UEFPC and in experiments with a NOM isolate suggests that kinetic reactions are controlling the complexation between Hg and NOM. The slow formation of Hg-NOM complexes is attributed to competitive ligand exchange among various moieties and functional groups in NOM with a range of binding strengths and configurations. This study demonstrates the need to consider the effects of Hg-NOM complexation kinetics on processes such as Hg methylation and solid phase partitioning.

In Situ ATR FTIR Studies of SO4 Adsorption on Goethite in the Presence of Copper Ions

Despite the existence of many single ion sorption studies on iron and aluminum oxides, fewer studies have been reported that describe cosorption reactions. In this work, we present an in situ ATR FTIR study of synergistic adsorption of sulfate (SO4) and copper (Cu) on goethite, which is representative of the minerals and ions present in mine wastes, acid sulfate soils, and other industrial and agricultural settings. Sulfate adsorption was studied as a function of varying pH, and as a function of increasing concentration in the absence and presence of Cu. The presence of Cu ions in solution had a complex effect on the ability of SO4 ions to be retained on the goethite surface with increasing pH, with complete desorption occurring near pH 7 and 9 in the absence and presence of Cu, respectively. In addition, Cu ions altered the balance of inner vs outer sphere adsorbed SO4. The solid phase partitioning of SO4 at pH 3 and pH 5 was elevated by the presence of Cu; in both cases Cu increased the affinity of SO4 for the goethite surface. Complementary ex situ sorption edge studies of Cu on goethite in the absence and presence of SO4 revealed that the Cu adsorption edge shifted to lower pH (6.3 --> 5.6) in the presence of SO4, consistent with a decrease of the electrostatic repulsion between the goethite surface and adsorbing Cu. Based on the ATR FTIR and bulk sorption data we surmise that the cosorption products of SO4 and Cu at the goethite-water interface were not in the nature of ternary complexes under the conditions studied here. This information is critical for the evaluation of the onset of surface precipitates of copper-hydroxy sulfates as a function of pH and solution concentration.

Metal speciation in sulphidic sediments: A new method based on oxidation kinetics modelling in the presence of EDTA

The solid phase partitioning of metals (Zn, Cu and Pb) was determined in four anoxic, metal polluted sediments by investigating at pH 8 the 1 day oxidation kinetics of the metal sulphide phases present in the sediments in a background solution containing excess EDTA. A mathematical model consisting of a combination of two pseudo-first order reactions was used to fit the metal release data as a function of oxidation time. The model permitted to fractionate the trace metals in a ‘quickly-oxidizable’ and a ‘slowly-oxidizable’ fraction, which could be assigned to two different trace metal pools, respectively (1) FeS minerals (e.g. amorphous FeS, mackinawite) and (2) discrete trace metal sulphide phases. The sum of the fractions associated with these sulphide pools was taken as an approximation for the sulphide-associated fraction of the trace metals and coincided (for the case of Zn and Pb) with the sulphide-associated fraction derived from the analysis of acid volatile sulphide (AVS) and simultaneously extracted metals (SEM). Oxidation kinetics modelling allowed also determining the sulphide-associated fraction of a broad range of trace metals (as demonstrated for Cu) more accurately than the AVS/SEM method, which suffers from non-efficient extraction of a number of trace metal sulphides. A correction was made for the determination of the sulphide-associated fraction by subtracting the trace metal fraction dissolved after 1 day under anoxic conditions in the background EDTA solution. The combination of (1) one day oxidation kinetics modelling and (2) correction for the 1 day anoxic EDTA-soluble fraction is a suitable method to determine accurately the true sulphide speciation of trace metals in anoxic sediments.

Distribution of dissolved species and suspended particulate copper in an intertidal ecosystem affected by copper mine tailings in Northern Chile

The coastline near Chañaral in Northern Chile is one of the most highly Cu-contaminated zones in the world due to discharges from mining activities for more than 60 years. The speciation of Cu has been studied to determine the importance of organic complexation in highly contaminated areas, and to assess the likely physiological impacts of Cu on marine organisms. Dissolved Cu concentrations of up to 500 nM were measured, completely saturating organic ligands and leading to free Cu 2+ concentrations in excess of 10 − 8 M. These values are higher than those reported in any other marine environment, and because they occur over an extensive area, provide a unique opportunity to study the effects of Cu on marine ecosystems and to see how Cu behaves when its speciation is predominantly inorganic. We found strong gradients in free Cu 2+ between Chañaral and adjacent areas with lower Cu, where speciation is dominated by organic complexation. There is also a significant increase in the partitioning of Cu onto suspended particles in the contaminated areas, consistent with previous studies that showed that organic ligands stabilize Cu in the dissolved phase, whilst “excess” Cu is rapidly scavenged. Those high dissolved Cu concentrations persist in spite of solid phase partitioning and advective processes along this open-ocean coastline, suggesting that Cu inputs into the system are still very large. Measurements were made using anodic stripping voltammetry with a thin mercury film coated with Nafion, which previous workers have shown can mitigate ambiguity in the data arising from inadvertent reduction of organic complexes. Our findings suggest that this is a useful methodology for contaminated systems.

Coulometric determination of total sulfur and reduced inorganic sulfur fractions in environmental samples

Evaluation of the solid-phase partitioning of sulfur is frequently an important analytical component of risk assessments at hazardous waste sites because minerals containing reduced-sulfur can significantly affect the transport and fate of organic and inorganic contaminants in natural environments. We applied selected methods for the determination of total sulfur, acid-volatile sulfide (AVS), chromium-reducible sulfur (CRS), and extractable-sulfate in standard reference materials and sediment samples from a contaminated site. A coulometric titration method is presented and evaluated for total sulfur, AVS, and CRS. This method is especially advantageous for AVS and CRS determinations because hydrogen sulfide gas evolved during chemical extraction is detected and quantitated in-line; consequently, measurement endpoints can be precisely determined without need for setting arbitrary time limits. The coulometric method allows for improved data quality and increased laboratory throughput of samples. Data on sulfur partitioning are presented for four standard reference materials (NIST 1646a, NIST 2780, CCRMP LKSD-1, CCRMP RTS-3) for the purpose of supporting quality control in environmental studies involving the geochemical and biochemical cycling of sulfur.

Arsenic solid-phase partitioning in reducing sediments of a contaminated wetland

The geochemical partitioning of arsenic in organic-rich sediments from a contaminated wetland is examined using X-ray absorption spectroscopy and selective chemical extraction procedures, and evaluated in context to the anoxic diagenesis of iron and sulfur. The interaction between ground water and surface water has a significant influence on iron sulfide formation in the wetland sediments. Ground-water seeps supply concentrations of sulfate, dissolved hydrocarbons, ferrous iron, and arsenic, and sediments located near seeps are anomalously enriched in arsenic, reactive iron, and acid-volatile sulfides. Degree-of-sulfidation (DOS) values are high in sediments adjacent to sites of ground-water discharge, ranging from 0.57 to 1.0. Pyrite (FeS 2) formation is apparently not limited by the abundance of any one primary reactant, e.g., organic carbon, sulfate, or reactive iron; instead, persistence of precursor iron monosulfides is attributed to slow pyrite formation kinetics due to low concentrations of reactive intermediate sulfur species or possibly due to high concentrations of arsenite, dissolved organic-carbon, or other solutes that adsorb to iron monosulfides surfaces and impede transformation reactions to pyrite. Greigite (Fe 3S 4) accounts for > 80% of total reduced sulfur in sediments rich in acid-volatile sulfide and X-ray absorption spectroscopy data for magnetic separates provide direct evidence that As(III) is, at least in part, associated with reduced sulfur in the form of greigite. However, pyrite can only account for a small percentage, < 20%, of the total arsenic budget in the reduced sediments. Although pyrite is the predicted stable endpoint for reactive iron and sulfur, it appears that within a 30 y time period pyrite is a relatively unimportant host for arsenic in the system investigated here. The abundance of reactive iron in the sediments prevents accumulation of dissolved sulfide and thus prevents formation of soluble thioarsenic species. X-ray absorption near-edge structure (XANES) spectroscopy indicates only the presence of As(III) in the reduced sediments. Results of linear combination fitting of reference spectra to sediment spectra are consistent with sulfur- and/or oxygen-coordinated As(III) in association with iron monosulfides and ferrous-bearing carbonates or hydroxides.

Controls on Arsenic Speciation and Solid-Phase Partitioning in the Sediments of a Two-Basin Lake

Arsenic (As) regeneration from sediments of Spy Pond, a two-basin lake near Boston, MA, continues to result in seasonally elevated As levels despite the several decades that have elapsed since the pond's historical contamination by a pulse input of As. Solid-phase speciation and partitioning of As in the sediments appear to be primary determinants of both potential As regeneration rate and, conversely, the rate at which long-term burial of the pond's As burden will occur. Although iron (Fe) chemistry often controls As speciation in lakes, a higher rate of As regeneration in the south basin, accompanied by the absence of a correlation between regenerated As and Fe in this basin, suggest that additional factors operate to control As cycling in this lake. Solid-phase As speciation was remarkably similar between sediments of the two basins of this lake, about 40% of sedimentary As in upper sediments being in relatively labile (ionically bound and strongly adsorbed) fractions and a larger fraction of As being associated with recalcitrant minerals, likely sulfides. Extraction, X-ray fluorescence, and acid-volatile sulfide data collectively suggest that sedimentary As cycling in both basins is largely controlled by the formation of sulfide minerals. An accounting of the size of sulfur (S) pools supports this conclusion, showing that sufficient S exists in the north basin to control both Fe and As, while the south basin has lower S levels resulting in seasonal accumulation of Fe in the porewater.

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments ( N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/ 207Pb ratios of roadside sediments (range = 1.1419–1.1681; mean 1.1576 ± 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.

Geochemistry of acidic Rio Tinto headwaters and role of bacteria in solid phase metal partitioning

Mining operations in the Rio Tinto area, southwest Spain, have created a historical pollution problem in the river and estuary. The fate of metals along the Rio Tinto river and estuary has been previously characterized, but little is known about transport and behaviour of metals and other elements in the headwaters of the river. The headwaters are situated approximately 100 km (north east) from Huelva at the Mediterranean Sea, with three investigated sites in this area distributed over 100 m. Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) of aqueous and solid samples revealed Ca, Fe, Mg, Na, S, Si, and Al concentrations above 0.5 mM in the stream surface waters at all sites. Trace elements included K, Cu, Li, Mn, and Zn. Concentrations of particulate elements generally accounted for less than 10% of the total load. In deeper pools along the stream, brine water was found with notably higher levels of Fe, Mg, S, Si, and Al compared to the stream water. The brine had a pH of 1.9, while the surface stream waters had pH values of about 2.7. Groundwater from the seep on the bank of the stream was found to be chemically distinct from both surface stream water and the brine. Fe, S and Al were in the solid samples at 100 mmol/kg or more. K, Na, P, Si, As, Ba, Cu, Li, and Mn were characterized by intermediate concentrations, 1.0–100 mmol/kg. A progressive downstream increase in particulate elemental concentrations was observed for P, Ba, Mn, Pb, Sr, V and Zn. Scanning electron microscopy (SEM) showed a variety of bacterial-like forms among the suspended particulates. In some instances, the bacteria appeared to be closely associated with or mineralized by inorganic precipitates. Transmission electron microscopy (TEM) revealed extensively mineralized bacterial cells in the solid sediment samples. The chemical composition of the investigated stream is attributed to inputs from groundwater and brines that likely evolve in response to evaporation during prolonged periods of moisture deficit in the summer. Planktonic bacteria were prominent components of the suspended particulate fraction in the stream; however, pH sorption edges for dissolved metals on bacteria are generally above pH 4.0, and therefore, it is unlikely that bacterial cells are an important component for transport of dissolved metals in the stream. Bottom sediments contain abundant highly mineralized bacteria with coatings of poorly crystalline iron oxyhydroxides and hydroxysulfate precipitates. Such bacterial–mineral composites likely contribute to increased solid phase partitioning of dissolved metals in the Tinto river system.

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH.

Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH.

Evaluation of a method for identification of host physico-chemical phases for trace metals and measurement of their solid-phase partitioning in soil samples by nitric acid extraction and chemometric mixture resolution

A sequential extraction methodology, designed to measure the solid phase partitioning of metals in soils and sediments, is described. The method uses centrifugation to pass increasing concentrations of HNO 3 through the sample, followed by ICP-AES analysis of major and trace elements of the extracts. A data-processing algorithm is used to identify the number of physico-chemical components extracted, their composition and the proportion of each in each extract. The algorithm has been successfully tested on a synthetic data set and the combination of the extraction methodology and data-processing algorithm have been tested on a contaminated soil sample (NIST SRM 2710). The 14 extracts from each duplicate experiment were analysed for 19 elements and data analysis identified nine chemically distinct soil components: pore-water residual solutes; organic, easily exchangeable; a Cu–Zn dominated phase; a Pb-dominated phase; amorphous Fe oxide/oxyhydroxide; crystalline Fe oxide; Fe–Ti oxide; and Mn oxide.

Arsenic speciation in surface waters and sediments in a contaminated waterway: an IC–ICP-MS and XAS based study

An integrated approach involving the use of ion chromatography–inductively coupled plasma-mass spectrometry (IC–ICP-MS), X-ray absorption spectroscopy (XAS) and sequential extraction procedures has been employed to elucidate the solution and solid phase speciation and partitioning of As in a polluted urban watercourse. Dissolved As concentrations exceeding 130 μg l −1 and comprising entirely inorganic species were determined in the waters of Tinker Brook, a contaminated stream. Upon mixing with a relatively As-free stream, White Ash Brook, both the total concentration of dissolved As and the proportion of As(V) were observed to decrease dramatically below values expected for conservative mixing. This was ascribed to adsorption onto the Fe (oxyhydr)oxides that characterise White Ash Brook on the basis of sequential extraction and direct analysis of the solids via XAS . The shift in oxidation state is speculated to be due to the faster rate of adsorption of As(V) on Fe (oxyhydr)oxides than As(III) in this fast flowing stream system. During periods of reduced supply of anthropogenic As, a small, secondary input of As(III) to White Ash Brook is detectable, delivered by a small ochreous seepage. The Fe (oxyhydr)oxide As-rich deposits surrounding this discharge may also act as a significant source of As upon dissolution during stormflow conditions.

Metal distribution during diagenesis in the contaminated sediments of Dulas Bay, Anglesey, N. Wales, UK

The Tessier sequential extraction procedure was applied to discrete layers from 9 sediment cores from Dulas Bay, Anglesey. Results provide data on the chemical association of heavy metals (Fe, Mn, Cu, Zn, Cd, and As with major) sedimentary phases, and provide information on changes in metal partitioning associated with the changing physico-chemical conditions encountered during burial. Extremely high concentrations of heavy metals were recorded (e.g. Zn 3000 μg g −1, Cu 2000 μg g −1) and resulting depth profiles clearly indicate the differential behaviour of metals during diagenesis where, with increasing depth, Fe, Mn and Cu become increasingly associated with sulphide phases. Substantial changes in porewater concentrations indicate zones of preferential mobilisation due to sharp alterations in physicochemical conditions. All metals are involved in processes of post depositional diagenetic cycling driven by organic matter degradation and O 2 utilisation in thermodynamically favoured sequence, Fe and Mn oxide and oxyhydroxide dissolution act as controlling variables leading to zones of solid phase metal enrichment. Phase equilibria have been calculated to elucidate observed solid phase partitioning at the redox boundary and processes of subsurface sulphide mineral formation.

Formation of Green Rust and Immobilization of Nickel in Response to Bacterial Reduction of Hydrous Ferric Oxide

This investigation documents the formation of Green Rust (GR) and immobilization of Ni 2+ in response to bacterial reduction of hydrous ferric oxide (HFO). In the absence of Ni 2+ , 79% of the total Fe(III) present as HFO was reduced; at 10 -3 and 10 -4 M Ni 2+ , 36% of the total Fe(III) was reduced, whereas 45 to 50% of the total Fe(III) was reduced at 10 -5 M Ni 2+ . The inhibitory effect of 10 -3 and 10 -4 M Ni 2+ on Fe(III)-reduction corresponded to a 50% decrease in number of viable cells relative to the Ni 2+ -free condition, and a 25% decrease at 10 -5 M Ni 2+ . A prominent GR peak at d = 10.9 nm was evident in X-ray diffraction patterns of postreduction residual solids from the cultures. Minor peaks arising for vivianite and magnetite were also present. In samples prepared for scanning electron microscopy, thin hexagonal plates of GR were easily distinguished as a solid phase transformation product of HFO. Small hexagonal sheets and fragments of larger GR plates were also observed in transmission electron microscopy whole mounts together with bacteria that were mineralized by surface precipitates of microcrystalline magnetite. Energy dispersive spectroscopy (EDS) confirmed that GR contained Fe and P, as well as Ni in those samples taken from the Ni 2+ -amended experiments. EDS detected neither P nor Ni in the magnetite precipitates associated with the bacterial cells. Dissolved Ni2 + concentrations decreased in an exponential fashion with respect to time in all experimental systems, corresponding to an overall first-order rate constant k of -0.030 day -1 . At the same time, a strong linear relationship (r 2 = 0.99) between the dissolved and solid phase Ni 2+ /Fe 2+ ratios over the entire period of the Fe(III)reduction experiments provided evidence that the solid-phase partitioning of Ni 2+ in GR extended from equilibrium solid-solution behavior.

Solid phase partitioning of metals in Managed Realignment soils: laboratory studies in timed soil sea-water batch mixtures

Geochemical interactions between agricultural soil and sea-water at a salt marsh restoration Managed Realignment site in Essex, UK were simulated through a series of laboratory experiments. Soil from the site was mixed with sea-water for 0–30 days in batch reactors. The resulting soil residue was subjected to a modified version of the Tessier sequential extraction procedure involving leaching with 5 reagents of progressively increasing strength. Differences in total metals extracted by the series of sequential extractions in comparison to a single digest hindered interpretation of data. Analysis of the sequential extracts and residual sea-water for a suite of metals revealed that Na, Mg and K were sorbed from sea-water to the soils, and from the readily exchangeable fraction of the soil, Ba, Ca, Mn, Ni and Zn were depleted. In the more strongly held fractions extractability of a number of metals, most notably Al, Fe and K by acid leaches was observed to increase as a result of contact with sea-water. The extractability of the heavy metals Cr, Pb, Ni and Zn from these tightly held fractions was also observed to increase as a result of sea-water mixing. However, results imply that tidal inundation of the soils at the site will not result in significant leaching of metals to the environment.

Geochemical changes in sulfidic mine tailings stored under a shallow water cover

The objective of this study was to assess the effectiveness of an engineered shallow water cover in reducing the oxidation of sulfidic mine tailings and thus preventing the development of acid rock drainage. Fresh tailings were submerged under a 0.3-m water cover in experimental field cells. From 1996 to 1998, we followed the chemistry of the interstitial water near the tailings-overlying water interface using in situ dialysis, and determined pH and dissolved oxygen (DO) profiles across the tailing–water interface using micro-electrodes. Penetration of DO into the tailings was limited to <7 mm, even in the presence of DO produced by benthic periphyton. Anoxia in the tailings was further demonstrated by the appearance of dissolved ΣH 2S, Fe and Mn in pore water at depths −1.5 cm below the interface. However, there was clear evidence of surface oxidation of the mine tailings at the mm scale (i.e., DO depletion, coupled with localized increases in [H +] and [SO 4 2−]). Mobilization of Cd and Zn from this surface layer was indicated by the presence of sub-surface peaks in the concentrations of these two metals in the tailings interstitial water and by a change in their solid phase partitioning from refractory to more labile fractions. In contrast, mobilization of Cu from tailings was less evident. Unlike previous reports, which suggested that submerged tailings were effectively inert, our results show alteration of the superficial layer over time.