Linking solid phase speciation of Pb sequestered to birnessite to oral Pb bioaccessibility: implications for soil remediation

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simulate the possible effects of ingestion of a soil contaminated with Pb. The changes in Pb speciation were determined using extended X-ray absorption fine structure and X-ray absorption near edge spectroscopy. Birnessite has a very high affinity for Pb with a sorption maximum of 0.59 mol Pb kg(-1) (approximately 12% Pb sorbed by mass) in which there was no detectable bioaccessible Pb (< 0.002%). Surface speciation of the birnessite Pb was determined to be a triple corner sharing complex in the birnessite interlayer. Lead sorbed to Mn oxide in contaminated media will have a very low (approximately equal to 0) Pb bioaccessibility and present little risk associated with incidental ingestion of soil. These results suggest that birnessite, and other Mn oxides would be powerful remediation tools for Pb-contaminated media because of their high affinity for Pb.     

Arsenate adsorption mechanisms at the allophane-water interface

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As-(V)]0 from 50 to 1000 microM (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline Al-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As-(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO4(2-)) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The inner-sphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments.     

Adsorption,sequestration, and bioaccessibility of As(V) in soils

The influence of various soil physical and chemical properties (Fe and Mn oxides, pH, cation exchange capacity, total inorganic and organic carbon, and particle size) on As(V) adsorption, sequestration, and relative bioaccessibility (as a surrogate for oral bioavailability) was investigated in a wide range of well-characterized soils over a 6-month period. Arsenic(V) bioaccessibility was measured using a streamlined version of a physiologically based extracton test (PBET), designed to replicate the solubility-limiting conditions in a child's digestive tract. The soil's dithionite-citrate-bicarbonate (DCB) extractable Fe oxide content was the most important land only statistically significant) soil property controlling the initial degree of adsorption. Sequestration, as measured by the reduction in bioaccessibility over time, occurred to a significant extent in 17 of 36 (47.2%) soils over the first 3 months. In contrast, only 4 of 36 (11.1%) soils exhibited a significant reduction in bioaccessibility from 3 to 6 months. Soil pH was the most important (and only statistically significant) soil property affecting the decrease in bioaccessibility upon aging for 6 months. Soils with pH < 6 generally sequestered As(V) more strongly over time, whereas those with pH > 6 generally did not. The Fe oxide content and pH were the most important soil properties governing the steady-state bioaccessibility of As(V) in soil. Two multivariable linear regression models of steady-state As(V) bioaccessibility were developed using soil properties as independent variables. Generally, soils having higher Fe oxide content and lower soil pH exhibited lower bioaccessibility. These models were able to account for approximately 75-80% of the variability in steady-state bioaccessibility and independently predict bioaccessibility in five soils within a root-mean-square error (RMSE) of 8.2-10.9%. One of these models was also able to predict within an RMSE of 9.5% the in vivo bioavailability of As in nine contaminated soils previously used in swine dosing trials. These results indicate the bioaccessibility, and thus, potentially the bioavailability of otherwise soluble As(V) added to soils (i.e., the worst-case bioavailability scenario) is significantly reduced in some soils over time, particularly those with lower pH and higher Fe oxide content. These results also provide a means of estimating As(V) bioaccessibility and bioavailability on the basis of soil properties.     

Adsorption, oxidation, and bioaccessibility of As(III) in soils

At As-contaminated sites, where the ingestion of soil by children is typically the critical human-health exposure pathway, information on the bioavailability of soil-bound As is often limited. The influence of various soil physical and chemical properties (iron and manganese oxides, pH, cation exchange capacity, total inorganic and organic carbon, and particle size) on As(III) adsorption, sequestration, bioaccessibility (as a surrogate for oral bioavailability), and oxidation was investigated in 36 well-characterized soils by use of a physiologically based extraction test (PBET). These results were compared to an earlier published study with As(V) on the same set of soils. The properties of the soils were able to explain >80% of the variability in the adsorption and sequestration (as measured by the reduction in bioaccessibility over time) of As(III) in these soils. The initial bioaccessibility of As(III) was significantly higher than the initial bioaccessibility of As(V) on the same set of soils. However, over a 6-month period of aerobic aging, a significant portion of the solid-phase As(III) on these soils was oxidized to As(V), decreasing its bioaccessibility markedly. A multivariable linear regression model previously developed to predict the steady-state bioaccessibility of As(V) in soils was able to predict the bioaccessibility in As(III)-spiked soils within a root-mean-square error (RMSE) of 16.8%. Generally, soils having a higher iron oxide content and lower soil pH exhibited lower bioaccessibility. This model was also able to predict the in vivo bioavailability of As in contaminated soils previously used in an independent juvenile swine dosing trial within an RMSE of 15.5%, providing a greatly improved yet conservative estimate of bioavailability relative to the typical default assumption of 100%. However, the model was not able to accurately predict the bioavailability of As in a different set of contaminated soils previously used in an independent Cebus monkey dosing trial, consistently overpredicting the bioavailability, resulting in an RMSE of 42.7%. This model can be used to provide an initial estimate of As bioavailability in soil to aid in screening sites and justifying expensive site-specific animal feeding studies. Further, as the model is based on major soil properties, the resulting estimates are valid as long as the major soil properties do not change, thus providing some confidence in the long-term applicability of the estimates.     

Scavenging of As from acid mine drainage by schwertmannite and ferrihydrite: a comparison with synthetic analogues

Ochreous precipitates containing 5.5-69.8 g/kg As were isolated from mine drainage in Finland and were composed of schwertmannite, ferrihydrite, and goethite. Schwertmannite formation was favored at pH 3-4, but its structure was degraded at high As levels. A series of coprecipitates were therefore prepared from mixed iron arsenate/sulfate solutions to define the limits of schwertmannite stability. Schwertmannite was replaced as the dominant phase by a poorly crystalline ironIII hydroxy arsenate (FeOHAs) when As/Fe mole ratios exceeded 0.15. The FeOHAs gave an X-ray diffraction pattern similar to that obtained from an "amorphous" ironIII arsenate (As/Fe = 1.0) with broad peaks at 0.30 and 0.16 nm. The FeOHAs possessed a magnetic hyperfinefield of 41.9T at 4.2 K that was intermediate to those of schwertmannite (46.1 T) and the ironIII arsenate (24.8 T). These data indicate a strong disruptive effect of arsenate on magnetic ordering and structure development in schwertmannite. Equilibration of 0.01 M arsenate solutions with freshly prepared schwertmannite and 2-line ferrihydrite at pH 3.0 for up to 60 d gave sorbed As contents of 175 and 210 g/kg, respectively. Arsenate sorption degraded the host schwertmannite and ferrihydrite, perhaps due to the formation of an FeOHAs surface phase.     

In vitro gastrointestinal bioavailability of arsenic in soils collected near CCA-treated utility poles

Because of the potentially high arsenic concentrations found in soils immediately adjacent to chromated copper arsenate (CCA)-treated wood structures and utility poles, CCA-contaminated soil ingestion may be a significant exposure route to arsenic for children. Therefore, a strong need exists to provide accurate data on oral relative bioavailability (RBA) of arsenic (in vivo or in vitro) in field-collected CCA-contaminated soils. The objectives of this study were (1) to assess arsenic bioaccessibility in contaminated soils collected near in-service CCA-treated utility poles, (2) to determine the influence of soil properties and arsenic fractionation on arsenic bioaccessibility, and (3) to estimate an average daily arsenic intake from incidental soil ingestion. Arsenic bioaccessibility (in vitro gastrointestinal (IVG) method) was determined on surface soil samples collected immediately adjacent to 12 CCA-treated utility poles after 18 months of service. Bioaccessible arsenic was also determined in 3 certified reference materials. Total arsenic concentrations in soils (<300 microm) varied from 37 +/- 2 to 251 +/- 12 mg/kg, irrespective of soil organic matter contentwith the major soil-bound arsenic species being As(V). Arsenic bioaccessibility ranged between 25.0 +/- 2.7 and 66.3 +/- 2.3% (mean value 40.7 +/- 14.9%). The mean value was in agreement with the in vivo arsenic RBA reported by Casteel et al. (2003) in soil near CCA-treated utility poles. Bioaccessible arsenic was positively correlated with total organic carbon content (r2 = 0.36, p < 0.05) and with water-soluble arsenic (2 = 0.51, p < 0.01), and was negatively correlated with clay content (r2 = 0.43, p < 0.05). Using conservative exposure parameters, the mean daily arsenic intake from incidental ingestion of contaminated soil near CCA-treated utility poles was 0.18 +/- 0.09 microg As kg(-1) d(-1). This arsenic intake appeared negligible compared to the daily intake of inorganic arsenic from water and food ingestion for children.     

In vivo-in vitro and XANES spectroscopy assessments of lead bioavailability in contaminated periurban soils

Lead (Pb) bioaccessibility was assessed using 2 in vitro methods in 12 Pb-contaminated soils and compared to relative Pb bioavailability using an in vivo mouse model. In vitro Pb bioaccessibility, determined using the intestinal phase of the Solubility Bioaccessibility Research Consortium (SBRC) assay, strongly correlated with in vivo relative Pb bioavailability (R(2) = 0.88) following adjustment of Pb dissolution in the intestinal phase with the solubility of Pb acetate at pH 6.5 (i.e., relative Pb bioaccessibility). A strong correlation (R(2) = 0.78) was also observed for the relative bioaccessibility leaching procedure (RBALP), although the method overpredicted in vivo relative Pb bioavailability for soils where values were <40%. Statistical analysis of fit results from X-ray absorption near-edge structure (XANES) data for selected soils (n = 3) showed that Pb was strongly associated with Fe oxyhydroxide minerals or the soil organic fraction prior to in vitro analysis. XANES analysis of Pb speciation during the in vitro procedure demonstrated that Pb associated with Fe minerals and the organic fraction was predominantly solubilized in the gastric phase. However, during the intestinal phase of the in vitro procedure, Pb was strongly associated with formation of ferrihydrite which precipitated due to the pH (6.5) of the SBRC intestinal phase. Soils where Fe dissolution was limited had markedly higher concentrations of Pb in solution and hence exhibited greater relative bioavailability in the mouse model. This data suggests that coexistence of Fe in the intestinal phase plays an important role in reducing Pb bioaccessibility and relative bioavailability.     

Impacts of Shewanella putrefaciens strain CN-32 cells and extracellular polymeric substances on the sorption of As(V) and As(III) on Fe(III)-(hydr)oxides

We investigated the effects of Shewanella putrefaciens cells and extracellular polymeric substances on the sorption of As(III) and As(V) to goethite, ferrihydrite, and hematite at pH 7.0. Adsorption of As(III) and As(V) at solution concentrations between 0.001 and 20 μM decreased by 10 to 45% in the presence of 0.3 g L(-1) EPS, with As(III) being affected more strongly than As(V). Also, inactivated Shewanella cells induced desorption of As(V) from the Fe(III)-(hydr)oxide mineral surfaces. ATR-FTIR studies of ternary As(V)-Shewanella-hematite systems indicated As(V) desorption concurrent with attachment of bacterial cells at the hematite surface, and showed evidence of inner-sphere coordination of bacterial phosphate and carboxylate groups at hematite surface sites. Competition between As(V) and bacterial phosphate and carboxylate groups for Fe(III)-(oxyhydr)oxide surface sites is proposed as an important factor leading to increased solubility of As(V). The results from this study have implications for the solubility of As(V) in the soil rhizosphere and in geochemical systems undergoing microbially mediated reduction and indicate that the presence of sorbed oxyanions may affect Fe-reduction and biofilm development at mineral surfaces.     

Arsenite oxidation by a poorly-crystalline manganese oxide. 3. Arsenic and manganese desorption

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese oxides (Mn oxides) have the ability to decrease overall As mobility both by oxidizing toxic arsenite (As(III)) to less toxic arsenate (As(V)), and by sorbing As. However, the effect of competing ions on the mobility of As sorbed on Mn-oxide surfaces is not well understood. In this study, desorption of As(V) and As(III) from a poorly crystalline phyllomanganate (δ-MnO(2)) by two environmentally significant ions is investigated using a stirred-flow technique and X-ray absorption spectroscopy (XAS). As(III) is not observed in solution after desorption under any conditions used in this study, agreeing with previous studies showing As sorbed on Mn-oxides exists only as As(V). However, some As(V) is desorbed from the δ-MnO(2) surface under all conditions studied, while neither desorptive used in this study completely removes As(V) from the δ-MnO(2) surface.     

Arsenic mobilization through microbially mediated deflocculation of ferrihydrite

This study examined the potential impact of microbially mediated reduction of Fe in the Fe(III)-(hydr)oxide mineral ferrihydrite on the mobility of As in natural waters. In microcosm experiments, the obligately anaerobic bacterium Geobacter metallireducens reduced on average 10% of the Fe(III) in ferrihydrite with varying sorbed As(V) surface coverages, which resulted in deflocculation of initially micron-sized As-bearing ferrihydrite aggregates to nanometersized colloids. No reduction of As(V) to As(III) was observed in microcosm samples. Measurement of Fe and As within operationally defined particulate, colloidal, and dissolved fractions of microcosm slurry samples revealed that little Fe or As was released from ferrihydrite as dissolved species. Microbially induced deflocculation of ferrihydrite in the presence of G. metallireducens was correlated with more negative zeta potential of ferrihydrite nanoparticles suggesting that G. metallireducens mediated As mobilization through alteration of ferrihydrite surface charge. TEM analysis and solution chemistry conditions suggested formation of a magnetite surface layer through topotactic recrystallization of ferrihydrite (2LFH) driven by sorbed Fe(II). The formation of nanometer-sized As-bearing colloids through microbially mediated reduction of Fe-(hydr)oxides has the potential to increase human As exposure by enhancing As mobility in natural waters and hindering As removal during subsequent drinking water treatment.     

Adsorption mechanism of arsenic on nanocrystalline titanium dioxide

Arsenate [As(V)] and arsenite [As(III)] interactions at the solid-water interface of nanocrystalline TiO2 were investigated using electrophoretic mobility (EM) measurements, Fourier transform infrared (FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. The adsorption of As(V) and As(III) decreased the point of zero charge of TiO2 from 5.8 to 5.2, suggesting the formation of negatively charged inner-sphere surface complexes for both arsenic species. The EXAFS analyses indicate that both As(V) and As(III) form bidentate binuclear surface complexes as evidenced by an average Ti-As(V) bond distance of 3.30 A and Ti-As(III) bond distance of 3.35 A. The FTIR bands caused by vibrations of the adsorbed arsenic species remained at the same energy levels at different pH values. Consequently, the surface complexes on TiO2 maintained the same nonprotonated speciation at pH values from 5 to 10, and the dominant surface species were (TiO)2AsO2- and (TiO)2AsO- for As(V) and As(III), respectively. The surface configurations constrained with the spectroscopic results were formulated in the diffuse layer model to describe the adsorption behavior of As in the pH range between 4 and 12. The study suggests that TiO2 is an effective adsorbent for As removal due to its high surface area and the presence of high affinity surface hydroxyl groups.     

Iron and arsenic cycling in intertidal surface sediments during wetland remediation

The accumulation and behavior of arsenic at the redox interface of Fe-rich sediments is strongly influenced by Fe(III) precipitate mineralogy, As speciation, and pH. In this study, we examined the behavior of Fe and As during aeration of natural groundwater from the intertidal fringe of a wetland being remediated by tidal inundation. The groundwater was initially rich in Fe(2+) (32 mmol L(-1)) and As (1.81 μmol L(-1)) with a circum-neutral pH (6.05). We explore changes in the solid/solution partitioning, speciation and mineralogy of Fe and As during long-term continuous groundwater aeration using a combination of chemical extractions, SEM, XRD, and synchrotron XAS. Initial rapid Fe(2+) oxidation led to the formation of As(III)-bearing ferrihydrite and sorption of >95% of the As(aq) within the first 4 h of aeration. Ferrihydrite transformed to schwertmannite within 23 days, although sorbed/coprecipitated As(III) remained unoxidized during this period. Schwertmannite subsequently transformed to jarosite at low pH (2-3), accompanied by oxidation of remaining Fe(2+). This coincided with a repartitioning of some sorbed As back into the aqueous phase as well as oxidation of sorbed/coprecipitated As(III) to As(V). Fe(III) precipitates formed via groundwater aeration were highly prone to reductive dissolution, thereby posing a high risk of mobilizing sorbed/coprecipitated As during any future upward migration of redox boundaries. Longer-term investigations are warranted to examine the potential pathways and magnitude of arsenic mobilization into surface waters in tidally reflooded wetlands.     

Coupling speciation and isotope dilution techniques to study arsenic mobilization in the environment

We have developed an approach to isolate mechanisms controlling mobility and speciation of As in soil-water systems. The approach uses a combination of isotopic exchange and chromatographic/mass spectrometric As speciation techniques. We used this approach to identify mechanisms responsible for changes in the concentration of soluble As in two contaminated soils (Eaglehawk and Tavistock) subjected to different redox conditions and microbial activity. A high proportion of the total As in both soils was present in a nonlabile form. Incubation of the soils under anaerobic conditions led to changes in the concentration of soluble As in each soil but did not change the As speciation or the proportion of total As in labile forms in the soils. Hence, a decrease in soluble As in the Eaglehawk soil was the result of an Eh-induced pH decrease, enhancing the solid-phase sorption of As(V). An increase in soluble As in the Tavistock soil was due to an Eh-induced pH increase, decreasing solid-phase sorption of As(V). Incubation of the soils under aerobic conditions with microbial activity stimulated by addition of glucose resulted in no change in the solution concentration or speciation of As in the Eaglehawk soil, but led to a large increase in the concentration of soluble As in the Tavistock soil. This increase was due to conversion of exchangeable forms of As(V) into less strongly sorbed As(III) species. Incubation under anaerobic conditions in the presence of glucose resulted in a large increase in the concentration of soluble As in both soils; however, different mechanisms were found to be responsible for the increase in each soil. In the Eaglehawk soil higher concentrations of As were again due to conversion of exchangeable forms of As(V) into less strongly sorbed As(III) species. In contrast in the Tavistock soil, the increased As in solution was the result of release of As(V) from the large reservoir of nonlabile soil As.     

Influence of arsenate adsorption to ferrihydrite, goethite, and boehmite on the kinetics of arsenate reduction by Shewanella putrefaciens strain CN-32

The kinetics of As(V) reduction by Shewanella putrefaciens strain CN-32 was investigated in suspensions of 0.2, 2, or 20 g L(-1) ferrihydrite, goethite, or boehmite at low As (10 μM) and lactate (25 μM) concentrations. Experimental data were compared with model predictions based on independently determined sorption isotherms and rates of As(V) desorption, As(III) adsorption, and microbial reduction of dissolved As(V), respectively. The low lactate concentration was chosen to prevent significant Fe(III) reduction, but still allowing complete As(V) reduction. Reduction of dissolved As(V) followed first-order kinetics with a 3 h half-life of As(V). Addition of mineral sorbents resulted in pronounced decreases in reduction rates (32-1540 h As(V) half-life). The magnitude of this effect increased with increasing sorbent concentration and sorption capacity (goethite < boehmite < ferrihydrite). The model consistently underestimated the concentrations of dissolved As(V) and the rates of microbial As(V) reduction after addition of S. putrefaciens (～5 × 10(9) cells mL(-1)), suggesting that attachment of S. putrefaciens cells to oxide mineral surfaces promoted As(V) desorption and thereby facilitated As(V) reduction. The interplay between As(V) sorption to mineral surfaces and bacterially induced desorption may thus be critical in controlling the kinetics of As reduction and release in reducing soils and sediments.     

Spectroscopic evidence for Ni(II) surface speciation at the iron oxyhydroxides-water interface

Understanding in situ metal surface speciation on mineral surfaces is critical to predicting the natural attenuation of metals in the subsurface environment. In this study, we have demonstrated the novel Ni K-edge X-ray absorption spectroscopy (XAS) measurements needed to understand Ni(ll) surface speciation in three synthetic iron oxyhydroxides (ferrihydrite, goethite, and hematite). The adsorption of Ni gradually increases with increasing pH from 5 to 8, and the adsorption edge appears at near the point of zero salt effect (PZSE) of the solids. The results of XAS analysis indicate four different Ni inner-sphere surface species are present. While total Ni surface species in hematite at pH 6.85 surfaces consist of approximately 63% face-sharing (interatomic distance of Ni-Fe (R(Ni-Fe)) approximately 2.9 A) and approximately 37% corner-sharing (R(Ni-Fe) approximately 4.0 A) surface species on iron octahedra, a combination of two different edge-sharing (between NiO6 and FeO6 octahedra, in chains or in rows) and corner-sharing surface species are observed in goethite and ferrihydrite at pH 5.09-6.89. In ferrihydrite, approximately 70% of surface species are edge-sharing surface species (in chains) (R(Ni-Fe) approximately 3.0 A), followed by approximately 30% of edge-sharing species (in rows) (R(Ni-Fe) approximately 3.2 A) and approximately 3-5% of corner-sharing surface species (R(Ni-Fe) approximately 4.0 A). Goethite contains approximately 54% edge-sharing (R(Ni-Fe) approximately 3.0 A), approximately 26% edge-sharing (R(Ni-Fe) approximately 3.2 A), and 20% corner-sharing surface species. These findings indicate that the reactivity and surface speciation of Ni are sensitive to the crystallinity of iron oxyhydroxides. The spectroscopic evidence for multi-Ni surface speciation should be factored into predictions of the transport of Ni in soil-water environments.     

Distinctive arsenic(V) trapping modes by magnetite nanoparticles induced by different sorption processes

Arsenic sorption onto iron oxide spinels such as magnetite may contribute to arsenic immobilization at redox fronts in soils, sediments, and aquifers, as well as in putative remediation and water treatment technologies. We have investigated As(V) speciation resulting from different sorption processes on magnetite nanoparticles, including both adsorption and precipitation, using X-ray absorption fine structure (XAFS) spectroscopy and transmission electron microscopy (TEM). XAFS results suggest that AsO(4) tetrahedra form predominantly inner-sphere bidentate corner-sharing ((2)C) complexes and outer-sphere complexes on magnetite in the adsorption experiments. In the precipitation experiments, an increasing fraction of AsO(4) tetrahedra appears to be incorporated in clusters having a magnetite-like local structure with increasing As loading, the remaining fraction of As being adsorbed at the surface of magnetite particles. In the sample with the highest As loading (15.7 μmol/m(2)) XAFS data indicate that As(V) is fully incorporated in such clusters. Such processes help to explain the significantly higher arsenic uptake in precipitation samples compared to those generated in adsorption experiments. In addition, for the precipitation samples, TEM observations indicate the formation of amorphous coatings and small (~3 nm) nanoparticles associated with larger (~20-40 nm) magnetite nanoparticles, which are absent in the adsorption samples. These results suggest that As(V) could form complexes at the surfaces of the small nanoparticles and could be progressively incorporated in their structure with increasing As loading. These results provide some of the fundamental knowledge about As(V)-magnetite interactions that is essential for developing effective water treatment technologies for arsenic.     

Lead sequestration and species redistribution during soil organic matter decomposition

The turnover of soil organic matter (SOM) maintains a dynamic chemical environment in the forest floor that can impact metal speciation on relatively short timescales. Here we measure the speciation of Pb in controlled and natural organic (O) soil horizons to quantify changes in metal partitioning during SOM decomposition in different forest litters. We provide a link between the sequestration of pollutant Pb in O-horizons, estimated by forest floor Pb inventories, and speciation using synchrotron-based X-rayfluorescence and X-ray absorption spectroscopy. When Pb was introduced to fresh forest O(i) samples, it adsorbed primarily to SOM surfaces, but as decomposition progressed over two years in controlled experiments, up to 60% of the Pb was redistributed to pedogenic birnessite and ferrihydrite surfaces. In addition, a significant fraction of pollutant Pb in natural soil profiles was associated with similar mineral phases (approximately 20-35%) and SOM (-65-80%). Conifer forests have at least 2-fold higher Pb burdens in the forest floor relative to deciduous forests due to more efficient atmospheric scavenging and slower organic matter turnover. We demonstrate that pedogenic minerals play an important role in surface soil Pb sequestration, particularly in deciduous forests, and should be considered in any assessment of pollutant Pb mobility.     

Thermodynamic stabilization of hydrous ferric oxide by adsorption of phosphate and arsenate

Hydrous ferric oxide (HFO) is an X-ray amorphous compound with a high affinity for anions under strongly or mildly acidic conditions. Because of the usually small particle size of HFO, the adsorption capacity is high and adsorption may significantly impact the thermodynamic properties of such materials. Here we show that adsorption of phosphate and arsenate stabilizes HFO by experimental determination of enthalpies of formation (by acid-solution calorimetry) and estimates of standard entropies for six phosphate- or arsenate-enriched HFO samples. At pH values lower than ～5, the phosphate-doped HFO is not only less soluble than ferrihydrite (anion-free HFO) but also crystalline FeOOH polymorphs feroxyhyte and lepidocrocite. The arsenate-doped HFO is also stabilized with respect to the ferrihydrite. Phosphate availability in soils can be controlled by the phosphate-enriched HFO which is many orders of magnitude less soluble than apatite or crystalline Fe(III) phosphates, for example strengite (FePO(4)·2H(2)O). Thermodynamic dissolution models for scorodite (FeAsO(4)·2H(2)O) and As-enriched HFO show that under mildly acidic or circumneutral conditions, scorodite dissolves, As-HFO precipitates, and a substantial amount of As(V) is released into the aqueous solution (at pH 7, log m(As) ～ -2.5). The data presented in this paper can be used to model the equilibrium concentration of Fe(III), P(V), or As(V) in soil solutions or in natural or anthropogenic sediments polluted by arsenic.     

Spatial and temporal association of As and Fe species on aquatic plant roots

The formation of an Fe(III) precipitate (plaque) on the surface of aquatic plant roots may provide a means of attenuation and external exclusion of metals. Presently, the mechanisms of metal(loid) sequestration at the root surface are unresolved. Accordingly, we investigated the mechanisms of Fe and As attenuation and association on the roots of two common aquatic plant species, Phalaris arundinacea (reed canarygrass) and Typha latifolia (cattail) using X-ray absorption spectroscopy and X-ray fluorescence microtomography. Iron plaque of both P. arundinacea and T. latifolia consist predominantly of hydrated iron oxides (ferrihydrite) with lesser amounts of goethite and minor levels of siderite. Typha latifolia, however, differs from P. arundinacea by having a significant contribution from lepidocrocite as well as a greater proportion of crystalline minerals. Coexistence of goethite and lepidocrocite suggests the presence of chemically diverse microenvironments at the root surface. Arsenic exists as a combination of two sorbed As species, being comprised predominantly of arsenate- (approximately 82%) with lesser amounts (approximately 18%) of As(III)-iron (hydr)oxide complexes. Furthermore, both spatial and temporal correlations between As and Fe on the root surfaces were observed. While the iron (hydr)oxide deposits form a continuous surficial rind around the root, As exists in isolated regions on the exterior and interior of the root. Root surface-associated As generally corresponds to regions of enhanced Fe levels and may therefore occur as a direct consequence of Fe phase heterogeneity and preferential As sorption reactions.     

Arsenic(III) oxidation and arsenic(V) adsorption reactions on synthetic birnessite

The oxidation of arsenite (As(III)) by manganese oxide is an important reaction in both the natural cycling of As and the development of remediation technology for lowering the concentration of dissolved As(III) in drinking water. This study used both a conventional stirred reaction apparatus and extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate the reactions of As(III) and As(V) with synthetic birnessite (MnO2). Stirred reactor experiments indicate that As(III) is oxidized by MnO2 followed by the adsorption of the As(V) reaction product on the MnO2 solid phase. The As(V)-Mn interatomic distance determined by EXAFS analysis for both As(III)- and As(V)-treated MnO2 was 3.22 A, giving evidence for the formation of As(V) adsorption complexes on MnO2 crystallite surfaces. The most likely As(V)-MnO2 complex is a bidentate binuclear corner sharing (bridged) complex occurring at MnO2 crystallite edges and interlayer domains. In the As(III)-treated MnO2 systems, reductive dissolution of the MnO2 solid during the oxidation of As(III) caused an increase in the adsorption of As(V) when compared with As(V)-treated MnO2. This suggested that As(III) oxidation caused a surface alteration, creating fresh reaction sites for As(V) on MnO2 surfaces.