Daniel G. Strawn

The kinetics of mixed Ni-Al hydroxide formation on clay and aluminum oxide minerals: a time-resolved XAFS study

Abstract In this study kinetic investigations were combined with X-ray Absorption Fine Structure (XAFS) measurements to determine Ni sorption processes on pyrophyllite, gibbsite, and montmorillonite over extended time periods (min-months). The kinetic investigations revealed that Ni sorption reactions (pH = 7.5, [Ni] initial = 3 mM, I = 0.1 M (NaNO 3 )) were initially fast (8–35% of the initial Ni was removed within the first 40 min). Thereafter, the rate of sorption decreased significantly and depended on the type of mineral surface. For the Ni/pyrophyllite system Ni removal was almost complete after a reaction time of 24h while for the Ni/gibbsite and Ni/montmorillonite systems metal sorption continued up to ≈2 months. XAFS data revealed the presence of a mixed Ni/Al phase in the Ni/pyrophyllite and Ni/gibbsite systems after a reaction time of minutes. These results suggest that adsorption and nucleation processes (mixed Ni/Al phase formation) can occur simultaneously over time scales of only minutes. However, our finding of a fast growing mixed Ni/Al phase cannot be extrapolated to other sorption systems. A reaction time of 48 h was required for the presence of a mixed Ni/Al phase in the Ni/mormorillonite system. As reaction time progressed, the number of second neighbor Ni atoms (N Ni-Ni ) at a distance of ≈3.05 A increased in all sorption systems, suggesting further growth of a mixed Ni/Al phase with increasing reaction time. Our study suggests that three phenomena occur at the mineral/liquid interface: (1) nonspecific (i.e, outer- sphere complexation) and/or specific adsorption (i.e., inner-sphere complexation), (2) dissolution of Al, and (3) nucleation of a mixed Ni/Al phase. The rate-limiting step is the dissolution of Al from the surface, which depends on the mineral substrate. Using the Ni linear sorption rates observed in the Ni/gibbsite and Ni/montmorillonite systems and assuming the Ni/Al ratios in our sorption samples are within the range of Ni/Al ratios provided in the literature (1.3–5.6), one can estimate an average Al dissolution rate which seems to be enhanced compared to the Al dissolution rates of the minerals alone. This finding indicates that the dissolution of clay and aluminum oxide minerals can be promoted by metal ions such as Ni(II) through the formation of a mixed Ni/Al phase.

Microscale investigation into the geochemistry of arsenic, selenium, and iron in soil developed in pyritic shale materials

Abstract In this study, we report on the distribution and mineralogy of micron-sized mineral aggregates formed in the top horizon of an acid sulfate soil. The distribution and oxidation state of arsenic (As) and selenium (Se) were also determined. The soil used in this study was formed from pyritic shale parent materials on the east side of the California Coast Range. Synchrotron-based X-ray fluorescence microprobe (μ-XRF) was used to generate elemental distribution maps of soil thin sections. Using the elemental distribution maps and optical micrographs, distinct mineral aggregates of iron oxide and iron sulfate were identified throughout the top horizon of the soil. These aggregates range in size from 10 to 100 μm in diameter and can be found only a few micrometers apart. The As and Se concentrations in the iron oxide aggregates were 5–10 times the concentrations in the iron sulfate aggregates and the weathered shale matrix. This suggests that the As and Se become preferentially associated with iron oxides during the weathering process. Using a focused micron-sized beam, Fe, As, and Se X-ray absorption spectroscopy (XAS) data were collected from the sub-millimeter soil aggregates. The micro-extended X-ray absorption fine structure (μ-EXAFS) spectrum collected from the iron oxide aggregate revealed that its mineralogy was a combination of ferrihydrite (>50%) and goethite. The μ-EXAFS spectra from the iron sulfate region suggest that these aggregates contain jarosite. Using micro-X-ray absorption near edge spectroscopy (μ-XANES), oxidation states of the As and Se were determined. Arsenic was present in the iron oxide aggregate as As(V). Selenium was present in the soil as both Se(IV) and Se(VI), with a higher percentage of Se(VI) in the jarosite aggregate than the iron oxide aggregate. These results provide direct evidence of the distribution, oxidation states, and speciation of As and Se in the solid phase of an unaltered native soil. Information on the weathering and geochemistry of the pyritic materials, and the associated arsenic and selenium is useful for predicting the pedogenic processes of acid sulfate soils and the long-term fate of newly exposed pyritic materials (e.g., mine tailings and drained wetlands).

COPPER SORPTION MECHANISMS ON SMECTITES

Due to the importance of clay minerals in metal sorption, many studies have attempted to derive mechanistic models that describe adsorption processes. These models often include several different types of adsorption sites, including permanent charge sites and silanol and aluminol functional groups on the edges of clay minerals. To provide a basis for development of adsorption models it is critical that molecular-level studies be done to characterize sorption processes. In this study we conducted X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) spectroscopic experiments on copper (II) sorbed on smectite clays using suspension pH and ionic strength as variables. At low ionic strength, results suggest that Cu is sorbing in the interlayers and maintains its hydration sphere. At high ionic strength, Cu atoms are excluded from the interlayer and sorb primarily on the silanol and aluminol functional groups of the montmorillonite or beidellite structures. Interpretation of the XAFS and EPR spectroscopy results provides evidence that multinuclear complexes are forming. Fitting of extended X-ray absorption fine structure spectra revealed that the Cu-Cu atoms in the multinuclear complexes are 2.65 Å apart, and have coordination numbers near one. This structural information suggests that small Cu dimers are sorbing on the surface. These complexes are consistent with observed sorption on mica and amorphous silicon dioxide, yet are inconsistent with previous spectroscopic results for Cu sorption on montmorillonite. The results reported in this paper provide mechanistic data that will be valuable for modeling surface interactions of Cu with clay minerals, and predicting the geochemical cycling of Cu in the environment.

Molecular characterization of copper in soils using X-ray absorption spectroscopy.

Bioavailability of Cu in the soil is a function of its speciation. In this paper we investigated Cu speciation in six soils using X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and synchrotron-based micro X-ray fluorescence (mu-XRF). The XANES and EXAFS spectra in all of the soils were the same. mu-XRF results indicated that the majority of the Cu particles in the soils were not associated with calcium carbonates, Fe oxides, or Cu sulfates. Principal component analysis and target transform of the XANES and EXAFS spectra suggested that Cu adsorbed on humic acid (HA) was an acceptable match. Thus it appears that Cu in all of the soils is primarily associated with soil organic matter (SOM). Theoretical fitting of the molecular structure in the soil EXAFS spectra revealed that the Cu in the soils existed as Cu atoms bound in a bidentate complex to O or N functional groups.

Micro-spectroscopic investigation of selenium-bearing minerals from the Western US Phosphate Resource Area

Mining activities in the US Western Phosphate Resource Area (WPRA) have released Se into the environment. Selenium has several different oxidation states and species, each having varying degrees of solubility, reactivity, and bioavailability. In this study we are investigating the speciation of Se in mine-waste rocks. Selenium speciation was determined using bulk and micro-x-ray absorption spectroscopy (XAS), as well as micro-x-ray fluorescence mapping. Rocks used for bulk-XAS were ground into fine powders. Shale used for micro-XAS was broken along depositional planes to expose unweathered surfaces. The near edge region of the XAS spectra (XANES) for the bulk rock samples revealed multiple oxidation states, with peaks indicative of Se(-II), Se(IV), and Se(+VI) species. Micro-XANES analysis of the shale indicated that three unique Se-bearing species were present. Using the XANES data together with ab initio fitting of the extended x-ray absorption fine structure region of the micro-XAS data (micro-EXAFS) the three Se-bearing species were identified as dzharkenite, a di-selenide carbon compound, and Se-substituted pyrite. Results from this research will allow for a better understanding of the biogeochemical cycling of Se in the WPRA.

Macroscopic and molecular investigations of copper sorption by a steam-activated biochar.

Excessive Cu concentrations in water systems can negatively affect biological systems. Because Cu can form strong associations with organic functional groups, we examined the ability of biochar (an O-C-enriched organic bioenergy by-product) to sorb Cu from solution. In a batch experiment, KOH steam-activated pecan shell biochar was shaken for 24 h in pH 6, 7, 8, or 9 buffered solutions containing various Cu concentrations to identify the effect of pH on biochar Cu sorption. Afterward, all biochar solids from the 24-h shaking period were air-dried and analyzed using X-ray absorption fine structure (XAFS) spectroscopy to determine solid-phase Cu speciation. In a separate batch experiment, biochar was shaken for 30 d in pH 6 buffered solution containing increasing Cu concentrations; the Cu sorption maximum was calculated based on the exponential rise to a maximum equation. Biochar sorbed increasing amounts of Cu as the solution pH decreased from 9 to 6. The XAFS spectroscopy revealed that Cu was predominantly sorbed onto a biochar organic phase at pH 6 in a molecular structure similar to Cu adsorbed on model humic acid (Cu-humic acid [HA]). The XAFS spectra at pH 7, 8, and 9 suggested that Cu was associated with the biochar as three phases: (i) a complex adsorbed on organic ligands similar to Cu-HA, (ii) carbonate phases similar to azurite (Cu(CO)(OH)), and (iii) a Cu oxide phase like tenorite (CuO). The exponential rise equation fit to the incubated samples predicted a Cu sorption maximum of 42,300 mg Cu kg. The results showed that KOH steam-activated pecan shell biochar could be used as a material for sorbing excess Cu from water systems, potentially reducing the negative effects of Cu in the environment.

Kinetics of phosphorus release from manure-amended alkaline soil

The release and transport of phosphate from manure-amended soils is detrimental to surface water because it leads to eutrophication. However, reaction rates and mechanisms of P release from manure-amended alkaline soils have not been completely characterized. The objectives of the present study were to determine the rate of P release from a manure-amended soil and to apply solubility models to predict the mineralogical phases that control soil-solution P concentrations. Phosphate release kinetics were measured on a soil that had received solid-dairy manure applications for more than a decade. To measure total P that would be released under leaching conditions, we conducted experiments in which we replenished the solution continuously until the P concentration reached a steady state (sequential desorption experiment). Measured P release kinetics indicate that 80% of the soluble P was released within 24 h, followed by a slow release that continued for up to 504 h. We applied several models, including a reversible first-order model, the Elovich model, and a modified version of the Elovich model that was empirically correlated to soil organic matter and percent clay, to describe our experimental data. The data were best fit with the Elovich model. Total P released from the manure-amended soil in the sequential desorption experiments was 29% from the surface soil (0–10 cm) and 8% from the subsurface soil (45–65 cm). Results from this study suggest that P release from manure-amended soils is controlled by rate-limited dissolution of meta-stable Ca-P mineral phases.

Chemical speciation and bioavailability of selenium in the rhizosphere of Symphyotrichum eatonii from reclaimed mine soils.

Knowledge of rhizosphere influences on Se speciation and bioavailability is required to predict Se bioavailability to plants. In the present study, plant-availability of Se to aster (Symphyotrichum eatonii (A. Gray) G.L. Nesom) was compared in rhizosphere soils and nonrhizosphere (bulk) soils collected from a reclaimed mine site in southeastern Idaho, U.S. X-ray spectroscopy was used to characterize the oxidation state and elemental distribution of Se in aster roots, rhizosphere soils, and bulk soils. Percent extractable Se in aster rhizosphere soil was greater than extractable Se in corresponding bulk soils in all samples (n = 4, p = 0.042, 0.051, and 0.052 for three extractions). Selenium oxidation state mapping of 28 regions within the samples and X-ray absorption near edge structure (XANES) spectra from 26 points within the samples indicated that the rhizosphere and bulk soil Se species was predominantly reduced Se(-II,0), while in the aster roots, high concentrations of Se(VI) were present. Results show that within the rhizosphere, enhanced Se bioavailability is occurring via oxidation of reduced soil Se to more soluble Se(VI) species.

Metal content of charcoal in mining-impacted wetland sediments

Charcoal is well known to accumulate contaminants, but its association with metals and other toxic elements in natural settings has not been well studied. Association of contaminants with charcoal in soil and sediment may affect their mobility, bioavailability, and fate in the environment. In this paper, natural wildfire charcoal samples collected from a wetland site that has been heavily contaminated by mine waste were analyzed for elemental contents and compared to the surrounding soil. Results showed that the charcoal particles were enriched over the host soils by factors of two to 40 times in all contaminant elements analyzed. Principal component analysis was carried out on the data to determine whether element enrichment patterns in the soil profile charcoal are related to those in the soils. The results suggest that manganese and zinc concentrations in charcoal are controlled by geochemical processes in the surrounding soil, whereas the concentrations of arsenic, lead, zinc, iron, phosphorus, and sulfur in charcoal are unrelated to those in the surrounding soil. This study shows evidence that charcoal in soils can have a distinct and important role in controlling contaminant speciation and fate in the environment.

Selenium biogeochemical cycling and fluxes in the hyporheic zone of a mining-impacted stream.

The influence of hyporheic exchange on selenium (Se) biogeochemistry and mobility in sediments is unknown. A multiscale investigation of Se biogeochemistry in the hyporheic zone of East Mill Creek (EMC), southeastern Idaho, USA, was performed using in situ surface water and pore water geochemical measurements, a field-based stream tracer test, and energy-dependent micro synchrotron X-ray fluorescence (mu-SXRF) measurements of Se speciation in sediments. The active hyporheic zone was determined to be 12 +/- 3 cm. Pore water redox profiles indicated that a transition to suboxic conditions begins at approximately 6 cm. Modeling pore water Se and solid phase analysis suggested Se uptake is occurring. Micro-SXRF analysis of sediments showed reduced elemental Se or selenides throughout the profile and selenite in surface sediments. Field geochemical measurements and microscale analysis both support the hypothesis that reduction in the hyporheic zone promotes sequestration of surface water Se.