Metals Coprecipitation with Barite: Nano-XRF Observation of Enhanced Strontium Incorporation.

Coprecipitation can be an effective treatment method for the removal of environmentally relevant metals from industrial wastewaters such as produced waters from the oil and gas industry. The precipitation of barite, BaSO4, through the addition of sulfate removes barium while coprecipitating strontium and other alkaline earth metals even when these are present at concentrations below their solubility limit. Among other analytical methods, X-ray fluorescence (XRF) nanospectroscopy at the Hard X-ray Nanoprobe (HXN) beamline at the National Synchrotron Light Source II (NSLS-II) was used to quantify Sr incorporation into barite. Thermodynamic modeling of (Ba,Sr)SO4 solid solutions was done using solid solution-aqueous solution (SS-AS) theory. The quantitative, high-resolution nano-XRF data show clearly that the Sr content in (Ba,Sr)SO4 solid solutions varies widely among particles and even within a single particle. We observed substantial Sr incorporation that is far larger than thermodynamic models predict, likely indicating the formation of metastable solid solutions. We also observed that increasing barite supersaturation of the aqueous phase led to increased Sr incorporation, as predicted by available kinetic models. These results suggest that coprecipitation offers significant potential for designing treatment systems for aqueous metals' removal in desired metastable compositions. Solution conditions may be optimized to enhance the incorporation of Sr by increasing sulfate addition such that the barite saturation index remains above ∼3 or by increasing the aqueous Sr to Ba ratio.

Targeted Permeability Control in the Subsurface via Calcium Silicate Carbonation.

Efforts to develop safe and effective next-generation energy and carbon-storage technologies in the subsurface require novel means to control undesired fluid migration. Here we demonstrate that the carbonation of calcium silicates can produce reaction products that dramatically reduce the permeability of porous media and that are stable. Most calcium silicates react with CO2 to form solid carbonates but some polymorphs (here, pseudowollastonite, CaSiO3) can react to form a range of crystalline calcium silicate hydrates (CCSHs) at intermediate pH. High-pressure (1.1-15.5 MPa) column and batch experiments were conducted at a range of temperatures (75-150 °C) and reaction products were characterized using SEM-EDS and synchrotron µXRD and µXRF. Two characteristics of CCSH precipitation were observed, revealing unique properties for permeability control relative to carbonate precipitates. First, precipitation of CCSHs tends to occur on the surface of sand grains and into pore throats, indicating that small amounts of precipitation relative to the total pore volume can effectively block flow, compared to carbonates which precipitate uniformly throughout the pore space. Second, the precipitated CCSHs are more stable at low pH conditions, which may form more secure barriers to flow, compared to carbonates, which dissolve under acidic conditions.

Nanoscale heterogeneity of arsenic and selenium species in coal fly ash particles: analysis using enhanced spectroscopic imaging and speciation techniques.

Coal combustion byproducts are known to be enriched in arsenic (As) and selenium (Se). This enrichment is a concern during the handling, disposal, and reuse of the ash as both elements can be harmful to wildlife and humans if mobilized into water and soils. The leaching potential and bioaccessibility of As and Se in coal fly ash depends on the chemical forms of these elements and their association with the large variety of particles that comprise coal fly ash. The overall goal of this research was to determine nanoscale and microscale solid phase mineral associations and oxidation states of As and Se in fly ash. We utilized nanoscale 2D imaging (30-50 nm spot size) with the Hard X-ray Nanoprobe (HXN) in combination with microprobe X-ray capabilities (∼5 µm resolution) to determine the As and Se elemental associations. Speciation of As and Se was also measured at the nano- to microscale with X-ray absorption spectroscopy. The enhanced resolution of HXN showed As and Se as either diffusely located around or comingled with Ca- and Fe-rich particles. The results also showed nanoparticles of Se attached to the surface of fly ash grains. Overall, a comparison of As and Se species across scales highlights the heterogeneity and complexity of chemical associations for these trace elements of concern in coal fly ash.

Nanospectroscopy Captures Nanoscale Compositional Zonation in Barite Solid Solutions.

Scientists have long suspected that compositionally zoned particles can form under far-from equilibrium precipitation conditions, but their inferences have been based on bulk solid and solution measurements. We are the first to directly observe nanoscale trace element compositional zonation in <10 µm-sized particles using X-ray fluorescence nanospectroscopy at the Hard X-ray Nanoprobe (HXN) Beamline at National Synchrotron Light Source II (NSLS-II). Through high-resolution images, compositional zonation was observed in barite (BaSO4) particles precipitated from aqueous solution, in which Sr2+ cations as well as HAsO42- anions were co-precipitated into (Ba,Sr)SO4 or Ba(SO4,HAsO4) solid solutions. Under high salinity conditions (NaCl ≥ 1.0 M), bands contained ~3.5 to ~5 times more trace element compared to the center of the particle formed in early stages of particle growth. Quantitative analysis of Sr and As fractional substitution allowed us to determine that different crystallographic growth directions incorporated trace elements to different extents. These findings provide supporting evidence that barite solid solutions have great potential for trace element incorporation; this has significant implications for environmental and engineered systems that remove hazardous substances from water.

Fourier-transform infrared spectroscopy (FTIR) analysis of triclinic and hexagonal birnessites.

The characterization of birnessite structures is particularly challenging for poorly crystalline materials of biogenic origin, and a determination of the relative concentrations of triclinic and hexagonal birnessite in a mixed assemblage has typically required synchrotron-based spectroscopy and diffraction approaches. In this study, Fourier-transform infrared spectroscopy (FTIR) is demonstrated to be capable of differentiating synthetic triclinic Na-birnessite and synthetic hexagonal H-birnessite. Furthermore, IR spectral deconvolution of peaks resulting from MnO lattice vibrations between 400 and 750cm-1 yield results comparable to those obtained by linear combination fitting of synchrotron X-ray absorption fine structure (EXAFS) data when applied to known mixtures of triclinic and hexagonal birnessites. Density functional theory (DFT) calculations suggest that an infrared absorbance peak at ~1628cm-1 may be related to OH vibrations near vacancy sites. The integrated intensity of this peak may show sensitivity to vacancy concentrations in the Mn octahedral sheet for different birnessites.