Dean Hesterberg

This chapter focuses mainly on the basic principles and methods of X-ray absorption near edge structure and extended X-ray absorption fine structure spectroscopy of soils, minerals, and mineral-associated (e.g., adsorbed or coprecipitated) chemical species. It focuses on sample preparation, data collection, and data analysis. The principles and terminology used in X-ray absorption spectroscopy are based on the interactions of X-rays with matter. The chapter begins with a description of some of the properties of atoms, X-rays, X-ray scattering, X-ray absorption, and X-ray absorption spectra. It then discusses the properties of the electronic transitions in more detail and outlines the measurement and interpretation of X-ray absorption spectra. X-ray absorption spectroscopy measurements can be performed on solids, gasses, or liquids, including moist or dry soils, mineral suspensions or pastes, and aqueous solutions. The preservation of samples related to soils and minerals can be susceptible to changes in element oxidation state, changes in hydration, and biodegradation.

Knowledge of phosphorus (P) species in P-rich soils is useful for assessing P mobility and potential transfer to ground water and surface waters. Soil P was studied using synchrotron X-ray absorption near-edge structure (XANES) spectroscopy (a nondestructive chemical-speciation technique) and sequential chemical fractionation. The objective was to determine the chemical speciation of P in long-term-fertilized, P-rich soils differing in pH, clay, and organic matter contents. Samples of three slightly acidic (pH 5.5-6.2) and two slightly alkaline (pH 7.4-7.6) soils were collected from A or B horizons in two distinct agrosystems in the province of Québec, Canada. The soils contained between 800 and 2100 mg total P kg(-1). Distinct XANES features for Ca-phosphate mineral standards and for standards of adsorbed phosphate made it possible to differentiate these forms of P in the soil samples. The XANES results indicated that phosphate adsorbed on Fe- or Al-oxide minerals was present in all soils, with a higher proportion in acidic than in slightly alkaline samples. Calcium phosphate also occurred in all soils, regardless of pH. In agreement with chemical fractionation results, XANES data showed that Ca-phosphates were the dominant P forms in one acidic (pH 5.5) and in the two slightly alkaline (pH 7.4-7.6) soil samples. X-ray absorption near-edge structure spectroscopy directly identified certain forms of soil P, while chemical fractionation provided indirect supporting data and gave insights on additional forms of P such as organic pools that were not accounted for by the XANES analyses.

Phosphate sorption on Fe- and Al-oxide minerals helps regulate the solubility and mobility of P in the environment. The objective of this study was to characterize phosphate adsorption and precipitation in single and binary systems of Fe- and Al-oxide minerals. Varying concentrations of phosphate were reacted for 42 h in aqueous suspensions containing goethite, ferrihydrite, boehmite, or noncrystalline (non-xl) Al-hydroxide, and in 1:1 (by mass) mixed-mineral suspensions of goethite/boehmite and ferrihydrite/ non-xl Al-hydroxide at pH 6 and 22 degrees C. X-ray absorption near edge structure (XANES) spectroscopy was used to detect precipitated phosphate and distinguish PO4 associated with Fe(III) versus Al(III) in mixed-mineral systems. Changes in the full width at half-maximum height (fwhm) in the white-line peak in P K-XANES spectra provided evidence for precipitation in Al-oxide single-mineral systems, but not in goethite or ferrihydrite systems. Similarly, adsorption isotherms and XANES data showed evidence for precipitation in goethite/boehmite mixtures, suggesting that mineral interactive effects on PO4 sorption were minimal. However, sorption in ferrihydrite/non-xl Al-hydroxide systems and a lack of XANES evidence for precipitation indicated that mineral interactions inhibited precipitation in these binary mixtures.

Organic matter is an important sorbent of heavy metals in soils and sediments. The heterogeneity of organic matter, including the presence of various reactive O-, N-, and S-bearing ligands, makes it difficult to precisely characterize the nature of metal-ligand binding sites. The objective of this research was to characterize the extent and nature of Hg(II) bonding with reduced organic S in soil organic matter. Sulfur-rich humic acid (0.7 +/- 0.1 mol of S kg-1) was extracted from samples of surface soil from a marine wetland. Synchrotron X-ray absorption near-edge structure (XANES) analysis at the S K edge indicated that 70 +/- 3 mol % of the organic S was in a reduced oxidation state. Aqueous solutions containing 2 mmol of Hg kg-1, 0.1 M NaNO3, and humic acid added at various S/Hg molar ratios at pH 5.60 +/- 0.02 were characterized using extended X-ray absorption fine structure (EXAFS) spectroscopy at the Hg LIII edge. Spectral fitting showed that as the total S/Hg ratio increased from 0.6 to 5.6 (reduced S/Hg of 0.4-4.0), the fraction of Hg-S bonding relative to Hg-O (or Hg-N) bonding increased from 0.4 to 0.9. Results demonstrated preferential bonding of Hg(II) to reduced organic S sites and indicated that multiple sulfur ligands were coordinated with Hg2+ ions at high S/Hg ratios, which corresponded to low levels of complexed Hg(II).