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.

The solubility of inorganic phosphorus in soils is regulated by surface-adsorbed phosphate or phosphate minerals. The objective of this study was to determine whether different phosphate species of relevance to soils showed distinguishing XAFS spectral features.Phosphorus K-XANES spectra for Fe-phosphates were characterized by a unique pre-edge feature near -3 eV (relative energy) that increased in intensity with increasing mineral crystallinity and was very weak for phosphate adsorbed on goethite. Spectra of Ca-phosphates and a soil sample exhibited a distinct shoulder on the high-energy side of the absorption edge. Spectra of Al-phosphates were characterized by a weak pre-edge feature at -1 eV.

This paper briefly reviews the existing literature and uses evidence from three studies to demonstrate the occurrence of preferential pathways of P transport through soil. Studies conducted in the St. Lawrence lowlands, Canada, indicated that particulate P (PP‐i.e., >0.45 µm) the main fraction of total P (TP) in tile‐drainage water generated by storm events after periods of low rainfall. In the remainder of the year, the concentration of TP and P forms were related to soil texture, primary tillage intensity and frequency, and showed wide seasonal variations. For a study conducted in the UK under grassland, higher TP concentrations were found in near‐surface runoff (0–30 cm) compared with concentrations measured in drainflow. Water passing through the artificial drainage system had a higher proportion of PP (43%) than water passing close to (<30 cm) or over the soil surface (31%). Installation of tile drainage in a poorly draining soil reduces P transfer by improving the infiltration capacity, thereby reducing overland flow volume and allowing P to be retained/sorbed by the soil matrix. Because of the absence of tillage, permanent grasslands accumulate P near the surface. We hypothesize that, if the soil P store is coincident with preferential flow pathways (either artificial mole drainage channels or natural macropores), permanent grassland will be vulnerable to transfer large amounts of P through subsurface pathways. Phosphorus transfer through preferential flow pathways may be particularly important after storm events that rapidly follow periods of drought and/or surface P inputs as inorganic fertilizer or manure.

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Vacuum samples were collected from 1025 randomly selected urban Canadian homes to investigate bioaccessible Pb (Pb(S)) concentrations in settled house dust. Results indicate a polymodal frequency distribution, consisting of three lognormally distributed subpopulations defined as "urban background" (geomean 58 μg g(-1)), "elevated" (geomean 447 μg g(-1)), and "anomalous" (geomean 1730 μg g(-1)). Dust Pb(S) concentrations in 924 homes (90%) fall into the "urban background" category. The elevated and anomalous subpopulations predominantly consist of older homes located in central core areas of cities. The influence of house age is evidenced by a moderate correlation between house age and dust Pb(S) content (R(2) = 0.34; n = 1025; p < 0.01), but it is notable that more than 10% of homes in the elevated/anomalous category were built after 1980. Conversely, the benefit of home remediation is evidenced by the large number of homes (33%) in the background category that were built before 1960. The dominant dust Pb species determined using X-ray Absorption Spectroscopy were as follows: Pb carbonate, Pb hydroxyl carbonate, Pb sulfate, Pb chromate, Pb oxide, Pb citrate, Pb metal, Pb adsorbed to Fe- and Al-oxyhydroxides, and Pb adsorbed to humate. Pb bioaccessibility estimated from solid phase speciation predicts Pb bioaccessibility measured using a simulated gastric extraction (R(2) = 0.85; n = 12; p < 0.0001). The trend toward increased Pb bioaccessibility in the elevated and anomalous subpopulations (75% ± 18% and 81% ± 8%, respectively) compared to background (63% ± 18%) is explained by the higher proportion of bioaccessible compounds used as pigments in older paints (Pb carbonate and Pb hydroxyl carbonate). This population-based study provides a nationally representative urban baseline for applications in human health risk assessment and risk management.