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.

Soil testing has been an accepted agricultural management practice for decades. Interpretations and fertility recommendations based on soil analyses and the information obtained with soil samples on cropping systems, tillage practices, soil types, manure use, and other parameters have contributed to the increased efficiency of agricultural production. Recently, however, analyses of long‐term trends in soil test P values have shown that soil P in many areas of the world is now excessive, relative to crop P requirements. The role of P in the eutrophication of surface waters and emerging concerns about the human health impacts of toxic algal/dinoflagellate blooms have heightened public awareness of nonpoint source pollution by agricultural P. The greatest concerns are with animal‐based agriculture, where farm and watershed‐scale P surpluses and over‐application of P to soils are common. The need for nutrient‐management plans based on N and P is now an issue of intense debate in the U.S. and Canada. This paper addresses three issues: Should the applications of organic wastes and fertilizers be based on soil P and, if so, what is the most appropriate testing method to assess environmental risk? How can our knowledge of soil P chemistry be integrated with the expertise of hydrologists, agronomists, aquatic ecologists, and others to assess the risks that P in agricultural soils poses to surface waters? And, finally, how can we use soil P testing to evaluate new best management practices (BMPs) now being developed to reduce P transport from soil to water?

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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.

In most mineral soils, P leaching is rarely viewed as an important environmental issue. However, P accumulation and decreased P sorption capacities in surface horizons of long‐term fertilized soils may increase downward P movement. The objective of this study was to measure the concentration and characterize the P forms in drainage waters from nine soil series widely differing in clay content. Twenty‐seven sites were sampled in 1994 and 1995 from an intensively cropped area of the province of Quebec, Canada. Drainage waters were characterized for their total P (TP), dissolved reactive P (DRP), dissolved organic P (DOP), and total particulate P (TPP) contents. The Quebec surface water quality standard of 0.03 mg TP L1 was exceeded in 14 out of 27 sites in 1994 but only in 6 out of 25 sites in 1995. Of the 14 sites exceeding 0.03 mg TP L−1 in 1994, 10 were clayey soils. Under these circumstances, more than 50% of the TP was as TPP whereas DOP forms represented <30%. In 1995, TPP forms accounted for, on average, <50% of TP and DOP accounted for more than 40% of the TP concentrations. This study suggests that flat clayey soils of medium to rich P status may be particularly at risk of exceeding water quality standards in subsurface runoff. Phosphorus losses in particulate form may be important in subsurface runoff from clayey soils when weather conditions favor rapid flow through cracks or macropores.