19Phosphorus (P) losses from agricultural soils constitute a main driver for eutrophication of the 20 Baltic Sea. There is limited knowledge about sorption and release processes of P in these soils, 21especially concerning the effects of fertilization. In this study, P speciation of the clay fractions 22 from six different soils in long-term fertility experiments in Sweden was investigated by P K-23 edge XANES spectroscopy. As expected, unfertilized soils had lower concentrations of acid- calcareous soil for which a greater proportion of P was fit as apatite. After long-term fertilization, 31P had accumulated mainly as Al-bound forms (adsorbed species and precipitates) according to 32 the XANES analysis. Our research shows that P speciation in fertilized agricultural soils 33 depended on the level of P buildup and on the soil properties.

The soil chemistry of phosphorus (P) is important for understanding the processes governing plant availability as well as the risk of environmental losses of P. The objective of this research was to investigate both the speciation and the pH-dependent solubility patterns of P in clayey agricultural soils in relation to soil mineralogy and fertilization history. The study focused on soil samples from six fields that were subjected to different P fertilization regimes for periods of 45 to 57years. Soil P speciation was analyzed by P K-edge XANES spectroscopy and chemical fractionation, sorption isotherms were constructed, and dissolved P was measured as a function of pH. The XANES fitting results showed that organic P and P adsorbed to Fe and Al (hydr)oxides were common P constituents in all soils. Calcium phosphates were identified in five of six soil samples. The XANES results also indicated an increase in P adsorbed to Al and to a lesser extent Fe (hydr)oxides as a result of fertilization. Moreover, the fluorescence intensity from the P K-edge XANES analysis was most strongly correlated with HCl-digestible P (r=0.81***). Consistent with the XANES analysis, laboratory sorption isotherm models showed that the Freundlich sorption coefficient (KF) was most closely related to oxalate-extractable Al. Greater proportions of Ca phosphate in two of the heavily fertilized soils in combination with enhanced PO4 solubilization upon sample acidification indicated neoformation of Ca-phosphate precipitates. The results for the unfertilized soil samples generally showed a minimum in dissolved PO4 between pH6.5 and 7.5, with increases particularly at lower pH. This behavior can be explained either by the dissolution of Al-hydroxide-type sorbents or Ca phosphates at lower pH. In fertilized soils, there was no consistent trend in pH-dependent solubilization of P, with a complex relationship to solid-phase speciation. To conclude, inorganic P species changed most dynamically in agricultural clay soils over a period of several decades, and the role of pH in the solubilization of P depended mainly on P fertilization history and the content of reactive Ca phosphates.

Available online xxxxWith time, different soil-forming processes such as weathering, plant growth, accumulation of organic matter, and cultivation are likely to affect phosphorus (P) speciation. In this study, the depth distribution of P species was investigated for an agricultural clay soil, Lanna, Sweden. Small amounts of apatite-P was demonstrated in the topsoil whereas the speciation of P at 70-100 cm depth consisted of approximately 86% apatite according to P K-edge XANES (X-ray absorption near-edge structure) spectroscopy. Because there were only minor differences in bulk mineralogy and texture, these variations in P speciation were interpreted as the result of apatite weathering of the topsoil. Speciation modeling on soil extracts supported this idea: hydroxyapatite was not thermodynamically stable in the top 50 cm of the soil. Apatite was enriched in the bulk soil relative to the clay fraction, as expected during apatite dissolution. Combined results from batch experiments, XANES spectroscopy and X-ray diffraction suggested chemical transformations of the topsoil as a result from accumulation of organic matter and airing from tillage followed by enhanced weathering of apatite, amphiboles, clay minerals, and iron oxides. This caused the formation of poorly crystalline secondary iron and aluminum (hydr)oxides in the topsoil, which retained part of the released P from apatite. Other P was incorporated into organic forms. Furthermore, the results also showed that short-term acidification below the current pH value (below 5.5 in the topsoil and 7.2 in the deeper subsoil) caused significant solubilization of P. This is attributed to two different mechanisms: the instability of Al-containing sorbents (e.g. Al hydroxides) at low pH (in the topsoil), and the acid-mediated dissolution of apatite (the subsoil).

High concentrations of Hg, Cd, Pb, Cu, and Zn were found in the euxinic sediment of the inner archipelago of Stockholm. In the sulfide-rich sediment, they are precipitated as metal sulfides with low dissolving capacity and bioavailability. In two experiments, the significance of acid-volatile sulfide (AVS) and dissolved sulfides for mobility, bioavailability, and toxicity of metals were studied by oxygenation of intact sediment cores. Influence of bioturbating deposit-feeding amphipods, that is, Monoporeia affinis, was examined on studied sediment processes. Results showed a low mobility of most metals except Cd and Zn. Bioturbation did not enhance mobility. Cd and Zn, released from the sediment, were not bioaccumulated in amphipods. In contrast, the less mobile metals Hg and Pb were bioaccumulated. A low toxicity of contaminated sediments, in terms of mortality and embryonic malformations of amphipods, was recorded. Results indicate that Cd, Zn, and Cu are comparatively unavailable after oxygenation of the metal sulfides. Similar results were recorded in contaminated sediments differing in redox potential, AVS, dissolved sulfides, and organic contents, suggesting that other metal ligands, in addition to AVS, are important for metal bioavailability and toxicity in anoxic and suboxic environments.

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