| 1. |
- Adediran, Gbotemi A., et al.
(författare)
-
Phosphorus in 2D : Spatially resolved P speciation in two Swedish forest soils as influenced by apatite weathering and podzolization
- 2020
-
Ingår i: Geoderma. - : Elsevier BV. - 0016-7061 .- 1872-6259. ; 376
-
Tidskriftsartikel (refereegranskat)abstract
- The cycling and long-term supply of phosphorus (P) in soils are of global environmental and agricultural concern. To advance the knowledge, a detailed understanding of both the vertical and lateral variation of P chemical speciation and retention mechanism(s) is required, a knowledge that is limited in postglacial forest soils. We combined the use of synchrotron X-ray fluorescence microscopy with multi-elemental co-localisation analysis and P K-edge XANES spectroscopy to reveal critical chemical and structural soil properties. We established a two-dimensional (2D) imagery of P retention and speciation at a microscale spatial resolution in two forest soil profiles formed in glaciofluvial and wave-washed sand. The abundance and speciation of P in the upper 40 cm was found to be influenced by soil weathering and podzolization, leading to spatial variability in P speciation on the microscale (< 200 pm) with P existing predominantly as organic P and as PO4 adsorbed to allophane and ferrihydrite, according to XANES spectroscopy. These species were mostly retained at sharp edges and in pore spaces within Al and Si-bearing particles. Despite the relatively young age ( < 15,000 years) of the soils, our results show primary mineral apatite to have weathered from the surface horizons. In the C horizon however, a large fraction of the P was in the form of apatite, which appeared as widely dispersed ( > 600 pm) hot spots of inclusions in aluminosilicates or as discrete micro-sized apatite grains. The subsoil apatite represents a pool of P that trees can potentially acquire and thus add to the biogeochemically active P pool in temperate forest soils.
|
|
| 2. |
- de Campos Pereira, Hugo, et al.
(författare)
-
The Adsorption of Per- and Polyfluoroalkyl Substances (PFASs) onto Ferrihydrite Is Governed by Surface Charge
- 2020
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 54, s. 15722-15730
-
Tidskriftsartikel (refereegranskat)abstract
- An improved quantitative and qualitative understanding of the interaction of per- and polyfluoroalkyl substances (PFASs) and short-range ordered Fe (hydr)oxides is crucial for environmental risk assessment in environments low in natural organic matter. Here, we present data on the pH-dependent sorption behavior of 12 PFASs onto ferrihydrite. The nature of the binding mechanisms was investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and by phosphate competition experiments. Sulfur K-edge XANES spectroscopy showed that the sulfur atom of the head group of the sulfonated PFASs retained an oxidation state of +V after adsorption. Furthermore, the XANES spectra did not indicate any involvement of inner-sphere surface complexes in the sorption process. Adsorption was inversely related to pH (p < 0.05) for all PFASs (i.e., C-3-C-5 and C-7-C-9 perfluorocarboxylates, C-4, C-6, and C-8 perfluorosulfonates, perfluorooctane sulfonamide, and 6:2 and 8:2 fluorotelomer sulfonates). This was attributed to the pH-dependent charge of the ferrihydrite surface, as reflected in the decrease of surface zeta-potential with increasing pH. The importance of surface charge for PFAS adsorption was further corroborated by the observation that the adsorption of PFASs decreased upon phosphate adsorption in a way that was consistent with the decrease in ferrihydrite zeta-potential. The results show that ferrihydrite can be an important sorbent for PFASs with six or more perfluorinated carbons in acid environments (pH <= 5), particularly when phosphate and other competitors are present in relatively low concentrations.
|
|
| 3. |
- Eriksson, Ann Kristin, et al.
(författare)
-
Evolution of phosphorus speciation with depth in an agricultural soil profile
- 2016
-
Ingår i: Geoderma. - : Elsevier. - 0016-7061 .- 1872-6259. ; 280, s. 29-37
-
Tidskriftsartikel (refereegranskat)abstract
- With 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 Pat 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).
|
|
| 4. |
- Eriksson, Ann Kristin, et al.
(författare)
-
Phosphorus dynamics in Swedish agricultural soils as influenced by fertilization and mineralogical properties : Insights gained from batch experiments and XANES spectroscopy
- 2016
-
Ingår i: Science of the Total Environment. - : Elsevier. - 0048-9697 .- 1879-1026. ; 566, s. 1410-1419
-
Tidskriftsartikel (refereegranskat)abstract
- 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 57 years. 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. Calciumphosphateswere 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 (K-F) 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 pH 6.5 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.
|
|
| 5. |
- Frisk, Andreas, et al.
(författare)
-
Magnetic and structural characterization of CoFeZr thin films grown by combinatorial sputtering
- 2019
-
Ingår i: Physical Review Materials. - 2475-9953. ; 3:7
-
Tidskriftsartikel (refereegranskat)abstract
- We report on a detailed investigation of structural and magnetic properties of thin CoFeZr films, produced by combinatorial cosputtering, with compositions in the ranges 30-85 at.% Co, 12-63 at.% Fe, and 4-8 at.% Zr. Extended x-ray absorption fine structure and x-ray diffraction measurements reveal that alloys with a Zr content below 5 at.% are polycrystalline with a bcc structure, while an amorphous morphology is stabilized at Zr contents above 6 at.%. All samples display a growth-induced in-plane uniaxial anisotropy, which is closely related to the Zr concentration gradients across the wafers. A model for the angular dependence of the reduced remanence, including a Gaussian distribution of easy/hard anisotropy axes, is presented and successfully used to fit the data for all samples. The magnetic moments of the polycrystalline films approximately follow the Slater-Pauling curve, and the magnetic moments of the amorphous films follow a similar trend, but with about 20 % lower values. X-ray magnetic circular dichroism measurements show, for the amorphous films, that the Co moments are virtually constant at 1.7(2)μB/atom.
|
|
| 6. |
- Persson, Ingmar, et al.
(författare)
-
Structure Determination of Phosphoric Acid and Phosphate Ions in Aqueous Solution Using EXAFS Spectroscopy and Large Angle X-ray Scattering
- 2018
-
Ingår i: Journal of Physical Chemistry A. - Washington : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 122:37, s. 7413-7420
-
Tidskriftsartikel (refereegranskat)abstract
- The structures of hydrated phosphoric acid and phosphate ions (H2PO4-, HPO42- and PO43-) in aqueous solution have been determined by P K-edge EXAFS and large angle X-ray scattering (LAXS). The P-O bond distance in all phosphate species studied is close to 1.53 Å. The P-(O)⋅⋅⋅Oaq distances have been refined to ca. 3.6 Å from the LAXS data giving a P-O⋅⋅⋅Oaq bond angle close to tetrahedral suggesting that each oxygen or OH group of phosphoric acid and dihydrogenphosphate, on average, hydrogen bind three water molecules. The (P-)O(-H)···Oaq and (P-)O···(H-)Oaq hydrogen bonds in hydrated phos-phoric acid and the H2PO4- ion are shorter than the hydrogen bonds in neat water. This supports previous infrared spectro-scopic studies claiming that the hydrogen bonds in hydrated phosphoric acid and phosphate ions are stronger than the hy-drogen bonds in neat water. Phosphoric acid and phosphate ions can therefore be regarded as structure making solutes. This is the first study applying transmission mode X-ray absorption spectroscopy (XAS) data collection on the P K-edge. It shows that XAS spectra collected in transmission mode have a much better S/N ratio than data collected in fluorescence mode, allowing accurate determination of P-O bond distances. Furthermore, P K-edge EXAFS data collected in fluorescence mode display a higher amplitude at high k than expected due to increasing radiated volume of the sample with increasing energy as the total absorption decreases sharply with increasing energy of the X-rays. As a result, the fluorescence signal becomes non-proportional to the intensity of the X-ray beam over the EXAFS spectrum. This results in an increasing amplitude of the EXAFS function with increasing energy of the X-ray beam resulting in too small Debye-Waller coefficients.
|
|
| 7. |
- Schmieder, Frank, et al.
(författare)
-
Phosphorus speciation in cultivated organic soils revealed by P K-edge XANES spectroscopy
- 2020
-
Ingår i: Journal of Plant Nutrition And Soil Science/Zeitschrift für Pflanzenernahrung und Bodenkunde. - : Wiley. - 1436-8730 .- 1522-2624. ; 183:3, s. 367-381
-
Tidskriftsartikel (refereegranskat)abstract
- Cultivated organic soils make a significant contribution to phosphorus (P) leaching losses from agricultural land, despite occupying a small proportion of cultivated area. However, less is known about P mobilisation processes and the P forms present in peat soils compared with mineral soils. In this study, P forms and their distribution with depth were investigated in two cultivated Histosol profiles, using a combination of wet chemical extraction and P K-edge X-ray absorption near-edge structure (XANES) spectroscopy. Both profiles had elevated P content in the topsoil, amounting to around 40 mmol kg(-1), and P speciation in both profiles was strongly dominated by organic P. Topsoils were particularly rich in organic P (P-org), with relative proportions of up to 80%. Inorganic P in the profiles was almost exclusively adsorbed to surface reactive aluminium (Al) and iron (Fe) minerals. In one of the pro-files, small contributions of Ca-phosphates were detected. A commonly used P saturation index (PSI) based on ammonium-oxalate extraction indicated a low to moderate risk of P leaching from both profiles. However, the capacity of soil Al and Fe to retain P in organic soils could be reduced by high competition from organic compounds for sorption sites. This is not directly accounted for in PSI and similar indices. Accumulation of P-org in the topsoil may be attributable by microbial peat decomposition and transformation of mineral fertiliser P by both microbiota and crops. Moreover, high carbon-phosphorus ratio in the surface peat material in both profiles suggests reduced net mineralisation of P-org in the two soils. However, advancing microbial peat decomposition will eventually lead to complete loss of peat horizons and to mineralisation of P-org. Hence, P-org in both profiles represents a huge potentially mobilised P pool.
|
|
| 8. |
- Tuyishime, J. R. Marius, et al.
(författare)
-
Phosphorus abundance and speciation in acid forest Podzols - Effect of postglacial weathering
- 2022
-
Ingår i: Geoderma. - : Elsevier BV. - 0016-7061 .- 1872-6259. ; 406
-
Tidskriftsartikel (refereegranskat)abstract
- The molecular speciation of phosphorus (P) in forest soils is of strategic importance for sustainable forest management. However, only limited information exists about soil P speciation in boreal forests. We combined P K-edge XANES spectroscopy, wet chemical P extractions, and X-ray diffraction analysis of soil minerals to investigate the vertical distribution of P species in seven podzolised forest soils differing in soil properties and climatic conditions. The results showed that the total P stock was on average, 4.0 g m(-2) in the Oe horizon, 9.5 g m(-2) in the A and E horizons, and substantially higher (117.5 g m(-2), and 109.3 g m(-2)) in the B and C horizons down to 80 cm depth, respectively. Although the Oe horizons contain a minor total P stock, 87% of it was stored as organic P. The composition of P species in the P-depleted A/E horizons was highly variable depending on the site. However, of the P stored in B and C horizons down to 80 cm, 58% was adsorbed P, mostly to Al, while apatite accounted for 25% of P, most of which was found in the C horizons. The apatite stocks in the A/E, B, and C horizons (down to 80 cm) accounted for 2.5%, 20%, and 77.2%, respectively, of the total apatite for all the mineral soils studied. These figures can be explained, first, by the dissolution of primary mineral apatite caused mainly by acidification. Second, P uptake by plants and microorganisms, and the associated formation of the Oe horizons, led to the formation of soil organic P. Further, the formation of organo-metal complexes and podzolization led to the translocation of P to the B horizons, where P accumulated mostly as P adsorbed to imogolite-type materials (e.g. allophane) and ferrihydrite, as shown by P K-edge XANES spectroscopy. In conclusion, this study shows that despite the young age of these soils (<15,000 years), most of the primary mineral apatite in the upper 30 cm has been transformed into organic P, and Fe-, Al-bound PO 4 . Moreover, the subsoil P, mainly consisting of adsorbed P to Al, and apatite, dominates the P inventory and probably serves as a long-term buffer of P.
|
|
| 9. |
- Zuo, Minyu, et al.
(författare)
-
Dual slag filters for enhanced phosphorus removal from domestic waste water : performance and mechanisms
- 2018
-
Ingår i: Environmental Science and Pollution Research. - : Springer Berlin/Heidelberg. - 0944-1344 .- 1614-7499. ; 25:8, s. 7391-7400
-
Tidskriftsartikel (refereegranskat)abstract
- The phosphorus (P) removal of five combinations of dual filters consisting of blast furnace slag (BFS), argon oxygen decarburisation slag (AOD) and electric arc furnace slag (EAF) was evaluated in column experiments with domestic waste water. The columns were fed with waste water for 24 days. The column with only EAF had the best P removal performance (above 93% throughout the experiment). The speciation of the bound P was evaluated by P K-edge X-ray absorption near-edge structure (XANES) spectroscopy. In all five columns, the main P species of the slag packed in the outlet chamber was amorphous calcium phosphate (ACP). In samples from the inlet chambers, the contributions from crystalline Ca phosphates, P adsorbed on gibbsite and P adsorbed on ferrihydrite were usually much greater, suggesting a shift of P removal mechanism as the waste water travelled from the inlet to the outlet. The results provide strong evidence that P was predominantly removed by the slags through the formation of ACP. However, as the pH decreased with time due to the progressively lower dissolution of alkaline silicate minerals from the slag, the ACP was rendered unstable and hence redissolved, changing the P speciation. It is suggested that this process strongly affected the lifespan of the slag filters. Of the slags examined, EAF slag had the best P removal characteristics and BFS the worst, which probably reflected different dissolution rates of alkaline silicates in the slags.
|
|
| 10. |
|
|
