4.7 Article

Phosphorus speciation along a soil to kettle hole transect: Sequential P

Journal

GEODERMA
Volume 429, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.geoderma.2022.116215

Keywords

Arable soil; Sediment; Kettle hole; Sequential fractionation; XANES; 31 P NMR

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Phosphorus is essential for all living organisms, but it can also contribute to eutrophication of aquatic ecosystems. Kettle holes, located in intensively used agricultural areas, pose a risk of nutrient transfer to larger water bodies. This study investigated the composition of phosphorus in arable soils and kettle hole sediments, revealing a dominance of stable forms of organic phosphorus. The results also showed a higher proportion of complex organic phosphorus in kettle hole sediments, suggesting their potential for conserving phosphorus and reducing its transfer to vulnerable aquatic ecosystems.
Phosphorus (P) is an essential element for all living organisms but can also be an important factor in the eutrophication of aquatic/marine ecosystems. Kettle holes are often situated in regions under intense agricultural land use where there is a high risk of nutrient transfer to larger waterbodies. The chemical speciation of soil P influences its rate of transfer from arable fields to aquatic environments. However, there is a paucity of information on the P speciation in kettle holes and their effect on the P cycle. Thus, we investigated the P composition of arable soils and kettle hole sediments in surface and subsurface layers along a transect of an agricultural field. Multiple P analyses were carried out including modified sequential Hedley P fractionation, P K-edge X-ray absorption near edge structure (XANES) spectroscopy, and 31P nuclear magnetic resonance (NMR) spectroscopy. The Pt concentrations ranged from 680 to 1123 mg kg  1 in the soils and 797 to 2591 mg kg  1 in the sediments. A predominance of the residual-P fraction, characterized as not extractable P, occluded P or stable forms of organic P (Po) was determined by sequential fractionation, ranging from 37 to 67 % followed by 3 to 38 % H2SO4-Pi and 3 to 16 % NaOH-Po of total P (Pt) in the soils and sediments. Analyses with P K-edge XANES spectroscopy assigned 61 to 100 % Fe- and Al-P, 0 to 14 % Ca-P, and 0 to 39 % Po in the arable soils and 46 to 74 % Fe- and Al-P, 14 to 43 % Ca-P, and 0 - 38 % Po in the adjoining kettle hole sediments. Solution 31P NMR spectra on alkaline extracts revealed a broad signal in the phosphomonoester region, which was the most abundant form of organic P across all samples. Besides, the proportion of 'complex' phosphomonesters (broad signal) to that of total extractable P was about 2-fold greater in the kettle hole sediments than in soils. Complex forms of organic P are known to be strongly associated with organic matter (OM) and appear to accumulate on a decadel timeframe. Therefore, it is desirable that kettle hole sediments are conserving P (and carbon), which will help reduce the transfer of P from agricultural fields to other, more vulnerable aquatic/marine ecosystems.

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