Fate of Phosphorus Originated from Treated Wastewater and Biosolids in Soils: Speciation, Transport, and Accumulation
Authors: Shenker Moshe , Bloom Paul R. , Shaviv Abraham , Paytan Adina , Cade-Menun Barbara J. , Chen Yona , Tarchitzky Jorge 
Published: March 2022

Beneficial use of reclaimed wastewater (RW) and biosolids (BS) in soils is accompanied by large input of sewage-originated P. Prolonged application may result in P accumulation up to levelsBeneficial use of reclaimed wastewater (RW) and biosolids (BS) in soils is accompanied by large input of sewage-originated P. Prolonged application may result in P accumulation up to levels that impair plant nutrition, increase P loss, and promote eutrophication in downstream waters. This study aims to shed light on the RW- and BS-P forms in soils and to follow the processes that determine P reactivity, solubility, availability, and loss in RW and BS treated soils. The Technion group used sequential P extraction combined with measuring stable oxygen isotopic composition in phosphate (δ18OP) and with 31P-NMR studies to probe P speciation and transformations in soils irrigated with RW or fresh water (FW). The application of the δ18OP method to probe inorganic P (Pi) speciation and transformations in soils was developed through collaboration between the Technion and the UCSC groups. The method was used to trace Pi in water-, NaHCO3-, NaOH-, and HCl- P fractions in a calcareous clay soil (Acre, Israel) irrigated with RW or FW. The δ18OP signature changes during a month of incubation indicated biogeochemical processes. The water soluble Pi (WSPi) was affected by enzymatic activity yielding isotopic equilibrium with the water molecules in the soil solution. Further it interacted rapidly with the NaHCO3-Pi. The more stable Pi pools also exhibited isotopic alterations in the first two weeks after P application, likely related to microbial activity. Isotopic depletion which could result from organic P (PO) mineralization was followed by enrichment which may result from biologic discrimination in the uptake. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with RW. Specific P compounds were identified by the Technion group, using solution-state 31P-NMR in wastewater and in soil P extracts from Acre soils irrigated by RW and FW. Few identified PO compounds (e.g., D-glucose-6-phosphate) indicated coupled transformations of P and C in the wastewater. The RW soil retained higher P content, mainly in the labile fractions, but lower labile PO, than the FW soil; this and the fact that P species in the various soil extracts of the RW soil appear independent of P species in the RW are attributed to enhanced biological activity and P recycling in the RW soil. Consistent with that, both soils retained very similar P species in the soil pools. The HUJ group tested P stabilization to maximize the environmental safe application rates and the agronomic beneficial use of BS. Sequential P extraction indicated that the most reactive BS-P forms: WSP, membrane-P, and NaHCO3-P, were effectively stabilized by ferrous sulfate (FeSul), calcium oxide (CaO), or aluminum sulfate (alum). After applying the stabilized BS, or fresh BS (FBS), FBS compost (BSC), or P fertilizer (KH2PO4) to an alluvial soil, P availability was probed during 100 days of incubation. A plant-based bioassay indicated that P availability followed the order KH2PO4 >> alum-BS > BSC ≥ FBS > CaO-BS >> FeSul-BS. The WSPi concentration in soil increased following FBS or BSC application, and P mineralization further increased it during incubation. In contrast, the chemically stabilized BS reduced WSPi concentrations relative to the untreated soil. It was concluded that the chemically stabilized BS effectively controlled WSPi in the soil while still supplying P to support plant growth. Using the sequential extraction procedure the persistence of P availability in BS treated soils was shown to be of a long-term nature. 15 years after the last BS application to MN soils that were annually amended for 20 years by heavy rates of BS, about 25% of the added BS-P was found in the labile fractions. The UMN group further probed soil-P speciation in these soils by bulk and micro X-ray absorption near edge structure (XANES). This newly developed method was shown to be a powerful tool for P speciation in soils. In a control soil (no BS added), 54% of the total P was PO and it was mostly identified as phytic acid; 15% was identified as brushite and 26% as strengite. A corn crop BS amended soil included mostly P-Fe-peat complex, variscite and Al-P-peat complex but no Ca-P while in a BS-grass soil octacalcium phosphate was identified and o-phosphorylethanolamine or phytic acid was shown to dominate the PO fraction that impair plant nutrition, increase P loss, and promote eutrophication in downstream waters. This study aims to shed light on the RW- and BS-P forms in soils and to follow the processes that determine P reactivity, solubility, availability, and loss in RW and BS treated soils. The Technion group used sequential P extraction combined with measuring stable oxygen isotopic composition in phosphate (δ18OP) and with 31P-NMR studies to probe P speciation and transformations in soils irrigated with RW or fresh water (FW). The application of the δ18OP method to probe inorganic P (Pi) speciation and transformations in soils was developed through collaboration between the Technion and the UCSC groups. The method was used to trace Pi in water-, NaHCO3-, NaOH-, and HCl- P fractions in a calcareous clay soil (Acre, Israel) irrigated with RW or FW. The δ18OP signature changes during a month of incubation indicated biogeochemical processes. The water soluble Pi (WSPi) was affected by enzymatic activity yielding isotopic equilibrium with the water molecules in the soil solution. Further it interacted rapidly with the NaHCO3-Pi. The more stable Pi pools also exhibited isotopic alterations in the first two weeks after P application, likely related to microbial activity. Isotopic depletion which could result from organic P (PO) mineralization was followed by enrichment which may result from biologic discrimination in the uptake. Similar transformations were observed in both soils although transformations related to biological activity were more pronounced in the soil treated with RW. Specific P compounds were identified by the Technion group, using solution-state 31P-NMR in wastewater and in soil P extracts from Acre soils irrigated by RW and FW. Few identified PO compounds (e.g., D-glucose-6-phosphate) indicated coupled transformations of P and C in the wastewater. The RW soil retained higher P content, mainly in the labile fractions, but lower labile PO, than the FW soil; this and the fact that P species in the various soil extracts of the RW soil appear independent of P species in the RW are attributed to enhanced biological activity and P recycling in the RW soil. Consistent with that, both soils retained very similar P species in the soil pools. The HUJ group tested P stabilization to maximize the environmental safe application rates and the agronomic beneficial use of BS. Sequential P extraction indicated that the most reactive BS-P forms: WSP, membrane-P, and NaHCO3-P, were effectively stabilized by ferrous sulfate (FeSul), calcium oxide (CaO), or aluminum sulfate (alum). After applying the stabilized BS, or fresh BS (FBS), FBS compost (BSC), or P fertilizer (KH2PO4) to an alluvial soil, P availability was probed during 100 days of incubation. A plant-based bioassay indicated that P availability followed the order KH2PO4 >> alum-BS > BSC ≥ FBS > CaO-BS >> FeSul-BS. The WSPi concentration in soil increased following FBS or BSC application, and P mineralization further increased it during incubation. In contrast, the chemically stabilized BS reduced WSPi concentrations relative to the untreated soil. It was concluded that the chemically stabilized BS effectively controlled WSPi in the soil while still supplying P to support plant growth. Using the sequential extraction procedure the persistence of P availability in BS treated soils was shown to be of a long-term nature. 15 years after the last BS application to MN soils that were annually amended for 20 years by heavy rates of BS, about 25% of the added BS-P was found in the labile fractions. The UMN group further probed soil-P speciation in these soils by bulk and micro X-ray absorption near edge structure (XANES). This newly developed method was shown to be a powerful tool for P speciation in soils. In a control soil (no BS added), 54% of the total P was PO and it was mostly identified as phytic acid; 15% was identified as brushite and 26% as strengite. A corn crop BS amended soil included mostly P-Fe-peat complex, variscite and Al-P-peat complex but no Ca-P while in a BS-grass soil octacalcium phosphate was identified and o-phosphorylethanolamine or phytic acid was shown to dominate the PO fraction.