Fate Of Phosphorus Research Articles

Generic phosphate affinity constants of the CD-MUSIC-eSGC model to predict phosphate adsorption and dominant speciation on iron (hydr)oxides

Estimating the availability of phosphorus in soils and sediments is complicated by the diverse mineralogical properties of iron (hydr)oxides that control the environmental fate of phosphorus. Despite various surface complexation models have been developed, lack of generic phosphate affinity constants (logKPO4s) for iron (hydr)oxides hinders the prediction of phosphate adsorption to iron (hydr)oxides in nature. The aim of this work is to derive generic logKPO4s for the Charge Distribution-Multisite Complexation extended-Stern-Gouy-Chapman (CD-MUSIC-eSGC) model using a large phosphate adsorption database and previously derived generic protonation parameters. The optimized logKPO4s of goethite, hematite and ferrihydrite are located in a much narrower range than those in the RES3T database. Specifically, the logKPO4 ranges of FeOPO3, FeOPO2OH, FeOPO(OH)2, (FeO)2PO2, and (FeO)2POOH complexes were 17.40–18.00, 24.20–27.40, 27.90–29.80, 26.50–29.60, and 30.70–33.40, respectively. A simplified CD-MUSIC-eSGC model with species FeOPO2OH and (FeO)2PO2 and generic logKPO4 values 26.0 ± 0.9 and 27.9 ± 0.8, respectively, provides an accurate prediction of phosphate adsorption and dominant speciation to the iron (hydr)oxides at environmental pH and phosphate levels. For ferrihydrite at low pH and high phosphate levels the species FeOPO(OH)2 and (FeO)2POOH cannot be neglected. The simplified model expands the application boundaries of CD-MUSIC-eSGC model in predicting the phosphate adsorption on natural iron (hydr)oxides without laborious characterization.

Phosphorus recovery potential from sewage sludge by struvite precipitation: remodelling policy framework in Rajasthan, India.

The manufacturing of fossil-based fertilizers by extraction of rock phosphate has contributed to carbon emissions and depleted the non-renewable phosphorus reserves. Sewage sludge, which is a waste product from Sewage Treatment Plants (STPs), is rich in phosphorus. The existing techniques for sludge management contribute to carbon emissions and ecological footprint. Struvite (raw fertilizer) and biochar recovery from sludge has emerged as viable methods to reduce carbon emission and ensure economic sustainability of STPs. In this work, the potential for phosphorus recovery and revenue generation is discussed for Rajasthan state in India. The fate of phosphorus and heavy metals in STPs is evaluated which indicates that about 70% of the phosphorus and trace amounts of metals end up in sewage sludge. Further, the power consumption is high in STPs due to industrial wastewater ingress. There is a need to bridge the gap between sewage treatment and generation in Rajasthan, improve STP performance before resource recovery inclusion at policy-level and scale-up. Mixing struvite with biochar can lead to safe application of struvite as raw fertilizer as heavy metals are sequestered by biochar. A business framework is developed to serve as a blueprint and potential model for linking technical and market viability.

Effect of limestone particle size and microbial phytase on phosphorus and calcium digestion kinetics along the gastrointestinal tract in laying hens

ABSTRACT 1. This study assessed the effect of limestone particle size and microbial phytase incorporation on the fate of phosphorus (P) and calcium (Ca) along the gastrointestinal tract in 72 laying hens. 2. Four experimental diets were formulated according to a 2 × 2 factorial arrangement to evaluate the effect of two coarse limestone (CL) inclusion. This included a mix (MIX) of 75% CL (2 − 4 mm) and 25% fine particles (FL, <0.5 mm) or 100% FL, in two different basal diets formulated without (MIX0 and FL0) or with 300 FTU of microbial phytase/kg (MIX300 and FL300). 3. Contents of the crop, gizzard, duodenum, jejunum and ileum were collected to determine the mean retention time (MRT) of dry matter (DM), the recovery rate of Ca and P in each segment of the gastrointestinal tract and the apparent fractional digestibility coefficient (AD) of Ca and P in each intestinal segment. 4. In hens fed FL, microbial phytase decreased the MRT of DM along the intestine (p < 0.05). In the crop and the gizzard, Ca recovery increased with MIX incorporation to a greater extent in hens fed without microbial phytase (p < 0.05). The mixed particle size incorporation decreased absorption kinetics of Ca in hens fed microbial phytase. The AD of P and the absorption kinetics of P were significantly decreased in hens receiving FL300, probably due to complex formation between Ca and phytic acid. 5. This study showed that coarse limestone particles incorporation improved mineral utilisation along the digestive tract.

Flood irrigation increases the release of phosphorus from aquifer sediments into groundwater

Nonpoint source pollution caused by agricultural activities has long attracted widespread attention from people in society and academia. Many studies have found that human activities not only convey exogenous pollutants into aquifers but also affect the mobilization and transport of geogenic pollutants in aquifers. Geogenic groundwater with high phosphorus concentrations has been found, but it is unclear whether the changes in hydrogeochemical conditions caused by flood irrigation in paddy fields affect the fate of phosphorus. We investigated the temporal and spatial distribution characteristics of phosphorus in groundwater under the influence of flood irrigation through laboratory experiments, proved its impact on phosphorus in groundwater, and explored the mechanisms influencing P concentrations. The results show that flood irrigation can increase the release of phosphorus in the aquifer media and greatly increase the phosphorus concentration in the groundwater of the study area, which has a negative impact on groundwater quality. The main mechanism of increase in phosphorus concentration in groundwater involves an increase in the reducibility of the aquifer via flood irrigation; as a result, iron oxides are reductively dissolved and iron-bound phosphorus is released into the groundwater. Changes in pH also result in the dissolution of calcium phosphate minerals and the release calcium-bound phosphorus. This study not only advances the theory of multielement-coupled hydrogeochemistry but also provides a reference for agricultural planning and groundwater pollution prevention and control in rice-growing areas.

An optimized method for extraction and purification of inorganic phosphate from plant material for oxygen isotope ratio analysis

Compound-specific stable isotope ratio analysis of oxygen isotopes in inorganic phosphate can be used to study biological phosphorus cycling and the transformation processes controlling the fate of phosphorus. However, methods for extraction of inorganic phosphate from plant tissue for oxygen isotope ratio analysis are not consistent. Further, the purification into solid silver phosphate can be challenging and laborious. In this work, a detailed and optimized method to provide a more consistent, easily implementable and reproducible extraction using trichloroacetic acid and subsequent purification of inorganic phosphate from plant material for oxygen isotope ratio analysis is presented. Key focus points were: uniform extraction of inorganic phosphate from barley leaves, removal of dissolved organic material, flexibility in regards to the amount of inorganic phosphate extracted for the purification into silver phosphate, reduced use of chemicals and, removal of co-precipitated oxygen-bearing compounds before analysis. Most notable optimizations to the method and associated effects were:•Drying of plant material before inorganic phosphate extraction increases the method applicability to a broader range of plant sample types.•Removal of dissolved organic matter improves inorganic phosphate purification.•Sample volume adjustment according to inorganic phosphate content is vital for effective and quantitative precipitations.

A comprehensive investigation to the fate of phosphorus in full-scale wastewater treatment plants using aluminum salts for enhanced phosphorus removal

This study investigated the fate of phosphorus (P) in 8 full-scale municipal wastewater treatment plants (WWTPs) in Shanghai, China, in which both biological nutrient removal and aluminum-based chemical phosphorus removal were used. The results showed that 83.8–98.9 % P was transferred to the sludge in the 8 WWTPs by both chemical and biological reactions. P speciation analysis indicated that chemical P precipitates accounted for 84.3 % in the activated sludge, of which crystalline AlPO4 and amorphous iron‑phosphorus compounds (FePs) were the main components. Sludge with more water-soluble and weakly adsorbed P was generated in the anaerobic-anoxic-oxic (A/A/O) process than in other processes. Among the 8 WWTPs, the one with the largest flow rate and relatively short sludge retention time (SRT) had the best potential to release P from all types of sludge. The recovery potential of P from thickened sludge can be improved by separately thickening the sludge produced in the high-efficiency sedimentation tank or feeding it into the dewatering process directly. Different P removal chemicals and dosing points changed the amount of chemical precipitate formed but had little effect on the composition of P accumulating organisms (PAOs) at the genus level. Although aluminum-based coagulants were applied in the investigated WWTPs, Fe in wastewater had the most positive effect on the proliferation of PAOs. The synthesis of polyphosphate was also related to the metabolism of PAOs as it affected transmembrane inorganic phosphate (Pi) transport and polyhydroxybutyrate (PHB) synthesis. The in-depth understanding of the fate of P is beneficial to improve P recovery efficiency in WWTPs.

Study on the fate of phosphorus, fluorine and chlorine in sludge during incineration

Sludge is often incinerated to achieve complete harmlessness and maximum capacity reduction, but the utilization of P (phosphorus) and the environmental pollution of F (fluorine) and Cl (chlorine) released from sludge incineration are usually ignored. In this paper, a series of experiments were employed to inquire into the conversion of various forms of P and the release of various forms of F and Cl after sludge incineration at different temperatures; the agriculture application prospect of P in sludge incineration ash and the environmental pollution caused by the release of F and Cl were discussed. The results show that P in sludge mainly exists as NAIP (non-apatite inorganic P) which biological effect was small. In the process of sludge incineration, InorgP (inorganic P) began to volatilize at 900 ℃, and the remaining P in sludge ash was 30.96 % at 1100 ℃. The forms of P in sludge incinerated at different temperatures varied considerably: a small amount of OrgP (organic P) in the sludge was converted into InorgP at 400 ℃; with the increase of incineration temperature, AP (apatite P) increased gradually, with 3.00 × 103–7.98 × 103 g/t in sludge ash at 700–1100 ℃. At 900 ℃, the content of AP in incineration ash was the highest, accounting for 58.98 % of Total P, which was the most suitable for slow-release phosphate fertilizer. At 600–1100 ℃, more Cl release, with a release rate of 50.61–92.70 %, among which the Cl for HCl (ClHCl) was 1.64 × 103–1.95 × 103 g/t at 700–1100 ℃. The F release rate was 1.52–37.39 %, among which the InorgF (inorganic F: mainly refers to F in HF and SiF4) was 1.13–27.91 g/t at 300–1100 ℃, the release amount of OrgF (organic F) was 1.59–1.86 g/t at 600–800 ℃. It can be seen that after incineration above 700 ℃, the sludge incineration ash may be used as a slow-release phosphate fertilizer, the release of Cl has greater environmental pollution and instrument corrosion than that of F, and the exhaust gas from sludge incineration cannot be discharged directly into the atmosphere.

Effects of ferrous sulfate modification on the fate of phosphorous in sewage sludge biochar and its releasing mechanisms in heavy metal contaminated soils.

Modifications of sludge biochar with metal-based materials can enhance its fertilizing efficiency and improve safety. To elucidate the effects of ferrous sulfate modification on the fate of phosphorus in sludge biochar and its effect on phosphorus fractionation in soil, we investigated the changes in fractionation and bioavailability of phosphorus in modified sludge biochar and studied the changes in soil characteristics, microbial diversity and response, bioavailability, plant uptake of phosphorus, and heavy metals in contaminated soils after treatment with ferrous sulfate modified sludge biochar. The results demonstrated that ferrous sulfate modifications were conducive to the formation of moderately labile phosphorus in sludge biochar, and the concentrations increased by a factor of 2.7 compared to control. The application of ferrous sulfate-modified sludge biochar to alkaline heavy metal-contaminated soils enhanced the bioavailable, labile, and moderately labile phosphorus contents by a factor of 2.9, 3.0, and 1.6, respectively, whereas it obviously reduced the leachability and bioavailability of heavy metals in soils, exhibited great potentials in the fertilization and remediation of actual heavy metal-contaminated soils in mining areas. The biochar-induced reduction in soil pH, enhancement of organic matter, surface oxygen-containing functional groups, the abundance of Gammaproteobacteria, and its phosphonate degradation activity were primarily responsible for the solubilization of phosphorus from modified biochar in heavy metal-contaminated soils.

Bubbling fluidized bed co-combustion and co-gasification of sewage sludge with agricultural residues with a focus on the fate of phosphorus

In this work, the fate of the ash-forming elements during bubbling fluidized bed combustion and gasification of P-rich sewage sludge (SS) and mixtures with either Si-K-rich wheat straw (WS) or K-Ca-rich sunflower husks (SH) were investigated. The focus of the study was assessing the feasibility of using fuel blends in fluidized bed systems and potential P recovery from the resulting ashes. The used fuels were pure SS and mixtures including 90 wt.% WS (WSS) and 85 wt.% SH (SHS). The analyzed operating conditions were combustion (930–960 °C, λ: 1.2–1.5) and gasification (780–810 °C, λ: 0.4–0.7) in a 5 kW bench-scale reactor. Residual ash and char fractions were collected from different parts of the 5 kW bubbling fluidized bed (bed, cyclone, filter) and analyzed by CHN, SEM/EDS, XRD, and ICP-AES.The conversion of the fuel mixtures achieved a steady state under the used process conditions except for the combustion of WSS, which led to the formation of large bed agglomerates with the bed material. The morphology of ash samples after combustion showed that SS fuel pellets mostly maintained their integrity during the experiment. In contrast, the ash and char particles from fuel mixtures were fragmented, and larger quantities were found in the cyclone, the filter, or on interior reactor surfaces. The fate of P was dominated by crystalline Ca-dominated whitlockites in all ash fractions, partially including K for the fuel mixtures SHS and WSS. 76–81 % of ingoing P was found in the bed residue after combustion and gasification of the SS-fuel. After conversion of the fuel mixtures SHS and WSS, the share was lower at 22–48 %, with larger shares of P in the entrained fractions (25–34 %). The quantity of identified crystalline compounds was lower after gasification than combustion, likely due to the limited interaction of ash-forming elements in the residual CHN matrix. Altogether, the results show that fuel mixtures of sewage sludge with agricultural residues could expand the fuel feedstock and enable P recovery. This may be used in the fuel and process design of upscaled fluidized bed processes or systems employing both combustion and gasification.

Review of Phosphorus Chemistry in the Thermal Conversion of Biomass: Progress and Perspectives

Phosphorus is vital for all life, which means that phosphorus is present in all biomass to some extent. Some types of biomass, such as certain agricultural residues, animal biomass, and sewage sludge, contain high levels of phosphorus. In thermal conversion of biomass, high levels of phosphorus can cause various operational problems. Extensive work has been carried out to understand the phosphorus chemistry taking place at higher temperatures. However, until now, knowledge about transformation chemistry and fate of phosphorus during thermal conversion of biomass was not easily accessible in one place. In this work, the outcome of an extensive literature review has been summarized. First, an introduction to the role of phosphorus in biomass, and in what forms it may be present, is given. Different analytical techniques relevant for characterization of phosphorus in biomass, biomass char, and biomass ash are described. A classification of phosphorus-rich biomass is proposed, and the potential of different phosphorus-rich biomass types is presented. To provide a common basis for the field of high-temperature phosphorus chemistry, fundamental chemistry relevant for thermal conversion of biomass is first discussed. This includes the gas phase chemistry and reaction pathways of light phosphorus species, pyrolysis, and combustion of organophosphorus compounds, and solid, liquid, and gaseous interactions with other ash-forming elements. Thereafter, an in-depth review of phosphorus transformations in biomass, including decomposition of organic phosphorus, ash transformations in the condensed phase, release to the gas phase, and formation of particulate matter in the flue gas follows. Finally, the review covers research focusing on phosphorus in different application aspects, such as the use of phosphorus as an additive to mitigate operational problems related to slag and deposit formation, the behavior of phosphorus in fluidized bed technologies, corrosion, and the deactivation of SCR catalysts.

Anaerobic digestion of hydrothermally pretreated dewatered sewage sludge: effects of process conditions on methane production and the fate of phosphorus.

The hydrothermal pretreatment (HTP) characteristics and the fate of phosphorus (P) and anaerobic digestion (AD) performance of dewatered sewage sludge (DSS) were investigated at different hydrothermal conditions. The maximum methane yield reached 241mL CH4/g COD when the hydrothermal conditions were 200°C-2h-10% (A4), and the yield was 78.28% higher than that without pretreatment (A0) and 29.62% higher than that of the initial hydrothermal conditions (A1, 140°C-1h-5%). Proteins, polysaccharides, and volatile fatty acids (VFAs) were the main hydrothermal products of DSS. 3D-EEM analysis revealed that tyrosine, tryptophan proteins, and fulvic acids decreased after HTP, but the content of humic acid-like substances increased, and this phenomenon was more noticeable after AD. Solid-organic P was converted into liquid-P during the hydrothermal process, and nonapatite inorganic P was converted into organic P during AD. All samples achieved positive energy balance, and the energy balance of A4 was 10.50kJ/g VS. Microbial analysis showed that the composition of the anaerobic microbial degradation community changed as the sludge organic composition was altered. Results showed that the HTP improved the anaerobic digestion of DSS.

Ash Transformation during Fixed-Bed Co-combustion of Sewage Sludge and Agricultural Residues with a Focus on Phosphorus.

This work investigates the ash transformation during fixed-bed co-combustion of sewage sludge mixtures with the agricultural residues wheat straw and sunflower husks, focusing on the fate of phosphorus (P) in the resulting ash fractions. The study aims to determine suitable process parameters for fixed-bed combustion of fuels previously investigated in single-pellet experiments. The pure fuels and fuel mixtures were combusted in a 20 kWth residential pellet burner while monitoring the flue gas composition, temperature, and particulate matter formation. Subsequently, the different ash fractions were collected and characterized by CHN, SEM/EDS, and XRD analysis. The results showed that co-combustion of sewage sludge and agricultural residues reduced the formation of particulate matter as well as the formation of slag. Co-combustion of sewage sludge with either agricultural residue resulted in a change in phosphate speciation, displaying higher shares of Ca and lower shares of Fe and Al in the formed orthophosphates as well as amorphous phases containing higher shares of K. The formation of K-bearing phosphates was hindered by the spatial association of P with Ca and Fe in the sewage sludge, the incorporation of available K in K-Al silicates, and the depletion of K in the P-rich melt phase. Compared to mono-combustion, co-combustion experiments showed the potential for improving the combustion performance and reducing the risk of slag formation. The outcome suggests that co-combustion is a feasible path to integrate waste streams in fixed-bed energy conversion with simultaneous formation of phosphates enabling P recovery.

The Fate of Phosphorus in Experimental Burials: Chemical and Ultramicroscopic Characterization and Environmental Control of Its Persistency

The permanence of a buried body in soil always induces the formation of a decomposition island that can serve as a significant recording location to understand how the persistence of a clandestine grave affects soil. This study aims to analyze the elemental exchange from buried bodies to soil, with a focus on phosphorus content, and to determine the effects of environmental factors on its persistency. The experiment was carried out using eleven swine carcasses buried in an open site (northern Italy). The analyses were performed using the Olsen P method, which allowed for a recognition of the trend of the amount of phosphorus over time, due to the decomposition of phospholipids, followed by the transfer of the element from bone to soil. Additionally, microanalyses performed using a scanning electron microscope (SEM-EDS) on two different soil sample specimens (i.e., “dust” and “plug”) allowed for the identification of numerous phosphatic features (i.e., coatings, infillings, impregnations, and organo-mineral associations), which are the result of the interaction between soil and body fluids and can thus be used as indicators of the former presence of decomposing body (even in its absence). The ultramicroscopic analysis also shows increasing and decreasing amounts of P2O5 over time in the soil, which could be related to environmental conditions (i.e., soil moisture), due to the leaching of phosphorus induced by the percolation of natural rainwater. The study underlines the potential use of these methods to evaluate the possibility of a cadaver–soil linkage and of assessing the burial in the soil for a variable period. Moreover, the study may aid in analyzing the dynamics of phosphorus migration from buried bodies to soil during and after the decomposition process.

Fate of phosphorus in pulverized fuel co-combustion of sewage sludge and agricultural residues

The fate of phosphorus concerning its distribution in the thermal process and chemical speciation was studied during the co-combustion of sewage sludge with wheat straw and sunflower husks in powder combustion conditions. Co-combustion experiments were performed in a lab-scale entrained flow reactor (EFR) at 1000 °C and 1400 °C. SEM-EDS and ICP-OES analyses were used for studies of deposits collected on a probe, bottom ash, and particulate matter samples collected during experiments. Deposition probe samples were further studied and interpreted using powder X-ray diffraction (XRD) and thermochemical equilibrium calculations (TECs). The inorganic material in the different fuel particles mainly interacted through a molten phase observed on deposition probes. Crystalline P was mainly identified in β-Ca3(PO4)2 whitlockites. TECs support the experimental findings and suggest that a mostly homogenous melt occurs at 1400 °C, whereas Fe-oxides and Ca-phosphates precipitate during the cooling of the formed deposits. It was found that <5 % of incoming P was collected in fine particulate matter (<1 µm), indicating that the majority of P can be found in deposits and bottom ash. This outcome implies that P recovery efforts should be focused on these ash fractions.

The fate of phosphorus from bone char-based fertilizers in soil pools in a 5-year crop rotation

Bone char (BC) is a promising P-recycling fertilizer but with rather low P-solubility, which can be increased by modifying the BC surface with elemental sulfur (BCplus), but effects on the soil P status have not been tested under field conditions yet. Hence, a long-time field experiment was started 2013 to track the fate of BC and BCplus P into different soil P pools compared to a control and triple superphosphate (TSP) treatment for severely P deficient (iSPTC-A) vs. sufficiently P fertilized (iSPTC-C) soil. The fingerprint of the recent land-use history (six years grassland prior arable land) was reflected by elevated labile-Po and NaOH-Po concentrations at the beginning of the experiment. However, after 3 years, labile Po concentrations converged and stabilized in both soils at a similar level. The formation of this new equilibrium of labile Po suggests that the rate of Po mineralization was, to some extent, controlled by the amount of available legacy P. After the first crop rotation, the effect of P fertilization on soil-P budgets and fractions were small and mostly insignificant. Only TSP increased the available-P pools in the soil. The other pools were not affected by treatments except stable-P increased significantly after BC application in iSPTC-A. The former laboratory results of higher P solubility of BCplus over BC could not be confirmed within the duration of the field trial. However, to prove that BC and BCplus are capable of maintaining adequate long-term crop P supply, the continuation of this unique field trial is highly recommended.

Relative Roles of Sediment Transport and Localized Erosion on Phosphorus Load in the Lower Susquehanna River and Its Mouth in the Chesapeake Bay, USA

AbstractParticle size greatly influences the fate of phosphorus (P) in estuaries as P adheres more readily to the larger surface area in smaller sized particles. Here, data on two size fractions of particulate matter, permanently suspended particulate matter (PSPM, ≤40 μm) and resuspended particulate matter (RSPM, &gt;40 μm), from field and controlled laboratory erosion experiments were analyzed to determine their relative contribution to water column P in the mouth of the Susquehanna River in the upper Chesapeake Bay. Based on the composition of sequentially extracted P pools, C and N isotopes, and elemental data, all PSPM and the majority of RSPM are most likely derived from allochthonous sources through river transport. A minor fraction of particulate matter in the water column was derived from sediment resuspension, which had a dominant role above the sediment‐water interface in the river's mouth. The proportion of biologically available P pools to recalcitrant P pools in suspended particulate matter decreased with water column depth, indicating their preferential removal or biological utilization during settling. Suspended particulate matter (SPM) mobilized during sediment erosion experiments, regardless of particle size, was richer in biologically available P pools than SPM in the field, suggesting higher mobility of these pools in the field. These complementary results from field and field‐simulated laboratory erosion experiments provide unique insights into the composition of particulate matter under different hydrodynamic regimes in the river estuary.

Expanding the Paradigm: The influence of climate and lithology on soil phosphorus

The fate of phosphorus (P) during pedogenesis has been historically conceptualized (Walker-Syers model) with time as the primary controlling state factor. Herein, we demonstrate that both climate and lithology exert a strong and interacting influence on the fate of P by examining coupled bioclimatic and parent material effects on soil P fractions. Three transects were investigated spanning a 2150-m elevation gradient (MAT = 17 → 3 °C/MAP = 330 → 1400 mm) across three separate bedrock lithologies (lithosequence: granite, andesite and basalt) within the Sierra Nevada and southern Cascades of California. The elevation gradient entails four bioclimatic zones (bioclimosequence: blue oak, ponderosa pine, white fir and red fir). Soil P fractions were determined by sequential fractionation and interpreted in the context of associated soil characterization data. The bioclimatic sequences demonstrate a weathering gradient with maximum intensity at mid-elevation sites, and corresponding changes in Fe/Al-(hydr)oxide content and aluminosilicate crystallinity. Phosphorus content of parent material varied by an order of magnitude (mean; mg P kg−1): andesite (1500) > basalt (1000) > granite (131). Differences in P content of parent material influenced Pt in soils. However, amounts and proportions of P in fractions were influenced by subtle to significant interactions between climate and lithology, owing to differences in chemical weathering and the abundance and crystallinity of Fe/Al-(hydr)oxides and aluminosilicates. This interactive effect of pedogenesis on clay mineralogy led to differences in P fractions dependent upon lithology and bioclimatic zone. Labile inorganic P (Pi) was uniformly higher in soils derived from granite, despite granite having significantly lower P content, a result of lower Fe/Al-(hydr)oxide generation in granitic soils. With descending elevation and increased weathering intensity, HCl-Pi (primary mineral bound P-apatite) declined in basalt and andesite but remained unchanged in granite owing to its greater resistance to chemical weathering. As weathering intensity increased, occluded P increased in basalt, decreased in andesite and was unchanged in granite, contradicting the paradigm of progressive P occlusion with increased weathering. This incongruity for andesite results from a dominance of poorly crystalline materials (e.g., ferrihydrite, allophane/imogolite) at less weathered sites versus more crystalline minerals at more weathered sites. This study highlights several caveats to the paradigm that time (i.e., degree of weathering) is universally the dominant pedogenic control of P fractionation. We identify the importance of interactions between lithology and climate in regulating the amount and types of weathering products that in turn control P fractionation and ecosystem P availability.

Fate of phosphorus from treated wastewater in soil-based constructed wetlands

In France, soil-based constructed wetlands for the discharge of treated wastewater have become a popular technique to both reduce flow to surface receiving water bodies and perform complementary treatments. This study focuses on the fate of phosphorus in three different soils, as well as its assimilation by Phragmites australis. The experimental set-up consisted of three lysimeters containing three soils selected to be representative of those typically found near wastewater treatment plants (i.e. a silt loam Fluvisol, a sandy loam Fluvisol and a sandy-clay loam Technosol). Lysimeters are undisturbed soil monoliths (1.5 m3 in volume), whose masses are continuously monitored in order to obtain an accurate water mass balance. The lysimeters here were intermittently fed for 3.5 days and then left to rest for 3.5 days. The experiment lasted 26 months, including 18 months of feeding with phosphorus (PO4-P, TP) fluxes in and out being monitored along with water content, oxygen content and redox potential at various depths. The quantities of phosphorus stored in the soils and assimilated in the Phragmites australis were measured. Phosphorus fractionation in soils was performed to better understand its distribution and potential remobilization. Low phosphate concentrations were measured at the outlets of all three lysimeters, thereby highlighting satisfactory phosphorus retention in the three soils (removal efficiencies >90%). A significant amount of phosphorus can be exported by harvesting Phragmites australis aerial parts (26%, 17% and 13% of the yearly incoming phosphorus mass for the silt loam Fluvisol, sandy loam Fluvisol and sandy-clay loam Technosol, respectively). The fractionation step served to determine that the phosphorus retained in the soil was primarily bound to iron oxides/hydroxides, calcium and clay. Moreover, it was found to be preferable to hold oxidizing (aerobic) conditions and pH close to neutral in order to maintain conditions under which the complexes formed with phosphorus remain stable.

Phosphorus Flows, Surpluses, and N/P Agronomic Balancing When Using Manure from Pig and Poultry Farms

The pig and poultry industries continue to grow across the world and together they provide the majority of meat consumed. The European Union (EU) in particular has the highest global relative meat production by monogastrics (i.e., pig and poultry). The fate of phosphorus (P) in pig and poultry farming was studied, accounting for P content in feed, animals, manure, soil, and runoff. P input from manure, and P offtake in crops receiving manure, were plotted against each other to arrive at “safe” P loading rates, in order to minimize soil P surpluses along the lines of the EU Nitrogen Expert Panel in their work with nitrogen (N). However, it was observed that it is the N/P ratio and the background soil P levels that determine whether a certain manure will end up producing surplus levels of soil P. Critical N/P weight ratios were derived over different crop P offtake rates when applying stored manure to croplands. At spreading rates of 170 and 250 kgN/ha/year and a crop P offtake of 15 or 30 kgP/ha/year, stored pig and chicken manure result in soil P surpluses. An important factor in determining effective N/P ratios is the plant availability of N in stored manure, which runs at around 47%, estimated from previously published results. The minimization of N losses to the atmosphere and to groundwater in housing, storage, and spreading of manure has a major impact on the N/P weight ratio of the manure that ends up on fields. In most cases, half of the ex-animal N content has been lost in stored or degraded manure, with N/P weight ratios running at two and less. Following only the EU Nitrates Directive, which allows for a maximum of 170 kgN/ha/year in NVZs (Nitrate Vulnerable Zones), will often result in soil P surpluses leading to runoff losses to adjacent water bodies. Therefore, for the pig and poultry industries to continue thriving, measures are required to better manage manure, including improved storage and spreading techniques, acidification, separation, struvite extraction and ammonia stripping of pig slurry, and drying and pelleting of poultry litter. This way, excess manure and derived biofertilizers from animal farms can find their way back into the commercial market, instead of ending up as legacy P in watersheds and coastal zones.

Soil acidification enhances the mobilization of phosphorus under anoxic conditions in an agricultural soil: Investigating the potential for loss of phosphorus to water and the associated environmental risk

Soil redox potential (EH) and pH are key parameters regulating the solubility and fate of phosphorus (P). However, the impact of soil acidification on the redox-induced mobilization and speciation of P in soils under a wide range of EH values has not been extensively studied. Here, we investigated the mobilization and speciation of P in an acidified agricultural soil at two different pH values (e.g., highly acidic soil; pH = 5.6 and slightly acidic soil; pH = 6.1) compared to the un-acidified soil (control soil; pH = 7.3) under a wide range of EH condition (+459 to −281 mV). The impacts of EH/pH-dependent changes of Fe-Mn oxides, and dissolved organic (DOC) and inorganic (DIC) carbon on P mobilization and speciation were also investigated using geochemical and spectroscopic (X-ray absorption near edge structure) techniques. The concentrations of dissolved P under anoxic conditions increased up to 69.3% in the highly acidic soil compared with the control soil. The decrease of the Fe-P fraction, the decrease of Ferrihydrite-Pads speciation, and the strong linear correlation between the dissolved P and Fe2+ (R2 > 0.85) supports the finding that enhanced P mobilization under anoxic conditions may be attributed to Fe reduction in the highly acidic soil. The concentration of dissolved Fe and P remained low until pH dropped below 6.35 for P and 6.28 for Fe, while a liner increase was found in dissolved Mn accompanying a general trend of pH decrease. This result suggests that the dissolution of reducible Mn under acidic soil conditions was an important factor for enhancing mobilization of dissolved P under anoxic conditions. This trend was due to the low amount of Mn, indirectly speeding up Fe reduction. These results can help to develop management practices to effectively mitigate P export and protect water resources from diffuse P pollution.