Understanding phosphorus mobilization mechanisms in acidic soil amended with calcium-silicon-magnesium-potassium fertilizer.

Calcium-silicon-magnesium-potassium fertilizer (CSMP) is usually used as an amendment to counteract soil acidification caused by historical excessive nitrogen (N) applications. However, the impact of CSMP addition on phosphorus (P) mobilization in acidic soils and the related mechanisms are not fully understood. Specifically, a knowledge gap exists with regards to changes in soil extracellular enzymes that contribute to P release. Such a knowledge gap was investigated by an incubation study with four treatments: i) initial soil (Control), ii) urea (60 mg kg-1) addition (U); iii) CSMP (1%) addition (CSMP) and iv) urea (60 mg kg-1) and CSMP (1%) additions (U + CSMP). Phosphorus mobilization induced by different processes was distinguished by biologically based P extraction. The Langmuir equation, K edge X-ray absorption near-edge structure spectroscopy, and ecoenzyme vector analysis according to the extracellular enzyme activity stoichiometry were deployed to investigate soil P sorption intensity, precipitation species, and microbial-driven turnover of organophosphorus. Results showed that CaCl2 extractable P (or citric acid extractable P) content increased by 63.4% (or 39.2%) in the soil with CSMP addition, compared with the study control. The accelerated mobilization of aluminum (Al)/iron (Fe)-bound P after CSMP addition, indicated by the reduction of the sum of FePO4·2H2O and AlPO4 proportion, contributed to this increase. The decrease of P sorption capacity can also be responsible for it. The CSMP addition increased enzyme extractable P in the soil nearly 7-fold and mitigated the limitations of carbon (C) and P for soil microorganisms (indicated by the enzyme stoichiometry and ecoenzyme vector analysis), suggesting that microbial turnover processes also contribute to P mobilization in amended acidic soil. These findings indicate that the P mobilization in CSMP amended acidic soil not only attributed to both decreasing P sorption capacity and dissolving phosphate precipitation, but also to the increase of the microbial turnover of the organophosphorus pool.

A comparative study of thermally and chemically treated dairy waste: Impacts on soil phosphorus turnover and availability using 33P isotope dilution.

Dairy processing sludge (DPS) and DPS-derived secondary products such as struvite, biochar, hydrochar and ash (collectively known as SRUBIAS) are emerging as alternatives to fertilizers produced from mined rock phosphate. However, little is known about how these products affect soil P availability and daily P turnover rates.. A lack of such information prevents precision nutrient management planning using these products out on farms. This study used a novel isotope dilution technique (IPD) with 33P as a tracer to compare P turnover in soils amended with chemically (alum-treated DPS and struvite) and thermally (biochar, hydrochar, ash) treated DPS. Results showed that thermally treated products exhibited poor agronomic performance as P fertilizers, potentially inhibiting P availability when applied to soils. For example, a P deficient soil amended with hydrochar treatment at the highest application rates did not record a build-up of available P to agronomic target values. In ash and biochar treated P deficient soils, available P increased but only with very high application rates of 150 and 80 mg P kg -1. The application of these products as fertilizers could have negative implications for both environmental and agronomic goals. Conversely, chemically treated fertilisers demonstrated better agronomic performance. The same agronomic target value was reached with application rates of only 20 mg P kg -1 soil for DPS and 50 mg P kg -1 soil for struvite. However, the techniques deployed revealed that these products exhibited slower rates of available and exchangeable P build-up when compared with chemical fertilisers. This suggests that these bio-based alternatives require higher application rates or earlier application times compared to conventional chemical fertilizers. Regulations providing advice on P use in agricultural soils need to account for slower P turnover in soils receiving recycled fertilizers. The IPD technique is transferrable to all wastes to examine their performance as fertilizers.

Factors controlling shallow subsurface dissolved reactive phosphorus concentration and loss kinetics from poorly drained saturated grassland soils.

Shallow subsurface pathways dominate dissolved reactive phosphorus (DRP) losses in grassland soils that are: poorly drained, shallow, or have a perched water table in wetter months causing saturation-excess runoff. Saturated conditions can lead to anoxia, which can accelerate phosphorus (P) loss. Two scales of investigation were utilized in this study. First, at the field scale, soil cores were extracted to 2.5 m, subdivided and samples extracted using water extractable P (WEP) and sodium-bicarbonate-dithionite extractable P (NaBD-P). Second, at the laboratory scale, detailed incubation studies using field-moist grassland topsoils from sites in Ireland and New Zealand examined the kinetics of WEP under anoxic (WEPanox ) and oxic (WEPox ) conditions with imposed temperature and soil P fertilizer input treatments. Results from soil-core samples showed that redox-sensitive NaBD-P concentrations were depleted where artificial drainage lines were installed (100 cm deep), but WEP concentrations available to shallow flow were enriched in topsoil. The laboratory scale incubation experiment investigated the influence of temperature (3 vs. 18 °C), anoxia (designed to simulate saturation following a rainfall event), and superphosphate fertilizer (10 to 60 kg P ha-1  yr-1 ) on WEP concentrations over 24 h in three grassland topsoils (clay, silt, and sandy loam textures). Concentrations increased with fertilizer rate, temperature, and-in two soils-anoxic conditions. This was commensurate with nitrate (NO3 - ) depletion and the reductive dissolution of iron and manganese. The release of P during anoxia was complete within 24 h. The results highlighted late winter to spring as the riskiest period for topsoil P losses in shallow subsurface flow due to wet soil conditions, increasing temperatures, and low soil NO3 - concentrations. This knowledge highlights the necessity to consider and refine tests used to assess topsoil P loss risk, where in the landscape P losses are likely, and what strategies can be used to mitigate losses.

Leached phosphorus apportionment and future management strategies across the main soil areas and cropping system types in northern China.

Excess phosphorus (P) leached from high fertiliser input cropping systems in northern China is having detrimental effects on water quality. Before improved management can be directed at specific soils and cropping system types estimates of P leached loss apportionment and mitigation potentials across the main soil (fluvo-aquic soil, FAS; cinnamon soil, CS; black soil, BS) areas and cropping systems (protected vegetable fields, PVFs; open vegetable fields, OVFs; cereal fields, CFs) are needed. The present study designed and implemented conventional fertilisation and low input system trials at 75 sites inclusive of these main soils and cropping system types in northern China. At all sites, a uniform lysimeter design (to 0.9 m depth) enabled the collection and analysis of leachate samples from 7578 individual events between 2008 and 2018. In addition, site-specific static and dynamic activity data were recorded. Results showed that annual total phosphorus (TP) leached losses across the main soil areas and cropping systems were 4.99 × 106 kg in northern China. A major finding was PVFs contributed to 48.5% of the TP leached losses but only accounted for 5.7% of the total cropping areas. The CFs and OVFs accounted for 40.3% and 11.2% of the TP leached losses, respectively. Across northern China, the TP leached losses in PVFs and OVFs were greatest in FAS areas followed by CS and BS areas. The higher TP leached losses in FAS areas were closely correlated with greater P fertiliser inputs and irrigation practices. From a management perspective in PVFs and OVFs systems, a decrease of P inputs by 10-30% would not negatively affect yields while protecting water quality. The present study highlights the importance of decreasing P inputs in PVFs and OVFs and supporting soil P nutrient advocacy for farmers in China.

Investigation of differential levels of phosphorus fixation in dolomite and calcium carbonate amended red soil.

BACKGROUND: The pH adjustment of acidic red soils with lime materials is beneficial for the reduction of phosphorus (P) fixation. However, the reasons for varying levels of P activation after adding different lime materials have not been fully investigated. Therefore, this study examined changes in soil labile P and P forms after phosphate application to calcium carbonate (CaCO3 ) and dolomite amended red soil during a 120-day incubation period. Also change of P sorption properties in the amended soil samples from day 120 were examined through a sorption-desorption experiment. RESULTS: The increase of soil H2 O-P and NaHCO3 -P in the CaCO3 and dolomite amended soil treatments was mainly ascribed to the decline of the NaOH-P. However, when compared with the control treatment after 120 days, soil Olsen-P significantly increased by 34% and 66% in the CaCO3 and dolomite treatments. The Hedley P fractionation results demonstrated that the CaCO3 application caused a notable increase of HCl-P (stable Ca-P), which was 88.4% higher than that in the dolomite treatment. However, the formation of stable P was strongly suppressed in the dolomite treatment due to the presence of magnesium (Mg), which was identified by the negative relationship between M3-Mg and HCl-P. In line with these findings, P sorption-desorption work showed weaker P binding energy in the dolomite treatment relative to the CaCO3 treatment. CONCLUSION: In terms of increasing P availability in red soil, this study suggests that dolomite should be used to substitute CaCO3 in order to reduce the soil P fixation. © 2021 Society of Chemical Industry.

Reductive dissolution of phosphorus associated with iron-oxides during saturation in agricultural soil profiles.

In soils with a fragipan or poor permeability, water may remain in a soil profile long enough to make it anoxic and reductive. The reductive dissolution of iron (Fe)- and manganese (Mn)-oxides can release associated phosphorus (P). Therefore, the dissolved P would be vulnerable to subsurface flow and could contaminate nearby streams. It was hypothesized that single rainfall events could cause subsurface P concentrations to increase via reductive dissolution in wet winter-spring conditions. Also, dissolution-being microbially mediated-would be buffered by the presence of nitrate (NO3 - ), which is preferred as an electron acceptor over Fe and Mn in microbial reactions. Unsaturated zone monitoring occurred from May to September in 2017 and 2019, using Teflon suction cups below the surface of a grassland soil in New Zealand. Events in July and August in 2017 and 2019 resulted in reducing conditions [Fe(III)/sulfate-reducing] and up to 77 and 96% greater P and Fe release, respectively. In an additional experiment in 2019, 100 mm of flood irrigation was applied, and 10 mg NO3 - -N + carbon was injected into half the cups at the site. The other cups received no N. Cups treated with N yielded up to 45% total dissolved P and 21% less Fe than the no-N cups. A laboratory incubation of soils from the site confirmed that NO3 - inhibited P release. This effect may act to decrease the amount of P lost in subsurface flow in systems regularly fertilized with N but should not be relied on as a method to mitigate P losses.

Alum split applications strengthened phosphorus fixation and phosphate sorption in high legacy phosphorus calcareous soil.

High phosphorus (P) saturation arising from historic P inputs to protected vegetable fields (PVFs) drives high P mobilisation to waterbodies. Amendment of soils with alum has shown potential in terms of fixing labile P and protecting water quality. The present 15 month pot experiment investigated P stabilisation across single alum application (Alum-1 treatment, 20 g alum/kg soil incorporated into soil before the maize was sown), alum split applications (Alum-4 treatment, 5 g alum/kg soil incorporated into soil before each crop was sown i.e. 4 × 5 g/kg) and soil only treatment (Control). Results showed that the Alum-1 treatment caused the strongest stabilisation of soil labile P after maize plant removal, whereas the P stabilisation effect was gradually weakened due to the transformation of soil non-labile P to labile P and the reduced active Al3+ in soil solution. For the Alum-4 treatment, soil labile P decreased gradually with each crop planting and was lower than the Alum-1 treatment at the end of the final crop removal, without any impairment on plant growth. The better P stabilisation at the end of Alum-4 treatment was closely correlated with a progressive supply of Al3+ and a gradual decrease of pH, which resulted in higher contents of poorly-crystalline Al, Fe and exchangeable Ca. These aspects were conducive to increasing the soil P stabilisation and phosphate sorption. In terms of management, growers in continuous cropping systems could utilise split alum applications as a strategy to alleviate P losses in high-P enriched calcareous soil.

Understanding phosphate sorption characteristics of mineral amendments in relation to stabilising high legacy P calcareous soil.

In China, excessive phosphorus (P) application in protected vegetable fields has led to high legacy P stores. Soil amendment with alum or dolomite is one of many best management practices (BMPs) used to reduce P losses in calcareous soils. However, both the kinetics and mechanisms of P sorption and soil available P in amended soils are understudied. Herein, both aspects were looked at under controlled conditions. Firstly, a sorption study which coupled P concentrations with poorly-crystalline Al hydroxides and dolomite was conducted. Results from this batch experiment showed that P sorption on poorly-crystalline Al hydroxides was homogenous and occurred mainly via displacement of inner-sphere hydroxyl (Al-OH) instead of the formation of AlPO4. However, the amount of sorbed P reached maximum sorption of 73.1 mg g-1 and did not change with further increase in P concentration. It was observed that P adsorbed onto the dolomite surface at low P concentrations, whereas hydroxyl replacement and uneven cluster precipitation of Ca3(PO4)2 occurred at high P concentrations. A second 90 day incubation experiment investigated changes to soil available P and sorption-desorption across variable rates of amendments (0-50 g kg-1). Results showed that alum amendment at a rate of 50 g kg-1 decreased soil CaCl2-P and Olsen-P concentrations by 91.9% and 57.8%, respectively. However, Olsen-P increased when the dolomite rates were <20 g kg-1. Phosphorus sorption-desorption of the amended soil showed alum had higher P sorption efficiency than dolomite at low addition rates (<10 g kg-1). However, soil amended with high dolomite rates (>10 g kg-1) could sorb more P in comparison with alum when P concentrations were increased. The P status of the amended soil was closely connected to the P sorption mechanisms on mineral amendments, soil P concentrations and soil properties.

Strategic differences in phosphorus stabilization by alum and dolomite amendments in calcareous and red soils.

Surplus phosphorus (P) above agronomic requirements can negatively affect the water status of connected surface and subsurface water bodies. The in situ stabilization of soil P through soil amendment has been recognized as an efficient way to reduce this environmental pressure. However, the mechanism of how P is stabilized during this process and how plant available P is affected are unknown. This can be achieved by sequential chemical extraction and synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy investigations. Therefore, in the present study, P-enriched calcareous and red soils were amended with alum, dolomite, and a 1:1 mixture of alum and dolomite (MAD) at a 20 g/kg soil rate, and soil properties and P fractions were measured after a 45-day period. Results showed that alum amendment significantly decreased CaCl2-P and Olsen-P contents in calcareous and red soils when compared with dolomite. However, dolomite incorporation maintained relatively high P availability and even increased CaCl2-P and Olsen-P contents by 1.32% and 40.5% in red soil, respectively, compared to control. Amendment with MAD was not as effectively as the alum in P stabilization. Sequential inorganic P extraction indicated that alum dominantly contributed labile P transformed to Al-P in both soils. P K-edge XANES spectroscopy measurements further explained that alum adsorbed phosphate in calcareous soil and precipitated phosphate as AlPO4 in red soil. Results of P fractionation and Mehlich-3-extracted Ca showed that dolomite mainly adsorbed loosely bound P in calcareous soil and red soil. However, dolomite incorporation in red soil led to Al-P and Fe-P release. The P sorption isotherms showed that dolomite and alum increased soil P sorption maxima and decreased the degree of P saturation (DPS) in both soils, while dolomite declined the Langmuir bonding energy in red soil. Differences in P stabilization by alum and dolomite addition across soil types were closely related to their characteristics, and soil properties changed, especially soil pH.

A quantitative microbial risk assessment model for total coliforms and E. coli in surface runoff following application of biosolids to grassland.

In Ireland, the land application of biosolids is the preferred option of disposing of municipal sewage waste. Biosolids provide nutrients in the form of nitrogen, phosphorus, potassium and increases organic matter. It is also an economic way for a country to dispose of its municipal waste. However, biosolids may potentially contain a wide range of pathogens, and following rainfall events, may be transported in surface runoff and pose a potential risk to human health. Thus, a quantitative risk assessment model was developed to estimate potential pathogens in surface water and the environmental fate of the pathogens following dilution, residence time in a stream, die-off rate, drinking water treatment and human exposure. Surface runoff water quality data was provided by project partners. Three types of biosolids, anaerobically digested (AD), lime stabilised (LS), and thermally dried (TD)) were applied on micro plots. Rainfall was simulated at three time intervals (24, 48 and 360 h) following land application. It was assumed that this water entered a nearby stream and was directly abstracted for drinking water. Consumption data for drinking water and body weight was obtained from an Irish study and assigned distributions. Two dose response models for probability of illness were considered for total and faecal coliform exposure incorporating two different exposure scenarios (healthy populations and immuno-compromised populations). The simulated annual risk of illness for healthy populations was below the US EPA and World Health Organisation tolerable level of risk (10-4 and 10-6, respectively). However, immuno-compromised populations may still be at risk as levels were greater than the tolerable level of risk for that subpopulation. The sensitivity analysis highlighted the importance of residence time in a stream on the bacterial die-off rate.

Holistic Evaluation of Field-Scale Denitrifying Bioreactors as a Basis to Improve Environmental Sustainability.

Denitrifying bioreactors convert nitrate-nitrogen (NO-N) to di-nitrogen and protect water quality. Herein, the performance of a pilot-scale bioreactor (10 m long, 5 m wide, 2 m deep) containing seven alternating cells filled with either sandy loam soil or lodgepole pine woodchip and with a novel "zig-zag" flow pattern was investigated. The influent water had an average NO-N concentration of 25 mg L. The performance of the bioreactor was evaluated in two scenarios. In Scenario 1, only NO-N removal was evaluated; in Scenario 2, NO-N removal, ammonium-N (NH-N), and dissolved reactive phosphorus (DRP) generation was considered. These data were used to generate a sustainability index (SI), which evaluated the overall performance taking these parameters into account. In Scenario 1, the bioreactor was a net reducer of contaminants, but it transformed into a net producer of contaminants in Scenario 2. Inquisition of the data using these scenarios meant that an optimum bioreactor design could be identified. This would involve reduction to two cells: a single sandy loam soil cell followed by a woodchip cell, which would remove NO-N and reduce greenhouse gas (GHG) emissions and DRP losses. An additional post-bed chamber containing media to eliminate NH-N and surface capping to reduce GHG emissions further is advised. Scenario modeling, such as that proposed in this paper, should ideally include GHG in the SI, but because different countries have different emission targets, future work should concentrate on the development of geographically appropriate weightings to facilitate the incorporation of GHG into a SI.

The Effect of Chemical Amendments Used for Phosphorus Abatement on Greenhouse Gas and Ammonia Emissions from Dairy Cattle Slurry: Synergies and Pollution Swapping.

Land application of cattle slurry can result in incidental and chronic phosphorus (P) loss to waterbodies, leading to eutrophication. Chemical amendment of slurry has been proposed as a management practice, allowing slurry nutrients to remain available to plants whilst mitigating P losses in runoff. The effectiveness of amendments is well understood but their impacts on other loss pathways (so-called 'pollution swapping' potential) and therefore the feasibility of using such amendments has not been examined to date. The aim of this laboratory scale study was to determine how the chemical amendment of slurry affects losses of NH3, CH4, N2O, and CO2. Alum, FeCl2, Polyaluminium chloride (PAC)- and biochar reduced NH3 emissions by 92, 54, 65 and 77% compared to the slurry control, while lime increased emissions by 114%. Cumulative N2O emissions of cattle slurry increased when amended with alum and FeCl2 by 202% and 154% compared to the slurry only treatment. Lime, PAC and biochar resulted in a reduction of 44, 29 and 63% in cumulative N2O loss compared to the slurry only treatment. Addition of amendments to slurry did not significantly affect soil CO2 release during the study while CH4 emissions followed a similar trend for all of the amended slurries applied, with an initial increase in losses followed by a rapid decrease for the duration of the study. All of the amendments examined reduced the initial peak in CH4 emissions compared to the slurry only treatment. There was no significant effect of slurry amendments on global warming potential (GWP) caused by slurry land application, with the exception of biochar. After considering pollution swapping in conjunction with amendment effectiveness, the amendments recommended for further field study are PAC, alum and lime. This study has also shown that biochar has potential to reduce GHG losses arising from slurry application.

Impact of chemically amended pig slurry on greenhouse gas emissions, soil properties and leachate.

The effectiveness of chemical amendment of pig slurry to ameliorate phosphorus (P) losses in runoff is well studied, but research mainly has concentrated only on the runoff pathway. The aims of this study were to investigate changes to leachate nutrient losses, soil properties and greenhouse gas (GHG) emissions due to the chemical amendment of pig slurry spread at 19 kg total phosphorus (TP), 90 kg total nitrogen (TN), and 180 kg total carbon (TC) ha(-1). The amendments examined were: (1) commercial grade liquid alum (8% Al2O3) applied at a rate of 0.88:1 [Al:TP], (2) commercial-grade liquid ferric chloride (38% FeCl3) applied at a rate of 0.89:1 [Fe:TP] and (3) commercial-grade liquid poly-aluminium chloride (PAC) (10% Al2O3) applied at a rate of 0.72:1 [Al:TP]. Columns filled with sieved soil were incubated for 8 mo at 10 °C and were leached with 160 mL (19 mm) distilled water wk(-1). All amendments reduced the Morgan's phosphorus and water extractable P content of the soil to that of the soil-only treatment, indicating that they have the ability to reduce P loss in leachate following slurry application. There were no significant differences between treatments for nitrogen (N) or carbon (C) in leachate or soil, indicating no deleterious impact on reactive N emissions or soil C cycling. Chemical amendment posed no significant change to GHG emissions from pig slurry, and in the cases of alum and PAC, reduced cumulative N2O and CO2 losses. Chemical amendment of land applied pig slurry can reduce P in runoff without any negative impact on nutrient leaching and GHG emissions. Future work must be conducted to ascertain if more significant reductions in GHG emissions are possible with chemical amendments.

Chemical amendment of pig slurry: control of runoff related risks due to episodic rainfall events up to 48 h after application.

Losses of phosphorus (P) from soil and slurry during episodic rainfall events can contribute to eutrophication of surface water. However, chemical amendments have the potential to decrease P and suspended solids (SS) losses from land application of slurry. Current legislation attempts to avoid losses to a water body by prohibiting slurry spreading when heavy rainfall is forecast within 48 h. Therefore, in some climatic regions, slurry spreading opportunities may be limited. The current study examined the impact of three time intervals (TIs; 12, 24 and 48 h) between pig slurry application and simulated rainfall with an intensity of 11.0 ± 0.59 mm h(-1). Intact grassed soil samples, 1 m long, 0.225 m wide and 0.05 m deep, were placed in runoff boxes and pig slurry or amended pig slurry was applied to the soil surface. The amendments examined were: (1) commercial-grade liquid alum (8 % Al2O3) applied at a rate of 0.88:1 [Al/ total phosphorus (TP)], (2) commercial-grade liquid ferric chloride (38 % FeCl3) applied at a rate of 0.89:1 [Fe/TP] and (3) commercial-grade liquid poly-aluminium chloride (10 % Al2O3) applied at a rate of 0.72:1 [Al/TP]. Results showed that an increased TI between slurry application and rainfall led to decreased P and SS losses in runoff, confirming that the prohibition of land-spreading slurry if heavy rain is forecast in the next 48 h is justified. Averaged over the three TIs, the addition of amendment reduced all types of P losses to concentrations significantly different (p < 0.05) to those from unamended slurry, with no significant difference between treatments. Losses from amended slurry with a TI of 12 h were less than from unamended slurry with a TI of 48 h, indicating that chemical amendment of slurry may be more effective at ameliorating P loss in runoff than current TI-based legislation. Due to the high cost of amendments, their incorporation into existing management practices can only be justified on a targeted basis where inherent soil characteristics deem their usage suitable to receive amended slurry.