Phosphorus speciation in different sewage sludges and their biochars and its implications for movement of labile phosphate in two soils.

It is essential to understand the P dynamics of recycled biomaterials, like biochar derived from sewage sludge, especially with potential application as fertilizers. The objective of this study was to understand how pyrolysis affects the speciation of P in sewage sludge and thereby the effect on labile P pools and mobility of P in soil. The P speciation and lability of two sewage sludges (one biologically treated and one iron-precipitated) and their biochars (pyrolyzed at 400 °C and 600 °C) were determined by liquid state 31P nuclear magnetic resonance spectroscopy, X-ray absorption near edge spectroscopy, and sequential chemical extraction. These biomaterials were applied in a concentrated band to two soils, and P lability was studied in the adjacent soil at varying distances. Speciation techniques showed P was more closely associated with Ca and Fe for the iron-precipitated sludge and its biochars than the biologically treated sludge and its biochars. Instead, the P in the biologically treated biochars was found to be largely (40% or more) in polymeric forms (pyro- or poly-phosphates). The relationship between the speciation and the mobility of P in soil (as assessed by incubating biomaterials in a one-dimensional reaction system) was more evident when incubating the sewage sludges than the respective biochars. Particularly, the biologically treated sludge had a high proportion of labile P (56% water-extractable P), as determined by sequential extraction, and upon incubation, it was also the only material where water-extractable P remained significantly above the control soil level up to 3 mm from the biomaterial layer. After pyrolysis, this lability decreased significantly (up to a 25-fold decrease in water-extractable P), and this was reflected in the immobility of P in the biochars during incubation in the two soils. Differences in speciation between biochars were not reflected in the incubation experiment, as the differences in P release and mobility were not significant.

Constructed wetlands and duckweed ponds as a treatment step in liquid manure handling - A life cycle assessment.

Life cycle assessment (LCA) was applied to evaluate duckweed ponds and constructed wetlands as polishing steps in pig manure liquid fraction treatment. Using nitrification-denitrification (NDN) of the liquid fraction as the starting point, the LCA compared direct land application of the NDN effluent with different combinations of duckweed ponds, constructed wetlands and discharge into natural waterbodies. Duckweed ponds and constructed wetlands are viewed as a viable tertiary treatment option and potential remedy for nutrient imbalances in areas of intense livestock farming, such as in Belgium. As the effluent stays in the duckweed pond, settling and microbial degradation reduce the remaining phosphorous and nitrogen concentrations. Combined with duckweed and/or wetland plants that take up nutrients in their plant body, this approach can reduce over-fertilisation and prevent excessive nitrogen losses to aquatic environments. In addition, duckweed could serve as an alternative livestock feed and replace imports of protein destined for animal consumption. The environmental performance of the overall treatment systems studied was found to depend greatly on assumptions about the possible avoidance of potassium fertiliser production through the field application of effluents. If it is assumed that the potassium contained in the effluent replaces mineral fertiliser, direct field application of the NDN effluent performed best. If the application of NDN effluent does not lead to mineral fertiliser savings or if the replaced K fertiliser is of low grade, duckweed ponds seem to be a viable additional step in the manure treatment chain. Consequently, whenever background concentrations of N and/or P in fields allow for effluent application and potassium fertiliser substitution, direct application should be favoured over further treatment. If direct land application of the NDN effluent is not an option, the focus should be on long residence times in duckweed ponds to allow for maximum nutrient uptake and feed production.

Effect of nitrification inhibitor (DMPP) on nitrous oxide emissions from agricultural fields: Automated and manual measurements.

Nitrogen fertilisation contributes significantly to the atmospheric increase of nitrous oxide (N2O). Application of nitrification inhibitors (NIs) is a promising strategy to mitigate N2O emissions and improve N-use efficiency in agricultural systems. This study investigated the effect of NI, 3,4-dimethylpyrazol phosphate (DMPP) on N2O mitigation from spring barley and spring oilseed rape. Manual and automatic chamber methodologies were used to capture spatial and temporal variability in N2O emissions. In a second experiment, we study the effect of N fertiliser levels without NI (0 %, 50 %, 100 %, 150 % and 200 % of recommended amount of N fertiliser), as well as 100 % of N with NI on N2O emissions in spring barley. The automated chamber measurements showed dynamics of N2O changes throughout the season, including positive and negative peaks that were unobservable with manual chambers due to low temporal resolution. Although not significant, application of NI tended to reduce N2O emissions. The reduction was on average 16 % in spring barley and 58 % in spring oilseed rape in manual chamber measurements. However, N2O reduction was 108 % in continuous automatic chamber measurements in spring barley. The N2O EFs for the growing season were very low (0.025 % to 0.148 %), with a greater reduction in EF in spring oilseed rape (76 %) than in spring barley (32 %) with NI application. A positive correlation (R = 80 %) was observed between N fertiliser levels and N2O emissions. Crop yield and crop N uptake were not significantly affected by the use of NI. This study highlighted that NI can reduce N2O emissions, but the reduction effects are plot, crop and microclimate specific. Long-term experiments with continuous plot-scale measurements are needed to capture and optimise N2O mitigation effect of NIs across wide variability in soils and microclimates in agroecosystems.

Life cycle assessment of struvite recovery and wastewater sludge end-use: A Flemish illustration.

Phosphate rock (PR) has been designated as a Critical Raw Material in the European Union (EU). This has led to increased emphasis on alternative P recovery (APR) from secondary streams like wastewater sludge (WWS). However, WWS end-use is a contentious topic, and EU member states prefer different end-use pathways (land application/incineration/valorisation in cement kilns). Previous Life Cycle Assessments (LCA) on APRs from WWS reached contrasting conclusions; while most considered WWS as waste and highlighted a net benefit relative to PR mining and beneficiation, others viewed WWS as a resource and highlighted a net burden of the treatment. We used a combined functional unit (that views WWS from a waste as well as a resource perspective) and applied it on a Flemish wastewater treatment plant (WWTP) with struvite recovery as APR technology. Firstly, a retrospective comparison was performed to measure the WWTP performance before and after struvite recovery and the analysis was complemented by uncertainty and global sensitivity analyses. The results showed struvite recovery provides marginal environmental benefits due to improved WWS dewatering and reduced polymer use. Secondly, a prospective LCA approach was performed to reflect policy changes regarding WWS end-use options in Flanders. Results indicated complete mono-incineration of WWS, ash processing to recover P and the subsequent land application appears to be less sustainable in terms of climate change, human toxicity, and terrestrial acidification relative to the status quo, i.e., co-incineration with municipal solid waste and valorisation at cement kilns. Impacts on fossil depletion, however, favour mono-incineration over the status quo.

Adequacy of nitrogen-based indicators for assessment of cropping system performance: A modelling study of Danish scenarios.

The EU nitrogen expert panel (EUNEP) has proposed nitrogen-based indicators for farm productivity (N output), efficiency (NUE) and environmental emissions (N surplus). This model-based study (using the Daisy model) was carried out, i) to study the effects of soil type, soil organic matter (SOM), cropping pre-histories varying in C input, 3-to-4 manure-to-mineral N proportions and ten crop rotations on the N-based indicators, and ii) to evaluate the adequacy of these indicators by establishing quantitative relationships between N surplus, N loss and soil organic N (SON) stock change. The results, averaged over 24-year simulation period, indicated that grass-clover dominant rotations had highest N output and showed a tendency to increase SON stocks when compared with spring-cereal monocultures. For most rotations, the NUE ranged between 70 and 75 %. The SON stocks were mainly influenced by initial SOM and cropping prehistory, and stocks increased only under low initial SOM and low C input cropping pre-history (spring barley). Overall, SON stocks tended to increase under low C input pre-history, coarse sand, low initial SOM and high manure N, however, this combination did not result in highest productivity, NUE, and lowest N losses. The relations between N surplus, N loss and SON stock change were strongly affected by crop rotations, emphasizing that using N surplus as an indicator for N leaching/losses while ignoring changes in SON stocks may result in biased conclusions, e.g. estimated average error for N losses ranged from -45 % (underestimation) for maize monoculture to +50 % (overestimation) for continuous grass-clover ley. The results also imply that the environmental assessment of cropping systems must be improved by combining above indicators with estimation of N loss and SON stock changes. This study provides a detailed account of N balance components/N indicators for diverse crop rotations and their use according to the recommendations of the EUNEP.

Application of Fourier transform mid-infrared photoacoustic spectroscopy for rapid assessment of phosphorus availability in digestates and digestate-amended soils.

Digestate is the anaerobic digestion by-product of biogas production that can be used as a phosphorus (P) fertilizer. To achieve the efficient utilization of digestate as a P fertilizer and evaluate P availability in digestate-amended soils, it is necessary to assess both available P in different digestates and digestate-amended soils. In this study, Fourier transform mid-infrared photoacoustic spectroscopy (FTIR-PAS) combined with multivariate analysis was applied to predict water-extractable P (WEP) in digestates and plant-available P in digestate-amended soils. The plant-available P was determined by the diffusive gradients in thin films (DGT) technique. 45 digestate samples were collected both from laboratory-scale digesters (26 samples) and operating biogas plants (19 samples) in Denmark for WEP determination. Three soils amended with the collected 19 digestate samples from biogas plants (that results to 57 digestate-amended soil samples in total) were deployed for DGT measurement of plant- available P. The WEP predicting model had a coefficient of determination (R2) of 0.80 and a root mean square error of 0.78 g kg-1 while the plant-available P predicting model exhibited an R2 of 0.70 and a root mean square error of 134.09 µg P L-1. Furthermore, regression coefficients with a significant contribution of the plant-available P predicting model were identified, indicating that FTIR-PAS is capable for correlating spectra information with plant-available P related chemical bonds. In conclusion, FTIR-PAS can be used as a faster and non-destructive alternative for the assessment of both WEP in digestates and plant-available P in digestate-amended soils.

Depth profiles of soil organic carbon isotopes across a lithosequence: implications for drivers of soil δ13C vertical changes.

To addresshow parent materials are affecting organic carbon dynamics in a soil profile, soils from a lithosequence comprising six parent lithologies under a rangeland ecosystem have been explored at three depth intervals for soil organic carbon (SOC) content and its 13C depth trends. Studied parent materials ranged from metamorphic (foliated: FM and non-foliated: NFM) to sedimentary (clastic carbonate: CCS) to plutonic (intermediate: IP, felsic: FP and intermediate felsic: IFP) geological contexts. The relationship between SOC concentration and its isotopic signatures to a depth of 50 cm in FM, NFM, FP and IFP profiles was well described by the kinetic fractionation of SOC during biodegradation. For CCS and IP lithologies, strong divergence from the Rayleigh equation was observed suggesting that the 13C enrichments in these soils resulted from both mixing different SOC pools and isotope fractionation related to the C mineralization. Results suggest that SOC across the lithosequence goes through different isotopic evolutions resulting from different 13C-enriched inputs and pedogenic properties as described by the extended Rayleigh equation (0 ≤ ßC ≤ 0.80). These are presumably caused by the bedrock lithology implying that parent material affects C storage and dynamics.

Scenario analysis using the Daisy model to assess and mitigate nitrate leaching from complex agro-environmental settings in Denmark.

Nitrate (N) leaching from intensively managed cropping systems is of environmental concern and it varies at local scale. To evaluate the performance of agricultural practices at this scale, there is a need to develop comprehensive assessments of N leaching and the N leaching reduction potential of mitigation measures. A model-based analysis was performed to (i) estimate N leaching from Danish cropping systems, representing 20 crop rotations, 3 soil types, 2 climates and 3-4 levels of manure (slurry)-to-fertilizer ratios, but with same available N (according to regulatory N fertilization norms), and (ii) appraise mitigation potential of on-farm measures (i.e. catch crops, early sowing of winter cereals) to reduce N leaching. The analysis was performed using a process-based agro-environmental model (Daisy). Simulated average N leaching over 24 years ranged from 16 to 85 kg N/ha/y for different crop rotations. Rotations with a higher proportion of spring crops were more prone to leaching than rotations having a higher proportion of winter cereals and semi-perennial grass-clover leys. N leaching decreased with increasing soil clay content under all conditions. The effect of two climates (different regions, mainly differing in precipitation) on N leaching was generally similar, with slight variation across rotations. Supplying a part of the available N as manure-N resulted in similar N leaching as mineral fertilizer N alone during the simulation period. Among the mitigation measures, both undersown and autumn sown catch crops were effective. Effectiveness of measures also depended on their place and frequency of occurrence in a rotation. Adopting catch crops during the most leaching-prone years and with higher frequency were effective choices. This analysis provided essential data-driven knowledge on N leaching risk, and potential of leaching reduction options. These results can serve as a supplementary guiding-tool for farmers to plan management practices, and for legislators to design farm-specific regulatory measures.

Prediction of biochemical methane potential of urban organic waste using Fourier transform mid-infrared photoacoustic spectroscopy and multivariate analysis.

Biochemical methane potential (BMP) assays are widely used to assess feedsocks in oder to control the process of biogas production. However, the continuous evaluation of feedstocks using a BMP assay is expensive, time-consuming and challenging. In this study, Fourier transform mid-infrared photoacoustic spectroscopy (FTIR-PAS) was used to predict the BMP values of 87 urban organic waste (UOW) samples derived from different sources in Denmark. The developed model of BMP prediction showed a coefficient of determination (R2) of 0.86 and a root mean square error (RMSE) of 59.3 mL CH4/g VS in prediction. The interpretation of the regression coefficients used in the calibration showed a positive correlation with BMP for relatively easily degradable compounds, such as aliphatics, most likely lipids and amides most likely in proteins, while a negative correlation was found with lignin and hemicellulose.

Increasing plant phosphorus availability in thermally treated sewage sludge by post-process oxidation and particle size management.

Thermal conversion of phosphorus (P)-rich waste materials such as sewage sludge offers several advantages: generation of bioenergy, concentration of plant nutrients and the destruction of organic pollutants. Different thermal processes modify the feedstock's chemical and physical structure in differing ways, which also affects P speciation and plant availability in the residual ashes or carbonization products. This study assessed to which extent the P plant availability of ashes and chars produced from one batch of sewage sludge by incineration, pyrolysis or gasification was affected by particle size management and post-process oxidation. Overall, a smaller particle size of the materials as well as post-process oxidation of non-oxidized materials increased the amount of plant-available P in the soil. In a pot experiment, all the materials increased plant biomass compared with the untreated control, but the pyrolysis chars had a substantially greater fertiliser value than the gasification ashes, while the two tested incineration ashes differed in their P fertilizing effect. P availability in non-oxidized materials was partly related to lower process temperatures and lower levels of crystallinity. However, downstream oxidation simultaneously increased crystallinity and P availability in a pyrolysis char and gasification ashes, resulting in an increase in plant P uptake of up to 60%. Results indicate that the oxidation of poorly soluble Fe-phosphates may contribute to the positive effect on P availability. The results suggest that changes to the design and settings of the thermal conversion processes of sewage sludge offer considerable potential for improving P availability in the residual material.

Three different Fourier-transform mid-infrared sampling techniques to characterize bio-organic samples.

In recent years, there has been a surge in the number of applications of Fourier-transform mid-infrared (FTIR) spectroscopy for the characterization of environmental samples and prediction of some of their properties whose measurement has traditionally involved time-consuming and costly methods. However, there are several different mid-infrared techniques available, and there is a gap in knowledge regarding the best-suited technique for recording informative spectra of different types of environmental samples. This study compared the three most widespread FTIR techniques using solid and liquid samples. A total of 11 environmental samples belonging to four categories were analyzed with attenuated total reflectance (ATR), photoacoustic (PAS), and diffuse reflectance (DR) FTIR spectroscopy. Overall, PAS-FTIR was the best technique, providing a greater amount of information, especially for opaque samples (i.e., organic waste, biochar, and soil), than ATR-FTIR and DR-FTIR spectroscopy. Attenuated total reflectance FTIR provided the best spectra for soft samples, such as plant materials, probably due to their ability to achieve good optical contact with the ATR crystal. Finally, DR-FTIR performed relatively well for most samples but was found to be more sensitive to moisture in the samples, resulting in noise in specific areas, and was less sensitive in bond vibrations related to Si.

Developing a management-oriented simulation model of pesticide emissions for use in the life cycle assessment of paddy rice cultivation.

Management of the negative environmental impact of pesticides used in paddy fields requires the quantification of the emissions reaching relevant environmental compartments and the determination of the factors that influence such emissions. The present study is the first to develop a simulation model for estimating the fractions emitted to the air (fair), surface water (fsw), and the fractions that leach vertically (fvl) of pesticides applied in paddy fields for life cycle assessments (LCA). The emission quantification methods are based on the properties of the active ingredients of the pesticides and management aspects such as formulations (granular or liquid) and the water-holding period following application. The emission fractions of 37 pesticides used commonly in Japan were estimated using the presented model. A sensitivity analysis was conducted by adjusting parameters applied in the model to reveal their influence on the emission fractions. The parameters influencing fair included the formulation applied, while the water-holding period and waterproofing of the levee influenced fsw regardless of the formulation adopted, suggesting that local management could effectively reduce emissions to surface water. In addition, soil organic carbon content influenced fvl greatly, suggesting considerable regional variation in the emission factor. The developed model is expected to greatly improve the realism of impact assessment of pesticide in LCAs for paddy rice cultivation, considering it fills a gap in the fate model used in LCAs to estimate pesticide emissions to air, surface water, and soil in paddy fields.

Life cycle assessment of garden waste management options including long-term emissions after land application.

A life cycle assessment (LCA) was performed on five garden waste treatment practices: the production of mature compost including the woody fraction (MCIW), the production of mature compost without the woody fraction (MCWW), the production of immature compost without the woody fraction (ICWW), fresh garden waste including the woody fraction (GWIW) and fresh garden waste without the woody fraction (GWWW). The assessment included carbon sequestration after land application of the garden waste and composts, and associated emissions. The removed woody fraction was incinerated and energy recovery included as heat and electricity. The functional unit of the assessment was treatment of 1000 kg of garden waste generated in Denmark. Overall, the results showed that composting of garden waste resulted in comparable or higher environmental impact potentials (depletion of abiotic resources, marine eutrophication, and terrestrial eutrophication and acidification) than no treatment before land application. The toxicity potentials showed the highest normalised impact potentials for all the scenarios, but were unaffected by the different garden waste treatments. The choice of energy source for substituted heat and electricity production affected the performance of the different treatment scenarios with respect to climate change. The scenarios with removal of the woody fraction performed better than the scenarios without removal of the woody fraction when fossil energy sources were substituted, but performed worse when renewable energy sources were substituted. Furthermore, the study showed the importance of including long-term emission factors after land application of fresh and composted garden waste products since the greatest proportion of carbon and nitrogen emissions occurred after land application in three out of the five scenarios for carbon and in all scenarios for nitrogen.

Low crystalline apatite in bone char produced at low temperature ameliorates phosphorus-deficient soils.

Globally, more than 30% of soils are poor in phosphorus (P) and the productivity of these soils is severely restricted without the addition of P fertiliser. With future P supplies becoming limited, it is becoming increasingly important to identify ways of optimising the use of waste materials as P fertilisers. One technology that has been promoted extensively in recent years to improve quality of degraded soils is the application of biochar. In this context, char produced from recycled animal bone is of special interest because of its high P content (∼15%). This study investigated how production temperature affects chemical P forms in bone char and the impact on soil P availability in different P-deficient soils. The major P form in dried bone meal was poorly crystalline hydroxyapatite. As the pyrolysis temperature increased to 1050 °C, the hydroxyapatite structure measured with X-ray absorption near edge structure (XANES) spectroscopy persisted. Furthermore, crystallinity increased at temperatures above 750 °C, as revealed by X-ray powder diffraction (XRD). Plant availability was highest for bone char produced between 300 °C and 500 °C in three acidic soils from three continents, and declined rapidly above 750 °C. This strongly indicated that crystallinity of hydroxyapatite limits plant availability at high pyrolysis temperatures. In a high pH soil, all materials resulted in low P availability. As pyrolysis increased the P availability in comparison with dried bone, it was concluded that bone char produced at temperatures between 300 °C and 500 °C has the potential to improve fertility of P-poor, low pH soils.

Biogas Digester Hydraulic Retention Time Affects Oxygen Consumption Patterns and Greenhouse Gas Emissions after Application of Digestate to Soil.

Knowledge about environmental impacts associated with the application of anaerobic digestion residue to agricultural land is of interest owing to the rapid proliferation of biogas plants worldwide. However, virtually no information exists concerning how soil-emitted NO is affected by the feedstock hydraulic retention time (HRT) in the biogas digester. Here, the O planar optode technique was used to visualize soil O dynamics following the surface application of digestates of the codigestion of pig slurry and agro-industrial waste. We also used NO isotopomer analysis of soil-emitted NO to determine the NO production pathways, i.e., nitrification or denitrification. Two-dimensional images of soil O indicated that anoxic and hypoxic conditions developed at 2.0- and 1.5-cm soil depth for soil amended with the digestate produced with 15-d (PO15) and 30-d (PO30) retention time, respectively. Total NO emissions were significantly lower for PO15 than PO30 due to the greater expansion of the anoxic zone, which enhanced NO reduction via complete denitrification. However, cumulative CO emissions were not significantly different between PO15 and PO30 for the entire incubation period. During incubation, NO emissions came from both nitrification and denitrification in amended soils. Increasing the HRT of the biogas digester appears to induce significant NO emissions, but it is unlikely to affect the NO production pathways after application to soil.

Earthworms change the quantity and composition of dissolved organic carbon and reduce greenhouse gas emissions during composting.

Dissolved organic carbon (DOC) has recently been proposed as an indicator of compost stability. We assessed the earthworms' effect on DOC content and composition during composting, and linked compost stability to greenhouse gas emissions and feeding ratio. Earthworms reduced total DOC content, indicating larger stability of vermicompost than of thermophilic compost. The concentrations of humic acid and fulvic acid were reduced by earthworms, whereas there was no significant effect on hydrophobic neutrals and hydrophilics. The humic acid fraction was depleted more quickly than the other compounds, indicating humic acid degradation during composting. The optimum feeding ratio decreased DOC content compared to the high feeding ratio. The lowest N2O emissions were also observed at the optimum feeding ratio. Our study confirmed the use of DOC content and composition as an indicator of compost stability and suggested that feeding ratio should be considered when assessing the earthworms' effect on stabilisation and greenhouse gas emissions.

Predicting the ethanol potential of wheat straw using near-infrared spectroscopy and chemometrics: The challenge of inherently intercorrelated response functions.

The combination of NIR spectroscopy and chemometrics is a powerful correlation method for predicting the chemical constituents in biological matrices, such as the glucose and xylose content of straw. However, difficulties arise when it comes to predicting enzymatic glucose and xylose release potential, which is matrix dependent. Further complications are caused by xylose and glucose release potential being highly intercorrelated. This study emphasizes the importance of understanding the causal relationship between the model and the constituent of interest. It investigates the possibility of using near-infrared spectroscopy to evaluate the ethanol potential of wheat straw by analyzing more than 1000 samples from different wheat varieties and growth conditions. During the calibration model development, the prime emphasis was to investigate the correlation structure between the two major quality traits for saccharification of wheat straw: glucose and xylose release. The large sample set enabled a versatile and robust calibration model to be developed, showing that the prediction model for xylose release is based on a causal relationship with the NIR spectral data. In contrast, the prediction of glucose release was found to be highly dependent on the intercorrelation with xylose release. If this correlation is broken, the model performance breaks down. A simple method was devised for avoiding this breakdown and can be applied to any large dataset for investigating the causality or lack of causality of a prediction model.

Does the combination of biochar and clinoptilolite enhance nutrient recovery from the liquid fraction of biogas digestate?

Concentrating nutrients on biochar and clinoptilolite and subsequently using the nutrient-enriched sorbents as a fertiliser could be an alternative way to manage nutrients in digestate. In this study, we investigated the use of biochar and clinoptilolite columns in removing ammonium, potassium, orthophosphate and dissolved organic carbon (DOC) from the liquid fraction of digestate. Our objectives were to investigate the effect of the initial loading ratio between liquid and biochar on nutrient removal, and to investigate the effect of combining biochar with clinoptilolite on nutrient and DOC removal efficiency. Increasing the initial loading ratios increased nutrient concentrations on biochar to 8.61 mg NH4-N g-1, 1.95 mg PO4-P g-1 and 13.01 mg DOC g-1, but resulted in decreasing removal efficiencies. The combination of biochar and clinoptilolite resulted in improved ammonium, potassium and DOC removal efficiencies compared to biochar alone, but did not significantly change PO4-P removal efficiencies. Removal efficiencies with combined sorbents were up to 67% for ammonium, 58% for DOC and 58% for potassium. Clinoptilolite showed higher removal efficiencies compared to biochar alone, and combining clinoptilolite with biochar improved only total P removal efficiency. Concentrating nutrients with clinoptilolite and biochar may be an option when both sorbents are available at low cost.

The effect of different pyrolysis temperatures on the speciation and availability in soil of P in biochar produced from the solid fraction of manure.

Biochar application to agricultural land has been proposed as a means for improving phosphorus (P) availability in soil. The purpose of the current study was to understand how pyrolysis temperature affects P speciation in biochar and how this affects availability of P in the amended soil. Biochar was produced at different temperatures from digestate solids. The primary species of P in digestate solids were simple calcium phosphates. However, a high co-occurrence of magnesium (Mg) and P, indicated that struvite or other magnesium phosphates may also be important species. At low temperatures, pyrolysis had little effect on P speciation; however, as the temperature increased above 600 °C, the P gradually became more thermodynamically stable in species such as apatite. At very high temperatures above 1000 °C, there were indications of reduced forms of P. Biochar production decreased the immediate availability of P in comparison with the original digestate solids. However, for biochar produced at low temperatures, availability quickly increased to the same levels as in the digestate solids. For biochar produced at higher temperatures, availability remained depressed for much longer. The low availability of P in the biochar produced at high temperatures can probably be explained by the formation of less soluble P species in the biochar. In contrast, the transient decrease of availability of the P in the biochar produced at low temperatures can be explained by mechanisms, such as sorption on biochar, which gradually decreases because of oxidation of the biochar surfaces or changes in pH around the biochar particles.