The spatiotemporal heterogeneity of fertosphere hotspots impacted by biochar addition and the implications for NH3 and N2O emissions.

The fertosphere, as the interfaces between fertilizer granular and soil particles, represents a key hotspot for nitrogen transformation processes, particularly for ammonia (NH3) and nitrous oxide (N2O) emissions. Understanding the heterogeneity of the fertosphere, especially when incorporating organic amendments like biochars, is crucial for predicting NH3 and N2O emissions after soil fertilization. In this study, we investigated the effects of three types of biochar (pristine, aged, and acid-washed biochar) on heterogeneity of fertosphere induced by localized urea application. pH-specific planar optodes were employed to visualize pH gradients in fertosphere hotspots with high spatial and temporal resolution. In addition, we conducted thorough measurements of the gradient distribution of electric conductivity (EC), mineral N, aqueous NH3 in soil and enzyme activities relevant to nitrification. Concurrently, NH3 and N2O emissions from the soil were continuously monitored at a high temporal resolution. Initially, urea-induced fertosphere exhibited significant NH3 emissions, primarily attributed to the pH elevation resulting from urea hydrolysis. However, after 6 days, NH3 emissions subsided, and there was a notable sharp increase in N2O emissions. Importantly, compared to urea application alone, the inclusion of pristine biochar led to a delay in soil pH decline with a 19% rise in NH3 emission. Aged biochar, characterized by a higher content of oxygen functional groups, demonstrated increased NH4+/NH3 adsorption capacity and enhanced ammonia monooxygenase (AMO) activity in soil, resulting in an 18% reduction in NH3 emission. While a slight decrease of 5% in NH3 cumulative emission was observed in the acid-washed biochar treatment. Notably, biochar could potentially promote nitrification-derived N2O emissions due to the accumulation of NH3 oxidation products (NH2OH). These findings could contribute to refining N transformation models for fertilized soils, and optimizing N fertilizer application strategies.

A mechanistic model of methane emission from animal slurry with a focus on microbial groups.

Liquid manure (slurry) from livestock releases methane (CH4) that contributes significantly to global warming. Existing models for slurry CH4 production-used for mitigation and inventories-include effects of organic matter loading, temperature, and retention time but cannot predict important effects of management, or adequately capture essential temperature-driven dynamics. Here we present a new model that includes multiple methanogenic groups whose relative abundance shifts in response to changes in temperature or other environmental conditions. By default, the temperature responses of five groups correspond to those of four methanogenic species and one uncultured methanogen, although any number of groups could be defined. We argue that this simple mechanistic approach is able to describe both short- and long-term responses to temperature where other existing approaches fall short. The model is available in the open-source R package ABM (https://github.com/sashahafner/ABM) as a single flexible function that can include effects of slurry management (e.g., removal frequency and treatment methods) and changes in environmental conditions over time. Model simulations suggest that the reduction of CH4 emission by frequent emptying of slurry pits is due to washout of active methanogens. Application of the model to represent a full-scale slurry storage tank showed it can reproduce important trends, including a delayed response to temperature changes. However, the magnitude of predicted emission is uncertain, primarily as a result of sensitivity to the hydrolysis rate constant, due to a wide range in reported values. Results indicated that with additional work-particularly on the magnitude of hydrolysis rate-the model could be a tool for estimation of CH4 emissions for inventories.

Understanding methane emission from stored animal manure: A review to guide model development.

National inventories of methane (CH4 ) emission from manure management are based on guidelines from the Intergovernmental Panel on Climate Change using country-specific emission factors. These calculations must be simple and, consequently, the effects of management practices and environmental conditions are only crudely represented in the calculations. The intention of this review is to develop a detailed understanding necessary for developing accurate models for calculating CH4 emission from liquid manure, with particular focus on the microbiological conversion of organic matter to CH4 . Themes discussed are (a) the liquid manure environment; (b) methane production processes from a modeling perspective; (c) development and adaptation of methanogenic communities; (d) mass and electron conservation; (e) steps limiting CH4 production; (f) inhibition of methanogens; (g) temperature effects on CH4 production; and (h) limits of existing estimation approaches. We conclude that a model must include calculation of microbial response to variations in manure temperature, substrate availability and age, and management system, because these variables substantially affect CH4 production. Methane production can be reduced by manipulating key variables through management procedures, and the effects may be taken into account by including a microbial component in the model. When developing new calculation procedures, it is important to include reasonably accurate algorithms of microbial adaptation. This review presents concepts for these calculations and ideas for how these may be carried out. A need for better quantification of hydrolysis kinetics is identified, and the importance of short- and long-term microbial adaptation is highlighted.

Removal of excess nutrients by Australian zeolite during anaerobic digestion of swine manure.

The objective of this study was to investigate the feasibility of using natural and NaCl-treated Australian zeolites to simultaneously remove excess nutrients from anaerobically digested swine manure. Ion adsorption and desorption properties of Australian zeolite during the anaerobic digestion of swine manure were investigated. Two experiments were conducted: the first was an adsorption experiment with multi-component solutions that corresponded with the ionic composition of swine manure digestates. The second experiment determined the effects of zeolite dose rates during anaerobic digestion of swine manure on the removal of N, P and K from solution. Adsorption isotherms confirmed selectivity for K+ over NH4+ by Australian natural and sodium zeolites. Therefore, NH4+ removal was considerably reduced when there was simultaneous K+ uptake. Natural zeolite desorbed more Ca2+ during K+ and NH4+ adsorption than sodium zeolite. The ion exchange reaction was independent of the presence of P. P removal was very dependent on the pH of the medium. Natural Australian zeolite was shown to be a potential sorbent for the removal of NH4+, K+ and P during the anaerobic digestion of swine manure. However, the application of high concentrations of zeolite at higher pH values (> 7.5) might not be appropriate for anaerobic digestion, because zeolite desorbed more Ca2+ ions into the solution at the higher doses of zeolite and then availability of P for microbial growth might be reduced as a result of PO43- precipitation with Ca2+ at the higher pH.

Biogas production from steer manures in Vietnam: Effects of feed supplements and tannin contents.

In developing countries, the simple biogas digesters installed underground without heating or stirring are seen as a 'green' technology to convert animal waste into biogas, a source of bio-energy. However, quantitative estimates of biogas production of manures from steers fed local feed diets at actual incubation temperatures have yet to be carried out. The aim of this study was to determine the methane (CH4) production potential of manures from steers in Vietnam offered traditional feed rations or supplemental diets. Biochemical CH4 production (BMP) was measured in batch tests at 30°C using manures collected from two different experiments of steers fed diets containing feed supplements. BMP was 110.1 (NLkg-1VS) for manure from steers receiving a control diet, significantly lower 79.0 (NL kg-1VS) for manure from steers fed a diet containing 0.3% tannin (%DM), but then showed an increasing trend to 90.9 and 91.2 (NL kg-1VS) for manures from steers receiving 0.4 and 0.5% tannin (%DM) supplements, respectively. Similarly, the CH4 production (NL kg-1VS) of manure from steers was 174 for control, 142 for control supplemented concentrate (C), 143 for control added rice straw treated with urea (R), and 127 for control supplemented C and R. Our results show there was a decrease in CH4 emissions from steer manures through using supplemented rations.

Transformation of Organic Matter and the Emissions of Methane and Ammonia during Storage of Liquid Manure as Affected by Acidification.

Acidification of livestock manure can reduce emission of the greenhouse gases methane (CH) and nitrous oxide (NO), as well as ammonia (NH). We examined the relation between emission of these gases and transformation of organic matter as affected by acidification. Liquid cattle manure was acidified with sulfuric acid to pH 5.5 at a pilot scale (100 L), and we measured effects on CH, NO, CO and NH emissions and on transformation of pH buffer components and organic matter. Acidification reduced NH emissions by 62% (47 d) and emission of CH by 68% (57 d). Emissions of NO were negligible, probably due to the absence of a surface crust. Reductions in NH and CH emission were highest at the start but declined over time concomitantly with a gradual increase in the stored liquid manure pH. Acidification did not significantly affect CO emissions. Emission of CO was high, five- to ten-fold of CH emissions, until Day 16 of storage, after which the CO emission rate declined to around twice the CH emission rate; consequently, the majority of C loss during the early stages of storage was CO. Cumulative emission of C in CO and CH closely matched depletion of dissolved organic carbon (DOC), suggesting that DOC may be a predictor for CH emission from dilute slurries. volatile fatty acid and total ammoniacal nitrogen concentrations in surface layers were substantially higher than at the center of stored liquid manure, perhaps resulting from microbial activity at the surface. This pattern deserves attention when predicting NH emission from stored slurry.

Estimation of Methane Emissions from Slurry Pits below Pig and Cattle Confinements.

Quantifying in-house emissions of methane (CH4) from liquid manure (slurry) is difficult due to high background emissions from enteric processes, yet of great importance for correct estimation of CH4 emissions from manure management and effects of treatment technologies such as anaerobic digestion. In this study CH4 production rates were determined in 20 pig slurry and 11 cattle slurry samples collected beneath slatted floors on six representative farms; rates were determined within 24 h at temperatures close to the temperature in slurry pits at the time of collection. Methane production rates in pig and cattle slurry differed significantly at 0.030 and 0.011 kg CH4 kg-1 VS (volatile solids). Current estimates of CH4 emissions from pig and cattle manure management correspond to 0.032 and 0.015 kg CH4 kg-1, respectively, indicating that slurry pits under animal confinements are a significant source. Fractions of degradable volatile solids (VSd, kg kg-1 VS) were estimated using an aerobic biodegradability assay and total organic C analyses. The VSd in pig and cattle slurry averaged 0.51 and 0.33 kg kg-1 VS, and it was estimated that on average 43 and 28% of VSd in fresh excreta from pigs and cattle, respectively, had been lost at the time of sampling. An empirical model of CH4 emissions from slurry was reparameterised based on experimental results. A sensitivity analysis indicated that predicted CH4 emissions were highly sensitive to uncertainties in the value of lnA of the Arrhenius equation, but much less sensitive to uncertainties in VSd or slurry temperature. A model application indicated that losses of carbon in VS as CO2 may be much greater than losses as CH4. Implications of these results for the correct estimation of CH4 emissions from manure management, and for the mitigation potential of treatments such as anaerobic digestion, are discussed.

Ammonium removal from high-strength aqueous solutions by Australian zeolite.

Removal of ammonium nitrogen (NH4(+)-N) particularly from sources which are highly rich in nitrogen is important for addressing environmental pollution. Zeolites, aluminosilicate minerals, are commonly used as commercial adsorbents and ion-exchange medium in number of commercial applications due to its high adsorption capacity of ammonium (NH4(+)). However, detailed investigations on NH4(+) adsorption and ion exchange capacities of Australian natural zeolites are rare, particularly under higher NH4(+) concentrations in the medium. Therefore, this study was conducted to determine NH4(+) adsorption characteristics of Australian natural zeolites at high NH4(+) concentrations with and without other chemical compounds in an aqueous solution. Results showed that initial NH4(+) concentration, temperature, reaction time, and pH of the solution had significant effects on NH4(+) adsorption capacity of zeolite. Increased retention time and temperature generally had a positive impact on adsorption. Freundlich model fitted well with adsorption process of Australian natural zeolites; however, Langmuir model had best fitted for the adsorption process of sodium (Na(+)) treated zeolites. NaCl treatment increased the NH4(+) adsorption capacity of Australian zeolites by 25% at 1000 mg-N, NH4(+) solution. The maximum adsorption capacity of both natural Australian zeolites and Na(+) treated zeolites were estimated as 9.48 and 11.83 mg-N/g, respectively, which is lower than many zeolites from other sources. Compared to the NH4(+) only medium, presence of other competitive ions and acetic acid in the medium (resembling composition in digested swine manure slurries) reduced NH4(+) removal of natural and Na(+) treated zeolites by 44% and 57%, respectively. This suggests detailed investigations are required to determine practically achievable NH4(+) -N removal potential of zeolites for applications in complex mediums such as animal manure slurries.

Comprehensive microbial analysis of combined mesophilic anaerobic-thermophilic aerobic process treating high-strength food wastewater.

A combined mesophilic anaerobic-thermophilic aerobic process was used to treat high-strength food wastewater in this study. During the experimental period, most of solid residue from the mesophilic anaerobic reactor (R1) was separated by centrifugation and introduced into the thermophilic aerobic reactor (R2) for further digestion. Then, thermophilic aerobically-digested sludge was reintroduced into R1 to enhance reactor performance. The combined process was operated with two different Runs: Run I with hydraulic retention time (HRT) = 40 d (corresponding OLR = 3.5 kg COD/m(3) d) and Run II with HRT = 20 d (corresponding OLR = 7 kg COD/m(3)). For a comparison, a single-stage mesophilic anaerobic reactor (R3) was operated concurrently with same OLRs and HRTs as the combined process. During the overall digestion, all reactors showed high stability without pH control. The combined process demonstrated significantly higher organic matter removal efficiencies (over 90%) of TS, VS and COD and methane production than did R3. Quantitative real-time PCR (qPCR) results indicated that higher populations of both bacteria and archaea were maintained in R1 than in R3. Pyrosequencing analysis revealed relatively high abundance of phylum Actinobacteria in both R1 and R2, and a predominance of phyla Synergistetes and Firmicutes in R3 during Run II. Furthermore, R1 and R2 shared genera (Prevotella, Aminobacterium, Geobacillus and Unclassified Actinobacteria), which suggests synergy between mesophilic anaerobic digestion and thermophilic aerobic digestion. For archaea, in R1 methanogenic archaea shifted from genus Methanosaeta to Methanosarcina, whereas genera Methanosaeta, Methanobacterium and Methanoculleus were predominant in R3. The results demonstrated dynamics of key microbial populations that were highly consistent with an enhanced reactor performance of the combined process.

Choosing co-substrates to supplement biogas production from animal slurry--a life cycle assessment of the environmental consequences.

Biogas production from animal slurry can provide substantial contributions to reach renewable energy targets, yet due to the low methane potential of slurry, biogas plants depend on the addition of co-substrates to make operations profitable. The environmental performance of three underexploited co-substrates, straw, organic household waste and the solid fraction of separated slurry, were assessed against slurry management without biogas production, using LCA methodology. The analysis showed straw, which would have been left on arable fields, to be an environmentally superior co-substrate. Due to its low nutrient content and high methane potential, straw yields the lowest impacts for eutrophication and the highest climate change and fossil depletion savings. Co-substrates diverted from incineration to biogas production had fewer environmental benefits, due to the loss of energy production, which is then produced from conventional fossil fuels. The scenarios can often provide benefits for one impact category while causing impacts in another.

Thermic model to predict biogas production in unheated fixed-dome digesters buried in the ground.

In many developing countries, simple biogas digesters are used to produce energy for domestic purposes from anaerobic digestion of animal manure. We developed a simple, one-dimensional (1-D), thermal model with easily available input data for unheated, unstirred, uninsulated, fixed-dome digesters buried in the soil to study heat transfer between biogas digester and its surroundings. The predicted temperatures in the dome, biogas, and slurry inside the digester and the resulting biogas production are presented and validated. The model was well able to estimate digester temperature (linear slope nearly 1, R(2) = 0.96). Model validation for methane production gave root-mean-square error (RMSE) of 54.4 L CH4 digester(-1) day(-1) and relative-root-mean-square errors (rRMSEP(%)) of 35.4%. The validation result was considerably improved if only using winter data (RMSE = 26.1 L CH4 digester(-1) day(-1); rRMSEP(%) = 17.7%). The model performed satisfactorily in light of the uncertainties attached to it. Since unheated digesters suffer critically low methane production during the winter, the model could be particularly useful for assessing methane production and for improving the ability of unheated digesters to provide sufficient energy during cold periods.

Biochemical methane potential and anaerobic biodegradability of non-herbaceous and herbaceous phytomass in biogas production.

The suitability of municipal plant waste for anaerobic digestion was examined using 57 different herbaceous and non-herbaceous samples. Biochemical methane potential (BMP) and anaerobic biodegradability were related to the degree of lignification and crystallinity of cellulose. The BMP of herbaceous garden plants (332.7 CH(4)NL kg VS(-1)) was high, although lower than that of energy crops (400-475 CH(4)NL kg VS(-1)). Herbaceous wild plants from natural grassland contained most lignocelluloses, leading to relatively low BMP (214.0 CH(4)NL kg VS(-1)). Non-herbaceous phytomass had a high degree of lignification and a high concentration of crystalline cellulose, but due to the content of non-woody parts with a low concentration of lignocellulose the BMP was relatively high, 199.9 and 172.0 CH(4)NL kg VS(-1) for hedge cuttings and woody cuttings, respectively. There were indications that a plant lignin concentration of 100 g kg VS(-1) is the critical biodegradability point in anaerobic digestion of phytomass.

A new algorithm to characterize biodegradability of biomass during anaerobic digestion: influence of lignin concentration on methane production potential.

We examined the influence of fibrous fractions of biomass on biochemical methane potential (BMP) with the objective of developing an economical and easy-to-use statistical model to predict BMP, and hence the biodegradability of organic material (BD) for biogas production. The model was developed either for energy crops (grass, maize, and straw) or for animal manures, or as a combined model for these two biomass groups. It was found that lignin concentration in volatile solids (VS) was the strongest predictor of BMP for all the biomass samples. The square of the sample correlation coefficient (R(2)) from the BMP versus lignin was 0.908 (p<0.0001), 0.763 (p<0.001) and 0.883 (p<0.001) for animal manure, energy crops and the combined model, respectively. Validation of the combined model was carried out using 65 datasets from the literature.

Biological degradation and greenhouse gas emissions during pre-storage of liquid animal manure.

Storage of manure makes a significant contribution to global methane (CH4) emissions. Anaerobic digestion of pig and cattle manure in biogas reactors before outside storage might reduce the potential for CH4 emissions. However, manure pre-stored at 15 to 20 degrees C in buildings before anaerobic digestion may be a significant source of CH4 and could reduce the potential CH4 production in the biogas reactor. Degradation of energy-rich organic components in slurry and emissions of CH4 and carbon dioxide (CO2) from aerobic and anaerobic degradation processes during pre-storage were examined in the laboratory. Newly mixed slurry was added to vessels and stored at 15 and 20 degrees C for 100 to 220 d. During storage, CH4 and CO2 emissions were measured with a dynamic chamber technique. The ratio of decomposition in the subsurface to that at the surface indicated that the aerobic surface processes contributed significantly to CO2 emission. The measured CH4 emission was used to calculate the methane conversion factor (MCF) in relation to storage time and temperature, and the total carbon-C emission was used to calculate the decrease in potential CH4 production by anaerobic digestion following pre-storage. The results show substantial methane and carbon dioxide production from animal manure in an open fed-batch system kept at 15 to 20 degrees C, even for short storage times, but the influence of temperature was not significant at storage times of <30 d. During long-term storage (90 d), a strong influence of temperature on the MCF value, especially for pig manure, was observed.

Reduction of ammonia emission by shallow slurry injection: injection efficiency and additional energy demand.

Ammonia (NH3) emission from livestock production causes undesirable environmental effects and a loss of plant-available nitrogen. Much atmospheric NH3 is lost from livestock manure applied in the field. The NH3 emission may be reduced by slurry injection, but slurry injection in general, and especially on grassland, increases the energy demand and places heavy demands on the slurry injection techniques used. The reduction in NH3 emission, injection efficiency, and energy demand of six different shallow slurry-injection techniques was examined. The NH3 emission from cattle slurry applied to grassland was reduced by all the injectors tested in the study, but there were major differences in the NH3 reduction potential of the different types of injectors. Compared with the trailing hose spreading technique, the NH3 loss was reduced by 75% when cattle slurry was injected using the most efficient slurry injection technique, and by 20% when incorporated by the least efficient injection technique. The reduction in NH3 emission was correlated with injection depth and the volume of the slot created. The additional energy demand for reducing ammonia emissions by slurry injection was approximately 13 000 kJ ha(-1) for a 20% reduction and 34 000 kJ ha(-1) for a 75% reduction. The additional energy demand corresponds to additional emissions of, respectively, 5.6 and 14.5 kg CO2 per ha injected.

Ammonia, methane, and nitrous oxide emission from pig slurry applied to a pasture in New Zealand.

Much animal manure is being applied to small land areas close to animal confinements, resulting in environmental degradation. This paper reports a study on the emissions of ammonia (NH3), methane (CH4), and nitrous oxide (N2O) from a pasture during a 90-d period after pig slurry application (60 m3 ha-1) to the soil surface. The pig slurry contained 6.1 kg total N m-3, 4.2 kg of total ammoniacal nitrogen (TAN = NH3 + NH4) m-3, and 22.1 kg C m-3, and had a pH of 8.14. Ammonia was lost at a fast rate immediately after slurry application (4.7 kg N ha-1 h-1), when the pH and TAN concentration of the surface soil were high, but the loss rate declined quickly thereafter. Total NH3 losses from the treated pasture were 57 kg N ha-1 (22.5% of the TAN applied). Methane emission was highest (39.6 g C ha-1 h-1) immediately after application, as dissolved CH4 was released from the slurry. Emissions then continued at a low rate for approximately 7 d, presumably due to metabolism of volatile fatty acids in the anaerobic slurry-treated soil. The net CH4 emission was 1052 g C ha-1 (0.08% of the carbon applied). Nitrous oxide emission was low for the first 14 d after slurry application, then showed emission peaks of 7.5 g N ha-1 h-1 on Day 25 and 15.8 g N ha-1 h-1 on Day 67, and decline depending on rainfall and nitrate (NO3) concentrations. Emission finally reached background levels after approximately 90 d. Nitrous oxide emission was 7.6 kg N ha-1 (2.1% of the N applied). It is apparent that of the two major greenhouse gases measured in this study, N2O is by far the more important tropospheric pollutant.