Effect of anaerobic digestion on odor and ammonia emission from land-applied cattle manure.

High ammonia (NH3) and odor emission can occur after land application of liquid animal manure. This study was aimed at evaluating NH3 loss and odor nuisance after field application of cattle manure and how it is affected by two anaerobic digestion strategies: i) digestion of cattle manure alone and ii) digestion with catch crops and dilution by water. A system of dynamic chambers with online measurements of NH3 and odorous compounds (summarized as odor activity value, OAV) was used. Two experiments were conducted under different temperature conditions. The results demonstrated that anaerobic digestion did not affect NH3 loss but did decrease OAV. Addition of catch crops and water to the digestion process reduced both NH3 loss and OAV. Cool temperature in one of the experiments had a large effect on both NH3 and odor emissions, and at high temperature the differences between treatments increased.

Effectiveness of mechanical separation for reducing ammonia loss from field-applied slurry: Assessment through literature review and model calculations.

To assess solid-liquid separation as a technology to reduce ammonia (NH3) emission from storage and field application of animal slurry, it is necessary to consider a possible higher NH3 loss from the solid fraction after application than from raw slurry, as well as losses during storage. A literature review was conducted, and a case study was developed for Denmark, including cattle slurry, pig slurry, and biogas digestate applied by trailing hose, trailing shoe, or open slot injection at five different periods of the year. Standard storage emission factors were used and emission factors after field application were estimated using the ALFAM2 model with input data for dry matter (DM), pH, total ammoniacal nitrogen (TAN), and separation efficiency all from the literature compilation. In general, a clear reduction in the emission factors after application of the liquid fraction was found relative to application of raw slurry in the literature data. Case study results provide some evidence that separation of cattle slurry or digestate, followed by storage and subsequent application by trailing hose or trailing shoe of the liquid fraction and broadcast application of the solid fraction reduces overall NH3 loss, with a higher reduction when the solid fraction is incorporated by plowing after 4 h. This effect was not present for pig slurry. For all slurry types when the raw slurry and liquid fraction is applied by open slot injection, the overall reduction in emission due to separation is not present or even negative.

Towards a standardization of biomethane potential tests: a commentary.

Inter-laboratory reproducibility of biomethane potential (BMP) is dismal, with differences in BMP values for the same sample exceeding a factor of two in some cases. A large group of BMP researchers directly addressed this problem during a workshop held in Leysin, Switzerland, in June 2015. The workshop resulted in a new set of guidelines for BMP tests published in 2016, which is the subject of the present commentary. The work has continued with two international inter-laboratory studies and one additional workshop held in Freising, Germany, in 2018. The dataset generated by the two inter-laboratory studies were used to refine the validation criteria for BMP tests. Based on these new results an update to the original guidelines is proposed here.

Inter-stage thermophilic aerobic digestion may increase organic matter removal from wastewater sludge without decreasing biogas production.

Combining aerobic and anaerobic digestion in a two-stage system can improve the degradation of wastewater sludge over the use of either technology alone. But use of aerobic digestion as a pre-treatment before anaerobic digestion generally reduces methane production due to loss of substrate through oxidation. An inter-stage configuration may avoid this reduction in methane production. Here, we evaluated the use of thermophilic aerobic digestion (TAD) as an inter-stage treatment for wastewater sludge using laboratory-scale semi-continuous reactors. A single anaerobic digester was compared to an inter-stage system, where a thermophilic aerobic digester (55 °C) was used between two mesophilic anaerobic digesters (37 °C). Both systems had retention times of approximately 30 days, and the comparison was based on measurements made over 97 days. Results showed that the inter-stage system provided better sludge destruction (52% volatile solids (VS) removal vs. 40% for the single-stage system, 44% chemical oxygen demand (COD) removal vs. 34%) without a decrease in total biogas production (methane yield per g VS added was 0.22-0.24 L g-1 for both systems).

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.

Potassium sorbate reduces production of ethanol and 2 esters in corn silage.

The objective of this work was to evaluate the effects of biological and chemical silage additives on the production of volatile organic compounds (VOC; methanol, ethanol, 1-propanol, methyl acetate, and ethyl acetate) within corn silage. Recent work has shown that silage VOC can contribute to poor air quality and reduce feed intake. Silage additives may reduce VOC production in silage by inhibiting the activity of bacteria or yeasts that produce them. We produced corn silage in 18.9-L bucket silos using the following treatments: (1) control (distilled water); (2) Lactobacillus buchneri 40788, with 400,000 cfu/g of wet forage; (3) Lactobacillus plantarum MTD1, with 100,000 cfu/g; (4) a commercial buffered propionic acid-based preservative (68% propionic acid, containing ammonium and sodium propionate and acetic, benzoic, and sorbic acids) at a concentration of 1 g/kg of wet forage (0.1%); (5) a low dose of potassium sorbate at a concentration of 91 mg/kg of wet forage (0.0091%); (6) a high dose of potassium sorbate at a concentration of 1g/kg of wet forage (0.1%); and (7) a mixture of L. plantarum MTD1 (100,000 cfu/g) and a low dose of potassium sorbate (91 mg/kg). Volatile organic compound concentrations within silage were measured after ensiling and sample storage using a headspace gas chromatography method. The high dose of potassium sorbate was the only treatment that inhibited the production of multiple VOC. Compared with the control response, it reduced ethanol by 58%, ethyl acetate by 46%, and methyl acetate by 24%, but did not clearly affect production of methanol or 1-propanol. The effect of this additive on ethanol production was consistent with results from a small number of earlier studies. A low dose of this additive does not appear to be effective. Although it did reduce methanol production by 24%, it increased ethanol production by more than 2-fold and did not reduce the ethyl acetate concentration. All other treatments increased ethanol production at least 2-fold relative to the control, and L. buchneri addition also increased the 1-propanol concentration to approximately 1% of dry matter. No effects of any treatments on fiber fractions or protein were observed. However, L. buchneri addition resulted in slightly more ammonia compared with the control. If these results hold under different conditions, a high dose of potassium sorbate will be an effective treatment for reducing VOC production in and emission from silage. Regulations aimed at reducing VOC emission could be ineffective or even increase emission if they promote silage additives without recognition of different types of additives.

Ammonia emission model for whole farm evaluation of dairy production systems.

Ammonia (NH) emissions vary considerably among farms as influenced by climate and management. Because emission measurement is difficult and expensive, process-based models provide an alternative for estimating whole farm emissions. A model that simulates the processes of NH formation, speciation, aqueous-gas partitioning, and mass transfer was developed and incorporated in a whole farm simulation model (the Integrated Farm System Model). Farm sources included manure on the floor of the housing facility, manure in storage (if used), field-applied manure, and deposits on pasture (if grazing is used). In a comprehensive evaluation of the model, simulated daily, seasonal, and annual emissions compared well with data measured over 2 yr for five free stall barns and two manure storages on dairy farms in the eastern United States. In a further comparison with published data, simulated and measured barn emissions were similar over differing barn designs, protein feeding levels, and seasons of the year. Simulated emissions from manure storage were also highly correlated with published emission data across locations, seasons, and different storage covers. For field applied manure, the range in simulated annual emissions normally bounded reported mean values for different manure dry matter contents and application methods. Emissions from pastures measured in northern Europe across seasons and fertilization levels were also represented well by the model. After this evaluation, simulations of a representative dairy farm in Pennsylvania illustrated the effects of animal housing and manure management on whole farm emissions and their interactions with greenhouse gas emissions, nitrate leaching, production costs, and farm profitability.

Process-based Modeling of Ammonia Emission from Beef Cattle Feedyards with the Integrated Farm Systems Model.

Ammonia (NH) volatilization from manure in beef cattle feedyards results in loss of agronomically important nitrogen (N) and potentially leads to overfertilization and acidification of aquatic and terrestrial ecosystems. In addition, NH is involved in the formation of atmospheric fine particulate matter (PM), which can affect human health. Process-based models have been developed to estimate NH emissions from various livestock production systems; however, little work has been conducted to assess their accuracy for large, open-lot beef cattle feedyards. This work describes the extension of an existing process-based model, the Integrated Farm Systems Model (IFSM), to include simulation of N dynamics in this type of system. To evaluate the model, IFSM-simulated daily per capita NH emission rates were compared with emissions data collected from two commercial feedyards in the Texas High Plains from 2007 to 2009. Model predictions were in good agreement with observations and were sensitive to variations in air temperature and dietary crude protein concentration. Predicted mean daily NH emission rates for the two feedyards had 71 to 81% agreement with observations. In addition, IFSM estimates of annual feedyard emissions were within 11 to 24% of observations, whereas a constant emission factor currently in use by the USEPA underestimated feedyard emissions by as much as 79%. The results from this study indicate that IFSM can quantify average feedyard NH emissions, assist with emissions reporting, provide accurate information for legislators and policymakers, investigate methods to mitigate NH losses, and evaluate the effects of specific management practices on farm nutrient balances.

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.

Systematic error in manometric measurement of biochemical methane potential: Sources and solutions.

This work focused on identification and quantification of systematic sources of error in manometric measurement of biochemical methane potential (BMP). Error was determined by comparison to gravimetric measurements and direct measurement of leakage. One out of three types of septa leaked above 1 bar (gauge) headspace pressure, losing 25 to 30% of biogas produced. But manometric BMP showed a negative bias even in the absence of leakage. Maximum error was 24% from 160 mL bottles with 40 mL of headspace (headspace fraction of 0.25). Error decreased with increasing headspace fraction, and was small (3%) for a headspace fraction of 0.75, showing that a high headspace volume is the best approach for minimizing error. Relative error in CH4 production measurement increased with headspace pressure as well, but controlling pressure alone is not sufficient for minimizing error. Calculations showed that observed error may be due to volatilization of CH4 during venting as well as inaccurate headspace volume determination, although these sources do not completely explain the magnitude of error observed. Measurement of biogas composition before and after venting showed that CO2 volatilization can occur, but is probably a minor source of error. Calculations showed that error in estimation of ambient pressure or headspace temperature had only minor effects (<3%). Gravimetric measurements, which were unaffected by leakage and insensitive to error in estimation of headspace pressure, temperature or volume, can provide a simple check on manometric results, or a complete replacement.

Comparison of pre- and inter-stage aerobic treatment of wastewater sludge: Effects on biogas production and COD removal.

The aim of this study was to investigate thermophilic (55°C) aerobic digestion (TAD) as pre- and inter-stage treatment of sludge anaerobic digestion and to analyse the change in organic matter accessibility and complexity. Pre-treatment decreased methane yield (up to -70%), due to oxidation losses whereas inter-stage treatment slightly improved overall methane yield (+2.6%) and total COD removal (+5%) compared to control. Anaerobic degradability and COD removal in the second anaerobic stage significantly increased, by 13-40%. Organic matter fractionation showed that TAD led to an increase in sludge organic matter accessibility in all cases. Organic matter complexity, measured by fluorimetry, increased after TAD pre-treatment whereas it remained constant after inter-stage treatment. TAD was shown to be more efficient if applied to a more recalcitrant substrate and should thus be used as inter-stage treatment to avoid decreasing methane production.

Modeling of ammonia speciation in anaerobic digesters.

Anaerobic digestion of high-nitrogen wastes such as animal manure can be inhibited by high concentrations of un-ionized ammonia, NH(3) (aq). Understanding the toxicity of NH(3) (aq) to anaerobic digestion requires a method for determining its concentration. Previous work on ammonia toxicity in anaerobic digesters has utilized a simple equilibrium calculation for estimating NH(3) (aq) concentration from total ammonia, temperature, and pH. This approach is not appropriate for concentrated solutions. In this work, a speciation model for major solutes in anaerobic digesters, based on Pitzer's ion-interaction approach, is presented. Model simulations show that the simple equilibrium calculation (without corrections for non-ideal behavior) substantially overestimates NH(3) (aq) concentration for all but dilute digesters. This error in concentration determination increases with total solids content and is estimated to be greater than 40% for a digester fed dairy manure with 5% total solids or swine manure with 3% total solids. However, including an estimate of the activity coefficient for NH(4)(+) in the simple equilibrium calculation results in much more accurate estimates of NH(3) (aq) concentration. In this case, the estimated error is less than 10% in the absence of struvite precipitation at the highest total solids contents considered.

Biological hydrogen production from nitrogen-deficient substrates.

Dark fermentation of biomass using mixed bacterial cultures is one approach to producing renewable H(2). The objective of this work was to determine if this approach could be applied to N-deficient feedstocks using an N(2)-fixing mixed culture. A mixed culture produced up to 240 mL H(2)/g glucose (1.9 mol H(2)/mol glucose) from a medium initially lacking combined N. Yields from sugarcane were also promising: 170 mL H(2)/g volatile solids (7.5 mmol H(2)/g volatile solids). This approach could reduce economic and environmental costs of fermentative H(2) production, provide combined N for subsequent bioconversion stages, and improve effluent suitability for subsequent uses.

Measurement of un-ionized ammonia in complex mixtures.

The toxicity of un-ionized ammonia, NH3 (aq), in anaerobic digestion of high-nitrogen wastes has been researched extensively. Previous estimates of NH3 (aq) concentration have relied on a simple speciation approach, based only on the acid dissociation constant and the sample pH and total ammonia concentration. The distinction between concentration and chemical activity has generally not been made, despite the potential for resulting errors in the calculation of NH3 (aq) concentration, and the greater applicability of activity to toxicity work. The currently accepted approach for estimating NH3 (aq) concentration is based on assumptions that are not valid in digested animal manure or other concentrated wastes. This work presents an approach for directly measuring NH3 (aq) activity in complex mixtures using gaseous/aqueous equilibrium across microporous tubing. Application of this approach to anaerobic digester samples confirms that the currently accepted approach is not accurate; it overestimated NH3 (aq) activity in unaltered samples by 45-200%. Previous work on the toxicity of ammonia to methanogenesis has probably overestimated the tolerance of consortia to NH3 (aq), due to overestimation of concentrations. The method introduced here is expected to be useful in a range of research on ammonia toxicity and volatilization.