Pig slurry organic matter transformation and methanogenesis at ambient storage temperatures.

Manure management is a significant source of global methane emissions, and there is an increased interest in understanding and predicting emissions. The hydrolysis rate of manure organic matter is critical for understanding and predicting methane emissions. We estimated hydrolysis rate constants of crude protein, fibers, and lipids and used the Arrhenius equation to describe its dependency on temperature. Simultaneously, measurements of methane emission, 13/12 C isotope ratios, and methanogen community were conducted. This was achieved by incubating fresh pig manure without inoculum at 10°C, 15°C, 20°C, and 25°C for 85 days in a lab-scale setup. Hydrolysis of hemicellulose and cellulose increased more with temperature than crude protein, but still, hydrolysis rate of crude protein was highest at all temperatures. Results suggested that crude protein consisted of multiple substrate groups displaying large differences in degradability. Lipids and lignin were not hydrolyzed during incubations. Cumulative methane emissions were 7.13 ± 2.69, 24.6 ± 8.00, 66.7 ± 4.8, and 105.7 ± 7.14 gCH4 kgVS -1 at 10°C, 15°C, 20°C, and 25°C, respectively, and methanogenic community shifted from Methanosphaera toward Methanocorpusculum over time and more quickly at higher temperatures. This study provides important parameter estimates and dependencies on temperature, which is important in mechanistic methane emission models. Further work should focus on characterizing quickly degradable substrate pools in the manure organic matter as they might be the main carbon source of methane emission from manure management.

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.

Key Odorants from Pig Production Based on Improved Measurements of Odor Threshold Values Combining Olfactometry and Proton-Transfer-Reaction Mass Spectrometry (PTR-MS).

Analytical measurements of odorants in combination with odor threshold values is an alternative to sensory measurements that can be used to evaluate abatement technologies for pig production facilities. The purpose of the present study was to estimate odor threshold values for key odorants found in pig house air. A new method was applied where an olfactometer was used to dilute the sample air and the concentrations of odorants presented to the panelists at the dilutions steps were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The results demonstrate that the odor threshold values of acetic acid, butanoic acid, and 4-methylphenol are considerably lower than reported previously, whereas the values of hydrogen sulfide, methanethiol and dimethylsulfide were comparable. Consequently, acetic acid, butanoic acid, and 4-methyl-phenol will have a larger influence on odor from pig production facilities than previously assumed. The results highlight the necessity for directly measuring exposure concentrations when determining odor threshold values.

Changing Feeding Regimes To Demonstrate Flexible Biogas Production: Effects on Process Performance, Microbial Community Structure, and Methanogenesis Pathways.

Flexible biogas production that adapts biogas output to energy demand can be regulated by changing feeding regimes. In this study, the effect of changes in feeding intervals on process performance, microbial community structure, and the methanogenesis pathway was investigated. Three different feeding regimes (once daily, every second day, and every 2 h) at the same organic loading rate were studied in continuously stirred tank reactors treating distiller's dried grains with solubles. A larger amount of biogas was produced after feeding in the reactors fed less frequently (once per day and every second day), whereas the amount remained constant in the reactor fed more frequently (every 2 h), indicating the suitability of the former for the flexible production of biogas. Compared to the conventional more frequent feeding regimes, a methane yield that was up to 14% higher and an improved stability of the process against organic overloading were achieved by employing less frequent feeding regimes. The community structures of bacteria and methanogenic archaea were monitored by terminal restriction fragment length polymorphism (T-RFLP) analysis of 16S rRNA and mcrA genes, respectively. The results showed that the composition of the bacterial community varied under the different feeding regimes, and the observed T-RFLP patterns were best explained by the differences in the total ammonia nitrogen concentrations, H2 levels, and pH values. However, the methanogenic community remained stable under all feeding regimes, with the dominance of the Methanosarcina genus followed by that of the Methanobacterium genus. Stable isotope analysis showed that the average amount of methane produced during each feeding event by acetoclastic and hydrogenotrophic methanogenesis was not influenced by the three different feeding regimes.

Quantifying contribution of synthrophic acetate oxidation to methane production in thermophilic anaerobic reactors by membrane inlet mass spectrometry.

A unique method was developed and applied for monitoring methanogenesis pathways based on isotope labeled substrates combined with online membrane inlet quadrupole mass spectrometry (MIMS). In our study, a fermentation sample from a full-scale biogas plant fed with pig and cattle manure, maize silage, and deep litter was incubated with 100 mM of [2-(13)C] sodium acetate under thermophilic anaerobic conditions. MIMS was used to measure the isotopic distribution of dissolved CO2 and CH4 during the degradation of acetate, while excluding interference from water by applying a cold trap. After 6 days of incubation, the proportion of methane derived from reduction of CO2 had increased significantly and reached up to 87% of total methane, suggesting that synthrophic acetate oxidation coupled to hydrogenotrophic methanogenesis (SAO-HM) played an important role in the degradation of acetate. This study provided a new approach for online quantification of the relative contribution of methanogenesis pathways to methane production with a time resolution shorter than one minute. The observed contribution of SAO-HM to methane production under the tested conditions challenges the current widely accepted anaerobic digestion model (ADM1), which strongly emphasizes the importance of the acetoclastic methanogenesis.

Recovery of odorants from an olfactometer measured by proton-transfer-reaction mass spectrometry.

The aim of the present study was to examine the recovery of odorants during the dilution in an olfactometer designed according to the European standard for dynamic olfactometry. Nine odorants in the ppmv-range were examined including hydrogen sulfide, methanethiol, dimethyl sulfide, acetic acid, propanoic acid, butanoic acid, trimethylamine, 3-methylphenol and n-butanol. Each odorant was diluted in six dilution steps in descending order from 4,096 to 128 times dilutions. The final recovery of dimethyl sulfide and n-butanol after a 60-second pulse was only slightly affected by the dilution, whereas the recoveries of the other odorants were significantly affected by the dilution. The final recoveries of carboxylic acids, trimethylamine and 3-methylphenol were affected by the pulse duration and the signals did not reach stable levels within the 60-second pulse, while sulfur compounds and n-butanol reach a stable signal within a few seconds. In conclusion, the dilution of odorants in an olfactometer has a high impact on the recovery of odorants and when olfactometry is used to estimate the odor concentration, the recoveries have to be taken into consideration for correct measurements.

PTR-MS measurement of partition coefficients of reduced volatile sulfur compounds in liquids from biotrickling filters.

Biological air filtration for reduction of emissions of volatile sulfur compounds (e.g., hydrogen sulfide, methanethiol and dimethyl sulfide) from livestock production facilities is challenged by poor partitioning of these compounds into the aqueous biofilm or filter trickling water. In this study, Henry's law constants of reduced volatile sulfur compounds were measured for deionized water, biotrickling filter liquids (from the first and second stages of a two-stage biotrickling filter), and NaCl solutions by a dynamic method using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a temperature range of 3-45°C. NaCl solutions were used to estimate salting-out constants up to an ionic strength of 0.7 M in order to evaluate the effect of ionic strength on partitioning between air and biofilter liquids. Thermodynamic parameters (enthalpy and entropy of phase exchange) were obtained from the measured partition coefficients as a function of temperature. The results show that the partition coefficients of organic sulfur compounds in the biotrickling filter liquids were generally very close to the corresponding partition coefficients in deionized water. Based on the estimated ionic strength of biofilter liquids, it is assessed that salting-out effects are of no importance for these compounds. For H(2)S, a higher enthalpy of air-liquid partitioning was observed for 2nd stage filter liquid, but not for 1st stage filter liquid. In general, the results show that co-solute effects for sulfur compounds can be neglected in numerical biofilter models and that the uptake of volatile sulfur compounds in biotrickling filter liquids cannot be increased by decreasing ionic strength.

Real-time measurement of volatile chemicals released by bed bugs during mating activities.

In recent years, bed bug (Hemiptera: Cimicidae) problems have increased dramatically in many parts of the world, leading to a renewed interest in their chemical ecology. Most studies of bed bug semiochemicals have been based on the collection of volatiles over a period of time followed by chemical analysis. Here we present for the first time, a combination of proton transfer reaction mass spectrometry and video analysis for real-time measurement of semiochemicals emitted by isolated groups of bed bugs during specific behavioural activities. The most distinct peaks in the proton transfer reaction mass spectrometry recordings were always observed close to the termination of mating attempts, corresponding to the defensive emissions that bed bugs have been suspected to exploit for prevention of unwanted copulations. The main components of these emissions were (E)-2-hexenal and (E)-2-octenal recorded in ratios between 1:3 and 3:1. In the current study, the quantity varied over 1000 fold for both of the compounds with up to 40 µg total release in a single emission. Males also emit defensive compounds due to homosexual copulation attempts by other males, and no significant differences were observed in the ratio or the amount of the two components released from males or females. In summary, this study has demonstrated that combining proton-transfer-reaction mass spectrometry with video analysis can provide detailed information about semiochemicals emitted during specific behavioural activities.

Sulfur turnover and emissions during storage of cattle slurry: effects of acidification and sulfur addition.

Slurry acidification using sulfuric acid reduces ammonia emissions but also affects sulfur (S) cycling. Emission of sulfur is a source of malodor and reduces the sulfur fertilizer value of the slurry. We investigated the effect of sulfate and methionine amendments, alone or in combination with acidification, on sulfur transformations in slurry and emissions of volatile sulfur compounds (VSC) during storage of fresh and aged cattle slurry. When pH was lowered to 5.5 it resulted in an almost complete inhibition of sulfate reduction. There was a huge emission of hydrogen sulfide (HS) with addition of sulfate and methionine ( < 0.01). Methanethiol (MT) was emitted in treatments with addition of methionine, especially when simultaneously acidified ( < 0.01). The large HS production in the sulfate-amended slurries resulted in little accumulation of MT and dimethyl sulfide (DMS) under neutral conditions, in contrast to acidic conditions where the degradation was inhibited and both MT and DMS accumulated. Based on odor activity values, untreated slurry had little odor development from S compounds, especially the aged slurry. Acidification did not significantly increase odor contribution from any of the compounds in fresh or aged slurry. Generally, addition of a sulfate increased the contribution from HS dramatically, whereas acidification lowered the HS contribution but increased that of MT. Thus, acidification of slurry with sulfuric acid may potentially produce more odor from S compounds than untreated slurry.

Evaluation of single column trapping/separation and chemiluminescence detection for measurement of methanethiol and dimethyl sulfide from pig production.

Reduced sulfur compounds are considered to be important odorants from pig production due to their low odor threshold values and low solubility in slurry. The objective of the present study was to investigate the use of a portable method with a single silica gel column for trapping/separation coupled with chemiluminescence detection (SCTS-CL) for measurement of methanethiol and dimethyl sulfide in sample air from pig production. Proton-transfer-reaction mass spectrometry (PTR-MS) was used to evaluate the trapping/separation. The silica gel column used for the SCTS-CL efficiently collected hydrogen sulfide, methanethiol and dimethyl sulfide. The measurement of methanethiol by SCTS-CL was clearly interfered by the high concentration of hydrogen sulfide found in pig production, and a removal of hydrogen sulfide was necessary to obtain reliable results. Air samples taken from a facility with growing-finishing pigs were analyzed by SCTS-CL, PTR-MS, and a gas chromatograph with sulfur chemiluminescence detection (GC-SCD) to evaluate the SCTS-CL. The difference between the concentrations of methanethiol and dimethyl sulfide measured with SCTS-CL, PTR-MS, and GC-SCD was below 10%. In conclusion, the SCTS-CL is a portable and low-cost alternative to the commercial methods that can be used to measure methanethiol and dimethyl sulfide in sample air from pig production.

Prediction of odor from pig production based on chemical odorants.

The present work was performed to investigate the use of odorant measurements for prediction of odor concentration in facilities with growing-finishing pigs and to analyze the odorant composition in facilities with different floor and ventilation systems. Air was sampled in Nalophan bags, odor concentrations were measured by dilution-to-threshold olfactometry, and concentrations of odorants were measured by proton-transfer-reaction mass spectrometry (PTR-MS). Olfactometry and chemical analyses were synchronized to take place at identical time intervals after sampling. A principal component analysis revealed that different facilities for growing-finishing pigs can be distinguished based on the odorants. Pit ventilation comprising a small amount of the total ventilation air (10-20%) in facilities with both room and pit ventilation can be used to concentrate odorants, whereas the room ventilation contains lower concentrations of most odorants. A partial least squares regression model demonstrated that prediction of the odor concentration based on odorants measured by PTR-MS is feasible. Hydrogen sulfide, methanethiol, trimethylamine, and 4-methylphenol were identified as the compounds having the largest influence on the prediction of odor concentration, whereas carboxylic acids had no significant influence. In conclusion, chemical measurement of odorants by PTR-MS is an alternative for expressing the odor concentration in facilities with growing-finishing pigs that can be used to increase the understanding of odor from different types of facilities and improve the development of odor reduction technologies.

Effects of airflow on odorants' emissions in a model pig house - A laboratory study using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS).

Identification of different factors that affect emissions of gasses, including volatile organic compounds (VOCs) is necessary to develop emission abatement technology. The objectives of this research were to quantify and study temporal variation of gas emissions from a model pig house under varying ventilation rates. The used model was a 1:12.5 scale of a section of a commercial finishing pig house. The VOC concentrations at inlet, outlet, and slurry pit of the model space were measured using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS). PTR-MS can measure the temporal variations of odor compounds' emission from the slurry pit in real time. The emissions of H(2)S and 14 VOCs were lower compared to real pig buildings except for ammonia, which indicated possible other sources of those compounds than the slurry in the slurry pit. The ventilation rate affected significantly on ammonia and trimethylamine emission (p<0.05). The hydrogen sulfide (H(2)S) emission was independent of the ventilation rate. VFAs' emission dependency on ventilation rate increased with the increase of carbon chain. Phenols, indoles and ketones showed the positive correlation with ventilation rate to some extent. Generally, compounds with high solubility (low Henry's constant) showed stronger correlation with ventilation rates than the compounds with high Henry's constant.

Emissions of sulfur-containing odorants, ammonia, and methane from pig slurry: effects of dietary methionine and benzoic acid.

Supplementation of benzoic acid to pig diets reduces the pH of urine and may thereby affect emissions of ammonia and other gases from slurry, including sulfur-containing compounds that are expected to play a role in odor emission. Over a period of 112 d, we investigated hydrogen sulfide (H(2)S), methanethiol (MT), dimethyl sulfide (DMS), dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS), as well as ammonia and methane emissions from stored pig slurry. The slurry was derived from a feeding experiment with four pig diets in a factorial design with 2% (w/w) benzoic acid and 1% (w/w) methionine supplementation as treatments. Benzoic acid reduced slurry pH by 1 to 1.5 units and ammonia emissions by 60 to 70% for up to 2 mo of storage, and a considerable, but transitory reduction of methane emissions was also observed after 4 to 5 wk. All five volatile sulfur (S) compounds were identified in gas emitted from the slurry of the control treatment, which came from pigs fed according to Danish recommendations for amino acids and minerals. The emission patterns of volatile S compounds suggested an intense cycling between pools of organic S in the slurries, with urinary sulfate as the main source. Diet supplementation with methionine significantly increased all S emissions. Diet supplementation with benzoic acid reduced emissions of H(2)S and DMTS compared with the control slurry and moderately increased the concentrations of MT. Sulfur gas emissions were influenced by a strong interaction between methionine and benzoic acid treatments, which caused a significant increase in emissions of especially MT, but also of DMDS. In conclusion, addition of 2% benzoic acid to pig diets effectively reduced ammonia volatilization, but interactions with dietary S may increase odor problems.