Dose-dependent effects of sodium dodecyl sulfate and hydrogen peroxide treatments on methane emission from pig manure during storage.

Mitigation of methane (CH4) emissions from slurry pits within pig barns can be achieved through treatment of residual slurry left after frequent flushing of the slurry pits. In this study, dosages of additives such as sodium dodecyl sulfate (SDS) and hydrogen peroxide (H2O2) were optimized to achieve reduction in CH4 emissions from residual pig slurry during storage. In addition, the effects on emissions when both the treatments were combined and the effects of SDS treatment on slurry acidified with sulfuric acid (H2SO4) were studied in order to reduce CH4 and ammonia (NH3) emissions from residual pig slurry storage. A maximum of 98% and 70% reduction in CH4 emissions were achieved with SDS and H2O2 treatments, respectively. The combination of SDS and H2O2 did not increase efficiency in reducing CH4 emissions compared to SDS treatment alone. Whereas the application of SDS to slurry acidified with H2SO4 (pH 6.2) increased the CH4 mitigation efficiency by 15-30% compared to treating slurry with only SDS. The combined treatment (SDS + H2SO4) reduced NH3 emissions by 20% compared to treating slurry with H2SO4 (pH 6.2) alone. Hereby, combined treatment (SDS + H2SO4) can reduce both CH4 and NH3 emissions, with a reduced amount of chemicals required for the treatment. Hence, application of SDS at concentrations <2 g kg-1 to acidified slurry is recommended to treat residual pig manure in pig barns.

CRISPR/Cas9-mediated mutation of Eil1 transcription factor genes affects exogenous ethylene tolerance and early flower senescence in Campanula portenschlagiana.

Improving tolerance to ethylene-induced early senescence of flowers and fruits is of major economic importance for the ornamental and food industry. Genetic modifications of genes in the ethylene-signalling pathway have frequently resulted in increased tolerance but often with unwanted side effects. Here, we used CRISPR/Cas9 to knockout the function of two CpEil1 genes expressed in flowers of the diploid ornamental plant Campanula portenschlagiana. The ethylene tolerance in flowers of the primary mutants with knockout of only one or all four alleles clearly showed increased tolerance to exogenous ethylene, although lower tolerance was obtained with one compared to four mutated alleles. The allele dosage effect was confirmed in progenies where flowers of plants with zero, one, two, three and four mutated alleles showed increasing ethylene tolerance. Mutation of the Cpeil1 alleles had no significant effect on flower longevity and endogenous flower ethylene level, indicating that CpEil1 is not involved in age-dependent senescence of flowers. The study suggests focus on EIN3/Eils expressed in the organs subjected to early senescence for obtaining tolerance towards exogenous ethylene. Furthermore, the observed allelic dosage effect constitutes a key handle for a gradual regulation of sensitivity towards exogenous ethylene, simultaneously monitoring possibly unwanted side effects.

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.

Simple Management Changes Drastically Reduce Pig House Methane Emission in Combined Experimental and Modeling Study.

Reducing methane from livestock slurry is one of the quickest ways to counteract global warming. A straightforward strategy is to reduce slurry retention time inside pig houses by frequent transfer to outside storages, where temperature and therefore microbial activity are lower. We demonstrate three frequent slurry removal strategies in pig houses in a year-round continuous measurement campaign. Slurry funnels, slurry trays, and weekly flushing reduced slurry methane emission by 89, 81, and 53%, respectively. Slurry funnels and slurry trays reduced ammonia emission by 25-30%. An extended version of the anaerobic biodegradation model (ABM) was fitted and validated using barn measurements. It was then applied for predicting storage emission and shows that there is a risk of negating barn methane reductions due to increased emission from outside storage. Therefore, we recommend combining the removal strategies with anaerobic digestion pre-storage or storage mitigation technologies such as slurry acidification. However, even without storage mitigation technologies, predicted net methane reduction from pig houses and following outside storage was at least 30% for all slurry removal strategies.

Regenerative one-stage catalytic absorption process with cupric ions for removal of reduced sulfur compounds in polluted air.

Reduced volatile sulfur compounds emitted from e.g. livestock production and biogas production facilities contribute to general air pollution and local odour nuisance. Improved technologies are required to mitigate the emissions of both hydrogen sulfide and organic sulfur compounds. The present study examines the oxidative absorption of reduced sulfur compounds, i.e. hydrogen sulfide, methanethiol and dimethyl sulfide in a wet oxidation process with cupric chloride. It was found that this process efficiently removes both hydrogen sulfide and methanethiol with removal efficiencies >94% under all process conditions tested, while the removal of dimethyl sulfide was in the range 20-40%. The main products determined were dimethyl disulfide, dimethyl trisulfide and elemental sulfur. It was shown that the process was more efficient than the similar process with ferric ions and higher removal could be obtained with lower residence times. Furthermore, though employing cupric ion as metal catalysts results in the production of gaseous sulfur compounds, it is estimated that this process is efficient for deodorization due to the higher odour threshold values of the product compounds and the pH range is optimal for gas streams containing CO2.

Reducing greenhouse gas emissions from pig slurry by acidification with organic and inorganic acids.

Methane (CH4) emission from pig slurry is a large contributor to the climate footprint of livestock production. Acidification of excreta from livestock animals with sulfuric acid, reduce CH4 emission and is practiced at many Danish farms. Possible interaction effects with other acidic agents or management practices (e.g. frequent slurry removal and residual slurry acidification) have not been fully investigated. Here we assessed the effect of pig slurry acidification with a range of organic and inorganic acids with respect to their CH4 inhibitor potential in several batch experiments (BS). After careful selection of promising CH4 inhibitors, three continuous headspace experiments (CHS) were carried out to simulate management of manure in pig houses. In BS experiments, more than <99% CH4 reduction was observed with HNO3 treatment to pH 5.5. Treatments with HNO3, H2SO4, and H3PO4 reduced CH4 production more than acetic acid and other organic acids when acidified to the same initial pH of 5.5. Synergistic effects were not observed when mixing inorganic and organic acids as otherwise proposed in the literature, which was attributed to the high amount of acetic acid in the slurry to start with. In the CHS experiments, HNO3 treatment reduced CH4 more than H2SO4, but increased nitrous oxide (N2O) emission, particularly when the acidification target pH was above 6, suggesting considerable denitrification activity. Due to increased N2O emission from HNO3 treatments, HNO3 reduced total CO2-eq by 67%, whereas H2SO4 reduced CO2-eq by 91.5% compared to untreated slurry. In experiments with daily slurry addition, weekly slurry removal, and residual acidification, HNO3 and H2SO4 treatments reduced CO2-eq by 27% and 48%, respectively (not significant). More cycles of residual acidification are recommended in future research. The study provides solid evidence that HNO3 treatment is not suitable for reducing CO2-eq and H2SO4 should be the preferred acidic agent for slurry acidification.

Characterisation of cellulose-degrading organisms in an anaerobic digester.

The recalcitrant nature of lignocellulosic biomass hinders efficient exploitation of this fraction for energy production. A better understanding of the microorganisms able to convert plant-based feedstocks is needed to improve anaerobic digestion of lignocellulosic biomass. In this study, active thermophilic cellulose-degrading microorganisms were identified from a full-scale anaerobic digester fed with maize by using metagenome-resolved protein stable isotope probing (protein-SIP). 13C-cellulose was converted into 13C-methane with a 13/12C isotope ratio of 0.127 after two days of incubation. Metagenomic analysis revealed 238 different genes coding for carbohydrate-active enzymes (CAZymes), six of which were directly associated with cellulose degradation. The protein-SIP analysis identified twenty heavily labelled peptides deriving from microorganisms actively assimilating labelled carbon from the degradation of 13C-cellulose, highlighting several members of the order Clostridiales. Corynebacterium was identified through CAZyme screening, amplicon analysis, and in the metagenome giving a strong identification of being a cellulose degrader.

Effect of storage and field acidification on emissions of NH3, NMVOC, and odour from field applied slurry in winter conditions.

Land spreading of liquid animal manure (slurry) is a major source of atmospheric emissions. Ammonia (NH3) emission is of concern, as it is one of the main contributors to ambient air pollution and nitrogen deposition. Storage and field acidification of the slurry prior to application is used to mitigate NH3 emission, but the effect of acidification on emissions of odorous non-methane volatile organic compounds (NMVOC) has not been investigated, and there is a scarcity of data investigating the effect of field acidification. Four field experiments, two with cattle slurry and two with pig slurry, were performed. Ammonia and NMVOC emissions were measured simultaneously in a system of dynamic chambers and online measurements by cavity ring-down spectroscopy (CRDS) and proton-transfer-reaction mass spectrometry (PTR-MS). The system allowed for a high time resolution and low variation. All four experiments were performed under cold conditions (<10°C average temperature). Storage and field acidification significantly lowered the NH3 emission by 79 ± 18% and 30 ± 6% on average, respectively. The NMVOC cumulative emission increased by 202 ± 133% and 17 ± 16% on average after storage and field acidification, respectively, even if the increase was only significant for storage acidification. Storage acidification significantly increased the emissions of odour at most measuring times. The increases of cumulative NMVOC emissions and odour was primarily caused by higher emissions of volatile fatty acids.

Effects of combined tannic acid/fluoride on sulfur transformations and methanogenic pathways in swine manure.

Livestock manure emits reduced sulfur compounds and methane, which affect nature and the climate. These gases are efficiently mitigated by addition of a tannic acid-sodium fluoride combination inhibitor (TA-NaF), and to some extent by acidification. In this paper, TA-NaF treatment was performed on swine manure to study the treatment influence on methanogenic pathways and sulfur transformation pathways in various laboratory experiments. Stable carbon isotope labeling revealed that both untreated and TA-NaF treated swine manures were dominated by hydrogenotrophic methanogenesis. However, in supplementary experiments in wastewater sludge, TA-NaF clearly inhibited acetoclastic methanogenesis, whereas acidification inhibited hydrogenotrophic methanogenesis. In swine manure, TA-NaF inhibited s-amino acid catabolism to a larger extent than sulfate reduction. Conversely, acidification reduced sulfate reduction activity more than s-amino acid degradation. TA-NaF treatment had no significant effect on methanogenic community structure, which was surprising considering clear effects on isotope ratios of methane and carbon dioxide. Halophile sulfate reducers adapted well to TA-NaF treatment, but the community change also depended on temperature. The combined experimental work resulted in a proposed inhibition scheme for sulfur transformations and methanogenic pathways as affected by TA-NaF and acidification in swine manure and in other inocula.

Analysis of the effect of air temperature on ammonia emission from band application of slurry.

Field application of liquid animal manure (slurry) is a significant source of ammonia (NH3) emission to the atmosphere. It is well supported by theory and previous studies that air temperature effects NH3 flux from field applied slurry. The objectives of this study was to statistically model the response of temperature at the time of application on cumulative NH3 emission. Data from 19 experiments measured with the same system of dynamic chambers and online measurements were included. A generalized additive model allowing to represent non-linear functional dependences of the emission on the temperature revealed that a positive response of the cumulative NH3 emission on the temperature at the time of application up to a temperature of approximately 14 °C. Above that, the temperature effect is insignificant. Average temperature over the measuring period was not found to carry any additional information on the cumulative NH3 emission. The lack of emission response on temperature above a certain point is assumed to be caused by drying out of the slurry and possible crust formation. This effect is hypothesized to create a physical barrier that reduce diffusion of NH3 to the soil surface, thereby lowering the emission rate. Furthermore, the effect of the interaction between soil type and application technique and the effect of dry matter content of the slurry was derived from the model, and found to be significant on cumulative NH3 emission predictions.

Low-Cost Fluorescence Sensor for Ammonia Measurement in Livestock Houses.

Measurements of ammonia with inexpensive and reliable sensors are necessary to obtain information about e.g., ammonia emissions. The concentration information is needed for mitigation technologies and documentation of existing technologies in agriculture. A flow-based fluorescence sensor to measure ammonia gas was developed. The automated sensor is robust, flexible and made from inexpensive components. Ammonia is transferred to water in a miniaturized scrubber with high transfer efficiency (>99%) and reacts with o-phthalaldehyde and sulfite (pH 11) to form a fluorescent adduct, which is detected with a photodiode. Laboratory calibrations with standard gas show good linearity over a dynamic range from 0.03 to 14 ppm, and the detection limit of the analyzer based on three-times the standard deviation of blank noise was approximately 10 ppb. The sampling frequency is 0.1 to 10 s, which can easily be changed through serial commands along with UV LED current and filter length. Parallel measurements with a cavity ring-down spectroscopy analyzer in a pig house show good agreement (R2 = 0.99). The fluorescence sensor has the potential to provide ammonia gas measurements in an agricultural environment with high time resolution and linearity over a broad range of concentrations.

New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals.

Dimethyl sulfide (DMS) is produced by plankton in oceans and constitutes the largest natural emission of sulfur to the atmosphere. In this work, we examine new particle formation from the primary pathway of oxidation of gas-phase DMS by OH radicals. We particularly focus on particle growth and mass yield as studied experimentally under dry conditions using the atmospheric simulation chamber AURA. Experimentally, we show that aerosol mass yields from oxidation of 50-200 ppb of DMS are low (2-7%) and that particle growth rates (8.2-24.4 nm/h) are comparable with ambient observations. An HR-ToF-AMS was calibrated using methanesulfonic acid (MSA) to account for fragments distributed across both the organic and sulfate fragmentation table. AMS-derived chemical compositions revealed that MSA was always more dominant than sulfate in the secondary aerosols formed. Modeling using the Aerosol Dynamics, gas- and particle-phase chemistry kinetic multilayer model for laboratory CHAMber studies (ADCHAM) indicates that the Master Chemical Mechanism gas-phase chemistry alone underestimates experimentally observed particle formation and that DMS multiphase and autoxidation chemistry is needed to explain observations. Based on quantum chemical calculations, we conclude that particle formation from DMS oxidation in the ambient atmosphere will most likely be driven by mixed sulfuric acid/MSA clusters clustering with both amines and ammonia.

Emissions of NMVOC and H2S from field-applied manure measured by PTR-TOF-MS and wind tunnels.

Field application of animal manure is a source of volatile organic compounds (VOC) and hydrogen sulfide (H2S) emission that contribute to air pollution and odor nuisance in local surroundings. In this study the non-methane volatile organic compounds (NMVOC) and H2S emission and odor activity dynamics over time after field application of pig and cattle manure were investigated. Furthermore, three different application techniques, trailing hoses, trailing shoes, and trailing hoses applying manure 20 cm above canopy, was compared. With a flexible system combining dynamic chambers and Proton-Transfer-Reaction Time-of-Flight Mass Spectroscopy (PTR-TOF-MS), H2S and 22 different NMVOC were measured, identified, and quantified. From pig manure high amounts of H2S was measured right after application, resulting in high odor activity values (OAV). During the first 10 h 4-methylphenol accounted for most of the cumulative emissions and OAV. Carboxylic acids were emitted for a longer period, and accounted for most of the long-term emissions and OAV. Acetic acid alone accounted for 33-57% of the total cumulative emissions. Trailing shoes were found to reduce NMVOC emission under certain conditions. It is suggested to use updated ratios from this study to calculate NMVOC emissions relative to ammonia emissions. The average ratios of cumulated NMVOC emission divided by cumulated ammonia emission 90 h after application of pig manure is 1.15±0.55 and 0.72±0.26 for trailing hoses and trailing shoes respectively, whereas the equivalent numbers for cattle manure is 0.43±0.11 and 0.18±0.04.

Copper Adsorption on Lignin for the Removal of Hydrogen Sulfide.

Lignin is currently an underutilized part of biomass; thus, further research into lignin could benefit both scientific and commercial endeavors. The present study investigated the potential of kraft lignin as a support material for the removal of hydrogen sulfide (H2S) from gaseous streams, such as biogas. The removal of H2S was enabled by copper ions that were previously adsorbed on kraft lignin. Copper adsorption was based on two different strategies: either directly on lignin particles or by precipitating lignin from a solution in the presence of copper. The H2S concentration after the adsorption column was studied using proton-transfer-reaction mass spectrometry, while the mechanisms involved in the H2S adsorption were studied with X-ray photoelectron spectroscopy. It was determined that elemental sulfur was obtained during the H2S adsorption in the presence of kraft lignin and the differences relative to the adsorption on porous silica as a control are discussed. For kraft lignin, only a relatively low removal capacity of 2 mg of H2S per gram was identified, but certain possibilities to increase the removal capacity are discussed.

Synergistic Tannic Acid-Fluoride Inhibition of Ammonia Emissions and Simultaneous Reduction of Methane and Odor Emissions from Livestock Waste.

Gaseous emissions from livestock production are complex mixtures including ammonia, methane, volatile organic compounds (VOC), and H2S. These contribute to eutrophication, reduced air quality, global warming, and odor nuisance. It is imperative that these gases are mitigated in an environmentally sustainable manner. We present the discovery of a microbial inhibitor combo consisting of tannic acid and sodium fluoride (TA-NaF), which exhibits clear synergistic inhibition of ammonia production in pure bacteria culture and in pig manure while simultaneously inhibiting methane and odorant (H2S and VOC) emissions. In laboratory headspace experiments on pig manure, we used proton-transfer-reaction mass spectrometry and cavity ring-down spectroscopy to measure the effect of TA-NaF on gaseous emissions. Ammonia emission was reduced by more than 95%, methane by up to ∼99%, and odor activity value by more than 50%. Microbial community analysis and gas emission data suggest that TA-NaF acts as an efficient generic microbial inhibitor, and we hypothesize that the synergistic inhibitory effect on ammonia production is related to tannic acid causing cell membrane leakage allowing fluoride ions easy access to urease.

Effect of tannic acid combined with fluoride and lignosulfonic acid on anaerobic digestion in the agricultural waste management chain.

Livestock waste is stored and used as soil fertilizer or directly as substrate for biogas production. Methane emissions from manure storages and ammonia inhibition of anaerobic digesters fed with manure, are well-known problems related to manure management. This study examines the effect of adding tannic acid with fluoride (TA-NaF) and lignosulfonic acid (LS) on methanogenic activity in batch reactors with ammonia inhibited maize silage digestate and in batch reactors with manure. Lignosulfonic acid counteracted urea induced ammonia inhibition of methanogenesis, whereas TA-NaF inhibited methanogenesis itself. Stable carbon isotope ratio analysis and methanogen community analysis suggested that TA-NaF affected acetoclastic methanogens the most. The combined findings suggest that TA-NaF could be used to reduce methane emissions from stored manure. Conversely, LS could be used as supplement in anaerobic digesters prone to urea induced ammonia inhibition.

Real-time quantification of emissions of volatile organic compounds from land spreading of pig slurry measured by PTR-MS and wind tunnels.

Volatile organic compounds (VOC) and hydrogen sulfide are emitted from land spreading of manure slurry to the atmosphere and contribute to odour nuisance, particle formation and tropospheric ozone formation. Data on emissions is almost non-existing partly due to lack of suitable quantitative methods for measuring emissions in full scale. Here we present a method based on application of wind tunnels for simulation of air exchange combined with the use of online mass spectrometry (PTR-MS). The focus was on odorous VOC but all relevant VOC were included. A method for quantification of VOC emission based on calculated proton-transfer reaction rate constants was validated by comparison to reference concentrations for typical VOC emitted from pig manure slurry. Wall losses of volatile sulfur compounds in the wind tunnels were assessed to be insignificant and recoveries >95% were observed for these compounds. An influence of air exchange rate was clearly observed highlighting the need to identify realistic air exchange rates for future application of the method. Emission data was obtained for spreading of pig manure slurry as an example of an important source of gases. Emissions were monitored for ~37 h following land spreading and time-resolved emission data was presented for the first time. Highest emissions were observed for short-chain volatile carboxylic acids (C2-C6) with acetic acid being the most abundant compound. Emission peaks were observed immediately following application and were followed by declining emissions until the second day at which emissions reached a second peak for several compounds. This second emission peak was speculated to be caused by a temperature-induced diurnal effect. Emissions of volatile sulfur compounds occurred on a short time-scale and ceased shortly after application. Odour activity values were dominated by C4-C5 carboxylic acids and 4-methylphenol with a less pronounced influence of 4-methylphenol on day 2.

Mechanisms of Loss of Agricultural Odorous Compounds in Sample Bags of Nalophan, Tedlar, and PTFE.

Alteration of the chemical composition of odor samples during storage in polymer sample bags can significantly impair the accuracy of subsequent odor evaluations. To overcome or minimize this effect, the mechanisms determining compound loss must be more thoroughly understood. The present study examines the storage stability of a selection of key odorants from livestock production in polymer sample bags of Nalophan, Tedlar, and polytetrafluoroethylene (PTFE). The compounds included are acetic acid, butanoic acid, propanoic acid, 3-methylbutanoic acid, hydrogen sulfide, methanethiol, dimethyl sulfide, trimethylamine, and 4-methylphenol. The fate of the unrecovered compound fractions is clarified by means of thermal desorption and concentric double bags, allowing estimation of the magnitude of losses due to adsorption and diffusion, respectively. The degree of recovery was found to be PTFE > Tedlar > Nalophan, and smaller ratios of bag surface area to sample volume improved the recovery significantly. Furthermore, PTFE bags were found far superior for maintaining the original sample humidity and for storing 4-methylphenol. Analysis of sample humidity, partitioning coefficients, and thermal desorption suggested that the loss in PTFE bags was mainly controlled by adsorption, whereas for Nalophan and Tedlar, compound loss is a combined effect of adsorption and diffusion. It is suggested to heat the bags when evacuating the sample for analysis, as this was found to improve the recovery significantly. For a 5-L PTFE bag, all odorants could be found at concentration levels between 71.6 and 98.8% even after 48 h of storage when heated to 57°C prior to analysis.

Parameters affecting acetate concentrations during in-situ biological hydrogen methanation.

Surplus electricity may be supplied to anaerobic digesters as H2 gas to upgrade the CH4 content of biogas. Acetate accumulation has been observed following H2 injections, but the parameters determining the degree of acetate accumulation are not well understood. The pathways involved during H2 consumption and acetate kinetics were evaluated in continuous lab reactors and parallel batch 13C experiments. Acetate accumulation increased during initial H2 injections as organic loading rate increased and CO2 levels decreased below 7%. The share of CH4 in H2 and 13C mass balances increased after repeated H2 injections, which corresponded with the increase of Methanomicrobiales observed via qPCR. The organic loading rate, the inorganic carbon level and level of methanogen adaption hence determine acetate kinetics during biomethanation of H2. The three identified parameters may form the base of a decision tool to assess acetate accumulation during H2 injections to an anaerobic digester.