RESUMEN
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.
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Estiércol , Metano , Animales , Porcinos , Amoníaco/análisis , Calentamiento Global , Óxido Nitroso/análisisRESUMEN
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.
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Amoníaco , Ganado , Agricultura , Animales , Análisis Espectral , PorcinosRESUMEN
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.
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Odorantes/análisis , Tereftalatos Polietilenos/química , Politetrafluoroetileno/química , Agricultura , Monitoreo del Ambiente , Humedad , TemperaturaRESUMEN
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.
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Olfatometría , Animales , Cresoles , Espectrometría de Masas , Odorantes , Protones , PorcinosRESUMEN
The present study provides an elaborate assessment of the performance of olfactometers in terms of odorant recovery for a selection of odorants emitted from livestock houses. The study includes three different olfactometer dilution systems, which have been in use at accredited odor laboratories. They consist of: (i) a custom-built olfactometer made of glass tubes, (ii) a TO8 olfactometer, and (iii) an Olfacton dilution system based on a mass flow controller. The odorants include hydrogen sulfide, methanethiol, dimethyl sulfide, acetic acid, butanoic acid, propanoic acid, 3-methylbutanoic acid, 4-methylphenol, and trimethylamine. Furthermore, n-butanol, as the reference gas in the European standard for olfactometry, EN13725, was included. All measurements were performed in real time with proton-transfer-reaction mass spectrometry (PTR-MS). The results show that only dimethyl sulfide was almost completely recovered in all cases, while for the remaining compounds, the performance was found to vary significantly (from 0 to 100%) depending on the chemical properties of the compounds, the concentration levels, the pulse duration, and the olfactometer material. To elucidate the latter, the recovery in different locations of the TO8 olfactometer and in tubes of different materials, that is, poly-tetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), stainless steel and SilcoTek-coated steel, were tested. Significant saturation effects were observed when odorants were in contact with stainless steel.
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Olfatometría , Animales , Cresoles , Ganado , Odorantes , ProtonesRESUMEN
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.
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Espectrometría de Masas , Odorantes/análisis , 1-Butanol/química , Animales , Ácidos Carboxílicos/química , Cresoles/química , Metilaminas/química , Sulfuros/químicaRESUMEN
Manure management is a significant source of methane (CH4) and ammonia (NH3), and there is an urgent need for strategies to reduce these emissions. More frequent export of manure for outside storage can lower gaseous emissions from housing facilities, but the longer residence time may then increase emissions during outside storage. This study examined CH4 and NH3 emissions from liquid pig manure (pig slurry) removed from the in-house slurry collection pits at three different frequencies, i.e., three times per week (T2.3), once per week (T7), or once after 40 days (T40, reference). The slurry from treatments T2.3 and T7 was transferred for outside storage weekly over four weeks, and slurry from treatment T40 once after 40 days, in connection with summer and winter production cycles with growing-finishing pigs. The slurry was stored in pilot-scale storage tanks with solid cover and continuous ventilation. Compared to T40, the treatments T2.3 and T7 increased CH4 emissions during outside storage, but in-house emissions were reduced even more, and the net effects on total CH4 emissions from manure management (housing unit and outside storage) were reductions of 18-41% in summer and 53-83% in winter. The frequent slurry export for outside storage led to more NH3 emissions, except for the treatment T2.3, which has slurry funnel inserts beneath the slatted floor. Measurements of in-vitro CH4 production rates suggested that shorter residence time for slurry in pig houses delayed the development of active methanogenic populations, and that this contributed to the reduction of CH4 emissions.
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Amoníaco , Metano , Animales , Porcinos , Amoníaco/análisis , Estiércol , Estaciones del Año , GasesRESUMEN
Biofiltration is a cost-effective technology for removing air contaminants from animal facilities. Kinetic analysis can be helpful in understanding and designing the process but has not been performed on full-scale filters treating complex mixtures. In this study, kinetics was investigated in a full-scale biological filter treating air pollutants from a pig facility. Due to the high air flow rates used in the filter, both a plug flow model and a model based on complete mixing were tested with respect to kinetic order and Michaelis-Menten kinetics. Application of these models only gave poor to moderate agreement with air filter removal data. Two alternative kinetic models (Stover-Kincannon model and Grau second-order model) adopted from wastewater biofiltration process analysis were introduced to analyze contaminant removal in the biological air filter. Data analysis demonstrated the applicability of these two models with a high degree of precision on contaminant removal in the biological air filter. Whereas the Stover-Kincannon model demonstrated that pollutant removal rates were related to the mass loading rates, the Grau second-order kinetic model indicated that the removal efficiencies were dependent on air loading rates. Therefore, the kinetic data can be used for comparing biofilter performances and for design purposes.
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Filtración/instrumentación , Odorantes , Cinética , Espectrometría de Masas , Modelos TeóricosRESUMEN
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.
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Bacterias/clasificación , Fluoruros/química , Estiércol/microbiología , Metano/análisis , Azufre/análisis , Taninos/química , Contaminantes Atmosféricos/análisis , Animales , Bacterias/genética , Bacterias/aislamiento & purificación , Isótopos de Carbono/análisis , ADN Bacteriano/genética , ADN Ribosómico/genética , Secuenciación de Nucleótidos de Alto Rendimiento , Estiércol/análisis , Filogenia , ARN Ribosómico 16S/genética , Análisis de Secuencia de ADN , Porcinos , Aguas Residuales/químicaRESUMEN
Hydrogen sulfide (H2S) from agricultural sources is generally not included in sulfur emission estimates even though H2S is the major sulfur compound emitted from livestock production. Here we show that in a country with intensive livestock production (Denmark), agriculture constitute the most important sulfur source category (~49% of all sources of sulfur dioxide), exceeding both the production industry and energy categories. The analysis is based on measurements of H2S using proton-transfer-reaction mass spectrometry. National emissions are obtained using ammonia as a reference pollutant with the validity of this approach documented by the high correlation of ammonia and hydrogen sulfide emissions. Finisher pig production is the most comprehensively characterized agricultural source of sulfur and is estimated to be the largest source of atmospheric sulfur in Denmark. The implication for other locations is discussed and the results imply that the understanding and modeling of atmospheric sulfate sources should include agricultural H2S.
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Monitoreo del Ambiente , Sulfuro de Hidrógeno/análisis , Ganado , Agricultura/estadística & datos numéricos , Amoníaco/análisis , Animales , DinamarcaRESUMEN
Methanethiol (MT) is a potent odorant that can be difficult to measure due to its high volatility and reactivity; it easily reacts to form dimethyl disulphide (DMDS) during sampling and/or analysis. This paper focuses on finding an optimal method for sampling and measuring MT with minimum artefact formation using sorbent materials and a thermal desorption-gas chromatography-mass spectrometry method (TD-GC-MS). Experiments were conducted to identify suitable sorbent materials and tubes for analysis. Breakthrough, desorption rate, the effects of storage and desorption temperatures were investigated and different drying methods were established with respect to quantitative sampling and formation of DMDS. Proton-transfer-reaction mass spectrometry (PTR-MS) was used in the development of the method and was an especially useful tool for determination of breakthrough. The results show that glass tubes packed with silica gel for pre-concentration of MT before analysis with TD-GC-MS give the best results. In addition, a combination of Tenax TA and carbonised molecular sieve or Tenax TA cooled to ≤0°C gives acceptable results. 80°C was found to be the optimal desorption temperature. For all the sampling methods tested, storage conditions were observed to be very critical for transformation of MT. Room temperature storage should be limited to few minutes and, in general, tubes should be kept at 0°C or lower during storage.
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Contaminantes Atmosféricos/aislamiento & purificación , Disulfuros/química , Extracción en Fase Sólida/métodos , Compuestos de Sulfhidrilo/aislamiento & purificación , Adsorción , Contaminantes Atmosféricos/química , Monitoreo del Ambiente , Extracción en Fase Sólida/instrumentación , Compuestos de Sulfhidrilo/química , TemperaturaRESUMEN
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.
RESUMEN
The present study was undertaken to investigate how three different fibre sources, sugar beet pulp, soya bean hulls and pectin residue, constituting 15% of diets for growing pigs, influenced daily body gain, feed conversion, apparent faecal digestibility and nitrogen and energy balances. Eight castrated crossbreed pigs (30-80 kg live weight) were used in a replicated 4 x 4 Latin-square design with one control diet and three fibre containing diets. Daily body weight gain and feed conversion were not affected by the dietary treatments. The apparent faecal digestibility of organic matter (OM) and energy were significantly lower for the fibre diets (OM: 0.81-0.85; energy: 0.78-0.83) compared to the control diet (OM: 0.88; energy: 0.86). The apparent faecal digestibility of crude protein (CP) was lower for the fibre diets (0.71-0.78) compared to the control diet (0.83), although it was only significantly lower for the sugar beet pulp and pectin residue diets. The pectin residue diet, which contained the highest amount of dietary fibre, lignin and insoluble non-starch polysaccharides, had the lowest digestibility of OM, CP and energy. There was a tendency (p = 0.07) for a diet effect on retained nitrogen in proportion to digested nitrogen, where the sugar beet pulp and pectin residue diets had numerically the highest values. Heat production and retained energy in proportion to metabolizable energy intake were not affected by fibre inclusion. It was concluded that the inclusion of sugar beet pulp, soya bean hulls and pectin residue in diets for growing pigs decreased the apparent faecal digestibility and in the diets with sugar beet pulp and pectin residue higher utilization of digested nitrogen for retention compensated for the lower amount of digested nitrogen.