Michael Jørgen Hansen

Odorant Emissions from Intensive Pig Production Measured by Online Proton-Transfer-Reaction Mass Spectrometry

Emission of odorous compounds from intensive livestock production is a cause of nuisance in populated rural areas. Knowledge on the chemical composition of odor and temporal variations in emissions are needed in order to identify factors of importance for emission rates and select proper abatement technologies. In this work, a method based on proton-transfer-reaction mass spectrometry (PTR-MS) has been developed and tested for continuous measurements of odorant emissions from intensive pig production facilities. The method is assessed to cover all presently known important odorants from this type of animal production with adequate sensitivity and a time resolution of less than one minute. The sensitivity toward hydrogen sulfide is demonstrated to exhibit a pronounced humidity dependency, which can be included in the calibration procedure in order to achieve quantitative results for this compound. Application of the method at an experimental pig facility demonstrated strong temporal variations in emissions, including diurnal variation. Based on these first results, air exchange and animal activity are suggested to be of importance for emission rates of odorants. Highest emissions are seen for hydrogen sulfide and acetic acid, whereas key odorants are evaluated from tabulated odor threshold values to be hydrogen sulfide, methanethiol, 4-methylphenol, and butanoic acid.

Stability of Odorants from Pig Production in Sampling Bags for Olfactometry

Odor from pig production facilities is typically measured with olfactometry, whereby odor samples are collected in sampling bags and assessed by human panelists within 30 h. In the present study, the storage stability of odorants in two types of sampling bags that are often used for olfactometry was investigated. The bags were made of Tedlar or Nalophan. In a field experiment, humid and dried air samples were collected from a pig production facility with growing-finishing pigs and analyzed with a gas chromatograph with an amperometric sulfur detector at 4, 8, 12, 28, 52, and 76 h after sampling. In a laboratory experiment, the bags were filled with a humid gas mixture containing carboxylic acids, phenols, indoles, and sulfur compounds and analyzed with proton-transfer-reaction mass spectrometry after 0, 4, 8, 12, and 24 h. The results demonstrated that the concentrations of carboxylic acids, phenols, and indoles decreased by 50 to >99% during the 24 h of storage in Tedlar and Nalophan bags. The concentration of hydrogen sulfide decreased by approximately 30% during the 24 h of storage in Nalophan bags, whereas in Tedlar bags the concentration of sulfur compounds decreased by <5%. In conclusion, the concentrations of odorants in air samples from pig production facilities significantly decrease during storage in Tedlar and Nalophan bags, and the composition changes toward a higher relative presence of sulfur compounds. This can result in underestimation of odor emissions from pig production facilities and of the effect of odor reduction technologies.

Application of proton-transfer-reaction mass spectrometry to the assessment of odorant removal in a biological air cleaner for pig production.

There is an urgent need to develop odor reduction technologies for animal production facilities, and this requires a reliable measurement technique for estimating the removal of odorants. The purpose of the present experiment was to investigate the application of proton-transfer-reaction mass spectrometry (PTR-MS) for continuous measurements at a biofilter from SKOV A/S installed at a pig production facility. PTR-MS was able to handle the harsh conditions with high humidity and dust load in a biofilter and provide reliable data for the removal of odorants, including the highly odorous sulfur compounds. The biofilter removed 80-99% of carboxylic acids, aldehydes, ketones, phenols, and indoles and ca. 75% of hydrogen sulfide. However, only ~0-15% of methanethiol and dimethyl sulfide was removed. In conclusion, PTR-MS is a promising tool that can be used to improve the development of biological air cleaning and other odor reduction technologies toward significant odorants.

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.

Supercritical fluid extraction of polychlorinated biphenyls from lyophilized fish tissue

A method for the rapid interference free analysis of polychlorinated biphenyl congeners (chlorinated biphenyls, CBs) in lyophilized fish tissue is presented. The method was developed on a lyophilized tuna muscle tissue that contained 2.8% lipid (dry mass based), and native CB concentrations in the range of 3-84 ng/g. Sample preparation was made by supercritical fluid extraction using pure CO2 as extraction fluid. Analysis by high-resolution gas chromatography-electron-capture detection analysis was carried out with on-column injection on two parallel coupled columns, a 60 m DB-17 column and a series combination of a 25 m SIL-8 column and a 25 m HT-5 column. Supercritical fluid extraction was compared with Soxhlet extraction and found to give quantitative recoveries, detection limits of 0.5-2 ng/g and standard deviations of less than 5% on average. The developed method was confirmed on nine different lyophilized fish samples which contained 6.1-26.5% lipid (dry mass based), and native CB concentrations in the range 0.8-134 ng/g.

Minimisation of artefact formation of dimethyl disulphide during sampling and analysis of methanethiol in air using solid sorbent materials.

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.

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.

Kinetic evaluation of removal of odorous contaminants in a three-stage biological air filter.

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.

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.

Effects of Dilution Systems in Olfactometry on the Recovery of Typical Livestock Odorants Determined by PTR-MS

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.