PIG-HOUSE ODOURS – A REVIEW USING ODOUR ACTIVITY VALUES Linda J Farmer, James T. Kennedy and Elizabeth Magowan Agri-Food and Biosciences Institute, Newforge Lane, Belfast, UK Abstract – This paper reviews the literature on pighouse odours using odour activity values to determine the main compound classes contributing to pig-house odour. These are short chain acids, sulphur compounds, phenols, indoles and amines. These compounds have the highest odour activity values and pungent and offensive odours. The contribution to the offensive odour by these compounds is affected by location, timing and method of analysis. Mitigation factors related to slurry management or pig diets have differential effects on these classes of odorous compounds. Key Words –animal house, pig odour, slurry odour. I. INTRODUCTION The odour downwind from pig-houses can be offensive to nearby residents. Researchers have reported up to five hundred different volatile organic compounds emitted from pig production facilities (1). However, it is often unclear which of these many compounds make the most important contribution to the noxious odour. Furthermore, the composition of the odour from the waste itself may differ depending on the location sampled and the methods used (2). Quantification of volatile compounds from pighouses has been used to estimate the effectiveness of any mitigation factors employed to reduce them. However, few have attempted to determine which of these many compounds makes the greatest contribution to the offensive odour. Calculation of an odour activity value (OAV) is a method widely used in flavour chemistry to identify those odours with the potential to contribute most to an odorant mixture and is defined as the concentration of a single compound divided by the odour threshold concentration for that compound (3). Compounds with an OAV greater than 1.0 are likely to contribute to the overall odour of a sample mix and compounds with large OAV would contribute substantially. The odour thresholds reported in the literature can vary considerably, with sometimes a range of several orders of magnitude for a particular chemical compound. In order to minimise the impact of this variability on the odour activity values derived, a consistent set of odour thresholds is required for the compounds determined in pighouse odour. Two research groups have used odour activity values (OAVs) for studies on pig-house and have assessed the impact of a limited list of compounds (<20) for their own analyses only (4, 5). The aim of this work was to evaluate the relative importance for pig-house odour of a comprehensive list of volatile compounds reported by a number of authors from pig house emissions. This was achieved through a reanalysis of the extensive published data using a consistent set of odour thresholds to calculate OAVs. II. MATERIALS AND METHODS The odour detection threshold (ODT) is usually determined as the concentration at which 50% of assessors can detect an odour. No one research group has determined odour detection thresholds for all the odour compounds of interest. Nagata et al. (6) measured the odour thresholds of 223 chemicals by the Japanese triangular bag method. For some compounds, Nagata et al (6) did not report an ODT; then one was estimated from another source. The methods used and the resulting set of odour threshold data, denoted “Nagata+”, is presented elsewhere (7). A second set of odour thresholds (“Devos+”) was based on the list published by Devos et al. (8), taken from over a hundred references for over six hundred chemical compounds. OAVs were also calculated using the “Devos+” list and are presented elsewhere (7). Out of 89 papers on pig-house odours, 22 were identified which presented quantitative data of the air or slurry headspace concentration of volatile compounds released from piggery facilities. Some of these had collected volatile odour compounds using Tedlar odour bags and others using thermal 61st International Congress of Meat Science and Technology, 23-28th August 2015, Clermont-Ferrand, France desorption from adsorption tubes. Furthermore, the location and type of sample varied. The concentrations of volatile compounds released from pig-houses have been collated from the literature and the OAV values presented in this paper were calculated by using the ODTs from the “Nagata+ list”. OAV = [compound in air (mg m-3)] ODT in air (mg m-3) III. RESULTS AND DISCUSSION Figure 1 presents the mean OAV, calculated using the “Nagata+ list”, from those publications which reported quantitative data using adsorption tubes for these compounds. A simple mean of variable data can only provide a very approximate picture of the relative OAVs of the compounds shown and the data is examined in more detail elsewhere (7). However, an examination of the results from the individual authors showed good agreement on the identity of the compounds with the highest OAVs. The OAVs calculated using the “Devos+ list” (not shown) showed similar relative trends. Figure 1 therefore provides a reasonable illustration of the relative importance of the compounds shown. Short chain acids were important for pig-house odour whether collected from slurry or adjacent to the pig-house itself. They were more prevalent when collected using thermal desorption rather than odour bags (7). These acids result from intestinal microbial activity in the large intestine and cause rancid, cheese, faecal odours. OAVs only show the relative importance of individual odour compounds and different compounds, especially from the same compound class, can have a cumulative effect. The large number of acids detected at above their ODT suggests that these may have a greater combined effect. Ammonia is frequently associated with pig-house odour within the industry. However, these results confirm previous work (2), showing that amines are only one of many odorous compound classes. Indoles, including the compounds 3-methylindole or skatole, and alkylphenols are well known for their faeces-like and pungent odours. They were consistently present at high odour activity values. Indoles are formed in the gut by microbial metabolism of tryptophan and the alkyphenols are formed by microbial fermentation of tyrosine and phenylalanine. Figure 1. Compounds contributing to pig-house odour, determined by thermal desorption ACIDS 10000 ALIPHATICS AMINES INDOLES PHENOLS BENZENES KETONES SULPHUR 1000 100 10 OAV 1 0.1 0.01 0.001 2-MethylButanoic Acid 2-MethylPropanoic Acid 3-MethylButanoic Acid 4-MethylPentanoic Acid Acetic Acid Butanoic Acid Dodecanoic Acid Heptanoic Acid Hexanoic Acid Nonanoic Acid Octanoic Acid Pentanoic Acid Propanoic Acid 1-Butanol 1-Decanol 1-Dodecanol 1-Pentanol 2-Butanol 3-Octanol 3-Methylbutanal Acetaldehyde Butanal Hexanal Pentanal Hexane Tetradecane Dimethylacetamide 2-Amino acetophenone Ammonia Trimethylamine Acetophenone Benzaldehyde Benzene Benzyl alcohol Butylated hydroxytoluene Toluene 2-Furanmethanol 3-methylindole Indole 2-Butanone 3-Hydroxy-2-butanone 3-Methyl-2-butanone Acetone 2-Methoxyphenol 4-Ethylphenol 4-Methylphenol 4-propylphenol Phenol Dimethyl disulphide Dimethyl sulphide Dimethyl trisulphide Hydrogen sulphide 0.0001 0.00001 61st International Congress of Meat Science and Technology, 23-28th August 2015, Clermont-Ferrand, France Some aliphatic and aromatic compounds (‘aliphatics’, ‘ketones’, ‘benzenes’) are reported occasionally at sufficient concentrations to give an OAV>1, and may sometimes contribute to pighouse odour. However, their odour is not generally unpleasant and their OAV is generally considerably lower than that of other compound classes and it is unlikely that they will make a large contribution to pig-house odour. These data (illustrated in Figure 1) show that the most important compound classes for pig-house odour are short chain acids, sulphur compounds, phenols, indoles and amines. Where suitable quantitative data was published, it has been possible to use the same approach to reevaluate data on potential mitigation factors. Figures 2 and 3 shows the results for two of these: covering the slurry tank (9) and increasing the liquid content of the diet (10). Figure 2 shows that the most important odour compounds change during 9 weeks storage and that covering the slurry reduces the impact of ammonia, indoles and phenols but has little effect on the impact of acids or sulphur compounds (9). In contrast, increasing the liquid component of the diet (Figure 3) decreases the contribution to the odour of acids and sulphur compounds, but has little effect on other compounds (10). Thus, different mitigation factors influence different compound classes. This suggests that there is no single method for reducing pig-house odour. This has implications for the selection of abatement strategies. Figure 2. Effect of covering and ageing slurry on odour activity of compound classes (9) (b) Covered slurry at start of expt 10000 1000 1000 100 100 10 10 1 1 OAV 0.1 0.1 0.01 0.01 OAV 1 0.1 1 0.1 Carbon disulphide Dimethyl sulphide Dimethyl disulphide Phenol 4-Methylphenol Indole 3-Methylindole Benzaldehyde 1-Butanol Benzyl alcohol Ammonia Trimethylamine Pentanoic acid Butanoic acid (d) Slurry covered with dry straw at 9 weeks Hydrogen sulphide 10 Compound 3-Methylbutanoic Acid 100 2-Methylpropanoic acid 1000 Acetic acid Carbon disulphide Dimethyl sulphide Dimethyl disulphide Hydrogen sulphide Phenol 4-Methylphenol Indole 3-Methylindole Benzaldehyde 1-Butanol Benzyl alcohol Ammonia 10 Compound 0.01 0.01 Compound Carbon disulphide Dimethyl disulphide Dimethyl sulphide Hydrogen sulphide Phenol 4-Methylphenol 3-Methylindole Indole Benzaldehyde 1-Butanol Benzyl alcohol Trimethylamine Ammonia Pentanoic acid 3-Methylbutanoic Acid Butanoic acid 2-Methylpropanoic acid 0.001 0.0001 Acetic acid 0.001 0.0001 propanoic acid OAV Trimethylamine Pentanoic acid Butanoic acid (c) Uncovered slurry at 9 weeks 0.00001 0.000001 propanoic acid 100 3-Methylbutanoic Acid 1000 2-Methylpropanoic acid Acetic acid 0.001 0.0001 propanoic acid 0.001 0.0001 Acetic acid propanoic acid 2-Methylpropanoic acid Butanoic acid 3-Methylbutanoic Acid Pentanoic acid Ammonia Trimethylamine 1-Butanol Benzyl alcohol Benzaldehyde Indole 3-Methylindole Phenol 4-Methylphenol Hydrogen sulphide Dimethyl sulphide Dimethyl disulphide Carbon disulphide OAV (a) Uncovered slurry at start of expt 10000 Compound 61st International Congress of Meat Science and Technology, 23-28th August 2015, Clermont-Ferrand, France Figure 3. Effect of liquid diet on odour activity of pighouse odours (10) (a) Dry feed 1000000 100000 OAV 10000 1000 100 methyl mercaptan Hydrogen sulphide Dimethyl sulphide Dimethyl disulphide Dimethyl disulphide Dimethyl trisulphide Phenol Phenol Phenol (b) 3:1 water/feed Dimethyl disulphide 4-Methylphenol 4-Methylphenol 4-Methylphenol Indole 4-Ethylphenol 4-Ethylphenol 4-Ethylphenol Indole Indole 3-Methylindole 3-Methylindole 3-Methylindole propanoic acid propanoic acid propanoic acid Pentanoic acid Pentanoic acid Pentanoic acid Acetic acid Butanoic acid Butanoic acid Butanoic acid 3-Methylbutanoic … 1000 2-Methylpropanoic… OAV 10000 3-Methylbutanoic… 100000 2-Methylpropanoic … 1000000 3-Methylbutanoic Acid 1 2-Methylpropanoic acid 10 100 Hydrogen sulphide methyl mercaptan Hydrogen sulphide methyl mercaptan 1000 Dimethyl sulphide OAV 10000 Dimethyl trisulphide 100000 (c) 4:1 water/feed Dimethyl sulphide 1000000 Dimethyl trisulphide 1 Acetic acid 10 100 10 IV. Acetic acid 1 CONCLUSION The most important odour compounds contributing to pig-house odour are short chain acids, sulphur compounds, phenols, indoles and amines. These compounds have the highest odour activity values and often have pungent and offensive odours. The odour activity of these compounds is affected by a number of factors, including method of analysis. Potential mitigation factors related to slurry management or pig diets have differential effects on these classes of odorous compounds, suggesting that there is no single solution to the problem of pig-house odour and that an analysis of the compounds responsible is essential before considering mitigation strategies. ACKNOWLEDGEMENTS The authors would like to thank the Department of Agriculture and Rural Development, Northern Ireland, for funding this research and Ms Barbara Alaejos for her assistance with the collation of the published data. REFERENCES (1) Ni, J.Q., Robarge, W. P., Xiao, C. H. & Heber, A. J. (2012) Volatile organic compounds at swine facilities: A critical review. Chemosphere. 89, 769-788. (2) O'Neill, D.H., & Phillips, V.R.A. (1992) Review of the control of odour nuisance from livestock buildings: Part 3: Properties of the odorous substances which have been identified in livestock wastes or in the air around them. Journal of Agricultural Engineering Research. 53, 23-50. (3) Acree, T., Barnard, J., & Cunningham, D. (1984) A procedure for the sensory analysis of gas chromatographic effluents. Food Chemistry. 14., 273-286. (4) Trabue, S.K., B.; Bearson, B. & Ziemer, C. (2011) Swine Odor Analyzed by Odor Panels and Chemical Techniques. Journal of Environmental Quality. 40, 1510-1520. (5) Parker, D.B., Koziel, J. A., Cai, L., Jacobson, L. D., Akdeniz, N., Bereznicki, S. D., Lim, T. T., Caraway, E. A., Zhang, S., Hoff, S. J., Heber, A. J., Heathcote, K. Y. & Hetchler, B. P. (2012) Odor and Odorous Chemical Emissions from Animal Buildings: Part 6. Odor Activity Value. 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Journal of the Science of Food and Agriculture. 73, 437445. 61st International Congress of Meat Science and Technology, 23-28th August 2015, Clermont-Ferrand, France
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