Watershed contamination from antibiotics is becoming a critical issue because of increased numbers of confined animal-feeding operations and the use of antibiotics in animal production. To understand the fate of tylosin in manure before it is land-applied, degradation in manure lagoon slurries at 228C was studied. Tylosin disappearance followed a biphasic pattern, where rapid initial loss was followed by a slow removal phase. The 90% disappearance times for tylosin, relomycin (tylosin D), and desmycosin (tylosin B) in anaerobically incubated slurries were 30 to 130 hours. Aerating the slurries reduced the 90% disappearance times to between 12 and 26 hours. Biodegradation and abiotic degradation occur, but strong sorption to slurry solids was probably the primary mechanism of tylosin disappearance. Dihydrodesmycosin and an unknown degradate with molecular mass of m/z 934.5 were detected. Residual tylosin remained in slurry after eight months of incubation, indicating that degradation in lagoons is incomplete and that residues will enter agricultural fields. Water Environ. Res., 77, 49 (2005).

Bovine rumen fluid was fermented anaerobically with 25 mM R-propylene glycol, S-propylene glycol, or glycerol added. After 24 h, all of the propylene glycol enantiomers and approximately 80% of the glycerol were metabolized. Acetate, propionate, butyrate, valerate, and caproate concentrations, in decreasing order, all increased with incubation time. Addition of any of the three substrates somewhat decreased acetate formation, while addition of either propylene glycol increased propionate formation but decreased that of butyrate. R-and S-propylene glycol did not differ significantly in either their rates of disappearance or the products formed when they were added to the fermentation medium. Fermentations of rumen fluid containing propylene glycol emitted the sulfur-containing gases 1-propanethiol, 1-(methylthio)propane, methylthiirane, 2,4-dimethylthiophene, 1-(methylthio)-1-propanethiol, dipropyl disulfide, 1-(propylthio)-1-propanethiol, dipropyl trisulfide, 3,5-diethyl-1,2,4-trithiolane, 2-ethyl-1,3-dithiane, and 2,4,6-triethyl-1,3,5-trithiane. Metabolic pathways that yield each of these gases are proposed. The sulfurcontaining gases produced during propylene glycol fermentation in the rumen may contribute to the toxic effects seen in cattle when high doses are administered for therapeutic purposes. KeywordsBiodiesel, glycerol, ketosis, propylene glycol, rumen, sulfur-containing gases, volatile fatty acids Disciplines Biochemical and Biomolecular Engineering | Biological Engineering | Bioresource and Agricultural Engineering | Chemical Engineering CommentsPosted with permission from Journal of Agricultural and Food Chemistry, 55, no. 17 (2007) Bovine rumen fluid was fermented anaerobically with 25 mM R-propylene glycol, S-propylene glycol, or glycerol added. After 24 h, all of the propylene glycol enantiomers and approximately 80% of the glycerol were metabolized. Acetate, propionate, butyrate, valerate, and caproate concentrations, in decreasing order, all increased with incubation time. Addition of any of the three substrates somewhat decreased acetate formation, while addition of either propylene glycol increased propionate formation but decreased that of butyrate. R-and S-propylene glycol did not differ significantly in either their rates of disappearance or the products formed when they were added to the fermentation medium. Fermentations of rumen fluid containing propylene glycol emitted the sulfur-containing gases 1-propanethiol, 1-(methylthio)propane, methylthiirane, 2,4-dimethylthiophene, 1-(methylthio)-1-propanethiol, dipropyl disulfide, 1-(propylthio)-1-propanethiol, dipropyl trisulfide, 3,5-diethyl-1,2,4-trithiolane, 2-ethyl-1,3-dithiane, and 2,4,6-triethyl-1,3,5-trithiane. Metabolic pathways that yield each of these gases are proposed. The sulfur-containing gases produced during propylene glycol fermentation in the rumen may contribute to the toxic effects seen in cattle when high doses are administered for therapeutic purposes.

Volatile sulfur compounds (VSCs) are a major class of chemicals associated with odor from animal feeding operations (AFOs). Identifying and quantifying VSCs in air is challenging due to their volatility, reactivity, and low concentrations. In the present study, a canister-based method collected whole air in fused silica-lined (FSL) mini-canister (1.4 L) following passage through a calcium chloride drying tube. Sampled air from the canisters was removed (10-600 mL), dried, pre-concentrated, and cryofocused into a GC system with parallel detectors (mass spectrometer (MS) and pulsed flame photometric detector (PFPD)). The column effluent was split 20:1 between the MS and PFPD. The PFPD equimolar sulfur response enhanced quantitation and the location of sulfur peaks for mass spectral identity and quantitation. Limit of quantitation for the PFPD and MSD was set at the least sensitive VSC (hydrogen sulfide) and determined to be 177 and 28 pg S, respectively, or 0.300 and 0.048 μg m −3 air, respectively. Storage stability of hydrogen sulfide and methanethiol was problematic in warm humid air (25 °C, 96% relative humidity (RH)) without being dried first, however, stability in canisters dried was still only 65% after 24 h of storage. Storage stability of hydrogen sulfide sampled in the field at a swine facility was over 2 days. The greater stability of field samples compared to laboratory samples was due to the lower temperature and RH of field samples compared to laboratory generated samples. Hydrogen sulfide was the dominant odorous VSCs detected at all swine facilities with methanethiol and dimethyl sulfide detected notably above their odor threshold values. The main odorous VSC detected in aged poultry litter was dimethyl trisulfide. Other VSCs above odor threshold values for poultry facilities were methanethiol and dimethyl sulfide. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. AbstractVolatile sulfur compounds (VSCs) are a major class of chemicals associated with odor from animal feeding operations (AFOs). Identifying and quantifying VSCs in air is challenging due to their volatility, reactivity, and low concentrations. In the present study, a canister-based method collected whole air in fused silica-lined (FSL) mini-canister (1.4 L) following passage through a calcium chloride drying tube. Sampled air from the canisters was removed (10-600 mL), dried, preconcentrated, and cryofocused into a GC system with parallel detectors (mass spectrometer (MS) and pulsed flame photometric detector (PFPD)). The column effluent was split 20:1 between the MS and PFPD. The PFPD equimolar sulfur response enhanced quantitation and the location of sulfur peaks for mass spectral identity and quantitation. Limit of quantitation for the PFPD and MSD was set at the least sensitive VSC (hydrogen sulfide) and determined to be 177 and 28 pg S, respectively, or 0.300 and 0.048 mg m À3 air, respectively. S...

There are approximately 2.5 million dairy cows in California. Emission inventories list dairy cows and their manure as the major source of regional air pollutants, but data on their actual emissions remain sparse, particularly for smog‐forming volatile organic compounds (VOCs) and greenhouse gases (GHGs). We report measurements of alcohols, volatile fatty acids, phenols, and methane (CH4) emitted from nonlactating (dry) and lactating dairy cows and their manure under controlled conditions. The experiment was conducted in an environmental chamber that simulates commercial concrete‐floored freestall cow housing conditions. The fluxes of methanol, ethanol, and CH4 were measured from cows and/or their fresh manure. The average estimated methanol and ethanol emissions were 0.33 and 0.51 g cow−1 h−1 from dry cows and manure and 0.7 and 1.27 g cow−1 h−1 from lactating cows and manure, respectively. Both alcohols increased over time, coinciding with increasing accumulation of manure on the chamber floor. Volatile fatty acids and phenols were emitted at concentrations close to their detection limit. Average estimated CH4 emissions were predominantly associated with enteric fermentation from cows rather than manure and were 12.35 and 18.23 g cow−1 h−1 for dry and lactating cows, respectively. Lactating cows produced considerably more gaseous VOCs and GHGs emissions than dry cows (P < 0.001). Dairy cows and fresh manure have the potential to emit considerable amounts of alcohols and CH4 and research is needed to determine effective mitigation.

Most air quality studies in agricultural environments use thermal desorption analysis for quantifying semivolatile organic compounds (SVOCs) associated with odor. The objective of this study was to develop a robust sampling technique for measuring SVOCs in humid environments. Test atmospheres were generated at ambient temperatures (23 ± 1.5 °C) and 25, 50, and 80% relative humidity (RH). Sorbent material used included Tenax, graphitized carbon, and carbon molecular sieve (CMS). Sorbent tubes were challenged with 2, 4, 8, 12, and 24 L of air at various RHs. Sorbent tubes with CMS material performed poorly at both 50 and 80% RH due to excessive sorption of water. Heating of CMS tubes during sampling or dry-purging of CMS tubes post sampling effectively reduced water sorption with heating of tubes being preferred due to the higher recovery and reproducibility. Tenax tubes had breakthrough of the more volatile compounds and tended to form artifacts with increasing volumes of air sampled. Graphitized carbon sorbent tubes containing Carbopack X and Carbopack C performed best with quantitative recovery of all compounds at all RHs and sampling volumes tested. The graphitized carbon tubes were taken to the field for further testing. Field samples taken from inside swine feeding operations showed that butanoic acid, 4-methylphenol, 4-ethylphenol, indole, and 3-methylindole were the compounds detected most often above their odor threshold values. Field samples taken from a poultry facility demonstrated that butanoic acid, 3-methylbutanoic acid, and 4-methylphenol were the compounds above their odor threshold values detected most often. Received December 14, 2007. Revised manuscript received February 08, 2008. Accepted February 14, 2008 Most air quality studies in agricultural environments use thermal desorption analysis for quantifying semivolatile organic compounds (SVOCs) associated with odor. The objective of this study was to develop a robust sampling technique for measuring SVOCs in humid environments. Test atmospheres were generated at ambient temperatures (23 ( 1.5°C) and 25, 50, and 80% relative humidity (RH). Sorbent material used included Tenax, graphitized carbon, and carbon molecular sieve (CMS). Sorbent tubes were challenged with 2, 4, 8, 12, and 24 L of air at various RHs. Sorbent tubes with CMS material performed poorly at both 50 and 80% RH due to excessive sorption of water. Heating of CMS tubes during sampling or drypurging of CMS tubes post sampling effectively reduced water sorption with heating of tubes being preferred due to the higher recovery and reproducibility. Tenax tubes had breakthrough of the more volatile compounds and tended to form artifacts with increasing volumes of air sampled. Graphitized carbon sorbent tubes containing Carbopack X and Carbopack C performed best with quantitative recovery of all compounds at all RHs and sampling volumes tested. The graphitized carbon tubes were taken to the field for further testing. Field samples taken from inside swine feeding operations show...

Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. Volatile organic compounds (VOCs) emitted from poultry production are leading source of air quality problems. However, little is known about the speciation and levels of VOCs from poultry production. The objective of this study was the speciation of VOCs from a poultry facility using evacuated canisters and sorbent tubes. Samples were taken during active poultry production cycle and between production cycles. Levels of VOCs were highest in areas with birds and the compounds in those areas had a higher percentage of polar compounds (89%) compared to aliphatic hydrocarbons (2.2%). In areas without birds, levels of VOCs were 1/3 those with birds present and compounds had a higher total percentage of aliphatic hydrocarbons (25%). Of the VOCs quantified in this study, no single sampling method was capable of quantifying more than 55% of compounds and in several sections of the building each sampling method quantified less than 50% of the quantifiable VOCs. Key classes of chemicals quantified using evacuated canisters included both alcohols and ketones, while sorbent tube samples included volatile fatty acids and ketones. The top five compounds made up close to 70% of VOCs and included: 1) acetic acid (830.1 mg m À3 ); 2) 2,3-butanedione (680.6 mg m À3 ); 3) methanol (195.8 mg m À3 ); 4) acetone (104.6 mg m À3 ); and 5) ethanol (101.9 mg m À3 ). Location variations for top five compounds averaged 49.5% in each section of the building and averaged 87% for the entire building.Published by Elsevier Ltd.

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Nonpoint source pollution of surface water by nitrate from agricultural activities is a national problem. An agricultural watershed in the Iowa Loess Hills with a 23year history of annual corn production with average N fertilization is studied. Headcut seepage is transported through a natural riparian zone and observed as weir baseflow; surface runoff is measured separately. Nitrate runoff graphs illustrate the importance of high-frequency sampling of each event to permit quantitative estimation of chemical loss. The concentration of nitrate carried from the field in basin drainage steadily increased from <1 mg L -1 in 1969 to >20 mg L -1 in 1991. The rate of cumulative increase in the amount of applied N is greater than the rate of removal by the crop. Over the 23-year record, 23% of the mean annual application of N remains stored and available for leaching or chemical conversion by soil microbes. Nitrate removal during early spring snowmelt surface runoff shows a diurnal pattern that corresponds to the daily freezing and thawing of the surface soil in early March. Contribution to the load of nitrate deposited on the soil surface by rainfall is very small in comparison to the amount applied by fertilizer application. Measurable changes in water quality within various hydrogeologic compartments are seldom observed in just a few years of monitoring. Therefore, these results emphasize the importance of long-term data sets incorporating temporal variability when evaluating the impact of agricultural practices on surface water resources.