Definition, analysis, and certification of biochar quality are crucial to the agronomic acceptance of biochar. While most biochars have a positive impact on plant growth, some may have adverse effects due to the presence of phytotoxic compounds. Conversely, some biochars may have the ability to adsorb and neutralize natural phytotoxic compounds found in soil. We evaluated the effects of biochars on seedling growth and absorption of allelochemicals present in corn (Zea mays L.) residues. Corn seeds were germinated in aqueous extracts of six biochars produced from varied feedstocks, thermochemical processes, and temperatures. Percent germination and shoot and radicle lengths were evaluated at the end of the germination period. Extracts from the six biochars had no effect on percent germination; however, extracts from three biochars produced at high conversion temperatures significantly inhibited shoot growth by an average of 16% relative to deionized (DI) water. Polycyclic aromatic hydrocarbons detected in the aqueous extracts are believed to be at least partly responsible for the reduction in seedling growth. Repeated leaching of biochars before extract preparation eliminated the negative effects on seedling growth. Biochars differ significantly in their capacity to adsorb allelochemicals present in corn residues. Germination of corn seeds in extracts of corn residue showed 94% suppression of radicle growth compared to those exposed to DI water; however, incubation of corn residue extracts with leached biochar for 24 h before initiating the germination test increased radicle length 6 to 12 times compared to the corn residue extract treatments. Germination tests appear to be a reliable procedure to differentiate between effects of different types of biochar on corn seedling growth.

Odor regulations typically specify the use of dynamic dilution olfactometery (DDO) as a method to quantify odor emissions, and Tedlar bags are the preferred holding container for grab samples. This study was conducted to determine if Tedlar bags affect the integrity of sampled air from animal operations. Air samples were collected simultaneously in both Tedlar bags and Tenax thermal desorption tubes. Sample sources originated from either a hydrocarbon-free air tank, dynamic headspace chamber (DHC), or swine-production facility, and were analyzed by gas chromatography-mass spectrometry-olfactometry (GC-MS-O). Several background contaminants were identified from Tedlar bags, which included the odorous compounds N,N-dimethyl acetamide (DMAC), acetic acid, and phenol. Samples from the DHC demonstrated that recovery of malodor compounds was dependent on residence time in the Tedlar bag with longer residence time leading to lower recovery. After 24 h of storage, recovery of C3-C6 volatile fatty acids (VFA) averaged 64%, 4-methylphenol and 4-ethylphenol averaged 10%, and indole and 3-methylindole were below the detection limits of GC-MS-O. The odor activity value (OAV) of grab samples collected in Tedlar bags were 33 to 65% lower following 24 h of storage. These results indicate that significant odorant bias occurs when using Tedlar bags for the sampling of odors from animal production facilities.

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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.

An experiment was conducted to investigate the effects of reducing dietary CP and increasing dietary cellulose concentrations on manure DM, C, N, S, VFA, indole, and phenol concentrations. Twenty-two pigs (105 kg initial BW) were fed diets containing either 14.5 or 12.0% CP, in combination with either 2.5 or 8.7% cellulose. Pigs were fed twice daily over the 56-d study, with feed intake averaging 2.74 kg/d. Feces and urine were collected after each feeding and added to the manure storage containers. Manure storage containers were designed to provide a similar unit area per animal as found in industry (7,393 cm2). Before sampling on d 56, the manure was gently stirred to obtain a representative sample for subsequent analyses. An interaction of dietary CP and cellulose was observed for manure acetic acid concentration, in that decreasing CP lowered acetic acid in pigs fed standard levels of cellulose but increased acetic acid in pigs fed greater levels of cellulose (P = 0.03). No other interactions were noted. Decreasing dietary CP reduced manure pH (P = 0.01), NH4 (P = 0.01), isovaleric acid (P = 0.06), phenol (P = 0.05), and 4-ethyl phenol (P = 0.02) concentrations. Increasing dietary cellulose decreased pH (P = 0.01) and NH4 (P = 0.07) concentration but increased manure C (P = 0.03), propionic acid (P = 0.01), butyric acid (P = 0.03), and cresol (P = 0.09) concentrations in the manure. Increasing dietary cellulose also increased manure DM (P = 0.11), N (P = 0.11), and C (P = 0.02) contents as a percentage of nutrient intake. Neither cellulose nor CP level of the diet affected manure S composition or output as a percentage of S intake. Headspace N2O concentration was increased by decreasing dietary CP (P = 0.03) or by increasing dietary cellulose (P = 0.05). Neither dietary CP nor cellulose affected headspace concentration of CH4. This study demonstrates that diets differing in CP and cellulose content can significantly impact manure composition and concentrations of VFA, phenol, and indole, and headspace concentrations of N(2)O, which may thereby affect the environmental impact of livestock production on soil, air, and water.

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