Characterization of volatile organic compounds and odors by in-vivo sampling of beef cattle rumen gas, by solid-phase microextraction, and gas chromatography–mass spectrometry–olfactometry

AbstractVolatile organic compounds (VOCs) and odors in cattle rumen gas have been characterized by in-vivo headspace sampling by solid-phase microextraction (SPME) and analysis by gas chromatography–mass spectrometry–olfactometry (GC–MS–O). A novel device enabling headspace SPME (HS-SPME) sampling through a cannula was designed, refined, and used to collect rumen gas samples from steers. A Carboxen–polydimethylsiloxane (PDMS) fiber (85 μm) was used for SPME sampling. Fifty VOCs from ten chemical groups were identified in the rumen headspace. The VOCs identified had a wide range of molecular weight (MW) (34 to 184), boiling point (−63.3 to 292 °C), vapor pressure (1.05 × 10−5 to 1.17 × 102 Pa), and water solubility (0.66 to 1 × 106 mg L−1). Twenty-two of the compounds have a published odor detection thresholds (ODT) of less than 1 ppm. More than half of the compounds identified are reactive and have an estimated atmospheric lifetime of <24 h. The amounts of VFAs, sulfide compounds, phenolic compounds, and skatole, and the odor intensity of VFAs and sulfide compounds in the rumen gas were all higher after feeding than before feeding. These results indicate that rumen gases can be an important potential source of aerial emissions of reactive VOCs and odor. In-vivo sampling by SPME then GC–MS–O analysis can be a useful tool for qualitative characterization of rumen gases, digestion, and its relationship to odor and VOC formation. FigureModified cannula for rumen gas sampling with SPME

[1]  J. Pawliszyn,et al.  Air Sampling and Analysis of Volatile Organic Compounds with Solid Phase Microextraction , 2001, Journal of the Air & Waste Management Association.

[2]  Christina Haberhauer-Troyer,et al.  Evaluation of solid-phase microextraction for sampling of volatile organic sulfur compounds in air for subsequent gas chromatographic analysis with atomic emission detection , 1999 .

[3]  T. Bates,et al.  Evidence for the climatic role of marine biogenic sulphur , 1987, Nature.

[4]  J. Pawliszyn Applications of Solid Phase Microextraction , 1999 .

[5]  J. Pawliszyn,et al.  Field sampling and determination of formaldehyde in indoor air with solid-phase microextraction and on-fiber derivatization. , 2001, Environmental science & technology.

[6]  J. Pawliszyn,et al.  Design and validation of portable SPME devices for rapid field air sampling and diffusion-based calibration. , 2001, Analytical chemistry.

[7]  R. E. Hungate,et al.  The Rumen and Its Microbes , 2013 .

[8]  Pawliszyn,et al.  Air sampling with porous solid-phase microextraction fibers , 2000, Analytical chemistry.

[9]  Jarett P. Spinhirne,et al.  Sampling and analysis of volatile organic compounds in bovine breath by solid-phase microextraction and gas chromatography-mass spectrometry. , 2004, Journal of chromatography. A.

[10]  S. Hoff,et al.  Solid-phase microextraction as a novel air sampling technology for improved, GC-olfactometry-based assessment of livestock odors. , 2006, Journal of chromatographic science.

[11]  G. Faichney Some notes on the separation of the volatile fatty acids in rumen fluid by gas-liquid chromatography. , 1967, Journal of chromatography.

[12]  S. Hoff,et al.  Characterization of volatile organic compounds and odorants associated with swine barn particulate matter using solid-phase microextraction and gas chromatography-mass spectrometry-olfactometry. , 2006, Journal of chromatography. A.

[13]  Jarett P. Spinhirne,et al.  Evaluation of Sample Recovery of Malodorous Livestock Gases from Air Sampling Bags, Solid-Phase Microextraction Fibers, Tenax TA Sorbent Tubes, and Sampling Canisters , 2005, Journal of the Air & Waste Management Association.

[14]  E. Kwiatkowska,et al.  Gas chromatography of C1 to C5 fatty acids in rumen fluid and fermentation media. , 1973, Journal of chromatography.

[15]  E. Godsy,et al.  Liquid Chromatographic Procedure for Fermentation Product Analysis in the Identification of Anaerobic Bacteria , 1981, Applied and environmental microbiology.

[16]  L. Armentano,et al.  Diagnostic methods for the detection of subacute ruminal acidosis in dairy cows. , 1999, Journal of dairy science.

[17]  G. D. Williams,et al.  An improved gas--liquid chromatographic procedure for the determination of 3-methylindole in rumen liquor, plasma, and tissue of ruminants. , 1979, Analytical biochemistry.

[18]  I. Schneider,et al.  Fermentation of cottonseed and other feedstuffs in cattle rumen fluid. , 2002, Journal of agricultural and food chemistry.

[19]  R. Dewhurst,et al.  Assessment of rumen processes by selected-ion-flow-tube mass spectrometric analysis of rumen gases. , 2001, Journal of dairy science.

[20]  M. Allen Relationship between fermentation acid production in the rumen and the requirement for physically effective fiber. , 1997, Journal of dairy science.

[21]  P. Doskey,et al.  Identification of nonmethane organic compound emissions from grassland vegetation. , 2000 .

[22]  J. Salanitro,et al.  Quantitative method for the gas chromatographic analysis of short-chain monocarboxylic and dicarboxylic acids in fermentation media. , 1975, Applied microbiology.

[23]  J. Dijkstra,et al.  Comparative analysis of gas production profiles obtained with buffalo and sheep ruminal fluid as the source of inoculum , 2005 .

[24]  G. Slavin,et al.  Experience with the sodium sulphate-Alcian Blue stain for amyloid in cardiac pathology. , 1976, Journal of clinical pathology.

[25]  W. Moore,et al.  Gas chromatographic analysis of amines and other compounds produced by several species of Clostridium. , 1969, Canadian journal of microbiology.

[26]  K. Phillips,et al.  Rapid diagnosis of anaerobic infections by gas-liquid chromatography of clinical material. , 1976, Journal of clinical pathology.

[27]  Jarett P. Spinhirne,et al.  Multidimensional gas chromatography-olfactometry for the identification and prioritization of malodors from confined animal feeding operations. , 2005, Journal of agricultural and food chemistry.

[28]  Robert G. Flocchini,et al.  Characterization and quantification of odorous and non-odorous volatile organic compounds near a commercial dairy in California , 2003 .

[29]  J. Pawliszyn,et al.  Determination of fatty acids using solid phase microextraction , 1995 .

[30]  M. Torremorell,et al.  Volatile fatty acids as odor indicators in swine manure - A critical review , 1999 .

[31]  S. Warren,et al.  Oceanic phytoplankton, atmospheric sulphur, cloud albedo and climate , 1987, Nature.

[32]  K. Keener,et al.  EVALUATION OF THERMAL DESORPTION FOR THE MEASUREMENT OF ARTIFICIAL SWINE ODORANTS IN THE VAPOR PHASE , 2002 .

[33]  L. B. Willett,et al.  Volatile Fatty Acid Emission During Composting of Swine Waste Amended With Sawdust as a Measure of Odor Potential , 2001 .

[34]  D. Schaefer,et al.  Simultaneous determination of lactic and volatile fatty acids in microbial fermentation extract by gas-liquid chromatography , 1987 .

[35]  J. Gullberg,et al.  Airborne chemical compounds on dairy farms. , 2001, Journal of environmental monitoring : JEM.

[36]  K. Yagi,et al.  Atmospheric methyl halides and dimethyl sulfide from cattle , 1999 .

[37]  M. Devos Standardized human olfactory thresholds , 1990 .