[Bouvier-Brown2007]
Bouvier-Brown, N. C., R. Holzinger, K. Palitzsch, and A. H. Goldstein,
"Quantifying sesquiterpene and oxygenated terpene emissions from live vegetation using solid-phase microextraction fibers.",
J Chromatogr A, vol. 1161, no. 1-2: University of California, Berkeley, CA, USA. nbouvier@nature.berkeley.edu, pp. 113–120, Aug, 2007.
Link:
http://dx.doi.org/10.1016/j.chroma.2007.05.094
Biogenic terpenes play important roles in ecosystem functioning and atmospheric chemistry. Some of these compounds are semi-volatile and highly reactive, such as sesquiterpenes and oxygenated terpenes, and are thus difficult to quantify using traditional air sampling and analysis methods. We developed an alternative approach to quantify emissions from live branches using a flow through enclosure and sample collection on solid-phase microextraction (SPME) fibers. This method allows for collection and analysis of analytes with minimal sample transfer through tubing to reduce the potential for losses. We characterized performance characteristics for 65 microm polydimethylsiloxane-divinylbenzene (PDMS/DVB) fibers using gas chromatography followed by mass spectrometry and optimized experimental conditions and procedures for field collections followed by laboratory analysis. Using 10-45 min sampling times and linear calibration curves created from mixtures of terpenes, emissions of methyl chavicol, an oxygenated terpene, and an array of sesquiterpenes were quantified from a Ponderosa pine branch. The detection limit was 4.36 pmol/mol (ppt) for methyl chavicol and 16.6 ppt for beta-caryophyllene. Concentrations determined with SPME fibers agreed with measurements made using proton transfer reaction mass spectrometry (PTR-MS) within the estimated error of the method for well calibrated compounds. This technique can be applied for quantification of biogenic oxygenated terpene and sesquiterpene emissions from live branches in the field.
[Shaw2007]
Shaw, S. L., F. M. Mitloehner, W. Jackson, E. J. Depeters, J. G. Fadel, P. H. Robinson, R. Holzinger, and A. H. Goldstein,
"Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry.",
Environ Sci Technol, vol. 41, no. 4: Department of Environmental Science, Policy, and Management, University of California, Berkeley, Hilgard Hall, Berkeley, California 94720, USA. slshaw@alum.mit.edu, pp. 1310–1316, Feb, 2007.
Link:
http://pubs.acs.org/doi/abs/10.1021/es061475e
California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.