Proton-Transfer Chemical-Ionization Mass Spectrometry Allows Real-Time Analysis of Volatile Organic Compounds Released from Cutting and Drying of Crops

The wounding and drying of plant material during crop harvest could be a significant source of volatile organic compounds (VOCs) that enter the atmosphere. Here, we show that these primarily oxygenated VOCs can be measured using proton-transfer chemical-ionization mass spectrometry (PT-CIMS), a method that allows online and simultaneous monitoring of oxygenated VOC levels. For clover, alfalfa, and corn, leaf wounding and in particular drying were shown to lead to strongly enhanced emissions of a series of C 6 aldehydes, alcohols, and esters derived from ( Z )-3-hexenal. Additionally, for the forage crops clover and alfalfa, enhanced emissions of methanol, acetaldehyde, acetone, and butanone were observed. The identities of the measured carbonyl compounds were confirmed using high-pressure liquid chromatography. For clover, initial cutting led to a VOC release of about 175 μg of C (g dry wt) - 1, while during drying the cut clover released >1000 μg of C (g dry wt) - 1; qualitatively, similar amounts of VOCs were released from alfalfa, the major hay crop in the United States. The atmospheric implications of these findings may include effects on the local air quality in agricultural areas, contributions to long-range transport of pollutants, and effects on the formation of HO x ( OH + HO 2 ) radicals in the upper troposphere.