Plants usually emit large amount and varieties of volatiles after being damaged by herbivores. However, analytical methods for measuring herbivore-induced volatiles do not normally monitor the whole range of volatiles and the response to large herbivores such as large mammals is much less studied than the response to other herbivores such as insects. In this paper we present the results of using a highly sensitive proton transfer reaction-mass spectrometry (PTR-MS) technique that allows simultaneous monitoring of leaf volatiles in the pptv range. The resulting mass scans in air over Mediterranean shrubland browsed by horses show 70 to 100% higher concentrations of the masses corresponding to mass fragments 57, 43 and 41 (mostly hexenals, acetone and acetic acid) than scans over control non-browsed shrubland. These compounds are biogeochemically active and they are significant components of the volatile organic carbon found in the atmosphere. They influence the performance of living organisms and, the chemical and physical processes of Earth's atmosphere.