Atmospheric sources of herbicides enable short- and long-range transport of these compounds to off-target areas but the concentrations and mechanisms are poorly understood due, in part, to the challenge of detecting these compounds in the atmosphere. We present chemical ionization time-of-flight mass spectrometry as a sensitive, real-time technique to detect chlorinated phenoxy acid herbicides in the atmosphere, using measurements during and after application over a field at Colorado State University as a case study. Gas-phase 2,4-dichlorophenoxyacetic acid (2,4-D) mixing ratios were greatest during application (up to 20 pptv), consistent with rapid volatilization from spray droplets. In contrast, atmospheric concentrations of 2-methyl-4-chlorophenoxyacetic acid (MCPA) increased for several hours after the initial application, indicative of a slower source than 2,4-D. The maximum observed gas-phase MCPA was 60 pptv, consistent with a post-application volatilization source to the atmosphere. Exposure to applied pesticides in the gas-phase can thus occur both during and at least several hours after application. Spray droplet volatilization and direct volatilization from surfaces may both contribute pesticides to the atmosphere, enabling pesticide transport to off-target and remote regions.
Keywords: atmospheric chemistry; chemical ionization; field; mass spectrometry; pesticides.