title: Temporal and spatial variability of trace volatile organic compounds in rainwater.
abstract: This study presents the first detailed concentration profile of trace VOCs in atmospheric waters. Analytes were detected and quantified in 111 unique rain events in Wilmington, NC, USA over a one-year period. Headspace solid phase microextraction was optimized for detection of these compounds at sub-nanomolar levels. Distinct seasonality in both the occurrence and concentration of compounds was observed with the lowest abundance occurring during low irradiance winter months. In contrast to other rainwater components studied at this location, VOCs did not show any correlation between rainfall amount and concentrations. There was significant spatial variation with regards to air-mass back-trajectory for methyfuran with higher concentrations observed in terrestrial events during the growing season. Air mass back trajectory also impacted CCl4 concentrations in rainwater with evidence of a possible oceanic input. However there was no significant impact of air-mass back-trajectory on the concentration of BTEX observed in rain indicating that storm origin is not the controlling factor driving concentrations of these analytes in precipitation. Members of the BTEX family did, however, have significant correlations with each other occurring in ratios aligned closely with ratios reported in the literature for gas-phase BTEX. Using available gas-phase data from locations with similar anthropogenic sources and Henry's Law constants, calculated concentrations agreed with VOC levels found in Wilmington rain. Results of this study indicate local gas-phase scavenging is the major source of VOCs in rain and wet deposition is not an efficient removal mechanism (<0.1%) of VOCs from the atmosphere.
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA. Electronic address: mullaughkm@cofc.edu.
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Mullaugh
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA.
authors.forename: Joanna M
authors.initials: JM
authors.lastname: Hamilton
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA.
authors.forename: G Brooks
authors.initials: GB
authors.lastname: Avery
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA.
authors.forename: J David
authors.initials: JD
authors.lastname: Felix
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA.
authors.forename: Ralph N
authors.initials: RN
authors.lastname: Mead
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA.
authors.forename: Joan D
authors.initials: JD
authors.lastname: Willey
authors.affiliation: Department of Chemistry & Biochemistry, University of North Carolina Wilmington, Wilmington, NC, USA.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Kieber
mesh_terms: D000393:Air Pollutants / Q000032:analysis*; D001272:Atmosphere / Q000032:analysis*; D001554:Benzene / Q000032:analysis; D001555:Benzene Derivatives / Q000032:analysis; D002251:Carbon Tetrachloride / Q000737:chemistry; D002712:Chlorides / Q000032:analysis; D005663:Furans / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry; D017665:Hydroxyl Radical; D011891:Rain / Q000737:chemistry*; D012621:Seasons; D012964:Sodium / Q000032:analysis; D062211:Spatio-Temporal Analysis; D014050:Toluene / Q000032:analysis; D055549:Volatile Organic Compounds / Q000032:analysis*; D014867:Water; D014874:Water Pollutants, Chemical / Q000032:analysis*; D014992:Xylenes / Q000032:analysis
chemical_list: D000393:Air Pollutants; D001555:Benzene Derivatives; D002712:Chlorides; D005663:Furans; D055549:Volatile Organic Compounds; D014874:Water Pollutants, Chemical; D014992:Xylenes; D014867:Water; D017665:Hydroxyl Radical; D014050:Toluene; C029060:2-methylfuran; D012964:Sodium; D002251:Carbon Tetrachloride; D001554:Benzene; C004912:ethylbenzene
keywords: BTEX; Carbon tetrachloride; HS-SPME; Methylfuran; Rainwater; VOCs