Quantifying biogenic and anthropogenic contributions to acetone mixing ratios in a rural environment

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Abstract

Acetone was one of the most abundant volatile organic compounds (VOCs) observed in the Sierra Nevada Mountains (California, USA). Mixing ratios were measured hourly above a ponderosa pine plantation using an automated in situ dual-channel GC-FID system throughout July 1997, from July through October 1998, and fluxes were measured with a relaxed eddy accumulator from July through September 1999. Acetone mixing ratios ranged from 1.4 to 7.8 ppb in July 1997, 1.1 to 7.8 ppb in July 1998, and 1.0 to 8.0 ppb in July 1999, and were correlated with compounds of biogenic and anthropogenic origin. During sunny periods in 1997 (PAR>1300 μmol cm−2 s−1) acetone was correlated with methylbutenol (biogenic emission from ponderosa pine, r2=0.48). Under the same conditions, acetone was also correlated with acetylene (anthropogenic emission, r2=0.52), yet acetylene and methylbutenol were not correlated with each other (r2=0.06). A linear combination of 1.34×methylbutenol+9.64×acetylene was highly correlated with acetone mixing ratios (r2=0.80), suggesting that the quantity of biogenic and anthropogenic contributions to the observed acetone could be determined using this correlation. Based on this method, 45% of the observed acetone could be attributed to biogenic sources, 14% to anthropogenic sources, and 41% to the regional background level. Comparison with direct emission ratios from tailpipe exhaust showed that the anthropogenic contribution to acetone mixing ratios could be attributed almost completely to secondary photochemical production (99%), with only a minor contribution from direct fuel combustion emissions (1%). Based on direct measurements of ecosystem scale fluxes, the biogenic contribution to acetone mixing ratios could be attributed to direct emissions (35%), methylbutenol oxidation (63%), and monoterpene oxidation (2%).

Introduction

Acetone is present in the global troposphere at mixing ratios that make it an important source for HOx radicals and a temporary sink for NOx radicals through formation of peroxy acetyl nitrate in the upper troposphere (Singh et al (1994), Singh et al (1995); Jaegle et al., 1997; Wennberg et al., 1998). Identified acetone sources include primary emissions from both biogenic and anthropogenic origins, secondary emissions from oxidation of biogenically and anthropogenically emitted volatile organic compounds (VOCs), and biomass burning. The atmospheric budget of acetone remains highly uncertain, however Singh et al. (2000) estimate a global source of 56 (37–80) Tg yr−1 (1 Tg=1012 g).

Direct biogenic emissions of acetone have been measured from trees (Isodorov et al., 1985), pastures (Kirstine et al., 1998) and dead plant matter (Warneke et al., 1999). Acetone production during oxidation of biogenically emitted VOC compounds has also recently been quantified; OH oxidation of α- and β-pinene yields 8–15% acetone (Aschmann et al., 1998; Reissell et al., 1999), and OH oxidation of 2-methyl-3-buten-2-ol (methylbutenol) yields 50% acetone (Alvarado et al., 1999; Ferronato et al., 1998). Singh et al. (2000) estimate more than half of the global acetone source is biogenic, including 11 (7–15) Tg yr−1 from oxidation of monoterpenes and methylbutenol, 15 (10–20) Tg yr−1 from primary biogenic emissions, and 6 (4–8) Tg yr−1 from decaying plant matter.

Elevated mixing ratios of acetone have been observed in many forested regions and it has been suggested that local biogenic emissions were responsible (Goldan et al., 1995; Riemer et al., 1998; Lamanna and Goldstein, 1999). However, no attempt has been made to quantify how much of the local acetone is derived from anthropogenic versus biogenic sources, or from primary versus secondary production. In this paper we report observations of acetone mixing ratios and direct biogenic emission rates measured above a ponderosa pine plantation in the Sierra Nevada Mountains, ∼75 km downwind of a major urban and industrial center (Sacramento, CA). We use observations of acetone mixing ratios and biogenic emission rates, along with biogenic and anthropogenic trace gases, to quantify the percentage of observed acetone which originates from primary biogenic, secondary biogenic, primary anthropogenic and secondary anthropogenic sources.

Section snippets

Experimental

Hydrocarbon measurements were made continuously throughout July 1997, from July to October 1998, and from June through October 1999 above a ponderosa pine (Pinus ponderosa L.) plantation at approximately hourly intervals. The measurements were part of a larger field experiment at the Blodgett Forest Research Station on the western slope of the Sierra Nevada mountains (38°53′42.9″N, 120°37′57.9″W, 1315 m elevation) to study biosphere–atmosphere exchange of trace gases and energy and its impact on

Results and discussion

Observed acetone mixing ratios at Blodgett Forest ranged from 1.4 to 7.8 ppb in 1997 (Fig. 2), 1.1 to 7.8 ppb in July 1998, and 1.0 to 8.0 ppb in July 1999. Acetone was one of the most abundant VOCs (after methane and methanol) measured over the ponderosa pine plantation. The range of acetone mixing ratios observed were similar to those reported from other rural regions, including 1.7–8 ppb during June and July 1995 at the YOUTH site in rural Tennessee (Riemer et al., 1998), 1.4–5.1 ppb during

Conclusions

Acetone is one of the dominant VOC compounds present in rural forested regions with mixing ratios that often exceed those observed in urban areas. We quantified the local acetone budget for a rural forested site in the Sierra Nevada Mountains, ∼75 km downwind of a major urban center (Sacramento, CA). Acetone could be attributed 14% to anthropogenic emissions (1% primary, 99% secondary) and 45% to biogenic emissions (35% primary, 63% secondary from methylbutenol oxidation, and 2% secondary from

Acknowledgements

This work was supported by a contract from the California Air Resources Board (award #98-328) and a grant from the University of California Agricultural Experiment Station. G. Schade acknowledges funding from the German Academic Exchange Service (DAAD). The authors thank M. Lamanna for collection of the 1997 VOC data set, and M. Bauer, N. Hultman, J. Panek, M. McKay, B. Heald, and the Blodgett Forest crew for their invaluable support. We gratefully acknowledge Sierra Pacific Industries for

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