Search

Toluene was measured using both a gas chromatographic system (GC), with a flame ionization detector (FID), and a proton transfer reaction-mass spectrometer (PTR-MS) at the AIRMAP atmospheric monitoring station Thompson Farm (THF) in rural Durham, NH during the summer of 2004. Simultaneous measurements of monoterpenes, including α- and β-pinene, camphene, Δ 3-carene, and d-limonene, by GC-FID demonstrated large enhancements in monoterpene mixing ratios relative to toluene, with median and maximum enhancement ratios of ~2 and ~30, respectively. A detailed comparison between the GC-FID and PTR-MS toluene measurements was conducted to test the specificity of PTR-MS for atmospheric toluene measurements under conditions often dominated by biogenic emissions. We derived quantitative estimates of potential interferences in the PTR-MS toluene measurements related to sampling and analysis of monoterpenes, including fragmentation of the monoterpenes and some of their primary carbonyl oxidation products via reactions with H3O+, O2+ and NO+ in the PTR-MS drift tube. The PTR-MS and GC-FID toluene measurements were in good quantitative agreement and the two systems tracked one another well from the instrumental limits of detection to maximum mixing ratios of ~0.5 ppbv. A correlation plot of the PTR-MS versus GC-FID toluene measurements was described by the least squares regression equation y=(1.13± 0.02)x−(0.008±0.003) ppbv, suggesting a small ~13% positive bias in the PTR-MS measurements. The bias corresponded with a ~0.055 ppbv difference at the highest measured toluene level. The two systems agreed quantitatively within the combined 1σ measurement precisions for 60% of the measurements. Discrepancies in the measured mixing ratios were not well correlated with enhancements in the monoterpenes. Better quantitative agreement between the two systems was obtained by correcting the PTR-MS measurements for contributions from monoterpene fragmentation in the PTR-MS drift tube; however, the improvement was minor (

Multi-year time series records of C2-C6 alkanes, C2-C4 alkenes, ethyne, isoprene, C6-C8 aromatics, trichloroethene (C2HCl3), and tetrachloroethene (C2Cl4) from canister samples collected during January 2004–February 2008 at the University of New Hampshire (UNH) AIRMAP Observatory at Thompson Farm (TF) in Durham, NH are presented. The objectives of this work are to identify the sources of nonmethane hydrocarbons (NMHCs) and halocarbons observed at TF, characterize the seasonal and interannual variability in ambient mixing ratios and sources, and estimate regional emission rates of NMHCs. Analysis of correlations and comparisons with emission ratios indicated that a ubiquitous and persistent mix of emissions from several anthropogenic sources is observed throughout the entire year. The highest C2-C8 anthropogenic NMHC mixing ratios were observed in mid to late winter. Following the springtime minimums, the C3-C6 alkanes, C7-C8 aromatics, and C2HCl3 increased in early to mid summer, presumably reflecting enhanced evaporative emissions. Mixing ratios of C2Cl4 and C2HCl3 decreased by 0.7±0.2 and 0.3±0.05 pptv/year, respectively, which is indicative of reduced usage and emissions of these halogenated solvents. Emission rates of C3-C8 NMHCs were estimated to be 109 to 1010 molecules cm−2 s−1 in winter 2006. The emission rates extrapolated to the state of New Hampshire and New England were ~2–60 Mg/day and ~12–430 Mg/day, respectively. Emission rates of benzene, toluene, ethylbenzene, xylenes, and ethyne in the 2002 and 2005 EPA National Emissions Inventories were within ±50% of the TF emission rates.

Seven C1-C5 alkyl nitrates were measured both on the mainland and off the coast of New Hampshire using gas chromatographic techniques. Five separate data sets are presented to characterize the seasonal and diurnal trends and the major sources and loss processes of these compounds. Based on in situ measurements conducted at the University of New Hampshire (UNH) Atmospheric Observing Station at Thompson Farm (TF) located in southeast NH during winter (January–February) 2002, summer (June–August) 2002, summer (July–August) 2004, and on daily canister samples collected at midday from January 2004–February 2008, the median total alkyl nitrate mixing ratio (ΣRONO2) was 23–25 pptv in winter and 14–16 pptv in summer. During summers 2002 and 2004, MeONO2 decreased overnight and reached minimum hourly average mixing ratios in the early morning. Comparison with wind speed and trace gas trends suggested that dry deposition contributed to the early morning MeONO2 minimum which is a previously unaccounted for removal mechanism. The mean dry deposition rate and velocity of MeONO2 was estimated to be −0.5 nmol m−2 hr−1 and 0.13 cm s−1, respectively. Results from ambient air and surface seawater measurements made onboard the NOAA R/V Ronald H. Brown in the Gulf of Maine during the 2002 New England Air Quality Study and from ambient canister samples collected throughout the Great Bay estuary in August 2003 are also presented. Comparisons between the alkyl nitrate trends with anthropogenic and marine tracers suggest that a marine source of alkyl nitrates is not significant in coastal New England. Given the apparent prominence of a secondary source, comparisons between observed and predicted alkyl nitrate/parent hydrocarbon ratios were made which demonstrated that background mixing ratios have a continuous and prevalent influence on the alkyl nitrate distribution.

Vegetation, soil and ecosystem level carbonyl sulfide (COS) exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1) and elevated (Ring 2, R2) CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ± standard error) and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ± standard error) reflecting a significant nighttime sink. Nocturnal vegetative uptake (−11 to −21 pmol m−2s−1, negative values indicate uptake from the atmosphere) dominated nighttime net ecosystem COS flux estimates (−10 to −30 pmol m−2s−1) in both CO2 regimes. In comparison, soil uptake (−0.8 to −1.7 pmol m−2 s−1) was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates) that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment.

Summertime atmospheric toluene enhancements at Thompson Farm in the rural northeastern United States were unexpected and resulted in a toluene/benzene seasonal pattern that was distinctly different from that of other anthropogenic volatile organic compounds. Consequently, three hydrocarbon sources were investigated for potential contributions to the enhancements during 2004–2006. These included: (1) increased warm season fuel evaporation coupled with changes in reformulated gasoline (RFG) content to meet US EPA summertime volatility standards, (2) local industrial emissions and (3) local vegetative emissions. The contribution of fuel evaporation emission to summer toluene mixing ratios was estimated to range from 16 to 30 pptv d−1, and did not fully account for the observed enhancements (20–50 pptv) in 2004–2006. Static chamber measurements of alfalfa, a crop at Thompson Farm, and dynamic branch enclosure measurements of loblolly pine trees in North Carolina suggested vegetative emissions of 5 and 12 pptv d−1 for crops and coniferous trees, respectively. Toluene emission rates from alfalfa are potentially much larger as these plants were only sampled at the end of the growing season. Measured biogenic fluxes were on the same order of magnitude as the influence from gasoline evaporation and industrial sources (regional industrial emissions estimated at 7 pptv d−1 and indicated that local vegetative emissions make a significant contribution to summertime toluene enhancements. Additional studies are needed to characterize the variability and factors controlling toluene emissions from alfalfa and other vegetation types throughout the growing season.

No abstract available.