Oceanic influence on atmospheric mercury at coastal and inland sites: a springtime noreaster in New England

Continuous measurements of elemental (Hg<sup>0</sup>) and reactive mercury were conducted at two sites in New Hampshire during a powerful April 2007 noreaster. During the most intense period of the storm, enhancements of ~30–50 ppqv in Hg<sup>0</sup> were observed at a coastal and a high elevation inland site. This enhancement occurred simultaneously with elevated mixing ratios of three marine tracers, CH<sub>3</sub>I, CH<sub>2</sub>Br<sub>2</sub> and CHBr<sub>3</sub>. These observations suggest a marine source of Hg<sup>0</sup>, possibly outgassing from the ocean surface during strong turbulence. The Hg<sup>0</sup> enhancement observed 100 km inland suggests that the impact of coastal storms on terrestrial Hg cycling may not be limited to near-shore environments. Combining Hg<sup>0</sup> and marine tracer measurements during the storm with estimates of oceanic tracer fluxes during previous strong storms yields an order-of-magnitude estimate of the oceanic source of Hg<sup>0</sup> during the storm (~7 ppqv h<sup>−1</sup>) which can account for the observed enhancement at the field sites

Coastal water source of short‐lived halocarbons in New England

Short‐lived halocarbon tracers were used to investigate marine influences on air quality in a coastal region of New England. Atmospheric measurements made at the University of New Hampshire\u27s Observing Station at Thompson Farm (TF) in Durham, New Hampshire, indicate that relatively large amounts of halocarbons are emitted from local estuarine and coastal oceanic regions. Bromine‐containing halocarbons of interest in this work include bromoform (CHBr3) and dibromomethane (CH2Br2). The mean mixing ratios of CHBr3 and CH2Br2 from 11 January to 5 March 2002 were 2.6 pptv and 1.6 pptv, and from 1 June to 31 August 2002 mean mixing ratios were 5.9 pptv and 1.4 pptv, respectively. The mean mixing ratio of CHBr3 was not only highest during summer, but both CHBr3 and CH2Br2 exhibited large variability in their atmospheric mixing ratios during this season. We attribute the greater variability to increased production combined with faster atmospheric removal rates. Other seasonal characteristics of CHBr3 and CH2Br2 in the atmosphere, as well as the impact of local meteorology on their distributions at this coastal site, are discussed. Tetrachloroethene (C2Cl4) and trichloroethene (C2HCl3) were used to identify time periods influenced by urban emissions. Additionally, measurements of CHBr3, CH2Br2, C2Cl4, methyl iodide (CH3I), and ethyl iodide (C2H5I) were made at TF and five sites throughout the nearby Great Bay estuarine area between 18 and 19 August 2003. These measurements were used to elucidate the effect of the tidal cycle on the distributions of these gases. The mean mixing ratios of CHBr3, CH2Br2, CH3I, and C2H5I were ∼82%, 46%, 14%, and 17% higher, respectively, near the coast compared to inland sites, providing evidence for a marine source of short‐lived halocarbons at TF. Correlation between the tidal cycle and atmospheric concentrations of marine tracers on the night of 18 August 2003 showed that the highest values for the brominated species occurred ∼2–3 hours after high tide. Emission fluxes of CHBr3, CH2Br2, CH3I, and C2H5I on this night were estimated to be 26 ± 57, 4.7 ± 5.4, 5.9 ± 4.6, and 0.065 ± 0.20 nmol m−2 h−1, respectively. Finally, the anthropogenic source strength of CHBr3 was calculated to determine its impact on atmospheric levels observed in this region. Although our results indicate that anthropogenic contributions could potentially range from 15 to 60% of the total dissolved CHBr3 in the Great Bay, based on the observed ratio of CH2Br2/CHBr3 and surface seawater measurements in the Gulf of Maine, it appears unlikely that anthropogenic activities are a significant source of CHBr3 in the region

A comparison of GC-FID and PTR-MS toluene measurements in ambient air under conditions of enhanced monoterpene loading

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 alpha- and beta-pinene, camphene, Delta(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 similar to 2 and similar to 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 H(3)O(+), O(2)(+) 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 similar to 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 similar to 13% positive bias in the PTR-MS measurements. The bias corresponded with a similar to 0.055 ppbv difference at the highest measured toluene level. The two systems agreed quantitatively within the combined 1 sigma 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 (\u3c10%). Interferences in the PTRMS measurements from fragmentation of the monoterpene oxidation products pinonaldehyde, caronaldehyde and alpha-pinene oxide were also likely negligible. A relatively large and variable toluene background in the PTR-MS instrument likely drove the measurement bias; however, the precise contribution was difficult to accurately quantify and thus was not corrected for in this analysis. The results from THF suggest that toluene can be reliably quantified by PTR-MS using our operating conditions (drift tube pressure, temperature and voltage of 2.0 mbar, 45 degrees C and 600V, respectively) under the ambient compositions probed. This work extends the range of field conditions under which PTR-MS validation studies have been conducted

Multi-year (2004–2008) record of nonmethane hydrocarbons and halocarbons in New England: seasonal variations and regional sources

Multi-year time series records of C<sub>2</sub>-C<sub>6</sub> alkanes, C<sub>2</sub>-C<sub>4</sub> alkenes, ethyne, isoprene, C<sub>6</sub>-C<sub>8</sub> aromatics, trichloroethene (C<sub>2</sub>HCl<sub>3</sub>), and tetrachloroethene (C<sub>2</sub>Cl<sub>4</sub>) 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 C<sub>2</sub>-C<sub>8</sub> anthropogenic NMHC mixing ratios were observed in mid to late winter. Following the springtime minimums, the C<sub>3</sub>-C<sub>6</sub> alkanes, C<sub>7</sub>-C<sub>8</sub> aromatics, and C<sub>2</sub>HCl<sub>3</sub> increased in early to mid summer, presumably reflecting enhanced evaporative emissions. Mixing ratios of C<sub>2</sub>Cl<sub>4</sub> and C<sub>2</sub>HCl<sub>3</sub> 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 C<sub>3</sub>-C<sub>8</sub> NMHCs were estimated to be 10<sup>9</sup> to 10<sup>10</sup> molecules cm<sup>−2</sup> s<sup>−1</sup> 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

Bromoform and dibromomethane measurements in the seacoast region of New Hampshire, 2002–2004

Atmospheric measurements of bromoform (CHBr3) and dibromomethane (CH2Br2) were conducted at two sites, Thompson Farm (TF) in Durham, New Hampshire (summer 2002–2004), and Appledore Island (AI), Maine (summer 2004). Elevated mixing ratios of CHBr3 were frequently observed at both sites, with maxima of 37.9 parts per trillion by volume (pptv) and 47.4 pptv for TF and AI, respectively. Average mixing ratios of CHBr3 and CH2Br2 at TF for all three summers ranged from 5.3–6.3 and 1.3–2.3 pptv, respectively. The average mixing ratios of both gases were higher at AI during 2004, consistent with AI\u27s proximity to sources of these bromocarbons. Strong negative vertical gradients in the atmosphere corroborated local sources of these gases at the surface. At AI, CHBr3 and CH2Br2 mixing ratios increased with wind speed via sea‐to‐air transfer from supersaturated coastal waters. Large enhancements of CHBr3 and CH2Br2 were observed at both sites from 10 to 14 August 2004, coinciding with the passage of Tropical Storm Bonnie. During this period, fluxes of CHBr3 and CH2Br2 were 52.4 ± 21.0 and 9.1 ± 3.1 nmol m−2 h−1, respectively. The average fluxes of CHBr3 and CH2Br2 during nonevent periods were 18.9 ± 12.3 and 2.6 ± 1.9 nmol m−2 h−1, respectively. Additionally, CHBr3 and CH2Br2 were used as marine tracers in case studies to (1) evaluate the impact of tropical storms on emissions and distributions of marine‐derived gases in the coastal region and (2) characterize the transport of air masses during pollution episodes in the northeastern United States

Are biogenic emissions a significant source of summertime atmospheric toluene in the rural Northeastern United States?

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

Long-term study of VOCs measured with PTR-MS at a rural site in New Hampshire with urban influences

A long-term, high time-resolution volatile organic compound (VOC) data set from a ground site that experiences urban, rural, and marine influences in the Northeastern United States is presented. A proton-transfer-reaction mass spectrometer (PTR-MS) was used to quantify 15 VOCs: a marine tracer dimethyl sulfide (DMS), a biomass burning tracer acetonitrile, biogenic compounds (monoterpenes, isoprene), oxygenated VOCs (OVOCs: methyl vinyl ketone (MVK) plus methacrolein (MACR), methanol, acetone, methyl ethyl ketone (MEK), acetaldehyde, and acetic acid), and aromatic compounds (benzene, toluene, C<sub>8</sub> and C<sub>9</sub> aromatics). Time series, overall and seasonal medians, with 10th and 90th percentiles, seasonal mean diurnal profiles, and inter-annual comparisons of mean summer and winter diurnal profiles are shown. Methanol and acetone exhibit the highest overall median mixing ratios 1.44 and 1.02 ppbv, respectively. Comparing the mean diurnal profiles of less well understood compounds (e.g., MEK) with better known compounds (e.g., isoprene, monoterpenes, and MVK + MACR) that undergo various controls on their atmospheric mixing ratios provides insight into possible sources of the lesser known compounds. The constant diurnal value of ~0.7 for the toluene:benzene ratio in winter, may possibly indicate the influence of wood-based heating systems in this region. Methanol exhibits an initial early morning release in summer unlike any other OVOC (or isoprene) and a dramatic late afternoon mixing ratio increase in spring. Although several of the OVOCs appear to have biogenic sources, differences in features observed between isoprene, methanol, acetone, acetaldehyde, and MEK suggest they are produced or emitted in unique ways

Volatile organic compounds in northern New England marine and continental environments during the ICARTT 2004 campaign

Volatile organic compound (VOC) measurements were made during the summer 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) at Thompson Farm (TF), a continental site 25 km from the New Hampshire coast, and Appledore Island (AI), a marine site 10 km off the Maine coast. The 24 h mean total hydroxyl radical (OH) reactivity (±1σ) for the suite of VOCs was 4.15 (±2.64) s−1 at TF and 2.57 (±1.10) s−1 at AI. The larger range of reactivity at TF was dominated by isoprene and the monoterpenes (mean combined reactivity = 2.01 (±2.57) s−1). The impact of local anthropogenic hydrocarbon sources such as liquefied petroleum gas (LPG) leakage and fossil fuel evaporation was evident at both sites. During the campaign, a propane flux of 9 (±2) × 109 molecules cm−2 s−1 was calculated from the linear regression of the mean 0100–0400 local time mixing ratios at TF. This is consistent with fluxes observed in 2003 at sites spread throughout the coastal area of New Hampshire indicating that LPG tank leakage is a major hydrocarbon source throughout the region. Net monoterpene fluxes during ICARTT at TF were 6 (±2), 1.8 (±0.4), 1.2 (±0.6), and 0.4 (±0.5) × 109 molecules cm−2 s−1 for α‐pinene, β‐pinene, camphene, and limonene, respectively. Comparison to estimated NO3 and O3 loss rates indicate that gross monoterpene emission rates were approximately double the observed net fluxes at TF and comparable to current monoterpene nighttime emission inventory estimates for the northeast

Carlsbad Caverns National Park Air Quality Study 2019

This data set includes fine particle and gas precursor measurements from Carlsbad Caverns National Park. The study was designed to examine the influence of regional sources, including urban emissions, oil and gas development, wildfires, and soil dust on air quality in the park. Field measurements of aerosols, trace gases and deposition were conducted from 25 July through 5 September 2019.Carlsbad Caverns National Park in southeastern New Mexico is adjacent to the Permian Basin, one of the most productive oil and gas regions in the country. The 2019 Carlsbad Caverns Air Quality Study (CarCavAQS) was designed to examine the influence of regional sources, including urban emissions, oil and gas development, wildfires, and soil dust on air quality in the park. Field measurements of aerosols, trace gases, and deposition were conducted from 25 July through 5 September 2019.This work was supported by the National Park Service Q5 [P20AC00679]

Tropospheric methanol observations from space: retrieval evaluation and constraints on the seasonality of biogenic emissions

Methanol retrievals from nadir-viewing space-based sensors offer powerful new information for quantifying methanol emissions on a global scale. Here we apply an ensemble of aircraft observations over North America to evaluate new methanol measurements from the Tropospheric Emission Spectrometer (TES) on the Aura satellite, and combine the TES data with observations from the Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp-A satellite to investigate the seasonality of methanol emissions from northern midlatitude ecosystems. Using the GEOS-Chem chemical transport model as an intercomparison platform, we find that the TES retrieval performs well when the degrees of freedom for signal (DOFS) are above 0.5, in which case the model : TES regressions are generally consistent with the model : aircraft comparisons. Including retrievals with DOFS below 0.5 degrades the comparisons, as these are excessively influenced by the a priori. The comparisons suggest DOFS > 0.5 as a minimum threshold for interpreting retrievals of trace gases with a weak tropospheric signal. We analyze one full year of satellite observations and find that GEOS-Chem, driven with MEGANv2.1 biogenic emissions, underestimates observed methanol concentrations throughout the midlatitudes in springtime, with the timing of the seasonal peak in model emissions 1-2 months too late. We attribute this discrepancy to an underestimate of emissions from new leaves in MEGAN, and apply the satellite data to better quantify the seasonal change in methanol emissions for midlatitude ecosystems. The derived parameters (relative emission factors of 11.0, 1.0, 0.05 and 8.6 for new, growing, mature, and old leaves, respectively, plus a leaf area index activity factor of 0.75 for expanding canopies with leaf area index < 2.0) provide a more realistic simulation of seasonal methanol concentrations in midlatitudes on the basis of IASI, TES, and ground-based measurements