The Marginal Ice Zone as a dominant source region of atmospheric mercury during central Arctic summertime.

Atmospheric gaseous elemental mercury (GEM) concentrations in the Arctic exhibit a clear summertime maximum, while the origin of this peak is still a matter of debate in the community. Based on summertime observations during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition and a modeling approach, we further investigate the sources of atmospheric Hg in the central Arctic. Simulations with a generalized additive model (GAM) show that long-range transport of anthropogenic and terrestrial Hg from lower latitudes is a minor contribution (~2%), and more than 50% of the explained GEM variability is caused by oceanic evasion. A potential source contribution function (PSCF) analysis further shows that oceanic evasion is not significant throughout the ice-covered central Arctic Ocean but mainly occurs in the Marginal Ice Zone (MIZ) due to the specific environmental conditions in that region. Our results suggest that this regional process could be the leading contributor to the observed summertime GEM maximum. In the context of rapid Arctic warming and the observed increase in width of the MIZ, oceanic Hg evasion may become more significant and strengthen the role of the central Arctic Ocean as a summertime source of atmospheric Hg.

Widespread detection of chlorine oxyacids in the Arctic atmosphere.

Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO3) and perchloric (HClO4) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO3 and HClO4. Significant levels of HClO3 were observed during springtime at Greenland (Villum Research Station), Ny-Ålesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 × 106 molecule cm-3. The increase in HClO3, concomitantly with that in HClO4, was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO3 and HClO4 by hydroxyl radicals. HClO3 and HClO4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.

Year-round trace gas measurements in the central Arctic during the MOSAiC expedition.

Despite the key role of the Arctic in the global Earth system, year-round in-situ atmospheric composition observations within the Arctic are sparse and mostly rely on measurements at ground-based coastal stations. Measurements of a suite of in-situ trace gases were performed in the central Arctic during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) expedition. These observations give a comprehensive picture of year-round near-surface atmospheric abundances of key greenhouse and trace gases, i.e., carbon dioxide, methane, nitrous oxide, ozone, carbon monoxide, dimethylsulfide, sulfur dioxide, elemental mercury, and selected volatile organic compounds (VOCs). Redundancy in certain measurements supported continuity and permitted cross-evaluation and validation of the data. This paper gives an overview of the trace gas measurements conducted during MOSAiC and highlights the high quality of the monitoring activities. In addition, in the case of redundant measurements, merged datasets are provided and recommended for further use by the scientific community.

Atmospheric biogenic volatile organic compounds in the Alaskan Arctic tundra: constraints from measurements at Toolik Field Station.

The Arctic is a climatically sensitive region that has experienced warming at almost 3 times the global average rate in recent decades, leading to an increase in Arctic greenness and a greater abundance of plants that emit biogenic volatile organic compounds (BVOCs). These changes in atmospheric emissions are expected to significantly modify the overall oxidative chemistry of the region and lead to changes in VOC composition and abundance, with implications for atmospheric processes. Nonetheless, observations needed to constrain our current understanding of these issues in this critical environment are sparse. This work presents novel atmospheric in situ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) measurements of VOCs at Toolik Field Station (TFS; 68°38' N, 149°36' W), in the Alaskan Arctic tundra during May-June 2019. We employ a custom nested grid version of the GEOS-Chem chemical transport model (CTM), driven with MEGANv2.1 (Model of Emissions of Gases and Aerosols from Nature version 2.1) biogenic emissions for Alaska at 0.25° × 0.3125° resolution, to interpret the observations in terms of their constraints on BVOC emissions, total reactive organic carbon (ROC) composition, and calculated OH reactivity (OHr) in this environment. We find total ambient mole fraction of 78 identified VOCs to be 6.3 ± 0.4 ppbv (10.8 ± 0.5 ppbC), with overwhelming (> 80 %) contributions are from short-chain oxygenated VOCs (OVOCs) including methanol, acetone and formaldehyde. Isoprene was the most abundant terpene identified. GEOS-Chem captures the observed isoprene (and its oxidation products), acetone and acetaldehyde abundances within the combined model and observation uncertainties (±25 %), but underestimates other OVOCs including methanol, formaldehyde, formic acid and acetic acid by a factor of 3 to 12. The negative model bias for methanol is attributed to underestimated biogenic methanol emissions for the Alaskan tundra in MEGANv2.1. Observed formaldehyde mole fractions increase exponentially with air temperature, likely reflecting its biogenic precursors and pointing to a systematic model underprediction of its secondary production. The median campaign-calculated OHr from VOCs measured at TFS was 0.7 s-1, roughly 5 % of the values typically reported in lower-latitude forested ecosystems. Ten species account for over 80 % of the calculated VOC OHr, with formaldehyde, isoprene and acetaldehyde together accounting for nearly half of the total. Simulated OHr based on median-modeled VOCs included in GEOS-Chem averages 0.5 s-1 and is dominated by isoprene (30 %) and monoterpenes (17 %). The data presented here serve as a critical evaluation of our knowledge of BVOCs and ROC budgets in high-latitude environments and represent a foundation for investigating and interpreting future warming-driven changes in VOC emissions in the Alaskan Arctic tundra.

Evaluation of selected solid adsorbents for passive sampling of atmospheric oil and natural gas non-methane hydrocarbons.

This project investigated passive adsorbent sampling of light (C2-C5) hydrocarbons which are sensitive tracers of fugitive emissions from oil and natural gas (O&NG) sources. Stronger adsorbent materials, i.e. Carboxen 1000 and Carboxen 1016, than those typically used in adsorbent sampling were considered. Experiments were conducted in laboratory and field settings using thermal desorption - gas chromatography analysis. Uptake of water vapor and system blanks were challenges inherent to the increased affinity of these adsorbents. Carboxen 1000 exhibited the best signal-to-noise ratio for the target compounds after optimizing conditioning parameters to reduce blanks, and by reducing the adsorbent mass loaded in the cartridge. This strategy reduced blanks to equivalent ambient air mole fractions of <0.05 nmol mol-1 (ppb), and allowed determination of these O&NG tracers over three-day sampling intervals with a lower detection limit of ≥0.5-1 ppb. Linear VOCs uptake was observed in dry air. Water uptake was as high as 0.65 gH2O g-1adsorbent at relative humidity (RH) above ≈ 75%. The water collection passivates adsorbent sites and competes with the uptake rates of VOCs; under the worst case relative humidity level of 95% RH, VOCs uptake rates dropped to 27-39% of those in dry air. This effect potentially causes results to be biased low when cartridges are deployed at high relative humidity (RH), including overnight, when RH is often elevated over daytime levels. Nonetheless, representative sampling results were obtained under ambient conditions during three field studies where cartridges were evaluated alongside whole air sample collection in canisters. Agreement varied by compound: Ethane and alkenes correlated poorly and could not be analyzed with satisfactory results; results for C3-C5 alkanes were much better: i-butane correlated with R2 > 0.5, and propane, n-butane, i-pentane, and n-pentane with R2 > 0.75, which demonstrates the feasibility of the passive sampling of these latter O&NG tracers. Implications: Oil and natural gas development has been associated with emissions of petroleum hydrocarbons that impact air quality and human health. This research characterizes and defines the application possibilities of solid adsorbent sampling for atmospheric passive sampling monitoring of low molecular weight volatile organic compounds (i.e. ethane through pentane isomers) that are most commonly emitted from natural gas drilling and well sites. The passive sampling of these pollutants offers a simple, low cost, and readily applicable monitoring method for assessing emissions and air quality impacts in the surroundings of oil and gas operations.

Unpiloted Aircraft System Instrument for the Rapid Collection of Whole Air Samples and Measurements for Environmental Monitoring and Air Quality Studies.

A new airborne system, the Whole Air Sampling Pilotless Platform (WASPP), is described for the collection of whole air samples and in situ meteorological measurements onboard a commercial hexacopter. Rapid sample collection enables the collection ≤15 air samples per flight in positively pressurized miniature canisters, subsequently analyzed on a mated analytical system for up to 80 nonmethane volatile organic compounds (VOCs). The WASPP is well suited to investigate VOC gradients in urban environments impacted by traffic, industry, and oil and natural gas (O&NG) development, but has the sensitivity to characterize continental background conditions, as shown here using a subset of >40 species. We document empirical tests to minimize the influence of rotor wash and other sampling artifacts and report favorable results of laboratory-based calibrations of the WASPP's meteorological sensors and field-based comparisons of WASPP's VOC measurements and horizontal wind velocity measurements. Airborne WASPP measurements can complement and enhance ground-based VOC monitoring efforts by providing substantial meteorological and VOC measurement capability across vertical and horizontal spatial scales. These measurements reveal strong vertical gradients in VOC mixing ratios, depending on local meteorology and sources. WASPP has wide applicability for pollution source identification and quantification of hazardous air pollutants and precursors of criteria pollutants, including monitoring O&NG emissions or industry fenceline monitoring.

Impact of U.S. Oil and Natural Gas Emission Increases on Surface Ozone Is Most Pronounced in the Central United States.

Observations of volatile organic compounds (VOCs) from a surface sampling network and simulation results from the EMAC (ECHAM5/MESSy for Atmospheric Chemistry) model were analyzed to assess the impact of increased emissions of VOCs and nitrogen oxides from U.S. oil and natural gas (O&NG) sources on air quality. In the first step, the VOC observations were used to optimize the magnitude and distribution of atmospheric ethane and higher-alkane VOC emissions in the model inventory for the base year 2009. Observation-based increases of the emissions of VOCs and NOx stemming from U.S. oil and natural gas (O&NG) sources during 2009-2014 were then added to the model, and a set of sensitivity runs was conducted for assessing the influence of the increased emissions on summer surface ozone levels. For the year 2014, the added O&NG emissions are predicted to affect surface ozone across a large geographical scale in the United States. These emissions are responsible for an increased number of days when the averaged 8-h ozone values exceed 70 ppb, with the highest sensitivity being in the central and midwestern United States, where most of the O&NG growth has occurred. These findings demonstrate that O&NG emissions significantly affect the air quality across most of the United States, can regionally offset reductions of ozone precursor emissions made in other sectors, and can have a determining influence on a region's ability to meet National Ambient Air Quality Standard (NAAQS) obligations for ozone.

Dry Deposition of Ozone over Land: Processes, Measurement, and Modeling.

Dry deposition of ozone is an important sink of ozone in near surface air. When dry deposition occurs through plant stomata, ozone can injure the plant, altering water and carbon cycling and reducing crop yields. Quantifying both stomatal and nonstomatal uptake accurately is relevant for understanding ozone's impact on human health as an air pollutant and on climate as a potent short-lived greenhouse gas and primary control on the removal of several reactive greenhouse gases and air pollutants. Robust ozone dry deposition estimates require knowledge of the relative importance of individual deposition pathways, but spatiotemporal variability in nonstomatal deposition is poorly understood. Here we integrate understanding of ozone deposition processes by synthesizing research from fields such as atmospheric chemistry, ecology, and meteorology. We critically review methods for measurements and modeling, highlighting the empiricism that underpins modeling and thus the interpretation of observations. Our unprecedented synthesis of knowledge on deposition pathways, particularly soil and leaf cuticles, reveals process understanding not yet included in widely-used models. If coordinated with short-term field intensives, laboratory studies, and mechanistic modeling, measurements from a few long-term sites would bridge the molecular to ecosystem scales necessary to establish the relative importance of individual deposition pathways and the extent to which they vary in space and time. Our recommended approaches seek to close knowledge gaps that currently limit quantifying the impact of ozone dry deposition on air quality, ecosystems, and climate.

Biogenic volatile organic compound ambient mixing ratios and emission rates in the Alaskan Arctic tundra.

Rapid Arctic warming, a lengthening growing season, and the increasing abundance of biogenic volatile-organic-compound-emitting shrubs are all anticipated to increase atmospheric biogenic volatile organic compounds (BVOCs) in the Arctic atmosphere, with implications for atmospheric oxidation processes and climate feedbacks. Quantifying these changes requires an accurate understanding of the underlying processes driving BVOC emissions in the Arctic. While boreal ecosystems have been widely studied, little attention has been paid to Arctic tundra environments. Here, we report terpenoid (isoprene, monoterpenes, and sesquiterpenes) ambient mixing ratios and emission rates from key dominant vegetation species at Toolik Field Station (TFS; 68°38' N, 149°36' W) in northern Alaska during two back-to-back field campaigns (summers of 2018 and 2019) covering the entire growing season. Isoprene ambient mixing ratios observed at TFS fell within the range of values reported in the Eurasian taiga (0-500 parts per trillion by volume - pptv), while monoterpene and sesquiterpene ambient mixing ratios were respectively close to and below the instrumental quantification limit (~ 2 pptv). Isoprene surface emission rates ranged from 0.2 to 2250 µgC m-2 h-1 (mean of 85 µgC m-2 h-1) and monoterpene emission rates remained, on average, below 1 µgC m-2 h-1 over the course of the study. We further quantified the temperature dependence of isoprene emissions from local vegetation, including Salix spp. (a known isoprene emitter), and compared the results to predictions from the Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1). Our observations suggest a 180 %-215 % emission increase in response to a 3-4°C warming, and the MEGAN2.1 temperature algorithm exhibits a close fit with observations for enclosure temperatures in the 0-30°C range. The data presented here provide a baseline for investigating future changes in the BVOC emission potential of the under-studied Arctic tundra environment.

A Phylogenetic and Functional Perspective on Volatile Organic Compound Production by Actinobacteria.

Soil microbes produce an immense diversity of metabolites, including volatile organic compounds (VOCs), which can shape the structure and function of microbial communities. VOCs mediate a multitude of microbe-microbe interactions, including antagonism. Despite their importance, the diversity and functional relevance of most microbial volatiles remain uncharacterized. We assembled a taxonomically diverse collection of 48 Actinobacteria isolated from soil and airborne dust and surveyed the VOCs produced by these strains on two different medium types in vitro using gas chromatography-mass spectrometry (GC-MS). We detected 126 distinct VOCs and structurally identified approximately 20% of these compounds, which were predominately C1 to C5 hetero-VOCs, including (oxygenated) alcohols, ketones, esters, and nitrogen- and sulfur-containing compounds. Each strain produced a unique VOC profile. While the most common VOCs were likely by-products of primary metabolism, most of the VOCs were strain specific. We observed a strong taxonomic and phylogenetic signal for VOC profiles, suggesting their role in finer-scale patterns of ecological diversity. Finally, we investigated the functional potential of these VOCs by assessing their effects on growth rates of both pathogenic and nonpathogenic pseudomonad strains. We identified sets of VOCs that correlated with growth inhibition and stimulation, information that may facilitate the development of microbial VOC-based pathogen control strategies. IMPORTANCE Soil microbes produce a diverse array of natural products, including volatile organic compounds (VOCs). Volatile compounds are important molecules in soil habitats, where they mediate interactions between bacteria, fungi, insects, plants, and animals. We measured the VOCs produced by a broad diversity of soil- and dust-dwelling Actinobacteria in vitro. We detected a total of 126 unique volatile compounds, and each strain produced a unique combination of VOCs. While some of the compounds were produced by many strains, most were strain specific. Importantly, VOC profiles were more similar between closely related strains, indicating that evolutionary and ecological processes generate predictable patterns of VOC production. Finally, we observed that actinobacterial VOCs had both stimulatory and inhibitory effects on the growth of bacteria that represent a plant-beneficial symbiont and a plant-pathogenic strain, information that may lead to the development of novel strategies for plant disease prevention.

Ambient Nonmethane Hydrocarbon Levels Along Colorado's Northern Front Range: Acute and Chronic Health Risks.

Oil and gas (O&G) facilities emit air pollutants that are potentially a major health risk for nearby populations. We characterized prenatal through adult health risks for acute (1 h) and chronic (30 year) residential inhalation exposure scenarios to nonmethane hydrocarbons (NMHCs) for these populations. We used ambient air sample results to estimate and compare risks for four residential scenarios. We found that air pollutant concentrations increased with proximity to an O&G facility, as did health risks. Acute hazard indices for neurological (18), hematological (15), and developmental (15) health effects indicate that populations living within 152 m of an O&G facility could experience these health effects from inhalation exposures to benzene and alkanes. Lifetime excess cancer risks exceeded 1 in a million for all scenarios. The cancer risk estimate of 8.3 per 10 000 for populations living within 152 m of an O&G facility exceeded the United States Environmental Protection Agency's 1 in 10 000 upper threshold. These findings indicate that state and federal regulatory policies may not be protective of health for populations residing near O&G facilities. Health risk assessment results can be used for informing policies and studies aimed at reducing and understanding health effects associated with air pollutants emitted from O&G facilities.

Tundra uptake of atmospheric elemental mercury drives Arctic mercury pollution.

Anthropogenic activities have led to large-scale mercury (Hg) pollution in the Arctic. It has been suggested that sea-salt-induced chemical cycling of Hg (through 'atmospheric mercury depletion events', or AMDEs) and wet deposition via precipitation are sources of Hg to the Arctic in its oxidized form (Hg(ii)). However, there is little evidence for the occurrence of AMDEs outside of coastal regions, and their importance to net Hg deposition has been questioned. Furthermore, wet-deposition measurements in the Arctic showed some of the lowest levels of Hg deposition via precipitation worldwide, raising questions as to the sources of high Arctic Hg loading. Here we present a comprehensive Hg-deposition mass-balance study, and show that most of the Hg (about 70%) in the interior Arctic tundra is derived from gaseous elemental Hg (Hg(0)) deposition, with only minor contributions from the deposition of Hg(ii) via precipitation or AMDEs. We find that deposition of Hg(0)-the form ubiquitously present in the global atmosphere-occurs throughout the year, and that it is enhanced in summer through the uptake of Hg(0) by vegetation. Tundra uptake of gaseous Hg(0) leads to high soil Hg concentrations, with Hg masses greatly exceeding the levels found in temperate soils. Our concurrent Hg stable isotope measurements in the atmosphere, snowpack, vegetation and soils support our finding that Hg(0) dominates as a source to the tundra. Hg concentration and stable isotope data from an inland-to-coastal transect show high soil Hg concentrations consistently derived from Hg(0), suggesting that the Arctic tundra might be a globally important Hg sink. We suggest that the high tundra soil Hg concentrations might also explain why Arctic rivers annually transport large amounts of Hg to the Arctic Ocean.

Evaluation of the Community Multiscale Air Quality Model for Simulating Winter Ozone Formation in the Uinta Basin.

The Weather Research and Forecasting (WRF) and Community Multiscale Air Quality (CMAQ) models were used to simulate a 10 day high-ozone episode observed during the 2013 Uinta Basin Winter Ozone Study (UBWOS). The baseline model had a large negative bias when compared to ozone (O3) and volatile organic compound (VOC) measurements across the basin. Contrary to other wintertime Uinta Basin studies, predicted nitrogen oxides (NO x ) were typically low compared to measurements. Increases to oil and gas VOC emissions resulted in O3 predictions closer to observations, and nighttime O3 improved when reducing the deposition velocity for all chemical species. Vertical structures of these pollutants were similar to observations on multiple days. However, the predicted surface layer VOC mixing ratios were generally found to be underestimated during the day and overestimated at night. While temperature profiles compared well to observations, WRF was found to have a warm temperature bias and too low nighttime mixing heights. Analyses of more realistic snow heat capacity in WRF to account for the warm bias and vertical mixing resulted in improved temperature profiles, although the improved temperature profiles seldom resulted in improved O3 profiles. While additional work is needed to investigate meteorological impacts, results suggest that the uncertainty in the oil and gas emissions contributes more to the underestimation of O3. Further, model adjustments based on a single site may not be suitable across all sites within the basin.

Investigation of the influence of transport from oil and natural gas regions on elevated ozone levels in the northern Colorado front range.

The Northern Colorado Front Range (NCFR) has been in exceedance of the ozone National Ambient Air Quality Standard (NAAQS) since 2004, which has led to much debate over the sources of ozone precursors to the region, as this area is home to both the Denver, CO, metropolitan area and the Denver-Julesburg Basin, which has experienced rapid growth of oil and natural gas (O&NG) operations and associated emissions. Several recent studies have reported elevated levels of atmospheric volatile organic compounds (VOCs) as a result of O&NG emissions and the potential for significant ozone production from these emissions, despite implementation of stricter O&NG VOC emissions regulations in 2008. Approximately 88% of 1-hr elevated ozone events (>75 ppbv) occur during June-August, indicating that elevated ozone levels are driven by regional photochemistry. Analyses of surface ozone and wind observations from two sites, namely, South Boulder and the Boulder Atmospheric Observatory, both near Boulder, CO, show a preponderance of elevated ozone events associated with east-to-west airflow from regions with O&NG operations in the N-ESE, and a relatively minor contribution of transport from the Denver Metropolitan area to the SE-S. Transport from upwind areas associated with abundant O&NG operations accounts for on the order of 65% (mean for both sites) of 1-hr averaged elevated ozone levels, while the Denver urban corridor accounts for 9%. These correlations contribute to mounting evidence that air transport from areas with O&NG operation has a significant impact on ozone and air quality in the NCFR. IMPLICATIONS: This article builds on several previous pieces of research that implied significant contributions from oil and natural gas emissions on ozone production in the Northern Colorado Front Range. By correlating increased ozone events with transport analyses we show that there is a high abundance of transport events with elevated ozone originating from the Denver-Julesburg oil and natural gas basin. These findings will help air quality regulators to better assess contributing sources to ozone production and in directing policies to curb ozone pollution in this region.

High winter ozone pollution from carbonyl photolysis in an oil and gas basin.

The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts and provide broader insight into the response of winter ozone to primary pollutants.

Herbivory and climate interact serially to control monoterpene emissions from pinyon pine forests.

The emission of volatile monoterpenes from coniferous trees impacts the oxidative state of the troposphere and multi-trophic signaling between plants and animals. Previous laboratory studies have revealed that climate anomalies and herbivory alter the rate of tree monoterpene emissions. However, no studies to date have been conducted to test these relations in situ. We conducted a two-year field experiment at two semiarid sites dominated by pinyon pine (Pinus edulis) during outbreaks of a specialist herbivore, the southwestern tiger moth (Lophocampa ingens: Arctiidae). We discovered that during the early spring, when herbivory rates were highest, monoterpene emission rates were approximately two to six times higher from undamaged needles on damaged trees, with this increase in emissions due to alpha-pinene, beta-pinene, and camphene at both sites. During mid-summer, emission rates did not differ between previously damaged and undamaged trees at the site on the Western Slope of the Rocky Mountains, but rather tracked changes in the temperature and precipitation regime characteristic of the region. As the mid-summer drought progressed at the Eastern Slope site, emission rates were low, but differences between previously damaged and undamaged trees were not statistically significant. Despite no difference in emissions, mid-summer tissue monoterpene concentrations were significantly lower in previously damaged trees at both sites. With the onset of monsoon rains during late summer, emission rates from previously damaged trees increased to levels higher than those of undamaged trees despite the lack of herbivory. We conclude that (1) herbivory systemically increases the flux of terpenes to the atmosphere during the spring, (2) drought overrides the effect of past herbivory as the primary control over emissions during the mid-summer, and (3) a release from drought and the onset of late-summer rains is correlated with a secondary increase in emissions, particularly from herbivore-damaged trees, possibly due to a drought-delayed stimulation of induced monoterpene synthesis and/or increases in stomatal conductance. A greater understanding of the interactive effects of seasonality and herbivory on monoterpene emissions provides much needed information regarding the atmospheric and ecological consequences that these compounds will have for semiarid ecosystems.

International comparison of a hydrocarbon gas standard at the picomol per mol level.

Studies of climate change increasingly recognize the diverse influences of hydrocarbons in the atmosphere, including roles in particulates and ozone formation. Measurements of key nonmethane hydrocarbons (NMHCs) suggest atmospheric mole fractions ranging from low picomoles per mol (ppt) to nanomoles per mol (ppb), depending on location and compound. To accurately establish mole fraction trends and to relate measurement records from many laboratories and researchers, it is essential to have accurate, stable, calibration standards. In February of 2008, the National Institute of Standards and Technology (NIST) developed and reported on picomoles per mol standards containing 18 nonmethane hydrocarbon compounds covering the mole fraction range of 60 picomoles per mol to 230 picomoles per mol. The stability of these gas mixtures was only characterized over a short time period (2 to 3 months). NIST recently prepared a suite of primary standard gas mixtures by gravimetric dilution to ascertain the stability of the 2008 picomoles per mol NMHC standards suite. The data from this recent chromatographic intercomparison of the 2008 to the 2011 suites confirm a much longer stability of almost 5 years for 15 of the 18 hydrocarbons; the double-bonded alkenes of propene, isobutene, and 1-pentene showed instability, in line with previous publications. The agreement between the gravimetric values from preparation and the analytical mole fractions determined from regression illustrate the internal consistency of the suite within ±2 pmol/mol. However, results for several of the compounds reflect stability problems for the three double-bonded hydrocarbons. An international intercomparison on one of the 2008 standards has also been completed. Participants included National Metrology Institutes, United States government laboratories, and academic laboratories. In general, results for this intercomparison agree to within about ±5% with the gravimetric mole fractions of the hydrocarbons.

Seasonal trends of biogenic terpene emissions.

Biogenic volatile organic compound (BVOC) emissions from six coniferous tree species, i.e. Pinus ponderosa (Ponderosa Pine), Picea pungens (Blue Spruce), Pseudotsuga menziesii (Rocky Mountain Douglas Fir) and Pinus longaeva (Bristlecone Pine), as well as from two deciduous species, Quercus gambelii (Gamble Oak) and Betula occidentalis (Western River Birch) were studied over a full annual growing cycle. Monoterpene (MT) and sesquiterpene (SQT) emissions rates were quantified in a total of 1236 individual branch enclosure samples. MT dominated coniferous emissions, producing greater than 95% of BVOC emissions. MT and SQT demonstrated short-term emission dependence with temperature. Two oxygenated MT, 1,8-cineol and piperitone, were both light and temperature dependent. Basal emission rates (BER, normalized to 1000µmolm(-2)s(-1) and 30°C) were generally higher in spring and summer than in winter; MT seasonal BER from the coniferous trees maximized between 1.5 and 6.0µgg(-1)h(-1), while seasonal lows were near 0.1µgg(-1)h(-1). The fractional contribution of individual MT to total emissions was found to fluctuate with season. SQT BER measured from the coniferous trees ranged from <0.01 to 0.15µgg(-1)h(-1). BER of up to 1.2µgg(-1)h(-1) of the SQT germacrene B were found from Q. gambelii, peaking in late summer. The ß-factor, used to define temperature dependence in emissions modeling, was not found to exhibit discernible growth season trends. A seasonal correction factor proposed by others in previous work to account for a sinusoidal shaped emission pattern was applied to the data. Varying levels of agreement were found between the data and model results for the different plant species seasonal data sets using this correction. Consequently, the analyses on this extensive data set suggest that it is not feasible to apply a universal seasonal correction factor across different vegetation species. A modeling exercise comparing two case scenarios, (1) without and (2) with consideration of the seasonal changes in emission factors illustrated large deviations when emission factors are applied for other seasons than those in which they were experimentally determined.

Long-term decline of global atmospheric ethane concentrations and implications for methane.

After methane, ethane is the most abundant hydrocarbon in the remote atmosphere. It is a precursor to tropospheric ozone and it influences the atmosphere's oxidative capacity through its reaction with the hydroxyl radical, ethane's primary atmospheric sink. Here we present the longest continuous record of global atmospheric ethane levels. We show that global ethane emission rates decreased from 14.3 to 11.3 teragrams per year, or by 21 per cent, from 1984 to 2010. We attribute this to decreasing fugitive emissions from ethane's fossil fuel source--most probably decreased venting and flaring of natural gas in oil fields--rather than a decline in its other major sources, biofuel use and biomass burning. Ethane's major emission sources are shared with methane, and recent studies have disagreed on whether reduced fossil fuel or microbial emissions have caused methane's atmospheric growth rate to slow. Our findings suggest that reduced fugitive fossil fuel emissions account for at least 10-21 teragrams per year (30-70 per cent) of the decrease in methane's global emissions, significantly contributing to methane's slowing atmospheric growth rate since the mid-1980s.