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In the second half of 2008 China's highly industrialized Pearl River Delta (PRD) region was hard-hit by the financial crisis (FC). This study reports volatile organic compounds measured in the PRD during November-December in both 2007 before the FC and 2008 after the FC. While total mixing ratios of non-methane hydrocarbons (NMHCs) on average were only about 7% lower from 40.2 ppbv in 2007 to 37.5 ppbv in 2008, their ozone formation potentials (OFPs) dropped about 30%, resulting from about 55% plummet of aromatic hydrocarbons (AHs) against a greater than 20% increase of total alkanes/alkenes. The elevated alkanes and alkenes in 2008 could be explained by greater emissions from vehicle exhausts and LPG combustion due to rapid increase of vehicle numbers and LPG consumption; the drop of AHs could be explained by reduced emissions from industries using AH-containing solvents due to the influence of the FC, as indicated by much lower ratios of toluene to benzene and of xylenes/ trichloroethylene/tetrachloroethylene to carbon monoxide (CO) in 2008. Source apportionment by positive matrix factorization (PMF) also revealed much less contribution of industry solvents to total anthropogenic NMHCs and particularly to toluene and xylenes in 2008 than in 2007. Based on PMF reconstructed source contributions, calculated OFPs by industrial emissions were responsible for 40.8% in 2007 in contrast to 18.4% in 2008. Further investigation into local industry output statistics suggested that the plummet of AHs in 2008 should be attributed to small enterprises, which contributed largely to ambient AHs due to their huge numbers and non-existent emission treatment, but were much more influenced by the FC. © 2012. American Geophysical Union. All Rights Reserved.

BackgroundAlthough altered metabolism has long been known to affect human breath, generating clinically usable metabolic tests from exhaled compounds has proven challenging. If developed, a breath-based lipid test would greatly simplify management of diabetes and serious pathological conditions (e.g., obesity, familial hyperlipidemia, and coronary artery disease), in which systemic lipid levels are a critical risk factor for onset and development of future cardiovascular events.MethodsWe, therefore, induced controlled fluctuations of plasma lipids (insulin-induced lipid suppression or intravenous infusion of Intralipid) during 4-h in vivo experiments on 23 healthy volunteers (12 males/11 females, 28.0 ± 0.3 years) to find correlations between exhaled volatile organic compounds and plasma lipids. In each subject, plasma triglycerides (TG) and free fatty acids (FFA) concentrations were both directly measured and calculated via individualized prediction equations based on the multiple linear regression analysis of a cluster of 4 gases. In the lipid infusion protocol, we also generated common prediction equations using a maximum of 10 gases.ResultsThis analysis yielded strong correlations between measured and predicted values during both lipid suppression (r = 0.97 for TG; r = 0.90 for FFA) and lipid infusion (r = 0.97 for TG; r = 0.94 for FFA) studies. In our most accurate common prediction model, measured and predicted TG and FFA values also displayed very strong statistical agreement (r = 0.86 and r = 0.81, respectively).ConclusionsOur results demonstrate the feasibility of measuring plasma lipids through breath analysis. Optimization of this technology may ultimately lead to the development of portable breath analyzers for plasma lipids, replacing blood-based bioassays.

BackgroundAlthough altered metabolism has long been known to affect human breath, generating clinically usable metabolic tests from exhaled compounds has proven challenging. If developed, a breath-based lipid test would greatly simplify management of diabetes and serious pathological conditions (e.g., obesity, familial hyperlipidemia, and coronary artery disease), in which systemic lipid levels are a critical risk factor for onset and development of future cardiovascular events.MethodsWe, therefore, induced controlled fluctuations of plasma lipids (insulin-induced lipid suppression or intravenous infusion of Intralipid) during 4-h in vivo experiments on 23 healthy volunteers (12 males/11 females, 28.0 ± 0.3 years) to find correlations between exhaled volatile organic compounds and plasma lipids. In each subject, plasma triglycerides (TG) and free fatty acids (FFA) concentrations were both directly measured and calculated via individualized prediction equations based on the multiple linear regression analysis of a cluster of 4 gases. In the lipid infusion protocol, we also generated common prediction equations using a maximum of 10 gases.ResultsThis analysis yielded strong correlations between measured and predicted values during both lipid suppression (r = 0.97 for TG; r = 0.90 for FFA) and lipid infusion (r = 0.97 for TG; r = 0.94 for FFA) studies. In our most accurate common prediction model, measured and predicted TG and FFA values also displayed very strong statistical agreement (r = 0.86 and r = 0.81, respectively).ConclusionsOur results demonstrate the feasibility of measuring plasma lipids through breath analysis. Optimization of this technology may ultimately lead to the development of portable breath analyzers for plasma lipids, replacing blood-based bioassays.

Effective management of diabetes mellitus, affecting tens of millions of patients, requires frequent assessment of plasma glucose. Patient compliance for sufficient testing is often reduced by the unpleasantness of current methodologies, which require blood samples and often cause pain and skin callusing. We propose that the analysis of volatile organic compounds (VOCs) in exhaled breath can be used as a novel, alternative, noninvasive means to monitor glycemia in these patients. Seventeen healthy (9 females and 8 males, 28.0 ± 1.0 yr) and eight type 1 diabetic (T1DM) volunteers (5 females and 3 males, 25.8 ± 1.7 yr) were enrolled in a 240-min triphasic intravenous dextrose infusion protocol (baseline, hyperglycemia, euglycemia-hyperinsulinemia). In T1DM patients, insulin was also administered (using differing protocols on 2 repeated visits to separate the effects of insulinemia on breath composition). Exhaled breath and room air samples were collected at 12 time points, and concentrations of ~100 VOCs were determined by gas chromatography and matched with direct plasma glucose measurements. Standard least squares regression was used on several subsets of exhaled gases to generate multilinear models to predict plasma glucose for each subject. Plasma glucose estimates based on two groups of four gases each (cluster A: acetone, methyl nitrate, ethanol, and ethyl benzene; cluster B: 2-pentyl nitrate, propane, methanol, and acetone) displayed very strong correlations with glucose concentrations (0.883 and 0.869 for clusters A and B, respectively) across nearly 300 measurements. Our study demonstrates the feasibility to accurately predict glycemia through exhaled breath analysis over a broad range of clinically relevant concentrations in both healthy and T1DM subjects.

The relationship of exhaled ethane and n-pentane to exhaled NO, carbonylated proteins, and indoor/outdoor atmospheric pollutants were examined in order to evaluate ethane and n-pentane as potential markers of airway inflammation and/or oxidative stress. Exhaled NO and carbonylated proteins were found to have no significant associations with either ethane (p = 0.96 and p = 0.81, respectively) or n-pentane (p = 0.44 and 0.28, respectively) when outliers were included. In the case where outliers were removed n-pentane was found to be inversely associated with carbonylated proteins. Exhaled hydrocarbons adjusted for indoor hydrocarbon concentrations were instead found to be positively associated with air pollutants (NO, NO(2) and CO), suggesting pollutant exposure is driving exhaled hydrocarbon concentrations. Given these findings, ethane and n-pentane do not appear to be markers of airway inflammation or oxidative stress.

A sampling campaign was conducted in the city of Milan, Italy before and during a transportation strike in January 2004. This strike provided a unique opportunity to investigate the influence of public transportation on the air quality in a major metropolitan area. Twenty-four air samples were collected each day around the city on January 2nd, 7th and 9th. The samples were analyzed for methane, carbon monoxide, non-methane hydrocarbons (NMHCs), halocarbons and alkyl nitrates. Significant differences in the mixing ratios were observed among the three days of sampling, with January 2nd showing the lowest concentrations as a result of decreased activity in the city during the holiday season. January 9th showed the highest NMHC concentrations because of increased vehicular activity in the city due to a public transportation strike. This paper investigates the correlation between the increased number of vehicles and decreased air quality because of a reduction in public transportation. Computer simulations were able to reproduce measurements of ozone production during the January 2004 strike and a July 2005 strike. The measurements and simulations suggest that reduced VOC emissions due to the existence of public transportation lowers peak ozone by 11-33% during the summer months. © 2008 Elsevier Ltd. All rights reserved.

The Pearl River Delta (PRD) region can be considered one of the most economically developed areas of mainland China. In September 2005, a total of 96 whole air samples were collected in Guangzhou and Dongguan, two important urban centers of the PRD region. Guangzhou is considered the economic center of Guangdong province, and Dongguan is a rapidly expanding industrial city. Here, we report mixing ratios of 50 nonmethane hydrocarbons (NMHCs) that were quantified in the ambient air of these PRD centers. The discussion focuses on understanding the main sources responsible for NMHC emissions, and evaluating the role of the identified sources towards ozone formation. Propane was the most abundant species in Guangzhou, with an average mixing ratio of 6.8 ppbv (±0.7 ppbv S.E.), compared to 2.5±0.2 ppbv in Dongguan. Toluene was the most abundant hydrocarbon in Dongguan (6.1±0.8 ppbv, compared to 5.9±0.7 ppbv in Guangzhou). Based on an analysis of the correlation between vehicular-emitted compounds and the measured NMHCs, together with the benzene-to-toluene (B/T) ratio, vehicular emission appears to be the dominant source of NMHCs measured in Guangzhou. By contrast, selected species (including toluene) in many of the Dongguan samples were influenced by an additional source, most likely related to industrial activities. A specific B/T ratio (

Between 1999 and 2005 a sampling campaign was conducted to identify and quantify the major species of atmospheric nonmethane hydrocarbons (NMHCs) in United States cities. Whole air canister samples were collected in 28 cities and analyzed for methane, carbon monoxide (CO) and NMHCs. Ambient mixing ratios exhibited high inter- and intra-city variability, often having standard deviations in excess of 50% of the mean value. For this reason, ratios of individual NMHC to CO, a combustion tracer, were examined to facilitate comparison between cities. Ratios were taken from correlation plots between the species of interest and CO, and most NMHCs were found to have correlation coefficients (r2) greater than 0.6, particularly ethene, ethyne and benzene, highlighting the influence of vehicular emissions on NMHC mixing ratios. Notable exceptions were the short-chain alkanes, which generally had poor correlations with CO. Ratios of NMHC vs. CO were also used to identify those cities with unique NMHC sources. © 2007 Elsevier Ltd. All rights reserved.

An extensive set of carbonyl sulfide (OCS) observations were made as part of the NASA Intercontinental Chemical Transport Experiment-North America (INTEX-NA) study, flown from 1 July to 14 August 2004 mostly over the eastern United States and Canada. These data show that summertime OCS mixing ratios at low altitude were dominated by surface drawdown and were highly correlated with CO2. Although local plumes were observed on some low-altitude flight legs, anthropogenic OCS sources were small compared to this sink. These INTEX-NA observations were in marked contrast to the early springtime 2001 Transport and Chemical Evolution over the Pacific experiment, which sampled Asian outflow dominated by anthropogenic OCS emissions. To test the gridded OCS fluxes used in past models, the INTEX-NA observations were combined with the sulfur transport Eulerian model (STEM) regional atmospheric chemistry model for a top-down assessment of bottom-up OCS surface fluxes for North America. Initial STEM results suggest that the modeled fluxes underestimate the OCS plant sink by more than 200%. Copyright 2008 by the American Geophysical Union.

We present data collected from a number of snow-covered environments including two polar locations (Summit, Greenland and the South Pole) and two mid-latitude regions (a remote site in northern Michigan, and Niwot Ridge, Colorado). At each site, concentrations of CH3 I and C2 H5 I were enhanced within the interstitial air near the snow surface, compared to levels in boundary layer air. Fluxes of CH3 Br from surface snow to the atmosphere were observed at each site except Niwot Ridge, where CH3 Br appeared to have a sink. The mid-latitude sites showed significant emissions of CH3 Cl, mostly originating at the ground surface and traveling up through the snow, while at the polar locations CH3 Cl emissions from firn air were relatively small. In general, methyl halide mixing ratios in firn air were significantly greater at Summit than at the South Pole, with Summit showing a strong diurnal cycle in the production of alkyl halides that was well correlated with actinic radiation and firn temperature. We suggest that the most likely route to alkyl halide formation is through an acid catalyzed nucleophilic substitution of an alcohol type function by a halide, both of which should be preferentially segregated to the quasi-liquid layer at the surface of the snow grains. A series of experiments using a snow-filled quartz chamber irradiated by natural sunlight allowed estimation of emission trends that were hard to measure in the natural snowpack. These static chamber experiments confirmed significant production of the primary alkyl halides, following the order CH3 Cl > CH3 Br > C2 H5 Cl > CH3 I > C2 H5 Br > C2 H5 I > 1 - C3 H7 Br > 1 - C3 H7 I. Our observations at all four locations, including polar and mid-latitude sites, imply that alkyl halide production may be associated with all surface snows. © 2007 Elsevier Ltd. All rights reserved.

Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10-12 July), with peak values of more than 3.2×106 molecules cm-3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 molecules cm-3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 molecules cm-3 in the early afternoon on 15 April and 1.5×106 molecules cm-3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer. © 2007 Elsevier Ltd. All rights reserved.

Increasing atmospheric mixing ratios Of CO2 have already lowered surface ocean pH by 0.1 units compared to preindustrial values and pH is expected to decrease an additional 0.3 units by the end of this century. Pronounced physiological changes in some phytoplankton have been observed during previous CO2 perturbation experiments. Marine microorganisms are known to consume and produce climate-relevant organic gases. Concentrations of (CH3)2S (DMS) and CH2ClI were quantified during the Third Pelagic Ecosystem CO2 Enrichment Study. Positive feedbacks were observed between control mesocosms and those simulating future CO2. Dimethyl sulfide was 26% (±10%) greater than the controls in the 2× ambient CO2 treatments, and 18% (±10%) higher in the 3xCO2 mesocosms. For CHClI the 2×CO2 treatments were 46% (±4%) greater than the controls and the 3×CO2 mesocosms were 131% (±11%) higher. These processes may help contribute to the homeostasis of the planet. Copyright 2007 by the American Geophysical Union.

With the phase-out of industrial methyl chloroform (MCF) production, the atmospheric burden of this ozone-depleting gas has rapidly declined. Therefore any non-industrial sources are taking on greater significance in the MCF budget. The only natural MCF source that has been proposed, biomass burning, has been reported to emit up to 2-10 Gg MCF yr-1. We have re-examined MCF data for thousands of airborne and ground-based air samples collected by our group since 1990 that were directly impacted by major biomass burning sources. Without exception, we have found no positive evidence that MCF is released from biomass burning. Our results indicate that global biomass burning emissions of MCF have been significantly overestimated and are unlikely to exceed 0.014 Gg MCF yr-1. Lowering the uncertainty regarding the magnitude of the global MCF biomass burning source may extend its period of usefulness for determining global abundances and trends of the hydroxyl radical (OH). Copyright 2007 by the American Geophysical Union.

During this study 158 whole air samples were collected in 45 Chinese cities in January and February 2001. The spatial distribution of different classes of halocarbons in the Chinese urban atmosphere, including chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), Halon-1211, and other chlorinated compounds is presented and discussed. Most of these compounds were enhanced compared to background levels. However, the mean enhancement of CFCs was relatively small, with CFC-12 and CFC-11 increases of 6% (range 1-31%) and 10% (range 2-89%), respectively, with respect to the global background. On the contrary, strongly enhanced levels of CFC replacement compounds and halogenated compounds used as solvents were measured. The average Halon-1211 concentration exceeded the background of 4.3 pptv by 75% and was higher than 10 pptv in several cities. Methyl chloride mixing ratios were also strongly elevated (78% higher than background levels), which is likely related to the widespread use of coal and biofuel in China. © 2006 Elsevier Ltd. All rights reserved.

Mixing ratios of seven C1-C5 alkyl nitrates (RONO2) were measured during a 16-month study (August 2001-December 2002) at Tai O, a coastal site 30 km west of central Hong Kong in the Pearl River Delta, the fastest-growing industrial region in the world. The C 3-C4 (rather than C1-C2) RONO 2 were most abundant throughout the study, showing the importance of photochemical (rather than marine) RONO2 production in the sampled air. A lack of methyl nitrate (MeONO2) enhancement during summer, when the prevailing winds are from the ocean, indicates that the South China Sea is not a region of strong RONO2 emissions. By contrast, MeONO 2 levels during pollution episodes (up to 25 parts per trillion by volume (pptv)) were the highest that our group has recorded during urban photochemical RONO2 production, as opposed to marine emissions or biomass burning. The highest summed RONO2 level of the study (204 pptv) was measured in the afternoon of 7 November 2002, during an intense pollution episode that captured the highest ozone (O3) level ever recorded in Hong Kong (203 ppbv). During pollution episodes, the average ratio of O3 to summed RONO2 was roughly 1000:1 in freshly polluted air (ethyne/CO∼3-5 pptv/ppbv) and 500:1 in very freshly polluted air (ethyne/CO∼6-8 pptv/ppbv). Ozone and RONO2 share a common photochemical source, and their good correlation in pollution plumes shows that RONO2 can be used as a tracer of photochemical O3 production. Even MeONO2 showed similar diurnal variations as the C2-C5 RONO2, indicating a strong photochemical source despite its very slow photochemical production from methane oxidation. The decomposition of longer-chain alkoxy radicals also does not explain the high MeONO2 levels, and rough calculations show that methoxy radical reaction with NO2 appears to be a viable alternate pathway for MeONO2 production in polluted atmospheres, though further measurements and modeling are required to confirm this mechanism. © 2005 Elsevier Ltd. All rights reserved.

During the past 15 years the annual growth rate of tropospheric methane (CH4) has shown striking changes over 2-3 year periods, varying from + 1% yr-1 to slightly negative values (-0.2% yr-1). These fluctuations are superimposed on an overall slowdown of the CH4 growth rate since the 1980s. Here we use our complementary measurement of other compounds (ethane, tetrachloroethene) to confirm the influence of biomass burning on large global CH4 pulses in 1998 and 2002-2003. Methane growth rate fluctuations also track ENSO indices, most likely via the influence of ENSO activity on large-scale biomass burning. We also report the seventh year of near-zero growth of global CH4 levels (Dec. 1998-Dec. 2005). The global CH4 mixing ratio was 1772 ± 1 ppbv in 2005, and CH4 increases of 118-376 ppbv between 2000-2020 (ten scenarios in the 2001 IPCC report, to levels around 1900+ ppbv by 2020, now appear quite unlikely. Copyright 2006 by the American Geophysical Union.

Atomic chlorine and bromine monoxide concentrations ([Cl] and [BrO]) and dimethyl sulfide (DMS) sea-air fluxes are estimated from data collected during a Lagrangian flight made near Christmas Island (2°N, 157°W) during August 1996 aboard the NASA P3-B aircraft. Intensive hydrocarbon sampling began in the surface layer (SL) one-half hour after sunrise and continued until ∼1300 local solar time. Our empirical model includes in situ observations of hydroxyl [HO] and precise measurements of ethane (C2H6) mixing ratios. Ethane was ∼40 pptv higher in the buffer layer (BuL) than in the SL, thus vertical exchange tended to replace any C2H6 that was photochemically removed in the SL. In spite of this, SL C2H6 mixing ratios decreased significantly during the flight. Using only the measured [HO] and estimated vertical mixing, our mass balance equation cannot explain all of the observed SL C2H6 loss. However, when an initial [Cl] of 8.4 (±2.0) × 104 Cl cm-3, decreasing to 5.7 (±2.0) × 104 Cl cm-3 at midday, is included, the observed and estimated C2H6 values are in excellent agreement. Using our [Cl], we estimate a DMS flux a factor of 2 higher than when HO is the only oxidant considered. This flux estimate, when compared to that derived by Lenschow et al. (1999), suggests that if the differences are real, we may be missing a loss term. Best agreement occurs when an average BrO mixing ratio of 1.3 (±1.3) pptv is included in our mass balance equation. Copyright 2005 by the American Geophysical Union.

Volatile organic compounds (VOCs) were measured at the South Pole (SP) from late Austral spring to mid-summer 2000 as part of the Investigation of Sulfur Chemistry in the Antarctic Troposphere Program (ISCAT-2000). This paper focuses on VOCs that are directly emitted from the ocean, specifically dimethyl sulfide (DMS), methyl nitrate (CH3ONO2), methyl iodide (CH 3I) and bromoform (CHBr3). A partial seasonal cycle of these gases was also recorded during the year following ISCAT-2000. During the summer, the SP periodically receives relatively fresh marine air containing short-lived oceanic trace gases, such as DMS (τ≈1 day). However, DMS was not detected at the SP until January even though DMS emissions from the Southern Ocean typically start peaking in November and elevated levels of other ocean-derived VOCs, including CH3ONO2 and CHBr 3, were observed in mid-November. We speculate that in November and December most of the DMS is oxidized before it reaches the SP: a strong correlation between CH3ONO2 and methane sulfonate (MSA), an oxidation product of DMS, supports this hypothesis. Based on a limited number of samples taken over the course of one year, CH3ONO2 apparently accumulates to a quasi-steady-state level over the SP in winter, most likely due to continuing emissions of the compound coupled with a lower rate of photochemical destruction. Oceanic emissions were concluded to be the dominant source of alkyl nitrates at the SP; this is in sharp contrast to northern high latitudes where total alkyl nitrate mixing ratios are dominated by urban sources. © 2004 Elsevier Ltd. All rights reserved.

An extensive set of carbonyl sulfide (OCS) and carbon disulfide (CS 2) observations were made as part of the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) project, which took place in the early spring 2001. TRACE-P sampling focused on the western Pacific region but in total included the geographic region 110°E to 290°E longitude, 5°N to 50°N latitude, and 0-12 km altitude. Substantial OCS and CS2 enhancements were observed for a great many air masses of Chinese and Japanese origin during TRACE-P. Over the western Pacific, mean mixing ratios of long-lived OCS and shorter-lived CS2 showed a gradual decrease by about 10% and a factor of 5-10, respectively, from the surface to 8-10 km altitude, presumably because land-based sources dominated their distribution during February through April 2001. The highest mean OCS and CS 2 levels (580 and 20 pptv, respectively, based on 2.5° × 2.5° latitude bins) were observed below 2 km near the coast of Asia, at latitudes between 25°N and 35°N, where urban Asian outflow was strongest. Ratios of OCS versus CO for continental SE Asia were much lower compared to Chinese and Japanese signatures and were strongly associated with biomass burning/biofuel emissions. We present a new inventory of anthropogenic Asian emissions (including biomass burning) for OCS and CS2 and compare it to emission estimates based on regional relationships of OCS and CS 2 to CO and CO2. The OCS and CS2 results for the two methods compare well for continental SE Asia and Japan plus Korea and also for Chinese CS2 emissions. However, it appears that the inventory underestimates Chinese emissions of OCS by about 30-100%. This difference may be related to the fact that we did not include natural sources such as wetland emissions in our inventory, although the contributions from such sources are believed to be at a seasonal low during the study period. Uncertainties in OCS emissions from Chinese coal burning, which are poorly characterized, likely contribute to the discrepancy. Copyright 2004 by the American Geophysical Union.

We present a 14-year record of tropospheric tetrachloroethene (C2Cl4) mixing ratios measured each season at remote surface locations throughout the Pacific Basin (71°N-47°S . Our calculated annual mean C2Cl4 mixing ratio for the extra-tropical northern hemisphere (NH) was 13.9 ± 0.5 pptv in 1989, but declined to less than half this value (to 6.5 ± 0.2 pptv) by 2002. Mid-latitude southern hemisphere (SH) mixing ratios, which were much smaller than NH values, showed interannual variations comparable to measured long-term changes, and the SH annual mean was slightly less in 2002 than in 1989. Driven by the relatively large decrease in NH values, the global C2Cl4, mixing ratio declined from 6.3 ± 0.6 pptv in 1989 to 3.5 ± 0.2 pptv in 2002. These values suggest that the global C2Cl4 burden decreased by roughly 205 Gg between 1989-2002, which is consistent with industrial estimates of declining NH emissions over a similar period. Copyright 2004 by the American Geophysical Union.

Elevated concentrations of methyl bromide (CH3Br) were observed in the Arctic atmospheric boundary layer (BL) during periods of widespread BL ozone (O3) depletion episodes (ODEs: O3 mixing ratios < 20 × 10-9 or parts per billion by volume, ppbv) particularly during major ODEs (MODES: O3 < 4 ppbv). No other organic gases measured during TOPSE (Tropospheric Ozone Production about the Spring Equinox) exhibited anti-correlations with O3 during these ODEs. Methyl bromide has both natural and anthropogenic sources and contributes ∼ half of the bromine (Br) to the stratosphere, where it can catalytically destroy O3. Several known CH3Br sources are evaluated, but the current knowledge cannot explain the observed enhancements. If the mechanism is direct gasphase photochemical production, a significant portion of the unknown CH3Br source may be found.

Airborne whole air samples collected over the western Pacific in spring, 2001 showed depletion of tetrachloroethene (C2Cl4) in every upper tropospheric (UT) air parcel that had interacted with large areas of cirrus less than three days upwind. The amount of C2Cl4 depletion showed a negative correlation with time since the interaction, consistent with the C2Cl4-depleted air parcels mixing with the ambient air as they moved downwind of the cirrus. Ethane and C2Cl4 both react relatively quickly with atomic chlorine (Cl) but ethane was not significantly depleted in these same air parcels, indicating that the C2Cl4 depletion cannot be attributed to Cl chemistry alone. Based on the minimum ethane depletion that can be detected by our measurements, a daytime upper limit of roughly 3 × 104 atom Cl cm-3 is indirectly estimated for heterogeneous chlorine activation by cirrus clouds in the UT in tropical- and mid-latitudes during spring. © 2003 by the American Geophysical Union.

We identify dimethyl disulfide (DMDS) as the major reduced sulfur-containing gas emitted from bushfires in Australia's Northern Territory. Like dimethyl sulfide (DMS), DMDS is oxidized in the atmosphere to sulfur dioxide (SO2) and methane sulfonic acid (MSA), which are intermediates in the formation of sulfuric acid (H2SO4). The mixing ratios of DMDS and DMS were the highest we have ever detected, with maximum values of 113 and 35 ppbv, respectively, whereas background values were below the detection limit (10 pptv). Molar emission ratios relative to carbon monoxide (CO) were [1.6 ± 0.1] × 10-5 and [6.2 ± 0.3] × 10-6, for DMDS and DMS respectively, while molar emission ratios relative to carbon dioxide (CO2) were [4.7 ± 0.4] × 10 6 and [1.4 ± 0.4] × 10 7, respectively. Assuming these observations are representative of biomass burning, we estimate that biomass burning could yield up to 175 Gg/yr of DMDS (119 Gg S/yr) and 13 Gg/yr of DMS.

Mexico City is the world's largest and most polluted urban center. We examine the distribution of methane and other hydrocarbons within the Valley of Mexico, using it as a model for the role developing megacities will play in the next century of geochemical cycling. Seventy-five whole air samples were analyzed with multivariate statistical techniques, including factor analysis using principal components. Methane concentrations are highly variable in space and time, due to air circulations and source distribution. Landfills and open sewage canals are major inputs. Emissions into and out from the valley are modeled to be ∼515 t per day. Per capita emission is 0.01 t per annum per person, consistent with the global average for human related anaerobic generation. Natural gas leaks are small, and likely to be higher in other developing megacities; Mexican natural gas use has been discouraged out of earthquake safety concerns. In contrast, liquefied petroleum gas loss constitutes the major emission of propane and butane estimated at a leak rate of 5-10%. Kyoto and other environmental conventions have ignored methane as a greenhouse gas. Our analysis underscores the need to consider methane and other hydrocarbons, and the urbanization process, in future emission protocols. © 2002 Elsevier Science Ltd. All rights reserved.

We report the first observations of the emission of five C1-C4 alkyl nitrates (methyl-, ethyl-, n-propyl-, i-propyl-, and 2-butyl nitrate) from savanna burning. Average alkyl nitrate mixing ratios in the immediate vicinity of three bushfires in Northern Australia were 47-122 times higher than local background mixing ratios. These are the highest alkyl nitrate mixing ratios we have ever detected, with maximum mixing ratios exceeding 3 ppbv for methyl nitrate. Methyl nitrate dominated the alkyl nitrate emissions during the flaming stage of savanna burning, whereas C2-C4 alkyl nitrates were mostly emitted during the smoldering stage. To explain the formation of alkyl nitrates from biomass burning, we propose a reaction mechanism involving the combination of reactive radicals at high temperature. Bearing in mind the uncertainties associated with extrapolating small data sets to much larger scales, alkyl nitrate emissions from global savanna burning are estimated to be on the order of 8 Gg/yr.

Mixing ratios of carbon monoxide (CO), methane (CH4), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998-1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3ppmv) and ethane (93ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH4 levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3-19ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O3) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O3 production in Karachi are ethene, CO, propene, m-xylene and toluene. © 2002 Elsevier Science Ltd. All rights reserved.

Global measurements show that the mixing ratio of tropospheric methane (CH4) increased by 1.1% (19.5 ± 1.7 ppbv) over the five-year period 1996-2000, with striking fluctuations in its annual growth rate. Whereas the global CH4 growth rate reached 15.9 ± 0.7 ppbv yr-1 in 1998, the growth rate was -2.1 ± 0.8 ppbv yr-1 in 2000. This is the first time in our 23-year global monitoring program that we have measured a negative annual CH4 growth rate. The CH4 growth rate fluctuates in an unpredictable fashion, and we reemphasize that global CH4 concentrations cannot be extrapolated into the future based on past trends. As a result, we suggest that the slowing of the CH4 growth rate during much of the 1980s and 1990s cannot be used to imply that CH4 will no longer be of concern in greenhouse gas studies during this century.

Measurements at Summit, Greenland, performed from June-August 1999, showed significant enhancement in concentrations of several trace gases in the snowpack (firn) pore air relative to the atmosphere. We report here measurements of alkenes, halocarbons, and alkyl nitrates that are typically a factor of 2-10 higher in concentration within the firn air than in the ambient air 1-10m above the snow. Profiles of concentration to a depth of 2m into the firn show that maximum values of these trace gases occur between the surface and 60cm depth. The alkenes show highest pore mixing ratios very close to the surface, with mixing ratios in the order ethene>propene>1-butene. Mixing ratios of the alkyl iodides and alkyl nitrates peak slightly deeper in the firn, with mixing ratios in order of methyl>ethyl>propyl. These variations are likely consistent with different near-surface photochemical production mechanisms. Diurnal mixing ratio variations within the firn correlate well with actinic flux for all these gases, with a temporal offset between the solar maximum and peak concentrations, lengthening with depth. Using a snow-filled chamber under constant flow conditions, we calculated production rates for the halocarbons and alkenes that ranged between 103-105 and 106molecules cm-3s-1, respectively. Taken together, these results suggest that photochemistry associated with the surface snowpack environment plays an important role in the oxidative capacity of the local atmospheric boundary layer, and influences post-depositional chemistry, which in turn may affect the interpretation of certain aspects of the ice core records collected previously at Summit. © 2002 Elsevier Science Ltd. All rights reserved.

Nonmethane hydrocarbons (NMHCs) and selected halocarbons were measured in whole air samples collected over the remote Pacific Ocean during NASA's Global Tropospheric Experiment (GTE) Pacific Exploratory Mission-Tropics B (PEM-Tropics B) in March and early April 1999. The large-scale spatial distributions of NMHCs and C2Cl4 reveal a much more pronounced north-south interhemispheric gradient, with higher concentrations in the north and lower levels in the south, than for the late August to early October 1996 PEM-Tropics A experiment. Strong continental outflow and winter-long accumulation of pollutants led to seasonally high Northern Hemisphere trace gas levels during PEM-Tropics B. Observations of enhanced levels of Halon 1211 (from developing Asian nations such as the PRC) and CH3Cl (from SE Asian biomass burning) support a significant southern Asian influence at altitudes above 1 km and north of 10° N. By contrast, at low altitude over the North Pacific the dominance of urban/industrial tracers, combined with low levels of Halon 1211 and CH3Cl, indicate a greater influence from developed nations such as Japan, Europe, and North America. Penetration of air exhibiting aged northern hemisphere characteristics was frequently observed at low altitudes over the equatorial central and western Pacific south to ∼5° S. The relative lack of southern hemisphere biomass burning sources and the westerly position of the South Pacific convergence zone contributed to significantly lower PEM-Tropics B mixing ratios of the NMHCs and CH3Cl south of 10° S compared to PEM-Tropics A. Therefore the trace gas composition of the South Pacific troposphere was considerably more representative of minimally polluted tropospheric conditions during PEM-Tropics B. Copyright 2001 by the American Geophysical Union.

The leakage of unburned liquefied petroleum gas (LPG) is a major source of urban nonmethane hydrocarbons (NMHCs) in the air of Santiago, Chile. Roughly 5% of the LPG that is sold in Santiago leaks in its unburned form to the atmosphere. Because of the leakage, propane is the most abundant NMHC in Santiago's air, even under heavy traffic conditions. NMHCs are an important precursor to the formation of ground-level ozone, and the LPG leakage may contribute as much as 15% to the excess ozone levels in Santiago. Improvement to the local air quality may be obtained by lowering the rates of LPG leakage, and by minimizing the use of alkene-rich LPG formulations.

Speciation of o-xylene, m-xylene, p-xylene and ethylbenzene was performed by gas chromatography from ambient air and liquid fuel samples collected at various locations in 19 cities in Europe, Asia and South America. The xylene's mixing ratios were compared to each other from the various locations, which included urban air, traffic air and liquid fuel. For all samples, the xylenes exhibited robust correlations, and the slopes remained constant. The m-xylene/p-xylene ratio was found to be 2.33±0.30, and the m-xylene/o-xylene ratio was found to be 1.84±0.25. These ratios remain persistent even in biomass combustion experiments (in South America and South Africa). Comparing the xylenes to toluene and benzene indicate that combustion, but not fuel evaporation, is the major common source of the xylenes in areas dominated by automotive emissions. Although a wide range of combustion types and combustion efficiencies were encountered throughout all the locations investigated, xylenes and ethylbenzene ratios remained persistent. We discuss the implications of the constancies in the xylenes and ethylbenzene ratios on atmospheric chemistry.

Canister sampling for the determination of atmospheric mixing ratios of nonmethane hydrocarbons (NMHCs), selected halocarbons, and methyl nitrate was conducted aboard the National Center for Atmospheric Research (NCAR) C-130 aircraft over the Pacific and Southern Oceans as part of the First Aerosol Characterization Experiment (ACE 1) during November and December 1995. A latitudinal profile, flown from 76°N to 60°S, revealed latitudinal gradients for most trace gases. NMHC and halocarbon gases with predominantly anthropogenic sources, including ethane, ethyne, and tetrachloroethene, exhibited significantly higher mixing ratios in the northern hemisphere at all altitudes. Methyl chloride exhibited its lowest mixing ratios at the highest northern hemisphere latitudes, and the distributions of methyl nitrate and methyl iodide were consistent with tropical and subtropical oceanic sources. Layers containing continental air characteristic of aged biomass burning emissions were observed above about 3 km over the remote southern Pacific and near New Zealand between approximately 19°S and 43°S. These plumes originated from the west, possibly from fires in southern Africa. The month-long intensive investigation of the clean marine southern midlatitude troposphere south of Australia revealed decreases in the mixing ratios of ethane, ethyne, propane, and tetrachloroethene, consistent with their seasonal mixing ratio cycle. By contrast, increases in the average marine boundary layer concentrations of methyl iodide, methyl nitrate, and dimethyl sulfide (DMS) were observed as the season progressed to summer conditions. These increases were most appreciable in the region south of 44°S over Southern Ocean waters characterized as subantarctic and polar, indicating a seasonal increase in oceanic productivity for these gases. Copyright 1999 by the American Geophysical Union.

During the First Aerosol Characterization Experiment (ACE 1) field campaign, 1419 whole air samples were collected over the Southern Ocean, of which approximately 700 samples were collected in the marine boundary layer (MBL), 300 samples were taken in the free troposphere (FT), and the remainder were collected in the buffer layer (BuL), the layer between the MBL and FT. Concentrations of tetrachloroethene, ethane, ethyne, and propane decayed over the 24 day duration of the intensive portion of the field campaign, which began November 18, 1995. This decline was consistent with what is known about seasonal increase of HO and the seasonal decrease in biomass burning. Using a simple empirical model, the best fit to the observations was obtained when the average [HO] was 6.1 ± 0.3 × 105 HO cm-3, and an average [Cl] of 720 ± 100 Cl cm-3. The corresponding exchange times were 14 ± 2 days between the MBL and FT, and 49 +40/-13 days between the MBL in the intensive campaign region and the MBL region to the north (nMBL). Copyright 1999 by the American Geophysical Union.

Aircraft measurements of nonmethane hydrocarbons (NMHCs) and halocarbons were made over the remote South Pacific Ocean during late August-early October 1996 for NASA's Global Tropospheric Experiment (GTE) Pacific Exploratory Mission-Tropics A (PEM-Tropics A). This paper discusses the large-scale spatial distributions of selected trace gases encountered during PEM-Tropics A. The PEM-Tropics A observations are compared to measurements made over the southwestern pacific in early November 1995 as part of Aerosol Characterization Experiment (ACE 1). Continental pollution in the form of layers containing elevated levels of O3 was observed during a majority of PEM-Tropics flights, as well as during several ACE 1 flights. The chemical composition of these air masses indicates that they were not fresh and were derived from nonurban combustion sources. The substantial impact of biomass burning on the vertical structure of the South Pacific troposphere is discussed. Copyright 1999 by the American Geophysical Union.

Between June 1 and June 8, 1996, 144 whole air samples were collected in Santiago, Chile. The temporal and geographical enhancement of CH3Br correlated with incomplete combustion tracers emitted from vehicles during the morning commute. From these, a city-wide CH3Br/CO volume emission ratio of 2.2 × 10-6 was measured in ambient air. Without using the CO measurements, we estimate an annual release of 8.9 tons of CH3Br in Santiago based solely upon enhanced concentrations observed throughout the study area during the morning traffic period. This enhancement corresponds to 8.0 × 10-6 kg CH3Br emitted for each liter of gasoline used (leaded and unleaded). By scaling the annual gasoline usage in Santiago to countries still using leaded gasoline, and assuming the above 8.0 × 10-6 kg/L value holds true, a global vehicular CH3Br emission of 4 ± 3 Gg/year is calculated. This small vehicular CH3Br emission source strength will not improve the current CH3Br budget imbalance.

The atmospheric distributions of CH4, C2H6, C3H8, C2H2, and C2Cl4 and their annual chemical removal rates in steady state are determined versus latitude using a modified version of the Oslo two-dimensional global tropospheric photochemical model. A photochemically calculated hydroxyl radical distribution, which has been validated with methylchloroform data, and seasonally varying surface measurements of the title species are used to compute their respective global annual surface source strengths and steady state lifetimes. Computed annual surface source strengths of CH4, C2H6, C3H8, C2H2, and C2Cl4 are 490, 10.4, 8.4, 3.1 Tg (1 Tg = 1012 g), and 432 kT (1 kT = 109 g), respectively. The calculated annual chemical removal rates of these compounds show distinct latitudinal distributions. Because their steady state global lifetimes are less than the model interhemispheric exchange time (about 1 year), the calculated north to south ratios of the deduced surface emission strengths of C2H6, C3H8, C2H2, and C2Cl4 probably reflect the locations of their sources. Within the limits of previously estimated industrial emissions of C2Cl4 (3-4 kT) for the southern hemisphere, our calculations indicate that about 47 kT of additional southern hemispheric source of C2Cl4 is required for 1989-1990 to attain steady state mass balance in this region. There are two possibilities for this needed source: either other industrial sources are missing, or there are unidentified natural sources of C2Cl4. So far, oceans have been suggested as a natural source. Normalization of monthly varying ratios of hemispherically averaged calculated surface mixing ratios of C2H6, C3H8, and C2H2 and their respective observed mixing ratios with respect to those for C2Cl4 indicates that the sources of these hydrocarbons are seasonal in nature. It is also shown that convective transport effectively redistributes these short-lived species but their calculated surface source strengths are relatively independent of this transport process. Copyright 1998 by the American Geophysical Union.