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Otto Hahn, a Pioneer of Radiochemistry, was the founder of this journal. Glenn T. Seaborg was a beacon of light for nuclear and actinide chemists and F. Sherwood Rowland for hot atom chemists. Yuan T. Lee performed extra-ordinary molecular beam studies of hot atom chemical reactions. Editor Radiochim. Acta 100, – (2012) / DOI 10.1524/ract.2012. © by Oldenbourg Wissenschaftsverlag, Munchen 503 509 8005

Background: Although 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. Methods: We, 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. Results: This 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). Conclusions: Our 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.

This work presents results from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Whole air samples were obtained on board research flights that flew over California during June 2008 and analyzed for selected volatile organic compounds, including several halogenated species. Samples collected over the South Coast Air Basin of California (SoCAB), which includes much of Los Angeles (LA) County, were compared with samples from inflow air masses over the Pacific Ocean. The levels of many halocarbon species were enhanced significantly over the SoCAB, including compounds regulated by the Montreal Protocol and subsequent amendments. Emissions estimates of HFC-152a (1,1-difluoroethane, CH3CHF2; 0.82 ± 0.11 Gg) and HFC-134a (1,1,1,2-tetrafluoroethane, CH2FCF3; 1.16 ± 0.22 Gg) in LA County for 2008 were obtained using the observed HFC:carbon monoxide (CO) enhancement ratio. Emission rates also were calculated for the SoCAB (1.60 ± 0.22 Gg yr−1 for HFC-152a and 2.12 ± 0.28 Gg yr−1 for HFC-134a) and then extrapolated to the United States (32 ± 4 Gg yr−1 for HFC-152a and 43 ± 6 Gg yr−1 for HFC-134a) using population data. In addition, emission rates of the two HFCs in LA County and SoCAB were calculated by a second method that utilizes air quality modeling. Emissions estimates obtained using both methods differ by less than 25% for the LA County and less than 45% for the SoCAB.

We present results from the Intercontinental Chemical Transport Experiment – Phase B (INTEX-B) aircraft mission conducted in spring 2006. By analyzing the mixing ratios of volatile organic compounds (VOCs) measured during the second part of the field campaign, together with kinematic back trajectories, we were able to identify five plumes originating from China, four plumes from other Asian regions, and three plumes from the United States. To identify specific tracers for the different air masses we characterized their VOC composition and we compared their background levels with those obtained during the 2004 INTEX-A mission. The Chinese and other Asian air masses were significantly enhanced in carbonyl sulfide (OCS) and methyl chloride (CH3Cl), while all CFC replacement compounds were elevated in US plumes, particularly HFC-134a. Although elevated mixing ratios of Halon-1211 were measured in some Chinese plume samples, several measurements at background levels were also observed. After analyzing the VOC distribution and correlations within the Chinese pollution plumes and applying principal component analysis (PCA), we suggest the use of a suite of species, rather than a single gas, as specific tracers of Chinese air masses (namely OCS, CH3Cl, 1,2-dichloroethane, ethyl chloride, and Halon-1211). In an era of constantly changing halocarbon usage patterns, this suite of gases best reflects new emission characteristics from China.

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.

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.

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.

Author(s): Dibb, JE; Albert, M; Anastasio, C; Atlas, E; Beyersdorf, AJ; Blake, NJ; Blake, DR; Bocquet, F; Burkhart, JF; Chen, G; Cohen, L; Conway, TJ; Courville, Z; Frey, MM; Friel, DK; Galbavy, ES; Hall, S; Hastings, MG; Helmig, D; Greg Huey, L; Hutterli, MA; Jarvis, JC; Lefer, BL; Meinardi, S; Neff, W; Oltmans, SJ; Sherwood Rowland, F; Sjostedt, SJ; Steig, EJ; Swanson, AL; Tanner, DJ

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. r 2006 Elsevier Ltd. All rights reserved.

Mixing ratios of seven C 1 –C 5 alkyl nitrates (RONO 2 ) 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 –C 4 (rather than C 1 –C 2 ) RONO 2 were most abundant throughout the study, showing the importance of photochemical (rather than marine) RONO 2 production in the sampled air. A lack of methyl nitrate (MeONO 2 ) enhancement during summer, when the prevailing winds are from the ocean, indicates that the South China Sea is not a region of strong RONO 2 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 RONO 2 production, as opposed to marine emissions or biomass burning. The highest summed RONO 2 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 (O 3 ) level ever recorded in Hong Kong (203 ppbv). During pollution episodes, the average ratio of O 3 to summed RONO 2 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 RONO 2 share a common photochemical source, and their good correlation in pollution plumes shows that RONO 2 can be used as a tracer of photochemical O 3 production. Even MeONO 2 showed similar diurnal variations as the C 2 –C 5 RONO 2 , 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 MeONO 2 levels, and rough calculations show that methoxy radical reaction with NO 2 appears to be a viable alternate pathway for MeONO 2 production in polluted atmospheres, though further measurements and modeling are required to confirm this mechanism.

Solar ultraviolet radiation creates an ozone layer in the atmosphere which in turn completely absorbs the most energetic fraction of this radiation. This process both warms the air, creating the stratosphere between 15 and 50 km altitude, and protects the biological activities at the Earth's surface from this damaging radiation. In the last half-century, the chemical mechanisms operating within the ozone layer have been shown to include very efficient catalytic chain reactions involving the chemical species HO, HO 2 , NO, NO 2 , Cl and ClO. The NO X and ClO X chains involve the emission at Earth's surface of stable molecules in very low concentration (N 2 O, CCl 2 F 2 , CCl 3 F, etc.) which wander in the atmosphere for as long as a century before absorbing ultraviolet radiation and decomposing to create NO and Cl in the middle of the stratospheric ozone layer. The growing emissions of synthetic chlorofluorocarbon molecules cause a significant diminution in the ozone content of the stratosphere, with the result that more solar ultraviolet-B radiation (290–320 nm wavelength) reaches the surface. This ozone loss occurs in the temperate zone latitudes in all seasons, and especially drastically since the early 1980s in the south polar springtime—the ‘Antarctic ozone hole’. The chemical reactions causing this ozone depletion are primarily based on atomic Cl and ClO, the product of its reaction with ozone. The further manufacture of chlorofluorocarbons has been banned by the 1992 revisions of the 1987 Montreal Protocol of the United Nations. Atmospheric measurements have confirmed that the Protocol has been very successful in reducing further emissions of these molecules. Recovery of the stratosphere to the ozone conditions of the 1950s will occur slowly over the rest of the twenty-first century because of the long lifetime of the precursor molecules.

Whole air samples were collected in 43 Chinese cities in January and February 2001, and methane and nonmethane hydrocarbon (NMHC) concentrations for those samples are here discussed. In order to identify the main sources of the hydrocarbons in these cities, cross-correlations with the general combustion tracer ethyne and the gasoline marker i-pentane were investigated. Most of the identified NMHCs correlated with ethyne or i-pentane suggesting that their primary source is combustion or gasoline evaporation. To differentiate between vehicular and other combustion sources, the benzene to toluene ratio characteristic of the Chinese vehicular fleet was calculated using roadside samples (collected in 25 cities). Cities where the main source of the NMHCs was traffic related were identified. The slope resulting from the correlation of selected gases was used to identify the likely sources of the NMHCs measured. Vehicular emissions were found to be an important source of isoprene in some cities. Different VOC mixing ratio distributions throughout the country were also investigated. This paper gives a general overview of urban VOCs in many Chinese cities. Future more rigorous studies will be necessary to further characterize VOC sources in China.

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 (CH3I) 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( tE1 day). However, DMSwas not detected at the S P until January even though DMSemissions from the Southern Ocean typically start peaking in November and elevated levels of other ocean-derived VOCs, including CH3ONO2 and CHBr3, were observed in mid-November. We speculate that in November and December most of the DMSis oxidized before it reaches the S P: 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. r 2004 Elsevier Ltd. All rights reserved.

Oceanic iron (Fe) fertilization experiments have advanced the understanding of how Fe regulates biological productivity and air–sea carbon dioxide (CO 2 ) exchange. However, little is known about the production and consumption of halocarbons and other gases as a result of Fe addition. Besides metabolizing inorganic carbon, marine microorganisms produce and consume many other trace gases. Several of these gases, which individually impact global climate, stratospheric ozone concentration, or local photochemistry, have not been previously quantified during an Fe-enrichment experiment. We describe results for selected dissolved trace gases including methane (CH 4 ), isoprene (C 5 H 8 ), methyl bromide (CH 3 Br), dimethyl sulfide, and oxygen (O 2 ), which increased subsequent to Fe fertilization, and the associated decreases in concentrations of carbon monoxide (CO), methyl iodide (CH 3 I), and CO 2 observed during the Southern Ocean Iron Enrichment Experiments.

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.

A large number of hydrocarbons, halocarbons, and organic nitrates were quantified in whole air samples acquired for the NASA-sponsored GTE missions PEM-Tropics A and B. The samples were collected in electro-polished stainless steel canisters from two aircraft while flying over the Pacific Basin. Two nominally identical multicolumn multidetector gas chromatographic analytical systems were employed. Whole air samples were also used as working and calibrated standards and were collected specifically for this purpose. This paper describes the analytical procedure employed during PEM-Tropics B. Minor differences in the PEM-Tropics A system will also be discussed. More than 3,900 samples were analyzed for 34 gases during PEM-Tropics A, over 4,500 samples were analyzed for 58 gases during PEM-Tropics B. An overview is presented of the collection, analysis, and quantification of whole air samples during the PEM-Tropics missions, along with an analysis of the analytical precision achieved during these missions.

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.

▪ Abstract This paper reviews the available data and models on energy and material flows through the world's 25 largest cities. Throughput is categorized as stored, transformed, or passive for the major flow modes. The aggregate, fuel, food, water, and air cycles are all examined. Emphasis is placed on atmospheric pathways because the data are abundant. Relevant models of urban energy and material flows, demography, and atmospheric chemistry are discussed. Earth system–level loops from cities to neighboring ecosystems are identified. Megacities are somewhat independent of their immediate environment for food, fuel, and aggregate inputs, but all are constrained by their regional environment for supplying water and absorbing wastes. We elaborate on analogies with biological metabolism and ecosystem succession as useful conceptual frameworks for addressing urban ecological problems. We conclude that whereas data are numerous for some individual cities, cross-cutting compilations are lacking in biogeochemical analysis and modeling. Synthesis of the existing information will be a crucial first step. Cross-cutting field research and integrated, multidisciplinary simulations will be necessary.

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.

Author(s): Wingenter, OW; Blake, DR; Blake, NJ; Sive, BC; Rowland, FS; Atlas, E; Flocke, F | Abstract: 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.

Author(s): Blake, NJ; Blake, DR; Wingenter, OW; Sive, BC; McKenzie, LM; Lopez, JP; Simpson, IJ; Fuelberg, HE; Sachse, GW; Anderson, BE; Gregory, GL; Carroll, MA; Albercook, GM; Rowland, FS | Abstract: 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.

During upcoming industrialization, the human population of Asia will exert a strong influence on both the Pacific Rim environment and the total earth system. We review energy-use trajectories both likely and possible on the continent, taking the historical market penetration series as a framework. Today, the People's Republic of China is coal rich, but as its economy grows in the short term, fuel substitution from solid fossils will occur. Major automakers will exploit new niches in the Orient, adding petroleum to the mix of fuels and producing photochemical smog on the regional scale. Demand is rising in coastal cities for cleaner fuels such as natural gas, but they must be imported. Nuclear industries in India and China are small and expanding only slowly. The Tibetan plateau confers exceptional hydroelectric potential but peripheral concerns plague the big dams. Solar and hydrogen are decades from implementation even in Europe. Fossil resources are largely remote from the Asian consumer class. The disconnect feeds back into the design of new transportation networks. Since for the moment development lags, the option exists to view Asia as a crucible for the techniques of cogeneration, sequestration and pollutant recapture.

The atmospheric distributions of CH4, C2H6, C3H8, C2H2, and C2Cl4and 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 C2Cl4are 490, 10.4, 8.4, 3.1 Tg (1 Tg = 1012g), and 432 kT (1 kT = 109g), 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 C2Cl4probably 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 C2Cl4is 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 C2H2and their respective observed mixing ratios with respect to those for C2Cl4indicates 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.

Although removal of tropospheric methyl bromide (CH3Br) is dominated by the reaction with the seasonally varying hydroxyl (HO) radical concentration, the anticipated corresponding seasonal dependence of CH3Br, as found for other gases with major HO sinks, has been sought previously without success [WMO, 1995]. Our observations of northern hemispheric boundary layer CH3Br concentrations do reveal substantial seasonal changes. The high latitude CH3Br North/South interhemispheric concentration ratio (IHR) varies from a maximum of 1.35±0.04 (1σ) in March–April to 1.10±0.04 in September, with an equal area and seasonally (EAS) weighted average IHR of 1.21±0.03. These observations suggest northern hemispheric emissions are about 15 kilotons/year less than when an IHR of 1.3 is considered [WMO, 1995]. The observed seasonality also partially explains the differences in the IHR reported by several research groups [WMO, 1995] and places needed constraints on the magnitude and seasonality of sources and sinks of CH3Br.

The atmospheric residence time for methyl bromide (CH 3 Br) has been estimated as 0.8 ± 0.1 years from its empirical spatial variability relative to C 2 H 6 , C 2 Cl 4 , CHCl 3 , and CH 3 Cl. This evaluation of the atmospheric residence time, based on Junge's 1963 general proposal, provides an estimate for CH 3 Br that is independent of source and sink estimates. Methyl bromide from combined natural and anthropogenic sources furnishes about half of the bromine that enters the stratosphere, where it plays an important role in ozone destruction. This residence time is consistent with the 0.7-year value recently calculated for CH 3 Br from the combined strength estimates for its known significant sinks.

Compared to measurements, atmospheric models have overestimated [ClO]/[HCl] and [ClONO2]/[HCl] in the upper and middle stratosphere, respectively, and consequently have predicted lower [O3] than observed. It is believed that a minor branch that produces HCl from the OH + ClO reaction can account for these discrepancies. Recent laboratory studies have indicated a 5 ( 2% yield for this channel. 1 By performing box model sensitivity analysis calculations using the output from the LLNL-2D diurnally averaged stratospheric model, we quantitatively confirm that this reaction is the most prominent contributor to the model [ClO]/ [HCl] and [ClONO2]/[HCl] uncertainties in the upper stratosphere and that it is most effective in increasing [O3] at higher latitudes during winter. Using theoretical methods, we examine the OH + ClO reaction mechanism, in which an initially energized HOOCl* complex is formed that can dissociate to HO2 + Cl (major) or HCl + O2( 1 ¢) (minor) products, redissociate to reactants, or be collisionally stabilized. Multichannel RRKM calculations guided by ab initio electronic structure calculations and the available kinetic data are presented. We show that the four-center transition state (TS3) for HCl production must lie at least 2 kcal/ mol below the reactants for the HCl yield to exceed 5%. Our ab initio relative energy of -2.3 ( 3 kcal/mol for TS3 demonstrates that this minor HCl channel is mechanistically feasible. We also predict small pressure, temperature, and H/D isotopic dependencies for the minor channel yield and insignificant rates of complex stabilization under atmospheric conditions.

Thermal chlorine atoms react with gaseous CH3I and CH3Br at 295K to produce CH3Cl with yields of 8.6% and 0.6%, respectively. The studies utilized radioactive 38Cl formed by the 37Cl (n,γ) 38Cl nuclear reaction in gaseous CClF3 at pressures from 760 to 4,000 torr. The initially energetic 38Cl atoms are thermalized by multiple inelastic collisions with CClF3 prior to reaction with the methyl halide. The reaction rate constant for thermal chlorine attack on CH3Br to form CH3Cl at 295K and 1–5 atmospheres pressure is (2.0±0.5) × 10−15 cm³ molecule−1 s−1. The substitution of Cl for Br/I in a methyl halide molecule cannot be a significant source of atmospheric CH3Cl because of its abundance from other sources. However, the replacement of I by Cl in other iodohalocarbons might in some cases provide a marker for the presence of atomic chlorine.

Nonmethane hydrocarbons (NMHCs) and halocarbons were measured in the troposphere over the northwestern Pacific as part of the airborne component of NASA's Pacific Exploratory Mission-West Phase B (PEM-West B). This study took place in late winter of 1994, a period characterized by maximum outflow from the Asian continent. The results are compared to those from Pacific Exploratory Mission-West Phase A (PEM-West A), which was flown in the same region during late summer of 1991, when flow from the subtropical western Pacific dominated the lower troposphere. Mixing ratios of NMHCs, tetrachloroethene (C2Cl4), and methyl bromide (CH3Br) were significantly higher during PEM-West B than during PEM-West A, particularly at latitudes north of 25 deg N and altitudes lower than 6 km. The primary reasons for these higher ambient concentrations were the seasonal increase in the atmospheric lifetimes of trace gases controlled by HO radical reactions, and the more frequent input of continental air masses. During PEM-West B, air masses of continental origin observed north of 25 deg N latitude were augmented with urban signature gases such as C2Cl4. By contrast, more southerly continental outflow had characteristics associated with combustion sources such as biomass burning, including wood fuel burning. During the summer PEM-West A period, the spatial distribution of methyl iodide (CH3I) was consistent with effective oceanic sources at all latitudes, being especially strong in tropical and subtropical regions. At low latitudes, PEM-West B CH3I mixing ratios in the lower troposphere were similar to PEM-West A, but at latitudes greater than about 25 deg N PEM-West B concentrations were significantly reduced. Equatorial regions exhibited enhanced CH3I mixing ratios extending into the upper tropical troposphere, consistent with fast vertical transport of air from the tropical marine boundary layer.

The People's Republic of China, the world's most populous nation, is considering extensive development of its automotive transportation infrastructure. Upper limits to the associated pollution increases can be defined through scenarios with Western style vehicles and vehicle-to-person ratios. Here we construct estimates of fundamental changes to chemistry of the Pacific ocean/atmosphere system through simple budgeting procedures. Regional increases in tropospheric ozone could reach tens of parts per billion. Observations/experiments suggest that enhanced nitrogen oxides will react with sea salt aerosols to yield chlorine atoms in the marine boundary layer. Nitrate deposition onto the open sea surface would support several percent of exported North Pacific carbon production. Transport of biologically active iron to surface waters may follow from increases in mineral dust and acid sulfate aerosols. Altered plankton ecodynamics will feed back into climate processes through sea to air flux of reduced sulfur gases and through carbon dioxide drawdown.

The saturated hydrocarbons propane and the butane isomers are both indirect greenhouse gases and key species in liquefied petroleum gas (LPG). Leakage of LPG and its component alkanes/alkenes is now thought to explain a significant fraction of the volatile organic burden and oxidative potential in the basin which confines Mexico City. Propane and the butanes, however, are stable enough to escape from the basin. The gas Chromatographie measurements which have drawn attention to their sources within the urban area are used here to estimate rates of ventilation into the free troposphere. The calculations are centered on several well studied February/March pollution episodes. Carbon monoxide observations and emissions data are first exploited to provide a rough time constant for the removal of typical inert pollutant species from the valley. The timescale obtained is validated through an examination of meteorological simulations of three-dimensional flow. Heuristic arguments and transport modeling establish that propane and the butanes are distributed through the basin in a manner analogous to CO despite differing emissions functions. Ventilation rates and mass loadings yield outbound fluxes in a box model type computation. Estimated in this fashion, escape from the Valley of Mexico constitutes of the order of half of 1% of the northern hemispheric inputs for both propane and n-butane. Uncertainties in the calculations are detailed and include factors such as flow into the basin via surface winds and the size of the polluted regime. General quantification of the global propane and butane emissions from large cities will entail studies of this type in a variety of locales.

Local surface travel needs in the People‘s Republic of China (mainlandChina) have traditionally been met largely by nonpolluting bicycles. A majorautomobile manufacturing/importing effort has begun in the country over thelast decade, and planning documents indicate that the Chinese may strive toacquire more than 100 million vehicles early in the next century. By analogywith large automotive fleets already existing in the western world, bothregional and global scale pollution effects are to be expected from theincrease. The present work adopts the latest projections of Chinese automobilemanufacture and performs some quantitative assessments of the extent ofpollution generation.Focus for the investigation is placed upon the oxidant ozone. Emissions of theprecursor species nitrogen oxides and volatile organics are constructed basedon data for the current automotive sector in the eastern portion of the UnitedStates. Ozone production is first estimated from measured values forcontinental/oceanic scale yields relative to precursor oxidation. Theestimates are then corroborated through idealized two dimensional modeling ofthe photochemistry taking place in springtime air flow off the Asian land massand toward the Pacific Ocean. The projected fleet sizes could increase coastaland remote oceanic ozone concentrations by tens of parts per billion (ppb)in the lower troposphere. Influences on the tropospheric aerosol system andon the major greenhouse gas carbon dioxide are treated peripherally. Nitrogenoxides created during the vehicular internal combustion process willcontribute to nitrate pollution levels measured in the open Pacific. Thepotential for soot and fugitive dust increases should be considered as theautomotive infrastructure develops. Since the emerging Chinese automotivetransportation system will represent a substantial addition to the globalfleet and all the carbon in gasoline is eventually oxidized completely, asignificant rise in global carbon dioxide inputs will ensue as well.Some policy issues are treated preliminary. The assumption is made thatalterations to regional oxidant/aerosol systems and to terrestrial climate areconceivable. The likelihood that the Chinese can achieve the latest vehiclefleet goals is discussed, from the points of view of new production, positivepollution feedbacks from a growing automobile industry, and known petroleumreserves. Vehicular fuel and maintenance options lying before the Chinese areoutlines and compared. To provide some perspective on the magnitude of theenvironmental changes associated with an Asian automotive buildup, recentestimates of the effects of future air traffic over the Pacific Rim aredescribed.

The NASA TRACE A experiment (September – October 1992) investigated effects of dry season biomass burning emissions from both South America and southern Africa on the tropical South Atlantic troposphere. Whole air canister samples were collected aboard the NASA DC-8 aircraft and analyzed for a wide range of nonmethane hydrocarbons (NMHCs) and halocarbons. Fast response in situ quantification of CH4, CO, and CO2 were also performed on the DC-8. Sampling took place over Brazilian agricultural areas and southern African savanna where there was active biomass burning. The vertical distribution of the measured gases revealed that the concentrations of most hydrocarbons, methyl halides, CH4, CO, and CO2, were enhanced in the boundary layer of these regions principally as a result of biomass fires. Brazilian and African biomass burning emission ratios were calculated for CH3Br, CH3Cl, CH3I, and NMHCs relative to CO and CO2. Although both fire regions were dominated by efficient (flaming) combustion (CO/CO2 ratios

In evaluating the cost of phasing out chlorofluorocarbons, it pays to look not only at current damage to the ozone layer but also at what might have happened had our use of these chemicals continued unimpeded.

Nonmethane hydrocarbons and halocarbons were measured during two Lagrangian experiments conducted in the lower troposphere of the North Atlantic as part of the June 1992, Atlantic Stratosphere Transition Experiment/Marine Aerosol and Gas Exchange (ASTEX/MAGE) expedition. The first experiment was performed in very clean marine air. Meteorological observations indicate that the height of the marine boundary layer rose rapidly, entraining free tropospheric air. However, the free tropospheric and marine boundary layer halocarbon concentrations were too similar to allow this entrainment to be quantified by these measurements. The second Lagrangian experiment took place along the concentration gradient of an aged continental air mass advecting from Europe. The trace gas measurements confirm that the National Center for Atmospheric Research (NCAR) Electra aircraft successfully intercepted the same air mass on consecutive days. Two layers, a surface layer and a mixed layer with chemically distinct compositions, were present within the marine boundary layer. The composition of the free troposphere was very different from that of the mixed layer, making entrainment from the free troposphere evident. Concentrations of the nonmethane hydrocarbons in the Lagrangian surface layer were observed to become depleted relative to the longer-lived tetrachloroethene. A best fit to the observations was calculated using various combinations of the three parameters, loss by reaction with hydroxyl, loss by reaction with chlorine, and/or dilution from the mixed layer. These calculations provided estimated average concentrations in the surface layer for a 5-hour period from dawn to 11 UT of 0.3 ± 0.5 × 106 molecules cm−3 for HO, and 3.3 ± 1.1 × 104 molecules cm−3 for Cl. Noontime concentration estimates were 2.6 ± 0.7 × 106 molecules cm−3 for HO and 6.5 ± 1.4 × 104 molecules cm−3 for Cl.

Aircraft measurements of selected nonmethane hydrocarbon and halocarbon species were made in the lower troposphere of the NE Atlantic near the Azores, Portugal, during June 1992 as part of the Atlantic Stratocumulus Transition Experiment/Marine Aerosol and Gas Exchange. In this paper, the impact of continental outflow from both Europe and North America on the study region were assessed. Four main air mass types were characterized from trajectories and trace gas concentrations: clean marine from the Atlantic, and continental air from the Iberian Peninsula, the British Isles and Northern Europe, and North America. Each classification exhibited trace gas concentrations that had been modified en route by photochemical processes and mixing. Comparison with the clean marine boundary layer (MBL) shows that the boundary layer of the predominantly continental air masses were enhanced in hydrocarbons and halocarbons by factors of approximately 2 for ethane, 5 for propane, 2–6 for ethyne and benzene, and 2–3 for C2Cl4. The same air masses also exhibited large ozone enhancements, with 2 to 3 times higher mixing ratios in the continental boundary layer air compared to the clean MBL. This indicates a primarily anthropogenic photochemical source for a significant fraction of the lower tropospheric ozone in this region. Methyl bromide exhibited on average 10–20% higher concentrations in the boundary layer affected by continental outflow than in the clean MBL, and was seen to be enhanced in individual plumes of air of continental origin. This is consistent with significant anthropogenic sources for methyl bromide. In addition, median MBL concentrations of ethene and methyl iodide showed enhancements of approximately a factor of 2 above free tropospheric values, suggesting primarily coastal/oceanic sources for these species.

Tropospheric mixing ratios of CCl2 = CCl2 were measured at remote surface locations in the Pacific between 71 deg N and 47 deg S during September and December of 1989, and March and June of 1990. The observed gradient of decreasing concentrations from the northern to the southern hemisphere, and very low concentrations in the southern hemisphere throughout the year, indicates a predominant input from the northern hemisphere. Seasonal measurements in the northern hemisphere showed maximum CCl2 = CCl2 concentrations occurring in the late summer. This distinct seasonal variation is strongly coupled to the atmompheric abundance of hydroxyl radical, the only important species responsible for CCl2 = CCl2 removal. With the estimated global CCl2 =CCl2 emissions, the lifetime is calculated to be about 5.4 months which is in good agreement with the 4.0 month estimate obtained from the inverse ratio of its measured hydroxyl reaction rate constant compared with that of methyl-chloroform CH3CCl3.

[1] 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.

The longest continuous record of global atmospheric ethane levels is presented, showing that global ethane emission rates decreased by 21 per cent from 1984 to 2010, probably owing to decreased venting and flaring of natural gas in oil fields; decreased venting and flaring also account for at least 30 to 70 per cent of the decrease in methane emissions over the same period. Ethane is the most abundant non-methane hydrocarbon in the remote atmosphere and is a precursor to tropospheric ozone. This paper presents the longest continuous record of global atmospheric ethane levels assembled so far and finds that global ethane-emission rates decreased by 21% between 1984 and 2010. This can probably be attributed to a decrease in fugitive emissions, such as the venting and flaring of natural gas from oil fields, rather than a decline in its other major sources, biofuel use and biomass burning. Because methane shares ethane's main sources of emissions, this new long-term ethane record can be used to investigate changes in global methane levels. This leads the authors to suggest that reduced fugitive fossil-fuel emissions also account for 30–70% of the decrease in global methane emissions. 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 sink1,2,3. 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 slow4,5. 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.

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.