Carbon monoxide exerts strong control over the chemistry of the troposphere and lower stratosphere through its influence over hydroxyl radical (OH) and ozone concentrations. Thus, CO affects the oxidizing power of the atmosphere and the concentrations of greenhouse gases. Because of its short atmospheric residence time (two or three months) the determination of a secular trend in CO concentrations is very difficult. Temporal increases of CO are expected because certain sources under human control have been growing; these include fossil-fuel usage and increasing atmospheric methane. From the data, it is likely that CO has increased in the Northern Hemisphere in the past 15-30 years. Southern Hemispheric data indicate no positive trend. -from Author

In qualitative agreement with previous MP2 level calculations of the 12C/13C kinetic isotope effects (KIEs) for H-abstraction of CH4 by OH and Cl, higher level calculations yield KIEs at 300 K that differ from the corresponding experimental values, but in different directions. At QCISD(T)/6-311+G(2df,p), the theoretical KIE for CH4 + Cl is 32 ‰ less than the measured value, while for CH4 + OH, the theoretical KIE is greater than the measured value, but only by 5 ‰. Noticeable differences in atmospheric model simulation studies can occur if the measured KIEs are replaced by the analogous theoretical values. For example, the effect of carbon isotopic fractionation from the CH4 + Cl reaction on stratospheric δ13CH4 will be significantly lower than that obtained by Bergamaschi et al. [1996]. It is suggested, for the CH4 + OH reaction and especially for the CH4 + Cl reaction, that additional KIE measurements are needed. Copyright 1997 by the American Geophysical Union.

Recent technical advances allow detection of several hundred volatile organic compounds (VOCs) in human exhaled air, many of which reflect unidentified endogenous pathways. Our group has previously estimated plasma glucose levels in healthy adults during a standard oral glucose tolerance test via exhaled VOC analysis. As a result of the metabolic characteristics of hyperglycemia in the diabetic (low insulin and increased free fatty acids and ketones), we hypothesized that different exhaled VOC profiles may be present in children with type 1 diabetes mellitus (T1DM) during spontaneous hyperglycemia. Exhaled methyl nitrate strongly correlated specifically with the acute, spontaneous hyperglycemia of T1DM children. Eighteen experiments were conducted among 10 T1DM children. Plasma glucose and exhaled gases were monitored during either constant euglycemia (n = 5) or initial hyperglycemia with gradual correction (n = 13); all subjects received i.v. insulin and glucose as needed. Gas analysis was performed on 1.9-liter breath samples via gas chromatography using electron capture, flame ionization, and mass selective detection. Among the approximately 100 measured exhaled gases, the kinetic profile of exhaled methyl nitrate, commonly present in room air in the range of 5-10 parts per trillion, was most strongly statistically correlated with that of plasma glucose (P = 0.003-0.001). Indeed, the kinetic profiles of the two variables paralleled each other in 16 of 18 experiments, including repeat subjects who at different times displayed either euglycemia or hyperglycemia.

We report tropospheric (altitudes > 5 km) observations of CO2, CO, CH4, and light hydrocarbons (C2 ‐ C4) over the latitude range from 90°N to 23°S recorded onboard the NASA DC‐8 aircraft during the winter 1992 Second Airborne Arctic Stratospheric Expedition (AASE‐II). Mixing ratios for these species exhibited significant north‐south gradients with maximum values in subpolar and arctic regions and minima over the southern tropics. At latitudes > 40°N, the mixing ratios of most species increased significantly over the course of the 3‐month measurement period. Also at high northern latitudes, the variations of all relatively long‐lived reactive carbon species were linearly correlated with fluctuations of CO2 with CO, CH4, C2H6, C2H2, C3H8, and n‐C4H10 exhibiting average enhancement ratios in terms of ppbV(X)/ppmv(CO2) of 13.8, 8.4, 0.21, 0.075, 0.085, and 0.037, respectively. Copyright 1993 by the American Geophysical Union.

The concentration of methane has been measured in tropospheric air samples collected in remote locations between 55°N and 53°S during six collection periods between November 1977 and November 1980. The observed concentrations of CH4 have increased in each of six latitude locations by an average of 0.052±0.005 ppmv between January 1978 and January 1980. This (1.4±0.2)×1014 gram increase in the total atmospheric burden of CH4 corresponds to 35±12% of the yearly flux of (4.0±1.3)×1014 grams needed to maintain the CH4 concentration in steady‐state at its recent level of about 1.6 ppmv. The 1978‐1980 excess of about 0.7×1014 grams per year of sources over sinks for CH4 could arise from either an increase in biogenic releases or from a decrease in the average OH radical concentration in the lower troposphere, or from both. Copyright 1982 by the American Geophysical Union.

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. © 2005 Elsevier Ltd. All rights reserved.

Multiyear (2000-2006) seasonal measurements of carbon monoxide, hydrocarbons, halogenated species, dimethyl sulfide, carbonyl sulfide and C1-C4 alkyl nitrates at the South Pole are presented for the first time. At the South Pole, short-lived species (such as the alkenes) typically were not observed above their limits of detection because of long transit times from source regions. Peak mixing ratios of the longer lived species with anthropogenic sources were measured in late winter (August and September) with decreasing mixing ratios throughout the spring. In comparison, compounds with a strong oceanic source, such as bromoform and methyl iodide, had peak mixing ratios earlier in the winter (June and July) because of decreased oceanic production during the winter months. Dimethyl sulfide (DMS), which is also oceanically emitted but has a short lifetime, was rarely measured above 5 pptv. This is in contrast to high DMS mixing ratios at coastal locations and shows the importance of photochemical removal during transport to the pole. Alkyl nitrate mixing ratios peaked during April and then decreased throughout the winter. The dominant source of the alkyl nitrates in the region is believed to be oceanic emissions rather than photochemical production due to low alkane levels.Sampling of other tropospheric environments via a Twin Otter aircraft included the west coast of the Ross Sea and large stretches of the Antarctic Plateau. In the coastal atmosphere, a vertical gradient was found with the highest mixing ratios of marine emitted compounds at low altitudes. Conversely, for anthropogenically produced species the highest mixing ratios were measured at the highest altitudes, suggesting long-range transport to the continent. Flights flown through the plume of Mount Erebus, an active volcano, revealed that both carbon monoxide and carbonyl sulfide are emitted with an OCS/CO molar ratio of 3.3 × 10-3 consistent with direct observations by other investigators within the crater rim. © 2010.