Stratospheric feedback from continued increases in tropospheric methane

Tropospheric concentrations of methane have increased steadily over the past ten years at an average rate of 16.5 ppbv per year, to a value in January 1988 of 1.69 ppmv. Measurements of CH sub 4 concentrations in air bubbles trapped in ice cores have shown concentrations of about 0.7 ppmv 200 years ago, with little further change for thousands of years before that. Interpolation earlier into this century suggests a concentration of about 1.1 to 1.2 ppmv in the 1940's. The only important pathway believed to be important for transfer of air from the troposphere to the stratosphere in through the tropical tropopause which is cold enough to reduce the mixing ratio of H sub 2 O in that air to about 3 ppmv. The only other major pathway for the delivery of H to the stratosphere is through the simultaneous injection of gaseous CH sub 4 in the same rising air. The formation of clouds in the stratosphere is dependent upon very low temperatures, and generally upon the amount of water vapor available. The possibility of a positive feedback exists, especially in well-oxidized methane air, that clouds are easier to form than earlier. This could mean enhancement of PSCs in both Antarctic and Arctic locations. Additional H sub 2 O in the stratosphere can also add to some of the greenhouse calculations

Methyl chloride and the U.S. cigarette.

Various brands and types of cigarettes were purchased at retail locations in southern California. Volatile gas samples were analyzed using multicolumn/multidetector gas chromatography. Results showed methyl chloride (CH(3)Cl) levels as much as four orders of magnitude higher than typical urban levels, about 30-500 ppmv (1.5-5.3 mg/cigarette), compared with about 500 pptv in urban air. The concentration of CH(3)Cl correlated well with the levels of both CO (r (2) = 0.63) and CO(2) (r (2) = 0.77), showing the link between CH(3)Cl and combustion. In some brands, CH(3)Cl levels were well above the U.S. Environmental Protection Agency's maximum exposure limit of 200 ppmv. Light branded cigarettes tended to have higher CH(3)Cl levels than the heavier and filtered brands, possibly showing the dependence of cigarette packing on CH(3)Cl production. In addition, CH(3)Cl emitted from cigarette smoke may prove to be an important anthropogenic source of CH(3)Cl in the United States, at about 5%

Air quality in the Industrial Heartland of Alberta, Canada and potential impacts on human health.

The "Industrial Heartland" of Alberta is Canada's largest hydrocarbon processing center, with more than 40 major chemical, petrochemical, and oil and gas facilities. Emissions from these industries affect local air quality and human health. This paper characterizes ambient levels of 77 volatile organic compounds (VOCs) in the region using high-precision measurements collected in summer 2010. Remarkably strong enhancements of 43 VOCs were detected, and concentrations in the industrial plumes were often similar to or even higher than levels measured in some of the world's largest cities and industrial regions. For example maximum levels of propene and i-pentane exceeded 100 ppbv, and 1,3-butadiene, a known carcinogen, reached 27 ppbv. Major VOC sources included propene fractionation, diluent separation and bitumen processing. Emissions of the measured VOCs increased the hydroxyl radical reactivity (kOH), a measure of the potential to form downwind ozone, from 3.4 s-1 in background air to 62 s-1 in the most concentrated plumes. The plume value was comparable to polluted megacity values, and acetaldehyde, propene and 1,3-butadiene contributed over half of the plume kOH. Based on a 13-year record (1994-2006) at the county level, the incidence of male hematopoietic cancers (leukemia and non-Hodgkin lymphoma) was higher in communities closest to the Industrial Heartland compared to neighboring counties. While a causal association between these cancers and exposure to industrial emissions cannot be confirmed, this pattern and the elevated VOC levels warrant actions to reduce emissions of known carcinogens, including benzene and 1,3-butadiene

Increasing external effects negate local efforts to control ozone air pollution: a case study of Hong Kong and implications for other Chinese cities.

It is challenging to reduce ground-level ozone (O3) pollution at a given locale, due in part to the contributions of both local and distant sources. We present direct evidence that the increasing regional effects have negated local control efforts for O3 pollution in Hong Kong over the past decade, by analyzing the daily maximum 8 h average O3 and Ox (=O3+NO2) concentrations observed during the high O3 season (September-November) at Air Quality Monitoring Stations. The locally produced Ox showed a statistically significant decreasing trend over 2002-2013 in Hong Kong. Analysis by an observation-based model confirms this decline in in situ Ox production, which is attributable to a reduction in aromatic hydrocarbons. However, the regional background Ox transported into Hong Kong has increased more significantly during the same period, reflecting contributions from southern/eastern China. The combined result is a rise in O3 and a nondecrease in Ox. This study highlights the urgent need for close cross-boundary cooperation to mitigate the O3 problem in Hong Kong. China's air pollution control policy applies primarily to its large cities, with little attention to developing areas elsewhere. The experience of Hong Kong suggests that this control policy does not effectively address secondary pollution, and that a coordinated multiregional program is required

Ambient mixing ratios of nonmethane hydrocarbons (NMHCs) in two major urban centers of the Pearl River Delta (PRD) region: Guangzhou and Dongguan

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 (<0.20) is proposed here and used as indicator of samples strongly affected by industrial emissions. The ozone formation potential (OFP) is calculated, and the role of the different NMHCs associated with industrial and combustion sources is evaluated. © 2008 Elsevier Ltd. All rights reserved

A quantitative assessment of distributions and sources of tropospheric halocarbons measured in Singapore.

This work reports the first ground-based atmospheric measurements of 26 halocarbons in Singapore, an urban-industrial city-state in Southeast (SE) Asia. A total of 166 whole air canister samples collected during two intensive 7 Southeast Asian Studies (7SEAS) campaigns (August-October 2011 and 2012) were analyzed for C1-C2 halocarbons using gas chromatography-electron capture/mass spectrometric detection. The halocarbon dataset was supplemented with measurements of selected non-methane hydrocarbons (NMHCs), C1-C5 alkyl nitrates, sulfur gases and carbon monoxide to better understand sources and atmospheric processes. The median observed atmospheric mixing ratios of CFCs, halons, CCl4 and CH3CCl3 were close to global tropospheric background levels, with enhancements in the 1-17% range. This provided the first measurement evidence from SE Asia of the effectiveness of Montreal Protocol and related national-scale regulations instituted in the 1990s to phase-out ozone depleting substances (ODS). First- and second-generation CFC replacements (HCFCs and HFCs) dominated the atmospheric halocarbon burden with HFC-134a, HCFC-22 and HCFC-141b exhibiting enhancements of 39-67%. By combining near-source measurements in Indonesia with receptor data in Singapore, regionally transported peat-forest burning smoke was found to impact levels of several NMHCs (ethane, ethyne, benzene, and propane) and short-lived halocarbons (CH3I, CH3Cl, and CH3Br) in a subset of the receptor samples. The strong signatures of these species near peat-forest fires were potentially affected by atmospheric dilution/mixing during transport and by mixing with substantial urban/regional backgrounds at the receptor. Quantitative source apportionment was carried out using positive matrix factorization (PMF), which identified industrial emissions related to refrigeration, foam blowing, and solvent use in chemical, pharmaceutical and electronics industries as the major source of halocarbons (34%) in Singapore. This was followed by marine and terrestrial biogenic activity (28%), residual levels of ODS from pre-Montreal Protocol operations (16%), seasonal incidences of peat-forest smoke (13%), and fumigation related to quarantine and pre-shipment (QPS) applications (7%)