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%

Bacteria in the airways of patients with cystic fibrosis are genetically capable of producing VOCs in breath.

Breath contains hundreds of volatile organic compounds (VOCs), the composition of which is altered in a wide variety of diseases. Bacteria are implicated in the formation of VOCs, but the biochemical mechanisms that lead to the formation of breath VOCs remain largely hypothetical. We hypothesized that bacterial DNA fragments in sputum of CF patients could be sequenced to identify whether the bacteria present were capable of producing VOCs found in the breath of these patients. Breath from seven patients with cystic fibrosis was sampled and analyzed by gas-chromatography and mass-spectrometry. Sputum samples were also collected and microbial DNA was isolated. Metagenomic sequencing was performed and the DNA fragments were compared to a reference database with genes that are linked to the metabolism of acetaldehyde, ethanol and methanol in the KEGG database. Bacteria in the genera Escherichia, Lactococcus, Pseudomonas, Rothia and Streptococcus were found to have the genetic potential to produce acetaldehyde and ethanol. Only DNA sequences from Lactococcus were implicated in the formation of acetaldehyde from acetate through aldehyde dehydrogenase family 9 member A1 (K00149). Escherichia was found to be genetically capable of producing ethanol in all patients, whilst there was considerable heterogeneity between patients for the other genera. The ethanol concentration in breath positively correlated with the amount of Escherichia found in sputum (Spearman rho  =  0.85,  P  =  0.015). Rothia showed the most versatile genetic potential for producing methanol. To conclude, bacterial DNA fragments in sputum of CF patients can be linked to enzymes implicated in the production of ethanol, acetaldehyde and methanol, which are VOCs that are predictive of respiratory tract colonization and/or infection. This supports that the lung microbiome can produce VOCs directly

Stable isotope profiles reveal active production of VOCs from human-associated microbes.

Volatile organic compounds (VOCs) measured from exhaled breath have great promise for the diagnosis of bacterial infections. However, determining human or microbial origin of VOCs detected in breath remains a great challenge. For example, the microbial fermentation product 2,3-butanedione was recently found in the breath of Cystic Fibrosis (CF) patients; parallel culture-independent metagenomic sequencing of the same samples revealed that Streptococcus and Rothia spp. have the genetic capacity to produce 2,3-butanedione. To investigate whether the genetic capacity found in metagenomes translates to bacterial production of a VOC of interest such as 2,3-butanedione, we fed stable isotopes to three bacterial strains isolated from patients: two gram-positive bacteria, Rothia mucilaginosa and Streptococcus salivarius, and a dominant opportunistic gram-negative pathogen, Pseudomonas aeruginosa. Culture headspaces were collected and analyzed using a gas chromatographic system to quantify the abundance of VOCs of interest; mass spectroscopy was used to determine whether the stable isotope label had been incorporated. Our results show that R. mucilaginosa and S. salivarius consumed D-Glucose-13C6 to produce labeled 2,3-butanedione. R. mucilaginosa and S. salivarius also produced labeled acetaldehyde and ethanol when grown with 2H2O. Additionally, we find that P. aeruginosa growth and dimethyl sulfide production are increased when exposed to lactic acid in culture. These results highlight the importance VOCs produced by P. aeruginosa, R. mucilaginosa, and S. salivarius as nutrients and signals in microbial communities, and as potential biomarkers in a CF infection

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

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

Air quality in Mecca and surrounding holy places in Saudi Arabia during Hajj: initial survey.

The Arabian Peninsula experiences severe air pollution, the extent and sources of which are poorly documented. Each year in Saudi Arabia this situation is intensified during Hajj, the Holy Pilgrimage of Islam that draws millions of pilgrims to Mecca. An initial study of air quality in Mecca and surrounding holy sites during the 2012 Hajj (October 24-27) revealed strongly elevated levels of the combustion tracer carbon monoxide (CO, up to 57 ppmv) and volatile organic compounds (VOCs) along the pilgrimage route-especially in the tunnels of Mecca-that are a concern for human health. The most abundant VOC was the gasoline evaporation tracer i-pentane, which exceeded 1200 ppbv in the tunnels. Even though VOC concentrations were generally lower during a follow-up non-Hajj sampling period (April 2013), many were still comparable to other large cities suffering from poor air quality. Major VOC sources during the 2012 Hajj study included vehicular exhaust, gasoline evaporation, liquefied petroleum gas, and air conditioners. Of the measured compounds, reactive alkenes and CO showed the strongest potential to form ground-level ozone. Because the number of pilgrims is expected to increase in the future, we present emission reduction strategies to target both combustive and evaporative fossil fuel sources

Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas

Characterization of carbon monoxide, methane and nonmethane hydrocarbons in emerging cities of Saudi Arabia and Pakistan and in Singapore

We investigate the composition of 63 C2-C10 nonmethane hydrocarbons (NMHCs), methane (CH4) and carbon monoxide (CO), in Jeddah, Mecca, and Madina (Saudi Arabia), in Lahore, (Pakistan), and in Singapore. We established a database with which to compare and contrast NMHCs in regions where ambient levels and emissions are poorly characterized, but where conditions are favorable to the formation of tropospheric ozone, and where measurements are essential for improving emission inventories and modeling. This dataset will also serve as a base for further analysis of air pollution in Western Saudi Arabia including, but not limited to, the estimation of urban emissions and long range pollution transport from these regions. The measured species showed enhanced levels in all Saudi Arabian cities compared to the local background but were generally much lower than in Lahore. In Madina, vehicle exhaust was the dominant NMHC source, as indicated by enhanced levels of combustion products and by the good correlation between NMHCs and CO, while in Jeddah and Mecca a combination of sources needs to be considered. Very high NMHC levels were measured in Lahore, and elevated levels of CH4 in Lahore were attributed to natural gas. When we compared our results with 2010 emissions from the MACCity global inventory, we found discrepancies in the relative contribution of NMHCs between the measurements and the inventory. In all cities, alkenes (especially ethene and propene) dominated the hydroxyl radical (OH) reactivity (kOH) because of their great abundance and their relatively fast reaction rates with OH