Simone Meinardi

Chemical data quantify Deepwater Horizon hydrocarbon flow rate and environmental distribution

Detailed airborne, surface, and subsurface chemical measurements, primarily obtained in May and June 2010, are used to quantify initial hydrocarbon compositions along different transport pathways (i.e., in deep subsurface plumes, in the initial surface slick, and in the atmosphere) during the Deepwater Horizon oil spill. Atmospheric measurements are consistent with a limited area of surfacing oil, with implications for leaked hydrocarbon mass transport and oil drop size distributions. The chemical data further suggest relatively little variation in leaking hydrocarbon composition over time. Although readily soluble hydrocarbons made up ∼25% of the leaking mixture by mass, subsurface chemical data show these compounds made up ∼69% of the deep plume mass; only ∼31% of the deep plume mass was initially transported in the form of trapped oil droplets. Mass flows along individual transport pathways are also derived from atmospheric and subsurface chemical data. Subsurface hydrocarbon composition, dissolved oxygen, and dispersant data are used to assess release of hydrocarbons from the leaking well. We use the chemical measurements to estimate that (7.8 ± 1.9) × 106 kg of hydrocarbons leaked on June 10, 2010, directly accounting for roughly three-quarters of the total leaked mass on that day. The average environmental release rate of (10.1 ± 2.0) × 106 kg/d derived using atmospheric and subsurface chemical data agrees within uncertainties with the official average leak rate of (10.2 ± 1.0) × 106 kg/d derived using physical and optical methods.

Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi, Pakistan

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 (6.3 ppmv) and ethane (93 ppbv) 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 (0.3–19 ppbv) 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 (1.2 ppbv) 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. r 2002 Elsevier Science Ltd. All rights reserved.

Source origins, modeled profiles, and apportionments of halogenated hydrocarbons in the greater Pearl River Delta region, southern China

[1] We analyze 16-month data of 13 major halocarbons measured at a southern China coastal site in the greater Pearl River Delta (PRD). A total of 188 canister air samples were collected from August 2001 to December 2002. Overall inspection indicated that CH2Cl2 ,C 2Cl4, and C2HCl3 had similar temporal variations while CFC-11, CFC-12, and CFC-113 showed the same emission patterns during the sampling period. Diurnal variations of halocarbons presented different patterns during ozone episode days, mainly related to emission strength, atmospheric dispersion, and photochemical lifetimes. For further statistics and source appointment, Lagrangian backward particle release simulations were conducted to help understand the potential source regions of all samples and classify them into different categories, including local Hong Kong, inner PRD, continental China, and marineairmasses.WiththeexceptionofHCFC-142b,themixingratiosofallhalocarbonsin marine air were significantly lower than those in urban and regional air (p < 0.01), whereas no significant difference was found between urban Hong Kong and inner PRD regional air, reflecting the dominant impact of the greater PRD regional air on the halocarbon levels. Thehalocarbonlevelsinthisregionweresignificantlyinfluencedbyanthropogenicsources, causing the halocarbon mixing ratios in South China Sea air to be higher than the corresponding background levels, as measured by global surface networks and by airborne missions such as Transport and Chemical Evolution Over the Pacific. Interspecies correlation analysis suggests that CHCl3 is mainly used as a solvent in Hong Kong but mostly as a feedstock for HCFC-22 in the inner PRD. Furthermore, CH3Cl is often used as a refrigerant and emitted from biomass/biofuel burning in the inner PRD. A positive matrix factorization receptor model was applied to the classified halocarbon samples in the greater PRD for source profiles and apportionments. Seven major sources were identified and quantified. Emissions from solvent use were the most significant source of halocarbons (71 ± 9%), while refrigeration was the second largest contributor (18 ± 2%). By further lookingatsamplesfromtheinnerPRDandfromurbanHongKongseparately,wefoundthat more solvent was used in the dry cleaning industry in Hong Kong, whereas the contribution of cleaning solvent in the electronic industry was higher in the inner PRD. Besides the two common sources of solvent use and refrigeration, the contributions of biomass/biofuel burning and feedstock in chemical manufacturing was remarkable in the inner PRD but negligible in Hong Kong. These findings are of help to effectively control and phase out the emissions of halocarbons in the greater PRD region of southern China.

Long-term decline of global atmospheric ethane concentrations and implications for methane.

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 sink. 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 slow. 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.

Exhaled methyl nitrate as a noninvasive marker of hyperglycemia in type 1 diabetes

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 ≈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.

Determination of toxic nitrophenols in the atmosphere by high-performance liquid chromatography

Abstract Seven HPLC columns were used for the optimization of the isocratic HPLC measurement of phenol, nitro- and dinitrophenols. A column constituted from 5 μm particles (100 A) of silica-based C 18 material was used for the analysis. Good separation of the analytes and their quantification in samples from the nitration of phenol in liquid and in gas phase in the laboratory was obtained. This approach allowed also to determine phenol in air samples.

Large‐scale latitudinal and vertical distributions of NMHCs and selected halocarbons in the troposphere over the Pacific Ocean during the March‐April 1999 Pacific Exploratory Mission (PEM‐Tropics B)

Nonmethane hydrocarbons (NMHCs) and selected halocarbons were measured in whole air samples collected over the remote Pacific Ocean during NASAs 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.

Noninvasive measurement of plasma glucose from exhaled breath in healthy and type 1 diabetic subjects

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.

Emission estimates of selected volatile organic compounds from tropical savanna burning in northern Australia

[i] Here we present measurements of a range of carbon-based compounds: carbon dioxide (CO 2 ), carbon monoxide (CO), methane (CH 4 ), nonmethane hydrocarbons (NMHCs), methyl halides, and dimethyl sulfide (DMS) emitted by Australian savanna fires studied as part of the Biomass Burning and Lightning Experiment (BIBLE) phase B aircraft campaign, which took place during the local late dry season (28 August to 13 September 1999). Significant enhancements of short-lived NMHCs were observed in the boundary layer (BL) over the region of intensive fires and indicate recent emissions for which the mean transport time was estimated to be about 9 hours. Emission ratios relative to CO were determined for 20 NMHCs, 3 methyl halides, DMS, and CH 4 based on the BL enhancements in the source region. Tight correlations with CO were obtained for most of those compounds, indicating the homogeneity of the local savanna source. The emission ratios were in good agreement with some previous measurements of savanna fires for stable compounds but indicated the decay of emission ratios during transport for several reactive compounds. Based on the observed emission ratios, emission factors were derived and compared to previous studies. While emission factors (g species/kg dry mole) of CO 2 varied little according to the vegetation types, those of CO and NMHCs varied significantly. Higher combustion efficiency and a lower emission factor for methane in this study, compared to forest fires, agreed well with results for savanna fires in other tropical regions. The amount of biomass burned was estimated by modeling methods using available satellite data, and showed that 1999 was an above average year for savanna burning. The gross emissions of the trace gases from Australian savanna fires were estimated.

Breath gas metabolites and bacterial metagenomes from cystic fibrosis airways indicate active pH neutral 2,3-butanedione fermentation

The airways of cystic fibrosis (CF) patients are chronically colonized by patient-specific polymicrobial communities. The conditions and nutrients available in CF lungs affect the physiology and composition of the colonizing microbes. Recent work in bioreactors has shown that the fermentation product 2,3-butanediol mediates cross-feeding between some fermenting bacteria and Pseudomonas aeruginosa, and that this mechanism increases bacterial current production. To examine bacterial fermentation in the respiratory tract, breath gas metabolites were measured and several metagenomes were sequenced from CF and non-CF volunteers. 2,3-butanedione was produced in nearly all respiratory tracts. Elevated levels in one patient decreased during antibiotic treatment, and breath concentrations varied between CF patients at the same time point. Some patients had high enough levels of 2,3-butanedione to irreversibly damage lung tissue. Antibiotic therapy likely dictates the activities of 2,3-butanedione-producing microbes, which suggests a need for further study with larger sample size. Sputum microbiomes were dominated by P. aeruginosa, Streptococcus spp. and Rothia mucilaginosa, and revealed the potential for 2,3-butanedione biosynthesis. Genes encoding 2,3-butanedione biosynthesis were disproportionately abundant in Streptococcus spp, whereas genes for consumption of butanedione pathway products were encoded by P. aeruginosa and R. mucilaginosa. We propose a model where low oxygen conditions in CF lung lead to fermentation and a decrease in pH, triggering 2,3-butanedione fermentation to avoid lethal acidification. We hypothesize that this may also increase phenazine production by P. aeruginosa, increasing reactive oxygen species and providing additional electron acceptors to CF microbes.