Characterizing anthropogenic methane sources in the Houston and Barnett Shale areas of Texas using the isotopic signature δ13C in CH4.

Methane (CH4) is an important greenhouse gas with its mixing ratio increasing in the global atmosphere. Identifying fingerprints of CH4 emissions is critical to understanding potential impacts of various anthropogenic sources in the Greater Houston area (GHA) and extensive natural gas operations in the Barnett Shale area (BSA) of Texas. Stable carbon isotope ratios of CH4 (δ13CCH4) has been proposed to be a useful technique for differentiating individual CH4 sources. Measurements of CH4 mixing ratios and δ13CCH4 were sampled using a mobile laboratory equipped with cavity ring-down spectrometers (CRDS). Areal CH4 distributions and the background δ13CCH4 signature were obtained from filtered ambient signals; -47.0‰ (GHA) and - 48.5‰ (BSA) were calculated. The fingerprint of thirty-three anthropogenic sources in the two study areas were sampled with forty-four δ13C analyses conducted. Repeated measurements indicated the natural variation of δ13CCH4 signatures of individual CH4 sources. An unexpected massive CH4 fugitive leak was detected near the San Jacinto River Fleet site in Houston exhibiting an δ13CCH4 value around -42‰. Our results and findings demonstrate the utility of δ13CCH4for facilitating emission inventories and atmospheric modeling.

Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L-1, respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( Nd) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients Kad (5.9-362.7 L g-1) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

Distribution and sources of particulate mercury and other trace elements in PM2.5 and PM10 atop Mount Tai, China.

The concentrations of particulate mercury (PHg) and other trace elements in PM2.5 and PM10 in the atmosphere were measured at the summit of Mount Tai during the time period of 15 June - 11 August 2015. The average PHg concentrations were 83.33 ±â€¯119.1 pg/m3 for PM2.5 and 174.92 ±â€¯210.5 pg/m3 for PM10. Average concentrations for other trace elements, including Al, Ca, Fe, K, Mg, Na, Pb, As, Se, Cu, Cd, Cr, V, Mo, Co, Ag, Ba, Mn, Zn and Ni ranged from 0.06 ng/m3 (Ag) to 354.33 ng/m3 (Ca) in PM2.5 and 0.11 ng/m3 (Co) to 592.66 ng/m3 (Ca) in PM10. The average concentrations of PHg were higher than those at other domestic mountain sites and cities in other counties, lower than those at domestic city sites. Other trace elements showed concentrations lower than those at the domestic mountain sites. Due possibly to increased control of emissions and the proportion of new energy, the PHg and trace element concentrations decreased, but the PHg showed concentrations higher than those at the Mountain sites, this showed that the reasons was not only severely affected by anthropogenic emissions, but also associated with other sources. The concentration changed trend of the main trace elements indicated that PHg, trace elements and particle matters present positive correlation and fine particulate matter has a greater surface area which was conductive to adsorption of Hg and trace elements to particles. On June 19, June 27 and July 6, according to the peak of mercury and trace elements, we can predict the potential sources of these three days. The results of principal component analysis (PCA) suggested that, crustal dust, coal combustion, and vehicle emissions were the main emission sources of PHg and other trace elements in Mount Tai. The 24-h backward trajectories and potential source contribution function (PSCF) analysis revealed that air masses arriving at Mount Tai were mainly affected by Shandong province. Mount Tai was subjected to five main airflow trajectories. Clusters 1, 2, 3, and 5 represented four pathways for local and regional sources and cluster 4 originated long-distance transportation. Central Shandong was the main source regions of PHg, Pb, Se, As, Cu and Cd. Southeastern and northwestern Shandong province and northern Jiangsu province were the most polluted source regions of Mn, Zn, and Ni. The crustal elements Fe and Ca had similar distributions of potential source regions, suggested by the highest PSCF values in southeastern Shandong and northern Jiangsu.

Characteristics and potential sources of atmospheric particulate mercury in Jinan, China.

Measurements of atmospheric particulate mercury (PHg) were conducted at a suburban site in Jinan, China from June 2014 to December 2015. The average PHg concentration was 508.5±402.7pgm-3, and the average Hg content in PM2.5 (particles with a diameter of 2.5µm or less) was 6.60±5.82µgg-1. Both PHg and Hg content in PM2.5 aerosols were comparable to levels in some cities in China and were much higher than in cities in North America and Europe. Weak correlations were found between PHg and meteorological parameters. The correlations between PHg and other pollutants in ambient air, including SO2, CO and NOχ, together with their wind dependence were used for source analysis, which suggested coal-fired industries, cement plants and traffic emissions as potential local sources for the site. Cluster analysis of 36-h backward trajectories suggested that the regional transport from southwestern Shandong Province also contributed to PHg in Jinan.

Reconciling divergent estimates of oil and gas methane emissions.

Published estimates of methane emissions from atmospheric data (top-down approaches) exceed those from source-based inventories (bottom-up approaches), leading to conflicting claims about the climate implications of fuel switching from coal or petroleum to natural gas. Based on data from a coordinated campaign in the Barnett Shale oil and gas-producing region of Texas, we find that top-down and bottom-up estimates of both total and fossil methane emissions agree within statistical confidence intervals (relative differences are 10% for fossil methane and 0.1% for total methane). We reduced uncertainty in top-down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution. Similarly, our bottom-up estimate incorporates a more complete count of facilities than past inventories, which omitted a significant number of major sources, and more effectively accounts for the influence of large emission sources using a statistical estimator that integrates observations from multiple ground-based measurement datasets. Two percent of oil and gas facilities in the Barnett accounts for half of methane emissions at any given time, and high-emitting facilities appear to be spatiotemporally variable. Measured oil and gas methane emissions are 90% larger than estimates based on the US Environmental Protection Agency's Greenhouse Gas Inventory and correspond to 1.5% of natural gas production. This rate of methane loss increases the 20-y climate impacts of natural gas consumed in the region by roughly 50%.

Characterizing Fugitive Methane Emissions in the Barnett Shale Area Using a Mobile Laboratory.

Atmospheric methane (CH4) was measured using a mobile laboratory to quantify fugitive CH4 emissions from Oil and Natural Gas (ONG) operations in the Barnett Shale area. During this Barnett Coordinated Campaign we sampled more than 152 facilities, including well pads, compressor stations, gas processing plants, and landfills. Emission rates from several ONG facilities and landfills were estimated using an Inverse Gaussian Dispersion Model and the Environmental Protection Agency (EPA) Model AERMOD. Model results show that well pads emissions rates had a fat-tailed distribution, with the emissions linearly correlated with gas production. Using this correlation, we estimated a total well pad emission rate of 1.5 × 10(5) kg/h in the Barnett Shale area. It was found that CH4 emissions from compressor stations and gas processing plants were substantially higher, with some "super emitters" having emission rates up to 3447 kg/h, more then 36,000-fold higher than reported by the Environmental Protection Agency (EPA) Greenhouse Gas Reporting Program (GHGRP). Landfills are also a significant source of CH4 in the Barnett Shale area, and they should be accounted for in the regional budget of CH4.

Constructing a Spatially Resolved Methane Emission Inventory for the Barnett Shale Region.

Methane emissions from the oil and gas industry (O&G) and other sources in the Barnett Shale region were estimated by constructing a spatially resolved emission inventory. Eighteen source categories were estimated using multiple data sets, including new empirical measurements at regional O&G sites and a national study of gathering and processing facilities. Spatially referenced activity data were compiled from federal and state databases and combined with O&G facility emission factors calculated using Monte Carlo simulations that account for high emission sites representing the very upper portion, or fat-tail, in the observed emissions distributions. Total methane emissions in the 25-county Barnett Shale region in October 2013 were estimated to be 72,300 (63,400-82,400) kg CH4 h(-1). O&G emissions were estimated to be 46,200 (40,000-54,100) kg CH4 h(-1) with 19% of emissions from fat-tail sites representing less than 2% of sites. Our estimate of O&G emissions in the Barnett Shale region was higher than alternative inventories based on the United States Environmental Protection Agency (EPA) Greenhouse Gas Inventory, EPA Greenhouse Gas Reporting Program, and Emissions Database for Global Atmospheric Research by factors of 1.5, 2.7, and 4.3, respectively. Gathering compressor stations, which accounted for 40% of O&G emissions in our inventory, had the largest difference from emission estimates based on EPA data sources. Our inventory's higher O&G emission estimate was due primarily to its more comprehensive activity factors and inclusion of emissions from fat-tail sites.

Toward a Functional Definition of Methane Super-Emitters: Application to Natural Gas Production Sites.

Emissions from natural gas production sites are characterized by skewed distributions, where a small percentage of sites-commonly labeled super-emitters-account for a majority of emissions. A better characterization of super-emitters is needed to operationalize ways to identify them and reduce emissions. We designed a conceptual framework that functionally defines superemitting sites as those with the highest proportional loss rates (methane emitted relative to methane produced). Using this concept, we estimated total methane emissions from natural gas production sites in the Barnett Shale; functionally superemitting sites accounted for roughly three-fourths of total emissions. We discuss the potential to reduce emissions from these sites, under the assumption that sites with high proportional loss rates have excess emissions resulting from abnormal or otherwise avoidable operating conditions, such as malfunctioning equipment. Because the population of functionally superemitting sites is not expected to be static over time, continuous monitoring will likely be necessary to identify them and improve their operation. This work suggests that achieving and maintaining uniformly low emissions across the entire population of production sites will require mitigation steps at a large fraction of sites.

Atmospheric Mercury in the Barnett Shale Area, Texas: Implications for Emissions from Oil and Gas Processing.

Atmospheric mercury emissions in the Barnett Shale area were studied by employing both stationary measurements and mobile laboratory surveys. Stationary measurements near the Engle Mountain Lake showed that the median mixing ratio of total gaseous mercury (THg) was 138 ppqv (140 ± 29 ppqv for mean ± S.D.) during the June 2011 study period. A distinct diurnal variation pattern was observed in which the highest THg levels appeared near midnight, followed by a monotonic decrease until midafternoon. The influence of oil and gas (ONG) emissions was substantial in this area, as inferred from the i-pentane/n-pentane ratio (1.17). However, few THg plumes were captured by our mobile laboratory during a ∼3700 km survey with detailed downwind measurements from 50 ONG facilities. One compressor station and one natural gas condensate processing facility were found to have significant THg emissions, with maximum THg levels of 963 and 392 ppqv, respectively, and the emissions rates were estimated to be 7.9 kg/yr and 0.3 kg/yr, respectively. Our results suggest that the majority of ONG facilities in this area are not significant sources of THg; however, it is highly likely that a small number of these facilities contribute a relatively large amount of emissions in the ONG sector.

Do we understand what the mercury speciation instruments are actually measuring? Results of RAMIX.

From August 22 to September 16, 2012, atmospheric mercury (Hg) was measured from a common manifold in the field during the Reno Atmospheric Mercury Intercomparison eXperiment. Data were collected using Tekran systems, laser induced fluorescence, and evolving new methods. The latter included the University of Washington-Detector for Oxidized Mercury, the University of Houston Mercury instrument, and a filter-based system under development by the University of Nevada-Reno. Good transmission of total Hg was found for the manifold. However, despite application of standard protocols and rigorous quality control, systematic differences in operationally defined forms of Hg were measured by the sampling systems. Concentrations of reactive Hg (RM) measured with new methods were at times 2-to-3-fold higher than that measured by Tekran system. The low RM recovery by the latter can be attributed to lack of collection as the system is currently configured. Concentrations measured by all instruments were influenced by their sampling location in-the-manifold and the instrument analytical configuration. On the basis of collective assessment of the data, we hypothesize that reactions forming RM were occurring in the manifold. Results provide a new framework for improved understanding of the atmospheric chemistry of Hg.

Air toxic emissions from snowmobiles in Yellowstone National Park.

A study on emissions associated with oversnow travel in Yellowstone National Park (YNP) was conducted for the time period of February 13-16, 2002 and February 12-16, 2003. Whole air and exhaust samples were characterized for 85 volatile organic compounds using gas chromatography. The toxics including benzene, toluene, ethylbenzene, xylenes (p-, m-, and o-xylene), and n-hexane, which are major components of two-stroke engine exhaust, show large enhancements during sampling periods resulting from increased snowmobile traffic. Evaluation of the photochemical history of air masses sampled in YNP revealed that emissions of these air toxics were (i) recent, (ii) persistent throughout the region, and (iii) consistent with the two-stroke engine exhaust sample fingerprints. The annual fluxes were estimated to be 0.35, 1.12, 0.24, 1.45, and 0.36 Gg yr(-1) for benzene, toluene, ethylbenzene, xylenes, and n-hexane, respectively, from snowmobile usage in YNP. These results are comparable to the flux estimates of 0.23, 0.77, 0.17, and 0.70 Gg yr(-1) for benzene, toluene, ethylbenzene, and xylenes, respectively, that were derived on the basis of (i) actual snowmobile counts in the Park and (ii) our ambient measurements conducted in 2003. Extrapolating these results, annual emissions from snowmobiles in the U.S. appear to be significantly higher than the values from the EPA National Emissions Inventory (1999). Snowmobile emissions represent a significant fraction ( approximately 14-21%) of air toxics with respect to EPA estimates of emissions by nonroad vehicles. Further investigation is warranted to more rigorously quantify the difference between our estimates and emission inventories.

Perforated diverticulitis presenting as necrotising fasciitis of the leg.

Diverticulosis of the colon is a common condition of increasing age. Complications of diverticulitis including stricture, perforation and fistula formation often require surgery. Perforated diverticulitis may rarely present with spreading superficial sepsis. We describe for the first time, to our knowledge, a case of retroperitoneal diverticula perforation presenting as necrotising fasciitis of the leg necessitating hind-quarter amputation.

Development of a cryogen-free concentration system for measurements of volatile organic compounds.

An innovative cryogen-free concentrator system for measurement of atmospheric trace gases at the parts per trillion level has been developed with detection by routinely used gas chromatographic methods. The first-generation system was capable of reaching a trapping temperature of -186 degrees C, while the current version can reach -195 degrees C. A Kleemenko cooler is used to create liquid nitrogen equivalent trapping conditions and eliminate the use of solid absorbents, a potential source of artifacts. The method utilizes dual-stage trapping with individual cold regions. The two stages are cooled to -20 and -175 degrees C for water management and sample enrichment, respectively. Both stages house a Silonite-coated stainless steel sample loop; the second stage loop is filled with 1-mm-diameter glass beads, which provide an inert surface area for analyte concentration. In our application, the complete system employed four channels utilizing two flame ionization detectors, one electron capture detector, and a mass spectrometer. The system was automated for unattended operation and was deployed off the New England east coast on Appledore Island to measure a suite of ambient non-methane hydrocarbons, halocarbons, alkyl nitrates, and oxygenated volatile organic compounds during the International Consortium for Atmospheric Research on Transport and Transformation field campaign in summer 2004. This robust system quantified 98 ambient volatile organic compounds with precisions ranging from 0.3 to 15%.

Optimization of a mist chamber (Cofer scrubber) for sampling water-soluble organics in air.

While the atmospheric fate and transport of biogenic and anthropogenic hydrocarbons has been extensively studied, little is known about the behavior of first-, second-, and third generation photo-oxidation products that arise from OH radical oxidation of the parent species. The results of chamber experiments establish that *OH oxidation of biogenic and anthropogenic hydrocarbons yields carbonyls, dicarbonyls, hydroxycarbonyls, and keto-acids. However, little is known about the generation and fate of these products in the ambient atmospheric environment. This is changing because of the advent of methods that rely on 0-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) derivatization of carbonyls in concert with gas chromatography/ion trap mass spectrometry. Such methods provide the means to identify and quantify water-soluble organics, which historically have been difficult to measure. A limitation of existing sampling methods, however, is the use of devices that require low flow rates (0.5-1 L min(-1)). Accordingly, long sampling times (3-4 h) are needed to obtain pptv-ppbv detection limits. The mist chamber is an attractive device because of the high flow rates (25-70 L min(-1)) compatible with its use. Herein, we evaluate a mist chamber using a flow rate of 25-30 L min(-1) to provide short (10 min) sampling times and pptv limits of detection. The results establish a relationship between the Henry's law constant (KH) and the collection efficiency and demonstrate the suitability of the method to measure analytes with KH > or = 10(3) M atm(-1). Adjusting the pH, adding quaternary ammonium salts, or decreasing the temperature of the collecting solution in the mist chamber did not significantly affect the collection efficiency. We tested the method by sampling photooxidation products of isoprene (glyoxal, methylglyoxal, hydroxyacetone, and glycolaldehyde) in the Blodgett Forest, CA. This is the first report of a study the employs the mist chamberto sample hydroxycarbonyls. The accuracy and the reproducibility of the method were evaluated by the analysis of duplicate samples and field spikes. The mean recovery of field spikes was > or =80%, and the relative standard deviation was < or =22% between duplicate measurements. The detection limits were 48, 15, 7.7, and 2.7 pptv for glycolaldehyde, hydroxyacetone, methylglyoxal, and glyoxal, respectively. This work demonstrates the power of the mist chamber in concert with PFBHA derivatization and mass spectrometry to measure pptv concentrations of water-soluble organics with a sampling time of 10 min.

Light extinction by fine atmospheric particles in the White Mountains region of New Hampshire and its relationship to air mass transport.

Chemical, optical, and physical measurements of fine aerosols (aerodynamic diameter < or = 2.5 microm) have been performed at a mountaintop location adjacent to the White Mountain National Forest in northern NH, USA. A 1-month long sampling campaign was conducted at Cranmore Mountain during spring 2000. We report on the apportionment of light extinction by fine aerosols into its major chemical components, and relationships between variations in aerosol parameters and changes in air mass origin. Filter-based, 24-h integrated samples were collected and analyzed for major inorganic ions, as well as organic (OC), elemental (EC), and total carbon. Light scattering and light absorption coefficients were measured at 5-min intervals using an integrating nephelometer and a light absorption photometer. Fine particle number density was measured with a condensation particle counter. Air mass origins and transport patterns were investigated through the use of 3-day backward trajectories and a synoptic climate classification system. Two distinct transport regimes were observed: (1) flow from the north/northeast (N/NE) occurred during 9 out of 18 sample-days; and (2) flow from the west/southwest (W/SW) occurred 8 out of 18 sample-days. All measured and derived aerosol and meteorological parameters were separated into two categories based on these different flow scenarios. During W/SW flow, higher values of aerosol chemical concentration, absorption and scattering coefficients, number density, and haziness were observed compared to N/NE flow. The highest level of haziness was associated with the climate classification Frontal Atlantic Return, which brought polluted air into the region from the mid-Atlantic corridor. Fine particle mass scattering efficiencies of (NH4)2SO4 and OC were 5.35 +/- 0.42 m2 g(-1) and 1.56 +/- 0.40 m2 g(-1), respectively, when transport was out of the N/NE. When transport was from the W/SW the values were 4.94 +/- 0.68 m2 g(-1) for (NH4)2SO4 and 2.18 +/- 0.91 m2 g(-1) for OC. EC mass absorption efficiency when transport was from the N/NE was 9.66 +/- 1.06 m2 g(-1) and 10.80 +/- 1.76 m2 g(-1) when transport was from the W/SW. Results from this work can be used to predict visual air quality in the White Mountain National Forest based on a forecasted synoptic climate classification and its associated visibility.