In this study, we test the performance of a compact gas chromatograph with photoionization detector (GC-PID) and optimize the configuration to detect ambient (sub-ppb) levels of benzene, toluene, ethylbenzene, and xylene isomers (BTEX). The GC-PID system was designed to serve as a relatively inexpensive (~10 k USD) and field-deployable air toxic screening tool alternative to conventional benchtop GCs. The instrument uses ambient air as a carrier gas and consists of a Tenax-GR sorbent-based preconcentrator, a gas sample valve, two capillary columns, and a photoionization detector (PID) with a small footprint and low power requirement. The performance of the GC-PID has been evaluated in terms of system linearity and sensitivity in field conditions. The BTEX-GC system demonstrated the capacity to detect BTEX at levels as high as 500 ppb with a linear calibration range of 0–100 ppb. A detection limit lower than 1 ppb was found for all BTEX compounds with a sampling volume of 1 L. No significant drift in the instrument was observed. A time-varying calibration technique was established that requires minimal equipment for field operations and optimizes the sampling procedure for field measurements. With an analysis time of less than 15 min, the compact GC-PID is ideal for field deployment of background and polluted atmospheres for near-real time measurements of BTEX. The results highlight the application of the compact and easily deployable GC-PID for community monitoring and screening of air toxics.

California methane (CH4) emissions are quantified for three years from two tower networks and one aircraft campaign. We used backward trajectory simulations and a mesoscale Bayesian inverse model, initialized by three inventories, to achieve the emission quantification. Results show total statewide CH4 emissions of 2.05 ± 0.26 (at 95% confidence) Tg/yr, which is 1.14 to 1.47 times greater than the anthropogenic emission estimates by California Air Resource Board (CARB). Some of differences could be biogenic emissions, superemitter point sources, and other episodic emissions which may not be completely included in the CARB inventory. San Joaquin Valley (SJV) has the largest CH4 emissions (0.94 ± 0.18 Tg/yr), followed by the South Coast Air Basin, the Sacramento Valley, and the San Francisco Bay Area at 0.39 ± 0.18, 0.21 ± 0.04, and 0.16 ± 0.05 Tg/yr, respectively. The dairy and oil/gas production sources in the SJV contribute 0.44 ± 0.36 and 0.22 ± 0.23 Tg CH4/yr, respectively. This study has important policy implications for regulatory programs, as it provides a thorough multiyear evaluation of the emissions inventory using independent atmospheric measurements and investigates the utility of a complementary multiplatform approach in understanding the spatial and temporal patterns of CH4 emissions in the state and identifies opportunities for the expansion and applications of the monitoring network.

Large urban emissions of greenhouse gases result in large atmospheric enhancements relative to background that are easily measured. Using CO2 mole fractions and Δ14C and δ13C values of CO2 in the Los Angeles megacity observed in inland Pasadena (2006–2013) and coastal Palos Verdes peninsula (autumn 2009–2013), we have determined time series for CO2 contributions from fossil fuel combustion (Cff) for both sites and broken those down into contributions from petroleum and/or gasoline and natural gas burning for Pasadena. We find a 10 % reduction in Pasadena Cff during the Great Recession of 2008–2010, which is consistent with the bottom-up inventory determined by the California Air Resources Board. The isotopic variations and total atmospheric CO2 from our observations are used to infer seasonality of natural gas and petroleum combustion. The trend of CO2 contributions to the atmosphere from natural gas combustion is out of phase with the seasonal cycle of total natural gas combustion seasonal patterns in bottom-up inventories but is consistent with the seasonality of natural gas usage by the area's electricity generating power plants. For petroleum, the inferred seasonality of CO2 contributions from burning petroleum is delayed by several months relative to usage indicated by statewide gasoline taxes. Using the high-resolution Hestia-LA data product to compare Cff from parts of the basin sampled by winds at different times of year, we find that variations in observed fossil fuel CO2 reflect seasonal variations in wind direction. The seasonality of the local CO2 excess from fossil fuel combustion along the coast, on Palos Verdes peninsula, is higher in autumn and winter than spring and summer, almost completely out of phase with that from Pasadena, also because of the annual variations of winds in the region. Variations in fossil fuel CO2 signals are consistent with sampling the bottom-up Hestia-LA fossil CO2 emissions product for sub-city source regions in the LA megacity domain when wind directions are considered.

Cities generate 70% of anthropogenic greenhouse gas emissions, a fraction that is growing with global urbanization. While cities play an important role in climate change mitigation, there has been little focus on reducing urban methane ( CH 4 ) emissions. Here, we develop a conceptual framework for CH 4 mitigation in cities by describing emission processes, the role of measurements, and a need for new institutional partnerships. Urban CH 4 emissions are likely to grow with expanding use of natural gas and organic waste disposal systems in growing population centers; however, we currently lack the ability to quantify this increase. We also lack systematic knowledge of the relative contribution of these distinct source sectors on emissions. We present new observations from four North American cities to demonstrate that CH 4 emissions vary in magnitude and sector from city to city and hence require different mitigation strategies. Detections of fugitive emissions from these systems suggest that current mitigation approaches are absent or ineffective. These findings illustrate that tackling urban CH 4 emissions will require research efforts to identify mitigation targets, develop and implement new mitigation strategies, and monitor atmospheric CH 4 levels to ensure the success of mitigation efforts. This research will require a variety of techniques to achieve these objectives and should be deployed in cities globally. We suggest that metropolitan scale partnerships may effectively coordinate systematic measurements and actions focused on emission reduction goals.

Measuring greenhouse gas (GHG) source emissions provides data for validation of GHG inventories, which provide the foundation for climate change mitigation. Two Toyota RAV4 electric vehicles were outfitted with high-precision instrumentation to determine spatial and temporal resolution of GHGs (e.g., nitrous oxide, methane [CH4], and carbon dioxide [CO2]), and other gaseous species and particulate metrics found near emission sources. Mobile measurement platform (MMP) analytical performance was determined over relevant measurement time scales. Pollutant residence times through the sampling configuration were measured, ranging from 3 to 11 sec, enabling proper time alignment for spatial measurement of each respective analyte. Linear response range for GHG analytes was assessed across expected mixing ratio ranges, showing minimal regression and standard error differences between 5, 10, 30, and 60 sec sampling intervals and negligible differences between the two MMPs. GHG instrument drift shows deviation of less than 0.8% over a 24-hr measurement period. These MMPs were utilized in tracer-dilution experiments at a California landfill and natural gas compressor station (NGCS) to quantify CH4 emissions. Replicate landfill measurements during October 2009 yielded annual CH4 emissions estimates of 0.10 0.01, 0.11 +/- 0.01, and 0.12 +/- 0.02 million tonnes of CO2 equivalent (MTCO2E). These values compare favorably to California GHG Emissions Inventory figures for 2007, 2008, and 2009 of 0.123, 0.125, and 0.126 MTCO2E/yr, respectively, for this facility. Measurements to quantify NGCS boosting facility-wide emissions, during June 2010 yielded an equivalent of 5400 +/- 100 TCO2E/yr under steady-state operation. However, measurements during condensate transfer without operational vapor recovery yield an instantaneous emission rate of 2-4 times greater, but was estimated to only add 12 TCO2E/yr overall. This work displays the utility for mobile GHG measurements to validate existing measurement and modeling approaches, so emission inventory values can be confirmed and associated uncertainties reduced.Implications:Measuring greenhouse gas (GHG) source emissions provides data and validation for GHG inventories, the foundation for climate change mitigation. Mobile measurement platforms with robust analytical instrumentation completed tracer-dilution experiments in California at a landfill and natural gas compressor station (NGCS) to quantify CH4 emissions. Data collected for landfill CH4 agree with the current California emissions inventory, while NGCS data show the possible variability from this type of facility. This work displays the utility of mobile GHG measurements to validate existing measurement and modeling approaches, such that emission inventory values can be confirmed, associated uncertainties reduced, and mitigation efforts quantified.

To provide information for greenhouse gas reduction policies, the California Air Resources Board (CARB) inventories annual emissions of high-global-warming potential (GWP) fluorinated gases, the fastest growing sector of greenhouse gas (GHG) emissions globally. Baseline 2008 F-gas emissions estimates for selected chlorofluorocarbons (CFC-12), hydrochlorofluorocarbons (HCFC-22), and hydrofluorocarbons (HFC-134a) made with an inventory-based methodology were compared to emissions estimates made by ambient-based measurements. Significant discrepancies were found, with the inventory-based emissions methodology resulting in a systematic 42% under-estimation of CFC-12 emissions from older refrigeration equipment and older vehicles, and a systematic 114% overestimation of emissions for HFC-134a, a refrigerant substitute for phased-out CFCs. Initial, inventory-based estimates for all F-gas emissions had assumed that equipment is no longer in service once it reaches its average lifetime of use. Revised emission estimates using improved models for equipment age at end-of-life, inventories, and leak rates specific to California resulted in F-gas emissions estimates in closer agreement to ambient-based measurements. The discrepancies between inventory-based estimates and ambient-based measurements were reduced from -42% to -6% for CFC-12, and from +114% to +9% for HFC-134a.

AbstractWe present an analysis of methane (CH4) emissions using atmospheric observations from five sites in California's Central Valley across different seasons (September 2010 to June 2011). CH4 emissions for spatial regions and source sectors are estimated by comparing measured CH4 mixing ratios with transport model (Weather Research and Forecasting and Stochastic Time‐Inverted Lagrangian Transport) predictions based on two 0.1° CH4 (seasonally varying “California‐specific” (California Greenhouse Gas Emission Measurements, CALGEM) and a static global (Emission Database for Global Atmospheric Research, release version 42, EDGAR42)) prior emission models. Region‐specific Bayesian analyses indicate that for California's Central Valley, the CALGEM‐ and EDGAR42‐based inversions provide consistent annual total CH4 emissions (32.87 ± 2.09 versus 31.60 ± 2.17 Tg CO2eq yr−1; 68% confidence interval (CI), assuming uncorrelated errors between regions). Summing across all regions of California, optimized CH4 emissions are only marginally consistent between CALGEM‐ and EDGAR42‐based inversions (48.35 ± 6.47 versus 64.97 ± 11.85 Tg CO2eq), because emissions from coastal urban regions (where landfill and natural gas emissions are much higher in EDGAR than CALGEM) are not strongly constrained by the measurements. Combining our results with those from a recent study of the South Coast Air Basin narrows the range of estimates to 43–57 Tg CO2eq yr−1 (1.3–1.8 times higher than the current state inventory). These results suggest that the combination of rural and urban measurements will be necessary to verify future changes in California's total CH4 emissions.

Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NO(x)), and particle mass with aerodynamic diameter below 2.5 microm (PM2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NO(x), black carbon (BC), PM2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NO(x) and CO fleet-average emission factors and more than 60% of PM2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM2.5, and NO(x) tended to cluster among the same vehicles.

Methane (CH4) and carbon monoxide (CO) mixing ratios were measured at an air quality monitoring station near the Mt. Wilson (MW) Observatory in southern California starting in the spring of 2007. Diurnal variation and mixing ratio correlation (R-2 = 0.81) were observed. The correlation results observed agree with previous aircraft measurements collected over the greater Los Angeles (LA) metropolitan area. The consistent agreement between CH4 and CO indicates these gases are well-mixed before reaching the sampling site and the emission source contributions of both compounds are reasonably constant. Since CH4 and CO are considered non-reactive on the time scale of dispersion within the LA urban area and their emission sources are likely to be similarly distributed (e.g., associated with human activities) they are subject to similar scales of atmospheric transport and dilution. This behavior allows the relationship of CH4 and CO to be applied for estimation of CH4 emissions using well-documented CO emissions. Applying this relationship a "top-down" CH4 inventory was calculated for LA County based on the measurements observed at MW and compared with the California Air Resources Board (CARB) "bottom-up" CH4 emissions inventory based on the Intergovernmental Panel on Climate Change recommended methodologies. The "top-down" CH4 emissions inventory is approximately one-third greater than CARB's "bottom-up" inventory for LA County. Considering the uncertainties in both methodologies, the different CH4 emissions inventory approaches are in good agreement, although some under and/or uninventoried CH4 sources may exist. Published by Elsevier Ltd.

ADVERTISEMENT RETURN TO ISSUEPREVCorrespondence/Rebut...Correspondence/RebuttalResponse to Comment on "Locating PCB Sources in Chicago: Receptor Modeling and Field Sampling"Ying-Kuang Hsu, Thomas M. Holsen, and Philip K. HopkeView Author Information Department of Civil and Environmental Engineering Clarkson University Potsdam, New York 13699 Department of Chemical Engineering Clarkson University Potsdam, New York 13699Cite this: Environ. Sci. Technol. 2003, 37, 24, 5838Publication Date (Web):November 11, 2003Publication History Published online11 November 2003Published inissue 1 December 2003https://pubs.acs.org/doi/10.1021/es030616zhttps://doi.org/10.1021/es030616zarticle-commentaryACS PublicationsCopyright © 2003 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views175Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (17 KB) Get e-AlertscloseSUBJECTS:Computational chemistry,Gases,Phenyls,Sludges,Wind Get e-Alerts