Spatio-temporally Resolved Methane Fluxes From the Los Angeles Megacity

We combine sustained observations from a network of atmospheric monitoring stations with inverse modeling to uniquely obtain spatiotemporal (3‐km, 4‐day) estimates of methane emissions from the Los Angeles megacity and the broader South Coast Air Basin for 2015–2016. Our inversions use customized and validated high‐fidelity meteorological output from Weather Research Forecasting and Stochastic Time‐Inverted Lagrangian model for South Coast Air Basin and innovatively employ a model resolution matrix‐based metric to disentangle the spatiotemporal information content of observations as manifested through estimated fluxes. We partially track and constrain fluxes from the Aliso Canyon natural gas leak and detect closure of the Puente Hills landfill, with no prior information. Our annually aggregated fluxes and their uncertainty excluding the Aliso Canyon leak period lie within the uncertainty bounds of the fluxes reported by the previous studies. Spatially, major sources of CH_4 emissions in the basin were correlated with CH_4‐emitting infrastructure. Temporally, our findings show large seasonal variations in CH_4 fluxes with significantly higher fluxes in winter in comparison to summer months, which is consistent with natural gas demand and anticorrelated with air temperature. Overall, this is the first study that utilizes inversions to detect both enhancement (Aliso Canyon leak) and reduction (Puente Hills) in CH_4 fluxes due to the unintended events and policy decisions and thereby demonstrates the utility of inverse modeling for identifying variations in fluxes at fine spatiotemporal resolution

Global emissions of perfluorocyclobutane (PFC-318, c-C4F8) resulting from the use of hydrochlorofluorocarbon-22 (HCFC-22) feedstock to produce polytetrafluoroethylene (PTFE) and related fluorochemicals

Abstract. Emissions of the potent greenhouse gas perfluorocyclobutane (c-C4F8, PFC-318, octafluorocyclobutane) into the global atmosphere inferred from atmospheric measurements have been increasing sharply since the early 2000s. We find that these inferred emissions are highly correlated with the production of hydrochlorofluorocarbon-22 (HCFC-22, CHClF2) for feedstock (FS) uses, because almost all HCFC-22 FS is pyrolyzed to produce (poly)tetrafluoroethylene ((P)TFE) and hexafluoropropylene (HFP), a process in which c-C4F8 is a known by-product, causing a significant fraction of global c-C4F8 emissions. We find a global emission factor of ∼0.003 kg c-C4F8 per kilogram of HCFC-22 FS pyrolyzed. Mitigation of these c-C4F8 emissions, e.g., through process optimization, abatement, or different manufacturing processes, such as refined methods of electrochemical fluorination and waste recycling, could reduce the climate impact of this industry. While it has been shown that c-C4F8 emissions from developing countries dominate global emissions, more atmospheric measurements and/or detailed process statistics are needed to quantify c-C4F8 emissions at country to facility levels

Spatio-temporally Resolved Methane Fluxes From the Los Angeles Megacity

We combine sustained observations from a network of atmospheric monitoring stations with inverse modeling to uniquely obtain spatiotemporal (3‐km, 4‐day) estimates of methane emissions from the Los Angeles megacity and the broader South Coast Air Basin for 2015–2016. Our inversions use customized and validated high‐fidelity meteorological output from Weather Research Forecasting and Stochastic Time‐Inverted Lagrangian model for South Coast Air Basin and innovatively employ a model resolution matrix‐based metric to disentangle the spatiotemporal information content of observations as manifested through estimated fluxes. We partially track and constrain fluxes from the Aliso Canyon natural gas leak and detect closure of the Puente Hills landfill, with no prior information. Our annually aggregated fluxes and their uncertainty excluding the Aliso Canyon leak period lie within the uncertainty bounds of the fluxes reported by the previous studies. Spatially, major sources of CH_4 emissions in the basin were correlated with CH_4‐emitting infrastructure. Temporally, our findings show large seasonal variations in CH_4 fluxes with significantly higher fluxes in winter in comparison to summer months, which is consistent with natural gas demand and anticorrelated with air temperature. Overall, this is the first study that utilizes inversions to detect both enhancement (Aliso Canyon leak) and reduction (Puente Hills) in CH_4 fluxes due to the unintended events and policy decisions and thereby demonstrates the utility of inverse modeling for identifying variations in fluxes at fine spatiotemporal resolution

Corrigendum to "Global and regional emission estimates for HCFC-22", Atmos. Chem. Phys., 12, 10033–10050, 2012

No abstract available

Carbon dioxide and methane measurements from the Los Angeles Megacity Carbon Project – Part 1: calibration, urban enhancements, and uncertainty estimates

We report continuous surface observations of carbon dioxide (CO_2) and methane (CH_4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban-scale CO_2 and CH_4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four extra-urban sites including two marine sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one continental site located in Victorville (VIC), in the high desert northeast of LA, and one continental/mid-troposphere site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within  ∼  1 ppm CO_2 and  ∼  10 ppb CH_4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. Urban and suburban sites show moderate to large CO_2 and CH_4 enhancements relative to a marine background estimate. The USC (University of Southern California) site near downtown LA exhibits median hourly enhancements of  ∼  20 ppm CO_2 and  ∼  150 ppb CH_4 during 2015 as well as  ∼  15 ppm CO_2 and  ∼  80 ppb CH_4 during mid-afternoon hours (12:00–16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO_2 and 1 ppb CH_4 based on the repeated standard gas measurements from the LA sites during the last 2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is due to the single-point calibration method; however, the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The background uncertainty for the marine background estimate is  ∼  10 and  ∼  15 % of the median mid-afternoon enhancement near downtown LA for CO_2 and CH_4, respectively. Overall, analytical and background uncertainties are small relative to the local CO_2 and CH_4 enhancements; however, our results suggest that reducing the uncertainty to less than 5 % of the median mid-afternoon enhancement will require detailed assessment of the impact of meteorology on background conditions

Estimating methane emissions in California's urban and rural regions using multitower observations

We present an analysis of methane (CH_4) emissions using atmospheric observations from 13 sites in California during June 2013 to May 2014. A hierarchical Bayesian inversion method is used to estimate CH_4 emissions for spatial regions (0.3° pixels for major regions) by comparing measured CH_4 mixing ratios with transport model (Weather Research and Forecasting and Stochastic Time-Inverted Lagrangian Transport) predictions based on seasonally varying California-specific CH_4 prior emission models. The transport model is assessed using a combination of meteorological and carbon monoxide (CO) measurements coupled with the gridded California Air Resources Board (CARB) CO emission inventory. The hierarchical Bayesian inversion suggests that state annual anthropogenic CH_4 emissions are 2.42 ± 0.49 Tg CH_4/yr (at 95% confidence), higher (1.2–1.8 times) than the current CARB inventory (1.64 Tg CH_4/yr in 2013). It should be noted that undiagnosed sources of errors or uncaptured errors in the model-measurement mismatch covariance may increase these uncertainty bounds beyond that indicated here. The CH_4 emissions from the Central Valley and urban regions (San Francisco Bay and South Coast Air Basins) account for ~58% and 26% of the total posterior emissions, respectively. This study suggests that the livestock sector is likely the major contributor to the state total CH_4 emissions, in agreement with CARB's inventory. Attribution to source sectors for subregions of California using additional trace gas species would further improve the quantification of California's CH_4 emissions and mitigation efforts toward the California Global Warming Solutions Act of 2006 (Assembly Bill 32)

Perfluorocyclobutane (PFC-318, <i>c</i>-C<sub>4</sub>F<sub>8</sub>) in the global atmosphere

We reconstruct atmospheric abundances of the potent greenhouse gas span classCombining double low line inline-formula span classCombining double low line inline-formula perfluorocyclobutane, perfluorocarbon PFC-318) from measurements of in situ, archived, firn, and aircraft air samples with precisions of span classCombining double low line inline-formula reported on the SIO-14 gravimetric calibration scale. Combined with inverse methods, we found near-zero atmospheric abundances from the early 1900s to the early 1960s, after which they rose sharply, reaching 1.66ppt (parts per trillion dry-air mole fraction) in 2017. Global span classCombining double low line inline-formula span classCombining double low line inline-formula emissions rose from near zero in the 1960s to span classCombining double low line inline-formula (1span classCombining double low line inline-formula gyrspan classCombining double low line inline-formula in the late 1970s to late 1980s, then declined to span classCombining double low line inline-formula classCombining double low line inline-formula in the mid-1990s to early 2000s, followed by a rise since the early 2000s to span classCombining double low line inline-formula 2.20±0.05 Ggyrspan classCombining double low line inline-formula in 2017. These emissions are significantly larger than inventory-based emission estimates. Estimated emissions from eastern Asia rose from 0.36Ggyrspan classCombining double low line inline-formula in 2010 to 0.73Ggyrspan classCombining double low line inline-formula in 2016 and 2017, 31% of global emissions, mostly from eastern China. We estimate emissions of 0.14Ggyrspan classCombining double low line inline-formula from northern and central India in 2016 and find evidence for significant emissions from Russia. In contrast, recent emissions from northwestern Europe and Australia are estimated to be small (span classCombining double low line inline-formula % each). We suggest that emissions from China, India, andspan idCombining double low line page10336 Russia are likely related to production of polytetrafluoroethylene (PTFE, Teflon ) and other fluoropolymers and fluorochemicals that are based on the pyrolysis of hydrochlorofluorocarbon HCFC-22 (span classCombining double low line inline-formula) in which span classCombining double low line inline-formula classCombining double low line inline-formula is a known by-product. The semiconductor sector, where span classCombining double low line inline-formula span classCombining double low line inline-formula is used, is estimated to be a small source, at least in South Korea, Japan, Taiwan, and Europe. Without an obvious correlation with population density, incineration of waste-containing fluoropolymers is probably a minor source, and we find no evidence of emissions from electrolytic production of aluminum in Australia. While many possible emissive uses of span classCombining double low line inline-formula span classCombining double low line inline-formula are known and though we cannot categorically exclude unknown sources, the start of significant emissions may well be related to the advent of commercial PTFE production in 1947. Process controls or abatement to reduce the span classCombining double low line inline-formula span classCombining double low line inline-formula by-product were probably not in place in the early decades, explaining the increase in emissions in the 1960s and 1970s. With the advent of by-product reporting requirements to the United Nations Framework Convention on Climate Change (UNFCCC) in the 1990s, concern about climate change and product stewardship, abatement, and perhaps the collection of span classCombining double low line inline-formula span classCombining double low line inline-formula by-product for use in the semiconductor industry where it can be easily abated, it is conceivable that emissions in developed countries were stabilized and then reduced, explaining the observed emission reduction in the 1980s and 1990s. Concurrently, production of PTFE in China began to increase rapidly. Without emission reduction requirements, it is plausible that global emissions today are dominated by China and other developing countries. We predict that span classCombining double low line inline-formula span classCombining double low line inline-formula emissions will continue to rise and that span classCombining double low line inline-formula span classCombining double low line inline-formula will become the second most important emitted PFC in terms of span classCombining double low line inline-formula equivalent emissions within a year or two. The 2017 radiative forcing of span classCombining double low line inline-formula span classCombining double low line inline-formula 0.52mWmspan classCombining double low line inline-formula) is small but emissions of span classCombining double low line inline-formula span classCombining double low line inline-formula and other PFCs, due to their very long atmospheric lifetimes, essentially permanently alter Earth's radiative budget and should be reduced. Significant emissions inferred outside of the investigated regions clearly show that observational capabilities and reporting requirements need to be improved to understand global and country-scale emissions of PFCs and other synthetic greenhouse gases and ozone-depleting substances.United States. National Aeronautics and Space Administration (Grant NNX07AE89G)United States. National Aeronautics and Space Administration (Grant NNX07AF09G)United States. National Aeronautics and Space Administration (Grant NNX07AE87G)Great Britain. Department for Business, Energy & Industrial Strategy (Grant 1028/06/2015)United States. National Oceanic and Atmospheric Administration (Grant RA-133-R15-CN-0008)National Natural Science Foundation of China (Grant 41575114)National Science Foundation (U.S.) (Grant ARC-1203779)National Science Foundation (U.S.) (Grant ARC-1204084)Natural Environment Research Council (Great Britain) (Grant NE/I027282/1