An observation-based, reduced-form model for oxidation in the remote marine troposphere.

The hydroxyl radical (OH) fuels atmospheric chemical cycling as the main sink for methane and a driver of the formation and loss of many air pollutants, but direct OH observations are sparse. We develop and evaluate an observation-based proxy for short-term, spatial variations in OH (ProxyOH) in the remote marine troposphere using comprehensive measurements from the NASA Atmospheric Tomography (ATom) airborne campaign. ProxyOH is a reduced form of the OH steady-state equation representing the dominant OH production and loss pathways in the remote marine troposphere, according to box model simulations of OH constrained with ATom observations. ProxyOH comprises only eight variables that are generally observed by routine ground- or satellite-based instruments. ProxyOH scales linearly with in situ [OH] spatial variations along the ATom flight tracks (median r2 = 0.90, interquartile range = 0.80 to 0.94 across 2-km altitude by 20° latitudinal regions). We deconstruct spatial variations in ProxyOH as a first-order approximation of the sensitivity of OH variations to individual terms. Two terms modulate within-region ProxyOH variations-water vapor (H2O) and, to a lesser extent, nitric oxide (NO). This implies that a limited set of observations could offer an avenue for observation-based mapping of OH spatial variations over much of the remote marine troposphere. Both H2O and NO are expected to change with climate, while NO also varies strongly with human activities. We also illustrate the utility of ProxyOH as a process-based approach for evaluating intermodel differences in remote marine tropospheric OH.

Carbon Monoxide Emissions from the Washington, DC, and Baltimore Metropolitan Area: Recent Trend and COVID-19 Anomaly.

We analyze airborne measurements of atmospheric CO concentration from 70 flights conducted over six years (2015-2020) using an inverse model to quantify the CO emissions from the Washington, DC, and Baltimore metropolitan areas. We found that CO emissions have been declining in the area at a rate of ≈-4.5 % a-1 since 2015 or ≈-3.1 % a-1 since 2016. In addition, we found that CO emissions show a "Sunday" effect, with emissions being lower, on average, than for the rest of the week and that the seasonal cycle is no larger than 16 %. Our results also show that the trend derived from the NEI agrees well with the observed trend, but that NEI daytime-adjusted emissions are ≈50 % larger than our estimated emissions. In 2020, measurements collected during the shutdown in activity related to the COVID-19 pandemic indicate a significant drop in CO emissions of 16 % relative to the expected emissions trend from the previous years, or 23 % relative to the mean of 2016 to February 2020. Our results also indicate a larger reduction in April than in May. Last, we show that this reduction in CO emissions was driven mainly by a reduction in traffic.

Strong Southern Ocean carbon uptake evident in airborne observations.

The Southern Ocean plays an important role in determining atmospheric carbon dioxide (CO2), yet estimates of air-sea CO2 flux for the region diverge widely. In this study, we constrained Southern Ocean air-sea CO2 exchange by relating fluxes to horizontal and vertical CO2 gradients in atmospheric transport models and applying atmospheric observations of these gradients to estimate fluxes. Aircraft-based measurements of the vertical atmospheric CO2 gradient provide robust flux constraints. We found an annual mean flux of ­0.53 ± 0.23 petagrams of carbon per year (net uptake) south of 45°S during the period 2009­2018. This is consistent with the mean of atmospheric inversion estimates and surface-ocean partial pressure of CO2 (Pco2)­based products, but our data indicate stronger annual mean uptake than suggested by recent interpretations of profiling float observations.

Large contribution of biomass burning emissions to ozone throughout the global remote troposphere.

Ozone is the third most important anthropogenic greenhouse gas after carbon dioxide and methane but has a larger uncertainty in its radiative forcing, in part because of uncertainty in the source characteristics of ozone precursors, nitrogen oxides, and volatile organic carbon that directly affect ozone formation chemistry. Tropospheric ozone also negatively affects human and ecosystem health. Biomass burning (BB) and urban emissions are significant but uncertain sources of ozone precursors. Here, we report global-scale, in situ airborne measurements of ozone and precursor source tracers from the NASA Atmospheric Tomography mission. Measurements from the remote troposphere showed that tropospheric ozone is regularly enhanced above background in polluted air masses in all regions of the globe. Ozone enhancements in air with high BB and urban emission tracers (2.1 to 23.8 ppbv [parts per billion by volume]) were generally similar to those in BB-influenced air (2.2 to 21.0 ppbv) but larger than those in urban-influenced air (-7.7 to 6.9 ppbv). Ozone attributed to BB was 2 to 10 times higher than that from urban sources in the Southern Hemisphere and the tropical Atlantic and roughly equal to that from urban sources in the Northern Hemisphere and the tropical Pacific. Three independent global chemical transport models systematically underpredict the observed influence of BB on tropospheric ozone. Potential reasons include uncertainties in modeled BB injection heights and emission inventories, export efficiency of BB emissions to the free troposphere, and chemical mechanisms of ozone production in smoke. Accurately accounting for intermittent but large and widespread BB emissions is required to understand the global tropospheric ozone burden.

Majority of US urban natural gas emissions unaccounted for in inventories.

Across many cities, estimates of methane emissions from natural gas (NG) distribution and end use based on atmospheric measurements have generally been more than double bottom-up estimates. We present a top-down study of NG methane emissions from the Boston urban region spanning 8 y (2012 to 2020) to assess total emissions, their seasonality, and trends. We used methane and ethane observations from five sites in and around Boston, combined with a high-resolution transport model, to calculate methane emissions of 76 ± 18 Gg/yr, with 49 ± 9 Gg/yr attributed to NG losses. We found no significant trend in the NG loss rate over 8 y, despite efforts from the city and state to increase the rate of repairing NG pipeline leaks. We estimate that 2.5 ± 0.5% of the gas entering the urban region is lost, approximately three times higher than bottom-up estimates. We saw a strong correlation between top-down NG emissions and NG consumed on a seasonal basis. This suggests that consumption-driven losses, such as in transmission or end-use, may be a large component of emissions that is missing from inventories, and require future policy action. We also compared top-down NG emission estimates from six US cities, all of which indicate significant missing sources in bottom-up inventories. Across these cities, we estimate NG losses from distribution and end use amount to 20 to 36% of all losses from the US NG supply chain, with a total loss rate of 3.3 to 4.7% of NG from well pad to urban consumer, notably larger than the current Environmental Protection Agency estimate of 1.4% [R. A. Alvarez et al., Science 361, 186-188 (2018)].

COS-derived GPP relationships with temperature and light help explain high-latitude atmospheric CO2 seasonal cycle amplification.

In the Arctic and Boreal region (ABR) where warming is especially pronounced, the increase of gross primary production (GPP) has been suggested as an important driver for the increase of the atmospheric CO2 seasonal cycle amplitude (SCA). However, the role of GPP relative to changes in ecosystem respiration (ER) remains unclear, largely due to our inability to quantify these gross fluxes on regional scales. Here, we use atmospheric carbonyl sulfide (COS) measurements to provide observation-based estimates of GPP over the North American ABR. Our annual GPP estimate is 3.6 (2.4 to 5.5) PgC · y-1 between 2009 and 2013, the uncertainty of which is smaller than the range of GPP estimated from terrestrial ecosystem models (1.5 to 9.8 PgC · y-1). Our COS-derived monthly GPP shows significant correlations in space and time with satellite-based GPP proxies, solar-induced chlorophyll fluorescence, and near-infrared reflectance of vegetation. Furthermore, the derived monthly GPP displays two different linear relationships with soil temperature in spring versus autumn, whereas the relationship between monthly ER and soil temperature is best described by a single quadratic relationship throughout the year. In spring to midsummer, when GPP is most strongly correlated with soil temperature, our results suggest the warming-induced increases of GPP likely exceeded the increases of ER over the past four decades. In autumn, however, increases of ER were likely greater than GPP due to light limitations on GPP, thereby enhancing autumn net carbon emissions. Both effects have likely contributed to the atmospheric CO2 SCA amplification observed in the ABR.

HCOOH in the remote atmosphere: Constraints from Atmospheric Tomography (ATom) airborne observations.

Formic acid (HCOOH) is an important component of atmospheric acidity but its budget is poorly understood, with prior observations implying substantial missing sources. Here we combine pole-to-pole airborne observations from the Atmospheric Tomography Mission (ATom) with chemical transport model (GEOS-Chem CTM) and back trajectory analyses to provide the first global in-situ characterization of HCOOH in the remote atmosphere. ATom reveals sub-100 ppt HCOOH concentrations over most of the remote oceans, punctuated by large enhancements associated with continental outflow. Enhancements correlate with known combustion tracers and trajectory-based fire influences. The GEOS-Chem model underpredicts these in-plume HCOOH enhancements, but elsewhere we find no broad indication of a missing HCOOH source in the background free troposphere. We conclude that missing non-fire HCOOH precursors inferred previously are predominantly short-lived. We find indications of a wet scavenging underestimate in the model consistent with a positive HCOOH bias in the tropical upper troposphere. Observations reveal episodic evidence of ocean HCOOH uptake, which is well-captured by GEOS-Chem; however, despite its strong seawater undersaturation HCOOH is not consistently depleted in the remote marine boundary layer. Over fifty fire and mixed plumes were intercepted during ATom with widely varying transit times and source regions. HCOOH:CO normalized excess mixing ratios in these plumes range from 3.4 to >50 ppt/ppb CO and are often over an order of magnitude higher than expected primary emission ratios. HCOOH is thus a major reactive organic carbon reservoir in the aged plumes sampled during ATom, implying important missing pathways for in-plume HCOOH production.

Aircraft-based inversions quantify the importance of wetlands and livestock for Upper Midwest methane emissions.

We apply airborne measurements across three seasons (summer, winter and spring 2017-2018) in a multi-inversion framework to quantify methane emissions from the US Corn Belt and Upper Midwest, a key agricultural and wetland source region. Combing our seasonal results with prior fall values we find that wetlands are the largest regional methane source (32 %, 20 [16-23] Gg/d), while livestock (enteric/manure; 25 %, 15 [14-17] Gg/d) are the largest anthropogenic source. Natural gas/petroleum, waste/landfills, and coal mines collectively make up the remainder. Optimized fluxes improve model agreement with independent datasets within and beyond the study timeframe. Inversions reveal coherent and seasonally dependent spatial errors in the WetCHARTs ensemble mean wetland emissions, with an underestimate for the Prairie Pothole region but an overestimate for Great Lakes coastal wetlands. Wetland extent and emission temperature dependence have the largest influence on prediction accuracy; better representation of coupled soil temperature-hydrology effects is therefore needed. Our optimized regional livestock emissions agree well with the Gridded EPA estimates during spring (to within 7 %) but are ∼25 % higher during summer and winter. Spatial analysis further shows good top-down and bottom-up agreement for beef facilities (with mainly enteric emissions) but larger (∼30 %) seasonal discrepancies for dairies and hog farms (with >40 % manure emissions). Findings thus support bottom-up enteric emission estimates but suggest errors for manure; we propose that the latter reflects inadequate treatment of management factors including field application. Overall, our results confirm the importance of intensive animal agriculture for regional methane emissions, implying substantial mitigation opportunities through improved management.

Constraining remote oxidation capacity with ATom observations.

The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July-August 2016 and January-February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NO y concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NO y . The severe model overestimate of NO y during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NO y partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3% to 9% and improves model-measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr-1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Enhanced North American carbon uptake associated with El Niño.

Long-term atmospheric CO2 mole fraction and δ13CO2 observations over North America document persistent responses to the El Niño-Southern Oscillation. We estimate these responses corresponded to 0.61 (0.45 to 0.79) PgC year-1 more North American carbon uptake during El Niño than during La Niña between 2007 and 2015, partially offsetting increases of net tropical biosphere-to-atmosphere carbon flux around El Niño. Anomalies in derived North American net ecosystem exchange (NEE) display strong but opposite correlations with surface air temperature between seasons, while their correlation with water availability was more constant throughout the year, such that water availability is the dominant control on annual NEE variability over North America. These results suggest that increased water availability and favorable temperature conditions (warmer spring and cooler summer) caused enhanced carbon uptake over North America near and during El Niño.

Synthesis of Urban CO2 Emission Estimates from Multiple Methods from the Indianapolis Flux Project (INFLUX).

Urban areas contribute approximately three-quarters of fossil fuel derived CO2 emissions, and many cities have enacted emissions mitigation plans. Evaluation of the effectiveness of mitigation efforts will require measurement of both the emission rate and its change over space and time. The relative performance of different emission estimation methods is a critical requirement to support mitigation efforts. Here we compare results of CO2 emissions estimation methods including an inventory-based method and two different top-down atmospheric measurement approaches implemented for the Indianapolis, Indiana, U.S.A. urban area in winter. By accounting for differences in spatial and temporal coverage, as well as trace gas species measured, we find agreement among the wintertime whole-city fossil fuel CO2 emission rate estimates to within 7%. This finding represents a major improvement over previous comparisons of urban-scale emissions, making urban CO2 flux estimates from this study consistent with local and global emission mitigation strategy needs. The complementary application of multiple scientifically driven emissions quantification methods enables and establishes this high level of confidence and demonstrates the strength of the joint implementation of rigorous inventory and atmospheric emissions monitoring approaches.

Anthropogenic and biogenic CO2 fluxes in the Boston urban region.

With the pending withdrawal of the United States from the Paris Climate Accord, cities are now leading US actions toward reducing greenhouse gas emissions. Implementing effective mitigation strategies requires the ability to measure and track emissions over time and at various scales. We report CO2 emissions in the Boston, MA, urban region from September 2013 to December 2014 based on atmospheric observations in an inverse model framework. Continuous atmospheric measurements of CO2 from five sites in and around Boston were combined with a high-resolution bottom-up CO2 emission inventory and a Lagrangian particle dispersion model to determine regional emissions. Our model-measurement framework incorporates emissions estimates from submodels for both anthropogenic and biological CO2 fluxes, and development of a CO2 concentration curtain at the boundary of the study region based on a combination of tower measurements and modeled vertical concentration gradients. We demonstrate that an emission inventory with high spatial and temporal resolution and the inclusion of urban biological fluxes are both essential to accurately modeling annual CO2 fluxes using surface measurement networks. We calculated annual average emissions in the Boston region of 0.92 kg C·m-2·y-1 (95% confidence interval: 0.79 to 1.06), which is 14% higher than the Anthropogenic Carbon Emissions System inventory. Based on the capability of the model-measurement approach demonstrated here, our framework should be able to detect changes in CO2 emissions of greater than 18%, providing stakeholders with critical information to assess mitigation efforts in Boston and surrounding areas.

Methane emissions from natural gas infrastructure and use in the urban region of Boston, Massachusetts.

Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4 ⋅ m(-2) ⋅ y(-1). Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼ 60-100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory.

Assessment of ground-based atmospheric observations for verification of greenhouse gas emissions from an urban region.

International agreements to limit greenhouse gas emissions require verification to ensure that they are effective and fair. Verification based on direct observation of atmospheric greenhouse gas concentrations will be necessary to demonstrate that estimated emission reductions have been actualized in the atmosphere. Here we assess the capability of ground-based observations and a high-resolution (1.3 km) mesoscale atmospheric transport model to determine a change in greenhouse gas emissions over time from a metropolitan region. We test the method with observations from a network of CO(2) surface monitors in Salt Lake City. Many features of the CO(2) data were simulated with excellent fidelity, although data-model mismatches occurred on hourly timescales due to inadequate simulation of shallow circulations and the precise timing of boundary-layer stratification and destratification. Using two optimization procedures, monthly regional fluxes were constrained to sufficient precision to detect an increase or decrease in emissions of approximately 15% at the 95% confidence level. We argue that integrated column measurements of the urban dome of CO(2) from the ground and/or space are less sensitive than surface point measurements to the redistribution of emitted CO(2) by small-scale processes and thus may allow for more precise trend detection of emissions from urban regions.