Anthropogenic Fingerprint Detectable in Upper Tropospheric Ozone Trends Retrieved from Satellite.

Tropospheric ozone (O3) is a strong greenhouse gas, particularly in the upper troposphere (UT). Limited observations point to a continuous increase in UT O3 in recent decades, but the attribution of UT O3 changes is complicated by large internal climate variability. We show that the anthropogenic signal ("fingerprint") in the patterns of UT O3 increases is distinguishable from the background noise of internal variability. The time-invariant fingerprint of human-caused UT O3 changes is derived from a 16-member initial-condition ensemble performed with a chemistry-climate model (CESM2-WACCM6). The fingerprint is largest between 30°S and 40°N, especially near 30°N. In contrast, the noise pattern in UT O3 is mainly associated with the El Niño-Southern Oscillation (ENSO). The UT O3 fingerprint pattern can be discerned with high confidence within only 13 years of the 2005 start of the OMI/MLS satellite record. Unlike the UT O3 fingerprint, the lower tropospheric (LT) O3 fingerprint varies significantly over time and space in response to large-scale changes in anthropogenic precursor emissions, with the highest signal-to-noise ratios near 40°N in Asia and Europe. Our analysis reveals a significant human effect on Earth's atmospheric chemistry in the UT and indicates promise for identifying fingerprints of specific sources of ozone precursors.

Unexpected nascent atmospheric emissions of three ozone-depleting hydrochlorofluorocarbons.

Global and regional atmospheric measurements and modeling can play key roles in discovering and quantifying unexpected nascent emissions of environmentally important substances. We focus here on three hydrochlorofluorocarbons (HCFCs) that are restricted by the Montreal Protocol because of their roles in stratospheric ozone depletion. Based on measurements of archived air samples and on in situ measurements at stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, we report global abundances, trends, and regional enhancements for HCFC-132b ([Formula: see text]), which is newly discovered in the atmosphere, and updated results for HCFC-133a ([Formula: see text]) and HCFC-31 ([Formula: see text]ClF). No purposeful end-use is known for any of these compounds. We find that HCFC-132b appeared in the atmosphere 20 y ago and that its global emissions increased to 1.1 Gg⋅y-1 by 2019. Regional top-down emission estimates for East Asia, based on high-frequency measurements for 2016-2019, account for ∼95% of the global HCFC-132b emissions and for ∼80% of the global HCFC-133a emissions of 2.3 Gg⋅y-1 during this period. Global emissions of HCFC-31 for the same period are 0.71 Gg⋅y-1 Small European emissions of HCFC-132b and HCFC-133a, found in southeastern France, ceased in early 2017 when a fluorocarbon production facility in that area closed. Although unreported emissive end-uses cannot be ruled out, all three compounds are most likely emitted as intermediate by-products in chemical production pathways. Identification of harmful emissions to the atmosphere at an early stage can guide the effective development of global and regional environmental policy.

Minimal Climate Impacts From Short-Lived Climate Forcers Following Emission Reductions Related to the COVID-19 Pandemic.

We present an assessment of the impacts on atmospheric composition and radiative forcing of short-lived pollutants following a worldwide decrease in anthropogenic activity and emissions comparable to what has occurred in response to the COVID-19 pandemic, using the global composition-climate model United Kingdom Chemistry and Aerosols Model (UKCA). Emission changes reduce tropospheric hydroxyl radical and ozone burdens, increasing methane lifetime. Reduced SO2 emissions and oxidizing capacity lead to a decrease in sulfate aerosol and increase in aerosol size, with accompanying reductions to cloud droplet concentration. However, large reductions in black carbon emissions increase aerosol albedo. Overall, the changes in ozone and aerosol direct effects (neglecting aerosol-cloud interactions which were statistically insignificant but whose response warrants future investigation) yield a radiative forcing of -33 to -78 mWm-2. Upon cessation of emission reductions, the short-lived climate forcers rapidly return to pre-COVID levels; meaning, these changes are unlikely to have lasting impacts on climate assuming emissions return to pre-intervention levels.

Long-Term Performance Assessment of Low-Cost Atmospheric Sensors in the Arctic Environment.

The Arctic is an important natural laboratory that is extremely sensitive to climatic changes and its monitoring is, therefore, of great importance. Due to the environmental extremes it is often hard to deploy sensors and observations are limited to a few sparse observation points limiting the spatial and temporal coverage of the Arctic measurement. Given these constraints the possibility of deploying a rugged network of low-cost sensors remains an interesting and convenient option. The present work validates for the first time a low-cost sensor array (AIRQino) for monitoring basic meteorological parameters and atmospheric composition in the Arctic (air temperature, relative humidity, particulate matter, and CO2). AIRQino was deployed for one year in the Svalbard archipelago and its outputs compared with reference sensors. Results show good agreement with the reference meteorological parameters (air temperature (T) and relative humidity (RH)) with correlation coefficients above 0.8 and small absolute errors (≈1 °C for temperature and ≈6% for RH). Particulate matter (PM) low-cost sensors show a good linearity (r2 ≈ 0.8) and small absolute errors for both PM2.5 and PM10 (≈1 µg m-3 for PM2.5 and ≈3 µg m-3 for PM10), while overall accuracy is impacted both by the unknown composition of the local aerosol, and by high humidity conditions likely generating hygroscopic effects. CO2 exhibits a satisfying agreement with r2 around 0.70 and an absolute error of ≈23 mg m-3. Overall these results, coupled with an excellent data coverage and scarce need of maintenance make the AIRQino or similar devices integrations an interesting tool for future extended sensor networks also in the Arctic environment.

Matworld - the biogeochemical effects of early life on land.

Contents 531 I. 531 II. 532 III. 534 IV. 535 V. 535 VI. 535 Acknowledgements 536 References 536 SUMMARY: There is growing evidence that life has been on land for billions of years. Microbial mats fuelled by oxygenic photosynthesis were probably present in terrestrial habitats from c. 3.0 billion yr ago (Ga) onwards, creating localized 'oxygen oases' under a reducing atmosphere, which left a characteristic oxidative weathering signal. After the Great Oxidation c. 2.4 Ga, the now oxidizing atmosphere masked that redox signal, but ancient soils record the mobilization of phosphorus and other elements by organic acids in weathering profiles. Evidence for Neoproterozoic 'greening of the land' and intensification of weathering c. 0.85-0.54 Ga is currently equivocal. However, the mid-Palaeozoic c. 0.45-0.4 Ga shows global atmospheric changes consistent with increased terrestrial productivity and intensified weathering by the first land plants.

The spectral evolution of white dwarfs: where do we stand?

White dwarfs are the dense, burnt-out remnants of the vast majority of stars, condemned to cool over billions of years as they steadily radiate away their residual thermal energy. To first order, their atmosphere is expected to be made purely of hydrogen due to the efficient gravitational settling of heavier elements. However, observations reveal a much more complex situation, as the surface of a white dwarf (1) can be dominated by helium rather than hydrogen, (2) can be polluted by trace chemical species, and (3) can undergo significant composition changes with time. This indicates that various mechanisms of element transport effectively compete against gravitational settling in the stellar envelope. This phenomenon is known as the spectral evolution of white dwarfs and has important implications for Galactic, stellar, and planetary astrophysics. This invited review provides a comprehensive picture of our current understanding of white dwarf spectral evolution. We first describe the latest observational constraints on the variations in atmospheric composition along the cooling sequence, covering both the dominant and trace constituents. We then summarise the predictions of state-of-the-art models of element transport in white dwarfs and assess their ability to explain the observed spectral evolution. Finally, we highlight remaining open questions and suggest avenues for future work.

Fine particulate matter air pollution and the mortality of children under five: a multilevel analysis of the Ethiopian Demographic and Health Survey of 2016.

Background: Every year, polluted air is costing the globe 543,000 deaths of children under five. The particulate matter below 2.5 µm diameter (PM2.5) is a part of air pollution that has adverse effects on children's health. In Ethiopia, the effect of ambient PM2.5 is least explored. This study aimed to assess the association between PM2.5 and under-five mortality in Ethiopia. Methods: The study used the data from the Ethiopian Demographic Health Surveys conducted in 2016, collected between January 18 and June 27. All children under five who had data on child mortality and location coordinates were included in the study. Exposure to ambient PM2.5 concentration was a satellite-based estimate by the Atmospheric Composition Analysis Group at Washington and Dalhousie University, in the United States and Canada, respectively. Annual mean pollution levels and mortality datasets were matched by children's geographical location and dates of birth, death, and interview. The relationship between ambient PM2.5 and under-five mortality was determined by a multilevel multivariable logistic regression on R software. The statistical analyses were two-sided at a 95% confidence interval. Results: The study addressed 10,452 children with the proportion of under-five mortality being 5.4% (95% CI 5.0-6.8%). The estimated lifetime annual mean exposure of ambient total PM2.5 was 20.1 ± 3.3 µgm-3. A 10-unit increase in the lifetime annual mean ambient total PM2.5 was associated with 2.29 [95% CI 1.44, 3.65] times more odds of under-five mortality after adjusting for other variables. Conclusion: Children under five are exposed to higher levels of ambient PM2.5 concentration, exceeding the limit set by the World Health Organization. Ambient PM2.5 is significantly associated with under-five mortality, adjusting for other variables. Strong measures need to be taken to reduce air pollution.

Observations of greenhouse gases as climate indicators.

Humans have significantly altered the energy balance of the Earth's climate system mainly not only by extracting and burning fossil fuels but also by altering the biosphere and using halocarbons. The 3rd US National Climate Assessment pointed to a need for a system of indicators of climate and global change based on long-term data that could be used to support assessments and this led to the development of the National Climate Indicators System (NCIS). Here we identify a representative set of key atmospheric indicators of changes in atmospheric radiative forcing due to greenhouse gases (GHGs), and we evaluate atmospheric composition measurements, including non-CO2 GHGs for use as climate change indicators in support of the US National Climate Assessment. GHG abundances and their changes over time can provide valuable information on the success of climate mitigation policies, as well as insights into possible carbon-climate feedback processes that may ultimately affect the success of those policies. To ensure that reliable information for assessing GHG emission changes can be provided on policy-relevant scales, expanded observational efforts are needed. Furthermore, the ability to detect trends resulting from changing emissions requires a commitment to supporting long-term observations. Long-term measurements of greenhouse gases, aerosols, and clouds and related climate indicators used with a dimming/brightening index could provide a foundation for quantifying forcing and its attribution and reducing error in existing indicators that do not account for complicated cloud processes.

Investigation of Venus Cloud Aerosol and Gas Composition Including Potential Biogenic Materials via an Aerosol-Sampling Instrument Package.

A lightweight, low-power instrument package to measure, in situ, both (1) the local gaseous environment and (2) the composition and microphysical properties of attendant venusian aerosols is presented. This Aerosol-Sampling Instrument Package (ASIP) would be used to explore cloud chemical and possibly biotic processes on future aerial missions such as multiweek balloon missions and on short-duration (<1 h) probes on Venus and potentially on other cloudy worlds such as Titan, the Ice Giants, and Saturn. A quadrupole ion-trap mass spectrometer (QITMS; Madzunkov and Nikolic, J Am Soc Mass Spectrom 25:1841-1852, 2014) fed alternately by (1) an aerosol separator that injects only aerosols into a vaporizer and mass spectrometer and (2) the pure aerosol-filtered atmosphere, achieves the compositional measurements. Aerosols vaporized <600°C are measured over atomic mass ranges from 2 to 300 AMU at <0.02 AMU resolution, sufficient to measure trace materials, their isotopic ratios, and potential biogenic materials embedded within H2SO4 aerosols, to better than 20% in <300 s for H2SO4 -relative abundances of 2 × 10-9. An integrated lightweight, compact nephelometer/particle-counter determines the number density and particle sizes of the sampled aerosols.

Increased ozone pollution alongside reduced nitrogen dioxide concentrations during Vienna's first COVID-19 lockdown: Significance for air quality management.

BACKGROUND: Lockdowns amid the COVID-19 pandemic have offered a real-world opportunity to better understand air quality responses to previously unseen anthropogenic emission reductions. METHODS AND MAIN OBJECTIVE: This work examines the impact of Vienna's first lockdown on ground-level concentrations of nitrogen dioxide (NO2), ozone (O3) and total oxidant (Ox). The analysis runs over January to September 2020 and considers business as usual scenarios created with machine learning models to provide a baseline for robustly diagnosing lockdown-related air quality changes. Models were also developed to normalise the air pollutant time series, enabling facilitated intervention assessment. CORE FINDINGS: NO2 concentrations were on average -20.1% [13.7-30.4%] lower during the lockdown. However, this benefit was offset by amplified O3 pollution of +8.5% [3.7-11.0%] in the same period. The consistency in the direction of change indicates that the NO2 reductions and O3 increases were ubiquitous over Vienna. Ox concentrations increased slightly by +4.3% [1.8-6.4%], suggesting that a significant part of the drops in NO2 was compensated by gains in O3. Accordingly, 82% of lockdown days with lowered NO2 were accompanied by 81% of days with amplified O3. The recovery shapes of the pollutant concentrations were depicted and discussed. The business as usual-related outcomes were broadly consistent with the patterns outlined by the normalised time series. These findings allowed to argue further that the detected changes in air quality were of anthropogenic and not of meteorological reason. Pollutant changes on the machine learning baseline revealed that the impact of the lockdown on urban air quality were lower than the raw measurements show. Besides, measured traffic drops in major Austrian roads were more significant for light-duty than for heavy-duty vehicles. It was also noted that the use of mobility reports based on cell phone movement as activity data can overestimate the reduction of emissions for the road transport sector, particularly for heavy-duty vehicles. As heavy-duty vehicles can make up a large fraction of the fleet emissions of nitrogen oxides, the change in the volume of these vehicles on the roads may be the main driver to explain the change in NO2 concentrations. INTERPRETATION AND IMPLICATIONS: A probable future with emissions of volatile organic compounds (VOCs) dropping slower than emissions of nitrogen oxides could risk worsened urban O3 pollution under a VOC-limited photochemical regime. More holistic policies will be needed to achieve improved air quality levels across different regions and criteria pollutants.

Transport of Asian surface pollutants to the global stratosphere from the Tibetan Plateau region during the Asian summer monsoon.

Due to its surrounding strong and deep Asian summer monsoon (ASM) circulation and active surface pollutant emissions, surface pollutants are transported to the stratosphere from the Tibetan Plateau region, which may have critical impacts on global climate through chemical, microphysical and radiative processes. This article reviews major recent advances in research regarding troposphere-stratosphere transport from the region of the Tibetan Plateau. Since the discovery of the total ozone valley over the Tibetan Plateau in summer from satellite observations in the early 1990s, new satellite-borne instruments have become operational and have provided significant new information on atmospheric composition. In addition, in situ measurements and model simulations are used to investigate deep convection and the ASM anticyclone, surface sources and pathways, atmospheric chemical transformations and the impact on global climate. Also challenges are discussed for further understanding critical questions on microphysics and microchemistry in clouds during the pathway to the global stratosphere over the Tibetan Plateau.

Atmospheric blockages as trigger of environmental contingencies in Mexico City.

Atmospheric pollution in cities is due to several human factors, for instance the number of cars in circulation, fuel efficiency and industrial waste, as well as orographic and meteorological conditions that determine air circulation. Ozone contingencies cause health disorders on the population, making it important to understand the factors that trigger such contingencies. Here, we analyze meteorological (wind, temperature, relative humidity) and atmospheric composition (ozone, and NOx) data of five atmospheric monitoring stations on Mexico City, from March 2004 to May 2018, comparing normal days with the extreme days in the 90th percentile of ozone. Moreover, we present the synoptic patterns of the seasonal differences of geopotential height at 500 hPa between extreme and control days. We found that, in the dry-hot season (from March to May) an atmospheric blockage with meteorological conditions of almost no wind, low relative humidity, and small temperature fluctuations occurs. Because the air in the city permanently contains large amounts of ozone precursors like NOx, this meteorological scenario raises ozone levels to those of an environmental contingency. Thus, during the dry-hot season on Mexico City, ozone contingencies are triggered by atmospheric blocking. This scenario will be present in cities surrounded by mountains with high levels of Ozone precursors.

The Dawn of Geostationary Air Quality Monitoring: Case Studies from Seoul and Los Angeles.

With the near-future launch of geostationary pollution monitoring satellite instruments over North America, East Asia, and Europe, the air quality community is preparing for an integrated global atmospheric composition observing system at unprecedented spatial and temporal resolutions. One of the ways that NASA has supported this community preparation is through demonstration of future space-borne capabilities using the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument. This paper integrates repeated high-resolution maps from GeoTASO, ground-based Pandora spectrometers, and low Earth orbit measurements from the Ozone Mapping and Profiler Suite (OMPS), for case studies over two metropolitan areas: Seoul, South Korea on June 9th, 2016 and Los Angeles, California on June 27th, 2017. This dataset provides a unique opportunity to illustrate how geostationary air quality monitoring platforms and ground-based remote sensing networks will close the current spatiotemporal observation gap. GeoTASO observes large differences in diurnal behavior between these urban areas, with NO2 accumulating within the Seoul Metropolitan Area through the day but NO2 peaking in the morning and decreasing throughout the afternoon in the Los Angeles Basin. In both areas, the earliest morning maps exhibit spatial patterns similar to emission source areas (e.g., urbanized valleys, roadways, major airports). These spatial patterns change later in the day due to boundary layer dynamics, horizontal transport, and chemistry. The nominal resolution of GeoTASO is finer than will be obtained from geostationary platforms, but when NO2 data over Los Angeles are up-scaled to the expected resolution of TEMPO, spatial features discussed are conserved. Pandora instruments installed in both metropolitan areas capture the diurnal patterns observed by GeoTASO, continuously and over longer time periods, and will play a critical role in validation of the next generation of satellite measurement.. These case studies demonstrate that different regions can have diverse diurnal patterns and that day-to-day variability due to meteorology or anthropogenic patterns such as weekday/weekend variations in emissions is large. Low Earth orbit measurements, despite their inability to capture the diurnal patterns at fine spatial resolution, will be essential for intercalibrating the geostationary radiances and cross-validating the geostationary retrievals in an integrated global observing system.

New insights for mesospheric OH: multi-quantum vibrational relaxation as a driver for non-local thermodynamic equilibrium.

The question of whether mesospheric OH(υ) rotational population distributions are in equilibrium with the local kinetic temperature has been debated over several decades. Despite several indications for the existence of non-equilibrium effects, the general consensus has been that emissions originating from low rotational levels are thermalized. Sky spectra simultaneously observing several vibrational levels demonstrated reproducible trends in the extracted OH(υ) rotational temperatures as a function of vibrational excitation. Laboratory experiments provided information on rotational energy transfer and direct evidence for fast multi-quantum OH(high-υ) vibrational relaxation by O atoms. We examine the relationship of the new relaxation pathways with the behavior exhibited by OH(υ) rotational population distributions. Rapid OH(high-υ) + O multi-quantum vibrational relaxation connects high and low vibrational levels and enhances the hot tail of the OH(low-υ) rotational distributions. The effective rotational temperatures of mesospheric OH(υ) are found to deviate from local thermodynamic equilibrium for all observed vibrational levels.

Methane emissions from the Marcellus Shale in southwestern Pennsylvania and northern West Virginia based on airborne measurements.

Natural gas production in the U.S. has increased rapidly over the past decade, along with concerns about methane (CH4) leakage (total fugitive emissions), and climate impacts. Quantification of CH4 emissions from oil and natural gas (O&NG) operations is important for establishing scientifically sound, cost-effective policies for mitigating greenhouse gases. We use aircraft measurements and a mass balance approach for three flight experiments in August and September 2015 to estimate CH4 emissions from O&NG operations in the southwestern Marcellus Shale region. We estimate the mean ± 1σ CH4 emission rate as 36.7 ± 1.9 kg CH4 s-1 (or 1.16 ± 0.06 Tg CH4 yr-1) with 59% coming from O&NG operations. We estimate the mean ± 1σ CH4 leak rate from O&NG operations as 3.9 ± 0.4% with a lower limit of 1.5% and an upper limit of 6.3%. This leak rate is broadly consistent with the results from several recent top-down studies but higher than the results from a few other observational studies as well as in the U.S. Environmental Protection Agency CH4 emission inventory. However, a substantial source of CH4 was found to contain little ethane (C2H6), possibly due to coalbed CH4 emitted either directly from coalmines or from wells drilled through coalbed layers. Although recent regulations requiring capture of gas from the completion venting step of the hydraulic fracturing appear to have reduced losses, our study suggests that for a 20 year time scale, energy derived from the combustion of natural gas extracted from this region will require further controls before it can exert a net climate benefit compared to coal.