Investigating stratospheric changes between 2009 and 2018 with halogenated trace gas data from aircraft, AirCores, and a global model focusing on CFC-11

We present new observations of trace gases in the stratosphere based on a cost-effective sampling technique that can access much higher altitudes than aircraft. The further development of this method now provides detection of species with abundances in the parts per trillion (ppt) range and below. We obtain mixing ratios for six gases (CFC-11, CFC-12, HCFC-22, H-1211, H-1301, and SF6), all of which are important for understanding stratospheric ozone depletion and circulation. After demonstrating the quality of the data through comparisons with ground-based records and aircraft-based observations, we combine them with the latter to demonstrate its potential. We first compare the data with results from a global model driven by three widely used meteorological reanalyses. Secondly, we focus on CFC-11 as recent evidence has indicated renewed atmospheric emissions of that species relevant on a global scale. Because the stratosphere represents the main sink region for CFC-11, potential changes in stratospheric circulation and troposphere–stratosphere exchange fluxes have been identified as the largest source of uncertainty for the accurate quantification of such emissions. Our observations span over a decade (up until 2018) and therefore cover the period of the slowdown of CFC-11 global mixing ratio decreases measured at the Earth's surface. The spatial and temporal coverage of the observations is insufficient for a global quantitative analysis, but we do find some trends that are in contrast with expectations, indicating that the stratosphere may have contributed to the slower concentration decline in recent years. Further investigating the reanalysis-driven model data, we find that the dynamical changes in the stratosphere required to explain the apparent change in tropospheric CFC-11 emissions after 2013 are possible but with a very high uncertainty range. This is partly caused by the high variability of mass flux from the stratosphere to the troposphere, especially at timescales of a few years, and partly by large differences between runs driven by different reanalysis products, none of which agree with our observations well enough for such a quantitative analysis

An Observationally Constrained Evaluation of the Oxidative Capacity in the Tropical Western Pacific Troposphere

Hydroxyl radical (OH) is the main daytime oxidant in the troposphere and determines the atmospheric lifetimes of many compounds. We use aircraft measurements of O3, H2O, NO, and other species from the Convective Transport of Active Species in the Tropics (CONTRAST) field campaign, which occurred in the tropical western Pacific (TWP) during January–February 2014, to constrain a photochemical box model and estimate concentrations of OH throughout the troposphere. We find that tropospheric column OH (OHCOL) inferred from CONTRAST observations is 12 to 40% higher than found in chemical transport models (CTMs), including CAM-chem-SD run with 2014 meteorology as well as eight models that participated in POLMIP (2008 meteorology). Part of this discrepancy is due to a clear-sky sampling bias that affects CONTRAST observations; accounting for this bias and also for a small difference in chemical mechanism results in our empirically based value of OHCOL being 0 to 20% larger than found within global models. While these global models simulate observed O3 reasonably well, they underestimate NOx (NO + NO2) by a factor of two, resulting in OHCOL ~30% lower than box model simulations constrained by observed NO. Underestimations by CTMs of observed CH3CHO throughout the troposphere and of HCHO in the upper troposphere further contribute to differences between our constrained estimates of OH and those calculated by CTMs. Finally, our calculations do not support the prior suggestion of the existence of a tropospheric OH minimum in the TWP, because during January–February 2014 observed levels of O3 and NO were considerably larger than previously reported values in the TWP

The state of the Martian climate

60°N was +2.0°C, relative to the 1981–2010 average value (Fig. 5.1). This marks a new high for the record. The average annual surface air temperature (SAT) anomaly for 2016 for land stations north of starting in 1900, and is a significant increase over the previous highest value of +1.2°C, which was observed in 2007, 2011, and 2015. Average global annual temperatures also showed record values in 2015 and 2016. Currently, the Arctic is warming at more than twice the rate of lower latitudes

State of the climate in 2018

In 2018, the dominant greenhouse gases released into Earth’s atmosphere—carbon dioxide, methane, and nitrous oxide—continued their increase. The annual global average carbon dioxide concentration at Earth’s surface was 407.4 ± 0.1 ppm, the highest in the modern instrumental record and in ice core records dating back 800 000 years. Combined, greenhouse gases and several halogenated gases contribute just over 3 W m−2 to radiative forcing and represent a nearly 43% increase since 1990. Carbon dioxide is responsible for about 65% of this radiative forcing. With a weak La Niña in early 2018 transitioning to a weak El Niño by the year’s end, the global surface (land and ocean) temperature was the fourth highest on record, with only 2015 through 2017 being warmer. Several European countries reported record high annual temperatures. There were also more high, and fewer low, temperature extremes than in nearly all of the 68-year extremes record. Madagascar recorded a record daily temperature of 40.5°C in Morondava in March, while South Korea set its record high of 41.0°C in August in Hongcheon. Nawabshah, Pakistan, recorded its highest temperature of 50.2°C, which may be a new daily world record for April. Globally, the annual lower troposphere temperature was third to seventh highest, depending on the dataset analyzed. The lower stratospheric temperature was approximately fifth lowest. The 2018 Arctic land surface temperature was 1.2°C above the 1981–2010 average, tying for third highest in the 118-year record, following 2016 and 2017. June’s Arctic snow cover extent was almost half of what it was 35 years ago. Across Greenland, however, regional summer temperatures were generally below or near average. Additionally, a satellite survey of 47 glaciers in Greenland indicated a net increase in area for the first time since records began in 1999. Increasing permafrost temperatures were reported at most observation sites in the Arctic, with the overall increase of 0.1°–0.2°C between 2017 and 2018 being comparable to the highest rate of warming ever observed in the region. On 17 March, Arctic sea ice extent marked the second smallest annual maximum in the 38-year record, larger than only 2017. The minimum extent in 2018 was reached on 19 September and again on 23 September, tying 2008 and 2010 for the sixth lowest extent on record. The 23 September date tied 1997 as the latest sea ice minimum date on record. First-year ice now dominates the ice cover, comprising 77% of the March 2018 ice pack compared to 55% during the 1980s. Because thinner, younger ice is more vulnerable to melting out in summer, this shift in sea ice age has contributed to the decreasing trend in minimum ice extent. Regionally, Bering Sea ice extent was at record lows for almost the entire 2017/18 ice season. For the Antarctic continent as a whole, 2018 was warmer than average. On the highest points of the Antarctic Plateau, the automatic weather station Relay (74°S) broke or tied six monthly temperature records throughout the year, with August breaking its record by nearly 8°C. However, cool conditions in the western Bellingshausen Sea and Amundsen Sea sector contributed to a low melt season overall for 2017/18. High SSTs contributed to low summer sea ice extent in the Ross and Weddell Seas in 2018, underpinning the second lowest Antarctic summer minimum sea ice extent on record. Despite conducive conditions for its formation, the ozone hole at its maximum extent in September was near the 2000–18 mean, likely due to an ongoing slow decline in stratospheric chlorine monoxide concentration. Across the oceans, globally averaged SST decreased slightly since the record El Niño year of 2016 but was still far above the climatological mean. On average, SST is increasing at a rate of 0.10° ± 0.01°C decade−1 since 1950. The warming appeared largest in the tropical Indian Ocean and smallest in the North Pacific. The deeper ocean continues to warm year after year. For the seventh consecutive year, global annual mean sea level became the highest in the 26-year record, rising to 81 mm above the 1993 average. As anticipated in a warming climate, the hydrological cycle over the ocean is accelerating: dry regions are becoming drier and wet regions rainier. Closer to the equator, 95 named tropical storms were observed during 2018, well above the 1981–2010 average of 82. Eleven tropical cyclones reached Saffir–Simpson scale Category 5 intensity. North Atlantic Major Hurricane Michael’s landfall intensity of 140 kt was the fourth strongest for any continental U.S. hurricane landfall in the 168-year record. Michael caused more than 30 fatalities and $25 billion (U.S. dollars) in damages. In the western North Pacific, Super Typhoon Mangkhut led to 160 fatalities and$6 billion (U.S. dollars) in damages across the Philippines, Hong Kong, Macau, mainland China, Guam, and the Northern Mariana Islands. Tropical Storm Son-Tinh was responsible for 170 fatalities in Vietnam and Laos. Nearly all the islands of Micronesia experienced at least moderate impacts from various tropical cyclones. Across land, many areas around the globe received copious precipitation, notable at different time scales. Rodrigues and Réunion Island near southern Africa each reported their third wettest year on record. In Hawaii, 1262 mm precipitation at Waipā Gardens (Kauai) on 14–15 April set a new U.S. record for 24-h precipitation. In Brazil, the city of Belo Horizonte received nearly 75 mm of rain in just 20 minutes, nearly half its monthly average. Globally, fire activity during 2018 was the lowest since the start of the record in 1997, with a combined burned area of about 500 million hectares. This reinforced the long-term downward trend in fire emissions driven by changes in land use in frequently burning savannas. However, wildfires burned 3.5 million hectares across the United States, well above the 2000–10 average of 2.7 million hectares. Combined, U.S. wildfire damages for the 2017 and 2018 wildfire seasons exceeded $40 billion (U.S. dollars)

Association between Carbonyl Sulfide Uptake and 18Δ during Gas Exchange in C3 and C4 Leaves1[OA]

Carbonyl sulfide (COS) and C18OO exchange by leaves provide potentially powerful tracers of biosphere-atmosphere CO2 exchange, and both are assumed to depend on carbonic anhydrase (CA) activity and conductance along the diffusive pathway in leaves. We investigated these links using C3 and C4 plants, hypothesizing that the rates of COS and C18OO exchange by leaves respond in parallel to environmental and biological drivers. Using CA-deficient antisense lines of C4 and C3 plants, COS uptake was essentially eliminated and discrimination against C18OO exchange (18Δ) greatly reduced, demonstrating CA’s key role in both processes. 18Δ showed a positive linear correlation with leaf relative uptake (LRU; ratio of COS to CO2 assimilation rates, As/Ac, normalized to their respective ambient concentrations), which reflected the effects of stomatal conductance on both COS and C18OO exchange. Unexpectedly, a decoupling between As and 18Δ was observed in comparing C4 and C3 plants, with a large decrease in 18Δ but no parallel reduction in As in the former. This could be explained by C4 plants having higher COS concentrations at the CA site (maintaining high As with reduced CA) and a high phosphoenolpyruvate carboxylase/CA activity ratio (reducing 18O exchange efficiency between CO2 and water, but not As). Similar As but higher Ac in C4 versus C3 plants resulted in lower LRU values in the former (1.16 ± 0.20 and 1.82 ± 0.18 for C4 and C3, respectively). LRU was, however, relatively constant in both plant types across a wide range of conditions, except low light (<191 μmol photon m−2 s−1)

Hydrofluorocarbons (HFCs)

The Montreal Protocol is an international agreement designed to heal the ozone layer. It outlines schedules for the phase-out of ozone-depleting substances (ODSs) such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), chlorinated solvents, halons, and methyl bromide. As a result of this phase-out, alternative chemicals and procedures were developed by industry for use in many applications including refrigeration, air-conditioning, foam-blowing, electronics, medicine, agriculture, and fire protection. Hydrofluorocarbons (HFCs) were used as ODS alternatives in many of these applications because they were suitable substitutes and they do not contain ozone-depleting chlorine or bromine; in addition, most HFCs have smaller climate impacts per molecule than the most widely used ODSs they replaced. Long-lived HFCs, CFCs, and HCFCs, however, are all potent greenhouse gases, and concerns were raised that uncontrolled future use of HFCs would lead to substantial climate warming. As a result of these concerns, HFCs were included as one group of greenhouse gases for which emissions controls were adopted by the 1997 Kyoto Protocol under the 1992 United Nations Framework Convention on Climate Change (UNFCCC). Consequently, developed countries (those listed in Annex I to this Convention, or “Annex I” Parties) supply annual emission estimates of HFCs to the UNFCCC. Since the Kyoto Protocol only specified limits on the sum of all controlled greenhouse gases, emissions of HFCs were not explicitly controlled. However, following the Kyoto Protocol, some countries enacted additional controls specifically limiting HFC use based on their global warming potentials (GWPs). Ultimately the Kigali Amendment to the Montreal Protocol was agreed upon in 2016, and this Amendment supplies schedules for limiting the production and consumption of specific HFCs. Although the radiative forcing supplied by HFCs is currently small, this Amendment was designed to ensure that the radiative forcing from HFCs will not grow uncontrollably in the future. The Kigali Amendment will come into force at the start of 2019. HFC concentrations are currently monitored through atmospheric measurements. All HFCs with large abundances are monitored, as are most with small abundances. Most HFCs that are emitted to the atmosphere are intentionally produced for use in a variety of applications that were once dependent on ODSs. An exception is HFC-23, which is emitted to the atmosphere primarily as a by-product of HCFC-22 production. HFC-23 is also unique in that it has a substantially longer atmospheric lifetime and higher GWP than nearly all other HFCs. As a result, the Kigali Amendment includes different control schedules for HFC-23 production than for other HFCs. To date, HFC-23 emissions have been partially abated in developed countries through regulations or voluntary measures and in developing countries with assistance from the UNFCCC’s Clean Development Mechanism (CDM)

Hydrofluorocarbons (HFCs)

The Montreal Protocol is an international agreement designed to heal the ozone layer. It outlines schedules for the phase-out of ozone-depleting substances (ODSs) such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), chlorinated solvents, halons, and methyl bromide. As a result of this phase-out, alternative chemicals and procedures were developed by industry for use in many applications including refrigeration, air-conditioning, foam-blowing, electronics, medicine, agriculture, and fire protection. Hydrofluorocarbons (HFCs) were used as ODS alternatives in many of these applications because they were suitable substitutes and they do not contain ozone-depleting chlorine or bromine; in addition, most HFCs have smaller climate impacts per molecule than the most widely used ODSs they replaced. Long-lived HFCs, CFCs, and HCFCs, however, are all potent greenhouse gases, and concerns were raised that uncontrolled future use of HFCs would lead to substantial climate warming. As a result of these concerns, HFCs were included as one group of greenhouse gases for which emissions controls were adopted by the 1997 Kyoto Protocol under the 1992 United Nations Framework Convention on Climate Change (UNFCCC). Consequently, developed countries (those listed in Annex I to this Convention, or “Annex I” Parties) supply annual emission estimates of HFCs to the UNFCCC. Since the Kyoto Protocol only specified limits on the sum of all controlled greenhouse gases, emissions of HFCs were not explicitly controlled. However, following the Kyoto Protocol, some countries enacted additional controls specifically limiting HFC use based on their global warming potentials (GWPs). Ultimately the Kigali Amendment to the Montreal Protocol was agreed upon in 2016, and this Amendment supplies schedules for limiting the production and consumption of specific HFCs. Although the radiative forcing supplied by HFCs is currently small, this Amendment was designed to ensure that the radiative forcing from HFCs will not grow uncontrollably in the future. The Kigali Amendment will come into force at the start of 2019. HFC concentrations are currently monitored through atmospheric measurements. All HFCs with large abundances are monitored, as are most with small abundances. Most HFCs that are emitted to the atmosphere are intentionally produced for use in a variety of applications that were once dependent on ODSs. An exception is HFC-23, which is emitted to the atmosphere primarily as a by-product of HCFC-22 production. HFC-23 is also unique in that it has a substantially longer atmospheric lifetime and higher GWP than nearly all other HFCs. As a result, the Kigali Amendment includes different control schedules for HFC-23 production than for other HFCs. To date, HFC-23 emissions have been partially abated in developed countries through regulations or voluntary measures and in developing countries with assistance from the UNFCCC’s Clean Development Mechanism (CDM)

Investigating stratospheric changes between 2009 and 2018 with halogenated trace gas data from aircraft, AirCores, and a global model focusing on CFC-11

We present new observations of trace gases in the stratosphere based on a cost-effective sampling technique that can access much higher altitudes than aircraft. The further development of this method now provides detection of species with abundances in the parts per trillion (ppt) range and below. We obtain mixing ratios for six gases (CFC-11, CFC-12, HCFC-22, H-1211, H-1301, and SF6), all of which are important for understanding stratospheric ozone depletion and circulation. After demonstrating the quality of the data through comparisons with ground-based records and aircraft-based observations, we combine them with the latter to demonstrate its potential. We first compare the data with results from a global model driven by three widely used meteorological reanalyses. Secondly, we focus on CFC-11 as recent evidence has indicated renewed atmospheric emissions of that species relevant on a global scale. Because the stratosphere represents the main sink region for CFC-11, potential changes in stratospheric circulation and troposphere-stratosphere exchange fluxes have been identified as the largest source of uncertainty for the accurate quantification of such emissions. Our observations span over a decade (up until 2018) and therefore cover the period of the slowdown of CFC-11 global mixing ratio decreases measured at the Earth's surface. The spatial and temporal coverage of the observations is insufficient for a global quantitative analysis, but we do find some trends that are in contrast with expectations, indicating that the stratosphere may have contributed to the slower concentration decline in recent years. Further investigating the reanalysis-driven model data, we find that the dynamical changes in the stratosphere required to explain the apparent change in tropospheric CFC-11 emissions after 2013 are possible but with a very high uncertainty range. This is partly caused by the high variability of mass flux from the stratosphere to the troposphere, especially at timescales of a few years, and partly by large differences between runs driven by different reanalysis products, none of which agree with our observations well enough for such a quantitative analysis

International Comparison of a Hydrocarbon Gas Standard at the Picomol per Mol Level

Studies of climate change increasingly recognize the diverse influences of hydrocarbons in the atmosphere, including roles in particulates and ozone formation. Measurements of key nonmethane hydrocarbons (NMHCs) suggest atmospheric mole fractions ranging from low picomoles per mol (ppt) to nanomoles per mol (ppb), depending on location and compound. To accurately establish mole fraction trends and to relate measurement records from many laboratories and researchers, it is essential to have accurate, stable, calibration standards. In February of 2008, the National Institute of Standards and Technology (NIST) developed and reported on picomoles per mol standards containing 18 nonmethane hydrocarbon compounds covering the mole fraction range of 60 picomoles per mol to 230 picomoles per mol. The stability of these gas mixtures was only characterized over a short time period (2 to 3 months). NIST recently prepared a suite of primary standard gas mixtures by gravimetric dilution to ascertain the stability of the 2008 picomoles per mol NMHC standards suite. The data from this recent chromatographic intercomparison of the 2008 to the 2011 suites confirm a much longer stability of almost 5 years for 15 of the 18 hydrocarbons; the double-bonded alkenes of propene, isobutene, and 1-pentene showed instability, in line with previous publications. The agreement between the gravimetric values from preparation and the analytical mole fractions determined from regression illustrate the internal consistency of the suite within ±2 pmol/mol. However, results for several of the compounds reflect stability problems for the three double-bonded hydrocarbons. An international intercomparison on one of the 2008 standards has also been completed. Participants included National Metrology Institutes, United States government laboratories, and academic laboratories. In general, results for this intercomparison agree to within about ±5% with the gravimetric mole fractions of the hydrocarbons