An improved estimate for the delta C-13 and delta O-18 signatures of carbon monoxide produced from atmospheric oxidation of volatile organic compounds

Atmospheric carbon monoxide (CO) is a key player in global atmospheric chemistry and a regulated pollutant in urban areas. Oxidation of volatile organic compounds (VOCs) is an important component of the global CO budget and has also been hypothesized to contribute substantially to the summertime urban CO budget. In principle, stable isotopic analysis of CO could constrain the magnitude of this source. However, the isotopic signature of VOC-produced CO has not been well quantified, especially for the oxygen isotopes. We performed measurements of CO stable isotopes on air samples from two sites around Indianapolis, US, over three summers to investigate the isotopic signature of VOC-produced CO. One of the sites is located upwind of the city, allowing us to quantitatively remove the background air signal and isolate the urban CO enhancements. as well as the isotopic signature of these enhancements. In addition, we use measurements of &Delta;14CO2 in combination with the CO:CO2 emission ratio from fossil fuels to constrain the fossil-fuel-derived CO and thereby isolate the VOC-derived component of the CO enhancement. Combining these measurements and analyses, we are able to determine the carbon and oxygen isotopic signatures of CO derived from VOC oxidation as &minus;32.8&permil;&plusmn;0.5&permil; and 3.6&thinsp;&permil;&plusmn;1.2&thinsp;&permil;, respectively. Additionally, we analyzed CO stable isotopes for 1 year at Beech Island, South Carolina, US, a site thought to have large VOC-derived contributions to the summertime CO budget. The Beech Island results are consistent with isotopic signatures of VOC-derived CO determined from the Indianapolis data. This study represents the first direct determination of the isotopic signatures of VOC-derived CO and will allow for improved use of isotopes in constraining the global and regional CO budgets.</p

Using ice core measurements from Taylor Glacier, Antarctica, to calibrate in situ cosmogenic 14 C production rates by muons

Cosmic rays entering the Earth’s atmosphere produce showers of secondary particles such as protons, neutrons, and muons. The interaction of these particles with oxygen-16 (16O) in minerals such as ice and quartz can produce carbon-14 (14C). In glacial ice, 14C is also incorporated through trapping of 14C-containing atmospheric gases (14CO2, 14CO, and 14CH4). Understanding the production rates of in situ cosmogenic 14C is important to deconvolve the in situ cosmogenic and atmospheric 14C signals in ice, both of which contain valuable paleoenvironmental information. Unfortunately, the in situ 14C production rates by muons (which are the dominant production mechanism at depths of > 6m solid ice equivalent) are uncertain. In this study, we use measurements of in situ 14C in ancient ice (> 50 ka) from the Taylor Glacier, an ablation site in Antarctica, in combination with a 2D ice flow model to better constrain the compound-specific rates of 14C production by muons and the partitioning of in situ 14C between CO2, CO, and CH4. Our measurements show that 33.7% (11.4%; 95% confidence interval) of the produced cosmogenic 14C forms 14CO and 66.1% (11.5%; 95% confidence interval) of the produced cosmogenic 14C forms 14CO2. 14CH4 represents a very small fraction (< 0.3%) of the total. Assuming that the majority of in situ muogenic 14C in ice forms 14CO2, 14CO, and 14CH4, we also calculated muogenic 14C production rates that are lower by factors of 5.7 (3.6–13.9; 95% confidence interval) and 3.7 (2.0–11.9; 95% confidence interval) for negative muon capture and fast muon interactions, respectively, when compared to values determined in quartz from laboratory studies (Heisinger et al., 2002a, b) and in a natural setting (Lupker et al., 2015). This apparent discrepancy in muogenic 14C production rates in ice and quartz currently lacks a good explanation and requires further investigation

Projections of hydrofluorocarbon (HFC) emissions and the resulting global warming based on recent trends in observed abundances and current policies

The emissions of hydrofluorocarbons (HFCs) have increased significantly in the past 2 decades, primarily as a result of the phaseout of ozone-depleting substances under the Montreal Protocol and the use of HFCs as their replacements. In 2015, large increases were projected in HFC use and emissions in this century in the absence of regulations, contributing up to 0.5° C to global surface warming by 2100. In 2019, the Kigali Amendment to the Montreal Protocol came into force with the goal of limiting the use of HFCs globally, and currently, regulations to limit the use of HFCs are in effect in several countries. Here, we analyze trends in HFC emissions inferred from observations of atmospheric abundances and compare them with previous projections. Total CO2eq. inferred HFC emissions continue to increase through 2019 (to about 0.8 GtCO2eq.yr-1) but are about 20 % lower than previously projected for 2017-2019, mainly because of the lower global emissions of HFC-143a. This indicates that HFCs are used much less in industrial and commercial refrigeration (ICR) applications than previously projected. This is supported by data reported by the developed countries and the lower reported consumption of HFC-143a in China. Because this time period preceded the beginning of the Kigali provisions, this reduction cannot be linked directly to the provisions of the Kigali Amendment. However, it could indicate that companies transitioned away from the HFC-143a with its high global warming potential (GWP) for ICR applications in anticipation of national or global mandates. There are two new HFC scenarios developed based (1) on current trends in HFC use and Kigali-independent (K-I) control policies currently existing in several countries and (2) current HFC trends and compliance with the Kigali Amendment (KA-2022). These current policies reduce projected emissions in 2050 from the previously calculated 4.0-5.3 GtCO2eq.yr-1 to 1.9-3.6 GtCO2eq.yr-1. The added provisions of the Kigali Amendment are projected to reduce the emissions further to 0.9-1.0 GtCO2eq.yr-1 in 2050. Without any controls, projections suggest a HFC contribution of 0.28-0.44° C to global surface warming by 2100, compared to a temperature contribution of 0.14-0.31° C that is projected considering the national K-I policies current in place. Warming from HFCs is additionally limited by the Kigali Amendment controls to a contribution of about 0.04°C by 2100

Carbon monoxide isotopic measurements in Indianapolis constrain urban source isotopic signatures and support mobile fossil fuel emissions as the dominant wintertime CO source

We present measurements of CO mole fraction and CO stable isotopes (δ13CO and δC18O) in air during the winters of 2013–14 and 2014–15 at tall tower sampling sites in and around Indianapolis, USA. A tower located upwind of the city was used to quantitatively remove the background CO signal, allowing for the first unambiguous isotopic characterization of the urban CO source and yielding 13CO of –27.7 ± 0.5‰ VPDB and C18O of 17.7 ± 1.1‰ VSMOW for this source. We use the tower isotope measurements, results from a limited traffic study, as well as atmospheric reaction rates to examine contributions from different sources to the Indianapolis CO budget. Our results are consistent with earlier findings that traffic emissions are the dominant source, suggesting a contribution of 96% or more to the overall Indianapolis wintertime CO emissions. Our results are also consistent with the hypothesis that emissions from a small fraction of vehicles without functional catalytic systems dominate the Indianapolis CO budget

Projections of hydrofluorocarbon (HFC) emissions and the resulting global warming based on recent trends in observed abundances and current policies:Atmospheric Chemistry and Physics

The emissions of hydrofluorocarbons (HFCs) have increased significantly in the past 2 decades, primarily as a result of the phaseout of ozone-depleting substances under the Montreal Protocol and the use of HFCs as their replacements. In 2015, large increases were projected in HFC use and emissions in this century in the absence of regulations, contributing up to 0.5° C to global surface warming by 2100. In 2019, the Kigali Amendment to the Montreal Protocol came into force with the goal of limiting the use of HFCs globally, and currently, regulations to limit the use of HFCs are in effect in several countries. Here, we analyze trends in HFC emissions inferred from observations of atmospheric abundances and compare them with previous projections. Total CO2eq. inferred HFC emissions continue to increase through 2019 (to about 0.8 GtCO2eq.yr-1) but are about 20 % lower than previously projected for 2017-2019, mainly because of the lower global emissions of HFC-143a. This indicates that HFCs are used much less in industrial and commercial refrigeration (ICR) applications than previously projected. This is supported by data reported by the developed countries and the lower reported consumption of HFC-143a in China. Because this time period preceded the beginning of the Kigali provisions, this reduction cannot be linked directly to the provisions of the Kigali Amendment. However, it could indicate that companies transitioned away from the HFC-143a with its high global warming potential (GWP) for ICR applications in anticipation of national or global mandates. There are two new HFC scenarios developed based (1) on current trends in HFC use and Kigali-independent (K-I) control policies currently existing in several countries and (2) current HFC trends and compliance with the Kigali Amendment (KA-2022). These current policies reduce projected emissions in 2050 from the previously calculated 4.0-5.3 GtCO2eq.yr-1 to 1.9-3.6 GtCO2eq.yr-1. The added provisions of the Kigali Amendment are projected to reduce the emissions further to 0.9-1.0 GtCO2eq.yr-1 in 2050. Without any controls, projections suggest a HFC contribution of 0.28-0.44° C to global surface warming by 2100, compared to a temperature contribution of 0.14-0.31° C that is projected considering the national K-I policies current in place. Warming from HFCs is additionally limited by the Kigali Amendment controls to a contribution of about 0.04°C by 2100

Global Climate

In 2021, both social and economic activities began to return towards the levels preceding the COVID-19 pandemic for some parts of the globe, with others still experiencing restrictions. Meanwhile, the climate has continued to respond to the ongoing increase in greenhouse gases and resulting warming. La Niña, a phenomenon which tends to depress global temperatures while changing rainfall patterns in many regions, prevailed for all but two months of the year. Despite this, 2021 was one of the six-warmest years on record as measured by global mean surface temperature with an anomaly of between +0.21° and +0.28°C above the 1991–2020 climatology. Lake surface temperatures were their highest on record during 2021. The number of warm days over land also reached a new record high. Exceptional heat waves struck the Pacific Coast of North America, leading to a new Canadian maximum temperature of 49.6°C at Lytton, British Columbia, on 29 June, breaking the previous national record by over 4°C. In Death Valley, California, the peak temperature reached 54.4°C on 9 July, equaling the temperature measured in 2020, and the highest temperature recorded anywhere on the globe since at least the 1930s. Over the Mediterranean, a provisional new European record of 48.8°C was set in Sicily on 11 August. In the atmosphere, the annual mean tropospheric temperature was among the 10 highest on record, while the stratosphere continued to cool. While La Niña was present except for June and July, likely influencing Australia’s coolest year since 2012 and wettest since 2016, other modes of variability played important roles. A negative Indian Ocean dipole event became established during July, associated with a warmer east and cooler west Indian Ocean. Northern Hemisphere winters were affected by a negative phase of the North Atlantic Oscillation at both the beginning and end of 2021. In the Southern Hemisphere, a very strong positive Southern Annular Mode (also known as the Antarctic Oscillation) contributed to New Zealand’s record warm year and to very cold temperatures over Antarctica. Land surface winds continued a slow reversal from the multi-decadal stilling, and over the ocean wind speeds were at their highest in almost a decade. La Niña conditions had a clear influence on the regional patterns of many hydrological variables. Surface specific humidity and total column water vapor over land and ocean were higher than average in almost all datasets. Relative humidity over land reached record or near-record low saturation depending on the dataset, but with mixed signals over the ocean. Satellite measurements showed that 2021 was the third cloudiest in the 19-year record. The story for precipitation was mixed, with just below-average mean precipitation falling over land and below-average mean precipitation falling over the ocean, while extreme precipitation was generally more frequent, but less intense, than average. Differences between means and extremes can be due to several factors, including using different indices, observing periods, climatological base reference periods, and levels of spatial completeness. The sharp increase in global drought area that began in mid-2019 continued in 2021, reaching a peak in August with 32% of global land area experiencing moderate or worse drought, and declining slightly thereafter. Arctic permafrost temperatures continued to rise, reaching record values at many sites, and the thickness of the layer which seasonally thaws and freezes also increased over 2020 values in a number of regions. It was the 34th-consecutive year of mass balance loss for alpine glaciers in mountainous regions, with glaciers on average 25 m thinner than in the late 1970s. And the duration of lake ice in the Northern Hemisphere was the fourth lowest in situ record dating back to 1991. The atmospheric concentrations of the major long-lived greenhouse gases, CO2, CH4, and N2O, all reached levels not seen in at least the last million years and grew at near-record rates in 2021. La Niña conditions did not appear to have any appreciable impact on their growth rates. The growth rate for CH4, of 17 ppb yr−1, was similar to that for 2020 and set yet another record, although the causes for this post-2019 acceleration are unknown presently. Overall, CO2 growth continues to dominate the increase in global radiative forcing, which increased from 3.19 to 3.23 W m−2 (watts per square meter) during the year. In 2021, stratospheric ozone did not exhibit large negative anomalies, especially near the poles, unlike 2020, where large ozone depletions appeared, mainly from dynamical effects. The positive impact of reductions in emissions of ozone depleting substances can be seen most clearly in the upper stratosphere, where such dynamical effects are less pronounced. It was the fourth-lowest fire year since global records began in 2003, though extreme regional fire activity was again seen in North America and also in Siberia; as in 2020, the effects of wildfires in these two regions led to locally large regional positive anomalies in tropospheric aerosol and carbon monoxide abundance. Vegetation is responding to the higher global mean temperatures, with the satellite-derived measures for the Northern Hemisphere for 2021 rated among the earliest starts of the growing season and the latest end of the season on record. The first bloom date for cherry trees in Kyoto, Japan, broke a 600-year record set in 1409. This year we welcome a sidebar on the global distribution of lightning, which has been recently declared an essential climate variable (ECV) by the Global Climate Observing System (GCOS). Time series and anomaly maps from many of the variables described in this chapter can be found in Plates 1.1 and 2.1. As with other chapters, many of the sections have moved from the previous 1981–2010 to the new 1991–2020 climatological reference period, in line with WMO recommendations (see Chapter 1). This is not possible for all datasets, as it is dependent on their length of record or legacy processing methods. While anomalies from the new climatology period are not so easily comparable with previous editions of this report, they more clearly highlight deviations from more recent conditions