Increase in global emissions of HFC-23 despite near-total expected reductions.

Under the Kigali Amendment to the Montreal Protocol, new controls are being implemented to reduce emissions of HFC-23 (CHF[Formula: see text]), a by-product during the manufacture of HCFC-22 (CHClF[Formula: see text]). Starting in 2015, China and India, who dominate global HCFC-22 production (75% in 2017), set out ambitious programs to reduce HFC-23 emissions. Here, we estimate that these measures should have seen global emissions drop by 87% between 2014 and 2017. Instead, atmospheric observations show that emissions have increased and in 2018 were higher than at any point in history (15.9 [Formula: see text]). Given the magnitude of the discrepancy between expected and observation-inferred emissions, it is likely that the reported reductions have not fully materialized or there may be substantial unreported production of HCFC-22, resulting in unaccounted-for HFC-23 by-product emissions. The difference between reported and observation-inferred estimates suggests that an additional ~309 Tg [Formula: see text]-equivalent emissions were added to the atmosphere between 2015 and 2017.

Increase in CFC-11 emissions from eastern China based on atmospheric observations.

The recovery of the stratospheric ozone layer relies on the continued decline in the atmospheric concentrations of ozone-depleting gases such as chlorofluorocarbons1. The atmospheric concentration of trichlorofluoromethane (CFC-11), the second-most abundant chlorofluorocarbon, has declined substantially since the mid-1990s2. A recently reported slowdown in the decline of the atmospheric concentration of CFC-11 after 2012, however, suggests that global emissions have increased3,4. A concurrent increase in CFC-11 emissions from eastern Asia contributes to the global emission increase, but the location and magnitude of this regional source are unknown3. Here, using high-frequency atmospheric observations from Gosan, South Korea, and Hateruma, Japan, together with global monitoring data and atmospheric chemical transport model simulations, we investigate regional CFC-11 emissions from eastern Asia. We show that emissions from eastern mainland China are 7.0 ± 3.0 (±1 standard deviation) gigagrams per year higher in 2014-2017 than in 2008-2012, and that the increase in emissions arises primarily around the northeastern provinces of Shandong and Hebei. This increase accounts for a substantial fraction (at least 40 to 60 per cent) of the global rise in CFC-11 emissions. We find no evidence for a significant increase in CFC-11 emissions from any other eastern Asian countries or other regions of the world where there are available data for the detection of regional emissions. The attribution of any remaining fraction of the global CFC-11 emission rise to other regions is limited by the sparsity of long-term measurements of sufficient frequency near potentially emissive regions. Several considerations suggest that the increase in CFC-11 emissions from eastern mainland China is likely to be the result of new production and use, which is inconsistent with the Montreal Protocol agreement to phase out global chlorofluorocarbon production by 2010.

Continued Emissions of the Ozone-Depleting Substance Carbon Tetrachloride From Eastern Asia.

Carbon tetrachloride (CCl4) is an ozone-depleting substance, accounting for about 10% of the chlorine in the troposphere. Under the terms of the Montreal Protocol, its production for dispersive uses was banned from 2010. In this work we show that, despite the controls on production being introduced, CCl4 emissions from the eastern part of China did not decline between 2009 and 2016. This finding is in contrast to a recent bottom-up estimate, which predicted a significant decrease in emissions after the introduction of production controls. We find eastern Asian emissions of CCl4 to be 16 (9-24) Gg/year on average between 2009 and 2016, with the primary source regions being in eastern China. The spatial distribution of emissions that we derive suggests that the source distribution of CCl4 in China changed during the 8-year study period, indicating a new source or sources of emissions from China's Shandong province after 2012.

Observational evidence for interhemispheric hydroxyl-radical parity.

The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane. It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4, 7-10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004-2011 the model predicts an annual mean NH-SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 ± 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns. Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated.

Net emissions of CH4 and CO2 in Alaska: implications for the region's greenhouse gas budget.

We used a biogeochemistry model, the Terrestrial Ecosystem Model (TEM), to study the net methane (CH4) fluxes between Alaskan ecosystems and the atmosphere. We estimated that the current net emissions of CH4 (emissions minus consumption) from Alaskan soils are approximately 3 Tg CH4/yr. Wet tundra ecosystems are responsible for 75% of the region's net emissions, while dry tundra and upland boreal forests are responsible for 50% and 45% of total consumption over the region, respectively. In response to climate change over the 21st century, our simulations indicated that CH4 emissions from wet soils would be enhanced more than consumption by dry soils of tundra and boreal forests. As a consequence, we projected that net CH4 emissions will almost double by the end of the century in response to high-latitude warming and associated climate changes. When we placed these CH4 emissions in the context of the projected carbon budget (carbon dioxide [CO2] and CH4) for Alaska at the end of the 21st century, we estimated that Alaska will be a net source of greenhouse gases to the atmosphere of 69 Tg CO2 equivalents/yr, that is, a balance between net methane emissions of 131 Tg CO2 equivalents/yr and carbon sequestration of 17 Tg C/yr (62 Tg CO2 equivalents/yr).

Climate change. Uncertainty and climate change assessments.

Clear and quantitative discussion of uncertainties is critical for public policy making on climate change. The recently completed report of the Intergovernmental Panel on Climate Change assessed the uncertainty in its findings and forecasts. The uncertainty assessment process of the IPCC should be improved in the future by using a consistent approach to quantifying uncertainty, focusing the quantification on the few key results most important for policy making. The uncertainty quantification procedure should be fully documented, and if expert judgment is used, a specific list of the experts consulted should be included.

Evidence for substantial variations of atmospheric hydroxyl radicals in the past two decades.

The hydroxyl radical (OH) is the dominant oxidizing chemical in the atmosphere. It destroys most air pollutants and many gases involved in ozone depletion and the greenhouse effect. Global measurements of 1,1,1-trichloroethane (CH3CCl3, methyl chloroform) provide an accurate method for determining the global and hemispheric behavior of OH. Measurements show that CH3CCl3 levels rose steadily from 1978 to reach a maximum in 1992 and then decreased rapidly to levels in 2000 that were lower than the levels when measurements began in 1978. Analysis of these observations shows that global OH levels were growing between 1978 and 1988, but the growth rate was decreasing at a rate of 0.23 +/- 0.18% year(-2), so that OH levels began declining after 1988. Overall, the global average OH trend between 1978 and 2000 was -0.64 +/- 0.60% year(-1). These variations imply important and unexpected gaps in current understanding of the capability of the atmosphere to cleanse itself.

Atmospheric Trends and Lifetime of CH3CCI3 and Global OH Concentrations.

Determination of the atmospheric concentrations and lifetime of trichloroethane (CH(3)CCI(3)) is very important in the context of global change. This halocarbon is involved in depletion of ozone, and the hydroxyl radical (OH) concentrations determined from its lifetime provide estimates of the lifetimes of most other hydrogen-containing gases involved in the ozone layer and climate. Global measurements of trichloroethane indicate rising concentrations before and declining concentrations after late 1991. The lifetime of CH(3)CCI(3) in the total atmosphere is 4.8 +/- 0.3 years, which is substantially lower than previously estimated. The deduced hydroxyl radical concentration, which measures the atmosphere's oxidizing capability, shows little change from 1978 to 1994.

Global atmospheric chemistry of CFC-123.

THE compound 1,1-dichloro-2,2,2-trifluoroethane (CFC-123), which is potentially usable as a foam-blowing agent in the plastics industry, an aerosol propellant and a refrigerant, has been proposed as an industrial substitute for trichlorofluoromethane (CFC-11), the use of which is increasingly restricted because of its effects on the ozone layer and on climate(1-3). It is expected that CFC-123, although like CFC-11 an absorber of infrared radiation, will be less stable in the atmosphere because of its expected reaction with OH radicals in the troposphere. Using a three-dimensional global model of the atmosphere, we have calculated the chemical destruction rates of CFC-123 by various processes, confirming that the chief sink is destruction by OH radicals below 12 km, which accounts for 88% of its loss. The calculated destruction rate is greatest in the equatorial region below 2 km. The calculated steady-state lifetime of CFC-123 is 1.5 years, based on the best available estimate of the rate constant of the reaction with OH. This lifetime is very much shorter than that of CFC-11, the destruction of which is largely confined to the stratosphere. For equal rates (by mass) of CFC-123 and CFC-11 emission to the atmosphere, the molar content in the atmosphere and the injection rate of chlorine into the stratosphere are, respectively, 48 and 14 times greater for CFC-11 than for CFC-123 in steady-state.

Chemical effects of large impacts on the Earth's primitive atmosphere.

Intense bombardment of the moon and terrestrial planets approximately 3.9-4.0 x 10(9) years ago could have caused the chemical reprocessing of the Earth's primitive atmosphere. In particular, the shock heating and rapid quenching caused by the impact of large bodies into the atmosphere could produce molecules such as HCN and H2CO4 which are important precursors for the abiotic synthesis of complex organic molecules. Here we model the production of HCN and H2CO by thermochemical equilibrium and chemical kinetic calculations of the composition of shocked air parcels for a wide range of temperatures, pressures and initial compositions. For atmospheres with C/O > or = 1, our results suggest that bolide impacts cause HCN volume mixing ratios of approximately 10(-3) to 10(-5) in the impact region and global average ratios of 10(-5) to 10(-12). The corresponding H2CO mixing ratios in the impact region are 10(-7) to 10(-9); no-global mixing can occur, however, as H2CO is rapidly destroyed or rained out of the atmosphere within days to hours. Rainout to the oceans of 3-15% of the HCN produced can provide approximately (3-14) x 10(11) mol HCN per year. This is somewhat larger than other predicted sources of HCN and H2CO on the primitive Earth.

Venus winds are zonal and retrograde below the clouds.

Winds in the lower atmosphere of Venus, inferred from three-dimensional radio interferometric tracking of the descents of the Pioneer day and north probes, are predominantly easterly with speeds of about 1 meter per second near the surface, 50 meters per second at the bottom of the clouds, and more than 200 meters per second within the densest, middle cloud layer. Between about 25 and 55 kilometers altitude the average flow was slanted equatorward, with superimposed wavelike motions and alternating layers of high and low shear.

Wind velocities on venus: vector determination by radio interferometry.

To determine the wind directions and speeds on Venus, as each Pioneer probe fell to the surface we tracked its motion in three dimensions using a combination of Doppler and long-baseline radio interferometric methods. Preliminary results from this tracking, coupled with results from test observations of other spacecraft, enable us to estimate the uncertainties of our eventual determinations of the velocity vectors of the probes with respect to Venus. For altitudes below about 65 kilometers and with time-averaging over 100-second intervals, all three components of the velocity should have errors of the order of 0.3 meter per second or less.

Carbon monoxide on jupiter and implications for atmospheric convection.

A study of the equilibrium and disequilibrium thermochemistry of the recently discovered carbon monoxide on Jupiter suggests that the presence of this gas in the visible atmosphere is a direct result of very rapid upward mixing from levels in the deep atmosphere where the temperature is about 1100 degrees K and where carbon monoxide is thermodynamically much more stable. As a consequence the observed carbon monoxide mixing ratio is a sensitive function of the vertical eddy mixing coefficient. We infer a value for this latter coefficient which is about three to four orders of magnitude greater than that in the earth's troposphere. This result directly supports existing structural and dynamical theories implying very rapid convection in the deep Jovian atmosphere, driven by an internal heat source.

Venus: composition and structure of the visible clouds.

It is proposed that the visible cloud deck on Venus is composed of droplets of sulfuric acid. These are formed by the very rapid photooxidation of carbonyl sulfide in the upper atmosphere. The clouds are best described as an extensive haze since the predicted particulate scale height probably exceeds the gas scale height within the layer. The predicted mixing ratio for water is 10(-6) (lower limit), and for both carbonyl sulfide and sulfur dioxide it is 10(-7) (upper limit); these are in good agreement with observations. Gaps in the layer are not possible unless the planetary scale dynamics produce cloud turnover times of less than a few days. Under these conditions the water mixing ratio could approach 10(-4) and the formation of a thin hydrochloric acid haze at high altitude above the main cloud is possible.

Jupiter's Clouds: Structure and Composition.

Recent infrared radiometric observations of Jupiter have disclosed local temperatures in the North Equatorial Belt far in excess of those at the level of the solid ammonia clouds, and visual observations reveal an orange-brown coloration within this belt. We suggest that, in a multilayer cloud model, solar ultraviolet photolysis of hydrogen sulfide in regions where ammonia clouds are sparse or absent should lead to the production of substantial quantities of inorganic chromophores.