Emissions Of Chlorofluorocarbons Research Articles

The recovery of the Antarctic ozone layer and suggestions for addressing the global warming

The ozone layer is a critical shield for humanity, located in the Earths atmosphere with a high ozone concentration. Its primary role is to absorb and filter out the majority of harmful ultraviolet rays emitted by the sun, which pose a threat to all living beings. However, the ozone layer suffered from very severe depletion. To counteract this, the Montreal Convention was established in 1987, mandating a reduction in chlorofluorocarbon emissions by humans. Because of the environmental problem of ozone layer destruction for a long time, based on some existing research background at this stage, people find that the ozone layer is gradually recovering through observation of some data. In this essay, it explains the causal factors behind the depletion of the Antarctic ozone layer, as well as the various elements that contribute to its recovery and their respective levels of significance, through some research. Additionally, this essay explores how these models can be applied to address other environmental concerns. To achieve a more comprehensive understanding of this subject, this paper has conducted an intensive search through various academic references. In conclusion, through the use of balloon and satellite ozone data, a chemistry-climate model, and volcanic aerosol measurements, the healing of the Antarctic ozone layer is contributed by three factors: chemical reduction, kinetics, and temperature. Among these factors, chemical factors have the greatest contribution.

Acclimation of intertidal macroalgae Ulva prolifera to UVB radiation: the important role of alternative oxidase

BackgroundSolar radiation is primarily composed of ultraviolet radiation (UVR, 200 − 400 nm) and photosynthetically active radiation (PAR, 400 − 700 nm). Ultraviolet-B (UVB) radiation accounts for only a small proportion of sunlight, and it is the primary cause of plant photodamage. The use of chlorofluorocarbons (CFCs) as refrigerants caused serious ozone depletion in the 1980s, and this had led to an increase in UVB. Although CFC emissions have significantly decreased in recent years, UVB radiation still remains at a high intensity. UVB radiation increase is an important factor that influences plant physiological processes. Ulva prolifera, a type of macroalga found in the intertidal zone, is intermittently exposed to UVB. Alternative oxidase (AOX) plays an important role in plants under stresses. This research examines the changes in AOX activity and the relationships among AOX, photosynthesis, and reactive oxygen species (ROS) homeostasis in U. prolifera under changes in UVB and photosynthetically active radiation (PAR).ResultsUVB was the main component of solar radiation impacting the typical intertidal green macroalgae U. prolifera. AOX was found to be important during the process of photosynthesis optimization of U. prolifera due to a synergistic effect with non-photochemical quenching (NPQ) under UVB radiation. AOX and glycolate oxidase (GO) worked together to achieve NADPH homeostasis to achieve photosynthesis optimization under changes in PAR + UVB. The synergism of AOX with superoxide dismutase (SOD) and catalase (CAT) was important during the process of ROS homeostasis under PAR + UVB.ConclusionsAOX plays an important role in the process of photosynthesis optimization and ROS homeostasis in U. prolifera under UVB radiation. This study provides further insights into the response of intertidal macroalgae to solar light changes.

Stratospherically induced circulation changes under the extreme conditions of the no-Montreal-Protocol scenario

Abstract. The Montreal Protocol and its amendments (MPA) have been a huge success in preserving the stratospheric ozone layer from being destroyed by unabated chlorofluorocarbon (CFC) emissions. The phaseout of CFCs has not only prevented serious impacts on our health and climate, but also avoided strong alterations of atmospheric circulation patterns. With the Earth system model SOCOLv4, we study the dynamical and climatic impacts of a scenario with unabated CFC emissions by 2100, disentangling radiative and chemical (ozone-mediated) effects of CFCs. In the stratosphere, chemical effects of CFCs (i.e., the resulting ozone loss) are the main drivers of circulation changes, weakening wintertime polar vortices and speeding up the Brewer–Dobson circulation. These dynamical impacts during wintertime are due to low-latitude ozone depletion and the resulting reduction in the Equator-to-pole temperature gradient. Westerly winds in the lower stratosphere strengthen, which is for the Southern Hemisphere (SH) similar to the effects of the Antarctic ozone hole over the second half of the 20th century. Furthermore, the winter and spring stratospheric wind variability increases in the SH, whereas it decreases in summer and fall. This seasonal variation in wind speed in the stratosphere has substantial implications for the major modes of variability in the tropospheric circulation in the scenario without the MPA (No-MPA). We find coherent changes in the troposphere, such as patterns that are reminiscent of negative Southern and Northern Annular modes (SAM and NAM) and North Atlantic Oscillation (NAO) anomalies during seasons with a weakened vortex (winter and spring); the opposite occurs during seasons with strengthened westerlies in the lower stratosphere and troposphere (summer). In the troposphere, radiative heating by CFCs prevails throughout the year, shifting the SAM into a positive phase and canceling out the ozone-induced effects on the NAO, whereas the North Pacific sector shows an increase in the meridional sea-level pressure gradient as both CFC heating and ozone-induced effects reinforce each other there. Furthermore, global warming is amplified by 1.7 K with regionally up to a 12 K increase over eastern Canada and the western Arctic. Our study sheds light on the adverse effects of a non-adherence to the MPA on the global atmospheric circulation, uncovering the roles of the underlying physical mechanisms. In so doing, our study emphasizes the importance of the MPA for Earth's climate to avoid regional amplifications of negative climate impacts.

Antarctic ozone hole modifies iodine geochemistry on the Antarctic Plateau

Polar stratospheric ozone has decreased since the 1970s due to anthropogenic emissions of chlorofluorocarbons and halons, resulting in the formation of an ozone hole over Antarctica. The effects of the ozone hole and the associated increase in incoming UV radiation on terrestrial and marine ecosystems are well established; however, the impact on geochemical cycles of ice photoactive elements, such as iodine, remains mostly unexplored. Here, we present the first iodine record from the inner Antarctic Plateau (Dome C) that covers approximately the last 212 years (1800-2012 CE). Our results show that the iodine concentration in ice remained constant during the pre-ozone hole period (1800-1974 CE) but has declined twofold since the onset of the ozone hole era (~1975 CE), closely tracking the total ozone evolution over Antarctica. Based on ice core observations, laboratory measurements and chemistry-climate model simulations, we propose that the iodine decrease since ~1975 is caused by enhanced iodine re-emission from snowpack due to the ozone hole-driven increase in UV radiation reaching the Antarctic Plateau. These findings suggest the potential for ice core iodine records from the inner Antarctic Plateau to be as an archive for past stratospheric ozone trends.

Land-atmosphere fluxes and concentrations of CFC-11 and CFC-12 based on in situ observations from a coastal salt marsh in eastern China: Implications for CFC remediation

Regional- and national-scale emissions of chlorofluorocarbons (CFCs), especially in Eastern China, are of great concern to environmentalists and policy makers. To determine the source-sink dynamics of coastal salt marshes for CFC-11 and CFC-12 in the local atmosphere, we studied a coastal salt marsh in Northern Jiangsu Province, taking measurements of the atmospheric concentrations and fluxes of CFC-11 and CFC-12 using static flux chambers in August (growing season) and December (non-growing season) of 2013, and along both creek-side and vegetated transects.We observed unexpectedly high concentrations of CFC-11 (676.5 × 10−12) and CFC-12 (794.6 × 10−12) in the salt marsh in 2013, with predominantly non-local emissions. Overall, the study salt marsh acted as a net sink for CFC-11 and CFC-12, with the average flux ranging from −11.4 μg m−2 h−1 to 5.0 μg m−2 h−1 for CFC-11 and from −7.4 μg m−2 h−1 to 0.7 μg m−2 h−1 for CFC-12. This clearly indicates that the high concentrations of CFC-11 and CFC-12 measured in the atmosphere were not caused by local emissions; terrigenous sources most likely act as the main exogenous input pathway. Our study suggests that salt marsh ecosystems may be worthy of attention as sinks for CFC-11 and CFC-12; as such, the ecological restoration of salt marshes is critical to better offset increasing CFC-11 and CFC-12 emissions.

Dual roles of reactive oxygen species in intertidal macroalgae Ulva prolifera under ultraviolet-B radiation

Ultraviolet-B (280−320 nm wavelength; UV-B) is one of the important reactive oxygen species (ROS) production factors in plants. The use of chlorofluorocarbons (CFCs) as refrigerants or propellants caused a serious depletion of ozone in the 1980s, which led to an increase of UV-B. Although the emissions of CFCs have decreased significantly in recent years, the ozone layer will not recover soon. The slow recovery of the ozone causes the slow decrease of UV-B intensity, and the intensity of UV-B varies with time and weather throughout the day. In the present study, typical intertidal macroalgae Ulva prolifera was exposed to moderate and extreme UV-B radiation (1 W m-2 and 5 W m-2), and the production and roles of ROS in U. prolifera under UV-B are discussed. The results are as follows: 1) ROS were mainly produced in the chloroplast under moderate UV-B radiation (1 W m-2). ROS played the signaling molecule function and led the secondary signaling pathways during this process. 2) Excessive ROS were produced in both the chloroplast and peroxisome. OH caused irreversible damage to the thalli exposed to 5 W m−2 radiation. Overall, these novel results support the idea of dual roles of ROS in U. prolifera under UV-B radiation (signaling molecules and oxidative damage). Moreover, they further highlight the role of photosynthesis in the production of ROS under UV-B.

Influence of post-annealing, defect chemistry and high pressure on the magnetocaloric effect of non-stoichiometric La0.8-xK0.2Mn1+xO3 compounds

In view of the need to limit harmful emissions of chlorofluorocarbons into the atmosphere and sharp increase in life support areas that require cooling, the search for new magnetocaloric materials is very urgent at the present time. In this work, we suggest the ways for improving the magnetocaloric properties of the promising La0.8-xK0.2Mn1+xO3 (0 ≤ x ≤ 0.2) perovskites and compare the functional properties of nanocrystalline samples of about 40 nm with polycrystalline samples of about 1 μm. The structure, morphology, magnetic properties and magnetocaloric effect of these compounds were studied as a function of manganese doping level. The main crystalline phase of all samples is a rhombohedral R3‾c perovskite structure. The maximum doping level of excess manganese for preserving single-phase structure of the nanocrystalline La0.8-xK0.2Mn1+xO3 compounds is x = 0.10. As x increases the Curie temperature TC is increased slightly. The best composition with the highest entropy change ΔSMmax = −3.629 J/(kg⋅K) under 3 T at TC = 332 K is the La0.8-xK0.2Mn1+xO3 with x = 0.05. On the other hand, the La0.8-xK0.2Mn1+xO3 polycrystalline manganite with x = 0.10 exhibits the highest ΔSMmax = −4.176 J/(kg⋅K) under 3 T at TC = 274 K. Additionally, the effect of hydrostatic pressure P up to 1.4 GPa has been investigated for the La0.7K0.2Mn1.1O3 polycrystalline sample that leads to increasing TC to 287 K and reducing ΔSMmax to −3.145 J/(kg⋅K) under 3 T. The obtained results demonstrate the ways for controlling magnetocaloric properties of the La0.8-xK0.2Mn1+xO3 compounds under internal and external conditions.

Joint inference of CFC lifetimes and banks suggests previously unidentified emissions

Chlorofluorocarbons (CFCs) are harmful ozone depleting substances and greenhouse gases. CFC production was phased-out under the Montreal Protocol, however recent studies suggest new and unexpected emissions of CFC-11. Quantifying CFC emissions requires accurate estimates of both atmospheric lifetimes and ongoing emissions from old equipment (i.e. ‘banks’). In a Bayesian framework we simultaneously infer lifetimes, banks and emissions of CFC-11, 12 and 113 using available constraints. We find lifetimes of all three gases are likely shorter than currently recommended values, suggesting that best estimates of inferred emissions are larger than recent evaluations. Our analysis indicates that bank emissions are decreasing faster than total emissions, and we estimate new, unexpected emissions during 2014-2016 were 23.2, 18.3, and 7.8 Gg/yr for CFC-11, 12 and 113, respectively. While recent studies have focused on unexpected CFC-11 emissions, our results call for further investigation of potential sources of emissions of CFC-12 and CFC-113, along with CFC-11.

The atmospheric concentrations and emissions of major halocarbons in China during 2009–2019

Due to the characteristics of ozone-depleting and high global warming potential, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) have been restricted by the Montreal Protocol and its amendments over the world. Considering that China is one of the main contributors to the emission of halocarbons, a long-term atmospheric observation on major substances including CFC-11 (CCl3F), CFC-12 (CCl2F2), HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HFC-134a (CH2FCF3) was conducted in five cities (Beijing, Hangzhou, Guangzhou, Lanzhou and Chengdu) of China during 2009–2019. The atmospheric concentrations of CFC-11, CFC-12, HCFC-141b and HCFC-142b all showed declining trends on the whole while those of HCFC-22 and HFC-134a were opposite. A paired sample t-test showed that the ambient mixing ratios of HCFC-22 and HFC-134a in cities were 41.9% and 25.7% higher on average than those in suburban areas, respectively, while the other substances did not show significant regional differences. The annual emissions of halocarbons were calculated using an interspecies correlation method and the results were generally consistent with the published estimates. Discrepancies between bottom-up inventories and the estimates in this study for CFCs emissions were found. Among the most consumed ozone depleting substances (ODSs) in China, CFCs accounted for 75.1% of the ozone depletion potential (ODP)-weighted emissions while HCFCs contributed a larger proportion (58.6%) of CO2-equivalent emissions in 2019. China's emissions of HCFC-141b and HCFC-142b contributed the most to the global emission (17.8%–48.0%). The elimination of HCFCs in China will have a crucial impact on the HCFCs phase-out in the world.

CFCs measurements at high altitudes in northern China during 2017–2018: Concentrations and potential emission source regions

Northern China was simulated as the main contributor to global chlorofluorocarbon (CFCs) that slowed down the recovery of stratospheric ozone layer in most recent studies. An atmospheric campaign was carried out from June 2017 to April 2018 to register the concentrations of typical chlorofluorocarbons (CFCs) (i.e., CFC-11, CFC-12, CFC-113, and CFC-114) at the top of Mount Tai, northern China. The mixing ratios of CFC-11 CFC-12, CFC-113, and CFC-114 were 257, 577, 80, and 18 pptv, respectively. These values are similar to the reported data 10 years ago at Mount Tai. CFC concentrations correlated well with those of benzene (an anthropogenic tracer) and were not affected by either humidity, temperature, or solar radiation. However, CFC concentrations were considerably influenced by regional transport: their backward trajectory and the PSCF (potential source contribution function) analysis suggested that higher concentrations (CFC-12, CFC-113 and CFC-114) were detected under the influence of air mass from the industrial regions in mid-eastern China and CFC-11 was through long-range transport from northwestern (i.e., from the higher atmosphere in western China) air masses. Overall, the findings of this study suggested that CFCs still have emissions in China, but no significant increase in recent years. Mid-eastern China might be responsible for the CFC emissions. The conclusions also highlight the need for the enforcement of effective control policies and the management of emissions, in order to avoid increasingly severe scenarios.

The discovery of the Antarctic ozone hole

To celebrate its 150 anniversary, Nature collected 10 extraordinary papers published on Nature in November, 2019. One of the papers is on the discovery of the Antarctic ozone hole, which was published by three British scientists, Joe C. Farman, Brian G. Gardiner, and Jonathan D. Shanklin, in 1985. They first showed observational evidence that Antarctic stratospheric ozone experienced drastic decrease in the early 1980s, by contrasting to the relative steady state in the 1970s. They also suggested that the ozone hole is due to human-made chlorofluorocarbons (CFCs). Nature invited Susan Solomon, who made outstanding contributions to our understanding of the ozone hole, to comment on the paper. She pointed out that “The unexpected discovery of a hole in the atmospheric ozone layer over the Antarctic revolutionized science—and helped to establish one of the most successful global environmental policies of the twentieth century.” The observational evidence by Farman et al. greatly confirmed earlier theoretical works by P. Cruzen, M. Molina, and F. Rowland who first emphasized in the 1970s that anthropogenic emissions of nitrogen oxides and CFCs would damage the ozone layer. Their observational confirmation led to the winning of the Nobel Prize in Chemistry by Cruzen, Molina, and Rowland in 1995. The discovery of the ozone hole also led to great international actions in reducing CFCs emissions and protecting the ozone layer, which is crucially important for screening solar ultraviolet radiation for surface life. A series of conventions has been organized by the United Nations, and the most successful one is the 1987 Montreal Protocol on Substances that Deplete the Ozone Layer. The Montreal Protocol and the succeeding amendments, adjustments, and decisions were subsequently negotiated to control the consumption and production of anthropogenic emissions of ozone-depleting substances (ODSs) and some hydrofluorocarbons (HFCs). Since then, ODSs emissions have been largely reduced and showed rapid decrease since the early 1990s. The global ozone layer and the ozone hole over Antarctic all have showed gradual increasing since the late 1990s. According to predictions of climate-chemistry models, the global total column ozone will return to its 1980 values by 2045 when ODSs decline to very low levels, and the Antarctic ozone hole will recover by 2060. The gradual recovery of the ozone hole, due to reducing anthropogenic emissions, from severe depletion also due to human emissions, is considered a successful story that human can protect their environment through self-efforts. It provides us with the confidence that we are able to reduce greenhouse gas emissions and to solve the problem of global greenhouse warming. In the present paper, we will first introduce the discovery of the Antarctic ozone hole by Farman et al. Then, we introduce the chemical mechanisms of the Chapman and the catalytic reactions that result in the formation of the ozone layer, and how anthropogenic perturbations caused the Antarctic ozone hole. We shall also introduce the actions that was taken by international communities to protect the ozone layer. In the final section, we point out the important implications of the discovery of the ozone hole.

Frank Sherwood ‘Sherry’ Rowland. 28 June 1927—10 March 2012

Sherry Rowland was a chemist who made substantial contributions in the fields of radiochemistry and atmospheric science. He is best known for his research on the stratosphere as, with Mario Molina, he wrote the seminal paper describing how chlorofluorocarbons deplete the stratospheric ozone layer, noting that any ozone depletion would be accompanied by a consequent increase in ultraviolet radiation at the earth's surface. In 1995 he, along with Paul Crutzen, was awarded the Nobel Prize for this ground-breaking work. Sherry's career was much more rounded than this brief précis suggests. His various roles included: manager of a semi-professional baseball team while in graduate school; founding chairman of the Chemistry Department at the University of California at Irvine (UCI); tireless and effective advocate for the need to take action on chlorofluorocarbon emissions and climate change; Foreign Secretary of the National Academy of Sciences; and last, but certainly not least, devoted husband, father and grandfather.

Australian chlorofluorocarbon (CFC) emissions: 1960–2017

Environmental contextChlorofluorocarbons (CFCs) are potent greenhouse and stratospheric ozone depleting trace gases. Their atmospheric concentrations are in decline, thanks to global production and consumption controls imposed by the Montreal Protocol. In recent years, the rates of decline of CFC atmospheric concentrations, especially for CFC-11 (CCl3F), are not as large as anticipated under the Protocol, resulting in renewed efforts to estimate CFC consumption and/or emissions to possibly identify new or poorly quantified sources. AbstractAustralian emissions of chlorofluorocarbons (CFCs) have been estimated from atmospheric CFC observations by both inverse modelling and interspecies correlation techniques, and from CFC production, import and consumption data compiled by industry and government. Australian and global CFC emissions show similar temporal behaviour, with emissions peaking in the late-1980s and then declining by ~10% per year through to the present. Australian CFC emissions since 1978 account for less than 1% of global emissions and therefore make a correspondingly small contribution to stratospheric ozone depletion. The current CFC emissions in Australia are likely from ‘banks’ of closed-cell foams, and refrigeration–air conditioning equipment now more than 20 years old. There is no evidence of renewed consumption or emissions of CFCs in Australia. The reduction in CFC emissions has made a significant contribution to reducing Australian greenhouse gas emissions.

Reduction in surface climate change achieved by the 1987 Montreal Protocol

The benefits of the 1987 Montreal Protocol in reducing chlorofluorocarbon emissions, repairing the stratospheric ozone hole, shielding incoming UV radiation, reducing the incidence of skin cancer and mitigating negative ecosystem effects are all well documented. Projected future climate impacts have also been described, mainly focused on a reduced impact of the mid-latitude jet as the ozone hole gradually repairs. However, there is little appreciation of the surface warming that has been avoided as a result of the Montreal Protocol, despite CFCs being potent greenhouse gases. Instead, the issue of ozone depletion and climate change are often thought of as two distinct problems, even though both ozone and CFCs impact Earth’s radiation budget. Here we show that a substantial amount of warming has been avoided because of the Montreal Protocol, even after factoring in the surface cooling associated with stratospheric ozone depletion. As of today, as much as 1.1 °C warming has been avoided over parts of the Arctic. Future climate benefits are even stronger, with 3 °C–4 °C Arctic warming and ∼1 °C global average warming avoided by 2050; corresponding to a ∼25% mitigation of global warming. The Montreal Protocol has thus not only been a major success in repairing the stratospheric ozone hole, it has also achieved substantial mitigation of anthropogenic climate change both today and into the future.

Emissions of halocarbons from India inferred through atmospheric measurements

Abstract. As the second most populous country and third fastest growing economy, India has emerged as a global economic power. As such, its emissions of greenhouse and ozone-depleting gases are of global significance. However, unlike neighbouring China, the Indian sub-continent is very poorly monitored by atmospheric measurement networks. India's halocarbon emissions, here defined as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) and chlorocarbons, are not well-known. Previous measurements from the region have been obtained at observatories many hundreds of kilometres from source regions, or at high altitudes, limiting their value for the estimation of regional emission rates. Given the projected rapid growth in demand for refrigerants and solvents in India, emission estimates of these halocarbons are urgently needed to provide a benchmark against which future changes can be evaluated. In this study, we report atmospheric-measurement-derived halocarbon emissions from India. With the exception of dichloromethane, these top-down estimates are the first for India's halocarbons. Air samples were collected at low altitude during an aircraft campaign in June and July 2016, and emissions were derived from measurements of these samples using an inverse modelling framework. These results were evaluated to assess India's progress in phasing out ozone-depleting substances under the Montreal Protocol. India's combined CFC emissions are estimated to be 54 (27–86) Tg CO2 eq. yr−1 (5th and 95th confidence intervals are shown in parentheses). HCFC-22 emissions of 7.8 (6.0–9.9) Gg yr−1 are of similar magnitude to emissions of HFC-134a (8.2 (6.1–10.7) Gg yr−1). We estimate India's HFC-23 emissions to be 1.2 (0.9–1.5) Gg yr−1, and our results are consistent with resumed venting of HFC-23 by HCFC-22 manufacturers following the discontinuation of funding for abatement under the Clean Development Mechanism. We report small emissions of HFC-32 and HFC-143a and provide evidence to suggest that HFC-32 emissions were primarily due to fugitive emissions during manufacturing processes. A lack of significant correlation among HFC species and the small emissions derived for HFC-32 and HFC-143a indicate that in 2016, India's use of refrigerant blends R-410A, R-404A and R-507A was limited, despite extensive consumption elsewhere in the world. We also estimate emissions of the regulated chlorocarbons carbon tetrachloride and methyl chloroform from northern and central India to be 2.3 (1.5–3.4) and 0.07 (0.04–0.10) Gg yr−1 respectively. While the Montreal Protocol has been successful in reducing emissions of many ozone-depleting substances, growth in the global emission rates of the unregulated very short-lived substances poses an ongoing threat to the recovery of the ozone layer. Emissions of dichloromethane are found to be 96.5 (77.8–115.6) Gg yr−1, and our estimate suggests a 5-fold increase in emissions since the last estimate derived from atmospheric data in 2008. We estimate perchloroethene emissions from India and chloroform emissions from northern–central India to be 2.9 (2.5–3.3) and 32.2 (28.3–37.1) Gg yr−1 respectively. Given the rapid growth of India's economy and the likely increase in demand for halocarbons such as HFCs, the implementation of long-term atmospheric monitoring in the region is urgently required. Our results provide a benchmark against which future changes to India's halocarbon emissions may be evaluated.

Evidence for a major missing source in the global chloromethane budget from stable carbon isotopes

Abstract. Chloromethane (CH3Cl) is the most important natural input of reactive chlorine to the stratosphere, contributing about 16 % to stratospheric ozone depletion. Due to the phase-out of anthropogenic emissions of chlorofluorocarbons, CH3Cl will largely control future levels of stratospheric chlorine. The tropical rainforest is commonly assumed to be the strongest single CH3Cl source, contributing over half of the global annual emissions of about 4000 to 5000 Gg (1 Gg = 109 g). This source shows a characteristic carbon isotope fingerprint, making isotopic investigations a promising tool for improving its atmospheric budget. Applying carbon isotopes to better constrain the atmospheric budget of CH3Cl requires sound information on the kinetic isotope effects for the main sink processes: the reaction with OH and Cl in the troposphere. We conducted photochemical CH3Cl degradation experiments in a 3500 dm3 smog chamber to determine the carbon isotope effect (ε=k13C/k12C-1) for the reaction of CH3Cl with OH and Cl. For the reaction of CH3Cl with OH, we determined an ε value of (-11.2±0.8) ‰ (n=3) and for the reaction with Cl we found an ε value of (-10.2±0.5) ‰ (n=1), which is 5 to 6 times smaller than previously reported. Our smaller isotope effects are strongly supported by the lack of any significant seasonal covariation in previously reported tropospheric δ13C(CH3Cl) values with the OH-driven seasonal cycle in tropospheric mixing ratios. Applying these new values for the carbon isotope effect to the global CH3Cl budget using a simple two hemispheric box model, we derive a tropical rainforest CH3Cl source of (670±200) Gg a−1, which is considerably smaller than previous estimates. A revision of previous bottom-up estimates, using above-ground biomass instead of rainforest area, strongly supports this lower estimate. Finally, our results suggest a large unknown CH3Cl source of (1530±200) Gg a−1.

IUPAC in the (real) clouds

Abstract As we approach the end of the second decade of the 21st century, changes in atmospheric chemical composition due to anthropogenic pollution continue to challenge the well-being of society. The IUPAC effort in atmospheric chemistry data evaluation can be traced back over 40 years. Global concerns over potentially catastrophic stratospheric ozone depletion resulting from emissions of chlorofluorocarbons (CFCs) led to the creation of the CODATA Task Group on Chemical Kinetics in 1977. The task of the CODATA group was to provide the evaluated kinetic data for atmospheric reactions needed to assess the threat to stratospheric ozone. In 1989, sponsorship of the data evaluation effort was transferred to IUPAC, leading to the formation of the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation.

Impact of the Montreal Protocol on Antarctic Surface Mass Balance and Implications for Global Sea Level Rise

Abstract The Montreal Protocol on Substances that Deplete the Ozone Layer, adopted in 1987, is an international treaty designed to protect the ozone layer by phasing out emissions of chlorofluorocarbons and other ozone-depleting substances (ODSs). A growing body of scientific evidence now suggests that the implementation of the Montreal Protocol will have significant effects on climate over the next several decades, both by enabling stratospheric ozone recovery and by decreasing atmospheric concentrations of ODSs, which are greenhouse gases. Here, using a state-of-the-art chemistry–climate model, the Community Earth System Model (Whole Atmosphere Community Climate Model) [CESM(WACCM)], it is shown that the Montreal Protocol, through its impact on atmospheric ODS concentrations, leads to a substantial decrease in Antarctic surface mass balance (SMB) over the period 2006–65 relative to a hypothetical “World Avoided” scenario in which the Montreal Protocol has not been implemented. This SMB decrease produces an additional 25 mm of global sea level rise (GSLR) by the year 2065 relative to the present day. It is found, however, that the additional GSLR resulting from the relative decrease in Antarctic SMB is more than offset by a reduction in ocean thermal expansion, leading to a net mitigation of future GSLR due to the Montreal Protocol.

Tropospheric observations of CFC-114 and CFC-114a with a focus on long-term trends and emissions

Abstract. Chlorofluorocarbons (CFCs) are ozone-depleting substances as well as strong greenhouse gases, and the control of their production and use under the Montreal Protocol has had demonstrable benefits to both mitigation of increasing surface UV radiation and climate forcing. A global ban on consumption came into force in 2010, but there is evidence of continuing emissions of certain CFCs from a range of sources. One compound has received little attention in the literature, namely CFC-114 (C2Cl2F4). Of particular interest here is the differentiation between CFC-114 (CClF2CClF2) and its asymmetric isomeric form CFC-114a (CF3CCl2F) as atmospheric long-term measurements in the peer-reviewed literature to date have been assumed to represent the sum of both isomers with a time-invariant isomeric speciation. Here we report the first long-term measurements of the two isomeric forms separately, and find that they have different origins and trends in the atmosphere. Air samples collected at Cape Grim (41° S), Australia, during atmospheric background conditions since 1978, combined with samples collected from deep polar snow (firn) enable us to obtain a near-complete record of both gases since their initial production and release in the 1940s. Both isomers were present in the unpolluted atmosphere in comparably small amounts before 1960. The mixing ratio of CFC-114 doubled from 7.9 to 14.8 parts per trillion (ppt) between the start of the Cape Grim record in 1978 and the end of our record in 2014, while over the same time CFC-114a trebled from 0.35 to 1.03 ppt. Mixing ratios of both isomers are slowly decreasing by the end of this period. This is consistent with measurements of recent aircraft-based samples showing no significant interhemispheric mixing ratio gradient. We also find that the fraction of CFC-114a mixing ratio relative to that of CFC-114 increased from 4.2 to 6.9 % over the 37-year period. This contradicts the current tacit assumption used in international climate change and ozone depletion assessments that both isomers have been largely co-emitted and that their atmospheric concentration ratio has remained approximately constant in time. Complementary observations of air collected in Taiwan indicate a persisting source of CFC-114a in South East Asia which may have been contributing to the changing balance between the two isomers. In addition we present top-down global annual emission estimates of CFC-114 and CFC-114a derived from these measurements using a two-dimensional atmospheric chemistry-transport model. In general, the emissions for both compounds grew steadily during the 1980s, followed by a substantial reduction from the late 1980s onwards, which is consistent with the reduction of emission in response to the Montreal Protocol, and broadly consistent with bottom-up estimates derived by industry. However, we find that small but significant emissions of both isomers remain in 2014. Moreover the inferred changes to the ratio of emissions of the two isomers since the 1990s also indicate that the sources of the two gases are, in part, independent.

Effect of supplemental UV-B on yield, seed quality, oil content and fatty acid composition ofBrassica campestrisL. under natural field conditions

Thinning of stratospheric ozone layer had been reported since last fifty years due to emission of chlorofluorocarbons, resulting in an increase in ultraviolet-B (UV-B) radiation. The present study was conducted to examine the effects of supplemental UV-B (sUV-B) radiation (+7.2 kJ/m2/s) on yield and quality of seeds and oil of two cultivars of mustard, (Brassica campestris) L. cv. Sanjukta and Vardan. Number of pods, harvest index, test weight and oil content decreased due to sUV-B exposure in both cultivars. Seed quality was also reduced under sUV-B in terms of protein, sugar and amino acid contents. Further, quality of oil was deteriorated due to increases in erucic acid, polyunsaturated fatty acid and ω-6 fatty acid contents and reductions in oleic acid and nervonic acid contents due to sUV-B exposure. Cultivar Vardan showed more negative impact on seed yield due to UV-B stress, whereas quality of seed and oil was more affected in Sanjukta. Results of the present study confirmed the potential loss in y...