On the stratospheric chemistry of midlatitude wildfire smoke.

SignificanceLarge wildfires have been observed to inject smoke into the stratosphere, raising questions about their potential to affect the stratospheric ozone layer that protects life on Earth from biologically damaging ultraviolet radiation. Multiple observations of aerosol and NO2 concentrations from three independent satellite instruments are used here together with model calculations to identify decreases in stratospheric NO2 concentrations following major Australian 2019 through 2020 wildfires. The data confirm that important chemistry did occur on the smoke particle surfaces. The observed behavior in NO2 with increasing particle concentrations is a marker for surface chemistry that contributes to midlatitude ozone depletion. The results indicate that increasing wildfire activity in a warming world may slow the recovery of the ozone layer.

The influence of iodine on the Antarctic stratospheric ozone hole.

The catalytic depletion of Antarctic stratospheric ozone is linked to anthropogenic emissions of chlorine and bromine. Despite its larger ozone-depleting efficiency, the contribution of ocean-emitted iodine to ozone hole chemistry has not been evaluated, due to the negligible iodine levels previously reported to reach the stratosphere. Based on the recently observed range (0.77 ± 0.1 parts per trillion by volume [pptv]) of stratospheric iodine injection, we use the Whole Atmosphere Community Climate Model to assess the role of iodine in the formation and recent past evolution of the Antarctic ozone hole. Our 1980-2015 simulations indicate that iodine can significantly impact the lower part of the Antarctic ozone hole, contributing, on average, 10% of the lower stratospheric ozone loss during spring (up to 4.2% of the total stratospheric column). We find that the inclusion of iodine advances the beginning and delays the closure stages of the ozone hole by 3 d to 5 d, increasing its area and mass deficit by 11% and 20%, respectively. Despite being present in much smaller amounts, and due to faster gas-phase photochemical reactivation, iodine can dominate (∼73%) the halogen-mediated lower stratospheric ozone loss during summer and early fall, when the heterogeneous reactivation of inorganic chlorine and bromine reservoirs is reduced. The stratospheric ozone destruction caused by 0.77 pptv of iodine over Antarctica is equivalent to that of 3.1 (4.6) pptv of biogenic very short-lived bromocarbons during spring (rest of sunlit period). The relative contribution of iodine to future stratospheric ozone loss is likely to increase as anthropogenic chlorine and bromine emissions decline following the Montreal Protocol.

Isotopic constraint on the twentieth-century increase in tropospheric ozone.

Tropospheric ozone (O3) is a key component of air pollution and an important anthropogenic greenhouse gas1. During the twentieth century, the proliferation of the internal combustion engine, rapid industrialization and land-use change led to a global-scale increase in O3 concentrations2,3; however, the magnitude of this increase is uncertain. Atmospheric chemistry models typically predict4-7 an increase in the tropospheric O3 burden of between 25 and 50 per cent since 1900, whereas direct measurements made in the late nineteenth century indicate that surface O3 mixing ratios increased by up to 300 per cent8-10 over that time period. However, the accuracy and diagnostic power of these measurements remains controversial2. Here we use a record of the clumped-isotope composition of molecular oxygen (18O18O in O2) trapped in polar firn and ice from 1590 to 2016 AD, as well as atmospheric chemistry model simulations, to constrain changes in tropospheric O3 concentrations. We find that during the second half of the twentieth century, the proportion of 18O18O in O2 decreased by 0.03 ± 0.02 parts per thousand (95 per cent confidence interval) below its 1590-1958 AD mean, which implies that tropospheric O3 increased by less than 40 per cent during that time. These results corroborate model predictions of global-scale increases in surface pollution and vegetative stress caused by increasing anthropogenic emissions of O3 precursors4,5,11. We also estimate that the radiative forcing of tropospheric O3 since 1850 AD is probably less than +0.4 watts per square metre, consistent with results from recent climate modelling studies12.

Coupling free radical catalysis, climate change, and human health.

We present the chain of mechanisms linking free radical catalytic loss of stratospheric ozone, specifically over the central United States in summer, to increased climate forcing by CO2 and CH4 from fossil fuel use. This case directly engages detailed knowledge, emerging from in situ aircraft observations over the polar regions in winter, defining the temperature and water vapor dependence of the kinetics of heterogeneous catalytic conversion of inorganic chlorine (HCl and ClONO2) to free radical form (ClO). Analysis is placed in the context of irreversible changes to specific subsystems of the climate, most notably coupled feedbacks that link rapid changes in the Arctic with the discovery that convective storms over the central US in summer both suppress temperatures and inject water vapor deep into the stratosphere. This places the lower stratosphere over the US in summer within the same photochemical catalytic domain as the lower stratosphere of the Arctic in winter engaging the risk of amplifying the rate limiting step in the ClO dimer catalytic mechanism by some six orders of magnitude. This transitions the catalytic loss rate of ozone in lower stratosphere over the United States in summer from HOx radical control to ClOx radical control, increasing the overall ozone loss rate by some two orders of magnitude over that of the unperturbed state. Thus we address, through a combination of observations and modeling, the mechanistic foundation defining why stratospheric ozone, vulnerable to increased climate forcing, is one of the most delicate aspects of habitability on the planet.

Photobiological Effects at Earth's Surface Following a 50 pc Supernova.

We investigated the potential biological impacts at Earth's surface of stratospheric O3 depletion caused by nearby supernovae known to have occurred about 2.5 and 8 million years ago at about 50 pc distance. New and previously published atmospheric chemistry modeling results were combined with radiative transfer modeling to determine changes in surface-level solar irradiance and biological responses. We find that UVB irradiance is increased by a factor of 1.1 to 2.8, with large variation in latitude, and seasonally at high-latitude regions. Changes in UVA and PAR (visible light) are much smaller. DNA damage (in vitro) is increased by factors similar to UVB, while other biological impacts (erythema, skin cancer, cataracts, marine phytoplankton photosynthesis inhibition, and plant damage) are increased by smaller amounts. We conclude that biological impacts due to increased UV irradiance in this SN case are not mass-extinction level but might be expected to contribute to changes in species abundances; this result fits well with species turnover observed around the Pliocene-Pleistocene boundary. Key Words: UV radiation-Supernovae-Ozone-Radiative transfer. Astrobiology 18, 481-490.

Iatrogenic greenhouse gases: the role of anaesthetic agents.

The contribution of health-care activity to climate change is not negligible and is increasing. Anaesthetic greenhouse gases, in particular the fluranes, have a much more potent global warming capacity, volume for volume, than carbon dioxide, but their emissions remain completely unregulated.

Solar ultraviolet radiation: properties, characteristics and amounts observed in Brazil and South America.

The beneficial and harmful effects of human exposure to solar ultraviolet radiation (UV-R) are topics that arouse great interest not only among physicians and scientists, but also the general public and the media. Currently, discussions on vitamin D synthesis (beneficial effect) are confronted with the high and growing number of new cases of non-melanoma skin cancer and other diseases of the skin and eyes (harmful effect) diagnosed each year in Brazil. However, the lack of scientific knowledge on the UV-R in Brazil and South America leads to adoption of protective measures based on studies conducted in Europe and USA, where the amounts of UV-R available at surface and the sun-exposure habits and characteristics of the population are significantly different from those observed in Brazil. In order to circumvent this problem, the Brazilian Society of Dermatology recently published the Brazilian Consensus of Photoprotection based on recent studies performed locally. The main goal of this article is to provide detailed educational information on the main properties and characteristics of UV-R and UV index in a simple language. It also provides: a) a summary of UV-R measurements recently performed in Brazil; b) a comparison with those performed in Europe; and, c) an evaluation to further clarify the assessment of potential harm and health effects owing to chronic exposures.

Solar ultraviolet radiation: properties, characteristics and amounts observed in Brazil and South America

Abstract The beneficial and harmful effects of human exposure to solar ultraviolet radiation (UV-R) are topics that arouse great interest not only among physicians and scientists, but also the general public and the media. Currently, discussions on vitamin D synthesis (beneficial effect) are confronted with the high and growing number of new cases of non-melanoma skin cancer and other diseases of the skin and eyes (harmful effect) diagnosed each year in Brazil. However, the lack of scientific knowledge on the UV-R in Brazil and South America leads to adoption of protective measures based on studies conducted in Europe and USA, where the amounts of UV-R available at surface and the sun-exposure habits and characteristics of the population are significantly different from those observed in Brazil. In order to circumvent this problem, the Brazilian Society of Dermatology recently published the Brazilian Consensus of Photoprotection based on recent studies performed locally. The main goal of this article is to provide detailed educational information on the main properties and characteristics of UV-R and UV index in a simple language. It also provides: a) a summary of UV-R measurements recently performed in Brazil; b) a comparison with those performed in Europe; and, c) an evaluation to further clarify the assessment of potential harm and health effects owing to chronic exposures.

Towards understanding the decomposition/isomerism channels of stratospheric bromine species: ab initio and quantum topology study.

The present study aims at a fundamental understanding of bonding characteristics of the C-Br and O-Br bonds. The target molecular systems are the isomeric CH3OBr/BrCH2OH system and their decomposition products. Calculations of geometries and frequencies at different density functional theory (DFT) and Hartree-Fock/Møller-Plesset (HF/MP2) levels have been performed. Results have been assessed and evaluated against those obtained at the coupled cluster single-double (Triplet) (CCSD(T)) level of theory. The characteristics of the C-Br and O-Br bonds have been identified via analysis of the electrostatic potential, natural bond orbital (NBO), and quantum theory of atoms in molecules (QTAIM). Analysis of the electrostatic potential (ESP) maps enabled the quantitative characterization of the Br σ-holes. Its magnitude seems very sensitive to the environment and the charge accumulated in the adjacent centers. Some quantum topological parameters, namely Ñ2ρ, ellipticity at bond critical points and the Laplacian bond order, were computed and discussed. The potential energy function for internal rotation has been computed and Fourier transformed to characterize the conformational preferences and origin of the barriers. NBO energetic components for rotation about the C-Br and O-Br bonds as a function of torsion angle have been computed and displayed.

The consequences for human health of stratospheric ozone depletion in association with other environmental factors.

Due to the implementation of the Montreal Protocol, which has limited, and is now probably reversing, the depletion of the stratospheric ozone layer, only modest increases in solar UV-B radiation at the surface of the Earth have occurred. For many fair-skinned populations, changing behaviour with regard to exposure to the sun over the past half century - more time in the sun, less clothing cover (more skin exposed), and preference for a tan - has probably contributed more to greater levels of exposure to UV-B radiation than ozone depletion. Exposure to UV-B radiation has both adverse and beneficial effects on human health. This report focuses on an assessment of the evidence regarding these outcomes that has been published since our previous report in 2010. The skin and eyes are the organs exposed to solar UV radiation. Excessive solar irradiation causes skin cancer, including cutaneous malignant melanoma and the non-melanoma skin cancers, basal cell carcinoma and squamous cell carcinoma, and contributes to the development of other rare skin cancers such as Merkel cell carcinoma. Although the incidence of melanoma continues to increase in many countries, in some locations, primarily those with strong sun protection programmes, incidence has stabilised or decreased over the past 5 years, particularly in younger age-groups. However, the incidence of non-melanoma skin cancers is still increasing in most locations. Exposure of the skin to the sun also induces systemic immune suppression that may have adverse effects on health, such as through the reactivation of latent viral infections, but also beneficial effects through suppression of autoimmune reactivity. Solar UV-B radiation damages the eyes, causing cataracts and pterygium. UV-B irradiation of the skin is the main source of vitamin D in many geographic locations. Vitamin D plays a critical role in the maintenance of calcium homeostasis in the body; severe deficiency causes the bone diseases, rickets in children and osteomalacia in adults. Although many studies have implicated vitamin D deficiency in a wide range of diseases, such as cancer and cardiovascular disease, more recent evidence is less compelling, with meta-analyses of supplementation trials failing to show a beneficial effect on the health outcomes that have been tested. It continues to be difficult to provide public health messages to guide safe exposure to the sun that are accurate, simple, and can be used by people with different skin types, in different locations, and for different times of the year or day. There is increasing interest in relating sun protection messages to the UV Index. Current sun protection strategies are outlined and assessed. Climatic factors affect the amount of UV radiation received by the skin and eyes, separately from the effect of ozone depletion. For example, cloud cover can decrease or increase the intensity of UV radiation at Earth's surface and warmer temperatures and changes in precipitation patterns may alter the amount of time people spend outdoors and their choice of clothing. The combination of changes in climate and UV radiation may affect the number of pathogenic microorganisms in surface waters, and could have an impact on food security through effects on plant and aquatic systems. It remains difficult to quantify these effects and their possible importance for human health.