Continuing benefits of the Montreal Protocol and protection of the stratospheric ozone layer for human health and the environment.

The protection of Earth's stratospheric ozone (O3) is an ongoing process under the auspices of the universally ratified Montreal Protocol and its Amendments and adjustments. A critical part of this process is the assessment of the environmental issues related to changes in O3. The United Nations Environment Programme's Environmental Effects Assessment Panel provides annual scientific evaluations of some of the key issues arising in the recent collective knowledge base. This current update includes a comprehensive assessment of the incidence rates of skin cancer, cataract and other skin and eye diseases observed worldwide; the effects of UV radiation on tropospheric oxidants, and air and water quality; trends in breakdown products of fluorinated chemicals and recent information of their toxicity; and recent technological innovations of building materials for greater resistance to UV radiation. These issues span a wide range of topics, including both harmful and beneficial effects of exposure to UV radiation, and complex interactions with climate change. While the Montreal Protocol has succeeded in preventing large reductions in stratospheric O3, future changes may occur due to a number of natural and anthropogenic factors. Thus, frequent assessments of potential environmental impacts are essential to ensure that policies remain based on the best available scientific knowledge.

Linkages between COVID-19, solar UV radiation, and the Montreal Protocol.

There are several connections between coronavirus disease 2019 (COVID-19), solar UV radiation, and the Montreal Protocol. Exposure to ambient solar UV radiation inactivates SARS-CoV-2, the virus responsible for COVID-19. An action spectrum describing the wavelength dependence of the inactivation of SARS-CoV-2 by UV and visible radiation has recently been published. In contrast to action spectra that have been assumed in the past for estimating the effect of UV radiation on SARS-CoV-2, the new action spectrum has a large sensitivity in the UV-A (315-400 nm) range. If this "UV-A tail" is correct, solar UV radiation could be much more efficient in inactivating the virus responsible for COVID-19 than previously thought. Furthermore, the sensitivity of inactivation rates to the total column ozone would be reduced because ozone absorbs only a small amount of UV-A radiation. Using solar simulators, the times for inactivating SARS-CoV-2 have been determined by several groups; however, many measurements are affected by poorly defined experimental setups. The most reliable data suggest that 90% of viral particles embedded in saliva are inactivated within ~ 7 min by solar radiation for a solar zenith angle (SZA) of 16.5° and within ~ 13 min for a SZA of 63.4°. Slightly longer inactivation times were found for aerosolised virus particles. These times can become considerably longer during cloudy conditions or if virus particles are shielded from solar radiation. Many publications have provided evidence of an inverse relationship between ambient solar UV radiation and the incidence or severity of COVID-19, but the reasons for these negative correlations have not been unambiguously identified and could also be explained by confounders, such as ambient temperature, humidity, visible radiation, daylength, temporal changes in risk and disease management, and the proximity of people to other people. Meta-analyses of observational studies indicate inverse associations between serum 25-hydroxy vitamin D (25(OH)D) concentration and the risk of SARS-CoV-2 positivity or severity of COVID-19, although the quality of these studies is largely low. Mendelian randomisation studies have not found statistically significant evidence of a causal effect of 25(OH)D concentration on COVID-19 susceptibility or severity, but a potential link between vitamin D status and disease severity cannot be excluded as some randomised trials suggest that vitamin D supplementation is beneficial for people admitted to a hospital. Several studies indicate significant positive associations between air pollution and COVID-19 incidence and fatality rates. Conversely, well-established cohort studies indicate no association between long-term exposure to air pollution and infection with SARS-CoV-2. By limiting increases in UV radiation, the Montreal Protocol has also suppressed the inactivation rates of pathogens exposed to UV radiation. However, there is insufficient evidence to conclude that the expected larger inactivation rates without the Montreal Protocol would have had tangible consequences on the progress of the COVID-19 pandemic.

The Montreal Protocol and the fate of environmental plastic debris.

Microplastics (MPs) are an emerging class of pollutants in air, soil and especially in all aquatic environments. Secondary MPs are generated in the environment during fragmentation of especially photo-oxidised plastic litter. Photo-oxidation is mediated primarily by solar UV radiation. The implementation of the Montreal Protocol and its Amendments, which have resulted in controlling the tropospheric UV-B (280-315 nm) radiation load, is therefore pertinent to the fate of environmental plastic debris. Due to the Montreal Protocol high amounts of solar UV-B radiation at the Earth's surface have been avoided, retarding the oxidative fragmentation of plastic debris, leading to a slower generation and accumulation of MPs in the environment. Quantifying the impact of the Montreal Protocol in reducing the abundance of MPs in the environment, however, is complicated as the role of potential mechanical fragmentation of plastics under environmental mechanical stresses is poorly understood.

Changes in tropospheric air quality related to the protection of stratospheric ozone in a changing climate.

Ultraviolet (UV) radiation drives the net production of tropospheric ozone (O3) and a large fraction of particulate matter (PM) including sulfate, nitrate, and secondary organic aerosols. Ground-level O3 and PM are detrimental to human health, leading to several million premature deaths per year globally, and have adverse effects on plants and the yields of crops. The Montreal Protocol has prevented large increases in UV radiation that would have had major impacts on air quality. Future scenarios in which stratospheric O3 returns to 1980 values or even exceeds them (the so-called super-recovery) will tend to ameliorate urban ground-level O3 slightly but worsen it in rural areas. Furthermore, recovery of stratospheric O3 is expected to increase the amount of O3 transported into the troposphere by meteorological processes that are sensitive to climate change. UV radiation also generates hydroxyl radicals (OH) that control the amounts of many environmentally important chemicals in the atmosphere including some greenhouse gases, e.g., methane (CH4), and some short-lived ozone-depleting substances (ODSs). Recent modeling studies have shown that the increases in UV radiation associated with the depletion of stratospheric ozone over 1980-2020 have contributed a small increase (~ 3%) to the globally averaged concentrations of OH. Replacements for ODSs include chemicals that react with OH radicals, hence preventing the transport of these chemicals to the stratosphere. Some of these chemicals, e.g., hydrofluorocarbons that are currently being phased out, and hydrofluoroolefins now used increasingly, decompose into products whose fate in the environment warrants further investigation. One such product, trifluoroacetic acid (TFA), has no obvious pathway of degradation and might accumulate in some water bodies, but is unlikely to cause adverse effects out to 2100.

Environmental effects of stratospheric ozone depletion, UV radiation, and interactions with climate change: UNEP Environmental Effects Assessment Panel, Update 2021.

The Environmental Effects Assessment Panel of the Montreal Protocol under the United Nations Environment Programme evaluates effects on the environment and human health that arise from changes in the stratospheric ozone layer and concomitant variations in ultraviolet (UV) radiation at the Earth's surface. The current update is based on scientific advances that have accumulated since our last assessment (Photochem and Photobiol Sci 20(1):1-67, 2021). We also discuss how climate change affects stratospheric ozone depletion and ultraviolet radiation, and how stratospheric ozone depletion affects climate change. The resulting interlinking effects of stratospheric ozone depletion, UV radiation, and climate change are assessed in terms of air quality, carbon sinks, ecosystems, human health, and natural and synthetic materials. We further highlight potential impacts on the biosphere from extreme climate events that are occurring with increasing frequency as a consequence of climate change. These and other interactive effects are examined with respect to the benefits that the Montreal Protocol and its Amendments are providing to life on Earth by controlling the production of various substances that contribute to both stratospheric ozone depletion and climate change.

Environmental effects of stratospheric ozone depletion, UV radiation, and interactions with climate change: UNEP Environmental Effects Assessment Panel, Update 2020.

This assessment by the Environmental Effects Assessment Panel (EEAP) of the United Nations Environment Programme (UNEP) provides the latest scientific update since our most recent comprehensive assessment (Photochemical and Photobiological Sciences, 2019, 18, 595-828). The interactive effects between the stratospheric ozone layer, solar ultraviolet (UV) radiation, and climate change are presented within the framework of the Montreal Protocol and the United Nations Sustainable Development Goals. We address how these global environmental changes affect the atmosphere and air quality; human health; terrestrial and aquatic ecosystems; biogeochemical cycles; and materials used in outdoor construction, solar energy technologies, and fabrics. In many cases, there is a growing influence from changes in seasonality and extreme events due to climate change. Additionally, we assess the transmission and environmental effects of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which is responsible for the COVID-19 pandemic, in the context of linkages with solar UV radiation and the Montreal Protocol.

Environmental effects of stratospheric ozone depletion, UV radiation and interactions with climate change: UNEP Environmental Effects Assessment Panel, update 2019.

This assessment, by the United Nations Environment Programme (UNEP) Environmental Effects Assessment Panel (EEAP), one of three Panels informing the Parties to the Montreal Protocol, provides an update, since our previous extensive assessment (Photochem. Photobiol. Sci., 2019, 18, 595-828), of recent findings of current and projected interactive environmental effects of ultraviolet (UV) radiation, stratospheric ozone, and climate change. These effects include those on human health, air quality, terrestrial and aquatic ecosystems, biogeochemical cycles, and materials used in construction and other services. The present update evaluates further evidence of the consequences of human activity on climate change that are altering the exposure of organisms and ecosystems to UV radiation. This in turn reveals the interactive effects of many climate change factors with UV radiation that have implications for the atmosphere, feedbacks, contaminant fate and transport, organismal responses, and many outdoor materials including plastics, wood, and fabrics. The universal ratification of the Montreal Protocol, signed by 197 countries, has led to the regulation and phase-out of chemicals that deplete the stratospheric ozone layer. Although this treaty has had unprecedented success in protecting the ozone layer, and hence all life on Earth from damaging UV radiation, it is also making a substantial contribution to reducing climate warming because many of the chemicals under this treaty are greenhouse gases.

Interactive effects of changing stratospheric ozone and climate on tropospheric composition and air quality, and the consequences for human and ecosystem health.

The composition of the air we breathe is determined by emissions, weather, and photochemical transformations induced by solar UV radiation. Photochemical reactions of many emitted chemical compounds can generate important (secondary) pollutants including ground-level ozone (O3) and some particulate matter, known to be detrimental to human health and ecosystems. Poor air quality is the major environmental cause of premature deaths globally, and even a small decrease in air quality can translate into a large increase in the number of deaths. In many regions of the globe, changes in emissions of pollutants have caused significant changes in air quality. Short-term variability in the weather as well as long-term climatic trends can affect ground-level pollution through several mechanisms. These include large-scale changes in the transport of O3 from the stratosphere to the troposphere, winds, clouds, and patterns of precipitation. Long-term trends in UV radiation, particularly related to the depletion and recovery of stratospheric ozone, are also expected to result in changes in air quality as well as the self-cleaning capacity of the global atmosphere. The increased use of substitutes for ozone-depleting substances, in response to the Montreal Protocol, does not currently pose a significant risk to the environment. This includes both the direct emissions of substitutes during use and their atmospheric degradation products (e.g. trifluoroacetic acid, TFA).

Environmental effects of ozone depletion, UV radiation and interactions with climate change: UNEP Environmental Effects Assessment Panel, update 2017.

The Environmental Effects Assessment Panel (EEAP) is one of three Panels of experts that inform the Parties to the Montreal Protocol. The EEAP focuses on the effects of UV radiation on human health, terrestrial and aquatic ecosystems, air quality, and materials, as well as on the interactive effects of UV radiation and global climate change. When considering the effects of climate change, it has become clear that processes resulting in changes in stratospheric ozone are more complex than previously held. Because of the Montreal Protocol, there are now indications of the beginnings of a recovery of stratospheric ozone, although the time required to reach levels like those before the 1960s is still uncertain, particularly as the effects of stratospheric ozone on climate change and vice versa, are not yet fully understood. Some regions will likely receive enhanced levels of UV radiation, while other areas will likely experience a reduction in UV radiation as ozone- and climate-driven changes affect the amounts of UV radiation reaching the Earth's surface. Like the other Panels, the EEAP produces detailed Quadrennial Reports every four years; the most recent was published as a series of seven papers in 2015 (Photochem. Photobiol. Sci., 2015, 14, 1-184). In the years in between, the EEAP produces less detailed and shorter Update Reports of recent and relevant scientific findings. The most recent of these was for 2016 (Photochem. Photobiol. Sci., 2017, 16, 107-145). The present 2017 Update Report assesses some of the highlights and new insights about the interactive nature of the direct and indirect effects of UV radiation, atmospheric processes, and climate change. A full 2018 Quadrennial Assessment, will be made available in 2018/2019.

Critical appraisal of data used to infer record UVI in the tropical andes.

When the data sets that suggested record high UVI values at Mt Licancabur, and Laguna Blanca, Bolivia are reviewed in full, we find that the reported peak values are incorrect, probably due to instrumental problems. These affect the UVB, UVA and PAR channels at different times and different solar zenith angles, with distinct diurnal patterns in each case. The outliers are consistent with errors that would result from build-up of ice or snow on the surface of the entrance dome, combined with incomplete baffling of light within the integrating spheres that form the entrance optic of these instruments, but we cannot unequivocally attribute them to this cause. The analysis shows that for all three channels, cloud enhancements over clear-sky values by a factor of ∼4 or more would be required to explain their highest values. Such repeated enhancements are not physically plausible and are more than twice those previously observed in the UV region. Further, at the time of peak reported UVB, the UVA cloud enhancement factor was less than 1.2 (i.e., UVA radiation was increased by less than 20% over clear-sky values), which implies that to explain the high UVB values, an atmospheric ozone amount (∼25 DU) far below the minimum ever observed would be required. The analysis also shows that the algorithm to convert from UVB to UVI is incorrect, and that if the correct algorithm had been used, the peak UVI values would have been even larger than reported. Disregarding the obviously incorrect measurements, the highest realistic values near solar noon from this dataset are in the range UVI = 25 ± 5, which is in agreement with previous estimates in the region.

Non-linear partitioning and organic volatility distributions of urban aerosols.

Gas-to-particle partitioning of organic aerosols (OA) is represented in most models by Raoult's law, and depends on the existing mass of particles into which organic gases can dissolve. This raises the possibility of non-linear response of particle-phase OA mass to the emissions of precursor volatile organic compounds (VOCs) that contribute to this partitioning mass. Implications for air quality management are evident: a strong non-linear dependence would suggest that reductions in VOC emission would have a more-than-proportionate benefit in lowering ambient OA concentrations. Chamber measurements on simple VOC mixtures generally confirm the non-linear scaling between OA and VOCs, usually stated as a mass-dependence of the measured OA yields. However, for realistic ambient conditions including urban settings, no single component dominates the composition of the organic particles, and deviations from linearity are presumed to be small. Here we re-examine the linearity question using volatility spectra from several sources: (1) chamber studies of selected aerosols, (2) volatility inferred for aerosols sampled in two megacities, Mexico City and Paris, and (3) an explicit chemistry model (GECKO-A). These few available volatility distributions suggest that urban OA may be only slightly super-linear, with most values of the normalized sensitivity exponent in the range 1.1-1.3, also substantially lower than seen in chambers for some specific aerosols. The rather low exponents suggest that OA concentrations in megacities are not an inevitable convergence of non-linear effects, but can be addressed (much like in smaller urban areas) by proportionate reductions in emissions.

Ozone depletion and climate change: impacts on UV radiation.

We assess the importance of factors that determine the intensity of UV radiation at the Earth's surface. Among these, atmospheric ozone, which absorbs UV radiation, is of considerable importance, but other constituents of the atmosphere, as well as certain consequences of climate change, can also be major influences. Further, we assess the variations of UV radiation observed in the past and present, and provide projections for the future. Of particular interest are methods to measure or estimate UV radiation at the Earth's surface. These are needed for scientific understanding and, when they are sufficiently sensitive, they can serve as monitors of the effectiveness of the Montreal Protocol and its amendments. Also assessed are several aspects of UV radiation related to biological effects and health. The implications for ozone and UV radiation from two types of geoengineering methods that have been proposed to combat climate change are also discussed. In addition to ozone effects, the UV changes in the last two decades, derived from measurements, have been influenced by changes in aerosols, clouds, surface reflectivity, and, possibly, by solar activity. The positive trends of UV radiation observed after the mid-1990s over northern mid-latitudes are mainly due to decreases in clouds and aerosols. Despite some indications from measurements at a few stations, no statistically significant decreases in UV-B radiation attributable to the beginning of the ozone recovery have yet been detected. Projections for erythemal irradiance (UVery) suggest the following changes by the end of the 21(st) century (2090-2100) relative to the present time (2010-2020): (1) Ozone recovery (due to decreasing ozone-depleting substances and increasing greenhouse gases) would cause decreases in UVery, which will be highest (up to 40%) over Antarctica. Decreases would be small (less than 10%) outside the southern Polar Regions. A possible decline of solar activity during the 21(st) century might affect UV-B radiation at the surface indirectly through changes induced in stratospheric ozone. (2) The projected changes in cloud cover would lead to relatively small effects (less than 3%), except at northern high latitudes where increases in cloud cover could lead to decreases in UVery by up to 7%. (3) Reductions in reflectivity due to the melting of sea-ice in the Arctic would lead to decreases of UVery by up to 10%, while at the margins of the Antarctic the decreases would be smaller (2-3%). The melting of the sea-ice would expose the ocean surface formerly covered by ice to UV-B radiation up to 10 times stronger than before. (4) The expected improvement of air-quality and reductions of aerosols over the most populated areas of the northern hemisphere may result in 10-20% increases in UVery, except over China where even larger increases are projected. The projected aerosol effect for the southern hemisphere is generally very small. Aerosols are possibly the most important factor for future UV levels over heavily populated areas, but their projected effects are the most uncertain.

Changes in air quality and tropospheric composition due to depletion of stratospheric ozone and interactions with changing climate: implications for human and environmental health.

UV radiation is an essential driver for the formation of photochemical smog, which includes ground-level ozone and particulate matter (PM). Recent analyses support earlier work showing that poor outdoor air quality is a major environmental hazard as well as quantifying health effects on regional and global scales more accurately. Greater exposure to these pollutants has been linked to increased risks of cardiovascular and respiratory diseases in humans and is associated globally with several million premature deaths per year. Ozone also has adverse effects on yields of crops, leading to loss of billions of US dollars each year. These detrimental effects also may alter biological diversity and affect the function of natural ecosystems. Future air quality will depend mostly on changes in emission of pollutants and their precursors, but changes in UV radiation and climate will contribute as well. Significant reductions in emissions, mainly from the energy and transportation sectors, have already led to improved air quality in many locations. Air quality will continue to improve in those cities/states that can afford controls, and worsen where the regulatory infrastructure is not available. Future changes in UV radiation and climate will alter the rates of formation of ground-level ozone and photochemically-generated particulate matter and must be considered in predictions of air quality. The decrease in UV radiation associated with recovery of stratospheric ozone will, according to recent global atmospheric model simulations, lead to increases in ground-level ozone at most locations. If correct, this will add significantly to future ground-level ozone trends. However, the spatial resolution of these global models is insufficient to inform policy at this time, especially for urban areas. UV radiation affects the atmospheric concentration of hydroxyl radicals, ˙OH, which are responsible for the self-cleaning of the atmosphere. Recent measurements confirm that, on a local scale, ˙OH radicals respond rapidly to changes in UV radiation. However, on large (global) scales, models differ in their predictions by nearly a factor of two, with consequent uncertainties for estimating the atmospheric lifetime and concentrations of key greenhouse gases and air pollutants. Projections of future climate need to consider these uncertainties. No new negative environmental effects of substitutes for ozone depleting substances or their breakdown-products have been identified. However, some substitutes for the ozone depleting substances will continue to contribute to global climate change if concentrations rise above current levels.

Oxidation and fragmentation of plastics in a changing environment; from UV-radiation to biological degradation.

Understanding the fate of plastics in the environment is of critical importance for the quantitative assessment of the biological impacts of plastic waste. Specially, there is a need to analyze in more detail the reputed longevity of plastics in the context of plastic degradation through oxidation and fragmentation reactions. Photo-oxidation of plastic debris by solar UV radiation (UVR) makes material prone to subsequent fragmentation. The fragments generated following oxidation and subsequent exposure to mechanical stresses include secondary micro- or nanoparticles, an emerging class of pollutants. The paper discusses the UV-driven photo-oxidation process, identifying relevant knowledge gaps and uncertainties. Serious gaps in knowledge exist concerning the wavelength sensitivity and the dose-response of the photo-fragmentation process. Given the heterogeneity of natural UV irradiance varying from no exposure in sediments to full UV exposure of floating, beach litter or air-borne plastics, it is argued that the rates of UV-driven degradation/fragmentation will also vary dramatically between different locations and environmental niches. Biological phenomena such as biofouling will further modulate the exposure of plastics to UV radiation, while potentially also contributing to degradation and/or fragmentation of plastics independent of solar UVR. Reductions in solar UVR in many regions, consequent to the implementation of the Montreal Protocol and its Amendments for protecting stratospheric ozone, will have consequences for global UV-driven plastic degradation in a heterogeneous manner across different geographic and environmental zones. The interacting effects of global warming, stratospheric ozone and UV radiation are projected to increase UV irradiance at the surface in localized areas, mainly because of decreased cloud cover. Given the complexity and uncertainty of future environmental conditions, this currently precludes reliable quantitative predictions of plastic persistence on a global scale.

Changes in air quality and tropospheric composition due to depletion of stratospheric ozone and interactions with climate.

Air pollution will be directly influenced by future changes in emissions of pollutants, climate, and stratospheric ozone, and will have significant consequences for human health and the environment. UV radiation is one of the controlling factors for the formation of photochemical smog, which includes tropospheric ozone (O(3)) and aerosols; it also initiates the production of hydroxyl radicals (˙OH), which control the amount of many climate- and ozone-relevant gases (e.g., methane and HCFCs) in the atmosphere. Numerical models predict that future changes in UV radiation and climate will modify the trends and geographic distribution of ˙OH, thus affecting the formation of photochemical smog in many urban and regional areas. Concentrations of ˙OH are predicted to decrease globally by an average of 20% by 2100, with local concentrations varying by as much as a factor of two above and below current values. However, significant differences between modelled and measured values in a limited number of case studies show that chemistry of hydroxyl radicals in the atmosphere is not fully understood. Photochemically produced tropospheric ozone is projected to increase. If emissions of anthropogenic air pollutants from combustion of fossil fuels, burning of biomass, and agricultural activities continue to increase, concentrations of tropospheric O(3) will tend to increase over the next 20-40 years in certain regions of low and middle latitudes because of interactions of emissions, chemical processes, and climate change. Climate-driven increases in temperature and humidity will also increase production of tropospheric O(3) in polluted regions, but reduce it in more pristine regions. Higher temperatures tend to increase emissions of nitrogen oxides (NO(x)) from some soils and release of biogenic volatile organic compounds (VOCs) from vegetation, leading to greater background concentrations of ozone in the troposphere. The net effects of future changes in UV radiation, meteorological conditions, and anthropogenic emissions may be large, thus posing challenges for prediction and management of air quality. Aerosols composed of organic substances have a major role in both climate and air quality, and contribute a large uncertainty to the energy budget of the atmosphere. These aerosols are mostly formed via the UV-initiated oxidation of VOCs from anthropogenic and biogenic sources, although the details of the chemistry are still poorly understood and current models under-predict their abundance. A better understanding of their formation, chemical composition, and optical properties is required to assess their significance for air quality and to better quantify their direct and indirect radiative forcing of climate. Emissions of compounds containing fluorine will continue to have effects on the chemistry of the atmosphere and on climate change. The HCFCs and HFCs used as substitutes for ozone-depleting CFCs can break down into trifluoroacetic acid (TFA), which will accumulate in oceans, salt lakes, and playas. Based on historical use and projections of future uses, including new products entering the market, such as the fluoro-olefins, increased loadings of TFA in these environmental sinks will be small. Even when added to existing amounts from natural sources, risks to humans or the environment from the historical use of CFCs or continued use of their replacements is judged to be negligible.

Ozone depletion and climate change: impacts on UV radiation.

The Montreal Protocol is working, but it will take several decades for ozone to return to 1980 levels. The atmospheric concentrations of ozone depleting substances are decreasing, and ozone column amounts are no longer decreasing. Mid-latitude ozone is expected to return to 1980 levels before mid-century, slightly earlier than predicted previously. However, the recovery rate will be slower at high latitudes. Springtime ozone depletion is expected to continue to occur at polar latitudes, especially in Antarctica, in the next few decades. Because of the success of the Protocol, increases in UV-B radiation have been small outside regions affected by the Antarctic ozone hole, and have been difficult to detect. There is a large variability in UV-B radiation due to factors other than ozone, such as clouds and aerosols. There are few long-term measurements available to confirm the increases that would have occurred as a result of ozone depletion. At mid-latitudes UV-B irradiances are currently only slightly greater than in 1980 (increases less than ~5%), but increases have been substantial at high and polar latitudes where ozone depletion has been larger. Without the Montreal Protocol, peak values of sunburning UV radiation could have been tripled by 2065 at mid-northern latitudes. This would have had serious consequences for the environment and for human health. There are strong interactions between ozone depletion and changes in climate induced by increasing greenhouse gases (GHGs). Ozone depletion affects climate, and climate change affects ozone. The successful implementation of the Montreal Protocol has had a marked effect on climate change. The calculated reduction in radiative forcing due to the phase-out of chlorofluorocarbons (CFCs) far exceeds that from the measures taken under the Kyoto protocol for the reduction of GHGs. Thus the phase-out of CFCs is currently tending to counteract the increases in surface temperature due to increased GHGs. The amount of stratospheric ozone can also be affected by the increases in the concentration of GHGs, which lead to decreased temperatures in the stratosphere and accelerated circulation patterns. These changes tend to decrease total ozone in the tropics and increase total ozone at mid and high latitudes. Changes in circulation induced by changes in ozone can also affect patterns of surface wind and rainfall. The projected changes in ozone and clouds may lead to large decreases in UV at high latitudes, where UV is already low; and to small increases at low latitudes, where it is already high. This could have important implications for health and ecosystems. Compared to 1980, UV-B irradiance towards the end of the 21st century is projected to be lower at mid to high latitudes by between 5 and 20% respectively, and higher by 2-3% in the low latitudes. However, these projections must be treated with caution because they also depend strongly on changes in cloud cover, air pollutants, and aerosols, all of which are influenced by climate change, and their future is uncertain. Strong interactions between ozone depletion and climate change and uncertainties in the measurements and models limit our confidence in predicting the future UV radiation. It is therefore important to improve our understanding of the processes involved, and to continue monitoring ozone and surface UV spectral irradiances both from the surface and from satellites so we can respond to unexpected changes in the future.

Stratospheric ozone depletion between 1979 and 1992: implications for biologically active ultraviolet-B radiation and non-melanoma skin cancer incidence.

The depletion of stratospheric ozone (O3) has predictable implications for increases in biologically damaging solar ultraviolet-B radiation (UVB, 280-320 nm) reaching the earth's surface. A radiative transfer analysis of satellite-based O3 measurements between January 1979 and December 1992 shows that surface UVB levels increased substantially at all latitudes except the tropics, if other factors such as cloud cover and local pollutant levels have remained constant over this period. Exposure to UVB radiation is known to induce basal cell and squamous cell skin cancers, and dose-response relationships derived from epidemiological data can be combined with the UVB enhancements to estimate the seasonal and latitudinal distribution of future expected increases in the incidence of these cancers.

Changes in tropospheric composition and air quality.

Reductions in stratospheric ozone (O3) cause increased penetration of ultraviolet-B (UV-B) radiation to the troposphere, and therefore increases in the chemical activity in the lower atmosphere (the troposphere). Tropospheric ozone levels are sensitive to local concentrations of nitrogen oxides (NOx) and hydrocarbons. Model studies suggest that additional UV-B radiation reduces tropospheric ozone in clean environments (low NOx), and increases tropospheric ozone in polluted areas (high NOx). Assuming other factors remain constant, additional UV-B will increase the rate at which primary pollutants are removed from the troposphere. Increased UV-B is expected to increase the concentration of hydroxyl radicals (OH) and result in faster removal of pollutants such as carbon monoxide (CO), methane (CH4), non-methane hydrocarbons (NMHCs), sulfur and nitrogen oxides, hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Concentrations of peroxy radicals (both inorganic and organic) are expected to increase, leading to higher atmospheric levels of hydrogen peroxide (H2O2) and organic peroxides. The effects of UV-B increases on tropospheric O3, OH, methane, CO, and possibly other tropospheric constituents, while not negligible, will be difficult to detect because the concentrations of these species are also influenced by many other variable factors (e.g., emissions). Trifluoroacetic acid (TFA, CF3COOH) is produced in the atmosphere by the degradation of HCFC-123 (CF3CHCl2), HCFC-124 (CF3CHFCl), and HFC-134a (CF3CH2F), which are used as substitutes for ozone-depleting substances. The atmospheric oxidation mechanisms of these replacement compounds are well established. Reported measurements of TFA in rain, rivers, lakes, and oceans show it to be a ubiquitous component of the hydrosphere, present at levels much higher than can be explained by reported sources. The levels of TFA produced by the atmospheric degradation of HFCs and HCFCs emitted up to the year 2020 are estimated to be orders of magnitude below those of concern, and to make only a minor contribution to the current environmental burden of TFA. No significant effects on humans or the environment have been identified from TFA produced by atmospheric degradation of HCFCs and HFCs. Numerous standard short-term studies have shown that TFA has, at most, moderate toxicity.

Changes in biologically active ultraviolet radiation reaching the Earth's surface.

Stratospheric ozone levels are near their lowest point since measurements began, so current ultraviolet-B (UV-B) radiation levels are thought to be close to their maximum. Total stratospheric content of ozone-depleting substances is expected to reach a maximum before the year 2000. All other things being equal, the current ozone losses and related UV-B increases should be close to their maximum. Increases in surface erythemal (sunburning) UV radiation relative to the values in the 1970s are estimated to be: about 7% at Northern Hemisphere mid-latitudes in winter/spring; about 4% at Northern Hemisphere mid-latitudes in summer/fall; about 6% at Southern Hemisphere mid-latitudes on a year-round basis; about 130% in the Antarctic in spring; and about 22% in the Arctic in spring. Reductions in atmospheric ozone are expected to result in higher amounts of UV-B radiation reaching the Earth's surface. The expected correlation between increases in surface UV-B radiation and decreases in overhead ozone has been further demonstrated and quantified by ground-based instruments under a wide range of conditions. Improved measurements of UV-B radiation are now providing better geographical and temporal coverage. Surface UV-B radiation levels are highly variable because of cloud cover, and also because of local effects including pollutants and surface reflections. These factors usually decrease atmospheric transmission and therefore the surface irradiances at UV-B as well as other wavelengths. Occasional cloud-induced increases have also been reported. With a few exceptions, the direct detection of UV-B trends at low- and mid-latitudes remains problematic due to this high natural variability, the relatively small ozone changes, and the practical difficulties of maintaining long-term stability in networks of UV-measuring instruments. Few reliable UV-B radiation measurements are available from pre-ozone-depletion days. Satellite-based observations of atmospheric ozone and clouds are being used, together with models of atmospheric transmission, to provide global coverage and long-term estimates of surface UV-B radiation. Estimates of long-term (1979-1992) trends in zonally averaged UV irradiances that include cloud effects are nearly identical to those for clear-sky estimates, providing evidence that clouds have not influenced the UV-B trends. However, the limitations of satellite-derived UV estimates should be recognized. To assess uncertainties inherent in this approach, additional validations involving comparisons with ground-based observations are required. Direct comparisons of ground-based UV-B radiation measurements between a few mid-latitude sites in the Northern and Southern Hemispheres have shown larger differences than those estimated using satellite data. Ground-based measurements show that summertime erythemal UV irradiances in the Southern Hemisphere exceed those at comparable latitudes of the Northern Hemisphere by up to 40%, whereas corresponding satellite-based estimates yield only 10-15% differences. Atmospheric pollution may be a factor in this discrepancy between ground-based measurements and satellite-derived estimates. UV-B measurements at more sites are required to determine whether the larger observed differences are globally representative. High levels of UV-B radiation continue to be observed in Antarctica during the recurrent spring-time ozone hole. For example, during ozone-hole episodes, measured biologically damaging radiation at Palmer Station, Antarctica (64 degrees S) has been found to approach and occasionally even exceed maximum summer values at San Diego, CA, USA (32 degrees N). Long-term predictions of future UV-B levels are difficult and uncertain. Nevertheless, current best estimates suggest that a slow recovery to pre-ozone depletion levels may be expected during the next half-century. (ABSTRACT TRUNCATED)

Epidemic influenza and vitamin D.

In 1981, R. Edgar Hope-Simpson proposed that a 'seasonal stimulus' intimately associated with solar radiation explained the remarkable seasonality of epidemic influenza. Solar radiation triggers robust seasonal vitamin D production in the skin; vitamin D deficiency is common in the winter, and activated vitamin D, 1,25(OH)2D, a steroid hormone, has profound effects on human immunity. 1,25(OH)2D acts as an immune system modulator, preventing excessive expression of inflammatory cytokines and increasing the 'oxidative burst' potential of macrophages. Perhaps most importantly, it dramatically stimulates the expression of potent anti-microbial peptides, which exist in neutrophils, monocytes, natural killer cells, and in epithelial cells lining the respiratory tract where they play a major role in protecting the lung from infection. Volunteers inoculated with live attenuated influenza virus are more likely to develop fever and serological evidence of an immune response in the winter. Vitamin D deficiency predisposes children to respiratory infections. Ultraviolet radiation (either from artificial sources or from sunlight) reduces the incidence of viral respiratory infections, as does cod liver oil (which contains vitamin D). An interventional study showed that vitamin D reduces the incidence of respiratory infections in children. We conclude that vitamin D, or lack of it, may be Hope-Simpson's 'seasonal stimulus'.