This Assessment Update by the Environmental Effects Assessment Panel (EEAP) of the United Nations Environment Programme (UNEP) addresses the interacting effects of changes in stratospheric ozone, solar ultraviolet (UV) radiation, and climate on the environment and human health. These include new modelling studies that confirm the benefits of the Montreal Protocol in protecting the stratospheric ozone layer and its role in maintaining a stable climate, both at low and high latitudes. We also provide an update on projected levels of solar UV-radiation during the twenty-first century. Potential environmental consequences of climate intervention scenarios are also briefly discussed, illustrating the large uncertainties of, for example, Stratospheric Aerosol Injection (SAI). Modelling studies predict that, although SAI would cool the Earth’s surface, other climate factors would be affected, including stratospheric ozone depletion and precipitation patterns. The contribution to global warming of replacements for ozone-depleting substances (ODS) are assessed. With respect to the breakdown products of chemicals under the purview of the Montreal Protocol, the risks to ecosystem and human health from the formation of trifluoroacetic acid (TFA) as a degradation product of ODS replacements are currently de minimis. UV-radiation and climate change continue to have complex interactive effects on the environment due largely to human activities. UV-radiation, other weathering factors, and microbial action contribute significantly to the breakdown of plastic waste in the environment, and in affecting transport, fate, and toxicity of the plastics in terrestrial and aquatic ecosystems, and the atmosphere. Sustainability demands continue to drive industry innovations to mitigate environmental consequences of the use and disposal of plastic and plastic-containing materials. Terrestrial ecosystems in alpine and polar environments are increasingly being exposed to enhanced UV-radiation due to earlier seasonal snow and ice melt because of climate warming and extended periods of ozone depletion. Solar radiation, including UV-radiation, also contributes to the decomposition of dead plant material, which affects nutrient cycling, carbon storage, emission of greenhouse gases, and soil fertility. In aquatic ecosystems, loss of ice cover is increasing the area of polar oceans exposed to UV-radiation with possible negative effects on phytoplankton productivity. However, modelling studies of Arctic Ocean circulation suggests that phytoplankton are circulating to progressively deeper ocean layers with less UV irradiation. Human health is also modified by climate change and behaviour patterns, resulting in changes in exposure to UV-radiation with harmful or beneficial effects depending on conditions and skin type. For example, incidence of melanoma has been associated with increased air temperature, which affects time spent outdoors and thus exposure to UV-radiation. Overall, implementation of the Montreal Protocol and its Amendments has mitigated the deleterious effects of high levels of UV-radiation and global warming for both environmental and human health.

There are close links between solar UV radiation, climate change, and plastic pollution. UV-driven weathering is a key process leading to the degradation of plastics in the environment but also the formation of potentially harmful plastic fragments such as micro- and nanoplastic particles. Estimates of the environmental persistence of plastic pollution, and the formation of fragments, will need to take in account plastic dispersal around the globe, as well as projected UV radiation levels and climate change factors.image

This Assessment Update by the Environmental Effects Assessment Panel (EEAP) of the United Nations Environment Programme (UNEP) considers the interactive effects of solar UV radiation, global warming, and other weathering factors on plastics. The Assessment illustrates the significance of solar UV radiation in decreasing the durability of plastic materials, degradation of plastic debris, formation of micro- and nanoplastic particles and accompanying leaching of potential toxic compounds. Micro- and nanoplastics have been found in all ecosystems, the atmosphere, and in humans. While the potential biological risks are not yet well-established, the widespread and increasing occurrence of plastic pollution is reason for continuing research and monitoring. Plastic debris persists after its intended life in soils, water bodies and the atmosphere as well as in living organisms. To counteract accumulation of plastics in the environment, the lifetime of novel plastics or plastic alternatives should better match the functional life of products, with eventual breakdown releasing harmless substances to the environment.

Changes in stratospheric ozone and climate over the past 40-plus years have altered the solar ultraviolet (UV) radiation conditions at the Earth’s surface. Ozone depletion has also contributed to climate change across the Southern Hemisphere. These changes are interacting in complex ways to affect human health, food and water security, and ecosystem services. Many adverse effects of high UV exposure have been avoided thanks to the Montreal Protocol with its Amendments and Adjustments, which have effectively controlled the production and use of ozone-depleting substances. This international treaty has also played an important role in mitigating climate change. Climate change is modifying UV exposure and affecting how people and ecosystems respond to UV; these effects will become more pronounced in the future. The interactions between stratospheric ozone, climate and UV radiation will therefore shift over time; however, the Montreal Protocol will continue to have far-reaching benefits for human well-being and environmental sustainability.

The Parties to the Montreal Protocol are informed by three Panels of experts. One of these is the Environmental Effects Assessment Panel (EEAP), which deals with two focal issues. The first focus is the effects of UV radiation on human health, animals, plants, biogeochemistry, air quality, and materials. The second focus is on interactions between UV radiation and global climate change and how these may affect humans and the environment. When considering the effects of climate change, it has become clear that processes resulting in changes in stratospheric ozone are more complex than previously believed. As a result of this, human health and environmental issues will be longer-lasting and more regionally variable. Like the other Panels, the EEAP produces a detailed report 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 Progress Reports of the relevant scientific findings. The most recent of these was for 2015 ( Photochem. Photobiol. Sci ., 2016, 15 , 141-147). The present Progress Report for 2016 assesses some of the highlights and new insights with regard to the interactive nature of the direct and indirect effects of UV radiation, atmospheric processes, and climate change. The more detailed Quadrennial Assessment will be made available in 2018.

The Environmental Effects Assessment Panel (EEAP) is one of three Panels that regularly informs the Parties (countries) to the Montreal Protocol on the effects of ozone depletion and the consequences of climate change interactions with respect to human health, animals, plants, biogeochemistry, air quality, and materials. The Panels provide a detailed assessment report every four years. The most recent 2014 Quadrennial Assessment by the EEAP was published as a special issue of seven papers in 2015 (Photochem. Photobiol. Sci., 2015, 14, 1-184). The next Quadrennial Assessment will be published in 2018/2019. In the interim, the EEAP generally produces an annual update or progress report of the relevant scientific findings. The present progress report for 2015 assesses some of the highlights and new insights with regard to the interactive nature of the effects of UV radiation, atmospheric processes, and climate change.

Local climates in the Northern and Southern Hemisphere are influenced by Arctic Amplification and by interactions of the Antarctic ozone hole with climate change, respectively. Polar changes may affect hydroclimatic conditions in temperate regions, for example, by increasing the length and intensity of precipitation events at Northern Hemisphere midlatitudes. Additionally, global warming has led to the thawing of ancient permafrost soils, particularly in Arctic regions, due to Arctic Amplification. Both heavy precipitation events and thawing of permafrost are increasing the net transfer of terrestrially derived dissolved organic matter (DOM) from land to surface waters. In aquatic ecosystems, UV-induced oxidation of terrigenous DOM (tDOM) produces atmospheric CO2 and this process is one of several mechanisms by which natural organic matter in aquatic and soil environments may play an important role in climate feedbacks. The Arctic is particularly affected by these processes: for example, melting of Arctic sea ice allows solar UV radiation to penetrate into the ice-free Arctic Ocean and to cause photochemical reactions that result in bleaching and mineralization of tDOM. Open questions, in addition to those shown in the Graphical Abstract, remain regarding the resulting contributions of tDOM photomineralization to CO2 production and global warming.

The light-induced redox cycling of iron plays an important role for the formation of iron species that are available to phytoplankton. In aquatic ecosystems, siderophore-type ligands are likely to be involved in the formation of bioavailable iron via photolysis of both solution and surface Fe(III) complexes. Atmospheric waters are important "reactors" for the formation of potentially bioavailable iron. Atmospheric iron input is a significant external iron source to many oceanographic regions. Since iron is an essential micronutrient for phytoplankton, the presence of bioavailable iron in the euphotic zone of oceans is a prerequisite for the removal of atmospheric CO2 via the biological pump, particularly in high-nitrate, low-chlorophyll regions. Light-induced reduction of Fe(III) is accompanied by the oxidation of dissolved organic matter (DOM). DOM photooxidation results in the formation of CO2 and to a smaller extent CO. Also the photooxidation of colored dissolved organic matter (CDOM) may be catalyzed by iron and results in CDOM bleaching. CDOM photobleaching is particularly pronounced in stratified aquatic systems and negatively affects the biological pump since CDOM protects phytoplankton from the damaging solar UV-B radiation. Changes in continental hydrology due to climate and land-use change are expected to enhance the flux of terrigenous DOM and iron from terrestrial to aquatic ecosystems, possibly increasing the rate of CO2 formation via iron-catalyzed photooxidation of DOM. Hence, the light-induced redox cycling of iron may play an important role in climate-carbon cycle feedbacks.

Climate change modulates the effects of solar UV radiation on biogeochemical cycles in terrestrial and aquatic ecosystems, particularly for carbon cycling, resulting in UV-mediated positive or negative feedbacks on climate. Possible positive feedbacks discussed in this assessment include: (i) enhanced UV-induced mineralisation of above ground litter due to aridification; (ii) enhanced UV-induced mineralisation of photoreactive dissolved organic matter (DOM) in aquatic ecosystems due to changes in continental runoff and ice melting; (iii) reduced efficiency of the biological pump due to UV-induced bleaching of coloured dissolved organic matter (CDOM) in stratified aquatic ecosystems, where CDOM protects phytoplankton from the damaging solar UV-B radiation. Mineralisation of organic matter results in the production and release of CO 2 , whereas the biological pump is the main biological process for CO 2 removal by aquatic ecosystems. This paper also assesses the interactive effects of solar UV radiation and climate change on the biogeochemical cycling of aerosols and trace gases other than CO 2 , as well as of chemical and biological contaminants. Interacting effects of solar UV radiation and climate change on biogeochemical cycles are particularly pronounced at terrestrial-aquatic interfaces.

Climate change modulates the effects of solar UV radiation on biogeochemical cycles in terrestrial and aquatic ecosystems, particularly for carbon cycling, resulting in UV-mediated positive or negative feedbacks on climate. Possible positive feedbacks discussed in this assessment include: (i) enhanced UVinduced mineralisation of above ground litter due to aridification; (ii) enhanced UV-induced mineralisation of photoreactive dissolved organic matter (DOM) in aquatic ecosystems due to changes in continental runoff and ice melting; (iii) reduced efficiency of the biological pump due to UV-induced bleaching of coloured dissolved organic matter (CDOM) in stratified aquatic ecosystems, where CDOM protects phytoplankton from the damaging solar UV-B radiation. Mineralisation of organic matter results in the production and release of CO2, whereas the biological pump is the main biological process for CO2 removal by aquatic ecosystems. This paper also assesses the interactive effects of solar UV radiation and climate change on the biogeochemical cycling of aerosols and trace gases other than CO2, as well as of chemical and biological contaminants. Interacting effects of solar UV radiation and climate change on biogeochemical cycles are particularly pronounced at terrestrial-aquatic interfaces.

The projected large increases in damaging ultraviolet radiation as a result of global emissions of ozone-depleting substances have been forestalled by the success of the Montreal Protocol. New challenges are now arising in relation to climate change. We highlight the complex interactions between the drivers of climate change and those of stratospheric ozone depletion, and the positive and negative feedbacks among climate, ozone and ultraviolet radiation. These will result in both risks and benefits of exposure to ultraviolet radiation for the environment and human welfare. This Review synthesizes these new insights and their relevance in a world where changes in climate as well as in stratospheric ozone are altering exposure to ultraviolet radiation with largely unknown consequences for the biosphere.

The parties to the Montreal Protocol are informed by three panels of experts. One of these is the Environmental Effects Assessment Panel (EEAP), which deals with two focal issues. The first focus is the effects of increased UV radiation on human health, animals, plants, biogeochemistry, air quality, and materials. The second focus is on interactions between UV radiation and global climate change and how these may affect humans and the environment. When considering the effects of climate change, it has become clear that processes resulting in changes in stratospheric ozone are more complex than believed previously. As a result of this, human health and environmental problems will be longer-lasting and more regionally variable. Like the other panels, the EEAP produces a detailed report every four years; the most recent was published in 2010 ( Photochem. Photobiol. Sci. , 2011, 10 , 173–300). In the years in between, the EEAP produces less detailed and shorter progress reports, which highlight and assess the significance of developments in key areas of importance to the parties. The next full quadrennial report will be published in 2014–2015.

The parties to the Montreal Protocol are informed by three panels of experts. One of these is the Environmental Effects Assessment Panel (EEAP), which deals with UV radiation and its effects on human health, animals, plants, biogeochemistry, air quality and materials. Since 2000, the analyses and interpretation of these effects have included interactions between 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 believed previously. As a result of this, human health and environmental problems will likely be longer-lasting and more regionally variable. Like the other panels, the EEAP produces a detailed report every four years; the most recent was that for 2006 (Photochem. Photobiol. Sci., 2007, 6, 201-332). In the years in between, the EEAP produces a less detailed and shorter progress report, as is the case for this present one for 2009. A full quadrennial report will follow for 2010.

After the enthusiastic celebration of the 20th Anniversary of the Montreal Protocol on Substances that Deplete the Ozone Layer in 2007, the work for the protection of the ozone layer continues. The Environmental Effects Assessment Panel is one of the three expert panels within the Montreal Protocol. This EEAP deals with the increase of the UV irradiance on the Earth's surface and its effects on human health, animals, plants, biogeochemistry, air quality and materials. For the past few years, interactions of ozone depletion with climate change have also been considered. It has become clear that the environmental problems will be long-lasting. In spite of the fact that the worldwide production of ozone depleting chemicals has already been reduced by 95%, the environmental disturbances are expected to persist for about the next half a century, even if the protective work is actively continued, and completed. The latest full report was published in Photochem. Photobiol. Sci., 2007, 6, 201-332, and the last progress report in Photochem. Photobiol. Sci., 2008, 7, 15-27. The next full report on environmental effects is scheduled for the year 2010. The present progress report 2008 is one of the short interim reports, appearing annually.

Batch adsorption and dissolution experiments with lepidocrocite (γ-FeOOH) and two siderophores, desferrioxamine B (DFOB) and aerobactin, were performed between pH 3 and 8 in the dark and under irradiation with UV–visible light. The increase in surface concentrations of adsorbed DFOB with increasing pH was explained in terms of electrostatic interactions between the protonated and charged terminal amine group of DFOB surface complexes and the charged lepidocrocite surface. The adsorption of aerobactin was consistent with the typical anion-like adsorption behavior of low molecular weight organic acids and indicated that the adsorption properties are strongly determined by the carboxylic acid groups. The adsorption experiments revealed furthermore that the Fe(III)–DFOB solution complex has a very low affinity for the surface, in contrast to Fe(III)–aerobactin solution complexes. In accordance with a surface-controlled mechanism of ligand-promoted dissolution, we found a linear correlation between dissolution rates of lepidocrocite and the surface concentrations of adsorbed DFOB. In the dark, 6- to 8-fold lower dissolution rate coefficients were determined for aerobactin in comparison to DFOB. These results suggested that aerobactin forms surface complexes that are less dissolution-active, characterized by a higher degree of multinuclear surface complexation and/or by less dissolution-active coordination modes of the involved iron-binding groups. For both DFOB and aerobactin, dissolution rate coefficients increased significantly under irradiation with UV–visible light. This increase was interpreted in terms of light-induced reduction of surface Fe(III), primarily by intrinsic photochemical processes of the lepidocrocite bulk phase, based on the observed photoreductive dissolution in the absence of organic ligands between pH 3 and 6. We hypothesize that the α-hydroxycarboxylate group of aerobactin may form a surface complex that additionally promotes photoreductive dissolution by a ligand-to-metal charge-transfer (LMCT) reaction, similar to citrate. However, LMCT reactions involving the α-hydroxycarboxylate group of aerobactin are rather ineffective, based on the comparison of light-induced dissolution rate coefficients determined in the presence of aerobactin and citrate.

This study investigated the kinetics of the photoreductive dissolution of various iron(III)(hydr)oxide phases, lepidocrocite (gamma-FeOOH), ferrihydrite, and hydrous ferric oxide, in the absence of organic ligands as a function of pH in deaerated and aerated suspensions. Photoreductive dissolution of lepidocrocite and ferrihydrite only occurred below pH 6. Under oxic conditions, we observed both the formation of aqueous Fe(II) and H2O2 during photoreductive dissolution of lepidocrocite and ferrihydrite at pH 3. These experimental findings are consistent with the light-induced reduction of surface Fe(III) at the (hydr)oxide surface and the concomitant oxidation of surface-coordinated water or hydroxyl groups, leading to surface Fe(II) and *OH radicals and subsequently to H2O2. The formation of *OH radicals atthe surface was confirmed by photodissolution experiments conducted in the presence of *OH radical scavengers. Kinetic modeling of the experimental data suggests that the relevant pathway for the formation of H2O2 is the reoxidation of surface lattice Fe(II) by molecular oxygen. This study furthermore shows that in the presence of strong iron binding ligands such as siderophores, specifically desferrioxamine B, the photoreductive dissolution of lepidocrocite, ferrihydrite, and to a lesser extent hydrous ferric oxide may also proceed at seawater pH.

UV-induced transformations of colored dissolved organic matter (CDOM, which is part of dissolved organic matter, DOM) affect CDOM absorption properties resulting in the loss of color (referred to as photobleaching). CDOM photobleaching increases the penetration depths of the damaging UV-B radiation into water bodies and strongly depends on the wavelength of solar radiation and on the pH of aquatic systems. UV-induced transformations also affect DOM availability to bacterioplankton, often enhancing the bioavailability of terrigenous DOM and in turn microbial respiration. The combination of UV-induced enhancement of DOM bioavailability and increased export of terrigeneous DOM into estuaries and coastal waters due to climate-related changes in continental hydrology could result in a UV-mediated positive feedback of CO2 accumulation in the atmosphere.The extent and type of CDOM photobleaching and of UV-induced changes in DOM bioavailability depend on (C)DOM chemical composition, which in turn undergoes drastic changes upon UV-induced transformations. Therefore, the chemical characterization of (C)DOM is key for rationalizing UV-induced transformations. In the second section (after the "Introduction"), we review important methods for the elucidation of the chemical composition of (C)DOM. However, this article is not intended to be comprehensive regarding (C)DOM chemical characterization. An important purpose is to provide photochemical bases for the understanding of UV-induced changes of (C)DOM absorption properties and bioavailability (mainly discussed in the sections "Pathways of DOM phototransformations" and "UV-induced changes of the absorption properties of CDOM").

Photoreductive dissolution of lepidocrocite (gamma-FeOOH) in the presence/absence of the siderophore desferrioxamine B (DFOB) was investigated at different wavelengths. At pH 3 in the absence of DFOB, Fe(II) formation rates normalized to the photon flux increased with decreasing wavelengths below 515 nm, consistent with enhanced Fe(II) formation at lower wavelengths by photolysis of surface Fe(III)-hydroxo groups or by surface scavenging of photoelectrons generated in the semiconducting bulk. In the presence of DFOB at pH 3, photoreductive dissolution rates, normalized to the photon flux, increased more strongly with decreasing wavelengths below 440 nm. We hypothesize that acid-catalyzed hydrolysis of DFOB generates degradation products that form photoreactive surface complexes leading to an increase in photodissolution rates at low pH. At pH 8 in the presence of DFOB, normalized photodissolution rates had a maximum in the spectral window 395-435 nm and were significantly smaller at lower wavelengths, suggesting that adsorbed DFOB is directly involved in the reduction of surface Fe(III) by a light-induced ligand-to-metal charge-transfer reaction within the surface Fe(III)-DFOB complex. The strong response in the visible light suggests that photoreductive dissolution of iron (hydr)oxides promoted by siderophores with hydroxamic acid groups may occur deep into in the euphotic zone of oceans.