Environmental plastics in the context of UV radiation, climate change, and the Montreal Protocol.

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.

Plastics in the environment in the context of UV radiation, climate change and the Montreal Protocol: UNEP Environmental Effects Assessment Panel, Update 2023.

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.

Relationship between ozone and biologically relevant UV at 4 NDACC sites.

Clouds and aerosols, as well as overhead ozone, can have large effects on ultraviolet (UV) irradiances. We use statistical methods to remove cloud effects and mean aerosol effects from spectral UV irradiance measurements to investigate the relationship between UV and total column ozone. We show that for fixed solar zenith angles (SZA), seasonal changes in ozone lead to marked changes in clear-sky UV irradiances. Such effects are larger at mid-latitudes than in the tropics. At mid-latitudes, the minimum ozone amount over the course of a year can be about 50 percent of its maximum, with the lowest values in autumn and the highest values in spring. These seasonal ozone changes lead to UV Index (UVI) values in autumn that can exceed those in spring at the same SZA by nearly a factor of two. Differences are even larger for UV spectra weighted by the action spectra for DNA-damaging UV, and for cutaneous previtamin D production. In some cases, the seasonal increase exceeds a factor of 4. The analysis experimentally demonstrates the limits of applicability of the concept of constant Radiative Amplification Factors (RAFs) for estimating effects of changes in ozone for some weighting functions. Changes in DNA-weighted UV and erythemally weighted UV are well represented by the published RAFs. However, there are large SZA dependencies in the case of UVB and vitamin D-weighted UV. For all weightings considered, RAFs calculated from the observations as a function of SZA show similar dependencies between sites, in good agreement with published values, independently of the ozone data source. High quality measurements show that natural variations in ozone are responsible for huge variations in biologically damaging UV, with seasonal changes at fixed solar zenith angles sometimes exceeding a factor of four. The measured changes from thousands of spectra agree well with calculations over a wide range of solar zenith angles.

Estimation of Skin and Ocular Damage Avoided in the United States through Implementation of the Montreal Protocol on Substances that Deplete the Ozone Layer.

Overexposure to ultraviolet (UV) radiation is a threat to human health. It can cause skin cancer and cataracts. Human-made ozone-depleting substances (ODSs) reduce the ozone concentration in the Earth's stratosphere, which acts as a protective shield from UV radiation. To protect and restore the ozone layer, the Montreal Protocol on Substances that Deplete the Ozone Layer was enacted in 1987 to phase out the production and consumption of certain ODSs and was later amended and adjusted to significantly strengthen its requirements. The United States Environmental Protection Agency (EPA) uses its Atmospheric and Health Effects Framework (AHEF) model to assess the adverse human health effects associated with stratospheric ozone depletion and the U.S. health benefits from the global implementation of the Montreal Protocol. Comparing the Montreal Protocol as amended and adjusted with a scenario of no controls on ODSs showed the prevention of an estimated 443 million cases of skin cancer and 63 million cataract cases for people born in the United States between 1890 and 2100. In addition, 2.3 million skin cancer deaths are avoided. Compared with the original 1987 Montreal Protocol, strengthening the Montreal Protocol, through its subsequent amendments and adjustments, resulted in an estimated 230 million fewer skin cancer cases, 1.3 million fewer skin cancer deaths, and 33 million fewer cataract cases.

The success of the Montreal Protocol in mitigating interactive effects of stratospheric ozone depletion and climate change on the environment.

The Montreal Protocol and its Amendments have been highly effective in protecting the stratospheric ozone layer, preventing global increases in solar ultraviolet-B radiation (UV-B; 280-315 nm) at Earth's surface, and reducing global warming. While ongoing and projected changes in UV-B radiation and climate still pose a threat to human health, food security, air and water quality, terrestrial and aquatic ecosystems, and construction materials and fabrics, the Montreal Protocol continues to play a critical role in protecting Earth's inhabitants and ecosystems by addressing many of the United Nations Sustainable Development Goals.

The Montreal Protocol protects the terrestrial carbon sink.

The control of the production of ozone-depleting substances through the Montreal Protocol means that the stratospheric ozone layer is recovering1 and that consequent increases in harmful surface ultraviolet radiation are being avoided2,3. The Montreal Protocol has co-benefits for climate change mitigation, because ozone-depleting substances are potent greenhouse gases4-7. The avoided ultraviolet radiation and climate change also have co-benefits for plants and their capacity to store carbon through photosynthesis8, but this has not previously been investigated. Here, using a modelling framework that couples ozone depletion, climate change, damage to plants by ultraviolet radiation and the carbon cycle, we explore the benefits of avoided increases in ultraviolet radiation and changes in climate on the terrestrial biosphere and its capacity as a carbon sink. Considering a range of strengths for the effect of ultraviolet radiation on plant growth8-12, we estimate that there could have been 325-690 billion tonnes less carbon held in plants and soils by the end of this century (2080-2099) without the Montreal Protocol (as compared to climate projections with controls on ozone-depleting substances). This change could have resulted in an additional 115-235 parts per million of atmospheric carbon dioxide, which might have led to additional warming of global-mean surface temperature by 0.50-1.0 degrees. Our findings suggest that the Montreal Protocol may also be helping to mitigate climate change through avoided decreases in the land carbon sink.

Ultraviolet Radiation Environment of a Tropical Megacity in Transition: Mexico City 2000-2019.

Tropical regions experience naturally high levels of UV radiation, but urban pollution can reduce these levels substantially. We analyzed 20 years of measurements of the UV index (UVI) at several ground-level locations in the Mexico City Metropolitan Area and compared these data with the UVI values derived from the satellite observations of ozone and clouds (but not local pollution). The ground-based measurements were systematically lower than the satellite-based estimates by ca. 40% in 2000 and 25% in 2019. Calculations with a radiative transfer model using observed concentrations of air pollutants explained well the difference between satellite and ground-based UVI and showed specific contributions from aerosols, O3, NO2, and SO2 in decreasing order of importance. Such large changes in UV radiation between 2000 and 2019 have important implications ranging from human health (skin cancer and cataract induction) to air pollution control (photochemical smog formation).

Correction: Are current guidelines for sun protection optimal for health? Exploring the evidence.

Correction for 'Are current guidelines for sun protection optimal for health? Exploring the evidence' by Robyn M. Lucas et al., Photochem. Photobiol. Sci., 2018, DOI: 10.1039/c7pp00374a.

Solar UV radiation and microbial life in the atmosphere.

Many microorganisms are alive while suspended in the atmosphere, and some seem to be metabolically active during their time there. One of the most important factors threatening their life and activity is solar ultraviolet (UV) radiation. Quantitative understanding of the spatial and temporal survival patterns in the atmosphere, and of the ultimate deposition of microbes to the surface, is limited by a number factors some of which are discussed here. These include consideration of appropriate spectral sensitivity functions for biological damage (e.g. inactivation), and the estimation of UV radiation impingent on a microorganism suspended in the atmosphere. We show that for several bacteria (E. coli, S. typhimurium, and P. acnes) the inactivation rates correlate well with irradiances weighted by the DNA damage spectrum in the UV-B spectral range, but when these organisms show significant UV-A (or visible) sensitivities, the correlations become clearly non-linear. The existence of these correlations enables the use of a single spectrum (here DNA damage) as a proxy for sensitivity spectra of other biological effects, but with some caution when the correlations are strongly non-linear. The radiative quantity relevant to the UV exposure of a suspended particle is the fluence rate at an altitude above ground, while down-welling irradiance at ground-level is the quantity most commonly measured or estimated in satellite-derived climatologies. Using a radiative transfer model that computes both quantities, we developed a simple parameterization to exploit the much larger irradiance data bases to estimate fluence rates, and present the first fluence-rate based climatology of DNA-damaging UV radiation in the atmosphere. The estimation of fluence rates in the presence of clouds remains a particularly challenging problem. Here we note that both reductions and enhancements in the UV radiation field are possible, depending mainly on cloud optical geometry and prevailing solar zenith angles. These complex effects need to be included in model simulations of the atmospheric life cycle of the organisms.

Are current guidelines for sun protection optimal for health? Exploring the evidence.

Exposure of the skin to ultraviolet (UV) radiation is the main risk factor for skin cancer, and a major source of vitamin D, in many regions of the world. Sun protection messages to minimize skin cancer risks but avoid vitamin D deficiency are challenging, partly because levels of UV radiation vary by location, season, time of day, and atmospheric conditions. The UV Index provides information on levels of UV radiation and is a cornerstone of sun protection guidelines. Current guidelines from the World Health Organization are that sun protection is required only when the UV Index is 3 or greater. This advice is pragmatic rather than evidence based. The UV Index is a continuous scale; more comprehensive sun protection is required as the UV Index increases. In addition, a wide range of UVA doses is possible with a UVI of 3, from which there may be health consequences, while full sun protection when the UVI is "moderate" (between 3 and 5) may limit vitamin D production. Finally, the duration of time spent in the sun is an essential component of a public health message, in addition to the intensity of ambient UV radiation as measured by the UV Index. Together these provide the dose of UV radiation that is relevant to both skin cancer genesis and vitamin D production. Further education is required to increase the understanding of the UV Index; messages framed using the UV Index need to incorporate the importance of duration of exposure and increasing sun protection with increasing dose of UV radiation.

Climate change-induced increases in precipitation are reducing the potential for solar ultraviolet radiation to inactivate pathogens in surface waters.

Climate change is accelerating the release of dissolved organic matter (DOM) to inland and coastal waters through increases in precipitation, thawing of permafrost, and changes in vegetation. Our modeling approach suggests that the selective absorption of ultraviolet radiation (UV) by DOM decreases the valuable ecosystem service wherein sunlight inactivates waterborne pathogens. Here we highlight the sensitivity of waterborne pathogens of humans and wildlife to solar UV, and use the DNA action spectrum to model how differences in water transparency and incident sunlight alter the ability of UV to inactivate waterborne pathogens. A case study demonstrates how heavy precipitation events can reduce the solar inactivation potential in Lake Michigan, which provides drinking water to over 10 million people. These data suggest that widespread increases in DOM and consequent browning of surface waters reduce the potential for solar UV inactivation of pathogens, and increase exposure to infectious diseases in humans and wildlife.

Sources, fates, toxicity, and risks of trifluoroacetic acid and its salts: Relevance to substances regulated under the Montreal and Kyoto Protocols.

Trifluoroacetic acid (TFA) is a breakdown product of several hydrochlorofluorocarbons (HCFC), regulated under the Montreal Protocol (MP), and hydrofluorocarbons (HFC) used mainly as refrigerants. Trifluoroacetic acid is (1) produced naturally and synthetically, (2) used in the chemical industry, and (3) a potential environmental breakdown product of a large number (>1 million) chemicals, including pharmaceuticals, pesticides, and polymers. The contribution of these chemicals to global amounts of TFA is uncertain, in contrast to that from HCFC and HFC regulated under the MP. TFA salts are stable in the environment and accumulate in terminal sinks such as playas, salt lakes, and oceans, where the only process for loss of water is evaporation. Total contribution to existing amounts of TFA in the oceans as a result of the continued use of HCFCs, HFCs, and hydrofluoroolefines (HFOs) up to 2050 is estimated to be a small fraction (<7.5%) of the approximately 0.2 µg acid equivalents/L estimated to be present at the start of the millennium. As an acid or as a salt TFA is low to moderately toxic to a range of organisms. Based on current projections of future use of HCFCs and HFCs, the amount of TFA formed in the troposphere from substances regulated under the MP is too small to be a risk to the health of humans and environment. However, the formation of TFA derived from degradation of HCFC and HFC warrants continued attention, in part because of a long environmental lifetime and due many other potential but highly uncertain sources.

Modeling the influence of alkane molecular structure on secondary organic aerosol formation.

Secondary Organic Aerosols (SOA) production and ageing is a multigenerational oxidation process involving the formation of successive organic compounds with higher oxidation degree and lower vapor pressure. Intermediate Volatility Organic Compounds (IVOC) emitted to the atmosphere are expected to be a substantial source of SOA. These emitted IVOC constitute a complex mixture including linear, branched and cyclic alkanes. The explicit gas-phase oxidation mechanisms are here generated for various linear and branched C10-C22 alkanes using the GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) and SOA formation is investigated for various homologous series. Simulation results show that both the size and the branching of the carbon skeleton are dominant factors driving the SOA yield. However, branching appears to be of secondary importance for the particle oxidation state and composition. The effect of alkane molecular structure on SOA yields appears to be consistent with recent laboratory observations. The simulated SOA composition shows, however, an unexpected major contribution from multifunctional organic nitrates. Most SOA contributors simulated for the oxidation of the various homologous series are far too reduced to be categorized as highly oxygenated organic aerosols (OOA). On a carbon basis, the OOA yields never exceeded 10% regardless of carbon chain length, molecular structure or ageing time. This version of the model appears clearly unable to explain a large production of OOA from alkane precursors.

Environmental effects of ozone depletion and its interactions with climate change: progress report, 2011.

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.

Influence of tropospheric ozone control on exposure to ultraviolet radiation at the surface.

Improving air quality by reducing ambient ozone (O(3)) will likely lower O(3) concentrations throughout the troposphere and increase the transmission of solar ultraviolet (UV) radiation to the surface. The changes in surface UV radiation between two control scenarios (nominally 84 and 70 ppb O(3) for summer 2020) in the Eastern two-thirds of the contiguous U.S. are estimated, using tropospheric O(3) profiles calculated with a chemistry-transport model (Community Multi-Scale Air Quality, CMAQ) as inputs to a detailed model of the transfer of solar radiation through the atmosphere (tropospheric ultraviolet-visible, TUV) for clear skies, weighed for the wavelengths known to induce sunburn and skin cancer. Because the incremental emission controls differ according to region, strong spatial variability in O(3) reductions and in corresponding UV radiation increments is seen. The geographically averaged UV increase is 0.11 ± 0.03%, whereas the population-weighted increase is larger, 0.19 ± 0.06%, because O(3) reductions are greater in more densely populated regions. These relative increments in exposure are non-negligible given the already high incidence of UV-related health effects, but are lower by an order of magnitude or more than previous estimates.

Empirical evaluation of a simple analytical formula for the ultraviolet index.

This paper focuses on the estimation of the UV Index (UVI) for all sky conditions using a simple analytical parameterization involving three independent variables: the solar zenith angle, the total ozone column and the clearness index. Measurements of the UVI made at Badajoz and Cáceres (Southwestern Spain) from January 2006 to December 2007 are used to estimate optimal fitting parameters for the model formula, while measurements from January to December 2008 are used to show that the formula-based estimations have mean absolute errors lower than 6% and R(2) ca 0.99.

Modeling the multiday evolution and aging of secondary organic aerosol during MILAGRO 2006.

In this study, we apply several recently proposed models to the evolution of secondary organic aerosols (SOA) and organic gases advected from downtown Mexico City at an altitude of ∼3.5 km during three days of aging, in a way that is directly comparable to simulations in regional and global models. We constrain the model with and compare its results to available observations. The model SOA formed from oxidation of volatile organic compounds (V-SOA) when using a non-aging SOA parameterization cannot explain the observed SOA concentrations in aged pollution, despite the increasing importance of the low-NO(x) channel. However, when using an aging SOA parameterization, V-SOA alone is similar to the regional aircraft observations, highlighting the wide diversity in current V-SOA formulations. When the SOA formed from oxidation of semivolatile and intermediate volatility organic vapors (SI-SOA) is computed following Robinson et al. (2007) the model matches the observed SOA mass, but its O/C is ∼2× too low. With the parameterization of Grieshop et al. (2009), the total SOA mass is ∼2× too high, but O/C and volatility are closer to the observations. Heating or dilution cause the evaporation of a substantial fraction of the model SOA; this fraction is reduced by aging although differently for heating vs dilution. Lifting of the airmass to the free-troposphere during dry convection substantially increases SOA by condensation of semivolatile vapors; this effect is reduced by aging.

Global methane emission estimates from ultraviolet irradiation of terrestrial plant foliage.

SUMMARY: *Several studies have reported in situ methane (CH(4)) emissions from vegetation foliage, but there remains considerable debate about its significance as a global source. Here, we report a study that evaluates the role of ultraviolet (UV) radiation-driven CH(4) emissions from foliar pectin as a global CH(4) source. *We combine a relationship for spectrally weighted CH(4) production from pectin with a global UV irradiation climatology model, satellite-derived leaf area index (LAI) and air temperature data to estimate the potential global CH(4) emissions from vegetation foliage. *Our results suggest that global foliar CH(4) emissions from UV-irradiated pectin could account for 0.2-1.0 Tg yr(-1), of which 60% is from tropical latitudes, corresponding to < 0.2% of total CH(4) sources. *Our estimate is one to two orders of magnitude lower than previous estimates of global foliar CH(4) emissions. Recent studies have reported that pectin is not the only molecular source of UV-driven CH(4) emissions and that other environmental stresses may also generate CH(4). Consequently, further evaluation of such mechanisms of CH(4) generation is needed to confirm the contribution of foliage to the global CH(4) budget.