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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., (© 2024. The Author(s).)

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., (© 2023. The Author(s).)

Terrestrial organisms and ecosystems are being exposed to new and rapidly changing combinations of solar UV radiation and other environmental factors because of ongoing changes in stratospheric ozone and climate. In this Quadrennial Assessment, we examine the interactive effects of changes in stratospheric ozone, UV radiation and climate on terrestrial ecosystems and biogeochemical cycles in the context of the Montreal Protocol. We specifically assess effects on terrestrial organisms, agriculture and food supply, biodiversity, ecosystem services and feedbacks to the climate system. Emphasis is placed on the role of extreme climate events in altering the exposure to UV radiation of organisms and ecosystems and the potential effects on biodiversity. We also address the responses of plants to increased temporal variability in solar UV radiation, the interactive effects of UV radiation and other climate change factors (e.g. drought, temperature) on crops, and the role of UV radiation in driving the breakdown of organic matter from dead plant material (i.e. litter) and biocides (pesticides and herbicides). Our assessment indicates that UV radiation and climate interact in various ways to affect the structure and function of terrestrial ecosystems, and that by protecting the ozone layer, the Montreal Protocol continues to play a vital role in maintaining healthy, diverse ecosystems on land that sustain life on Earth. Furthermore, the Montreal Protocol and its Kigali Amendment are mitigating some of the negative environmental consequences of climate change by limiting the emissions of greenhouse gases and protecting the carbon sequestration potential of vegetation and the terrestrial carbon pool., (© 2023. The Author(s).)

Nanomaterials are increasingly used in polymer composites to enhance their properties, such as mechanical performance and durability, increased electrical conductivity, and improved optical clarity. Here results are presented of a study simulating effects of weathering on degradation of a nanosilica-low-density polyethylene (LDPE) composite. Release of nanosilica from LDPE composites is a potential source of toxic SiO 2 . Nanosilica based LDPE composites were weathered under carefully controlled conditions by exposure to simulated sunlight. The effects of an added pro-oxidant on weathering was examined. Weathering of the composites with pro-oxidant was determined by quantifying changes in infrared spectroscopic properties (Fourier transform infrared spectroscopy / FTIR); mechanical properties, atomic force microscopy (AFM), scanning electron microscopy and other procedures. Wavelength effects on weathering rates were determined in a series of irradiations using simulated solar radiation passed through light filters that blocked different parts of the ultraviolet spectral region. Rates and spectral irradiance were then analyzed to develop spectral weighting functions (SWFs) that quantify wavelength effects on the sunlight-induced weathering of the pro-oxidant amended composites.

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

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., (© 2022. The Author(s).)

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.

Fecal indicator organisms (FIOs), such as Escherichia coli and enterococci, are often used as surrogates of contamination in the context of beach management; however, bacteriophages may be more reliable indicators than FIO due to their similarity to viral pathogens in terms of size and persistence in the environment. In the past, mechanistic modeling of environmental contamination has focused on FIOs, with virus and bacteriophage modeling efforts remaining limited. In this paper, we describe the development and application of a fate and transport model of somatic and F-specific coliphages for the Washington Park beach in Lake Michigan, which is affected by riverine outputs from the nearby Trail Creek. A three-dimensional model of coliphage transport and photoinactivation was tested and compared with a previously reported E. coli fate and transport model. The light-based inactivation of the phages was modeled using organism-specific action spectra. Results indicate that the coliphage models outperformed the E. coli model in terms of reliably predicting observed E. coli/coliphage concentrations at the beach. This is possibly due to the presence of additional E. coli sources that were not accounted for in the modeling. The coliphage models can be used to test hypotheses about potential sources and their behavior and for predictive modeling., (© 2020 The Authors. Journal of Environmental Quality © 2020 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.)

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.

Increases in the production and applications of graphene oxide (GO), coupled with reports of its toxic effects, are raising concerns about its health and ecological risks. To better understand GO's fate and transport in aquatic environments, we investigated its reactivity with three major reactive oxygen species (ROS): HO˙, 1 O 2 , and O 2 ˙ - . Second-order degradation rate constants were calculated on the loss of dissolved organic carbon (DOC) and steady-state concentration of individual ROS species. Absolute second-order rate constants were determined by competition kinetics to be 6.24 × 10 4 , 8.65 × 10 2 , and 0.108 mg-C -1 L s -1 for HO˙, 1 O 2 , and O 2 ˙ - , respectively. Photoreduced GO products had a similar reactivity to HO˙ as GO, with rate constants comparable to polycyclic aromatic compounds, but about two times higher than dissolved organic matter on a per carbon basis. Reaction with HO˙ resulted in decomposition of GO, with loss of color and formation of photoluminescent products. In contrast, reaction with 1 O 2 showed no effect on DOC, UV-vis spectra or particle size, while reaction with O 2 ˙- slightly reduced GO. These results demonstrate that interactions with ROS will affect GO's persistence in water and should be considered in exposure assessment or environmental application of GO., Competing Interests: Conflicts of interest There are no conflicts of interest to declare.

In aerobic natural surface water, a silver ion (Ag + ) exists in various Ag + -Cl - complexes because of a strong affinity for a chloride ion (Cl - ); however, little information is available about the role of the Ag + -Cl - complex in the formation of silver nanoparticles (AgNPs). This study demonstrates that soluble AgCl x ( x -1)- species act as a precursor of AgNPs under simulated sunlight irradiation. The AgNP photoproduction increases with Cl - levels up to 0.0025 M ([Ag + ] = 5 × 10 -7 M) and decreases with continued Cl - level increase (0.09 to 0.5 M). At [Cl - ] ≤ 0.0025 M (freshwater systems), photoproduction of AgNP correlates with the formation of AgCl (aq) , suggesting that it is the most photoactive species in those systems. Matching the ionic strength of experiments containing various Cl - levels indicates that the trend in AgNP photoproduction correlates with Cl - concentrations rather than ionic strength-induced effects. The photoproduction of AgNPs is highly pH-dependent, especially at pH > 8.3. The UV and visible light portions of the solar light spectrum are equally important in photoreduction of Ag + . Overall, we show evidence that AgCl x ( x -1)- species irradiated under sunlight conditions contributes to the formation of nanosized silver (Ag) in the environment.

Global change influences biogeochemical cycles within and between environmental compartments (i.e., the cryosphere, terrestrial and aquatic ecosystems, and the atmosphere). A major effect of global change on carbon cycling is altered exposure of natural organic matter (NOM) to solar radiation, particularly solar UV radiation. In terrestrial and aquatic ecosystems, NOM is degraded by UV and visible radiation, resulting in the emission of carbon dioxide (CO 2 ) and carbon monoxide, as well as a range of products that can be more easily degraded by microbes (photofacilitation). On land, droughts and land-use change can reduce plant cover causing an increase in exposure of plant litter to solar radiation. The altered transport of soil organic matter from terrestrial to aquatic ecosystems also can enhance exposure of NOM to solar radiation. An increase in emission of CO 2 from terrestrial and aquatic ecosystems due to the effects of global warming, such as droughts and thawing of permafrost soils, fuels a positive feedback on global warming. This is also the case for greenhouse gases other than CO 2 , including methane and nitrous oxide, that are emitted from terrestrial and aquatic ecosystems. These trace gases also have indirect or direct impacts on stratospheric ozone concentrations. The interactive effects of UV radiation and climate change greatly alter the fate of synthetic and biological contaminants. Contaminants are degraded or inactivated by direct and indirect photochemical reactions. The balance between direct and indirect photodegradation or photoinactivation of contaminants is likely to change with future changes in stratospheric ozone, and with changes in runoff of coloured dissolved organic matter due to climate and land-use changes.

Coliphages can indicate contamination of recreational waters and previous studies show that sunlight is important in altering densities of coliphages, other indicator microorganisms, and pathogens in aquatic environments. Here, we report on laboratory studies of light-induced inactivation of two coliphage groups-male-specific (F+) and somatic coliphage-under various conditions in phosphate-buffered water (PBW). Strains isolated from wastewater treatment facilities and laboratory strains (MS2 and phiX174 coliphages) were evaluated. Inactivation rates were determined in a series of irradiations using simulated solar radiation passed through light filters that blocked different parts of the ultraviolet spectral region. Inactivation rates and spectral irradiance from these experiments were then analyzed to develop biological weighting functions (BWFs) for the light-induced inactivation. BWFs were used to model the inactivation of coliphages over a range of conditions in aquatic environments that included two beach sites in Lake Michigan and one in Lake Erie. For example, modeled effects of sunlight attenuation, using UV absorption data from the three Great Lakes beach sites, inferred that direct photoinactivation rate constants, averaged over a one-meter water column in swimmable areas, were reduced 2- to 5-fold, compared to near-surface rate constants.

Health-relevant microorganisms present in natural surface waters and engineered treatment systems that are exposed to sunlight can be inactivated by a complex set of interacting mechanisms. The net impact of sunlight depends on the solar spectral irradiance, the susceptibility of the specific microorganism to each mechanism, and the water quality; inactivation rates can vary by orders of magnitude depending on the organism and environmental conditions. Natural organic matter (NOM) has a large influence, as it can attenuate radiation and thus decrease inactivation by endogenous mechanisms. Simultaneously NOM sensitizes the formation of reactive intermediates that can damage microorganisms via exogenous mechanisms. To accurately predict inactivation and design engineered systems that enhance solar inactivation, it is necessary to model these processes, although some details are not yet sufficiently well understood. In this critical review, we summarize the photo-physics, -chemistry, and -biology that underpin sunlight-mediated inactivation, as well as the targets of damage and cellular responses to sunlight exposure. Viruses that are not susceptible to exogenous inactivation are only inactivated if UVB wavelengths (280-320 nm) are present, such as in very clear, open waters or in containers that are transparent to UVB. Bacteria are susceptible to slightly longer wavelengths. Some viruses and bacteria (especially Gram-positive) are susceptible to exogenous inactivation, which can be initiated by visible as well as UV wavelengths. We review approaches to model sunlight-mediated inactivation and illustrate how the environmental conditions can dramatically shift the inactivation rate of organisms. The implications of this mechanistic understanding of solar inactivation are discussed for a range of applications, including recreational water quality, natural treatment systems, solar disinfection of drinking water (SODIS), and enhanced inactivation via the use of sensitizers and photocatalysts. Finally, priorities for future research are identified that will further our understanding of the key role that sunlight disinfection plays in natural systems and the potential to enhance this process in engineered systems.

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.

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.

Engineered nanomaterials (ENM) are a growing aspect of the global economy, and their safe and sustainable development, use, and eventual disposal requires the capability to forecast and avoid potential problems. This review provides a framework to evaluate the health and safety implications of ENM releases into the environment, including purposeful releases such as for antimicrobial sprays or nano-enabled pesticides, and inadvertent releases as a consequence of other intended applications. Considerations encompass product life cycles, environmental media, exposed populations, and possible adverse outcomes. This framework is presented as a series of compartmental flow diagrams that serve as a basis to help derive future quantitative predictive models, guide research, and support development of tools for making risk-based decisions. After use, ENM are not expected to remain in their original form due to reactivity and/or propensity for hetero-agglomeration in environmental media. Therefore, emphasis is placed on characterizing ENM as they occur in environmental or biological matrices. In addition, predicting the activity of ENM in the environment is difficult due to the multiple dynamic interactions between the physical/chemical aspects of ENM and similarly complex environmental conditions. Others have proposed the use of simple predictive functional assays as an intermediate step to address the challenge of using physical/chemical properties to predict environmental fate and behavior of ENM. The nodes and interactions of the framework presented here reflect phase transitions that could be targets for development of such assays to estimate kinetic reaction rates and simplify model predictions. Application, refinement, and demonstration of this framework, along with an associated knowledgebase that includes targeted functional assay data, will allow better de novo predictions of potential exposures and adverse outcomes.

Single-walled carbon nanotubes (SWCNTs) with proper functionalization are desirable for applications that require dispersion in aqueous and biological environments, and functionalized SWCNTs also serve as building blocks for conjugation with specific molecules in these applications. In this study, we examined the phototransformation of carboxylated SWCNTs and associated amorphous carbon impurities in the presence or absence of H2O2 under simulated sunlight conditions. We found that while carboxylated SWCNTs were rather unreactive with respect to direct solar photolysis, they photoreacted in the presence of H2O2, forming CO2 and strongly aggregated SWCNT products that precipitated. Photoreaction caused SWCNTs to lose oxygen-containing functionalities, and interestingly, the resulting photoproducts had spectral characteristics similar to those of parent carboxylated SWCNTs whose amorphous carbon was removed by base washing. These results indicated that photoreaction of the amorphous carbon was likely involved. The removal of amorphous carbon after indirect photoreaction was confirmed with thermogravimetric analysis (TGA). Further studies using carboxylated SWCNTs with and without base washing indicate that amorphous carbon reduced the extent of aggregation caused by photoreaction. The second-order rate constant for carboxylated SWCNTs reacting with (•)OH was estimated to be in the range of 1.7-3.8 × 10(9) MC(-1) s(-1). The modeled phototransformation half-lives fall in the range of 2.8-280 days in typical sunlit freshwaters. Our study indicates that photosensitized reactions involving (•)OH may be a transformation and removal pathway of functionalized SWCNTs in the aquatic environment, and that the residual amorphous carbon associated with SWCNTs plays a role in SWCNT stabilization.

Carbon nanotubes (CNTs) photosensitize the production of reactive oxygen species that may damage organisms by biomembrane oxidation or mediate environmental transformations of CNTs. Photosensitization by derivatized carbon nanotubes from various synthetic methods, and thus with different intrinsic characteristics (e.g., diameter and electronic properties), has been investigated under environmentally relevant aquatic conditions. We used the CNT-sensitized photoisomerization of sorbic acid ((2E,4E)-hexa-2,4-dienoic acid) and singlet oxygen formation to quantify the triplet states ((3)CNT*) formed upon irradiation of selected single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs). The CNTs used in our studies were derivatized by carboxyl groups to facilitate their dispersion in water. Results indicate that high-defect-density (thus well-stabilized), small-diameter, and semiconducting-rich CNTs have higher-measured excited triplet state formation and therefore singlet oxygen ((1)O2) yield. Derivatized SWCNTs were significantly more photoreactive than derivatized MWCNTs. Moreover, addition of sodium chloride resulted in increased aggregation and small increases in (1)O2 production of CNTs. The most photoreactive CNTs exhibited comparable photoreactivity (in terms of (3)CNT* formation and (1)O2 yield) to reference natural organic matter (NOM) under sunlight irradiation with the same mass-based concentration. Selected reference NOM could therefore be useful in evaluating environmental photoreactivity or intended antibacterial applications of CNTs.

In this study, we investigate the role of simulated sunlight on the physicochemical properties, aggregation, and deposition of graphene oxide (GO) in aquatic environments. Results show that light exposure under varied environmental conditions significantly impacts the physicochemical properties and aggregation/deposition behaviors of GO. Photo-transformation has negligible effects on GO surface charge, however, GO aggregation rates increase with irradiation time for direct photo-transformation under both aerobic and anaerobic conditions. Under anaerobic conditions, photo-reduced GO has a greater tendency to form aggregates than under aerobic conditions. Aggregation of photo-transformed GO is notably influenced by ion valence, with higher aggregation found in the presence of divalent ions versus monovalent, but adding natural organic matter (NOM) reduces it. QCM-D studies show that deposition of GO on surfaces coated with organic matter decreases with increased GO irradiation time, indicating a potential increase in GO mobility due to photo-transformation. General deposition trends on Suwannee River Humic Acid (SRHA)-coated surfaces are control GO > aerobically photo-transformed GO ≈ anaerobically photo-transformed GO. The release of deposited GO from SRHA-coated surfaces decreases with increased irradiation time, indicating that photo-transformed GO is strongly attached to the NOM-coated surface., (Published by Elsevier Ltd.)

Graphene oxide (GO) is promising in scalable production and has useful properties that include semiconducting behavior, catalytic reactivity, and aqueous dispersibility. In this study, we investigated the photochemical fate of GO under environmentally relevant sunlight conditions. The results indicate that GO readily photoreacts under simulated sunlight with the potential involvement of electron-hole pair creation. GO was shown to photodisproportionate to CO2, reduced materials similar to reduced GO (rGO) that are fragmented compared to the starting material, and low molecular-weight (LMW) species. Kinetic studies show that the rate of the initially rapid photoreaction of GO is insensitive to the dissolved oxygen content. In contrast, at longer time points (>10 h), the presence of dissolved oxygen led to a greater production of CO2 than the same GO material under N2-saturated conditions. Regardless, the rGO species themselves persist after extended irradiation equivalent to 2 months in natural sunlight, even in the presence of dissolved oxygen. Overall, our findings indicate that GO phototransforms rapidly under sunlight exposure, resulting in chemically reduced and persistent photoproducts that are likely to exhibit transport and toxic properties unique from parent GO.

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 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.

Single-wall carbon nanotubes (SWCNTs) have a variety of potential and demonstrated applications, and their production rates are increasing rapidly. This increase in production has motivated research on their transport and potential transformation and their toxicity in the environment. In this work, we examined the direct and indirect photoreactivity of SWCNTs under sunlight conditions. We found that the direct photoreactivity of pristine SWCNTs is generally low; however, indirect photoreaction involving ·OH may be significant in natural aquatic environments. Environmental photochemical reactions generating ·OH lead to distinct changes in SWCNT fluorescence efficiency in the near-infrared (NIR) region, Raman spectra, and light attenuation spectra in the UV, visible, and NIR regions, indicating that covalent functionalization of SWCNTs occurs. The reactivity of SWCNTs to ·OH is dependent on the specific chiral structure of the SWCNTs and the surfactant associated with it. An operationally defined second-order rate constant (based on the decrease in NIR fluorescence signals) for all SWCNT chiral species reacting with ·OH was estimated to be (2.91 ± 1.30) × 10(10) M(-1 )s(-1). Our work suggests that photochemical reactions may be a significant transformation pathway of SWCNTs in aquatic systems.

Photobiogeochemical reactions involving metal species can be a source of naturally occurring nanoscale materials in the aquatic environment. This study demonstrates that, under simulated sunlight exposure, ionic Ag is photoreduced in river water or synthetic natural water samples that contain natural organic matter (NOM), forming Ag nanoparticles (AgNPs) that transform in size and shape and precipitate out upon extended irradiation. We show that the dissolved oxygen concentration does not appear to affect AgNP formation rates, indicating that reactive transients such as superoxide, hydrated electron, and triplet NOM do not play a large role. By varying pH and NOM concentrations and adding competing cations on the AgNP formation, we present three lines of evidence to show that Ag ion photoreduction likely involves ionic Ag binding to NOM. Our work suggests that photochemical reactions involving ionic Ag and NOM can be a source of nanosized Ag in the environment.

Effects of natural organic matter (NOM) on the photoreaction kinetics of fullerenes (i.e., C60 and fullerenol) were investigated using simulated sunlight and monochromatic radiation (365 nm). NOM from several sources quenched (slowed) the photoreaction of C60 aggregates in water (aqu/nC60), but sensitized (accelerated) photoreaction of fullerenol. Kinetic studies indicated that the quenching occurred through a static mechanism involving NOM molecules adsorbed on the aqu/nC60 surface. Quenching constants for the photoreaction of aqu/nC60 correlated approximately with optical parameters related to the aromaticity and molecular size of the NOM. Association of aqu/nC60 particles with NOM was investigated indirectly via the study of the aggregation kinetics of colloidal C60 in the presence and absence of NOM as a function of NaCl strength at pH 7. In contrast to aqu/nC60, the photoreaction efficiencies of the hydrophilic fullerene, fullerenol, increased linearly with increasing NOM concentrations and kinetic parameters for the sensitized photoreactions increased as the spectral slope coefficients and ratio of absorption coefficients at 254 to 365 nm (E2:E3) of the NOM increased. The results indicate that triplet excited states of the NOM are key intermediates in the photosensitized reactions.

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., (This journal is © The Royal Society of Chemistry and Owner Societies 2012)

Reactive oxygen species (ROS) are one of the most important intermediates in chemical, photochemical, and biological processes. To understand the environmental exposure and toxicity of fullerenes better, the production and consumption of ROS (singlet oxygen, superoxide, hydrogen peroxide, and hydroxyl radicals) by Buckminster fullerene (C(60) ) and fullerenol were investigated in aqueous systems. Fullerenol exhibits higher photoproduction efficiency of singlet oxygen and superoxide than aqueous suspensions of C(60) aggregates (aqu/nC(60) ), and this higher efficiency results in higher steady-state concentrations of these two ROS. Transmission electron microscopy indicates that the C(60) molecules in aqu/nC(60) are much more closely packed than the C(60) cages in fullerenol. These observations provide additional evidence that the lower ROS production efficiency of aqu/nC(60) is attributable primarily to efficient self-quenching of C(60) triplet states. Production of singlet oxygen by aqu/nC(60) is accelerated by increasing oxygen concentration and in part is sensitized by fluorescent photoproducts that accumulate during irradiation. The fullerenes react slowly with singlet oxygen (second-order rate constant <4 × 10(5)  M(-1)  s(-1) ), but react rapidly with hydroxyl radicals (second-order rate constants of 5.4 × 10(9) and 4 × 10(8)  M(-1)  s(-1) for aqu/nC(60) and fullerenol, respectively). These results show that environmental conditions, including light exposure and oxygen concentration, have the potential to impact the generation of toxic ROS by fullerenes., (Copyright © 2011 SETAC.)

Solar UV radiation, climate and other drivers of global change are undergoing significant changes and models forecast that these changes will continue for the remainder of this century. Here we assess the effects of solar UV radiation on biogeochemical cycles and the interactions of these effects with climate change, including feedbacks on climate. Such interactions occur in both terrestrial and aquatic ecosystems. While there is significant uncertainty in the quantification of these effects, they could accelerate the rate of atmospheric CO(2) increase and subsequent climate change beyond current predictions. The effects of predicted changes in climate and solar UV radiation on carbon cycling in terrestrial and aquatic ecosystems are expected to vary significantly between regions. The balance of positive and negative effects on terrestrial carbon cycling remains uncertain, but the interactions between UV radiation and climate change are likely to contribute to decreasing sink strength in many oceanic regions. Interactions between climate and solar UV radiation will affect cycling of elements other than carbon, and so will influence the concentration of greenhouse and ozone-depleting gases. For example, increases in oxygen-deficient regions of the ocean caused by climate change are projected to enhance the emissions of nitrous oxide, an important greenhouse and ozone-depleting gas. Future changes in UV-induced transformations of aquatic and terrestrial contaminants could have both beneficial and adverse effects. Taken in total, it is clear that the future changes in UV radiation coupled with human-caused global change will have large impacts on biogeochemical cycles at local, regional and global scales.

To construct accurate risk assessment models for engineered nanomaterials, there is urgent need for information on the reactivity (or conversely, persistence) and transformation pathways of these materials in the natural environment. As an important step toward addressing this issue, we have characterized the products formed when aqueous C(60) clusters (nC(60)) are exposed to natural sunlight and also have assessed the wavelengths primarily responsible for phototransformation. Long-wavelength light (λ ≥ 400 nm) isolated from sunlight, was shown to be important in both the phototransformation of nC(60) and in the production of (1)O(2). The significance of visible light in mediating the phototransformation of nC(60) was supported by additional experiments with monochromatic light in which the apparent quantum yield at 436 nm (Φ(436 nm) = (2.08 ± 0.08) × 10(-5)) was comparable to that at 366 nm (Φ(366 nm) = (2.02 ± 0.07) × 10(-5)). LDI-TOF mass spectrometry indicated that most of the photoproducts formed after 947 h of irradiation in natural sunlight retain a 60 atom carbon structure. A combination of (13)C NMR analysis of (13)C-enriched nC(60), X-ray photoelectron spectroscopy and FTIR indicated that photoproducts have olefinic carbon atoms as well as a variety of oxygen-containing functional groups, including vinyl ether and carbonyl or carboxyl groups, whose presence destroys the native π-electron system of C(60). Thus, the photoreactivity of nC(60) in sunlight leads to the formation of water-soluble C(60) derivatives.

The quantitative polymerase chain reaction (qPCR) method provides rapid estimates of fecal indicator bacteria densities that have been indicated to be useful in the assessment of water quality. Primarily because this method provides faster results than standard culture-based methods, the U.S. Environmental Protection Agency is currently considering its use as a basis for revised ambient water quality criteria. In anticipation of this possibility, we sought to examine the relationship between qPCR-based and culture-based estimates of enterococci in surface waters. Using data from several research groups, we compared enterococci estimates by the two methods in water samples collected from 37 sites across the United States. A consistent linear pattern in the relationship between cell equivalents (CCE), based on the qPCR method, and colony-forming units (CFU), based on the traditional culturable method, was significant (P < 0.05) at most sites. A linearly decreasing variance of CCE with increasing CFU levels was significant (P < 0.05) or evident for all sites. Both marine and freshwater sites under continuous influence of point-source contamination tended to reveal a relatively constant proportion of CCE to CFU. The consistency in the mean and variance patterns of CCE versus CFU indicates that the relationship of results based on these two methods is more predictable at high CFU levels (e.g., log(10)CFU > 2.0/100 mL) while uncertainty increases at lower CFU values. It was further noted that the relative error in replicated qPCR estimates was generally higher than that in replicated culture counts even at relatively high target levels, suggesting a greater need for replicated analyses in the qPCR method to reduce relative error. Further studies evaluating the relationship between culture and qPCR should take into account analytical uncertainty as well as potential differences in results of these methods that may arise from sample variability, different sources of pollution, and environmental factors.

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.

We provide the first evidence that a fullerene derivative can be extensively mineralized under environmental conditions by direct photolysis. Dissolved inorganic carbon (DIC) was identified as a major photoproduct of fullerenol, a hydroxylated C(60) molecule and the ratio of moles DIC produced to moles of fullerenol reacted reached 28 or approximately 47% of complete mineralization on extensive irradiation by simulated solar radiation. The direct photoreaction kinetics of fullerenol in dilute aqueous solution can be described by pH-dependent biexponential rate expressions. This photoreaction slowed by a factor of 2 in nitrogen-saturated water. The oxygen dependence is attributed to photoinduced electron or hydrogen atom transfer from fullerenol to oxygen to produce superoxide ions with a quantum yield of 6.2 x 10(-4). Fullerenol can photosensitize the production of singlet oxygen ((1)O(2)) in dilute aqueous solution with quantum yields ranging from 0.10 in acidic water to 0.05 in neutral and basic solution. However our results indicate that chemical reactions involving diffusive encounters between (1)O(2) or superoxide and fullerenol are too slow to significantly contribute to the fast component of fullerenol photoreaction in sunlight. The pH dependence of the direct and sensitized photoreactions is attributed to changes in intramolecular hemiketal formation in fullerenol.

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.

Public concern over microbial contamination of recreational waters has increased in recent years. A common approach to evaluating beach water quality has been to use the persistence model which assumes that day-old monitoring results provide accurate estimates of current concentrations. This model is frequently incorrect Recent studies have shown that statistical regression models based on least-squares fitting often are more accurate. To make such models more generally available, the Virtual Beach (VB) tool was developed. VB is public-domain software that prescribes site-specific predictive models. In this study we used VB as a tool to evaluate statistical modeling for predicting Escherichia coli (E. coli levels at Huntington Beach, on Lake Erie. The models were based on readily available weather and environmental data, plus U.S. Geological Service onsite data. Although models for Great Lakes beaches have frequently been fitted to multiyear data sets, this work demonstrates that useful statistical models can be based on limited data sets collected over much shorter time periods, leading to dynamic models that are periodically refitted as new data become available. Comparisons of the resulting nowcasts (predictions of current, but yet unknown, bacterial levels) with observations verified the effectiveness of VB and showed that dynamic models are about as accurate as long-term static models. Finally, fitting models to forecasted explanatory variables, bacteria forecasts were found to compare favorably to nowcasts, yielding adjusted coefficients of determination (adjusted R2) of about 0.40.

Under UV irradiation, an important primary photochemical reaction of colored dissolved organic matter (CDOM) is electron ejection to produce hydrated electrons (e-aq). The efficiency of this process has been studied in both fresh water and seawater samples with both steady-state scavenger (S-SS) and time-resolved laser flash photolysis (LFP) methods. However, the apparent quantum yields (AQYs) of e-aq for the same samples using the two methods differ by as much as a factor of 100, necessitating a closer re-examination of how the process is measured. We developed a highly sensitive multipass LFP apparatus that allows detection of transient species at very low and variable UV irradiation intensities. Under single-photon conditions, we measured the AQY of e-aq from Laurentian fulvic acid as 1.3 x 10(-4), and set the upper limit for other CDOM samples at 6 x 10(-5), bringing the LFP results into agreement with those from S-SS methods. We also examined the ionization at elevated irradiation intensities and clearly demonstrated that multiphoton ionization occurs at intensities well below those usually used in LFP experiments, but well above those likely to occur at the earth's surface. This multiphoton ionization is probably the cause of the high AQYs reported by earlier LFP work. In addition, we also observed in real time other photochemical reactions, such as triplet quenching and bleaching, in the single photon regime.

This report assesses research on the interactions of UV radiation (280-400 nm) and global climate change with global biogeochemical cycles at the Earth's surface. The effects of UV-B (280-315 nm), which are dependent on the stratospheric ozone layer, on biogeochemical cycles are often linked to concurrent exposure to UV-A radiation (315-400 nm), which is influenced by global climate change. These interactions involving UV radiation (the combination of UV-B and UV-A) are central to the prediction and evaluation of future Earth environmental conditions. There is increasing evidence that elevated UV-B radiation has significant effects on the terrestrial biosphere with implications for the cycling of carbon, nitrogen and other elements. The cycling of carbon and inorganic nutrients such as nitrogen can be affected by UV-B-mediated changes in communities of soil organisms, probably due to the effects of UV-B radiation on plant root exudation and/or the chemistry of dead plant material falling to the soil. In arid environments direct photodegradation can play a major role in the decay of plant litter, and UV-B radiation is responsible for a significant part of this photodegradation. UV-B radiation strongly influences aquatic carbon, nitrogen, sulfur and metals cycling that affect a wide range of life processes. UV-B radiation changes the biological availability of dissolved organic matter to microorganisms, and accelerates its transformation into dissolved inorganic carbon and nitrogen, including carbon dioxide and ammonium. The coloured part of dissolved organic matter (CDOM) controls the penetration of UV radiation into water bodies, but CDOM is also photodegraded by solar UV radiation. Changes in CDOM influence the penetration of UV radiation into water bodies with major consequences for aquatic biogeochemical processes. Changes in aquatic primary productivity and decomposition due to climate-related changes in circulation and nutrient supply occur concurrently with exposure to increased UV-B radiation, and have synergistic effects on the penetration of light into aquatic ecosystems. Future changes in climate will enhance stratification of lakes and the ocean, which will intensify photodegradation of CDOM by UV radiation. The resultant increase in the transparency of water bodies may increase UV-B effects on aquatic biogeochemistry in the surface layer. Changing solar UV radiation and climate also interact to influence exchanges of trace gases, such as halocarbons (e.g., methyl bromide) which influence ozone depletion, and sulfur gases (e.g., dimethylsulfide) that oxidize to produce sulfate aerosols that cool the marine atmosphere. UV radiation affects the biological availability of iron, copper and other trace metals in aquatic environments thus potentially affecting metal toxicity and the growth of phytoplankton and other microorganisms that are involved in carbon and nitrogen cycling. Future changes in ecosystem distribution due to alterations in the physical and chemical climate interact with ozone-modulated changes in UV-B radiation. These interactions between the effects of climate change and UV-B radiation on biogeochemical cycles in terrestrial and aquatic systems may partially offset the beneficial effects of an ozone recovery.

Solar-radiation-induced photochemistry can be considered as a new source of nutrients when photochemical reactions release bioavailable nitrogen from biologically nonreactive dissolved organic nitrogen (DON). Pretreatments of Baltic Sea waters in the dark indicated that >72% of DON was recalcitrant to biological mineralization. When this DON (16-21.5 microM) was exposed to simulated solar radiation, the concentration of NH4+ increased 0.5-2.5 microM more in irradiated waters than in the dark controls. The photochemical production of NH4+ and the dose of absorbed photons were used to calculate the apparent quantum yield spectrum for photoammonification [mol NH4+ (mol photons)(-1) nm(-1)] at wavelengths (lambda) of 290-700 nm (phiNH4,lambda). The modeled mean rates of photoammonification based on phiNH4,lambda were 143 and 53 micromol NH4+ m(-2) d(-1) at the surface and in the whole water column, respectively, of Baltic Sea stations during summer. The results of this study indicate thatthe rate of photoammonification approximately equals and periodically exceeds the rate of atmospheric deposition of reactive inorganic nitrogen to the northern Baltic Sea. Forthese stratified surface waters beyond riverine input of labile nitrogen, photoammonification can periodically be the largest source of new bioavailable nitrogen.

The complexity of the linkages between ozone depletion, UV-B radiation and climate change has become more apparent.

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.

The effects of ozone depiction on global biogeochemical cycles, via increased UV-B radiation at the Earth's surface, have continued to be documented over the past 4 years. In this report we also document various effects of UV-B that interact with global climate change because the detailed interactions between ozone depletion and climate change are central to the prediction and evaluation of future Earth environmental conditions. There is increasing evidence that elevated UV-B has significant effects on the terrestrial biosphere with important implications for the cycling of carbon, nitrogen and other elements. Increased UV has been shown to induce carbon monoxide production from dead plant matter in terrestrial ecosystems, nitrogen oxide production from Arctic and Antarctic snowpacks, and halogenated substances from several terrestrial ecosystems. New studies on UV effects on the decomposition of dead leaf material confirm that these effects are complex and species-specific. Decomposition can be retarded, accelerated or remain unchanged. It has been difficult to relate effects of UV on decomposition rates to leaf litter chemistry, as this is very variable. However, new evidence shows UV effects on some fungi, bacterial communities and soil fauna that could play roles in decomposition and nutrient cycling. An important new result is that not only is nitrogen cycling in soils perturbed significantly by increased UV-B, but that these effects persist for over a decade. As nitrogen cycling is temperature dependent, this finding clearly links the impacts of ozone depletion to the ability of plants to use nitrogen in a warming global environment. There are many other potential interactions between UV and climate change impacts on terrestrial biogeochemical cycles that remain to be quantified. There is also new evidence that UV-B strongly influences aquatic carbon, nitrogen, sulfur, and metals cycling that affect a wide range of life processes. UV-B accelerates the decomposition of colored dissolved organic matter (CDOM) entering the sea via terrestrial runoff, thus having important effects on oceanic carbon cycle dynamics. Since UV-B influences the distribution of CDOM, there is an impact of UV-B on estimates of oceanic productivity based on remote sensing of ocean color. Thus, oceanic productivity estimates based on remote sensing require estimates of CDOM distributions. Recent research shows that UV-B transforms dissolved organic matter to dissolved inorganic carbon and nitrogen, including carbon dioxide and ammonium and to organic substances that are either more or less readily available to micro-organisms. The extent of these transformations is correlated with loss of UV absorbance by the organic matter. Changes in aquatic primary productivity and decomposition due to climate-related changes in circulation and nutrient supply, which occur concurrently with increased UV-B exposure, have synergistic influences on the penetration of light into aquatic ecosystems. New research has confirmed that UV affects the biological availability of iron, copper and other trace metals in aquatic environments thus potentially affecting the growth of phytoplankton and other microorganisms that are involved in carbon and nitrogen cycling. There are several instances where UV-B modifies the air sea exchange of trace gases that in turn alter atmospheric chemistry, including the carbon cycle.

DDE and DMDE, degradation products of the pesticides DDT and methoxychlor, rapidly undergo an unusual photoisomerization in solution when exposed to sunlight. The isomerization involves the exchange of a vinyl chlorine and an ortho aromatic hydrogen. Other photoproducts identified were corresponding benzophenones and 1,1-diaryl-2-chloroethylenes. Quantum yields for the reactions were measured and then used to compute sunlight photolysis half-lives for DMDE and DDE. Although both compounds absorb only the short-wavelength ultraviolet component of sunlight, their photolysis was found to be surprisingly rapid. During summer at latitude 40 degrees N, the photolysis half-lives near the surface of a water body are one hour and one day for dissolved DMDE and DDE, respectively. Photolysis of the DDE photoisomers is about an order of magnitude slower than that of DDE, suggesting that they may accumulate under environmental conditions. The DDE photoisomers photocyclize to form chlorinated dibenzofulvene and dichlorofluorenone. Neither DDE nor its photoisomers photoreact in solution to form PCB's. The environmental significance of these results is discussed, and its is suggested that the persistence of DDE in inland surface waters may be related to its tendency to sorb onto sediments and biota where not light is present.