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1. The interactive effects of stratospheric ozone depletion, UV radiation, and climate change on aquatic ecosystems

   https://doi.org/10.1039/c8pp90062k  

   Williamson, Craig E. ; Neale, Patrick J. ; Hylander, Samuel ; Rose, Kevin C. ; Figueroa, Félix L. ; Robinson, Sharon A. ; Häder, Donat-P. ; Wängberg, Sten-Åke ; Worrest, Robert C. ( March 2019 , Photochemical & Photobiological Sciences)

   This assessment summarises the current state of knowledge on the interactive effects of ozone depletion and climate change on aquatic ecosystems, focusing on how these affect exposures to UV radiation in both inland and oceanic waters. The ways in which stratospheric ozone depletion is directly altering climate in the southern hemisphere and the consequent extensive effects on aquatic ecosystems are also addressed. The primary objective is to synthesise novel findings over the past four years in the context of the existing understanding of ecosystem response to UV radiation and the interactive effects of climate change. If it were not for the Montreal Protocol, stratospheric ozone depletion would have led to high levels of exposure to solar UV radiation with much stronger negative effects on all trophic levels in aquatic ecosystems than currently experienced in both inland and oceanic waters. This “world avoided” scenario that has curtailed ozone depletion, means that climate change and other environmental variables will play the primary role in regulating the exposure of aquatic organisms to solar UV radiation. Reductions in the thickness and duration of snow and ice cover are increasing the levels of exposure of aquatic organisms to UV radiation. Climate change was also expectedmore »to increase exposure by causing shallow mixed layers, but new data show deepening in some regions and shoaling in others. In contrast, climate-change related increases in heavy precipitation and melting of glaciers and permafrost are increasing the concentration and colour of UV-absorbing dissolved organic matter (DOM) and particulates. This is leading to the “browning” of many inland and coastal waters, with consequent loss of the valuable ecosystem service in which solar UV radiation disinfects surface waters of parasites and pathogens. Many organisms can reduce damage due to exposure to UV radiation through behavioural avoidance, photoprotection, and photoenzymatic repair, but meta-analyses continue to confirm negative effects of UV radiation across all trophic levels. Modeling studies estimating photoinhibition of primary production in parts of the Pacific Ocean have demonstrated that the UV radiation component of sunlight leads to a 20% decrease in estimates of primary productivity. Exposure to UV radiation can also lead to positive effects on some organisms by damaging less UV-tolerant predators, competitors, and pathogens. UV radiation also contributes to the formation of microplastic pollutants and interacts with artificial sunscreens and other pollutants with adverse effects on aquatic ecosystems. Exposure to UV-B radiation can decrease the toxicity of some pollutants such as methyl mercury (due to its role in demethylation) but increase the toxicity of other pollutants such as some pesticides and polycyclic aromatic hydrocarbons. Feeding on microplastics by zooplankton can lead to bioaccumulation in fish. Microplastics are found in up to 20% of fish marketed for human consumption, potentially threatening food security. Depletion of stratospheric ozone has altered climate in the southern hemisphere in ways that have increased oceanic productivity and consequently the growth, survival and reproduction of many sea birds and mammals. In contrast, warmer sea surface temperatures related to these climate shifts are also correlated with declines in both kelp beds in Tasmania and corals in Brazil. This assessment demonstrates that knowledge of the interactive effects of ozone depletion, UV radiation, and climate change factors on aquatic ecosystems has advanced considerably over the past four years and confirms the importance of considering synergies between environmental factors.« less
2. Molecular investigation of the multi-phase photochemistry of Fe( iii )–citrate in aqueous solution

   https://doi.org/10.1039/D1EM00503K  

   West, Christopher P. ; Morales, Ana C. ; Ryan, Jackson ; Misovich, Maria V. ; Hettiyadura, Anusha P. ; Rivera-Adorno, Felipe ; Tomlin, Jay M. ; Darmody, Andrew ; Linn, Brittany N. ; Lin, Peng ; et al ( February 2023 , Environmental Science: Processes & Impacts)

   Iron (Fe) is ubiquitous in nature and found as Fe II or Fe III in minerals or as dissolved ions Fe 2+ or Fe 3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of Fe III into natural aquatic systems, organic carboxylic acids efficiently chelate Fe III to form [Fe III –carboxylate] 2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of Fe III –carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of Fe III –citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of ( φ ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe 3+ –citrates (aq) were expressed as twomore »generalized consecutive reactions of with the experimental rate constants of j 1 ∼ 0.12 min −1 and j 2 ∼ 0.05 min −1 , respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe–organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe–carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of Fe III –citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments.« less
3. The response of aquatic ecosystems to the interactive effects of stratospheric ozone depletion, UV radiation, and climate change

   https://doi.org/10.1007/s43630-023-00370-z  

   Neale, P. J. ; Williamson, C. E. ; Banaszak, A. T. ; Häder, D.-P. ; Hylander, S. ; Ossola, R. ; Rose, K. C. ; Wängberg, S.-Å. ; Zepp, R. ( January 2023 , Photochemical & Photobiological Sciences)

   Abstract Variations in stratospheric ozone and changes in the aquatic environment by climate change and human activity are modifying the exposure of aquatic ecosystems to UV radiation. These shifts in exposure have consequences for the distributions of species, biogeochemical cycles, and services provided by aquatic ecosystems. This Quadrennial Assessment presents the latest knowledge on the multi-faceted interactions between the effects of UV irradiation and climate change, and other anthropogenic activities, and how these conditions are changing aquatic ecosystems. Climate change results in variations in the depth of mixing, the thickness of ice cover, the duration of ice-free conditions and inputs of dissolved organic matter, all of which can either increase or decrease exposure to UV radiation. Anthropogenic activities release oil, UV filters in sunscreens, and microplastics into the aquatic environment that are then modified by UV radiation, frequently amplifying adverse effects on aquatic organisms and their environments. The impacts of these changes in combination with factors such as warming and ocean acidification are considered for aquatic micro-organisms, macroalgae, plants, and animals (floating, swimming, and attached). Minimising the disruptive consequences of these effects on critical services provided by the world’s rivers, lakes and oceans (freshwater supply, recreation, transport, and food security)more »will not only require continued adherence to the Montreal Protocol but also a wider inclusion of solar UV radiation and its effects in studies and/or models of aquatic ecosystems under conditions of the future global climate. Graphical abstract« less
4. Identifying photochemical alterations of dissolved pyrogenic organic matter using fluorescence spectroscopy

   https://doi.org/10.1007/s00027-022-00919-7  

   Egan, Jessica K. ; McKnight, Diane M. ; Bowman, Maggie M. ; SanClements, Michael D. ; Gallo, Adrian C. ; Hatten, Jeff A. ; Matosziuk, Lauren M. ( January 2023 , Aquatic Sciences)

   Many streams originate in forested watersheds at risk of wildfires. Wildfires can introduce thermally altered organic compounds to terrestrial and aquatic systems. Understanding the degradation of leachates from these burned organic materials, referred to as dissolved pyrogenic organic material (PyDOM), is critical in determining water quality impacts in forested watersheds. This study used fluorescence spectroscopy to examine photochemical alterations of PyDOM generated by leaching organic matter burned at various temperatures. The PyDOM was exposed to natural sunlight for 25 days and the photochemical formation of hydrogen peroxide was monitored. PyDOM was characterized using ultraviolet–visible absorption, excitation–emission matrix (EEM) fluorescence spectroscopy, and fluorescence indices. Throughout the experiment, the emission intensity of the humic peak for all light-exposed leachates decreased while dark leachates exhibited no significant change in their fluorescence spectra. Additionally, hydrogen peroxide concentrations and UV absorbance decreased progressively over time, providing direct evidence that PyDOM concentrations can be significantly reduced by photodegradation. A characteristically low emission peak was observed in the EEMs of the fresh PyDOM, which could help in detecting fresh PyDOM. These results demonstrate that PyDOM derived from burned leachates is susceptible to photodegradation and that fluorescence measurements could be used as proxies for detecting PyDOM immediately post-wildfire.
5. Smoke from regional wildfires alters lake ecology

   https://doi.org/10.1038/s41598-021-89926-6  

   Scordo, Facundo ; Chandra, Sudeep ; Suenaga, Erin ; Kelson, Suzanne J. ; Culpepper, Joshua ; Scaff, Lucia ; Tromboni, Flavia ; Caldwell, Timothy J. ; Seitz, Carina ; Fiorenza, Juan E. ; et al ( May 2021 , Scientific Reports)

   Wildfire smoke often covers areas larger than the burned area, yet the impacts of smoke on nearby aquatic ecosystems are understudied. In the summer of 2018, wildfire smoke covered Castle Lake (California, USA) for 55 days. We quantified the influence of smoke on the lake by comparing the physics, chemistry, productivity, and animal ecology in the prior four years (2014–2017) to the smoke year (2018). Smoke reduced incident ultraviolet-B (UV-B) radiation by 31% and photosynthetically active radiation (PAR) by 11%. Similarly, underwater UV-B and PAR decreased by 65 and 44%, respectively, and lake heat content decreased by 7%. While the nutrient limitation of primary production did not change, shallow production in the offshore habitat increased by 109%, likely due to a release from photoinhibition. In contrast, deep-water, primary production decreased and the deep-water peak in chlorophylladid not develop, likely due to reduced PAR. Despite the structural changes in primary production, light, and temperature, we observed little significant change in zooplankton biomass, community composition, or migration pattern. Trout were absent from the littoral-benthic habitat during the smoke period. The duration and intensity of smoke influences light regimes, heat content, and productivity, with differing responses to consumers.