Development of a sampling protocol for collecting leaf surface material for multiphase chemistry studies.

Plant leaves and water drops residing on them interact with atmospheric oxidants, impacting the deposition and emission of trace gases and mediating leaf damage from air pollution. Characterizing the chemical composition and reactivity of the water-soluble material on leaf surfaces is thus essential for improving our understanding of atmosphere-biosphere interactions. However, the limited knowledge of sources and nature of these chemicals challenges sampling decisions. This work investigates how sampling variables and environmental factors impact the quantity and composition of water-soluble material sampled from wet leaves and proposes a flexible protocol for its collection. The ratio of solvent volume-to-leaf area, the solvent-to-leaf contact time, and environmental parameters - including the occurrence of rain, plant location and its metabolism - drive solute concentration in leaf soaks. Despite minor variations, UV-vis absorption spectra of leaf soaks are comparable to authentic raindrops collected from the same tree and share features with microbial dissolved organic matter - including overall low aromaticity, low chromophore content, and low average molecular weight. In addition to guiding the development of a sampling protocol, our data corroborate recent hypotheses on the amount, origin, nature, and reactivity of water-soluble organics on wet leaves, providing new directions of research into this highly interdisciplinary topic.

The Chemical Landscape of Leaf Surfaces and Its Interaction with the Atmosphere.

Atmospheric chemists have historically treated leaves as inert surfaces that merely emit volatile hydrocarbons. However, a growing body of evidence suggests that leaves are ubiquitous substrates for multiphase reactions-implying the presence of chemicals on their surfaces. This Review provides an overview of the chemistry and reactivity of the leaf surface's "chemical landscape", the dynamic ensemble of compounds covering plant leaves. We classified chemicals as endogenous (originating from the plant and its biome) or exogenous (delivered from the environment), highlighting the biological, geographical, and meteorological factors driving their contributions. Based on available data, we predicted ≫2 µg cm-2 of organics on a typical leaf, leading to a global estimate of ≫3 Tg for multiphase reactions. Our work also highlighted three major knowledge gaps: (i) the overlooked role of ambient water in enabling the leaching of endogenous substances and mediating aqueous chemistry; (ii) the importance of phyllosphere biofilms in shaping leaf surface chemistry and reactivity; (iii) the paucity of studies on the multiphase reactivity of atmospheric oxidants with leaf-adsorbed chemicals. Although biased toward available data, we hope this Review will spark a renewed interest in the leaf surface's chemical landscape and encourage multidisciplinary collaborations to move the field forward.

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.

Extended ozone depletion and reduced snow and ice cover-Consequences for Antarctic biota.

Stratospheric ozone, which has been depleted in recent decades by the release of anthropogenic gases, is critical for shielding the biosphere against ultraviolet-B (UV-B) radiation. Although the ozone layer is expected to recover before the end of the 21st century, a hole over Antarctica continues to appear each year. Ozone depletion usually peaks between September and October, when fortunately, most Antarctic terrestrial vegetation and soil biota is frozen, dormant and protected under snow cover. Similarly, much marine life is protected by sea ice cover. The ozone hole used to close before the onset of Antarctic summer, meaning that most biota were not exposed to severe springtime UV-B fluxes. However, in recent years, ozone depletion has persisted into December, which marks the beginning of austral summer. Early summertime ozone depletion is concerning: high incident UV-B radiation coincident with snowmelt and emergence of vegetation will mean biota is more exposed. The start of summer is also peak breeding season for many animals, thus extreme UV-B exposure (UV index up to 14) may come at a vulnerable time in their life cycle. Climate change, including changing wind patterns and strength, and particularly declining sea ice, are likely to compound UV-B exposure of Antarctic organisms, through earlier ice and snowmelt, heatwaves and droughts. Antarctic field research conducted decades ago tended to study UV impacts in isolation and more research that considers multiple climate impacts, and the true magnitude and timing of current UV increases is needed.

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.

Photochemical Production of Carbon Monoxide from Dissolved Organic Matter: Role of Lignin Methoxyarene Functional Groups.

Carbon monoxide (CO) is the second most abundant identified product of dissolved organic matter (DOM) photodegradation after CO2, but its formation mechanism remains unknown. Previous work showed that aqueous photodegradation of methoxy-substituted aromatics (ArOCH3) produces CO considerably more efficiently than aromatic carbonyls. Following on this precedent, we propose that the methoxy aromatic groups of lignin act as the C source for the photochemical formation of CO from terrestrial DOM via a two-step pathway: formal hydrolytic demethylation to methanol and methanol oxidation to CO. To test the reasonableness of this mechanism, we investigated the photochemistry of eight lignin model compounds. We first observed that initial CO production rates are positively correlated with initial substrate degradation rates only for models containing at least one ArOCH3 group, regardless of other structural features. We then confirmed that all ArOCH3-containing substrates undergo formal hydrolytic demethylation by detecting methanol and the corresponding phenolic transformation products. Finally, we showed that hydroxyl radicals, likely oxidants to initiate methanol oxidation to CO, form during irradiation of all models. This work proposes an explicit mechanism linking ubiquitous, abundant, and easily quantifiable DOM functionalities to CO photoproduction. Our results further hint that methanol may be an abundant (yet overlooked) DOM photoproduct and a likely precursor of formaldehyde, formic acid, and CO2 and that lignin photodegradation may represent a source of hydroxyl radicals.

Singlet Oxygen Quantum Yields in Environmental Waters.

Singlet oxygen (1O2) is a reactive oxygen species produced in sunlit waters via energy transfer from the triplet states of natural sensitizers. There has been an increasing interest in measuring apparent 1O2 quantum yields (ΦΔ) of aquatic and atmospheric organic matter samples, driven in part by the fact that this parameter can be used for environmental fate modeling of organic contaminants and to advance our understanding of dissolved organic matter photophysics. However, the lack of reproducibility across research groups and publications remains a challenge that significantly limits the usability of literature data. In the first part of this review, we critically evaluate the experimental techniques that have been used to determine ΦΔ values of natural organic matter, we identify and quantify sources of errors that potentially explain the large variability in the literature, and we provide general experimental recommendations for future studies. In the second part, we provide a qualitative overview of known ΦΔ trends as a function of organic matter type, isolation and extraction procedures, bulk water chemistry parameters, molecular and spectroscopic organic matter features, chemical treatments, wavelength, season, and location. This review is supplemented with a comprehensive database of ΦΔ values of environmental samples.

Mechanistic Insights into Dissolved Organic Sulfur Photomineralization through the Study of Cysteine Sulfinic Acid.

Photochemical reactions convert dissolved organic matter (DOM) into inorganic and low-molecular-weight organic products, contributing to its cycling across environmental compartments. However, knowledge on the formation mechanisms of these products is still scarce. In this work, we investigate the triplet-sensitized photodegradation of cysteine sulfinic acid, a (photo)degradation product of cysteine, to sulfate (SO42-). We use kinetic analysis, targeted experiments, and previous literature from several fields of chemistry to explain the elementary steps that lead to the release of sulfate. Our analysis indicates that triplet sensitizers act as one-electron oxidants on the sulfinate S lone pair. The resulting radical undergoes C-S fragmentation to form SO2, which becomes hydrated to sulfite/bisulfite (S(IV)). S(IV) is further oxidized to SO42- in the presence of triplet sensitizers and oxygen. We point out that the reaction sequence SO2 ⇌ S(IV) → SO42- is valid independently of the chemical structure of the model compound and might represent a sulfate photoproduction mechanism with general validity for DOS. Our mechanistic investigation revealed that amino acids in general might also be photochemical precursors of CO2, ammonia, acetaldehyde, and H2O2 and that reaction byproducts can influence the rate and mechanism of S(IV) (photo)oxidation.

Photochemical Production of Sulfate and Methanesulfonic Acid from Dissolved Organic Sulfur.

Photodegradation processes play an important role in releasing elements tied up in biologically refractory forms in the environment, and are increasingly being recognized as important contributors to biogeochemical cycles. While complete photo-oxidation of dissolved organic carbon (to CO2) and dissolved organic phosphorous (to PO43-) has been documented, the analogous photoproduction of sulfate from dissolved organic sulfur (DOS) has not yet been reported. Recent high-resolution mass spectrometry studies showed a selective loss of organic sulfur during photodegradation of dissolved organic matter, which was hypothesized to result in the production of sulfate. Here, we provide evidence of ubiquitous production of sulfate, methanesulfonic acid (MSA), and methanesulfinic acid (MSIA) during photodegradation of DOM samples from a wide range of natural terrestrial environments. We show that photochemical production of sulfate is generally more efficient than the production of MSA and MSIA, as well as volatile S-containing compounds such as CS2 and COS. We also identify possible molecular precursors for sulfate and MSA, and we demonstrate that a wide range of relevant classes of DOS compounds (in terms of S oxidation state and molecular structure) can liberate sulfate upon photosensitized degradation. This work suggests that photochemistry may play a more significant role in the aquatic and atmospheric fate of DOS than currently believed.

Furan Carboxamides as Model Compounds To Study the Competition between Two Modes of Indirect Photochemistry.

Singlet oxygen (1O2) and triplet chromophoric dissolved organic matter (3CDOM*) are photochemically produced reactive intermediates responsible for the photodegradation of several micropollutants in the sunlit surface waters. However, elucidating the mechanism of reactions involving both 1O2 and 3CDOM* can be complicated by the deeply interconnected nature of these two reactive species. In this work, we synthesized a series of model compounds inspired by the chemical structure of fenfuram, a fungicide used in the 1980s, and used them to investigate structure-reactivity relationships in photodegradation reactions involving 1O2 and 3CDOM*. A combination of steady-state and time-resolved approaches was employed to successfully predict the extent of 1O2-induced degradation. Conversely, the prediction of triplet-induced reactivity was complicated by the presence of repair mechanisms whose extent and relative importance were difficult to predict. The results of our work indicate that bimolecular rate constants measured via time-resolved techniques alone are not sufficient to accurately predict environmental half-lives, as intrinsic differences in the reaction mechanism can amplify the importance of secondary degradation pathways.

Intriguing C-HCu interactions in bis-(phenanthroline)Cu(i) redox mediators for dye-sensitized solar cells.

We have synthesized and characterized a series of bis-(phenanthroline)Cu(i) complexes of interest as redox mediators for dye-sensitized solar cells. This study led to the discovery of intriguing anagostic interactions between the hydrogen atom and the copper center as evidenced by X-ray diffraction studies on a single crystal. Remarkably, an anagostic interaction was found between a H atom of a methyl group and a copper site.

Energy and charge transfer cascade in methylammonium lead bromide perovskite nanoparticle aggregates.

Highly photoluminescent hybrid lead halide perovskite nanoparticles have recently attracted wide interest in the context of high-stake applications, such as light emitting diodes (LEDs), light emitting transistors and lasers. In addition, they constitute ideal model systems to explore energy and charge transport phenomena occurring at the boundaries of nanocrystalline grains forming thin films in high-efficiency perovskite solar cells (PSCs). Here we report a complete photophysical study of CH3NH3PbBr3 perovskite nanoparticles suspended in chlorobenzene and highlight some important interaction properties. Colloidal suspensions under study were constituted of dispersed aggregates of quasi-2D platelets of a range of thicknesses, decorated with 3D-like spherical nanoparticles. These types of nanostructures possess different optical properties that afford a handle for probing them individually. The photophysics of the colloidal particles was studied by femtosecond pump-probe spectroscopy and time-correlated single-photon counting. We show here that a cascade of energy and exciton-mediated charge transfer occurs between nanostructures: upon photoexcitation, localized excitons within one nanostructure can either recombine on a ps timescale, yielding a short-lived emission, or form charge-transfer states (CTSs) across adjacent domains, resulting in longer-lived photoluminescence in the millisecond timescale. Furthermore, CTSs exhibit a clear signature in the form of a strong photoinduced electroabsorption evidenced in femtosecond transient absorption measurements. Charge transfer dynamics at the surface of the nanoparticles have been studied with various quenchers in solution. Efficient hole transfer to N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD) and 1,4-bis(diphenyl-amino)benzene (BDB) donors was attested by the quenching of the nanoparticles emission. The charge transfer rate was limited by the organic layer used to stabilize the nanoparticles, which acted as a wide spacer between reactants. The forward charge transfer was found to take place in the sub-microsecond time-scale in competition with slow carrier recombination, while back transfer was shown to occur with a time-constant τ = 25 ms.

Cross-Resistance of UV- or Chlorine Dioxide-Resistant Echovirus 11 to Other Disinfectants.

The emergence of waterborne viruses with resistance to disinfection has been demonstrated in the laboratory and in the environment. Yet, the implications of such resistance for virus control remain obscure. In this study we investigate if viruses with resistance to a given disinfection method exhibit cross-resistance to other disinfectants. Chlorine dioxide (ClO2)- or UV-resistant populations of echovirus 11 were exposed to five inactivating treatments (free chlorine, ClO2, UV radiation, sunlight, and heat), and the extent of cross-resistance was determined. The ClO2-resistant population exhibited cross-resistance to free chlorine, but to none of the other inactivating treatments tested. We furthermore demonstrated that ClO2 and free chlorine act by a similar mechanism, in that they mainly inhibit the binding of echovirus 11 to its host cell. As such, viruses with host binding mechanisms that can withstand ClO2 treatment were also better able to withstand oxidation by free chlorine. Conversely, the UV-resistant population was not significantly cross-resistant to any other disinfection treatment. Overall, our results indicate that viruses with resistance to multiple disinfectants exist, but that they can be controlled by inactivating methods that operate by a distinctly different mechanism. We therefore suggest to utilize two disinfection barriers that act by different mechanisms in order to control disinfection-resistant viruses.

Aqueous singlet oxygen reaction kinetics of furfuryl alcohol: effect of temperature, pH, and salt content.

The rate constant for the reaction between furfuryl alcohol (FFA) and singlet oxygen (1O2) in aqueous solution was measured as a function of temperature, pH and salt content employing both steady-state photolysis (ß value determination) and time-resolved singlet oxygen phosphorescence methods. The latter provided more precise and reproducible data. The reaction rate constant, krxn,FFA, had a relatively small temperature dependence, no pH dependence and showed a small increase in the presence of high salt concentrations (+19% with 1 M NaCl). A critical review of the available literature suggested that the widely used value of 1.2 × 108 M-1 s-1 is likely overestimated. Therefore, we recommend the use of 1.00 × 108 M-1 s-1 for reactions performed in low ionic strength aqueous solutions (freshwater) at 22 °C. Furthermore, corrections are provided that should be applied when working at higher or lower temperatures, and/or at high salt concentrations (seawater).