Assessing the photodegradation potential of compounds derived from the photoinduced weathering of polystyrene in water.

Benzoate (Bz-) and acetophenone (AcPh) are aromatic compounds known to be produced by sunlight irradiation of polystyrene aqueous suspensions. Here we show that these molecules could react with •OH (Bz-) and •OH + CO3•- (AcPh) in sunlit natural waters, while other photochemical processes (direct photolysis and reaction with singlet oxygen, or with the excited triplet states of chromophoric dissolved organic matter) are unlikely to be important. Steady-state irradiation experiments were carried out using lamps, and the time evolution of the two substrates was monitored by liquid chromatography. Photodegradation kinetics in environmental waters were assessed by a photochemical model (APEX: Aqueous Photochemistry of Environmentally-occurring Xenobiotics). In the case of AcPh, a competitive process to aqueous-phase photodegradation would be volatilisation followed by reaction with gas-phase •OH. As far as Bz- is concerned, elevated dissolved organic carbon (DOC) levels could be important in protecting this compound from aqueous-phase photodegradation. Limited reactivity of the studied compounds with the dibromide radical (Br2•-, studied by laser flash photolysis) suggests that •OH scavenging by bromide, which yields Br2•-, would be poorly offset by Br2•--induced degradation. Therefore, photodegradation kinetics of Bz- and AcPh should be slower in seawater (containing [Br-] ~ 1 mM) compared to freshwaters. The present findings suggest that photochemistry would play an important role in both formation and degradation of water-soluble organic compounds produced by weathering of plastic particles.

Evaluation of the Environmental Fate of a Semivolatile Transformation Product of Ibuprofen Based on a Simple Two-Media Fate Model.

Partitioning between surface waters and the atmosphere is an important process, influencing the fate and transport of semi-volatile contaminants. In this work, a simple methodology that combines experimental data and modeling was used to investigate the degradation of a semi-volatile pollutant in a two-phase system (surface water + atmosphere). 4-Isobutylacetophenone (IBAP) was chosen as a model contaminant; IBAP is a toxic transformation product of the non-steroidal, anti-inflammatory drug ibuprofen. Here, we show that the atmospheric behavior of IBAP would mainly be characterized by reaction with •OH radicals, while degradation initiated by •NO3 or direct photolysis would be negligible. The present study underlines that the gas-phase reactivity of IBAP with •OH is faster, compared to the likely kinetics of volatilization from aqueous systems. Therefore, it might prove very difficult to detect gas-phase IBAP. Nevertheless, up to 60% of IBAP occurring in a deep and dissolved organic carbon-rich water body might be eliminated via volatilization and subsequent reaction with gas-phase •OH. The present study suggests that the gas-phase chemistry of semi-volatile organic compounds which, like IBAP, initially occur in natural water bodies in contact with the atmosphere is potentially very important in some environmental conditions.

Degradation of nanoplastics in the environment: Reactivity and impact on atmospheric and surface waters.

Microplastics (MPs) and nanoplastics (NPs) are ubiquitous and contaminate soil, surface waters, atmospheric aerosol, precipitations, indoor and outdoor environments. However, the occurrence, transformation and fate of NPs in the environment are still unclear. In this work, polystyrene nanoparticles (PS-NPs) are used as a proxy of NPs to study their reactivity and potential impact on atmospheric and surface waters. In particular, the reactivity with hydroxyl radicals (OH) in the aqueous phase is investigated. For the first time, a reactivity constant for the reaction of NPs with OH is measured, strongly dependent on the exposed particle surface area of NPs. Degradation products (short chain carboxylic acids and aromatic compounds), obtained by direct and OH-mediated photolysis of PS-NPs suspensions, are identified by mass spectrometry. Irradiation of a PS-NPs suspension under natural sunlight for 1 year has shown the formation of formic acid and organic compounds similar to those found in riverine and cloud dissolved organic matter, which could contribute significantly to the dissolved organic matter in the aqueous phase.

The role of direct photolysis in the photodegradation of the herbicide bentazone in natural surface waters.

The photochemical fate of the herbicide bentazone was assessed by lab experiments and modeling tools. Experimental and modeling results showed that bentazone is mainly photodegraded by direct photolysis in natural water samples, even in the presence of dissolved organic matter (DOM) that can act as light-screening agent, photosensitizer and scavenger of reactive species. Even when it was dissolved in natural water samples containing different DOM amounts, the phototransformation kinetics of bentazone was unchanged compared to irradiation runs in ultrapure water. This finding suggests that the DOM and the other components of our samples did not affect the direct photolysis of bentazone by light-absorption competition, at least at the experimental optical path lengths, and did not induce significant indirect photodegradation by producing reactive transient species. Photochemical modeling in a lake-water photoreactivity scenario corroborated the observed experimental results, showing the predominant role of direct photolysis in the overall (direct + indirect) photodegradation of bentazone at different water depths and DOM contents. However, the model predicted a minor but non-negligible contribution of indirect photochemistry (i.e., reactions triggered by HO•, CO3•- and 3CDOM*) to the herbicide degradation. This contribution (especially by 3CDOM*) could become crucial in deep and DOM-rich water bodies. Finally, several photoproducts formed by direct photolysis and HO•-induced photodegradation were identified, which should not be particularly toxic for aquatic organisms and Vibrio fischeri bacteria.

Photochemistry of the Cloud Aqueous Phase: A Review.

This review paper describes briefly the cloud aqueous phase composition and deeply its reactivity in the dark and mainly under solar radiation. The role of the main oxidants (hydrogen peroxide, nitrate radical, and hydroxyl radical) is presented with a focus on the hydroxyl radical, which drives the oxidation capacity during the day. Its sources in the aqueous phase, mainly through photochemical mechanisms with H2O2, iron complexes, or nitrate/nitrite ions, are presented in detail. The formation rate of hydroxyl radical and its steady state concentration evaluated by different authors are listed and compared. Finally, a paragraph is also dedicated to the sinks and the reactivity of the HO• radical with the main compounds found in the cloud aqueous phase. This review presents an assessment of the reactivity in the cloud aqueous phase and shows the significant potential impact that this medium can have on the chemistry of the atmosphere and more generally on the climate.

Visualizing reaction and diffusion in xanthan gum aerosol particles exposed to ozone.

Atmospheric aerosol particles with a high viscosity may become inhomogeneously mixed during chemical processing. Models have predicted gradients in condensed phase reactant concentration throughout particles as the result of diffusion and chemical reaction limitations, termed chemical gradients. However, these have never been directly observed for atmospherically relevant particle diameters. We investigated the reaction between ozone and aerosol particles composed of xanthan gum and FeCl2 and observed the in situ chemical reaction that oxidized Fe2+ to Fe3+ using X-ray spectromicroscopy. Iron oxidation state of particles as small as 0.2 µm in diameter were imaged over time with a spatial resolution of tens of nanometers. We found that the loss off Fe2+ accelerated with increasing ozone concentration and relative humidity, RH. Concentric 2-D column integrated profiles of the Fe2+ fraction, α, out of the total iron were derived and demonstrated that particle surfaces became oxidized while particle cores remained unreacted at RH = 0-20%. At higher RH, chemical gradients evolved over time, extended deeper from the particle surface, and Fe2+ became more homogeneously distributed. We used the kinetic multi-layer model for aerosol surface and bulk chemistry (KM-SUB) to simulate ozone reaction constrained with our observations and inferred key parameters as a function of RH including Henry's Law constant for ozone, HO3, and diffusion coefficients for ozone and iron, DO3 and DFe, respectively. We found that HO3 is higher in our xanthan gum/FeCl2 particles than for water and increases when RH decreased from about 80% to dry conditions. This coincided with a decrease in both DO3 and DFe. In order to reproduce observed chemical gradients, our model predicted that ozone could not be present further than a few nanometers from a particle surface indicating near surface reactions were driving changes in iron oxidation state. However, the observed chemical gradients in α observed over hundreds of nanometers must have been the result of iron transport from the particle interior to the surface where ozone oxidation occurred. In the context of our results, we examine the applicability of the reacto-diffusive framework and discuss diffusion limitations for other reactive gas-aerosol systems of atmospheric importance.

How well can we predict cluster fragmentation inside a mass spectrometer?

Fragmentation of molecular clusters inside mass spectrometers is a significant source of uncertainty in a wide range of chemical applications. We have measured the fragmentation of sulfuric acid clusters driving atmospheric new-particle formation, and developed a novel model, based on first principles calculations, capable of quantitatively predicting the extent of fragmentation.

Ecotoxic effects of loratadine and its metabolic and light-induced derivatives.

Loratadine and desloratadine are second-generation antihistaminic drugs. Because of human administration, they are continuously released via excreta into wastewater treatment plants and occur in surface waters as residues and transformation products (TPs). Loratadine and desloratadine residues have been found at very low concentrations (ng/L) in the aquatic environment but their toxic effects are still not well known. Both drugs are light-sensitive even under environmentally simulated conditions and some of the photoproducts have been isolated and characterized. The aim of the present study was to investigate the acute and chronic ecotoxicity of loratadine, desloratadine and their light-induced transformation products in organisms of the aquatic trophic chain. Bioassays were performed in the alga Pseudokirchneriella subcapitata, the rotifer Brachionus calyciflorus and in two crustaceans, Thamnocephalus platyurus and Ceriodaphnia dubia. Loratadine exerted its acute and chronic toxicity especially on Ceriodaphnia dubia (LC50: 600 µg/L, EC50: 28.14 µg/L) while desloratadine showed similar acute toxicity among the organisms tested and it was the most chronically effective compound in Ceriodaphnia dubia and Pseudokirchneriella subcapitata. Generally, transformation products were less active in both acute and chronic assays.

Modeling on Fragmentation of Clusters inside a Mass Spectrometer.

Atmospheric clusters are weakly bound and can fragment inside the measuring instruments, in particular, mass spectrometers. Since the clusters accelerate under electric fields, the fragmentation cannot be described in terms of rate constants under equilibrium conditions. Using basic statistical principles, we have developed a model for fragmentation of clusters moving under an external force. The model describes an energy transfer to the cluster internal modes caused by collisions with residual carrier gas molecules. As soon as enough energy is accumulated in the cluster internal modes, it can fragment. The model can be used for interpreting experimental measurements by atmospheric pressure interface mass spectrometers.

Rapid growth of organic aerosol nanoparticles over a wide tropospheric temperature range.

Nucleation and growth of aerosol particles from atmospheric vapors constitutes a major source of global cloud condensation nuclei (CCN). The fraction of newly formed particles that reaches CCN sizes is highly sensitive to particle growth rates, especially for particle sizes <10 nm, where coagulation losses to larger aerosol particles are greatest. Recent results show that some oxidation products from biogenic volatile organic compounds are major contributors to particle formation and initial growth. However, whether oxidized organics contribute to particle growth over the broad span of tropospheric temperatures remains an open question, and quantitative mass balance for organic growth has yet to be demonstrated at any temperature. Here, in experiments performed under atmospheric conditions in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN), we show that rapid growth of organic particles occurs over the range from [Formula: see text]C to [Formula: see text]C. The lower extent of autoxidation at reduced temperatures is compensated by the decreased volatility of all oxidized molecules. This is confirmed by particle-phase composition measurements, showing enhanced uptake of relatively less oxygenated products at cold temperatures. We can reproduce the measured growth rates using an aerosol growth model based entirely on the experimentally measured gas-phase spectra of oxidized organic molecules obtained from two complementary mass spectrometers. We show that the growth rates are sensitive to particle curvature, explaining widespread atmospheric observations that particle growth rates increase in the single-digit-nanometer size range. Our results demonstrate that organic vapors can contribute to particle growth over a wide range of tropospheric temperatures from molecular cluster sizes onward.

Guanidine: A Highly Efficient Stabilizer in Atmospheric New-Particle Formation.

The role of a strong organobase, guanidine, in sulfuric acid-driven new-particle formation is studied using state-of-the-art quantum chemical methods and molecular cluster formation simulations. Cluster formation mechanisms at the molecular level are resolved, and theoretical results on cluster stability are confirmed with mass spectrometer measurements. New-particle formation from guanidine and sulfuric acid molecules occurs without thermodynamic barriers under studied conditions, and clusters are growing close to a 1:1 composition of acid and base. Evaporation rates of the most stable clusters are extremely low, which can be explained by the proton transfers and symmetrical cluster structures. We compare the ability of guanidine and dimethylamine to enhance sulfuric acid-driven particle formation and show that more than 2000-fold concentration of dimethylamine is needed to yield as efficient particle formation as in the case of guanidine. At similar conditions, guanidine yields 8 orders of magnitude higher particle formation rates compared to dimethylamine. Highly basic compounds such as guanidine may explain experimentally observed particle formation events at low precursor vapor concentrations, whereas less basic and more abundant bases such as ammonia and amines are likely to explain measurements at high concentrations.

Fatty Acid Surfactant Photochemistry Results in New Particle Formation.

Organic interfaces that exist at the sea surface microlayer or as surfactant coatings on cloud droplets are highly concentrated and chemically distinct from the underlying bulk or overlying gas phase. Therefore, they may be potentially unique locations for chemical or photochemical reactions. Recently, photochemical production of volatile organic compounds (VOCs) was reported at a nonanoic acid interface however, subsequent secondary organic aerosol (SOA) particle production was incapable of being observed. We investigated SOA particle formation due to photochemical reactions occurring at an air-water interface in presence of model saturated long chain fatty acid and alcohol surfactants, nonanoic acid and nonanol, respectively. Ozonolysis of the gas phase photochemical products in the dark or under continued UV irradiation both resulted in nucleation and growth of SOA particles. Irradiation of nonanol did not yield detectable VOC or SOA production. Organic carbon functionalities of the SOA were probed using X-ray microspectroscopy and compared with other laboratory generated and field collected particles. Carbon-carbon double bonds were identified in the condensed phase which survived ozonolysis during new particle formation and growth. The implications of photochemical processes occurring at organic coated surfaces are discussed in the context of marine SOA particle atmospheric fluxes.

Diamines Can Initiate New Particle Formation in the Atmosphere.

Recent experimental evidence suggests that diamines can enhance atmospheric new particle formation more efficiently compared to monoamines such as dimethylamine. Here we investigate the molecular interactions between sulfuric acid (sa) and the diamine putrescine (put) using computational methods. The molecular structure of up to four sulfuric acid molecules and up to four putrescine molecules were obtained at the ωB97X-D/6-31++G(d,p) level of theory. We utilized a domain local pair natural orbital coupled cluster method (DLPNO-CCSD(T)/aug-cc-pVTZ) to obtain highly accurate binding energies of the clusters. We find that the (sa)1-4(put)1-4 clusters show more ionic character than clusters consisting of sulfuric acid and dimethylamine (dma) by readily forming several sulfate ions in the cluster. To estimate the stability of the clusters, we calculate the evaporation rates and compare them to ESI-APi-TOF measurements. Using the atmospheric cluster dynamics code (ACDC), we simulate and compare the new particle formation rates between the (sa)1-4(put)1-4 and (sa)1-4(dma)1-4 cluster systems. We find that putrescine significantly enhances the formation of new particles compared to dimethylamine. Our findings suggest that a large range of amines with different basicity is capable of explaining various regions of the observed new particle formation events. These results indicate that diamines, or related compounds with high basicity, might be important species in forming the initial cluster with sulfuric acid and subsequently more abundant amines with lower basicity can assist in the new particle formation process by attaching to the sulfuric acid-diamine nucleus.

Mechanistic Insights on the Photosensitized Chemistry of a Fatty Acid at the Air/Water Interface.

Interfaces are ubiquitous in the environment and many atmospheric key processes, such as gas deposition, aerosol, and cloud formation are, at one stage or another, strongly impacted by physical and chemical processes occurring at interfaces. Here, the photoinduced chemistry of an air/water interface coated with nonanoic acid-a fatty acid surfactant we use as a proxy for chemically complex natural aqueous surface microlayers-was investigated as a source of volatile and semivolatile reactive organic species. The carboxylic acid coating significantly increased the propensity of photosensitizers, chosen to mimic those observed in real environmental waters, to partition to the interface and enhance reactivity there. Photochemical formation of functionalized and unsaturated compounds was systematically observed upon irradiation of these coated surfaces. The role of a coated interface appears to be critical in providing a concentrated medium allowing radical-radical reactions to occur in parallel with molecular oxygen additions. Mechanistic insights are provided from extensive analysis of products observed in both gas and aqueous phases by online switchable reagent ion-time of flight-mass spectrometry and by off-line ultraperformance liquid chromatography coupled to a Q Exactive high resolution mass spectrometer through heated electrospray ionization, respectively.

Atmospheric photochemistry at a fatty acid-coated air-water interface.

Although fatty acids are believed to be photochemically inert in the actinic region, complex volatile organic compounds are produced during illumination of an air-water interface coated solely with a monolayer of carboxylic acid. When aqueous solutions containing nonanoic acid (NA) at bulk concentrations that give rise to just over a monolayer of NA coverage are illuminated with actinic radiation, saturated and unsaturated aldehydes are seen in the gas phase, and more highly oxygenated products appear in the aqueous phase. This chemistry is probably initiated by triplet-state NA molecules excited by direct absorption of actinic light at the water surface. Because fatty acids-covered interfaces are ubiquitous in the environment, such photochemical processing will have a substantial impact on local ozone and particle formation.

Siderophores in Cloud Waters and Potential Impact on Atmospheric Chemistry: Photoreactivity of Iron Complexes under Sun-Simulated Conditions.

In the present work, the photoreactivity of a mixture of iron(III)­pyoverdin (Fe(III)­Pyo) complexes was investigated under simulated cloud conditions. Pyoverdins are expected to complex ferric ions naturally present in cloudwater, thus modifying their availability and photoreactivity. The spectroscopic properties and photoreactivity of Fe(III)-Pyo were investigated, with particular attention to their fate under solar irradiation, also studied through simulations. The photolysis of the Fe(III)­Pyo complex leads to the generation of Fe(II), with rates of formation (RFe(II)f) of 6.98 and 3.96 × 10­9 M s­1 at pH 4.0 and 6.0, respectively. Interestingly, acetate formation was observed during the iron-complex photolysis, suggesting that fragmentation can occur after the ligand-to-metal charge transfer (LMCT) via a complex reaction mechanism. Moreover, photogenerated Fe(II) represent an important source of hydroxyl radical via the Fenton reaction in cloudwater. This reactivity might be relevant for the estimation of the rates of formation and steady-state concentrations of the hydroxyl radical by cloud chemistry models and for organic matter speciation in the cloud aqueous phase. In fact, the conventional models, which describe the iron photoreactivity in terms of iron­aqua and oxalate complexes, are not in accordance with our results.

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes.

The heterogeneous reaction between SO2 and unsaturated compounds results in the efficient production of organosulfates for several fatty acids and long-chain alkenes. The presence of an acid group, the physical state of the reactants (solid or liquid), the nature of the double bond (cis, trans, terminal), and the use of light irradiation all have an impact on the reaction rate. The reaction was investigated using different set-ups (coated flow tube, aerosol flow tube, and diffuse reflectance infrared Fourier transform cell). The reaction products were identified by high-resolution mass spectrometry and the impact of this reaction on organosulfate formation in the atmosphere is discussed.

Photosensitized Production of Atmospherically Reactive Organic Compounds at the Air/Aqueous Interface.

We report on experiments that probe photosensitized chemistry at the air/water interface, a region that does not just connect the two phases but displays its own specific chemistry. Here, we follow reactions of octanol, a proxy for environmentally relevant soluble surfactants, initiated by an attack by triplet-state carbonyl compounds, which are themselves concentrated at the interface by the presence of this surfactant. Gas-phase products are determined using PTR-ToF-MS, and those remaining in the organic layer are determined by ATR-FTIR spectroscopy and HPLC-HRMS. We observe the photosensitized production of carboxylic acids as well as unsaturated and branched-chain oxygenated products, compounds that act as organic aerosol precursors and had been thought to be produced solely by biological activity. A mechanism that is consistent with the observations is detailed here, and the energetics of several key reactions are calculated using quantum chemical methods. The results suggest that the concentrating nature of the interface leads to its being a favorable venue for radical reactions yielding complex and functionalized products that themselves could initiate further secondary chemistry and new particle formation in the atmospheric environment.

Photochemical fate and eco-genotoxicity assessment of the drug etodolac.

The photochemical behavior of etodolac was investigated under various irradiation conditions. Kinetic data were obtained after irradiation of 10(-4) M aqueous solutions by UVB, UVA and direct exposure to sunlight. The Xenon lamp irradiation was used in order to determine the photodegradation quantum yield under sun-simulated condition (ϕsun). The value was determined to be=0.10±0.01. In order to obtain photoproducts and for mechanistic purposes, experiments were carried out on more concentrated solutions by exposure to sunlight and to UVA and UVB lamps. The drug underwent photooxidative processes following an initial oxygen addition to the double bond of the five membered ring and was mainly converted into a spiro compound and a macrolactam. Ecotoxicity tests were performed on etodolac, its photostable spiro derivative and its sunlight irradiation mixture on two different aquatic trophic levels, plants (algae) and invertebrates (rotifers and crustaceans). Mutagenesis and genotoxicity were detected on bacterial strains. The results showed that only etodolac had long term effects on rotifers although at concentrations far from environmental detection values. A mutagenic and genotoxic potential was found for its derivative.

Fe(III)-EDDS complex in Fenton and photo-Fenton processes: from the radical formation to the degradation of a target compound.

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)-EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe(2+) under UV irradiation of the iron complex and the photochemical formation of HO(•) from the photolysis of the complex Fe(III)-EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)-EDDS concentration, H2O2 concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe(2+) quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)-EDDS and H2O2 concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.