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1.
Chemosphere ; 258: 127268, 2020 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-32569955

RESUMO

In this work, UVA radiation that is part of solar light is taken as the irradiation source and radicals (HO, SO4- and HO2/O2-) are generated through activation of hydrogen peroxide (H2O2), sodium persulfate (Na2S2O8) and Bismuth catalyst (BiOCl), respectively. The distinguished performance in removing acetaminophen (ACTP), a model pharmaceutical pollutant, by these three radicals was compared for the first time. Effect of pH, halide ions concentration and interfacial mechanism have been investigated in detail. Interestingly, results show that heterogeneous UVA/BiOCl process has higher degradation efficiency than homogeneous UVA/H2O2 and UVA/Na2S2O8 systems whatever the solution's pH. To explain these results, second order reaction rate constant (kradical, ACTP) have been determined with laser flash photolysis (LFP) or radical scavenging experiments. The strongly interfacial-depended HO2/O2- radicals have the lowest second order rate constant with ACTP but highest steady state concentration. BiOCl is much easier activated by UVA, and outstanding ACTP mineralization can be achieved. Combination of BiOCl and Na2S2O8 exhibits synergistic effects rather than antagonism effects with H2O2. This study highlights the relative effective utilization of solar light through interfacial directed BiOCl photocatalysis and its synergistic effects with traditional oxidants.

2.
Environ Sci Pollut Res Int ; 27(16): 19736-19745, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32222922

RESUMO

In this work, a new combination of oxidation treatments for the degradation of bisphenol A (BPA) is investigated. This innovative wastewater (WW) treatment includes the use of ferrate (FeO42-) and its decomposition byproducts under dark and UVA irradiation. The oxidation by ferrate leads to a fast but incomplete degradation of BPA with a degradation extent of 45% after 60 min under adopted experimental conditions. However, the ferrate decomposition byproducts which are constituted by solid iron species can be used to further improve the pollutant degradation efficiency. Indeed, ferrate-mediated heterogeneous photo-Fenton process is employed for the first time to enhance the degradation of BPA. With respect to the application for wastewater treatment, UVA irradiation (which is part of solar light), non-toxic and natural origin compounds such as ascorbic acid (AA) and ethylenediamine-N,N'-disuccinic acid (EDDS), are used to design a sustainable process. Under optimized conditions, the degradation extent of BPA using this newly designed treatment reaches almost 100% with AA and 70% with EDDS. In order to assess the feasibility of this treatment, the ferrate-mediated photo-Fenton process is applied to treat municipal wastewater. The obtained results in WW are highly encouraging since a maximum BPA degradation extent of 63% and 60% is observed after 300 min by using AA and EDDS, respectively.


Assuntos
Águas Residuárias , Poluentes Químicos da Água , Peróxido de Hidrogênio , Ferro , Oxirredução , Luz Solar
3.
Molecules ; 25(2)2020 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-31968643

RESUMO

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.

4.
Environ Sci Technol ; 2019 Dec 27.
Artigo em Inglês | MEDLINE | ID: mdl-31830784

RESUMO

While the use of transition metal oxides in catalyzing advanced oxidation reactions has been widely investigated, very few reports have focused on how the preliminary contact of oxides with target compounds may affect the succession of reaction. In this study, we examined the adsorption and electron transfer reactions of two fluoroquinolones, flumequine (FLU), and norfloxacin (NOR), with goethite (α-FeOOH) or manganese (Mn) oxide, and their impact on the subsequent mineralization of target compounds using H2O2 or S2O82- under UVA irradiation. Intriguingly, higher total organic carbon (TOC) removal was achieved when antibiotics and metal oxides were allowed for preequilibration before starting the oxidation reaction. The rate and extent of TOC removal are strongly dependent on the molecule structure and the redox-active mineral used, and much less on the preequilibration time. This high efficiency can be ascribed to the presence of reduced metal ions, chemically or photochemically generated during the first stage, onto oxide minerals. Oxide-bound MnII plays a crucial role in catalyzing oxidant decomposition and then producing greater amounts of radical species through a photoassisted redox cycle, regardless of the underlying surface, MnIVO2 or MnIIIOOH. This finding will be of fundamental and practical significance to Mn-based oxidation reactions and wastewater treatment processes.

5.
Sci Total Environ ; 697: 134188, 2019 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-31491635

RESUMO

Persulfate (PS) activation reaction, which forms sulfate radical (SO4-), can be used to degrade organic pollutants in water. However, a drawback of this reaction is that the regeneration of ferrous ions requires a high concentration of hydrogen peroxide (Fenton-like reaction) or use of UV radiation. Catechin (CAT), a non-toxic antioxidant of natural origin from tea, is used in this work to improve the sulfate radical-mediated degradation of atenolol (ATL, a model pollutant) in water using relatively low concentrations of reactive chemical species (less than 100 µM). To the best of the author's knowledge, the direct effect of CAT on the oxidation state of iron, which is promoted by the reduction of ferric into ferrous ions with the enhancement of SO4- formation in the presence of PS, is demonstrated for the first time. The enhancement versus inhibition effect of CAT and the chemical mechanism of the iron-based activation process are explained. Results show that UVA radiation, which is representative of solar light, accelerates the initial degradation of ATL by more than 30% through ferric iron photolysis. Finally, a reaction mechanism leading to the formation of hydroxyl radicals (HO) and SO4- is proposed considering the implication of different activation/reaction chemical steps.


Assuntos
Atenolol/química , Catequina/química , Sulfatos/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Atenolol/análise , Peróxido de Hidrogênio , Radical Hidroxila , Ferro/química , Poluentes Químicos da Água/análise
6.
Chemosphere ; 236: 124366, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31344624

RESUMO

In this work, for the first time, the nonionic surfactant polyoxyethylene-(20)-sorbitan monooleate (Tween 80, C64H124O26) aided soil washing effluent was treated by enhanced activation of persulfate (PS) using Fe(III)-EDDS (EDDS: ethylenediamine-N, N-disuccinic acid) complexes under simulated solar light irradiation. The performance of this system was followed via the production and reactivity of radical species (SO4-, HO, Cl2-) and degradation of phenanthrene (PHE) used as a model pollutant in soils. Different physico-chemical parameters such as the concentration of reactive species and pH were investigated through the PHE degradation efficiency. The second-order rate constants of the reactions for generated radicals with PHE and Tween 80 in solution were identified through competitive reaction experiments under steady-state conditions and application of nanosecond laser flash photolysis (LFP) as well. A kinetic approach was applied to assess the selectivity and reactivity of photo-generated radicals in aqueous medium in order to explain the observed degradation trends. This work proposes an innovative technology of management of soil washing solutions using Fe(III)-EDDS complexes and solar light for the activation of persulfate.


Assuntos
Compostos Férricos/química , Fenantrenos/química , Solo/química , Energia Solar
7.
Environ Sci Process Impacts ; 20(7): 1007-1019, 2018 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-29876570

RESUMO

By a combination of transient absorption spectroscopy and steady-state irradiation experiments, we investigated the transformation of phenol and furfuryl alcohol (FFA) sensitised by irradiated 4-carboxybenzophenone (CBBP). The latter is a reasonable proxy molecule to assess the reactivity of the excited triplet states of the chromophoric dissolved organic matter that occurs in natural waters. The main reactive species for the transformation of both phenol and FFA was the CBBP triplet state, despite the fact that FFA is a commonly used probe for 1O2. In the case of FFA it was possible to develop a simple kinetic model that fitted well the experimental data obtained by steady-state irradiation, in a wide range of FFA concentration values. In the case of phenol the model was made much more complex by the likely occurrence of back reactions between radical species (e.g., phenoxyl and superoxide). This problem can be tackled by considering only the experimental data at low phenol concentration, where the degradation rate increases linearly with concentration. We do not recommend the use of 1O2 scavengers/quenchers such as sodium azide to elucidate CBBP photoreaction pathways, because the azide provides misleading results by also acting as a triplet-state quencher. Based on the experimental data, we propose a methodology for the measurement of the CBBP triplet-sensitisation rate constants from steady-state irradiation experiments, allowing for a better assessment of the triplet-sensitised degradation of emerging contaminants.


Assuntos
Benzofenonas/química , Inativação Luminosa Assistida por Cromóforo , Monitoramento Ambiental/métodos , Furanos/química , Fenol/química , Fotólise , Poluentes Químicos da Água/química , Tempo de Reação
8.
Materials (Basel) ; 11(7)2018 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-29949864

RESUMO

The exploitation of organic waste as a source of bio-based substances to be used in environmental applications is gaining increasing interest. In the present research, compost-derived bio-based substances (BBS-Cs) were used to prepare hybrid magnetic nanoparticles (HMNPs) to be tested as an auxiliary in advanced oxidation processes. Hybrid magnetic nanoparticles can be indeed recovered at the end of the treatment and re-used in further water purification cycles. The research aimed to give new insights on the photodegradation of caffeine, chosen as marker of anthropogenic pollution in natural waters, and representative of the contaminants of emerging concern (CECs). Hybrid magnetic nanoparticles were synthetized starting from Fe(II) and Fe(III) salts and BBS-C aqueous solution, in alkali medium, via co-precipitation. Hybrid magnetic nanoparticles were characterized via X-ray diffraction (XRD), thermo-gravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The effect of pH, added hydrogen peroxide, and dissolved oxygen on caffeine photodegradation in the presence of HMNPs was assessed. The results allow for the hypothesis that caffeine abatement can be obtained in the presence of HMNPs and hydrogen peroxide through a heterogeneous photo-Fenton mechanism. The role of hydroxyl radicals in the process was assessed examining the effect of a selective hydroxyl radical scavenger on the caffeine degradation kinetic.

9.
Environ Sci Technol ; 52(11): 6334-6342, 2018 06 05.
Artigo em Inglês | MEDLINE | ID: mdl-29676902

RESUMO

The secondary pollutant 3,4-dichloroaniline (DCA) is produced by the biological degradation of several herbicides, including propanil in paddy fields. The enzymatic hydrolysis of propanil yields DCA with almost quantitative yield. DCA undergoes rather fast photodegradation in paddy water, mostly by direct photolysis. An exception might be represented by the cases (rather rare in paddies) of quite high nitrate concentration (around 50 mg of NO3- L-1), when DCA degradation by CO3•- would play a comparable role to that by direct photolysis. The experimentally measured photoreactivity parameters were used as input data for a photochemical model, which predicted a DCA lifetime of 0.5-1 days in sunlit paddy fields in late May, when propanil is usually applied. The model predictions compare remarkably well with the DCA attenuation data reported in field studies, carried out in paddies in temperate regions. Moreover, a consecutive reaction model based on typical biological (propanil) and photochemical (DCA) lifetimes reproduced quite well the time trends of both compounds in paddies, as reported in the literature. These successful comparisons suggest that photodegradation in general, and direct photolysis in particular, may play a key role in DCA attenuation in paddy water.


Assuntos
Propanil , Poluentes Químicos da Água , Compostos de Anilina , Fotoquímica , Fotólise , Água
10.
J Hazard Mater ; 347: 279-287, 2018 04 05.
Artigo em Inglês | MEDLINE | ID: mdl-29329010

RESUMO

In the present work we investigate the activation efficiency of H2O2 and S2O82- using UVA and UVB radiation. Bisphenol-A (BPA) is used as model pollutants to estimate the oxidative process efficiency in simulated and real sewage treatment plant waters. Particular attention is paid to the BPA removal efficiency and to the radical mechanism involvement considering the effect of typical inorganic water constituents (carbonates and chloride ions) and organic matter. Despite a detrimental effect observed when carbonate ions are in solution using both hydrogen peroxide and persulafate, the presence of high chloride ions concentration was found to improve BPA removal using S2O82- as radical precursor. This enhancement, investigated combining chemical kinetic model approach and laser flash photolysis experiments, is attributed to the formation of hydroxyl radical and chlorine radical species from sulfate radical. Different transformation products are identified by means of GC-MS and HPLC-MS analyses. Moreover, experiments using sewage treatment plant water (STPW) spiked with BPA are performed in order to assess the efficiency of oxidative processes in a simulated treatment systems activated using UVA + UVB radiations.

11.
Molecules ; 22(8)2017 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-28800072

RESUMO

By exploiting the regioselective protection of the hydroxyl groups of silibinin along with the well-known phosphoramidite chemistry, we have developed an efficient strategy for the synthesis of new silibinin-modified species, which we have named Phosphate-Linked Silibinin Dimers (PLSd), in which the monomer units are linked by phosphodiester bonds. The antioxidant abilities of the new PLSd were estimated on HepG2 cells using DPPH free radical scavenging and xanthine/xanthine oxidase assays. The new phosphate-metabolites showed a higher anti-oxidant activity than the silibinin, as well as very low toxicity. The ability to scavenge reactive oxygen species (ROS) such as singlet oxygen () and hydroxyl radical () reveals that the two dimers are able to scavenge about two times more effectively than silibinin. Finally, solubility studies have shown that the PLSd present good water solubility (more than 20 mg·L-1) under circumneutral pH values, whereas the silibinin was found to be very poorly soluble (less than 0.4 mg·L-1) and not stable under alkaline conditions. Together, the above promising results warrant further investigation of the future potential of the PLSd as anti-oxidant metabolites within the large synthetic polyphenols field.


Assuntos
Antioxidantes/síntese química , Fosfatos/química , Polifenóis/síntese química , Silimarina/síntese química , Antioxidantes/farmacologia , Sobrevivência Celular/efeitos dos fármacos , Dimerização , Depuradores de Radicais Livres/síntese química , Depuradores de Radicais Livres/farmacologia , Células Hep G2 , Humanos , Radical Hidroxila/metabolismo , Oxirredução , Estresse Oxidativo/efeitos dos fármacos , Polifenóis/farmacologia , Espécies Reativas de Oxigênio/metabolismo , Silibina , Silimarina/farmacologia , Solubilidade , Xantina/metabolismo , Xantina Oxidase/metabolismo
12.
Environ Sci Technol ; 51(13): 7486-7495, 2017 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-28581723

RESUMO

Irradiated nitrophenols can produce nitrite and nitrous acid (HONO) in bulk aqueous solutions and in viscous aqueous films, simulating the conditions of a high-solute-strength aqueous aerosol, with comparable quantum yields in solution and viscous films (10-5-10-4 in the case of 4-nitrophenol) and overall reaction yields up to 0.3 in solution. The process is particularly important for the para-nitrophenols, possibly because their less sterically hindered nitro groups can be released more easily as nitrite and HONO. The nitrophenols giving the highest photoproduction rates of nitrite and HONO (most notably, 4-nitrophenol and 2-methyl-4-nitrophenol) could significantly contribute to the occurrence of nitrite in aqueous phases in contact with the atmosphere. Interestingly, dew-water evaporation has shown potential to contribute to the gas-phase HONO levels during the morning, which accounts for the possible importance of the studied process.


Assuntos
Aerossóis , Nitritos , Processos Fotoquímicos , Nitrofenóis , Ácido Nitroso
13.
Environ Sci Technol ; 51(5): 2695-2704, 2017 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-28145687

RESUMO

When irradiated in paddy-field water, propanil (PRP) undergoes photodegradation by direct photolysis, by reactions with •OH and CO3•-, and possibly also with the triplet states of chromophoric dissolved organic matter. Irradiation also inhibits the nonphotochemical (probably biological) degradation of PRP. The dark- and light-induced pathways can be easily distinguished because 3,4-dichloroaniline (34DCA, a transformation intermediate of considerable environmental concern) is produced with almost 100% yield in the dark but not at all through photochemical pathways. This issue allows an easy assessment of the dark process(es) under irradiation. In the natural environment, we expect PRP photodegradation to be important only in the presence of elevated nitrate and/or nitrite levels, e.g., [NO3-] approaching 1 mmol L-1 (corresponding to approximately 60 mg L-1). Under these circumstances, •OH and CO3•- would play a major role in PRP phototransformation. Because flooded paddy fields are efficient denitrification bioreactors that can achieve decontamination of nitrate-rich water used for irrigation, irrigation with such water would both enhance PRP photodegradation and divert PRP dissipation processes away from the production of 34DCA, at least in the daylight hours.


Assuntos
Propanil , Água , Herbicidas , Fotólise , Poluentes Químicos da Água
14.
J Hazard Mater ; 322(Pt B): 380-386, 2017 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-27776849

RESUMO

In this study, the activation of persulfate induced by Fe(III) species, including 5 kinds of iron oxhydroxides (IOs) and dissolved Fe3+ under dark condition were investigated. Ferrihydrite (FH) and akaganeite (AK) showed the highest activity in 4-tert-butylphenol (4tBP) removal. The 4tBP degradation rate constant decreased as the solution pH increased from pH 3.2 to 7.8 in FH/S2O82- system. However, the pH value had no significant effect on the 4tBP degradation in AK/S2O82- system. The degradation of 4tBP in Fe3+/S2O82- system was also performed to investigate the role of ferric species in persulfate activation. The pH dependency of 4tBP degradation rate was closely related to the speciation of FeIII, whereas the Fe(H2O)63+ was found to be the most active soluble iron complex form in the activation of S2O82-. 4tBP degradation was mainly due to the SO4- in IOs/S2O82- system, while SO4- and HO2 both had great contribution on 4tBP degradation in Fe3+/S2O82- system. Further investigations showed clearly that 4tBP degradation efficiency was decreased significantly due to the trapping of SO4- by chloride. This finding may have promising implications in developing a new technology for the treatment of contaminated waters and soils, especially where Fe3+ species are naturally occurring.

15.
Sci Rep ; 6: 37420, 2016 11 23.
Artigo em Inglês | MEDLINE | ID: mdl-27876758

RESUMO

Improving our understanding of cloud chemistry depends on achieving better chemical characterization (90% of the organic carbon [OC] fraction remains uncharacterized) and, consequently, assessing the reactivity of this complex system. In this manuscript, we report for the first time the concentrations of 16 amino acids (AAs) in 25 cloud water samples. The concentrations of individual AAs ranged from a few nM up to ~2.0 µM, and the average contribution of AAs corresponded to 9.1% (4.4 to 21.6%) of the dissolved OC (DOC) concentration. Considering their occurrence and concentrations, AAs were expected to represent an important hydroxyl radical (HO•) sink in aqueous cloud samples. In this work, we estimated that approximately 17% (from 7 to 36%) of the hydroxyl radical-scavenging ability of the DOC could be attributed to the presence of AAs, whereas comparing the AAs suggested that an average of 51% (from 22 to 80%) of their reactivity with HO• could account for the presence of tryptophan. These results clearly demonstrate that the occurrence and reactivity of AAs must be considered to better estimate the chemical composition and oxidant capacity of the cloud aqueous phase.


Assuntos
Aminoácidos/química , Carbono/química , Compostos Orgânicos/química , Água/química , Radical Hidroxila/química , Oxidantes/química , Triptofano/química
16.
Water Res ; 105: 383-394, 2016 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-27657658

RESUMO

Phototransformation is important for the fate in surface waters of the pharmaceuticals diclofenac (DIC) and naproxen (NAP) and for clofibric acid (CLO), a metabolite of the drug clofibrate. The goal of this paper is to provide an overview of the prevailing photochemical processes, which these compounds undergo in the different conditions found in freshwater environments. The modelled photochemical half-life times of NAP and DIC range from a few days to some months, depending on water conditions (chemistry and depth) and on the season. The model indicates that direct photolysis is the dominant degradation pathway of DIC and NAP in sunlit surface waters, and potentially toxic cyclic amides were detected as intermediates of DIC direct phototransformation. With modelled half-life times in the month-year range, CLO is predicted to be more photostable than DIC or NAP and to be degraded mainly by reaction with the •OH radical and with the triplet states of chromophoric dissolved organic matter (3CDOM*). The CLO intermediates arising from these processes and detected in this study (hydroquinone and 4-chlorophenol) are, respectively, a chronic toxicant to aquatic organisms and a possible carcinogen for humans. Hydroquinone is formed with only ∼5% yield upon CLO triplet-sensitised transformation, but it is highly toxic for algae and crustaceans. In contrast, the formation yield of 4-chlorophenol reaches ∼50% upon triplet sensitisation and ∼10% by ·OH reaction. The comparison of model predictions with field data from a previous study yielded a very good agreement in the case of DIC and, when using 4-carboxybenzophenone as proxy for triplet sensitisation by CDOM, a good agreement was found for CLO as well. In the case of NAP, the comparison with field data suggests that its direct photolysis quantum yield approaches or even falls below the lower range of literature values.


Assuntos
Ácido Clofíbrico , Naproxeno , Diclofenaco , Cinética , Modelos Químicos , Fotólise , Poluentes Químicos da Água/química
17.
Environ Sci Technol ; 50(20): 11041-11048, 2016 10 18.
Artigo em Inglês | MEDLINE | ID: mdl-27611489

RESUMO

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.


Assuntos
Processos Fotoquímicos , Água/química , Aerossóis , Fenômenos Químicos , Ácidos Graxos
18.
Science ; 353(6300): 699-702, 2016 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-27516601

RESUMO

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.

19.
Environ Sci Technol ; 50(17): 9324-32, 2016 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-27487120

RESUMO

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.


Assuntos
Ferro , Fotólise , Sideróforos , Compostos Férricos , Radical Hidroxila , Oxalatos
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