Dissolved Organic Matter Photoreactivity Is Determined by Its Optical Properties, Redox Activity, and Molecular Composition.

Predicting the formation of photochemically produced reactive intermediates (PPRI) during the irradiation of dissolved organic matter (DOM) has remained challenging given the complex nature of this material and differences in PPRI formation mechanisms. We investigate the role of DOM composition in photoreactivity using 48 samples that span the range of DOM in freshwater systems and wastewater. We relate quantum yields for excited triplet-state organic matter (fTMP), singlet oxygen (Φ1O2), and hydroxylating species (Φ•OH) to DOM composition determined using spectroscopy, Fourier-transform ion cyclotron resonance mass spectrometry, and electron-donating capacity (EDC). fTMP and Φ1O2 follow similar trends and are correlated with bulk properties derived from UV-vis spectra and EDC. In contrast, no individual bulk property can be used to predict Φ•OH. At the molecular level, the subset of DOM that is positively correlated to both Φ•OH and EDC is distinct from DOM formulas related to Φ1O2, demonstrating that •OH and 1O2 are formed from different DOM fractions. Multiple linear regressions are used to relate quantum yields of each PPRI to DOM composition parameters derived from multiple techniques, demonstrating that complementary methods are ideal for characterizing DOM because each technique only samples a subset of DOM.

An efficient removal approach for degradation of metformin from aqueous solutions with sulfate radicals.

Metformin consumption for diabetes treatment is increasing, leading to its presence in wastewater treatment plants where conventional methods cannot remove it. Therefore, this work aims to analyze the performance of advanced oxidation processes using sulfate radicals in the degradation of metformin from water. Experiments were performed in a photoreactor provided with a low-pressure Hg lamp, using K2S2O8 as oxidant and varying the initial metformin concentration (CA0), oxidant concentration (Cox), temperature (T), and pH in a response surface experimental design. The degradation percentages ranged from 26.1 to 87.3%, while the mineralization percentages varied between 15.1 and 64%. Analysis of variance (ANOVA) showed that the output variables were more significantly affected by CA0, Cox, and T. Besides, a reduction of CA0 and an increase of Cox up to 5000 µM maximizes the metformin degradation since the generation of radicals and their interaction with metformin molecules are favored. For the greatest degradation percentage, the first order apparent rate constant achieved was 0.084 min-1. Furthermore, while in acidic pH, temperature benefits metformin degradation, an opposite behavior is obtained in a basic medium because of recombination and inhibition reactions. Moreover, three degradation pathways were suggested based on the six products detected by HPLC-MS: N-cyanoguanidine m/z = 85; N,N-dimethylurea m/z = 89; N,N-dimethyl-cyanamide m/z = 71 N,N-dimethyl-formamide m/z = 74; glicolonitrilo m/z = 58; and guanidine m/z = 60. Finally, it was shown that in general the toxicity of the degradation byproducts was lower than the toxicity of metformin toward Chlamydomonas reinhardtii.

A Model Assessment of the Occurrence and Reactivity of the Nitrating/Nitrosating Agent Nitrogen Dioxide (•NO2) in Sunlit Natural Waters.

Nitrogen dioxide (•NO2) is produced in sunlit natural surface waters by the direct photolysis of nitrate, together with •OH, and upon the oxidation of nitrite by •OH itself. •NO2 is mainly scavenged by dissolved organic matter, and here, it is shown that •NO2 levels in sunlit surface waters are enhanced by high concentrations of nitrate and nitrite, and depressed by high values of the dissolved organic carbon. The dimer of nitrogen dioxide (N2O4) is also formed in the pathway of •NO2 hydrolysis, but with a very low concentration, i.e., several orders of magnitude below •NO2, and even below •OH. Therefore, at most, N2O4 would only be involved in the transformation (nitration/nitrosation) of electron-poor compounds, which would not react with •NO2. Although it is known that nitrite oxidation by CO3•- in high-alkalinity surface waters gives a minor-to-negligible contribution to •NO2 formation, it is shown here that NO2- oxidation by Br2•- can be a significant source of •NO2 in saline waters (saltwater, brackish waters, seawater, and brines), which offsets the scavenging of •OH by bromide. As an example, the anti-oxidant tripeptide glutathione undergoes nitrosation by •NO2 preferentially in saltwater, thanks to the inhibition of the degradation of glutathione itself by •OH, which is scavenged by bromide in saltwater. The enhancement of •NO2 reactions in saltwater could explain the literature findings, that several phenolic nitroderivatives are formed in shallow (i.e., thoroughly sunlit) and brackish lagoons in the Rhône river delta (S. France), and that the laboratory irradiation of phenol-spiked seawater yields nitrophenols in a significant amount.

Photo-transformation of ofloxacin in natural aquatic conditions: Impact of indirect photolysis on the product profile and transformation mechanism.

The natural phototransformation of organic pollutants in the environment depends on several water constituents, including inorganic ions, humic substances, and pH. However, the literature information concerning the influence of various water components on the amount of phototransformation and their impact on the development of various transformation products (TPs) is minimal. This study investigated the phototransformation of ofloxacin (OFL), a fluoroquinolone antibiotic, in the presence of various water components such as cations (K+, Na+, Ca2+, NH4+, Mg2+), anions (NO3-, SO42-, HCO3-, CO32-, PO43-), pH, and humic substances when exposed to natural sunlight. The study reveals that neutral pH levels (0.39374 min⁻1) enhance the phototransformation of OFL in aquatic environments. Carbonate, among anions, shows the highest rate constant (2.89966 min⁻1), significantly influencing OFL phototransformation, while all anions exhibit a notable impact. In aquatic environments, indirect phototransformation of OFL, driven by increased reactive oxygen species, expedites light-induced reactions, potentially enhancing OFL phototransformation. A clear difference was visible in the type of transformation products (TPs) formed during direct and indirect photolysis. The impact of indirect photolysis in the product profile was evaluated by examining the unique properties of TPs in direct and indirect photolysis. The primary transformation products were generated by oxidation and cleavage processes directed towards the ofloxacin piperazinyl, oxazine, and carboxyl groups. The toxicity assessment of TPs derived from OFL revealed that among the 26 identified TPs, TP3 (demethylated product), TP7 and TP8 (decarboxylated products), and TP15 (piperazine ring cleaved product) could potentially have some toxicological effects. These findings suggest that the phototransformation of OFL in the presence of various water components is necessary when assessing this antibiotic's environmental fate.

Fate of dimethylsilanediol (DMSD) via indirect photolysis in water.

Dimethylsilanediol (DMSD) is the common degradation product of ubiquitous polydimethylsiloxane (PDMS) and volatile methylsiloxanes (VMS) in water and soil. Given the high solubility of DMSD in water, the further degradation of DMSD in this compartment is of particular importance. While DMSD appears relatively resistant to degradation in standard hydrolysis or biodegradation studies, it may degrade by indirect photolysis in surface waters through oxidation by hydroxyl radicals. The formation of hydroxyl radicals is governed by nitrate ions or other promoters in the presence of sunlight. In this study, we investigated the impact of nitrate ions on the oxidative decomposition of DMSD in water under simulated solar light. When exposed to solar light, DMSD can degrade all the way to the natural, mineralized substances, namely carbon dioxide (in the form of carbonic acid) and silicic acid, via the intermediate methylsilanetriol (MST).

Organic peroxyl radicals from biacetyl accelerated the visible-light degradation of steroid estrogens in aqueous solution.

Indirect photodegradation is an important pathway for the reduction of steroid estrogens in sunlit surface waters. Nevertheless, the kinetics and mechanisms governing the interaction between coexisting carbonyl compounds and estrogens under visible light (Vis) remain unexplored. This study systematically investigates the Vis-induced photodegradation of 17ß-estradiol (E2) in the presence of five specific carbonyl compounds-biacetyl (BD), acetone, glyoxal, pyruvic acid, and benzoquinone. The results demonstrate that, among these compounds, only BD significantly enhanced the photodegradation of E2 under Vis irradiation (λ > 400 nm). The pseudo-first order photodegradation rate constants (k1) of E2 in the Vis/BD system were 0.025 min-1 and 0.076 min-1 in ultrapure water and river water, respectively. The enhancing effect of BD was found to be pH-dependent, increasing the pH from 3.0 to 11.0 resulted in a 76% reduction in the k1 value of E2 in the Vis/BD system. Furthermore, the presence of humic acid, NO3-, or HCO3- led to an increase of more than 35% in the k1 value of E2, while NO2- exerted a pronounced inhibitory effect, resulting in a 92% decrease. Peroxyacetyl and peroxymethyl radicals, derived from BD in a yield ratio of 9, played a crucial role in the degradation of E2. These peroxyl radicals primarily targeted electron-rich hydroxyl sites of E2, initiating hydroxylation and ring-opening reactions that culminated in the formation of acidic byproducts. Notably, toxicity evaluation indicates that these hydroxylated and acidic products exhibited lower toxicity than the parent compound E2. This study highlights the important role of peroxyl radicals in estrogen degradation within aquatic environment, and also helps to design efficient visible light-responsive photo-activators for the treatment of estrogen-contaminated waters.

Photo-transformation of isoproturon under UV-A irradiation: The synergy of nitrite and natural organic matter.

Isoproturon (IPU), a widely utilized phenylurea herbicide, is recognized as an emerging contaminant. Previous studies have predominantly attributed the degradation of IPU in natural waters to indirect photolysis by natural organic matter (NOM). Here, we demonstrate that nitrite (NO2-) also serves as an important photosensitizer that induces the photo-degradation of IPU. Through radical quenching tests, we identify hydroxyl radicals (•OH) and nitrogen dioxide radicals (NO2•) originating from NO2- photolysis as key players in IPU degradation, resulting in the generation of a series of hydroxylated and nitrated byproducts. Moreover, we demonstrate a synergistic effect on the photo-transformation of IPU when both NOM and NO2- are present in the reaction mixture. The observed rate constant (kobs) for IPU removal increases to 0.0179 ± 0.0002 min-1 in the co-presence of NO2- (50 µM) and NOM (2.5 mgC/L), surpassing the sum of those in the presence of each alone (0.0135 ± 0.0004 min-1). NOM exhibits multifaceted roles in the indirect photolysis of IPU. It can be excited by UV and transformed to excited triplet states (3NOM*) which oxidize IPU to IPU•+ that undergoes further degradation. Simultaneously, NOM can mitigate the reaction by reducing the IPU•+ intermediate back to the parent IPU. However, the presence of NO2- alters this dynamic, as IPU•+ rapidly couples with NO2•, accelerating IPU degradation and augmenting the formation of mono-nitrated IPU. These findings provide in-depth understandings on the photochemical transformation of environmental contaminants, especially phenylurea herbicides, in natural waters where NOM and NO2- coexist.

Solar light photodegradation of nicotine in the presence of aged polystyrene microplastics.

Limited information exists on the potential of aged microplastics to induce photodegradation of organic pollutants under sunlight irradiation. In this work, nicotine (NIC), a widespread emerging contaminant, was used as a model organic substrate to investigate this innovative degradation process. Polystyrene (PS) pellets were artificially aged and became rich in oxygenated moieties with their carbonyl index reaching 0.43 ± 0.04 after 4 d of aging. The degradation of NIC photosensitized by aged PS at different pH values was monitored for 6 h under simulated sunlight irradiation (650 W/m2). The maximum degradation rate was observed at pH = 11 (75 % NIC removal from a 10 mg L-1 solution containing 50 g L-1 aged PS pellets), suggesting that the unprotonated NIC is the most photoreactive form. Increasing the PS load from 50 to 200 g L-1 accelerated NIC degradation. The addition of 2.5 mg L-1 humic acids had a slight enhancement role (82 % NIC degradation), which confirms their effectiveness as photosensitizers. NIC photosensitization by aged PS was also studied in the presence of t-butanol (55 % NIC removal in solutions containing 100 mg L-1 t-butanol) and in anoxic conditions (NIC solution purged with N2; 95 % NIC removal), to gain insight into the respective roles of the potentially formed •OH and 1O2. The main photo-produced reactive species involved in NIC degradation likely were the triplet states of the PS beads (3PS*). Differently from most advanced oxidation processes, NIC's photodegradation by aged PS was not affected by increasing amount of chloride and we observed negligible differences between NIC degradation in ultra-pure water and seawater. The effectiveness of irradiated PS towards NIC photodegradation was also investigated in tap water and secondary wastewater. Overall, the possibility to decontaminate polluted water with waste-derived materials is interesting in the framework of circular economy.

The environmental degradability of DEMNUM, a typical PFPE polymer.

The three environmental degradation tests of hydrolysis, indirect photolysis and Zahn-Wellens microbial degradation were conducted according to the OECD and the US EPA guidelines on DEMNUM, a typical linear perfluoropolyether polymer. Low mass degradation products that formed in each test were structurally characterized and indirectly quantified by liquid chromatography mass spectrometry (LC/MS) using a reference compound and an internal standard of similar structure. The degradation of the polymer was assumed to directly correlate with the appearance of lower mass species. The hydrolysis experiment at 50 °C showed the appearance of less than a dozen low mass species with increasing pH but at the negligible total estimated amount of ∼2 ppm relative to polymer. A dozen low mass perfluoro acid entities also appeared following the indirect photolysis experiment in synthetic humic water. Their maximum total amount was at ∼150 ppm relative to polymer. The largest total amount of low mass species formed during the Zahn-Wellens biodegradation test amounted to only ∼80 ppm relative to polymer. The Zahn-Wellens conditions tended to produce larger low mass molecules than the ones formed under photolysis. The results from all three tests indicate that the polymer is stable and non-degradable in the environment.

Apparent quantum yield for photo-production of singlet oxygen in reservoirs and its relation to the water matrix.

Man-made reservoirs are important for human daily lives and offer different functions, however they are contaminated due to anthropogenic activities. Dissolved organic matter (DOM) from each reservoir is unique in composition, which further determines its photo-reactivity. Thus, this study aimed to investigate the photo-reactivity of reservoir DOM in terms of the quantum yield for photo-production of singlet oxygen (Ф1O2). We sampled surface water of 50 reservoirs in Japan and determined their Ф1O2 using simulated sunlight together with bulk water analysis. Their Ф1O2 ranged from 1.46 × 10-2 to 6.21 × 10-2 (mean, 2.55 × 10-2), which was identical to those of lakes and rivers reported in the literature, but lower than those of wetland water and wastewater. High-energy triplet-state of DOM accounted for 59.4% of the 1O2 production in the reservoir water on average. Among the bulk water properties, the spectral slope of wavelength from 350 to 400 nm (S350-400) was statistically detected as the most important predictor for Ф1O2. Furthermore, the multiple linear regression model employed S350-400 and the biological index as predictors with no intercorrelations and reasonable accuracy (r2 = 0.86), while the random forest model showed a better accuracy (r2 = 0.90). Overall, these major findings are beneficial for understanding the photo-reactivity of reservoir waters.

An inevitable but underestimated photoaging behavior of plastic waste in the aquatic environment: Critical role of nitrate.

Photoaging is an important reaction for waste plastics in the aquatic environment and plays a key role in the lifetime of plastics. Nevertheless, when natural photosensitive substances such as nitrate participate in this process, the physiochemical changes in plastics and the corresponding reaction mechanisms are not well-understood. In this work, the photochemical behavior of polyethylene terephthalate (PET) bottles in deionized water and nitrate solution was systematically investigated under ultraviolet (UV) irradiation. The analyses of the surface physicochemical properties of the photoaged PET bottles indicated that, after 20 days of photo-irradiation, the presence of nitrate reduced the contact angle from 69.8 ± 0.9° to 60.0 ± 0.3°, and increased the O/C ratio from 0.23 to 0.32, respectively. The leaching rate of dissolved organic carbon (DOC), which was 0.0193 mg g-1·day-1 in nitrate solution, was twice that of 0.00941 mg g-1·day-1 in deionized water. Furthermore, fluorescence spectroscopy revealed that the increasing DOC had aromatic rings with hydroxyl on the side-chain formed after UV irradiation. The positive effect of nitrate on the degradation of PET bottles was mainly through the generation of hydroxyl radicals that were produced through the photolysis of nitrate. In addition, two-dimensional correlation spectroscopy analysis showed that the chain scission of PET plastics could be initiated by nitrate-induced ·OH attacking the carbon-oxygen bonds instead of forming peroxides with oxygen. This work elucidates the mechanism of photodegradation of plastics that was induced by nitrate and highlights the important role of natural photosensitive substances in the photoaging process of plastics.

A mini review on microwave and contemporary based biohydrogen production technologies: a comparison.

Hydrogen gas, along with conventional fossil fuels, has been used as a green fuel with enormous potential. Due to the rapid depletion of fossil fuels, a new dimension of hydrogen production technology has arrived to reduce reliance on nonrenewable energy sources. Microwave-based hydrogen production is a more promising and cost-effective technology than other existing green hydrogen production methods such as fermentation and gasification. Microwave heating may be superior to traditional heating due to several advantages such as less power consumption compared to other methods, higher yield, and a higher rate of conversion. Compared to another process for hydrogen production, the microwave-driven process worked efficiently at lower temperatures by providing more than 70% yield. The process of production can be optimized by using properly sized biomass, types of biomass, water flow, temperature, pressure, and reactor size. This method is the most suitable, attractive, and efficient technique for hydrogen production in the presence of a suitable catalyst. Hot spots formed by microwave irradiation would have a substantial impact on the yield and properties of microwave-processed goods. The current techno-economic situation of various technologies for hydrogen production is discussed here, with cost, efficiency, and durability being the most important factors to consider. The present review shows that a cost-competitive hydrogen economy will necessitate continual efforts to increase performance, scale-up, technical prospects, and political backing.

Photolysis of polycyclic aromatic hydrocarbons adsorbed on polyethylene microplastics.

Contaminants adsorbed on microplastics (MPs) are a potential risk to aquatic environments. Several studies have demonstrated that polycyclic aromatic hydrocarbons (PAHs), which adsorb on MPs, can be photolyzed in aqueous solutions. We investigated photolysis of PAHs on MPs under sunlight conditions to estimate their environmental fate for the first time. The PAHs (25 ng each) were added to polyethylene powder, which was used as the MP sample. The MP sample was agitated in water with sunlight irradiation; thereafter, the concentration of the PAHs on the MP sample was determined by high-pressure liquid chromatography with a fluorescence detector. The half-life values of the PAHs were estimated between 3.4 × 102 (pyrene) and 3.2 × 104 min (benz[j]fluoranthene). These values are 0.5 (fluoranthene) to 25 (benzo[a]pyrene) times larger than those in the aqueous phase. Additionally, the degradation of PAHs by OH radicals produced by the photolysis of nitrate was observed.

Photochemical fate of medetomidine in coastal and marine environments.

Medetomidine has been authorized in ship hull paints as an antifouling biocide under the biocidal product regulation in Europe since 2016. Its release into marine systems causes concerns over persistence and toxicity. However, the environmental fate of medetomidine has not been fully investigated. In this study, the photodegradation of medetomidine under natural sunlight conditions was investigated using collected coastal and sea waters. In addition, the phototransformation of medetomidine with reactive species (i.e., singlet oxygen, excited triplet state organic matter, and hydroxyl radicals) under UVA light was examined. Photoproducts were isolated by high-performance liquid chromatography (HPLC), identified by a combination of nuclear magnetic resonance (NMR) spectroscopy and time-of-flight mass spectrometry (qTOF), and reaction mechanisms were proposed. The results show that medetomidine is a neutral base (pKa of protonated form = 7.2) that leads to two different protonation states in the aquatic environment. Photodegradation of neutral medetomidine was dominated by reaction with singlet oxygen, while protonated medetomidine was relatively photostable. The contribution of reactive species to the overall photodegradation of neutral medetomidine was calculated to provide an assessment of phototransformation of medetomidine. The half-live of medetomidine was < 1.5 days in natural waters (pHcoastal = 8.3; pHsea = 8.1) under sunlit near-surface conditions, suggesting that it is not persistent in the aquatic environment. Because medetomidine has a relatively short half-life in sunlit aquatic ecosystems, a number of products, such as 2-(2,3-dimethylphenyl)propanamide, can be formed by photochemical reactions of medetomidine, with unknown consequences for marine and coastal waters.

Photodegradation of metoprolol in the presence of aquatic fulvic acids. Kinetic studies, degradation pathways and role of singlet oxygen, OH radicals and fulvic acids triplet states.

Metoprolol is a pharmaceutical used for the treatment of cardiovascular diseases and disorders, whose frequent detection in surface waters raises concern. Indirect photodegradation is an important degradation pathway in waters and dissolved organic matter has a major role as photosensitizer. In this study, metoprolol photodegradation, in the absence and in the presence of fulvic acids extracted from the Vouga River (Portugal) (VRFA), was assessed under simulated sunlight. While metoprolol direct photodegradation was deniable, indirect photolysis occurred under the presence of VRFA. It followed a pseudo-first order kinetics and after 72 h of irradiation there was a decrease of metoprolol concentration of ∼80 %. The OH radical (OH) was verified to be the main reactive species (RS) responsible for the photosensitized degradation of metoprolol, but other RS are also involved, probably triplet excited states of FA (3FA*) and singlet oxygen (1O2), as demonstrated by the higher inhibition of the photodegradation in presence of sodium azide than in presence of 2-propanol. Based on a previous identification of photoproducts, tentative degradation mechanisms were here proposed. Photoproducts analysis after 24 h irradiation in the absence and presence of scavengers, shown that different RS are involved in the formation of different products/intermediates.

Influence of pigments on phototransformation of biocides in paints.

Biocides are commonly applied to construction materials such as facade renders and paints in order to protect them from microbial spoilage. These renders and paints are exposed to weathering conditions, e.g., sunlight and rain. Pigments are interacting intensively with the spectrum of the incoming light; thus, an effect of paint pigments on phototransformation rates and reaction pathways of the biocides is hypothesized. In this study, the phototransformation of four commonly used biocides (carbendazim, diuron, octylisothiazolinone (OIT) and terbutryn) in four different paint formulations differing solely in pigments (red and black iron oxides, white titanium dioxide, and one pigment-free formulation) were investigated. Paints surfaces were irradiated under controlled conditions. The results show that biocides degrade most rapidly in the pigment-free formulation. The degradation in the pigment-free formulation followed a first-order kinetic model with the respective photolysis rate constants: kp,Diuron = 0.0090 h-1, kp,OIT = 0.1205 h-1, kp,Terbutryn = 0.0079 h-1. Carbendazim concentrations did not change significantly. The degradation was considerably lower in the pigment-containing paints. The determination of several phototransformation products of terbutryn and octylisothiazolinone showed different transformation product ratios dependent on the pigment. Consequently, pigments not only reflect the incoming light, but also interact with the biocide photodegradation.

Photodegradation of the novel brominated flame retardant 2,4,6-Tris-(2,4,6-tribromophenoxy)-1,3,5-triazine in solvent system: Kinetics, photolysis products and pathway.

In this study the direct and indirect photolysis of the novel brominated flame retardant 2,4,6-Tris-(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) in an organic solvent mixture (60:30:10, ACN:MeOH:THF) under UV-(C) and simulated sunlight irradiation was investigated, and the formed photo-transformation products were identified for the first time. TTBP-TAZ was almost completely degraded within 10 min under UV-(C) irradiation. Due to the fast degradation no specific kinetic order could be observed. In comparison, the reaction under simulated sunlight irradiation was much slower and thus, the kinetic first-order could be determined. The observed photolysis rate constant k as well as the half-life time t1/2 were estimated to be k = (0.0163 ±â€¯0.0002) h-1 and t1/2 = 42.3 h, respectively. The addition of 2-propanol and hydrogen peroxide to investigate the influence of indirect photolysis under UV-(C) irradiation causes no influence on the degradation of TTBP-TAZ. Nevertheless, the removal of TTBP-TAZ under UV-(C) and simulated sunlight without additional chemicals (except solvent) indicates that the direct photolysis plays a significant role in the degradation mechanism of TTBP-TAZ. In both irradiation experiments, TTBP-TAZ was quantitatively degraded that involve the formation of previously unknown PTPs. Overall, two main PTPs were determined when irradiated with UV-(C) and eight sequential debromination products were observed when irradiated by simulated sunlight. These were determined by HPLC-DAD and - MS/(MS), respectively. Based on the chosen experimental conditions the consecutive debromination as well as photo-Fries rearrangement was confirmed as the main degradation pathway by high resolution mass spectrometry and X-ray diffraction.

Influence of chemical speciation on photochemical transformation of three fluoroquinolones (FQs) in water: Kinetics, mechanism, and toxicity of photolysis products.

This study investigated the contribution of direct, indirect, and self-sensitized photolysis to the photochemical fate of three model fluoroquinolones (FQs), i.e., lomefloxacin (LOM), norfloxacin (NOR), and ofloxacin (OFL), and demonstrated the influence of chemical speciation on their photodegradation behavior, a topic that has received relatively little attention. Results suggest that these FQs in water transformed mainly via direct photolysis, while hydroxyl radical played a key role in their indirect and self-sensitized photolysis. Chemical speciation of such zwitterionic compounds significantly affected the kinetics of their phototransformation, with the quantum yields of photodegradation decreased in the order of zwitterionic (FQsH) > anionic (FQs-) > cationic (FQsH2+). The photodegradation pathways of FQs depended on both their structures and chemical speciation. Defluorination for LOM in C-8 and NOR in C-6 was more significant when they were present in zwitterionic form than in the other forms. Cationic FQs underwent direct piperazinyl ring cleavage, and zwitterionic ones underwent piperazinyl ring oxidation, while the degradation pathway of piperazinyl ring for FQs in anionic form was structure dependent. Decarboxylation for zwitterionic FQs occurred more slowly compared to both cationic and anionic ones, and the FQs bearing electron-donating groups in C-8 position degraded more easily in cationic form than the anionic ones, while the opposite was true for the FQs without such a group in C-8 position. Results of Vibrio fischeri bioluminescence inhibition tests showed the toxicity of zwitterionic NOR and OFL significantly decreased after photodegradation, while the degradation products of LOM exhibited greater toxicity. These findings indicate that chemical speciation of zwitterionic compounds could affect the kinetics and pathways of their photochemical transformation, and thus have important implications on their fate and risk in aquatic environment.

The different fate of antibiotics in the Thames River, UK, and the Katsura River, Japan.

Little is known about the mechanisms influencing the differences in attenuation of antibiotics between rivers. In this study, the natural attenuation of four antibiotics (azithromycin, clarithromycin, sulfapyridine, and sulfamethoxazole) during transport along the Thames River, UK, over a distance of 8.3 km, and the Katsura River, Japan, over a distance of 7.6 km was compared. To assist interpretation of the field data, the individual degradation and sorption characteristics of the antibiotics were estimated by laboratory experiments using surface water or sediment taken from the same rivers. Azithromycin, clarithromycin, and sulfapyridine were attenuated by 92, 48, and 11% in the Thames River stretch. The first-order decay constants of azithromycin and sulfapyridine were similar to those in the Katsura River, while that of clarithromycin was 4.4 times higher. For sulfamethoxazole, the attenuation was limited in both rivers. Loss of sulfapyridine was attributed to both direct and indirect photolysis in the Thames River, but to only direct photolysis in the Katsura River. Loss of azithromycin and clarithromycin was attributed to sorption to sediment in both rivers. The probable explanation behind the difference in loss rates of clarithromycin between the two rivers was considered to be sediment sorption capacity.

Key environmental processes affecting the fate of the insecticide chloropyrifos applied to leaves.

Chlorpyrifos (CP) is still a commonly employed organophosphorus insecticide worldwide. In semi-arid and Mediterranean climates, applied CP is expected to remain on leaves surfaces for relatively long time due to the lack of summer rains and common use of drip irrigation. The present work examines the loss rate of CP from leaves via different surface processes: evaporation, direct photolysis and reactions with ozone and OH radicals. Laboratory experiments showed that evaporation rate constant of CP increased from 0.109 to 0.492 h-1 with the increase in wind speed up to 4 m/s. First-order rate constant of direct photolysis, measured using a solar simulator, was k'UV = 1.15 (±0.01) x 10-20 cm2 photon-1. Second-order rate constants for the reaction of CP with ozone and OH were measured as 6 × 10-20 and 6 × 10-12 cm3 molecule-1 s-1, respectively. The above rate constants were applied successfully in an outdoor experiment to predict the disappearance of chloropyrifos under specific environmental conditions. Further modeling showed that the insecticide half-life time on exposed surfaces under typical Mediterranean environment will be in the range of 0.9-6.9 h. Evaporation is expected to be the dominant removal path under most environmental conditions, followed by direct photolysis and reaction with OH.