Experimental determination of the partitioning of representative organic pollutants to the air-water interface.

Using glancing-angle laser-induced fluorescence (GALIF) spectroscopy as a probe, the partitioning of naphthalene, fluoranthene, pyrene, umbelliferone, phenol red, and bisphenol A from bulk solution to the air-water interface was examined in both pure water and aqueous solutions of 6 mM octanol. Previous studies provided similar Langmuir adsorption isotherms for anthracene and imidazole 2-carboxaldehyde. The surface partitioning behaviour of each compound in both environments was well described using a Langmuir adsorption model; partitioning coefficients were derived from the fits to such isotherms. Only the PAH molecules, naphthalene, fluoranthene and pyrene, saw an enhancement in the surface partitioning in octanol solution compared to pure water. The surface partitioning to pure water surfaces could be fairly well described using a one parameter linear free energy relationship based on either solubility or KOW.

Photodegradation of Triclosan on the Kaolinite Surface: Kinetic, Mechanistic, and Molecular Modeling Approach.

The photodegradation of triclosan (TCS) was investigated on the kaolinite surface. The quantum yield was evaluated, and the photoproducts were identified by HPLC/MS (LC/Q-TOF), showing that the phototransformation is completely different from that reported in aqueous solutions. In particular, the formation of dioxin derivatives was fostered and occurred with a higher efficiency when compared to aqueous solutions. This suggests that TCS has specific interactions with the clay that clearly modifies its photochemical behavior. Moreover, it has also been shown that higher concentrations of TCS, namely, higher than 1.0 µmol g-1 of kaolinite, lead to a significant decrease of the photodegradation rate constant and enhance the formation yield of dimer-type photoproducts. This suggests that the distribution of TCS is clearly not homogeneous at the clay surface and the formation of aggregates is more likely occurring. To get a better insight into this specific interaction, a molecular dynamic modeling of TCS adsorption at the surface of kaolinite was carried out. This clearly shows that when equilibrium is reached, TCS binds to the kaolinite surface by hydrogen bonds involving the phenol function of TCS and the hydroxyl groups of the kaolinite surface. Such behavior confers a particular conformation to the adsorbed TCS that is different from that obtained in water and which could be a key step to partially explain the specific photochemical reactivity in both media. In addition, several TCS molecules appear to interact with each other through the π-stacking (aromatic stacking) process while retaining this hydrogen bond with the kaolinite surface. This is clearly in favor of cluster formation on the clay surface and promotes dimer-type photoproducts.

Study of the ageing and the sorption of polyaromatic hydrocarbons as influencing factors on the effects of microplastics on blue mussel.

The mussels are species with high socio-economic weights and are often used as bioindicators of biological and chemical contamination. In the field and aquaculture, they can intake microplastics during filter-feeding, and the microplastics can have a negative impact on their health, even at low concentrations. The effects of microplastics have yet to be fully examined on the blue mussel (Mytilus edulis), considering the factors of ageing and sorption of some polyaromatic hydrocarbons (PAHs), ubiquitous environmental contaminants. In this work, 5 different exposure conditions were studied: pristine microplastics, microplastics aged for 1000 days under UV radiation, microplastics sorbing PAHs, as well as microplastics both aged and sorbing PAHs, in parallel to controls. The microplastic changes after ageing were studied with spectroscopic and chromatographic methods. Then, 8-day laboratory exposures of mussels at 10 µg/L of microplastics were performed. The oxidative stress, as well as neurotoxic and immunological responses of M. edulis, were measured using a battery of biomarkers (catalase/CAT, superoxide dismutase/SOD, glutathione S-transferases/GST, acetylcholinesterase/AChE) in 3 different organs (digestive gland, gills and mantle), and acid phosphatase in hemolymph. Then, a study of lipid impairments on the digestive gland was performed through the use of lipidomic tools. No significant difference of oxidative stress activity was observed for all the tissues of mussels exposed to pristine microplastics at 10 µg/L, compared to controls. The ageing and the PAH soption onto microplastics were influencing factors of the oxydative stress in mussels with increased CAT activities in the digestive glands and decreased SOD activities in the mantles. The neurotoxicity was highlighted by higher AChE activities measured in the mantle of mussels exposed to all the microplastic treatments, compared to controls. Concerning lipidomics, no compound was determined as a biomarker of microplastic exposure. The study demonstrated a low toxicity of microplastics at environmental relevant concentration with a 8-day exposure and using the chosen biomarkers. However, some microplastic changes seemed to lead to specific effects on mussels.

Sol-Gel Synthesis of New TiO2 Ball/Activated Carbon Photocatalyst and Its Application for Degradation of Three Hormones: 17α-EthinylEstradiol, Estrone, and ß-Estradiol.

Many approaches have been investigated to eliminate pharmaceuticals in wastewater treatment plants during the last decades. However, a lack of sustainable and efficient solutions exists for the removal of hormones by advanced oxidation processes. The aim of this study was to synthesize and test new photoactive bio composites for the elimination of these molecules in wastewater effluents. The new materials were obtained from the activated carbon (AC) of Arganian spinosa tree nutshells and titanium tetrachloride by the sol gel method. SEM analysis allowed one to confirm the formation of TiO2 particles homogeneously dispersed at the surface of AC with a controlled titanium dioxide mass ratio, a specific TiO2 anatase structure, and a highly specific surface area, evidenced by ATG, XRD, and BET analysis, respectively. The obtained composites were revealed to quantitatively absorb carbamazepine (CBZ), which is used as a referred pharmaceutical, and leading to its total elimination after 40 min under irradiation with the most effective material. TiO2 high content disfavors CBZ adsorption but improves its degradation. In the presence of the composite, three hormones (17α-ethinylestradiol, estrone, and ß-estradiol) are partially adsorbed onto the composite and totally degraded after 60 min under UV light exposure. This study constitutes a promising solution for the efficient treatment of wastewater contaminated by hormones.

Characteristics, fate, and impact of marine plastic debris exposed to sunlight: A review.

The increase of plastic production from the middle of the twentieth century was inevitably followed by an increase in the amount of plastic dumped in the natural environment. There, the plastic debris are exposed to sunlight, temperature, humidity, and physical stress. This can induce photo-oxidative and thermal degradation. This review discusses the mechanism of plastics UV weathering and its characteristics. Comparison of the photodegradation rate and physico-chemical properties are made according to the weathering mode (natural/accelerated) and medium (air/water). Since the photodegradation can lead to plastics fragmentation, this phenomenon is described along with the methodologies used in literature to evaluate the fragmentation. The impact of the photodegraded plastic debris on the marine environment is also presented in term of (i) photodegradation products and stabilizers leakage, (ii) organic pollutants accumulation, transfer, and leakage, and (iii) toxicity on marine organisms.

Experimental evidence of plastic particles transfer at the water-air interface through bubble bursting.

Plastic debris in the marine environment are the subject of an extensive literature. According to studies dedicated to the determination of plastic litter abundance and to the characterisation of degradation and fragmentation processes, models were used to estimate the global plastic debris abundance and to simulate their transfer and distribution. Despite these efforts, there is still missing plastic in the models used as areas exist where plastic abundance is less than that estimated. In parallel, microplastics presence in the atmosphere and in remote areas was confirmed suggesting long range atmospheric transport. Potentially addressing both these issues, recent literature suggests that microplastics (MPs) and nanoplastics (NPs) can be transferred from the marine environment to the atmosphere via the bursting of air bubbles at the sea surface. Nevertheless, to date there is no direct evidence of this transfer. In this study, we evaluate plastic particles transfer as a function of MPs/NPs characteristics and water composition by simulating the bubble bursting phenomenon in a laboratory reactor. Size distribution of transferred particles were recorded, and their plastic nature was confirmed using electron microscopy. Results show that under tested conditions, the transfer is possible but limited to particles smaller than 1 µm. The influence of the presence of proxies of components of the sea surface microlayer in the water was evaluated showing a higher particle transfer rate in the presence of a surfactant (sodium dodecyl sulfate) and no significant effect of polysaccharides (xanthan gum and dextran). The surface state of the particles can alter their behaviour in the aqueous phase and thus their transfer to the atmosphere. The effect of bubble size was also evaluated showing a higher transfer rate with the smaller bubble size. In addition, experiments performed with grounded polyethylene (PE) samples showed higher transfer for UV-aged PE than for pristine PE.

Pharmaceuticals in the marine environment: What are the present challenges in their monitoring?

During the last years, there has been a growing interest in the research focused on the pharmaceutical residues in the environment. Those compounds have been recognized as a possible threat to aquatic ecosystems, due to their inherent biological activity and their "pseudo-persistence". Their presence has been relatively few investigated in the marine environment, though it is the last receiver of the continental contamination. Thus, pharmaceuticals monitoring data in marine waters are necessary to assess water quality and to allow enhancing future regulations and management decisions. A review of the current practices and challenges in monitoring strategies of pharmaceuticals in marine matrices (water, sediment and biota) is provided through the analysis of the available recent scientific literature. Key points are highlighted for the different steps of marine waters monitoring as features to consider for the targeted substance selection, the choice of the marine site configuration and sampling strategies to determine spatio-temporal trends of the contamination. Some marine environment specific features, such as the strong dilution occurring, the complex hydrodynamic and local logistical constraints are making this monitoring a very difficult and demanding task. Thus key knowledge gap priorities for future research are identified and discussed. Suitable passive samplers to monitor pharmaceutical seawater levels need further development and harmonization. Non-target analysis approaches would be promising to understand the fate of the targeted molecules and to enhance the list of substances to analyze. The implementation of integrated monitoring through long-term ecotoxicological tests on sensitive marine species at environmental levels would permit to better assess the ecological risk of these compounds for the marine ecosystems.

Nanocomposite material from TiO2 and activated carbon for the removal of pharmaceutical product sulfamethazine by combined adsorption/photocatalysis in aqueous media.

This work was dedicated to the elaboration of new composite materials based on activated carbon and titanium oxide as an ecological solution for the cleaning of water contaminated with pharmaceutical pollutants. Such new composite materials allowed the combining of adsorption and photocatalytic process, which allows a cleaning process that is low cost making them promising materials. The functionalization of the surface of activated carbon (AC) by TiO2 nanoparticles forms the core of the nanocomposite material. This was accomplished using sol-gel process with molar ratios Rn (nTi/nAC) in the range of 1/10 to 7/10 followed by a calcination step (400 °C, N2, 2 h). Using various characterization techniques, AC surface functionalization was confirmed and the formation of a TiO2 coating on the AC was noticed with TiO2 under its unique anatase crystallographic form. The study of adsorption and photocatalytic degradation of the sulfamethazine antibiotic demonstrated that the most photoactive nanocomposite corresponds to the one with Rn = 0.5. Freundlich model was proved to be a perfect fit with the experimental results stating that the adsorption is of multilayer nature on the surface of the adsorbent and with interactions between the pollutants adsorbed on its surface. The photocatalytic degradation of the remaining pharmaceutical pollutant in the solution was evidenced and essentially occurred through the involvement of hydroxyl radicals formed by the excitation of the photocatalyst. The formation of the photoproducts analyzed by the LC/MS technique implies the splitting of the sulfonamide bridge, and by the hydroxylation of the aromatic ring and the pyrimidine group.

Zebrafish toxicity assessment of the photocatalysis-biodegradation of diclofenac using composites of TiO2 and activated carbon from Argania spinosa tree nutshells and Pseudomonas aeruginosa.

The occurrence and persistence of pharmaceutical products (PPs) in the environment have recently been well-documented and are a major concern for public health. Their incidence in aquatic ecosystems is the result of their direct release without any prior treatment or insufficient wastewater treatment. Therefore, an efficient and safe posttreatment process for removing PPs must be developed. In this study, we focused on the ability of photocatalysis or combined photocatalysis and biodegradation to effectively and safely remove diclofenac (DCF) and its by-products from water. The heterogeneous photocatalysis system was based on bio-sourced activated carbon obtained from Argania spinosa tree nutshells and Degussa P25 titanium dioxide (ACP-TiO2), and biodegradation involved Pseudomonas aeruginosa. Toxicity tests were conducted with zebrafish embryos to evaluate the applicability of the treatment processes. The results showed that photocatalytic treatment with 0.1 mg/L of ACP-TiO2 9% for 7.5 h is sufficient to eliminate DCF (50 mg L-1) and its by-products from water. Low levels of malformation (< 20%) were detected in zebrafish embryos treated with photocatalyzed DCF solutions at 1, 5, and 7 mg L-1 after 4 days of exposure. After 3 h of incubation, P. aeruginosa was found to reduce the toxicity of DCF (10 mg L-1) photocatalyzed for 2 and 4 h. Additional studies should be conducted to elucidate the biodegradation mechanism.

Microstructure Characterization of Oceanic Polyethylene Debris.

Plastic pollution has become a worldwide concern. It was demonstrated that plastic breaks down to nanoscale particles in the environment, forming so-called nanoplastics. It is important to understand their ecological impact, but their structure is not elucidated. In this original work, we characterize the microstructure of oceanic polyethylene debris and compare it to the nonweathered objects. Cross sections are analyzed by several emergent mapping techniques. We highlight deep modifications of the debris within a layer a few hundred micrometers thick. The most intense modifications are macromolecule oxidation and a considerable decrease in the molecular weight. The adsorption of organic pollutants and trace metals is also confined to this outer layer. Fragmentation of the oxidized layer of the plastic debris is the most likely source of nanoplastics. Consequently the nanoplastic chemical nature differs greatly from plastics.

Advances and limits of two model species for ecotoxicological assessment of carbamazepine, two by-products and their mixture at environmental level in freshwater.

In order to evaluate the environmental impacts associated with the presence of low-level of pharmaceuticals in waters, chronic ecotoxicity of carbamazepine (CBZ), oxcarbazepine (OxCBZ) and acridine 9-carboxylic acid (9-CAA) and their mixture was investigated using two species from different trophic levels. Innovative approaches were developed by monitoring: (i) phytometabolites in the duckweed Lemna minor L. and, (ii) alterations at the population, cellular and molecular levels on the cnidarian Hydra circumcincta Schulze 1914, to assess the effects of 14-day chronic exposure. On H. circumcincta, the approach was conducted at 19.5 °C, the optimal growth temperature, and at 23 °C, to simulate global warming impact. In L. minor, results showed alterations of the nitrogen balance and the chlorophyll indices for OxCBZ and 9-CAA separately at environmental concentrations and for the mixture of the three studied products. However, phenolic compound index deeply varied depending on pharmaceuticals and time of exposure with no specific trend. In H. circumcincta, effects on morphology, reproduction and lipid peroxidation were observed at low level of CBZ. OxCBZ impacted the total antioxidant capacity of H. circumcincta, whereas exposure to 9-CAA affected all parameters, except the reproduction rate. Finally, 14-day exposure to the mixture of the three products also slowed the reproduction rate and altered the morphology of this cnidarian. Higher damages were detected when experiments were conducted at a temperature 3.5 °C above the optimum for Hydra growth, suggesting the relevance of taking into account possible ecotoxicological consequences of global warming. Our results confirmed the necessity of selecting sensitive organisms at different trophic levels to better assess ecotoxicity of pharmaceuticals and their mixture, especially at environmental levels and facing global changes.

Simultaneous grading of microplastic size sampling in the Small Islands of Bintan water, Indonesia.

Despite Indonesia being considered as second highest source of marine plastic debris in the world, few studies have been conducted on plastic debris in Indonesia, particularly microplastics. By using a simple device to simultaneously grade floating microplastics, we investigated microplastic contamination in the ecosystem of small islands in Bintan Regency, Riau Island Province, Indonesia. The average number of floating microplastics from 11 beach stations around Bintan Island was 122.8 ±â€¯67.8 pieces per station, which corresponds to 0.45 pieces per m3 and represents a low-medium microplastic pollution level compared to the levels of other marine environments worldwide. Polymer identification using Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) Spectroscopy successfully identified Polyethylene (PE) (17.3 ±â€¯8.3%), Low Density PE (17.6 ±â€¯5.5%), Oxidized LDPE (<0.1%), Polypropylene (PP) (54 ±â€¯13%), PP Atactic (<0.4%), PP isotactic (<0.2%) and Polystyrene (PS) (10.4 ±â€¯9.1%) from different forms and shapes of microplastics i.e., fragments (50.9 ±â€¯4.9%), fibers (26.2 ±â€¯3%), granule (13.1 ±â€¯3.8%) and films (9.8 ±â€¯5.1%). We suggest that the generation of these microplastics was likely due to physicochemical processes, including biological degradation in this tropical ecosystem. Environmental implication of microplastics in this area increases the problems associated with ingestion, bioaccumulation and biomagnification across trophic levels and co-pollutants absorbed onto microplastics.

Occurrence and ecotoxicological assessment of pharmaceuticals: Is there a risk for the Mediterranean aquatic environment?

Due to their pseudo-persistence and their biological activity, pharmaceuticals are emerging contaminants of major concern for the environment. The aim of this review is to provide an updated inventory of the contamination of aquatic environments by 43 drugs representing different classes of pharmaceuticals, such as antibiotics, anti-inflammatory drugs, anti-depressants, sex hormones, lipid regulators and beta-blockers. The data collected is focused on contamination levels reported in marine coastal waters and in waste and river waters flowing into the Mediterranean Sea. The most widely produced/prescribed classes of medicines are compared with the substances most widely searched for in the environment. Ranges of pollution levels according to the type of water body are also presented, to examine the fate in sewage treatment plants and the persistence in the environment of the targeted molecules. Levels of pharmaceuticals ranged from 100 to 10,000 or even 100,000 ng·L-1 in sewage waters, dropping to 1 to 10,000 ng·L-1 in rivers and to not detected to 3000 ng·L-1 in sea water. However, this paper evidences a lack of data for seawater and also for several countries along the southern coast of the Mediterranean Sea. In order to assess the risk for aquatic ecosystems associated with pharmaceuticals, experimental ecotoxicological values obtained using normalized acute and/or chronic bioassays carried out with different trophic levels were collected for each drug. Targeted biological species and associated bioassays are classified on the basis of their sensitivity to each class of compounds. Occurrence and ecotoxicology are then linked by using the Hazard Quotient (HQ) to assess the environmental risk caused by pharmaceuticals in the Mediterranean Basin. Correlations between HQ and frequency of detection of pharmaceuticals highlighted thirteen compounds that are cause for concern in Mediterranean fresh and sea waters, such as 17α-ethinylestradiol, metoprolol, 8 antibiotics and 3 analgesics/anti-inflammatories.

Beach macro-litter monitoring and floating microplastic in a coastal area of Indonesia.

Qualitative analysis of the structures of the polymers composing floating plastic debris was performed using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and the aging of the debris was assessed by measuring carbonyl group formation on the particle surfaces. Plastic material made up >75% of the 2313 items collected during a three-year survey. The size, shape and color of the microplastic were correlated with the polymer structure. The most abundant plastic materials were polypropylene (68%) and low-density polyethylene (11%), and the predominant colors of the plastics were white, blue and green. Cilacap Bay, Indonesia, was contaminated with microplastic at a concentration of 2.5mg·m3. The carbonyl index demonstrated that most of the floating microplastic was only slightly degraded. This study highlights the need to raise environmental awareness through citizen science education and adopting good environmental practices.

From the conventional biological wastewater treatment to hybrid processes, the evaluation of organic micropollutant removal: A review.

Because of the recalcitrance of some micropollutants to conventional wastewater treatment systems, the occurrence of organic micropollutants in water has become a worldwide issue, and an increasing environmental concern. Their biodegradation during wastewater treatments could be an interesting and low cost alternative to conventional physical and chemical processes. This paper provides a review of the organic micropollutants removal efficiency from wastewaters. It analyses different biological processes, from conventional ones, to new hybrid ones. Micropollutant removals appear to be compound- and process- dependent, for all investigated processes. The influence of the main physico-chemical parameters is discussed, as well as the removal efficiency of different microorganisms such as bacteria or white rot fungi, and the role of their specific enzymes. Even though some hybrid processes show promising micropollutant removals, further studies are needed to optimize these water treatment processes, in particular in terms of technical and economical competitiveness.

Heterogeneous photocatalytic degradation of pesticides using decatungstate intercalated macroporous layered double hydroxides.

Decatungstate W10O32(4-) was efficiently intercalated between the layers of three-dimensionally ordered macroporous Mg2Al-layered double hydroxide. The structural and textural properties of as-prepared intercalated compound were characterized using different solid-state characterization techniques such as X-ray powder diffraction, FTIR and Raman spectroscopies and electronic microscopy. The photocatalytic properties of immobilized W10O32 (4-) within Mg2Al structure were investigated using 2-(1-naphthyl) acetamide (NAD) as a model of pesticide. The influence of different parameters such as amount of catalyst, pH and oxygen concentration were investigated. An optimal NAD degradation was obtained for a photocatalyst concentration of 60 mg l(-1). Under our experimental conditions, this heterogeneous photocatalyst induces photodegradation of 60 % of NAD after 17 h of irradiation at 365 nm and at pH 6.6. Interestingly, pesticide photodegradation leads to the mineralization of substrates to H2O and CO2 and the photocatalyst can be recycled and reused without any loss of activity over four cycles.

Evaluation of two (125)I-radiolabeled acridine derivatives for Auger-electron radionuclide therapy of melanoma.

We previously selected two melanin-targeting radioligands [(125)I]ICF01035 and [(125)I]ICF01040 for melanoma-targeted (125)I radionuclide therapy according to their pharmacological profile in mice bearing B16F0 tumors. Here we demonstrate in vitro that these compounds present different radiotoxicities in relation to melanin and acidic vesicle contents in B16F0, B16F0 PTU and A375 cell lines. ICF01035 is effectively observed in nuclei of achromic (A375) melanoma or in melanosomes of melanized melanoma (B16F0), while ICF01040 stays in cytoplasmic vesicles in both cells. [(125)I]ICF01035 induced a similar survival fraction (A50) in all cell lines and led to a significant decrease in S-phase cells in amelanotic cell lines. [(125)I]ICF01040 induced a higher A50 in B16 cell lines compared to [(125)I]ICF01035 ones. [(125)I]ICF01040 induced a G2/M blockade in both A375 and B16F0 PTU, associated with its presence in cytoplasmic acidic vesicles. These results suggest that the radiotoxicity of [(125)I]ICF01035 and [(125)I]ICF01040 are not exclusively reliant on DNA alterations compatible with γ rays but likely result from local dose deposition (Auger electrons) leading to toxic compound leaks from acidic vesicles. In vivo, [(125)I]ICF01035 significantly reduced the number of B16F0 lung colonies, enabling a significant increase in survival of the treated mice. Targeting melanosomes or acidic vesicles is thus an option for future melanoma therapy.

Photochemical degradation of the plant growth regulator 2-(1-naphthyl) acetamide in aqueous solution upon UV irradiation.

The photochemical degradation of 2-(1-naphthyl) acetamide (NAD) in aqueous solution using simulated sunlight excitation as well as UV light within the 254-300 nm range was investigated to obtain an insight into the transformation mechanism that could occur under environmental conditions. Several photoproducts were identified using HPLC/MS/MS techniques. The degradation quantum yield was found to be independent of the excitation wavelength, but showed a dependence of oxygen concentration. This increased by a factor of approximately 3 from aerated to oxygen-free solutions. There is a clear involvement of both triplet and singlet excited states in NAD photoreactivity. The participation of singlet oxygen as a significant route in NAD degradation was ruled out by comparison with the behavior using Rose Bengal as a photosensitizer. A mechanistic pathway implying hydroxylation process through NAD radical cation species as well as an oxidation reaction by molecular oxygen is proposed. The photochemical behavior of NAD appears to mainly involve the aromatic moieties without any participation of the amide side chain. Toxicity tests clearly show that the generated primary photoproducts are responsible for a significant increase in the toxicity. However, upon prolonged irradiation this toxicity tends to decrease.

Fate of a stilbene-type fluorescent whitening agent (DSBP) in the presence of Fe(III) aquacomplexes: from the redox process to the photodegradation.

The behaviour of 4,4'-bis(2-sulfostyryl)biphenyl (DSBP), a fluorescent whitening agent, was investigated in the presence of Fe(III) aquacomplexes at room temperature. In the dark, a two-step reaction was observed when adding Fe(III) to a solution of DSBP: an initial fast redox reaction between DSBP and the monomeric species Fe(OH)(2+) and a slower reaction leading to the coagulation of oxidised DSBP and iron. This phenomenon is due to the formation of a complex or an ion-pair between Fe(II) and/or Fe(III) with oxidised DSBP and it probably occurs by charge neutralisation in our experimental conditions. The precipitation of DSBP depends on the initial concentration in Fe(OH)(2+) and is achieved for a ratio [Fe(OH) (2+)]/[DSBP] of 5 approximately. Under irradiation at 365 nm, a complicated behaviour was observed: a complexation of iron by oxidised DSBP favoured by irradiation and a degradation of DSBP induced by an intramolecular electron transfer in the complex or by a photoredox of Fe(OH)(2+) species generating .OH radicals in the supernatant. The complete degradation of DSBP is reached four times faster in the presence of Fe(III) with respect to the direct photolysis of DSBP alone. Moreover, the total mineralization of DSBP obtained in less than 120 h upon irradiation at 365 nm is only observed in the presence of the ferric ions, enlightening the efficiency of the method involving Fe(III) and UV irradiation.

A comparative study of water soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrin and its metal complexes as efficient sensitizers for photodegradation of phenols.

5,10,15,20-Tetrakis(2,6-dichloro-3-chlorosulfophenyl)porphyrin and its tin and zinc complexes were synthesized with high yields and fully characterized. The corresponding water-soluble 5,10,15,20-tetrakis(2,6-dichloro-3-sulfophenyl)porphyrins were obtained by hydrolysis with water. An extensive photophysical study of the new water soluble porphyrinic compounds was carried out including absorption and fluorescence spectra, fluorescence quantum yields, triplet absorption spectra, triplet lifetimes, triplet and singlet oxygen quantum yields. These sensitizers were successfully used in the photodegradation of 4-chlorophenol and 2,6-dimethylphenol. A comparison is made of their efficiencies, and some mechanistic considerations are highlighted.