First Detection of Thiamethoxam in a Free-Ranging Insectivorous Bird After its Agricultural Use Ban in Spain.

Neonicotinoids are insecticides used worldwide in phytosanitary and biocidal products and veterinary pharmaceuticals. Recently, some restrictions and bans have been imposed due to their adverse effects on nontarget invertebrates, including pollinators. Although they may have direct and indirect effects on wild vertebrates, few studies have assessed exposure to these compounds in wild birds, so our knowledge remains limited. In the present pilot study we have assessed the prevalence of seven neonicotinoid insecticides and some of their metabolites in whole blood samples from 19 European roller (Coracias garrulus) nestlings and five adult common kestrels (Falco tinnunculus) in an area treated with neonicotinoids to control the palm weevil (Rynchophorus ferrugineus) in southeastern Spain. One European roller nestling born in a palm tree was positive for thiamethoxam, with a concentration of 2.26 ng mL-1, but no residues of neonicotinoids or their metabolites were found in adult common kestrels. Future studies are needed to elucidate potential exposure to neonicotinoids at different times of the year. To our knowledge, this is the first report of the presence of thiamethoxam residues in whole blood of a wild bird species after its ban in Spain. Environ Toxicol Chem 2024;00:1-8. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Active monitoring of long-eared owl (Asio otus) nestlings reveals widespread exposure to anticoagulant rodenticides across different agricultural landscapes.

The widespread use of anticoagulant rodenticides (ARs) poses a worldwide threat to farmland wildlife. These compounds accumulate in tissues of both target and non-target species, potentially endangering both direct consumers and their predators. However, investigations on ARs in blood of free-ranging predatory birds are rare. Here, the long-eared owl (Asio otus) has been used as a model predator to assess AR exposure in different agricultural landscapes from a Mediterranean semiarid region. A total of 69 owlets from 38 nests were blood-sampled over 2021 and 2022, aiming to detect AR residues and explore factors that determine their exposure, such as land uses. In addition, prothrombin time (PT) test was conducted to assess potential effects of AR contamination. Overall, nearly all the samples (98.6 %) tested positive for at least one compound and multiple ARs were found in most of the individuals (82.6 %). Among the ARs detected, flocoumafen was the most common compound (88.4 % of the samples). AR total concentration (ΣARs) in blood ranged from 0.06 to 34.18 ng mL-1, detecting the highest levels in the most intensively cultivated area. The analysis of owl pellets from 19 breeding territories showed relevant among-site differences in the contribution of rodents and birds into the diet of long-eared owls, supporting its high dietary plasticity and indicating AR presence at multiple trophic levels. Moreover, a positive and significant correlation was found between ΣARs and PT (Rho = 0.547, p < 0.001), which demonstrates the direct effect of ARs on free-living nestlings. Our results provide a preliminary overview of AR exposure in a little-studied owl species inhabiting agricultural and rural landscapes. Despite the low detected levels, these findings indicate widespread exposure -often to multiple compounds- from early life stages, which raises concern and draws attention to an ongoing and unresolved contamination issue.

Chemical Composition of Wild Collected and Cultivated Edible Plants (Sonchus oleraceus L. and Sonchus tenerrimus L.).

The present work investigates the nutritional and bioactive composition, as well as the organoleptic and sensory properties, of S. oleraceus and S. tenerrimus, two wild plant species traditionally used in the gastronomy of the Mediterranean area. Additionally, the effect of cultivation on leaf composition was assessed to explore their potential for large-scale production and commercialization from the point of view of possible losses or gains in quality. Both species were characterized as a good source of bioactive compounds, such as vitamins, pro-vitamins and carotenoids, with health-promoting and antioxidant properties that are highly appreciated. The sensory profile revealed a good general acceptance of S. oleraceus and S. tenerrimus, indicating that they could be included in the diet. Although the cultivation of S. oleraceus resulted in a decrease in the concentration of phenolic compounds when compared to wild-harvested plants, the opposite occurred for vitamin C. In S. tenerrimus, cultivation also increased the concentration of other compounds with important nutritional and healthy properties, such as sugars, organic acids and ß-carotene. The results of the composition, organoleptic and sensory properties of S. oleraceus and S. tenerrimus support the idea of their potential to be used as edible leafy vegetables and as promising assets for functional foods.

Evaluation of distribution of emerging mycotoxins in human tissues: applications of dispersive liquid-liquid microextraction and liquid chromatography-mass spectrometry.

In this work, a complete study of the distribution of emerging mycotoxins in the human body has been carried out. Specifically, the presence of enniatins (A, A1, B, B1) and beauvericin has been monitored in brain, lung, kidney, fat, liver, and heart samples. A unique methodology based on solid-liquid extraction (SLE) followed by dispersive liquid-liquid microextraction (DLLME) was proposed for the six different matrices. Mycotoxin isolation was performed by adding ultrapure water, acetonitrile, and sodium chloride to the tissue sample for SLE, while the DLLME step was performed using chloroform as extraction solvent. Subsequently, the analysis was carried out by high-performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS). The proposed method allowed limits of quantification (LOQs) to be obtained in a range of 0.001-0.150 ng g-1, depending on the tissue and mycotoxin. The precision was investigated intraday and interday, not exceeding of 9.8% of relative standard deviation. In addition, trueness studies achieved 75 to 115% at a mycotoxin concentration of 25 ng g-1 and from 82 to 118% at 5 ng g-1. The application of this methodology to 26 forensic autopsies demonstrated the bioaccumulation of emerging mycotoxins in the human body since all mycotoxins were detected in tissues. Enniatin B (ENNB) showed a high occurrence, being detected in 100% of liver (7 ± 13 ng g-1) and fat samples (0.2 ± 0.8 ng g-1). The lung had a high incidence of all emerging mycotoxins at low concentrations, while ENNB, ENNB1, and ENNA1 were not quantifiable in heart samples. Co-occurrence of mycotoxins was also investigated, and statistical tests were applied to evaluate the distribution of these mycotoxins in the human body.

Abatement of pesticides residues in commercial farm soils by combined ozonation-solarization treatment.

The widespread use of pesticides against agricultural pest and diseases introduces these pollutants and their transformation products into soils. The toxicity and permanence of these substances make it necessary for the development of remediation strategies in order to mitigate contamination and to further protect consumers. This work was aimed to evaluate the applicability of ozonation-solarization technology in the degradation of pesticide residues in commercial farm soils. The trial was conducted in two exploitations devoted during decades to tomato cultivation under greenhouse and net systems. Treatments were carried out using a pipping network (both superficial and sub-superficial) that delivered ozone in gaseous state after covering the soil with gas-tight plastic film to avoid ozone leaks to atmosphere. Control soil treatments, without ozone exposure, were also conducted. After 40 days of treatment, mean degradation percentages of about 55-61% for both cultivation systems were obtained, when the reduction of these pollutants in the control soils was about 8-15%. Ozonation-solarization impact was also assessed by changes on soil physical-chemical properties. Results suggest that ozonation in combination with solarization technique could be considered as a feasible approach for the remediation of pesticide-polluted farm soils.

Use of polypyrrole ferrite microparticles and liquid chromatography-mass spectrometry for testing natural grass contamination by multiclass mycotoxins.

An analytical methodology based on the combination of dispersive magnetic solid-phase extraction (DMSPE) and liquid chromatography-mass spectrometry (LC-MS) is proposed to explore the occurrence of 13 mycotoxins (aflatoxins B1, G1, B2, and G2; deoxynivalenol; T-2 toxin; ochratoxin A; HT-2 toxin; enniatins A, A1, B, and B2; and beauvericin) and their derivatives in natural grass samples. Magnetic microparticles (Fe3O4) coated with polypyrrole (PPy) polymer were used in DMSPE sample treatment as adsorbent phase, and Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy have been used for its characterization. The experimental parameters influencing the adsorption and desorption steps of DMSPE have been optimized. Method validation has been carried out obtaining limits of quantification between 0.07 and 92 µg kg-1 corresponding to enniatin B or A1 and DON, respectively. A total of 83 natural grass samples from 8 dehesa farms were analysed. Enniatin B was found in all the samples (0.29 to 488 µg kg-1 concentration range) followed by enniatin B1 (92.8% of the samples) with a 0.12-137 µg kg-1 concentration range. Moreover, co-occurrence of mycotoxins was studied and between 2 and 5 mycotoxins appeared simultaneously in 97.6% of the samples. Distribution of the contamination according to natural grass location was also investigated.

Free and glycosylated aroma compounds in grapes monitored by solid-liquid extraction and dispersive liquid-liquid microextraction combined with gas chromatography-mass spectrometry.

Fifteen aroma compounds have been determined in their free and glycosylated forms in grapes using dispersive liquid-liquid microextraction with gas chromatography-mass spectrometry. The sample treatment includes a previous solid-liquid extraction stage and subsequent parallel microextraction approaches to preconcentrate total aroma content and the free fraction. Thus, the extraction of the total content of analytes requires previous enzymatic hydrolysis of the bound forms. For preconcentration, chloroform (250 µl) and acetonitrile (1.5 ml) were added to 10 ml of the sample extract in the presence of 0.5 g sodium chloride. The absence of matrix effect in the samples allowed quantification against aqueous external standards. Limits of detection ranged between 5 and 30 ng/g, depending on the compound. Method accuracy was studied through recovery assays, with recoveries in the 82-115% range being obtained. Relative standard deviations for repeatability studies were lower than 12%. Four different samples of grapes were analyzed, being quantified linalool in its free form at concentrations in the 359-470 ng/g range, and benzyl alcohol, 2-phenylethanol, and linalool oxide I and II in their bound forms between 52 and 464 ng/g.

Photocatalytic degradation of four insecticides and their main generated transformation products in soil and pepper crop irrigated with reclaimed agro-wastewater under natural sunlight.

This work is the first-ever study of the concurrence of four insecticides (chlorantraniliprole, imidacloprid, pirimicarb and thiamethoxam) and their main transformation products (TPs) in soil and pepper crop irrigated with reclaimed and non-reclaimed water under agricultural field conditions. Field experiments were conducted using different irrigation supplies: control water (CW), wastewater polluted with phytosanitary commercial products containing the studied insecticides (WW) and reclaimed wastewater after a photocatalytic processing with TiO2/Na2S2O8 at pilot plant under sunlight (RWW). Photocatalytic treatments removed most of the insecticides and their TPs generated during the photoperiod. Neither target insecticides nor their TPs were detected in pepper samples when CW and RWW were used as irrigation source, whereas the four insecticides and two TPs were detected when WW was used. In the experiment carried out with WW, all insecticides and eight TPs were detected in soil samples. The impact of using reclaimed water on the quality of pepper crop was also assessed, showing barely any significant difference.

Mobility of insecticide residues and main intermediates in a clay-loam soil, and impact of leachate components on their photocatalytic degradation.

This work assesses the behavior (adsorption, degradation and leaching) of four insecticides (chlorantraniliprole, thiametoxam, imidacloprid and pirimicarb) and their main reaction intermediates in a clay-loam textured soil (1.6% OM). Following the batch equilibrium method, the KOC (as log values) ranged from 1.2 to 3.9 (thiametoxam and pirimicarb, respectively). All the insecticides were moderately persistent (t½ = 39-100 days) in the following order: thiametoxam > imidacloprid > pirimicarb > chlorantraniliprole. Two major transformation products, desmethyl-formamido pirimicarb and desmethyl pirimicarb, were formed as consequence of dealkylation of the parent compound. Using disturbed soil columns only thiametoxam (93% of the initial amount) and imidacloprid (42% of the initial amount) were recovered from leachates. In the case of pirimicarb and chlorantraniliprole, 74% and 30%, respectively, were recovered from the soil. Thiametoxam and imidacloprid can be catalogued as mobile compounds, while pirimicarb and chlorantraniliprole are classified as immobile according to the screening indices used (GUS and ELI). Leachates containing thiametoxam and imidacloprid were subjected to photocatalytic treatment for 240 min using TiO2/Na2S2O8 with the help of a photochemical reactor equipped with LED lamp. Both compounds had a very fast degradation rate (half-lives ≤ 0.5 min) in deionized water, while their half-lives were 112 min and 178 min, respectively, in leaching water. This implies a strong effect of the water matrix composition, mainly due to organic matter dissolved (quenching). Only traces of thiametoxam urea and hydroxy imidacloprid were detected during the photocatalytic experiment.

Phenolic and Carotenoid Profile of Lamb's Lettuce and Improvement of the Bioactive Content by Preharvest Conditions.

This study characterizes the phenolic, carotenoid and chlorophyll profile of lamb's lettuce, a vegetable whose consumption in salads and ready-to-eat products is constantly growing. The MS/MS analysis allowed the identification of thirty-five phenolic compounds including hydroxybenzoic and hydroxycinnamic acids, flavanones, flavanols and flavanones, many of which are reported here in lamb's lettuce for the first time. Chlorogenic acid was the principal phenolic compound found (57.1% of the total phenolic concentration) followed by its isomer cis-5-caffeoylquinic. Other major phenolic compounds were also hydroxycinnamic acids (coumaroylquinic, dicaffeoylquinic and feruloylquinic acids) as well as the flavones luteolin-7-rutinoside, diosmetin-apiosylglucoside and diosmin. Regarding carotenoids, seven xanthophyll and four carotenes, among which ß-carotene and lutein were the major compounds, were detected from their UV-Vis absorption spectrum. In addition, chlorophylls a and b, their isomers and derivatives (pheophytin) were identified. Preharvest factors such as reduced fertilization levels or salinity increased some secondary metabolites, highlighting the importance of these factors on the final nutritional value of plant foods. Lamb's lettuce was seen to be a good potential source of bioactive compounds, and fertilization management might be considered a useful tool for increasing its nutritional interest.

Combined ozonation and solarization for the removal of pesticides from soil: Effects on soil microbial communities.

Pesticides have been used extensively in agriculture to control pests and soil-borne diseases. Most of these pesticides can persist in soil in harmful concentrations due to their intrinsic characteristics and their interactions with soil. Soil solarization has been demonstrated to enhance pesticide degradation under field conditions. Recently, ozonation has been suggested as a feasible method for reducing the pesticide load in agricultural fields. However, the effects of ozonation in the soil microbial community have not been studied so far. Here, we evaluate the combined effects of solarization and ozonation on the microbial community of a Mediterranean soil. For this purpose, soil physico-chemical characteristics and enzyme activities and the biomass (through analysis of microbial fatty acids) and diversity (through 16S rRNA and ITS amplicon sequencing) of soil microbial communities were analyzed in a 50-day greenhouse experiment. The degradation of the pesticides was increased by 20%, 28%, and 33% in solarized soil (S), solarized soil with surface ozonation (SOS), and solarized soil with deep ozonation (SOD), respectively, in comparison to control (untreated) soil. Solarization and its combination with ozonation (SOS and SOD) increased the ammonium content as well as the electrical conductivity, while enzyme activities and soil microbial biomass were negatively affected. Despite the biocidal character of ozone, several microbial populations with demonstrated pesticide-degradation capacity showed increases in their relative abundance. Overall, the combination of solarization plus ozone did not exacerbate the effects of solarization on the soil chemistry and microbial communities, but did improve pesticide degradation.

Solar photocatalysis as strategy for on-site reclamation of agro-wastewater polluted with pesticide residues on farms using a modular facility.

One of the consequences of phytosanitary treatments applied to crops is the generation of a great volume of agro-wastewater having pesticide residues. These pollutants can be considered a serious threat to the environment and human health due to their capacity to affect distant areas remaining for a long time after their application. We have assessed the degradation of five pesticides in agro-waste water produced in two farms by the cleaning pesticide containers and phytosanitary treatment equipment used in the farms. For this purpose, a pilot facility was installed in both farms and advanced oxidation treatments were conducted using natural sunlight by means of Na2S2O8 and heterogeneous photocatalysis (TiO2/Na2S2O8). The remaining percentages obtained at the end of the experiments ranged from 5 to 90.1% for chlorantraniliprole, 5 to 82.3% for difenoconazole, 0.02 to 19.1% for metalaxyl, 1.4 to 74.4% for myclobutanil, and 0.3 to 61% for triadimenol. We observed a correlation between the higher remaining percentages and the total initial concentration of pollutant because of other commercial formulations applied in the farms. The results showed that this equipment could be used to eliminate or reduce the presence of pesticide residues in agro-waste water using an innovative facility installed in the farms and a renewable and economical source of energy (sunlight).

Appraisal of water matrix on the removal of fungicide residues by heterogeneous photocatalytic treatment using UV-LED lamp as light source.

In this study, the photocatalytic degradation of four fungicides, myclobutanil, penconazole and difenoconazole (triazole compounds) and boscalid (carboxamide), has been examined in different aqueous matrices (tap water, irrigation water and two WWPT effluents). Experiments were conducted at laboratory scale with different reagents-zinc oxide (ZnO), titanium dioxide (TiO2), sodium persulphate (Na2S2O8) and the combined systems ZnO/Na2S2O8 and TiO2/Na2S2O8-in water exposed to UV-LED irradiation. Previously, the effect of catalyst and oxidant loading on the disappearance kinetics of the different fungicides was assessed to know maximum degradation efficiency. The influence of water matrices and pesticide loading in removal effectiveness has been evaluated. It was observed a greater efficiency in processes conducted using the tandems ZnO/Na2S2O8 and TiO2/Na2S2O8 in irrigation and tap waters. Results showed that UV-LED are a suitable alternative for tackling the removal of organic pollutants in water.

Use of Index-Based Screening Models to Evaluate the Leaching of Triclopyr and Fluroxypyr Through a Loam Soil Amended with Vermicompost.

The effect of vermicompost added to a loam soil on the leaching behaviour of two herbicides (triclopyr and fluroxypyr) was examined. Mobility of the herbicides was assessed using disturbed soil columns under laboratory conditions. In both cases, the addition of vermicompost significantly increased the sorption of the compounds. For both, DT50 values were slightly higher in the amended soil, due to the increased adsorption. Rate constants (k) calculated according to pseudo-first order model were significantly lower in the case of triclopyr (very persistent), which led to a much lower degradation rate compared to fluroxypyr (persistent) in both unamended and amended soils. Values calculated for the experimental leaching index (ELI) in unamended and amended soils showed medium and high leachability for fluroxypyr (0.31 and 0.29) and triclopyr (0.72 and 0.70), respectively. Other index-based screening models (GUS, RLPI, LIX) also catalogue both herbicides as potential leachers. Results confirm that triclopyr and fluroxypyr may contaminate groundwater resources.

Electrospun silk fibroin/TiO2 mats. Preparation, characterization and efficiency for the photocatalytic solar treatment of pesticide polluted water.

The photocatalytic properties of silk fibroin (SF) incorporating TiO2 nanoparticles using an electrospinning technique were examined. Electrospun SF/TiO2 mats were successfully prepared and characterized by different techniques (XRD, FE-SEM, XPS, XDS, FTIR and BET). The photocatalytic efficiency of these materials were assessed by their ability to degrade four pesticides (boscalid, hexythiazox, pyraclostrobin and trifloxystrobin) in water exposed to solar irradiation. The effect of catalyst loading on the disappearance kinetics of the different pesticides was studied in order to determine the maximum degradation efficiency. The degradation rate significantly increases upon adding the TiO2. However, no significant differences (p < 0.05) were observed when the TiO2 loading was increased from 25 to 50 mg for most compounds. Thus, SF mats with 25 mg of TiO2 were selected. Therefore, a new and simple approach to produce materials with photocatalytic activity, safety and potential application in the purification of water contaminated by pesticides has been developed.

Solar-driven photocatalytic treatment as sustainable strategy to remove pesticide residues from leaching water.

We have demonstrated the potential leaching of eight compounds, one insecticide (flonicamid) and seven fungicides (myclobutanil, penconazole, boscalid, difenoconazole, trifloxystrobin, pyraclostrobin and fenpyroximate) trough a typical Mediterranean soil (Calcaric regosol). The concentrations found in leaching water were in all cases above the limit set by the EU in groundwater (0.1 µg L-1). For this, the efficiency of different homogeneous (photo-Fenton and photo-Fenton-like) and heterogeneous (ZnO and TiO2) photocatalytic systems was tested in deionized water to choose the most appropriate treatment to remove pesticide residues from leaching water. The efficiency was in the order: ZnO + S2O82- (pH 7) > TiO2+ S2O82- (pH 7) > ZnO (pH 7) > TiO2 (pH 7) > Fe3+ (pH 3) > Fe3+ (pH 5) > Fe2+ (pH 3) > Fe2+ (pH 5). Thus, in the subsequent experiment we focus on the efficacy of solar heterogeneous photocatalysis (ZnO/Na2S2O8 and TiO2/ Na2S2O8) on their removal from leaching water. A fast removal was observed for all pesticides at the end of the photoperiod, noticeably higher in the case of ZnO system, with the exception of flonicamid, a recalcitrant pesticide where the degradation rate only reached about 20% after 240 min of solar exposure. Although the mineralisation of the initial dissolved organic carbon was not complete due to the presence of interfering substances in the leaching water, the conversion rate under ZnO/Na2S2O8 treatment was about 1.3 times higher than using TiO2/Na2S2O8.

Microwave Assisted Cloud Point Extraction for the Determination of Vitamin K Homologues in Vegetables by Liquid Chromatography with Tandem Mass Spectrometry.

Liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) with a triple quadrupole (QqQ) is proposed for determining the vitamin K homologues, phylloquinone (PK), menaquinone-4 (MK) and menadione (MD), in vegetables. The analytes were isolated from the samples (1-1.5 g) by ultrasound assisted extraction using acetonitrile (2 mL), and the liquids were submitted to microwave assisted cloud point extraction with Triton X-45. The enrichment factors were between 20 and 50, depending on the vitamin homologue in question. The analytes were determined by LC-ESI-QqQ-MS/MS in the multiple reaction monitoring (MRM) mode, providing unequivocal identification and quantification, with limits of detection of 0.8, 1.0, and 16 ng/g for MK, PK, and MD, respectively. Recovery assays for samples spiked at two concentration levels, between 40 and 600 ng/g depending on the compound, provided recoveries in the 90-114% range. Only PK was detected in the samples analyzed, at concentrations in the 90-2350 ng/g range.

Reclamation of agro-wastewater polluted with pesticide residues using sunlight activated persulfate for agricultural reuse.

The removal of 17 pesticides (pymetrozine, flonicamid, imidacloprid, acetamiprid, cymoxanil, thiachloprid, spinosad, chlorantraniliprole, triadimenol, tebuconazole, fluopyram, difenoconazole, cyflufenamid, hexythiazox, spiromesifen, folpet and acrinathrin) found in agro-wastewater from washing of containers and phytosanitary treatments equipment, has been carried out using sodium persulfate (Na2S2O8) at pilot plant scale under natural sunlight. Persulfate is a strong oxidant, inexpensive and environmentally appropriate. However, this oxidant is slow in kinetics under ordinary conditions. Na2S2O8 can be activated by ultraviolet light, generating SO4- radicals, which are also a very strong oxidizing species (E0 = 2.6 V). Previously, preliminary experiments were carried out at laboratory scale using a photoreactor to optimize the Na2S2O8 (300 mg L-1) concentration on the rate constants of the found pesticides. The residual levels of the studied pesticides in agro-wastewater (900 L) were in the range 0.02-1.17 mg L-1 for acrinathrin and fluopyram, respectively. After treatment, nearly complete degradation (>97%) of the parent molecules was achieved although 13% of initial DOC was measured. No significant differences (p < 0.05) were found when comparing grown broccoli using reclaimed and unreclaimed water.

Solar photocatalytic reclamation of agro-waste water polluted with twelve pesticides for agricultural reuse.

This study aims to demonstrate a technically feasible alternative to remove pesticide residues from agro-waste water produced in farms from remnants in containers and treatment tanks, rinse in tanks after treatments, and cleaning of machines and equipment. For this, the photocatalyzed degradation of 12 pesticides commonly used on vegetables, vines, citrus and fruit crops was investigated in aqueous suspensions of TiO2 in tandem with Na2S2O8 at pilot plant scale under natural sunlight in Murcia (SE of Spain) during summer and winter seasons. Previously, preliminary experiments were carried out at laboratory scale using a photoreactor to optimize the photocatalyst (200 mg L-1) and oxidant (250 mg L-1) concentrations on the rate constants of the studied pesticides. The photodegradation of all pesticides can be modelled assuming a pseudo-first-order kinetics. The time needed for disappearance of 90% (DT90) of the studied pesticides, was lower than 4 h in summer in all cases with the exception of cyproconazole (4.9 h), while, cyproconazole (8.9 h), metalaxil (6.1 h) and propyzamide (7.9 h) showed DT90 higher than 6 h in winter. The reaction rate was enhanced 3-fold in summer season, which is directly correlated to the higher accumulated fluence per time received during this season (about a factor of 2.9 higher than in winter). In both cases, the higher and lower degradation rates were obtained for cyprodinil and cyproconazole, respectively. The total fluence to get a 90% reduction (H90) ranged from 4.6 to 5.2 J cm-2 (cyprodinil) to 71.5-76 J cm-2 (cyproconazole).

Solar reclamation of wastewater effluent polluted with bisphenols, phthalates and parabens by photocatalytic treatment with TiO2/Na2S2O8 at pilot plant scale.

Investigations of anthropogenic contaminants in fresh- and wastewater have shown a wide variety of undesirable organic compounds such as Endocrine Disruptors (EDs). As a result, wastewater treatments using innovative technologies to remove those organic compounds are required. In this paper, the photodegradation of six EDs in wastewater at pilot plant scale is reported. The EDs were bisphenol A, bisphenol B, diamyl phthalate, butyl benzylphthalate, methylparaben and ethylparaben. Commercial TiO2 nanopowders (P25, Alfa Aesar and Kronos vlp 7000) were used as photocatalysts. The operating variables (type and loading catalyst, effect of electron acceptor and pH) were previously optimized under laboratory conditions. The results show that the use of TiO2 alongside an electron acceptor like Na2S2O8 strongly enhances the degradation rate of the studied compounds compared with photolytic tests, especially P25. The oxidation rates of the EDs at pilot plant scale were calculated following the disappearance of the target compound as a function of fluence (H). The ED degradation followed a pseudo-first order kinetics in all cases. In our experimental conditions, the half-fluence (H50) varied from 79 to 173 J cm-2 (photolytic test), 10-117 J cm-2 (TiO2 vlp 7000) and 3-58 J cm-2 (TiO2 P25), for bisphenol B and butyl benzylphthalate, respectively. It is concluded that solar photocatalysis using the tandem TiO2/Na2S2O8 can be considered as an environmental-friendly tool for water detoxification and a sustainable technology for environmental remediation, especially in the Mediterranean Basin, where many places receive more than 3000 h of sunshine per year. Although the cost depends on the nature of the pollutant, the treatment cost was estimate to be about 150 € m-3 for photocatalytic treatment with TiO2 P25.