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Abstract: This paper deals with the multiple response optimization for the removal of organophosphorus pesticide quinalphos [QP: O,O-diethyl O-2-quinoxalinyl phosphorothioate] from the aqueous solution onto low-cost material and tried to overcome the drawbacks of univariate optimization. Used tea leaves were used as low-cost adsorbent and batch equilibration method was followed for this study. A Box–Behnken design was used to develop response model and desirability function was then used for simultaneous optimization of all affecting parameters in order to achieve the highest removal% of quinalphos. The optimum conditions of factors predicted for quinalphos removal% were found to be: pH 8.83, concentration 7mgL−1 and dose 0.40g. Under these conditions, maximum removal% of quinalphos was obtained 96.31%. Considering the above optimum conditions, the adsorption isotherms were developed and provided adsorption capacity of 196.07μgg−1 by using Langmuir equation, indicating that used tea leaves may be applied as a low-cost material for pesticides removal from aqueous matrices. [Copyright &y& Elsevier]

Abstract: A rapid and simple method for the determination of two phthalates and five polycyclic musks in water samples using dispersive liquid–liquid microextraction (DLLME) mated to chemometrics and coupled to GC–MS was developed. Volume of extraction (CCl4) and disperser solvent (MeOH), pH, ionic strength, extraction time, centrifugation time as well as centrifugation speed were optimized in a 27–4 Plackett–Burman design. The obtained significant factors were optimized by using a central composite design (CCD) and the quadratic model between the dependent and the independent variables was built. The optimum experimental conditions of the proposed method were: 250μL carbon tetrachloride, 0.62mL methanol, 7.5min centrifugation time, natural pH containing 0% (w/v) NaCl, while keeping centrifugation speed fixed at 4000rpm. The calculated calibration curves gave high-level linearity for all target analytes with correlation coefficients ranging between 0.9970 and 0.9992. The repeatability and reproducibility of the proposed method, expressed as relative standard deviation, varied between 2.6% to 9.7% and 5.7% to 12.2%, respectively. The obtained LOD values were in the range of 8–63ngL−1. [Copyright &y& Elsevier]

Abstract: Matrix solid-phase dispersion (MSPD) as a sample preparation method for the determination of two potential endocrine disruptors, linuron and diuron and their common metabolites, 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl) urea (DCPU) and 3,4-dichloroaniline (3,4-DCA) in food commodities has been developed. The influence of the main factors on the extraction process yield was thoroughly evaluated. For that purpose, a 3(4–1) fractional factorial design in further combination with artificial neural networks (ANNs) was employed. The optimal networks found were afterwards used to identify the optimum region corresponding to the highest average recovery displaying at the same time the lowest standard deviation for all analytes. Under final optimal conditions, potato samples (0.5g) were mixed and dispersed on the same amount of Florisil. The blend was transferred on a polypropylene cartridge and analytes were eluted using 10ml of methanol. The extract was concentrated to 50μl of acetonitrile/water (50:50) and injected in a high performance liquid chromatography coupled to UV–diode array detector system (HPLC/UV–DAD). Recoveries ranging from 55 to 96% and quantification limits between 5.3 and 15.2ng/g were achieved. The method was also applied to other selected food commodities such as apple, carrot, cereals/wheat flour and orange juice demonstrating very good overall performance. [Copyright &y& Elsevier]

Abstract: Headspace microextraction procedures such as solid-phase microextraction (SPME) and single drop microextraction (SDME) or liquid-phase microextraction (LPME) are increasingly used for the extraction of environmental organic pollutants from a variety of aqueous, viscous, semisolid and solid environmental and biological matrices. In this article, recent analytical applications of these methodologies when used as an isolation and trace enrichment step prior to the analysis of organic pollutants (pesticides, polycyclic aromatic hydrocarbons, polychlorinated compounds, organotin compounds, phenolic derivatives, aromatic amines, phthalates, etc.) by gas and liquid chromatography are reviewed. The applicability and inherent limitations of headspace microextraction are also discussed. The future direction of research in this field and general trends toward commercial applications are considered. [Copyright &y& Elsevier]

Abstract: A simple and reliable sample methodology based on simultaneous ultrasonic extraction, sulfuric acid clean-up and headspace solid-phase microextraction (SPME)–gas chromatography–mass spectrometry has been developed as an advantageous analytical tool for the determination of seven polychlorinated biphenyl congeners in bird livers at low levels. The influence of several parameters on the efficiency of the proposed method was systematically investigated. The clean-up efficiency of sulfuric acid treatment was tested and compared with those of column chromatography (Flosiril, silica gel and alumina) and solid-phase extraction (SPE) (Supelclean ENVI-Carb cartridge) procedures. The use of sulfuric acid in the clean-up step prior to headspace solid-phase microextraction analysis allows the removal of interfering matrix compounds present in the liver extracts that would otherwise cause severe ionization suppression of the polychlorinated biphenyls (PCBs) during the ionization process. The optimized method had good linearity (R 2 >0.99) over the range studied (5–500ng/g wet weight) and showed satisfactory level of precision, with RSD values lower than 10.6%. The obtained relative recoveries ranged between 63 and 94%. The limits of detection (0.06–0.63ng/g wet weight) were low enough to check for harmful levels of polychlorinated biphenyls in biological samples, and were well below most of the restrictive limits established by European Union regulations. The method was found to be reliable under the operational conditions proposed and was applied successfully to the analysis of individual polychlorinated biphenyls in liver tissues. The results obtained from five bird species from Greece revealed the presence of the target compounds in all samples analyzed, at levels ranging between 0.54 and 39.45ng/g wet weight. [Copyright &y& Elsevier]

Abstract: In the present study a combined analytical method involving ultrasonic extraction (USE), sulfuric acid clean-up and headspace solid-phase microextraction (HS-SPME) was developed for the determination of chlorinated pesticides (CPs) in bird livers. Extraction of CPs from 1g of liver was performed by ultrasonication for 30min using 20mL of solvent mixture (n-hexane:acetone (4:1, v/v)). The extract was subsequently subjected to a clean-up step for lipid removal. A comparative study on several clean-up procedures prior to the HS-SPME enrichment step was performed in order to achieve maximum recovery and optimal clean-up efficiency, which would provide suitable limits of detection in the gas chromatographic analysis. For this purpose, destructive (sulfuric acid or sodium hydroxide treatment) and non-destructive (alumina column) clean-up procedures has been assayed. The treatment of the extract with 40% (v/v) H2SO4 prior to HS-SPME process showed the best performance since lower detection limits and higher extraction efficiencies were obtained. The method detection limit ranged from 0.5 to 1.0ngg−1 wet weight and peak areas were proportional to analyte concentrations (r 2 >0.990) in the range of 5–500ngg−1 wet wt. The method was found to be reproducible (R.S.D.<10%) and effective under the operational conditions proposed and was applied successfully to the analysis of CPs in liver tissues of various bird species from Greece. [Copyright &y& Elsevier]

Abstract: A preconcentration methodology utilizing the cloud point phenomenon is described in this study for the determination of sunscreen agent residues in bathing waters by reversed phase liquid chromatography with UV detection and gas chromatography (GC) with mass spectrometric (MS) detection. The method employs the entrapment of the analytes in the micelles of the non-ionic surfactant TX-114, upon increase of the solution temperature to 60°C. The analytes are either re-extracted or back extracted from the final micellar extract into appropriate organic solvents, a procedure that facilitates the direct application of the method not only with liquid chromatography but mostly importantly with gas chromatographic analysis. Ultrasonication was employed to assist the procedure and accelerate the extraction of the analytes into the solvent phase. Under the optimum experimental conditions, the method affords satisfactory recoveries in the range of 95–102% and relative standard deviation lower than 6% without interference from the presence of the surfactant. The method was successfully applied to the determination of UV filters in natural waters. [Copyright &y& Elsevier]

A new method used for the extraction of 10 organophosphorous insecticides from water samples coupling single-drop microextraction with gas chromatography–mass spectrometry is presented here. Parameters, such as organic solvent, exposure time, agitation, organic drop volume and salt concentration were controlled and optimised. Overall, extraction was achieved by suspending a 1.5 μl toluene drop to the tip of a microsyringe immersed in a 5 ml donor aqueous solution containing 2.5% NaCl (w/v) and stirred at 800 rpm. The developed protocol was found to yield a linear calibration curve in the concentration range from 0.5 to 100 μg l-1 for all target analytes. Under selected ion monitoring mode, the limits of detection were found to be in the range between 0.010 and 0.073 μg l-1. The intra-day and inter-day repeatability of the method varied between 8.6 and 16, and 11 and 19%, respectively. The relative recoveries from several types of natural water samples were evaluated and the effect of dissolved organic matter (humic acids) was investigated. Finally, the performance of the proposed method was compared to that of solid-phase microextraction. Overall, single-drop microextraction proved to be a fast and simple tool for the preconcentration of organophosphorous insecticides from water samples. [Copyright &y& Elsevier]

The aquatic photochemistry of trifluralin has been investigated under simulated solar irradiation (Suntest apparatus) in different types of natural waters (sea, river and lake water) as well as in distilled water. In order to examine the effect of dissolved organic matter (DOM), photodegradation of the tested herbicide was also examined under the presence of humic and fulvic acids isolated from Pamvotis Lake at various concentrations. The influence of nitrate ions on the degradation kinetics was also examined. It was found that photodegradation proceeds via a pseudo first-order reaction in all cases and that the presence of DOM inhibits the photolysis reaction whereas rate constants measured in the presence of NO3- ions indicated higher degradation efficiency. Kinetic experiments were monitored by GC-FTD with half-lives ranging from 7.22 to 50.58 min. In addition Microtox bioassay (vibrio fischeri) was employed in evaluating the ecotoxicity of irradiated solutions. The major photodecomposition products formed mainly through dealkylation, cyclization and reduction processes were isolated by means of solid phase extraction (SPE) and were identified by GC-MS. Based upon this byproduct identification, a possible degradation pathway is proposed for the photolysis of trifluralin in aqueous media. [Copyright &y& Elsevier]

Solid-phase microextraction (SPME) coupled to gas chromatography–mass spectrometry was applied to determine the antifouling biocides chlorothalonil, dichlofluanid, sea nine 211 and irgarol 1051 in marine sediments. Two experimental approaches were selected before the submission of the aqueous extracts to SPME prior to GC determination. The extraction of the biocides from the sediment samples was conducted using (a) water (containing 5%, v/v, acetone) and (b) acetone which was then diluted with water to give a 5% (v/v) content. The recommended procedures were found to be applicable for quantitative determination of the selected antifouling compounds in sediments with R.S.D.s below 17% and limits of detection ranging from 0.5 to 25 ng/g. The acetone/SPME procedure showed lower detection limits (0.5 to 6 ng/g) and R.S.D. values (<11%) as well as better recoveries (73 to 92%), proving that it could be successfully performed for the determination of antifouling compounds in sediment analysis, even in samples with high organic matter content. Both optimized water/SPME and acetone/SPME procedures were applied to the analysis of antifouling compounds in marine sediments and compared with the conventional liquid–liquid extraction with subsequent clean up by solid-phase extraction. [Copyright &y& Elsevier]

The photochemical behaviour of the biocide Sea-Nine 211 was carried out in order to investigate several transformation products formed in different environmental matrices and under different conditions. Sea-Nine 211 photodecomposition was performed under laboratory conditions using a xenon light source and under natural sunlight conditions in sea, river, lake as well as in distilled water. In order to examine the effect of dissolved organic matter (DOM), the phototransformation of the tested biocide was studied also in the presence of various concentrations of humic and fulvic acids. The phototransformation was shown to proceed via pseudo-first-order reaction in all cases and the presence of humic and fulvic acids enhanced the photolysis reaction. Kinetic experiments were monitored with GC–ECD and the half-lives (t1/2) varied between 6 and 433 h. Irradiation of the aqueous Sea-Nine 211 solutions gave rise to a great number of transformation products that were isolated by means of SPE using SDB extraction disks while six of them were tentatively identified using GC–MS techniques. Based on this byproduct identification a possible transformation pathway is proposed for the decomposition of Sea-Nine 211 in aqueous media. [Copyright &y& Elsevier]

The light-induced degradation of propachlor (2-chloro-N-isopropylacetanilide) under simulated solar irradiation has been investigated in aqueous solutions containing TiO2 suspensions as photocatalysts. The study focuses on the identification of possible intermediate products and the determination of inorganic ions formed during the process, using several powerful analytical techniques such as gas chromatography mass-spectrometry (GC-MS) and ion chromatography. The primary degradation of propachlor has been a fast process with a half-live time of 2.3 min and followed pseudo-first-order kinetics according to the Langmuir–Hinshelwood model. The mineralization of the organic carbon to CO2 after 240 min of irradiation was found to be <63%. The corresponding stoichiometric transformation of organic chlorine into chloride ion was reached in 30 min, whereas oxidation of nitrogen to nitrate ions took place at delayed irradiation times. Various aromatic intermediates have been identified by GC/MS techniques during the treatment, which were involved into three tentative degradation routes. One, was based on the dechlorination through positive holes or solvated electrons to form the hydroxy or aliphatic derivative. The second route consists of the rupture of amide bond or the N–C bond via nitrogen ionization by positive holes and through the ring hydroxylation, respectively. Finally, the third possible degradation route was based on hydrogen abstraction by the hydroxyl radicals or positive holes, followed either by the addition of oxygen to the alkyl radical or the decomposition of the peroxyl radical formed. From the analytical data, a possible multi-step degradation scheme was proposed. This work points to the necessity of extended knowledge of the successive steps in a solar-assisted detoxification process. [Copyright &y& Elsevier]

This study develops a method for the analysis of biocides Irgarol 1051 and Sea Nine 211 in environmental water samples, using solid-phase microextraction (SPME). Their determination was carried out using gas chromatography with flame thermionic (FTD), electron-capture (ECD) and mass spectrometric detection. The main parameters affecting the SPME process such as adsorption–time profile, salt additives and memory effect were studied for five polymeric coatings commercially available for solid-phase microextraction: poly(dimethylsiloxane) (100 and 30 μm), polyacrylate, poly(dimethylsiloxane)–divinylbenzene (PDMS–DVB 65 μm) and Carbowax–divinylbenzene (65 μm). The method was developed using spiked natural waters such as tap, river, sea and lake water in a concentration range of 0.5–50 μg/l. All the tested fiber coatings have been evaluated with regard to sensitivity, linear range, precision and limits of detection. Typical RSD values (triplicate analysis) in the range of 3–10% were obtained depending on the fiber coating and the compound investigated. The recoveries of biocides were in relatively high levels 60–118% and the calibration curves were reproducible and linear (R2>0.990) for both analytes. The SPME partition coefficients (Kf) of both compounds were also calculated experimentally in the proposed conditions for all fibers using direct sampling. Finally the influence of organic matter such as humic acids on extraction efficiency was studied, affecting mostly Sea Nine 211 uptake by the fiber. Optimum analytical SPME performance was achieved using the PDMS–DVB 65 μm fiber coating in ECD and FTD systems for Sea Nine 211 and Irgarol 1051, respectively. [Copyright &y& Elsevier]

The photochemical degradation of irgarol 1051 has been studied in different natural waters (sea, river, lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate was also studied under simulated sunlight. The addition of DOM in distilled water was shown to greatly increase the rate of degradation, however, a decrease was observed in natural waters. The photodegradation proceeds via pseudo-first-order reaction in all cases with half-lives ranged from 2 to 1432 h. In natural and humic water irgarol 1051 photodegradation gave rise to the dealkylated derivative demonstrating that the transformation of irgarol 1051 depend on the constitution of the irradiated media and especially from DOM concentration and type. The byproducts identified by GC–MS techniques were: 2-methylsulfonyl-4-terbutylamino-6-cyclopropylamino-s-triazine, 2-hydroxy-4-terbutylamino-6-cyclopropylamino-s-triazine, 2-methylthio-4-terbutylamino-6-ethylamino-s-triazine, 2-methylsulfonyl-4-terbutylamino-6-amino-s-triazine and diaminohydroxy-s-triazine. [Copyright &y& Elsevier]

• Method development, validation for multiclass pesticide determination in white/red wine. • QuEChERS extraction combined with UPLC-Orbitrap-MS was applied for the first time. • High performance of the method fulfilling validation requirements. • Expanded uncertainties were <43.6% and HorRat values <0.8 in all cases. • Method was applied successfully in different varieties wine samples. In this research, a quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction procedure and Ultra-High Performance Liquid Chromatography-Orbitrap-Mass Spectrometry (UHPLC-Orbitrap-MS), were combined to obtain a sensitive and rapid method for the determination of multiclass pesticides in white and red wines. The optimization strategy involved the selection of buffering conditions, by applying different QuEChERS procedures and sorbents for the cleanup step in order to achieve acceptably high recoveries and low co-extractives in the final extracts. Identification was based on both accurate mass and retention time, while further confirmation was achieved by MS fragmentation. The method was evaluated in terms of linearity, recovery, precision, limit of detection (LOD) and quantification (LOQ), matrix effects (ME) and expanded uncertainty. The validated method was successfully applied to real samples (home-made and commercial) revealing the presence of two selected fungicides, in relatively low levels compared to the MRLs defined by the EU for vinification grapes. [ABSTRACT FROM AUTHOR]

The last few decades, Pharmaceutical Active Compounds (PhACs) have been considered as emerging contaminants due to their continuous release and persistence to aquatic environment even at low concentrations. A growing number of research articles have shown the occurrence of numerous PhACs in various wastewater treatment plant influents, hospital effluents, and surface waters all over the world. The rising concern regarding PhACs, which present high recalcitrance towards conventional treatment methods, has provoked extensive research in the field of their effective remediation. This review provides a comprehensive assessment of homogeneous and heterogeneous photocatalytic applications for the removal of PhACs, from real or artificial hospital wastewater effluents. These two representative advanced oxidation processes (AOPs) are assessed in terms of their efficiency to remove PhACs, reduce the COD and toxicity as well as increase the biodegradability of the effluent. Simultaneously with their efficiency the operational costs of the processes are considered. Their potential combination with other processes is critically discussed, as this option seems to enhance the treatment efficiency and simultaneously overcome the limitations of each individual process. Moreover, the type of reactors as well as the main parameters that should be considered for the design and the development of photoreactors for wastewater treatment are reviewed. Finally, based on the literature survey, indications for future work are provided. Unlabelled Image • Photocatalytic applications for the treatment of hospital wastewaters are reviewed. • Focus is placed on the removal of pharmaceutical compounds and their metabolites. • Processes, catalytic systems, and operational parameters effects are presented. • Overall efficiency and operational costs of the processes are assessed. • Potential integration with other processes and perspectives for future work are discussed. [ABSTRACT FROM AUTHOR]

Abstract The study aim was to determine a range of relevant persistent and emerging pollutants in oysters produced in an aquaculture facility located in an important production area, to assure their safety for human consumption. Pollutants, including 16 PAHs, 3 butyltins (BTs), 29 flame retardants (FRs, including organophosphate and halogenated FRs), 35 pesticides (including 9 pyrethroid insecticides) and 13 personal care products (PCPs, including musks and UV filters), were determined in oysters' tissues collected during one year in four seasonal sampling surveys. The seasonal environmental pollution on the production site was evaluated by water and sediment analysis. Furthermore, oysters' nutritional quality was also assessed and related with the consumption of healthy seafood, showing that oysters are a rich source of protein with low fat content and with a high quality index all year around. Results showed that most analysed pollutants were not detected either in oyster tissues or in environmental matrixes (water and sediments). The few pollutants detected in oyster tissues, including both regulated and non-legislated pollutants, such as a few PAHs (fluorene, phenanthrene, anthracene, fluoranthene, pyrene and indenopyrene), FRs (TPPO, TDCPP, DCP, BDE-47, BDE-209 and Dec 602) and PCPs (galaxolide, galaxolidone, homosalate and octocrylene), were present at low levels (in the ng/g dw range) and did not represent a significant health risk to humans. The observed seasonal variations related to human activities (e.g. tourism in summer) highlights the need for environmental protection and sustainable resource exploration for safe seafood production. Graphical abstract Unlabelled Image Highlights • Bioaccumulation of organic contaminants assessed in aquaculture farmed oysters. • Emerging and persistent organic contaminants detected, generally at low levels • Most frequently detected families were halogenated flame retardants and personal care products. • Seasonal variations related with human activities were detected. • Results highlights the need for environmental protection and sustainable resource exploration. [ABSTRACT FROM AUTHOR]

Abstract The occurrence, removal, mass loading, seasonal influence and environmental risk assessment of nine psychiatric pharmaceuticals and four of their selected metabolites, were studied in one hospital and one urban wastewater treatment plant (WWTP) in Ioannina city, in northwestern Greece, providing information about the efficiency of the plants and their contribution into the final receiver's flow. Samples were collected from the influents and the effluents of the plants in different sampling campaigns, from July to December 2016. Analytical methodology was based on ultra-high performance liquid chromatography-Orbitrap high-resolution mass spectrometry, after solid-phase extraction through Oasis HLB cartridges. Concentrations in both WWTPs ranged between

Abstract Estuarine environments are being constantly stressed by new sources of pollution (e.g. pesticides) derived from activities of industry and intensive agriculture. The present study aims at quantify pesticides of three different categories (fungicides, herbicides and insecticides) in the Louros River (Epirus region, North-Western Greece). A monitoring study of 34 compounds was carried out in surface river waters from June 2011 until May 2012. Seven water sampling stations were established and 35 water samples were collected. A solid-phase extraction (SPE) method coupled with gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-mass spectrometry (LC-MS), depending on the compound, was developed and validated. During the monitoring study 25 pesticides were detected (13 herbicides, 9 insecticides, 3 fungicides). The most commonly encountered pesticides were quizalofop-ethyl, trifluralin and pendimethaline. Tebufenpyrad was found in all sampling stations and seasons, with the highest concentrations of 0.330 μg/L at Tsopeli Lagoon exceeding the rather low concentrations reported nationwide. Regarding the environmental risk due to the presence of target compounds in surface waters, this was estimated by calculating risk quotients (RQs) for different aquatic organisms (algae, zooplankton and fish). The results denoted a possible threat for the aquatic environment, rendering in this way the RQ method as a useful screening tool. In any case, further extensive study is needed for acetochlor, pirimiphos-methyl, endosulfan-a and azinphos-ethyl in order to better correlate their occurrence and potential toxic effects in aquatic life and humans. Graphical abstract Unlabelled Image Highlights • A chemometric approach was used for the extraction optimization. • Pesticide occurrence was studied with a combination of GC–MS/SPE and LC-ESI-MS/SPE. • One year monitoring survey was carried out. • Ecological risk assessment associated with detected pesticides was performed. [ABSTRACT FROM AUTHOR]

Photocatalytic degradation and mineralization of the herbicide bentazon in aqueous solutions has been investigated. The pseudo-first order degradation kinetics was studied under different operational conditions, such as type of photocatalyst, catalyst loading, initial pH and addition of electron acceptors. The degradation rates proved to be strongly influenced by these parameters. Organic sulfur and nitrogen were only partially converted into inorganic in the presence of TiO 2 P25 or TiO 2 Kronos vlp 7000 and UV-A. The presence of H 2 O 2 led to either enhancement or decrease of the initial degradation rates, depending on the type of catalyst employed. Intermediate products formed during photocatalytic treatment were identified by means of a high resolution LIT Orbitrap LC-ESI/MS system. 21 intermediates including dimers, hydroxy and/or keto bentazon derivatives, and further oxidized species were identified and detailed transformation pathways have been proposed. Acute toxicity profiles using marine bacteria Vibrio fischeri showed an increasing trend at the first stages of oxidation, implying the progressive formation of intermediates more toxic than the parent molecule, or synergistic effects among the transformation products. Thereafter, ecotoxicity was completely eliminated within 90 min of irradiation under the investigated conditions. Phytotoxicity tests, carried out on the monocotyl Sorghum saccharatum and the dicotyls Sinapis alba and Lepidium sativum , showed similar responses of the three plant species to the photocatalytically treated samples, resulting to complete removal of phytotoxicity under the employed conditions. [ABSTRACT FROM AUTHOR]

Highlights: [•] Fe3O4@SiO2@C18 particles were synthesized to serve as solid-phase extraction sorbents. [•] MSPE optimization was evaluated with the aid of response surface methodology. [•] Method complies with MRLs established by European Commission and Codex Alimentarius. [Copyright &y& Elsevier]

Abstract: A matrix solid-phase dispersion (MSPD) method for the simultaneous determination of 20 organochlorine pesticides (OCPs) (aldrin, endrin, dieldrin, α-BHC, β-BHC, γ-BHC, δ-BHC, α-chlordane, γ-chlordane, p,p′-DDE, p,p′-DDT, p,p′-DDD, endosulfan I, endosulfan II, endosulfan sulfate, endrin aldehyde, heptachlor, heptachlor epoxide, endrin ketone and methoxychlor) and six polychlorinated biphenyl (PCB) congeners (PCB 28, 52, 101, 138, 153 and 180) in post-mortem human lung has been developed and validated. Response surface methodology (RSM) and desirability function were employed to optimize the extraction conditions of MSPD. Extraction was carried out using Florisil (2.0g) as the sorbent material as well as clean-up adsorbent (1.5401g), n-hexane:dichloromethane (11:89, v/v) as the eluting solvent (15.45mL) and Na2SO4 (2.0g) as dehydrating agent. Determination and quantification of OCPs and PCBs residues were carried out using a gas chromatograph equipped with an electron capture detector (GC-ECD). A mass spectrometric detector (GC–MS) in the selected ion monitoring (SIM) mode was also used for confirmation purposes. Method detection limits by GC–MS ranged from 0.42 to 0.87ngg−1 and 0.51 to 1.35ngg−1, for OCPs and PCBs, respectively. Lower detection limits were calculated for GC-ECD ranging between 0.15–0.30ngg−1 and 0.18–0.48ngg−1, respectively. Relative standard deviations did not exceed 9%. Analytes provided recoveries ranging from 65% to 106%. The proposed method was successfully applied to the analysis of lung tissues from six autopsy cases. [Copyright &y& Elsevier]

Abstract: Olive mill wastewater (OMW) is one of the major and most challenging organic pollutants in olive oil production countries. However, the knowledge about the in-situ effects of olive mill wastewaters to lotic ecosystems and their benthic organisms is very limited. To resolve this, eight sampling sites were selected upstream and downstream the outflow of several olive mills to assess the spatial and temporal effects of OMW to stream macroinvertebrates and to ecological status of stream ecosystems. Biotic (macroinvertebrates) and abiotic (physicochemical, hydromorphological) data were monitored for two years thus following the biennial cycle of olive growth and production and hydrological variation (drought–wet years). The results of this study revealed the spatial and temporal structural deterioration of the aquatic community due to OMW pollution with consequent reduction of the river capacity for reducing the effects of polluting substances through internal mechanisms of self-purification. OMW, even highly diluted, had dramatic impacts on the aquatic fauna and to the ecological status of the receiving stream ecosystems. The organic load of the wastewater expressed as BOD5, COD and TSS, substrate contamination (sewage bacteria) and distance from the mill outlet, were the most important factors affecting macroinvertebrate assemblages while the typology (i.e. slope, altitude) and hydrology of the stream site (i.e. mountainous–lowland) and the intensity and volume of the wastewater were the most important determinants of self-purification processes. As OMW are usually being discharged in small size streams that are not considered in the Water Framework Directive 2000/60/EC, there is a need for including such systems into monitoring and assessment schemes as they may significantly contribute to the pollution load of the river basin. Furthermore, guidelines to manage these wastes through technologies that minimise their environmental impact and lead to a sustainable use of resources are critical. [Copyright &y& Elsevier]

Abstract: The multi-residue trace-level determination of six pesticides (diazinon, dimethoate, chlorpyrifos, vinclozolin, fenthion and quinalphos) in wine samples, after their single-drop microextraction (SDME) is presented herein. The extraction procedure was optimized using the multivariate optimization approach following a two-stage process. The first screening experimental design brought out the significant parameters and was followed by a central composite design (CCD) experiment, which revealed the simultaneous effect of the significant factors affecting the SDME process. High level of linearity for all target analytes was recorded with r 2 ranging between 0.9978 and 0.9999 while repeatability (intra-day) and reproducibility (inter-day) varied from 5.6% to 7.4% and 4.9% to 12.5%, respectively. Limits of detection (LODs) and limits of quantification (LOQs) were found to range in the low μgL−1 level. In general, the developed methodology presented simplicity and enhanced sensitivity, rendering it appropriate for routine wine screening purposes. [ABSTRACT FROM AUTHOR]

Abstract: Chemometric experimental design in microextraction plays a crucial role in sustaining the highest quality of analytical data. Making use of the main significant points of chemometric experimental design and microextraction in analytical chemistry we formed the core of this review article. A step-by-step chemometric approach is provided to optimize and validate microextraction-based analytical processes. Significant applications are reported with developments related to microextraction combined with chemometric optimization processes. As it appears from the numerous examples provided in this review, a great number of researchers give credit to the combination of microextraction and chemometrics recognizing that it significantly streamlines sample processing. Moreover, the combination of microextraction with chemometrics addresses problems relating to improvement in detectability and method validation. A worked example on the microextraction of polychlorinated biphenyls is incorporated into the relevant sections of this article and comprehensively provides in a rational and integrated way guidance to people dealing with this subject. [Copyright &y& Elsevier]

Abstract: The photocatalytic degradation of methyl parathion in aqueous solutions, using two different photocatalysts (TiO2 and ZnO) has been investigated. The degradation of methyl parathion follows first order kinetics according to the Langmuir–Hinshelwood model. Complete degradation is achieved within 45 or 150min when treated with illuminated TiO2 or ZnO, respectively. It was observed that the initial rate increases linearly with an increase of the amount of catalyst up to a level where it reaches a plateau corresponding to the optimum of light absorption. The addition of an oxidant (K2S2O8) leads to an increase in the rate of photooxidation. Moreover, illuminated TiO2 suspensions were proved to be more effective in mineralizing the insecticide compared to ZnO suspensions. Measurements of phosphate, sulfate and nitrate ions gave valuable information about how this process is achieved. Addition of the oxidant enhances mineralization for both photocatalytic systems. Up to eight by-products were identified by GC–MS technique during the photocatalytic degradation of the insecticide that proceeds via oxidation, hydroxylation, dealkylation and hydrolysis of the ester group reaction pathways. Finally, the toxicity of the treated solution was reduced only in the presence of TiO2, while ZnO suspensions appear to increase the toxicity due to photo-dissolution of ZnO releasing zinc in the treated solution. [Copyright &y& Elsevier]

Abstract: A multiresidue method for the determination of 20 organochlorine pesticides (aldrin, endrin, dieldrin, α-BHC, β-BHC, γ-BHC, δ-BHC, α-chlordane, γ-chlordane, 4,4′-DDE, 4,4′-DDT, 4,4′-DDD, endosulfan I, endosulfan II, endosulfan sulfate, endrin aldehyde, heptachlor, heptachlor epoxide, endrin ketone and methoxychlor) and eight PCB congeners (PCB 20, 28, 52, 101, 118, 138, 153, 180) in chicken eggs has been developed and validated. The samples were extracted by a simple and fast matrix solid-phase dispersion (MSPD) method using Florisil as the sorbent material and dichloromethane/hexane (1:1) as the eluting system. Further purification of the extracts was conducted using a conventional clean-up procedure with concentrated sulphuric acid. Determination and quantitation of PCBs and OCs residues was carried out using a gas chromatograph equipped with an electron capture detector (GC-ECD). A mass spectrometric detector (GC–MS) in the selected ion monitoring (SIM) mode was used for confirmation purposes. The method detection limits were <0.7ngg−1 for all PCBs and OCs and the relative standard deviations for analyses of samples fortified over the range of 10–200ngg−1 were <8%. All compounds provided average recoveries (spiked at five concentration levels) ranging from 82% to 110%. The proposed method was used to analyze 30 commercial products taken from local markets in the course of a 3-month sampling campaign. [Copyright &y& Elsevier]

Abstract: An inter-laboratory comparison exercise was conducted under the European Union funded project entitled: Screening Methods for Water Data Information in Support of the Implementation of the Water Framework Directive (SWIFT-WFD) and coordinated by the Consejo Superior de Investigaciones Científicas (CSIC), in order to evaluate the reproducibility of different toxicity tests based on the bioluminescence inhibition of Vibrio fischeri, for the rapid water toxicity assessment. For the first time, this type of exercise has been organized in Europe, and using different tests based on the same principle. In this exercise, 10 laboratories from 8 countries (Austria, Cyprus, Germany, Greece, Italy, Portugal, Romania, and Spain) took place, and a total number of 360 samples were distributed. During the exercise, six series of six samples were analyzed along 5 months. Every batch of samples was composed by three real samples and three standard solutions. The real samples were: a raw influent and the effluent of a wastewater treatment plant (WWTP), and a sample from a first settlement of the WWTP spiked with a mixture of toxicant standards. A final number of 330 (91.7%) samples was analyzed, 3300 values in duplicate were collected, and the results for each sample were expressed as the 50% effective concentration (EC50) values calculated through five points of dilution inhibition curves, after 5 and 15min of incubation times. A statistical study was initiated using 660 results. The mean values, standard deviations (σ), variances (σ 2), and upper and lower warning limits (UWL and LWL) were obtained, using the EC50 values calculated with the result from the participating laboratories. The main objectives of this toxicity ring study were to evaluate the repeatability (r) and reproducibility (R) when different laboratories conduct the test, the influence of complex matrix samples, the variability between different tests based on the same principle, and to determine the rate at which participating laboratories successfully completed tests initiated. In this exercise, the 3.93% toxicity values were outliers according with the Z-score values and the Dixon test. The samples with the greater number of outliers were those with the smallest variability coefficient, corresponding to the greater and the smaller toxicity level. No relation was found through the cluster analysis, between the final results and the different commercial devices involved. Testing by multiple commercial devices did not appear to reduce the precision of the results, and the variability coefficient for the exercise was nearby to the average value for past editions carried out at national level, where the different participants used the same commercial device. Stability of samples was also followed during the exercise. While statistical significance differences were not found for the greater part of samples, for the sample from the WWTP influent, a significant decrease of the toxicity value was found along this study. Nevertheless, this was a type of sample with a high toxicity level during all the exercise. On the other hand, in order to obtain the chemical characterization of real samples, those were analyzed by chromatographic techniques, using different sequential solid phase extraction (SSPE) procedures, followed by liquid chromatography coupled with mass spectrometry (LC–MS), and gas chromatography–mass spectrometry (GC–MS). Good agreement was found between the chemical analysis results and the toxicity level of the samples. [Copyright &y& Elsevier]

The photocatalytic degradation of the organophosphorus insecticides fenthion and ethyl parathion has been studied in aqueous titanium dioxide suspensions under simulated solar irradiation. The degradation kinetics followed a pseudo-first order reaction and monitored by headspace solid-phase microextraction (SPME) and gas chromatography (GC) with flame thermionic detection. The degradation of both insecticides was a fast process with half-lives varying between 1.0 and 12.2 min depending on the TiO2 concentration as well as on the structure of the compound. The generated transformation products formed during the process were extracted by SPME: (a) by direct immersion of the fiber in the filtered sample and (b) by exposing the fiber in the headspace. The intermediates were formed predominately via oxidation processes and were identified by gas chromatography and mass spectrometry (MS). [Copyright &y& Elsevier]

A solid-phase microextraction (SPME) method was applied to an extended monitoring survey of priority pesticides for the European Union for a period of 12 months in water of the Kalamas River (Epirus region of northwestern Greece) in order to determine their concentrations and seasonal variations. Polydimethylsiloxane-coated fiber (100 μm) was used. The samples were screened using gas chromatography with flame thermionic detection. Detection was confirmed by gas chromatography–mass spectroscopy. The most frequently detected pesticides were some of the more commonly used herbicides, such as S-ethyl-N,N-di-n-propylthiol carbamate (EPTC), trifluralin, atrazine, deethylatrazine, terbuthylazine and alachlor, and insecticides, such as carbofuran, diazinon, disulfoton, parathion methyl, parathion ethyl, fenthion and ethion. Concentrations of individual compounds ranged from 0.020 to 0.3 μg/L. Greater pesticide concentrations occurred during the seasons of application. A comparison with a well-established solid-phase extraction (C18 disks) procedure was performed for samples of high-season application (May–September) in order to confirm the effectiveness of the SPME technique. The results demonstrate the suitability of the SPME method for routine screening multiresidue analysis in natural waters. [Copyright &y& Elsevier]

Nowadays the occurrence and associated risks of Pharmaceutical Active Compounds (PhACs) in the aquatic environment comprises a major issue. In the present study, a comprehensive survey on contamination profiles, occurrence, removals, temporal variation and ecological risk of multiclass multiresidue PhACs, such as antibiotics, non-steroidal anti-inflammatories, lipid regulators and phsychiatrics, (including past and newly monitored PhACs as well as some of their metabolites) was performed in wastewaters from the WWTP of Ioannina University hospital along one year period on a monthly sampling basis. WWTP influent and effluent samples were analyzed for physicochemical quality parameters and PhACs concentration levels using Ultra High Performance Liquid Chromatography-Orbitrap-Mass Spectrometry (UHPLC-Orbitrap-MS), after Solid Phase Extraction (SPE) through Oasis HLB cartridges. Influent concentrations ranged between < LOQ (Limit of Quantification) for diclofenac and tolfenamic acid and 48586 ng/L for caffeine, while effluent concentrations between < LOQ for tolfenamic acid and simvastatin and 3361 ng/L for caffeine. Removal efficiencies ranged between −132.6% for venlafaxine and 100% for caffeine. Environmental risk assessment by means of Risk Quotient (RQ) for maximum and minimum concentration levels as well as optimized by the frequency of exceeding toxicity threshold values, RQ f , was applied revealing that up to 12 PhACs posed acute toxicity (clofibric acid, fenofibrate, sulfadiazine, sulfamethoxazole, trimethoprim, amitryptiline, fluoxetine, fluvoxamine, norfluoxetine, sertraline, venlafaxine, caffeine) while up to 4 compounds exerted long-term toxicity (sulfamethoxazole, fluoxetine, sertraline, caffeine) at least for one of the studied organisms. Furthermore, mixture RQ MEC/PNEC and RQ STU effect of multiple compounds showed high potential risks of the target groups in some cases, although some contaminants were not included due to lack of available data. Results can be used to prioritization of PhACs and their metabolites for surveillance in receiving water bodies as well as development of knowledge on toxicity and mechanism(s) of action. Image 1 • Hospital WWTP effluents contain multiclass mixtures among 35 PhACs monitored. • Caffeine, salicylic acid, fenofibrate were the most frequently detected compounds. • Removal efficiencies ranged between −132.6% and 100%. • Risk assessment was applied for single compounds and observed mixture cases. • Optimized RQs calculated using PhAC mean concentration and detection frequency. [ABSTRACT FROM AUTHOR]

In recent years, the occurrence, fate, and adverse effects of pharmaceutically active compounds (PhACs) in aquatic organisms have become a noteworthy issue. In the present study, a rapid and sensitive multiresidue analytical method was developed for the determination of 18 parent PhACs and 5 metabolites in sea bream (Sparus aurata), by combining a modified QuEChERS (quick, easy, cheap, effective, rugged and safe) procedure with ultra-high performance liquid chromatography-Orbitrap-mass spectrometry (UHPLC-Orbitrap-MS). The method development involved optimization of extraction solvent, extraction salts, clean-up sorbents, and amount of sample evaluation, while identification on Orbitrap MS was based on accurate mass and further confirmation with MS/MS fragmentation. The developed method was validated, and linearity was higher than 0.99. Recoveries in all cases ranged between 62 and 107% (at 10, 50, and 100 ng g -1 ), while intra-day and inter-day precision, expressed as relative standard deviation, RSD, was lower than 4% and 7%, respectively. In addition, limits of quantification (LOQs) ranged between 0.5 and 19 ng g -1 . The compounds presented a low matrix effect, between - 13 and 4%, while the expanded uncertainty U% estimated at the three spiking levels 10, 50, and 100 ng g -1 was found below 49% in all cases. Finally, the validated method was applied to sea bream samples from an aquaculture farm located in the Mediterranean Sea, with one positive finding for the antibiotic trimethoprim at a concentration of 26 ng g -1 , presenting negligible human health risk., (© 2021. Springer-Verlag GmbH Germany, part of Springer Nature.)

In the National Park of Dadia-Lefkimi-Soufli Forest (Dadia NP, Greece), seven "target" PCBs and 16 organochlorine pesticides (OCs) were analysed in blood samples of cinereous vultures (Aegypius monachus) and Eurasian griffon vultures (Gyps fulvus). PCB congeners 138, 153 and 180 predominated in both species' blood samples. In both species, no differences were detected in congener levels between successive age classes, but in cinereous vulture, there were significant differences between adult and nestling in levels of PCB 28, 52, 101, 118 and between nestling and immature in levels of PCB 101. Regarding pesticides, p,p'-DDE dominated in both vultures followed by β-HCH, lindane and endosulfan sulphate, but ∑OCs were higher in griffon vulture. Significant differences were detected only between nestling and sub-adult cinereous vultures in heptachlor levels and between nestling and adult in p,p'-DDT. The origin of pollutants differs between the two vulture species and pollution patterns may not reflect those at Dadia NP.

Much progress has been made in pesticide analysis over the past decade, during which time hyphenated techniques involving highly efficient separation and sensitive detection have become the techniques of choice. Among these, methods based on chromatographic separation with mass spectrometric detection have resulted in greater likelihood of identification and are acknowledged to be extremely useful and authoritative methods for determination of pesticide residues. Even with such powerful instrumental techniques, however, the risk of interference increases with the complexity of the matrix studied, so sample preparation before instrumental analysis is still mandatory in many applications, for example food analysis. This article summarizes the analytical characteristics of the different methods of sample-preparation for determination of pesticide residues in a variety of food matrices, and surveys their recent applications in combination with chromatographic mass spectrometric analysis. We discuss the advantages and the disadvantages of the different methods, address instrumental aspects, and summarize conclusions and perspectives for the future.

Modern trends in analytical chemistry are towards the simplification and miniaturization of sample preparation, as well as the minimization of organic solvent used. In view of this aspect, several novel micro-extraction techniques are being developed in order to reduce the analysis step, increase the sample throughput and to improve the quality and the sensitivity of analytical methods. One of the emerging techniques in this area is liquid-phase micro-extraction (LPME). It is a miniaturized implementation of conventional liquid/liquid extraction (LLE) in which only microliters of solvents are used instead of several hundred milliliters in LLE. It is quick, inexpensive and can be automated. In the last few years, LPME has been combined with liquid chromatography (LC) and capillary electrophoresis (CE), besides the generally used coupling to gas chromatography (GC), and has been applied to various matrices, including biological, environmental, and food samples. This work is aimed at providing an overview of the major developments of LPME, coupled with chromatography and CE, as reported in the literature. The paper will focus on the application of the technique to different matrices and the aim is to reveal the panorama of opportunities and to try to indicate the potential of LPME in pesticide analysis. A critical review of the first applications to pesticide analyses is presented in the main part of the manuscript. The optimization of LPME as well as advantages and disadvantages are discussed. It is concluded that, because of its high pre-concentration factor, LPME can be introduced with benefit into water analysis for several pesticide groups. In particular, the application of LPME to non-polar pesticides in environmental analysis appears to be promising. However, similar to other micro-extraction techniques, such as solid phase micro-extraction (SPME), serious limitations still remain when analyzing semi-solid and solid environmental, food or biological matrices and/or highly polar compounds. Thus, other pre-concentration techniques may be a good alternative if an analytical problem cannot be sufficiently dealt with LPME.

A method for the multiresidue determination of 35 pesticides (30 insecticides and five herbicides) in olive oil by gas chromatography (GC) is described. Three liquid-liquid extraction (LLE) procedures based on (i) partition of pesticides between acetonitrile (ACN) and oil solution in n-hexane, (ii) partition of pesticides between saturated ACN with n-hexane and oil solution in n-hexane saturated with ACN, and (iii) partition of pesticides between ACN and oil were tested for the optimization of the highest pesticide recoveries with the lowest oil residue in the final extracts. Experimental tests were preformed in order to study the efficiency of different clean up procedures with N-Alumina, Florisil, C18, and ENVI-Carb solid-phase extraction (SPE) cartridges for the compounds analyzed by GC-nitrogen phosphorus detection. A second step of clean up was also performed for the compounds analyzed by GC-electron capture detection (ECD), by using phenyl-bonded silica (Ph), diol-bonded silica (Diol), cyanopropyl-bonded silica (CN), and amino propyl-bonded silica (NH2) SPE cartridges. LLE of the oil solution in hexane with ACN followed by an ENVI-Carb SPE clean up of the extract gave the best results for all target compounds. The ACN extract was additionally cleaned through a Diol-SPE cartridge for the determination of pesticides analyzed mainly by GC-ECD. Pesticide recoveries form virgin olive oil spiked with 20, 100, and 500 microg/kg concentrations of pesticides ranged from 70.9 to 107.4%. The proposed method featured good sensitivity, pesticide quantification limits were low enough, and the precision, expressed as relative standard deviation, ranged from 2.4 to 12.0%. The proposed method was applied successfully for the residue determination of the selected pesticides in commercial olive oil samples.

In the present work, a novel sample pre-treatment technique for the determination of trace concentrations of some insecticide compounds in aqueous samples has been developed and applied to the determination of the selected analytes in environmental water samples. The extraction procedure is based on coupling polypropylene hollow fiber liquid phase microextraction (HF-LPME) with gas chromatography by flame thermionic detection (GC-FTD). For the development of the method, seven organophosphorous insecticides (dichlorvos, mevinphos-cis, ethoprophos, chlorpyrifos methyl, phenthoate, methidathion and carbofenothion) and one carbamate (carbofuran) were considered as target analytes. Several factors that influence the efficiency of HF-LPME were investigated and optimized including agitation, organic solvent, sample volume, exposure time, salt additives and pH. The optimized methodology exhibited good linearity with correlation coefficient = 0.990. The analytical precision for the target analytes ranged from 4.3 to 11.1 for within-day variation and 4.6 to 12.0% for between-day variation. The detection limits for all analytes were found in the range from 0.001 to 0.072 microg/L, well below the limits established by the EC Drinking Water Directive (EEC 80/778). Relative recoveries obtained by the proposed method from drinking and river water samples ranged from 80 to 104% with coefficient of variations ranging from 4.5 to 10.7%. The present methodology is easy, rapid, sensitive and requires small sample volumes to screen environmental water samples for insecticide residues.

The presence of vinclozolin in the environment as far as the endocrine disruption effects in biota are concerned has raised interest in the environmental fate of this compound. In this respect, the present study attempts to investigate the feasibility of applying a novel quantitative method, liquid-phase microextraction (LPME), so as to determine this environmental andiandrogen in environmental samples such as water and sediment samples. The technique involved the use of a small amount (3 microL) of organic solvent impregnated in a hollow fiber membrane, which was attached to the needle of a conventional GC syringe. The extracted samples were analyzed by gas chromatography coupled with electron-capture detection. Experimental LPME conditions such as extraction solvent, stirring rate, content of NaCl and pH were tested. Once LPME was optimized, the performance of the proposed technique was evaluated for the determination of vinclozolin in different types of natural water samples. The recovery of spiked water samples was from 80 to 99%. The procedure was adequate for quantification of vinclozolin in waters at levels of 0.010 to 50 microg/L (r> 0.994) with a detection limit of 0.001 microg/L (S/N= 3). Natural sediment samples from the Aliakmonas River area (Macedonia, Greece) spiked with the target andiandrogen compound were liquid-liquid extracted and analyzed by the methodology developed in this work. No significant interferences from the samples matrix were noticed, indicating that the reported methodology is an innovative tactic for sample preparation in sediment analysis, with a considerable improvement in the achieved detection limits. The results demonstrated that apart from analyte enrichment, the proposed LPME procedure also serves as clean-up method and could be successfully performed to determine trace amounts of vinclozolin in water and sediment samples.

A new, rapid microextraction technique termed solvent microextraction (SME) has been developed for the simultaneous determination of new generation antifouling agents, in water samples. Chlorothalonil, dichlofluanid and Sea nine 211 were employed as model compounds to asses the extraction procedure and were determined by gas chromatography with electron capture detection. Experimental parameters which control the performance of SME, such as selection of solvent, exposure time, agitation, organic drop volume, and salt concentration were optimized. The new method provided good average enrichment factors of >10.7 for all analytes, good precision (RSD < 8.5%) and good linearity (r2 > 0.9880). The limits of detection (LODs) were in the range of 0.00025-0.003 microg/L (S/N = 3). The SME was performed in different type of natural water samples and acceptable recoveries were obtained for the tested analytes. The results demonstrated that SME is a rapid, accurate and effective preparation method and could be successfully performed for the determination of antifouling agents in water samples.

The light-induced degradation of propachlor (2-chloro-N-isopropylacetanilide) under simulated solar irradiation has been investigated in aqueous solutions containing TiO2 suspensions as photocatalysts. The study focuses on the identification of possible intermediate products and the determination of inorganic ions formed during the process, using several powerful analytical techniques such as gas chromatography mass-spectrometry (GC-MS) and ion chromatography. The primary degradation of propachlor has been a fast process with a half-live time of 2.3 min and followed pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. The mineralization of the organic carbon to CO2 after 240 min of irradiation was found to be < 63%. The corresponding stoichiometric transformation of organic chlorine into chloride ion was reached in 30 min, whereas oxidation of nitrogen to nitrate ions took place at delayed irradiation times. Various aromatic intermediates have been identified by GC/MS techniques during the treatment, which were involved into three tentative degradation routes. One, was based on the dechlorination through positive holes or solvated electrons to form the hydroxy or aliphatic derivative. The second route consists of the rupture of amide bond or the N-C bond via nitrogen ionization by positive holes and through the ring hydroxylation, respectively. Finally, the third possible degradation route was based on hydrogen abstraction by the hydroxyl radicals or positive holes, followed either by the addition of oxygen to the alkyl radical or the decomposition of the peroxyl radical formed. From the analytical data, a possible multi-step degradation scheme was proposed. This work points to the necessity of extended knowledge of the successive steps in a solar-assisted detoxification process.

Since the restriction imposed by European Union regulations on the use of TBT-based antifouling paints on boats below 25 m in length, new terms have been introduced in the 'small boat' market. Replacement products are generally based on copper metal oxides and organic biocides. Several studies have demonstrated the presence of these biocides in European ports and marinas of Spain, France, Germany and the United Kingdom. An extended survey of the antifouling biocides chlorothalonil, dichlofluanid, irgarol 1051 and sea-nine 211 was carried out in Greek ports and marinas of high boating activities from October 1999 to September 2000. The sampling sites were: Piraeus, Elefsina, Thessaloniki, Patras, Chalkida, Igoumenitsa, and Preveza (Aktio). The extraction of these compounds from the seawater samples was performed off-line with C18 solid phase extraction (SPE) disks while the determination was carried out with gas chromatography coupled to electron capture (ECD), thermionic (FTD) and mass spectroscopy (MS) detectors. The concentration levels of biocides were higher during the period from April to October. This seasonal impact depends on the application time of antifouling paints and mimic trends in the seasonal distribution of biocides in other European sites.