Investigation of pharmaceutical and personal care product interactions of soil and beets (Beta vulgaris L.) under the effect of wastewater reuse.

Although, several recent greenhouse studies are beginning to address the uptake of pharmaceuticals and personal care products (PPCPs) by a variety of crops, few studies have assessed the effects of exposure to complex, realistic wastewater effluents on uptake. Hence, in this study, a greenhouse experiment was conducted in order to study the interactions occurring exclusively between PPCPs in soil, and in the edible plant part of beets (Beta vulgaris) after exposure to treated wastewater effluent. According to the findings, the interactions between the pharmaceuticals caffeine (CFN) with bisoprolol (BSP), carbamezapine (CMZ), clarithromycin (CMC), metoprolol (MPL), sulfamethoxazole (SMX), and trimethoprim (TMP) occurring in soil were almost 99% synergistic; it was noted variability in the interactive capacity of the pharmaceuticals; the concentrations of pharmaceuticals which measured did not affect unfavorably beet yield; interactions between the PPCPs via the PPCPs contribution in plant and soil affect the qualitative and quantitative characteristics of the beets.

Photolysis and photocatalysis of the non-steroidal anti-inflammatory drug Nimesulide under simulated solar irradiation: Kinetic studies, transformation products and toxicity assessment.

In this study, the degradation of Nimesulide (NIM), a non-steroidal anti-inflammatory drug, using photolysis, heterogeneous (TiO2 in dispersion) and homogeneous (photo-Fenton reactant) photocatalysis, under simulated solar light (SSL) radiation, was investigated. Various parameters affecting the degradation rate of the target compound during the applied processes were optimized. The efficiency of all treatments used (direct photolysis; TiΟ2/SSL; TiΟ2/Η2Ο2/SSL; TiΟ2/S2Ο82-/SSL; Fe3+/H2O2/SSL; Fe3+/S2O82-/SSL and [Fe(C2O4)3]3-/H2O2/SSL) was evaluated by means of initial reaction rate and mineralization. Moreover, the generated transformation products (TPs) by each basic process (photolysis; TiΟ2/SSL and Fe3+/H2O2/SSL) were identified, using liquid chromatography coupled to high resolution mass spectrometry, and their formation kinetic profiles were given. The main transformation routes of NIM were hydroxylation and fragmentation, for all three treatments applied. Finally, toxicity measurements were conducted using Microtox bioassay in order to evaluate the potential risk of NIM and its TPs to aqueous organisms. Although, the acute toxicity increased during the first stages of treatment the final outcome lead to very low toxicity levels even within 60 min of TiO2/SSL treatment. Concluding, the obtained results suggest that the photocatalytic degradation of NIM can lead to its complete elimination and simultaneously to the detoxification of the solution.

The dynamics of the pharmaceutical and personal care product interactive capacity under the effect of artificial enrichment of soil with heavy metals and of wastewater reuse.

A greenhouse experiment was conducted, using a randomized block design, including twelve heavy metal (Mn, Zn, Cu, Cd, Co, Cr, Ni, Pb) mixture treatments, with each metal participating in the treatment with 0, 2, 4, 6, 8, 10, and 12 mg/kg, respectively. Common beet (Beta vulgaris L.) was chosen as test plant. The plants were irrigated with treated municipal wastewater taken from the Wastewater Treatment Plant of the town of Amaliada, N.W., Peloponnese, Greece. The experiment aimed at studying the interactions between heavy metals and macro-microelements, and pharmaceuticals and personal care products (PPCPs). The basic scope was to shed some light on the potential environmental implications, of these interactions on the soil PPCPs for a more effective monitoring of these emerging contaminants in the plants and soil continuum. It was found that the PPCPs have a very high potential interactive capacity, having interacted with all the studied metals, and metalloids, as well as with plant macro elements (P, and K). The uptake of PPCPs by plants was statistically significantly related with their respective content in the soil. The general inference is that the interactive relations between heavy metals, macro-, microelements, and emerging contaminants, being mainly antagonistic, which contribute to the decrease the uptake of soil PPCPs.

Photo-Fenton and Fenton-like processes for the treatment of the antineoplastic drug 5-fluorouracil under simulated solar radiation.

In the present study, photo-Fenton and Fenton-like processes were investigated for the degradation and mineralization of the antineoplastic drug 5-fluorouracil (5-FU). For the optimization of photo-Fenton treatment under simulated solar light (SSL) radiation, the effects of several operating parameters (i.e., 5-FU concentration, Fe3+, and oxidant concentration) on the treatment efficiency were studied. According to the results, SSL/[Fe(C2Ο4)3]3-/Η2Ο2 process was the most efficient, since faster degradation of 5-FU and higher mineralization percentages were achieved. All the applied processes followed quite similar transformation routes which include defluorination-hydroxylation as well as pyrimidine ring opening, as demonstrated by the transformation products identified by high resolution mass spectrometry analysis. The toxicity of the treated solutions was evaluated using the Microtox assay. In general, low toxicity was recorded for the initial solution and the solution at the end of the photocatalytic treatment, while an increase in the overall toxicity was observed only at the first stages of SSL/Fe3+/Η2Ο2 and SSL/Fe3+/S2O82- processes.

Photocatalytical removal of fluorouracil using TiO2-P25 and N/S doped TiO2 catalysts: A kinetic and mechanistic study.

In the present study, the photocatalytic activity of TiO2-based photocatalysts toward degradation and mineralization of the anti-cancer drug 5-fluorouracil (5-FU) in aqueous phase was investigated under simulated solar and visible irradiation. Commercial TiO2 (P25) and N/S-doped TiO2 catalysts synthesized by a simple sol-gel method were used as photocatalysts. TiO2 P-25 was found to be the most photoactive catalyst for the removal of 5-FU, under simulated solar irradiation. Among N/S-doped TiO2 catalysts, the one with molar Ti:N/S ratio equal to 0.5 was the most efficient under simulated solar irradiation. In contrast, under visible irradiation the catalyst with equimolar Ti:N/S ratio showed the highest performance for the removal of 5-FU. Scavenging experiments revealed that HO radicals and h+ were the major reactive species mediating photocatalytic degradation of 5-FU using TiO2 P-25 and N/S-doped TiO2 catalysts, under simulated solar irradiation. On the other hand, the essential contribution of 1O2 and O2- in the degradation of 5-FU under visible light was proved. The transformation products (TPs) of 5-FU, were identified by LC-MS-TOF suggesting that defluorination followed by hydroxylation and oxidation are the main transformation pathways, under all the studied photocatalytic systems.

Degradation of venlafaxine using TiO2/UV process: Kinetic studies, RSM optimization, identification of transformation products and toxicity evaluation.

The photochemical degradation of the antidepressant drug venlafaxine (VNF) by UV/TiO2 process was investigated in the present study. Prescreening experiments were conducted to study the effects of main parameters affecting the photocatalytic process. In addition, the effects and interactions of most influenced parameters were evaluated and optimized by using a central composite design model and a response surface methodology. Results indicated that VNF was quickly removed in all the irradiation experiments and its degradation was mainly affected by the studied variables (catalyst dose, initial VNF concentration and pH), as well as their interaction effects. Parallel to kinetic studies, the transformation products (TPs) generated during the treatment was investigated using LC coupled to low and high resolution mass spectrometry. Based on identification of the main TPs, tentative transformation pathways were proposed, including hydroxylation, demethylation and dehydration as major transformation routes. Τhe potential risk of VNF and its TPs to aqueous organisms was also investigated using Microtox bioassay before and during the processes. The obtained results showed an increment in the acute toxicity in the first stages and a continuously decreasing after then to very low values reached within 240min of the photocatalytic treatment, demonstrating that UV/TiO2 can lead to the elimination of parent compound and the detoxification of the solution.

Adsorption and photocatalysis of nanocrystalline TiO2 particles for Reactive Red 195 removal: effect of humic acids, anions and scavengers.

In the present study, the coupling of adsorption capacity and photocatalytic efficiency of two different industrially produced titania catalysts was investigated and compared. The azo dye Reactive Red 195 was selected as a model compound. The tested catalysts, PK-10 and PK-180, exhibited different adsorption capacities due to their significant difference in their specific surface, but both have proven to be effective photocatalysts for photodegradation of the studied dye. PK-10 exhibited strong adsorption of the studied dye due to its high specific surface area, while the second studied catalyst, PK-180, demonstrated negligible adsorption of Reactive Red 195. The effect of the pH, the concentration of the catalyst and the initial concentration of the dye appear to affect the photocatalytic rate. The effect of the presence of humic acids and inorganic ions was also examined, while the contribution of various reactive species was indirectly evaluated through the addition of various scavengers. To evaluate the extent of mineralisation of the studied dye, total organic carbon (TOC) measurements during the experiment were also conducted. Besides total colour removal, evident reduction of TOC was also achieved using both catalysts.

Photocatalytic degradation of molinate in aqueous solutions.

In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO2 as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H2O2 and K2S2O8) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron's and electron scavenger's concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.

A review on advanced oxidation processes for the removal of taste and odor compounds from aqueous media.

In view of the global concern about the occurrence of taste and odor (T&O) compounds in waters for drinking water supply and the necessity for the development of more innovative and efficient technologies for water treatment and depuration, the focus of this study is to provide a state of the art overview on current knowledge for the application of advanced oxidation technologies for the treatment of T&O compounds in aquatic media. The most representative and newly emerging compounds belonging to the major groups of T&O compounds, such as geosmin, methylisoborneol, benzothiazoles, mercaptans and sulfides as well as aromatic and other miscellaneous T&O compounds, are included in the systematic overview. The current data has been compiled and extensively discussed in terms of the degree of degradation, reaction kinetics, effect of operational parameters and water quality, identity of intermediate and final products and possible transformation pathways.

Transformation products and reaction pathways of carbamazepine during photocatalytic and sonophotocatalytic treatment.

This study examines the degradation of the antiepileptic carbamazepine (CBZ) by sonolysis, TiO2-based heterogeneous photocatalysis under UV-A and simulated solar irradiation, and by the combined use of UV-A and ultrasound irradiation (i.e. sonophotocatalysis) in demineralized water, ground water and effluent wastewater. The processes were compared with respect to substrate conversion rate and the extent of DOC reduction as a measure of mineralization. CBZ was degraded following a pseudo-first order kinetics. Sonophotocatalysis provided the highest rate of CBZ transformation over the time-course of the experiment while the degree of DOC removal in pure water was similar for all the studied treatments (around 40%), and always lower than CBZ conversion. This indicated that a considerable organic load remained in the treated solutions that could also be attributed to the presence of persistent oxidation products. UPLC-(+ESI)-QToF-MS was employed to determine major CBZ-related transformation products. Several recalcitrant hydroxy- and keto-derivatives of CBZ were tentatively identified. A Daphnia magna bioassay was used to evaluate the potential toxicity of the samples collected at different time points showing that the mixtures were highly toxic to D. magna.

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways.

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO(2)-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10mgL(-1)) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the ()OH radical attack. Moreover, products resulted from the cleavage of the amide and NH-dichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.

Removal of Reactive Red 195 from aqueous solutions by adsorption on the surface of TiO2 nanoparticles.

Nanoparticles of TiO2 were synthesized and characterized by XRD, BET, TG/DTA and TEM measurements. The commercial azo dye Reactive Red 195 (RR195) was selected as a model dye in order to examine the adsorption capacity of TiO2 at room temperature, under dark conditions. It was demonstrated that RR195 could be efficiently adsorbed in aqueous suspension of TiO2. A study on the effects of various parameters like initial pH, concentration of dye and concentration of adsorbent has been carried out in order to find optimum adsorption conditions. The optimum pH of sorption was 3. Substantial reduction of COD, besides removal of colour, was also achieved. The experimental data were analyzed by the Langmuir and Freundlich adsorption models. Equilibrium data fitted very well with the Langmuir model signifying the energetic homogeneity of TiO2 surface adsorption sites. At the temperature of 30 degrees C, the maximum monolayer adsorption capacity obtained from the Langmuir model is approximately 87 mg/g (pH 3.0). Kinetic studies were carried out and showed a rapid sorption of dye in the first 30 min while equilibrium was reached at 1h. Three kinetic adsorption models were used to describe the kinetics data, the pseudo-first-order model, the pseudo-second-order model and the intraparticle diffusion model. The sorption kinetics of dye was best described by the pseudo-second-order kinetic model.

Identification of photocatalytic degradation products of bezafibrate in TiO(2) aqueous suspensions by liquid and gas chromatography.

In the present study the photocatalytic degradation of bezafibrate (BZF), a lipid regulator agent, has been investigated using TiO(2) suspensions and simulated solar light. The study focus on the identification of degradation products (DPs) using powerful analytical techniques such as liquid chromatography time of flight mass spectrometry (LC-TOF-MS), gas chromatography mass spectrometry (GC-MS), and high-performance liquid chromatography with diode-array detection (HPLC-DAD). Each technique provided complementary information that enabled the identification of 21 DPs. Accurate mass measurements obtained by LC-TOF-MS provided the elucidation of 17 DPs. Mass errors lower than 2mDa, allowed the assignment of empirical formula for the mayor DPs to be determined confidently. Three DPs were identified by GC-MS through the structural information provided by full scan mass spectra obtained by electron impact (EI) ionization and two more by HPLC-DAD by comparing the retention times (t(R)) and the UV spectra of the unknown DPs with those of commercial standards. Based on this by-product identification a possible multi-step degradation scheme was proposed. The pathways include single or multiple hydroxylation of BZF with subsequent phenoxy ring opening and the cleavage of the amide and ether bonds.

Persistent organochlorine contaminants in liver and fat of birds of prey from Greece.

The concentrations of persistent organic pollutants, such as DDT and its metabolites (DDTs), hexachlorocyclohexane isomers (HCHs), cyclodienes (Cycls), and polychlorinated biphenyls (PCBs), were measured in livers and subcutaneous fat tissues of six Accipitridae and four Falconidae bird species from different areas in Greece. This is the first report of persistent organochlorine (OC) pollutants in birds of prey tissues presented for Greece and the Eastern Mediterranean region. Accumulation patterns of OCs found in birds suggested that the predominant contaminants were p,p'-dichlorodiphenyldichloro-1,1-ethylene (DDE) and PCBs, whereas Cycls and HCHs occurred at low concentrations only. Concentration values of p,p'-DDE ranged from nondetected to 19,518.72 ng/g wet wt in livers and from nondetected to 2679.19 ng/g wet wt in fat. Total PCB levels ranged from 1.01 to 7419.43 ng/g and from 3.25 to 490.10 ng/g wet weight for liver and fat samples, respectively. Higher-chlorinated PCBs such as 118, 138, 153, and 180 predominated in both the liver and subcutaneous fat samples, a pattern comparable to that observed in birds from other European countries. No significant differences in mean concentrations of OCs are detected between species. Hepatic concentrations were in general higher than the fat concentrations showing depleted fat stores in most birds. Concentration ranges were also found in lower or similar levels to those reported for birds in other regions. Variation of OCs levels in bird tissues could be due to different causes of death, with a subsequent effect on body lipid levels, and different feeding and migration habits. The liver PCB levels reported in this study are below the concentrations currently believed to exert mortality or ecotoxicological effects. On the contrary, in some cases p,p'-DDE concentrations were higher than the reported effect values for birds of the same families and could be associated with sublethal effects.

Accumulation profiles of persistent organochlorines in liver and fat tissues of various waterbird species from Greece.

Waterbirds are particularly subject to accumulation of persistent organic pollutants (POPs) that have been shown to constitute a major hazard for this group of birds. Liver and fat tissue from ten species belonging to the orders Ciconiformes (Ardeidae, Ciconiidae, Phoenicopteridae) and Pelicaniformes (Pelecanidae, Phalacrocoracidae) were used as bioindicators in order to assess environmental pollution by POPs (HCHs, DDTs, cyclodienes, PCBs) in Greek wetlands. To our knowledge, this is the first study on POPs in livers of water birds in Greece and Eastern Mediterranean area. The DDTs consisted mainly of p,p'-DDE with percentages over 60% in the great majority of the samples. The highest summation SigmaDDT concentrations were measured in the liver and subcutaneous fat of Phoenicopterus rubber and in Ardea purpurea liver (15565, 24706 and 10406 ng g(-1) wet weight, respectively). Low concentrations of cyclodienes (Cycls) and HCHs were detected occasionally and the contamination pattern of OCPs in most species of waterbirds followed the order summation SigmaDDTs> summation SigmaCycls> summation SigmaHCHs. Individual values of total PCBs reached the levels of 4468 and 3252 ng g(-1) wet weight, for Nycticorax nycticorax and Egretta garzetta samples respectively. Some of the recorded differences in organochlorine concentrations could be due to different causes of death, with a subsequent effect on body lipid levels. Organochlorine pesticides and PCBs residues were lower than those commonly associated with mortality and reduced reproductive success in most species. However, low level exposure to these contaminants may constitute one of the many stressors that in combination could adversely affect bird populations.

Aqueous photolysis of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid. Formation of disinfection byproducts in chlorinated swimming pool water.

The photochemical behavior of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid (ODPABA) was studied in different aqueous solutions and under different conditions. ODPABA photolysis was performed under laboratory conditions using a xenon light source and under natural sunlight conditions in sea, swimming pool as well as in distilled water. The influence of dissolved organic matter (DOM) on the degradation kinetics was also studied in the presence of various concentrations of humic acids (HA). The phototransformation was shown to proceed via pseudo-first-order reaction in all cases and the reaction rates followed the order: distilled water > swimming pool water > seawater, depending mainly on the presence of dissolved organic matter that retarded the photolysis reaction. Kinetic experiments were monitored with HPLC/UV-DAD and the half-lives (t 1/2) varied between 1.6 and 39 h in simulated solar irradiation and between 27 and 39 h in natural sunlight conditions. The product distribution during illumination was strongly dependent on the constitution of the irradiated media. Irradiation of the aqueous ODPABA solutions gave rise to several transformation products that were isolated by means of solid-phase extraction (SPE) and identified using GC-MS techniques. These were formed mainly through dealkylation and hydroxylation reactions and were detected in all aqueous solutions investigated. In the case of swimming pool water some additional byproducts were isolated and were tentatively identified as chlorinated intermediates, formed by the subsequent chlorination of the parent molecule as well as other intermediates.

Validation of an SPME method, using PDMS, PA, PDMS-DVB, and CW-DVB SPME fiber coatings, for analysis of organophosphorus insecticides in natural waters.

Solid-phase microextraction (SPME) has been optimized and applied to the determination of the organophosphorus insecticides diazinon, dichlofenthion, parathion methyl, malathion, fenitrothion, fenthion, parathion ethyl, bromophos methyl, bromophos ethyl, and ethion in natural waters. Four types of SPME fiber coated with different stationary phases (PDMS, PA, PDMS-DVB, and CW-DVB) were used to examine their extraction efficiencies for the compounds tested. Conditions that might affect the SPME procedure, such as extraction time and salt content, were investigated to determine the analytical performance of these fiber coatings for organophosphorus insecticides. The optimized procedure was applied to natural waters - tap, sea, river, and lake water - spiked in the concentration range 0.5 to 50 micro g L(-1) to obtain the analytical characteristics. Recoveries were relatively high - >80% for all types of aqueous sample matrix - and the calibration plots were reproducible and linear (R(2)>0.982) for all analytes with all the fibers tested. The limits of detection ranged from 2 to 90 ng L(-1), depending on the detector and the compound investigated, with relative standard deviations in the range 3-15% at all the concentration levels tested. The SPME partition coefficients (K(f)) of the organophosphorus insecticides were calculated experimentally for all the polymer coatings. The effect of organic matter such as humic acids on extraction efficiency was also studied. The analytical performance of the SPME procedure using all the fibers in the tested natural waters proved effective for the compounds.

Antifouling paint booster biocide contamination in Greek marine sediments.

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin in 1987. In this study, the concentrations of three biocides commonly used as antifoulants, Irgarol 1051 (2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-triazine), dichlofluanid (N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl sulphamide) and chlorothalonil (2,4,5,6-tetrachloro isophthalonitrile) were determined in sediments from ports and marinas of Greece. Piraeus (Central port, Mikrolimano and Pasalimani marinas), Thessaloniki (Central port and marina), Patras (Central port and marina), Elefsina, Igoumenitsa, Aktio and Chalkida marinas were chosen as representative study sites for comparison with previous monitoring surveys of biocides in coastal sediments from other European countries. Samples were collected at the end of one boating season (October 1999), as well before and during the 2000 boating season. All the compounds monitored were detected at most of sites and seasonal dependence of biocide concentrations were found, with maxima during the period June-September, while the winter period (December-February) lower values were encountered. The concentrations levels ranged from 3 to 690 ng/g dw (dry weight). Highest levels of the biocides were found in marinas (690, 195 and 165 ng/g dw, for Irgarol, dichlofluanid and chlorothalonil respectively) while in ports lower concentrations were observed. Antifouling paints are implicated as the likely sources of biocides since agricultural applications possibly contributed for chlorothalonil and dichlofluanid inputs in a few sampling sites.

Gas chromatographic determination of 2-hydroxy-4-methoxybenzophenone and octyldimethyl-p-aminobenzoic acid sunscreen agents in swimming pool and bathing waters by solid-phase microextraction.

A method has been developed for the trace determination of two sunscreen constituents (2-hydroxy-4-methoxybenzophenone and octyldimethyl-p-aminobenzoic acid) in water samples, which are commonly used in commercial formulations. The method employs solid-phase microextraction (SPME) and gas chromatography with flame ionization and mass spectrometric detection. The technique was developed with headspace and direct sampling in order to demonstrate the applicability of these SPME extraction modes for the identification of these two UV absorbing compounds in waters. The main parameters affecting the SPME process, such as desorption time, extraction time profile, salt additives, pH, and temperature, were investigated. The poly(dimethylsiloxane) 100-microm and polyacrylate 85-microm fiber coatings were found to be the most efficient for the extraction of these compounds from aqueous matrices. Linear calibration curves in the wide range of 10-500 microg/l were obtained for both compounds yielding typical RSD values of 5-9% for both extraction modes. The recoveries were relatively high, 82-98%, with quantitation limits below 1 microg/l. A comparison between the proposed methods and the conventional multiresidue solid-phase extraction revealed that the proposed technique(s) can be reliably used for sunscreen residue measurement in water samples with satisfactory results.

Optimization of headspace solid-phase microextraction conditions for the determination of organophosphorus insecticides in natural waters.

Headspace solid-phase microextraction (HS-SPME) has been developed for the analysis of seven organophosphorus insecticides, i.e. diazinon, fenitrothion, fenthion, ethyl parathion, methyl bromophos, ethyl bromophos and ethion in natural waters. Their determination was carried out using gas chromatography with flame thermionic and mass spectrometric detection. To perform the HS-SPME, two types of fibre have been assayed and compared: polyacrylate (PA 85 microm), and polydimethylsiloxane (PDMS 100 microm). The main parameters affecting the HS-SPME process such as temperature, salt additives, memory effect, stirring rate and adsorption-time profile were studied. The method was developed using spiked natural waters such as ground, sea, river and lake water in a concentration range of 0.05-1 microg/l. The HS-SPME conditions were optimized in order to obtain the maximum sensitivity. Detection limits varied from 0.01 to 0.04 microg/l and relative standard deviations (RSD <17%) were obtained showing that the precision of the method is reliable. The method showed also good linearity for the tested concentration range with regression coefficients ranging between 0.985 and 0.999. Recoveries were in relatively high levels for all the analytes and ranged from 80 to 120%. Water samples collected from different stations along the flow of Kalamas river (NW Greece) were analyzed using the optimized conditions in order to evaluate the potential of the proposed method to the trace-level screening determination of organophosphorus insecticides. The analysis with HS-SPME has less background interference and the advantage of its non-destructive nature reveal the possibility of the repetitive use of the SPME fibre.