Assessment and management of pesticide pollution at a river basin level part I: Aquatic ecotoxicological quality indices.

During the last decade numerous monitoring programs have been conducted in order to assess pesticide pollution in catchments. This effort has led to the production of large, complex data sets of environmental results making the task of evaluation of the aquatic chemical status more difficult. Furthermore, the evaluation of the chemical status of the water ecosystems is one of the main aspects which should be considered in a River Basin Management Plan. In this study, two indices were developed in order to assess the combined pesticide ecotoxicity to aquatic non-target organisms, the Aquatic Quality Index of Short term Toxicity of Pesticides (AQI ShToxP) and the Aquatic Quality Index of Long term Toxicity of Pesticides (AQI LToxP). These indices were applied to the environmental results obtained from an intensive monitoring study of 302 pesticides in 102 stationary sampling stations located on the surface aquatic network of the Pinios River Basin, in Greece, in 2011 and 2012. The evaluation of the surface water quality was achieved by taking into consideration the frequency and the intensity of exposure of the aquatic organisms to pesticides above the respective ecotoxicological quality objectives such as the acute or chronic term predicted no-effect concentrations derived from risk assessment. Seventy-five pesticides, that have been previously identified as the River Basin Specific Pollutants of Pinios by an environmental and human risk hierarchy exercise, were assessed. It appears, from the implementation of the two indices, that the detected pesticides in the surface aquatic ecosystem of the Pinios River Basin exert significant pressure on the aquatic non-target organisms especially at the chronic effect level. The developed AQI ShToxP and AQI LToxP indices, as well as the proposed quality classification system could be valuable communication and interpretation tools for River Basin Management Plans that can contribute in the restoration of environmental health.

Assessment and management of pesticide pollution at a river basin level part II: Optimization of pesticide monitoring networks on surface aquatic ecosystems by data analysis methods.

The high cost of extensive pesticide monitoring studies, required for the protection of water resources, and the necessity of early identification of environmental threats, highlighted the need for prioritization of pesticides and sampling sites to be monitored. The aim of this study was to develop an optimum surface water monitoring network at a catchment scale including only the sites of a catchment vulnerable to pesticide pollution. The identification of sampling sites vulnerable to pesticide pollution (VPS) was based on the data of an intensive monitoring survey of 302 pesticides in 102 stationary sampling sites located on the surface water network of a river basin. In the proposed methodology the left-censored data of the analytical results derived from the above mentioned monitoring campaign were included in the statistical analyses by transforming all the raw data into categorical variables and arranging them in ordinal scales based on ecotoxicological thresholds derived from pesticide toxicity tests on aquatic non-target organisms. The categorized data were subjected to Categorical Principal Component Analysis with Optimal Scaling. For the identification of the VPS, the Squared Mahalanobis Distance criterion was applied on the extracted values (scores) of the significant principal components. With this methodology a 46% reduction in the number of the monitoring stations was achieved. This approach will be valuable in establishing more cost effective monitoring schemes in the future in other basins and in developing targeted measures to eliminate or limit the effect of critical pollution sources in surface aquatic systems. Moreover, by applying the proposed methodology, historical monitoring data can be used to initiate more efficient pesticide monitoring campaigns in the future.

Pesticides in the rivers and streams of two river basins in northern Greece.

The pollution caused by pesticides, and their ecotoxicological implications were investigated in water samples from the Strymonas and Nestos river basins (Northern Greece). Chlorpyrifos was the most frequently detected pesticide in both basins (42 and 37% in the Strymonas and Nestos basins, respectively), followed by fluometuron and terbuthylazine (25 and 12%, Strymonas), and bentazone and boscalid (24 and 10%, Nestos). The Annual Average and the Maximum Allowable Concentration of Environmental Quality Standards set in European Union Directives were exceeded in several cases by alphamethrin and chlorpyrifos. Risk Quotient assessment revealed significant ecological risk towards the aquatic organisms in over 20% of the water samples. Insecticides (mostly pyrethroids and organophosphosphates) contributed more in the ecotoxicological risk than herbicides and fungicides. The three main rivers in the current study (Strymonas, Aggitis, Nestos) exhibited similar sum of RQs indicating that aquatic life in all three of them was at the same risk level. However, the sums of RQs were higher in the various streams monitored than the three rivers.

Variability of pesticide residues in eggplant units collected from a field trial and marketplaces in Greece.

BACKGROUND: Variability of pesticide residues among food items is very important when assessing the risks and food safety for the consumers. Therefore, the present study was undertaken to estimate the unit-to-unit residue variability factors for eggplant. RESULTS: In total, 120 samples from a trial field and 142 samples from different marketplaces in Thessaloniki, Greece, were collected to estimate the variability of pesticide residues in eggplant units. They were extracted by the QuEChERS method and the residues were determined by LC-MS/MS. For the field samples, the unit-to-unit variability factors (VFs) obtained for cypermethrin and deltamethrin residues were 2.54 and 2.51, respectively. The mean residue levels of both pesticides were higher in the composite samples than in the individual samples. The average VFs for the marketplace samples was 3.89. The eggplant units exposed to pesticides were higher in residues than the non-exposed units. CONCLUSION: The variability factors obtained in the marketplace samples were higher than those in the samples collected from the field trial. A default VF value of 3 for field trials is appropriate for use when assessing the acute dietary intake but a VF for the marketplace samples should be reconsidered with a larger data. © 2017 Society of Chemical Industry.

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece.

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography-tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R(2)) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.

Environmental and human risk hierarchy of pesticides: A prioritization method, based on monitoring, hazard assessment and environmental fate.

A pesticide prioritization approach was developed and implemented in the Pinios River Basin of Central Greece. It takes under consideration the Level of Environmental Risk containing information on the frequency of occurrence of pesticides above environmental thresholds, the intensity of this occurrence and the spatial distribution as well as information about the fate and behavior of pesticides in the environment and the potential to have adverse impact on humans' health. Original 3-year monitoring data from 102 Stationary Sampling Sites located on rivers and their tributaries, reservoirs, streams and irrigation/drainage canals giving rise to a collection of 2382 water samples resulting in 7088 data sets, were included in this integrated prioritization study. Among 302 monitored active ingredients, 119 were detected at least once and the concentrations found in the aquatic systems for 41% of compounds were higher than the respective lowest Predicted Non-Effect Concentration (PNEC) values. Sixteen and 5 pesticides were found with risk ratios (MECmax/PNEC) above 10 (high concern) and 100 (very high concern), respectively. However, pesticides with maximum Measured Environmental Concentration (MECmax) values exceeding by 1000 times the respective lowest PNEC values were also found which were considered of extremely high concern; in the latter group were included prometryn, chlorpyrifos, diazinon, λ-cyhalothrin, cypermethrin, α-cypermethrin deltamethrin, ethalfluralin and phosmet. The sensitivity of the analytical methods used in the monitoring study was considered inadequate to meet the toxicological endpoints for 32 pesticides. The widest distribution of occurrence in the Stationary Sampling Sites of the monitoring program was found for the pesticides, prometryn, fluometuron, terbuthylazine, S-metolachlor, chlorpyrifos, diphenylamine, acetochlor, alachlor, 2,4-D, etridiazole, imidacloprid and lindane (γ-ΗCH). Among the 27 priority pesticides included in the Directive 2013/39/EU, in the present study 13 pesticides were considered as candidates for River Basin Specific Pollutants (RBSP) for the River Basin of Pinios. Among the 30 pesticide specific pollutants that were established by the Greek authorities, in the present study only 6 were considered as candidates for RBSP for the river basin of Pinios. As a result of the implementation of the prioritization approach developed in this study a total of 71 pesticides were identified as being RBSP for the river basin of Pinios. The higher Level of Environmental Risk was found to be exerted by the organophosphorus insecticide chlorpyrifos, followed by lindane and prometryn. The present study provides background information for important decisions to be made concerning the selection of pesticides which should be included in the target analyte list of new monitoring and screening programs of surface water quality in the Pinios River Basin. In addition, the prioritization approach proposed here can be useful for the development of River Basin Management Plans.

Pesticides in the surface waters of Lake Vistonis Basin, Greece: Occurrence and environmental risk assessment.

A study was undertaken for the evaluation of the pesticide pollution caused by the agricultural activities in the basin of Lake Vistonis, Greece during the years 2010-2012. Water samples were collected from Lake Vistonis, four major rivers and various small streams and agriculture drainage canals. The concentration of 302 compounds was determined after solid-phase extraction of the water samples and subsequent LC-MS/MS and GC-MS/MS analysis of the extracts. Overall, herbicides were the most frequently detected pesticides (57%), followed by insecticides (28%) and fungicides (14%). In Lake Vistonis 11 pesticides were detected. Specifically, fluometuron was detected in the 75% of the samples (maximum concentration 0.088 µg/L) whereas lambda-cyhalothrin was detected in all the samples of spring 2011 and alphamethrin in all the samples of spring 2012 (maximum concentration 0.041 and 0.168 µg/L, respectively). In the rivers and drainage canals 68 pesticides were detected. Specifically, fluometuron was detected in the 53% of the samples (maximum concentration 317.6 µg/L) followed by chlorpyrifos and prometryn (16 and 13% of the samples respectively). An environmental risk assessment was performed by employing the Risk Quotient (RQ) method. The risk assessment revealed that at least one pesticide concentration led to a RQ>1 in 20% of the samples. In Lake Vistonis, alphamethrin and lambda-cyhalothrin concentrations resulted in RQ>1, whereas in the other water bodies this was mainly the result of chlorpyrifos-methyl and alphamethrin exposure. In contrast, herbicide and fungicide concentrations contributed substantially less to environmental risks.

Determination of mycotoxins in pomegranate fruits and juices using a QuEChERS-based method.

A rapid and accurate analytical method for the determination of three Alternaria mycotoxins (alternariol, alternariol monomethyl ether, and tentoxin) in pomegranate samples (fruits and juices) was developed and validated. The overall average recoveries ranged for 82.0-109.4% and the relative standard deviations were from 1.2% to 10.9%. The optimized and validated method was applied to detect the presence of the target mycotoxins in real samples (fruits and juices) purchased from Greek markets. Mycotoxins were not found in any of the analyzed samples. Also, artificially inoculated pomegranate fruits with six different Alternaria alternata species complex isolates, known to produce the target mycotoxins on pure cultures, were analyzed and alternariol concentrations found ranged from 0.3 to 50.5 µg/g, alternariol monomethyl ether from 0.5 to 32.3 µg/g, while tentoxin was not detected. The developed analytical method can be used for the routine monitoring of the major Alternaria mycotoxins in pomegranates.

A pesticide monitoring survey in rivers and lakes of northern Greece and its human and ecotoxicological risk assessment.

A pesticide monitoring study covering the main rivers and lakes of Northern Greece (Macedonia, Thrace and Thessaly) was undertaken. A total of 416 samples were collected over a 1.5-year sampling period (September 1999- February 2001) from six rivers and ten lakes. The water samples were analyzed with an off-line solid phase extraction technique coupled with a gas chromatography ion trap mass spectrometer using an analytical method for 147 pesticides and their metabolites, including organochlorines, organophosphates, triazines, chloroacetanilides, pyrethroids, carbamates, phthalimides and other pesticides (herbicides, insecticides and fungicides). Based on the pesticide survey results, a human health carcinogenic and non-carcinogenic risk assessment was conducted for adults and children. Ecotoxicological risk assessment was also conducted using default endpoint values and the risk quotient method. Results showed that the herbicides metolachlor, prometryn, alachlor and molinate, were the most frequently detected pesticides (29%, 12.5%, 12.5% and 10%, respectively). They also exhibited the highest concentration values, often exceeding 1 µg/L. Chlorpyrifos ethyl was the most frequently detected insecticide (7%). Seasonal variations in measured pesticide concentrations were observed in all rivers and lakes. The highest concentrations were recorded during May-June period, right after pesticide application. Concentrations of six pesticides were above the maximum allowable limit of 0.1 µg/L set for drinking water. Alachlor, atrazine and a-HCH showed unacceptable carcinogenic risk estimates (4.5E-06, 4.6E-06 and 1.3E-04, respectively). Annual average concentrations of chlorpyriphos ethyl (0.031 µg L), dicofol (0.01 µg/L), dieldrin (0.02 µg/L) and endosulfan a (0.065 µg/L) exceeded the EU environmental quality standards. The risk quotient estimates for the insecticides chorpyrifos ethyl, diazinon and parathion methyl and herbicide prometryn were above acceptable risk values. The coupling of monitoring data to probabilistic human and ecotoxicological risk estimates could find use by Greek regulatory authorities, proposing effective pollution management schemes.

Identification, characterization and mycotoxigenic ability of Alternaria spp. causing core rot of apple fruit in Greece.

Alternaria core rot is a major postharvest disease of apple fruit in several countries of the world, including Greece. The study was conducted aiming to identify the disease causal agents at species level, investigate the aggressiveness of Alternaria spp. isolates and the susceptibility of different apple varieties and determine the mycotoxigenic potential of Alternaria spp. isolates from apple fruit. Seventy-five Alternaria spp. isolates obtained from apple fruit showing core rot symptoms were identified as either Alternaria tenuissima or Alternaria arborescens at frequencies of 89.3 and 11.7%, respectively, based on the sequence of endopolygalacturonase (EndoPG) gene. Artificial inoculations of fruit of 4 different varieties (Fuji, Golden Delicious, Granny Smith and Red Delicious) and incubation at two different temperatures (2 and 25°C) showed that fruit of Fuji variety were the most susceptible and fruit of Golden Delicious the most resistant to both pathogens. In addition, the production of 3 mycotoxins, alternariol (AOH), alternariol monomethyl ether (AME) and tentoxin (TEN) was investigated in 30 isolates of both species. Mycotoxin determination was conducted both in vitro, on artificial nutrient medium and in vivo on artificially inoculated apple fruit, using a high performance liquid chromatography with diode array detector (HPLC-DAD). The results showed that most of the isolates of both species were able to produce all the 3 metabolites both in vivo and in vitro. On apple fruit A. tenuissima isolates produced more AOH than A. arborescens isolates, whereas the latter produced more TEN than the former. Such results indicate that Alternaria core rot represents a major threat of apple fruit production not only due to quantitative yield losses but also for qualitative deterioration of apple by-products.

Effect of specific plant-growth-promoting rhizobacteria (PGPR) on growth and uptake of neonicotinoid insecticide thiamethoxam in corn (Zea mays L.) seedlings.

BACKGROUND: Corn (Zea mays L.) is one of the most important cereal crops in the world and is used for food, feed and energy. Inoculation with plant-growth-promoting rhizobacteria (PGPR) would reduce the use of chemical fertilisers and pesticides and could be suggested as an alternative practice for sustainable production of corn in modern agricultural systems. In this study, the effect of two Bacillus PGPR formulated products, Companion (B. subtilis GB03) and FZB24 (B. subtilis FZB24), on corn growth and root uptake of insecticide thiamethoxam was investigated. RESULTS: All bacterial treatments enhanced root biomass production by 38-65% compared with the uninoculated control, with no stimulatory effect of PGPR on above-ground biomass of corn. The uptake results revealed that, in plants inoculated with the PGPR B. subtilis FZB24 and B. subtilis GB03, singly or in combination, the uptake and/or systemic translocation of thiamethoxam in the above-ground corn parts was significantly higher at the different growth ages compared with the control receiving no bacterial treatment. CONCLUSION: The findings suggest that the PGPR-elicited enhanced uptake of thiamethoxam could lead to improved efficiency of thiamethoxam using reduced rates of pesticides in combination with PGPR as an alternative crop protection technique.

Occurrence of pesticides in transboundary aquifers of North-eastern Greece.

A five-year groundwater monitoring program undertaken in Evros (north-east Greece), showed a diversification in the levels of pesticide residues detected in adjacent transboundary aquifers. During the first two years 37 wells, including irrigation, drinking water and artesian wells were monitored while the next three years the survey was focused on the 11 most contaminated wells. The presence of pesticide residues was also monitored in the phreatic horizon (shallow groundwater) of four experimental boreholes drilled in the respective margins of four fields. Among the compounds found alachlor, metolachlor, atrazine, desethylatrazine (DEA), desisopropylatrazine (DIA) and caffeine were constantly detected. Pesticide concentrations were much lower (up to 1.54 µg/L) in the water of the monitored drinking water wells (deep groundwater aquifers) compared to those found in the phreatic horizon (experimental boreholes) of the respective areas (up to 5.20 µg/L). DEA to atrazine concentration ratios (DAR) determined for the phreatic horizon of the three boreholes and respective wells were lower than 1, indicating that preferential flow was the cause of the fast downward movement of atrazine to the phreatic horizon. In contrast the DAR for the fourth borehole and the adjacent well were greater than 1 indicating the absence of preferential flow of atrazine. Catabolic processes of the soil converted atrazine to DEA which is more mobile than atrazine itself through chromatographic (darcian) flow. This differential behavior of pesticides in adjacent aquifers (3 km) was further investigated by determining the apparent age of water in the two wells. The apparent age of the water present in the first aquifer was 21.7 years whereas the apparent age of that in the second aquifer was approximately 1.2 years. The faster replenishing rate of the latter is an indication that this aquifer is very vulnerable to contamination with pollutants present in the infiltrated soil water.

Biotransformation of atrazine and metolachlor within soil profile and changes in microbial communities.

Biotransformation studies of atrazine, metolachlor and evolution of their metabolites were carried out in soils and subsoils of Northern Greece. Trace atrazine, its metabolites and metolachlor residues were detected in field soil samples 1 year after their application. The biotransformation rates of atrazine were higher in soils and subsoils of field previously exposed to atrazine (maize field sites) than in respective layers of the field margin. The DT(50) values of atrazine ranged from 5 to 18d in the surface layers of the adapted soils. DT(50) values of atrazine increased as the soil depth increased reaching the value of 43 d in the 80-110 cm depth layer of adapted soils. Metolachlor degraded at slower rates than atrazine in surface soils, subsoils of field and field margins with the respective DT(50) values ranging from 56 to 72 d in surface soils and from 165 to 186 d in subsoils. Hydroxyatrazine was the most frequently detected metabolite of atrazine. The maximum concentrations of metolachlor-OXA and metolachlor-ESA were detected in the soil layers of 20-40 cm depth after 90 d of incubation. Principal Component Analysis (PCA) of soil Phospholipid Fatty Acids (PLFAs), fungal/bacterial and Gram-negative/Gram-positive ratios of the PLFA profiles revealed that the higher biotransformation rates of atrazine were simultaneously observed with the abundance of Gram-negative bacteria while the respective rates of metolachlor were observed in soil samples with abundance of fungi.

Evaluation of plant-growth-promoting rhizobacteria, acibenzolar-S-methyl and hymexazol for integrated control of Fusarium crown and root rot on tomato.

BACKGROUND: Plant growth-promoting rhizobacteria (PGPR) can be potential agents for biological control of plant pathogens, while their combined use with conventional pesticides may increase their efficacy and broaden the disease control spectrum. The effect of four different Bacillus sp. PGPR strains (B. subtilis GB03 and FZB24, B. amyloliquefaciens IN937a and B. pumilus SE34) applied individually and in mixtures, as well as in combined use with acibezolar-S-methyl (ASM) and hymexazol, on plant growth promotion and on the control of Fusarium crown and root rot (FCRR) of tomato was evaluated. RESULTS: All PGPR strains promoted the tested plant growth characteristics significantly. A higher promoting effect was provided by SE34. Experiments on population dynamics of PGPR strains revealed that, after 28 days of incubation, populations of strain SE34 remained stable, while the remaining bacterial strains showed a slight decline in their population densities. The GB03 and FZB24 strains provided a higher disease suppression when applied individually. However, application of IN937a in a mixture with GB03 provided a higher control efficacy of Fusarium oxysporum f. sp. radicis-lycopersici (Forl). Treatment of tomato plants with ASM resulted in a small reduction in disease index, while application of hymexazol provided significantly higher control efficacy. Combined applications of the four PGPR strains with either ASM or hymexazol were significantly more effective. CONCLUSION: The results of the study indicate that, when bacilli PGPR strains were combined with pesticides, there was an increased suppression of Forl on tomato plants, and thus they may prove to be important components in FCRR integrated management.

Biodegradation of soil-applied pesticides by selected strains of plant growth-promoting rhizobacteria (PGPR) and their effects on bacterial growth.

A laboratory study was conducted to investigate the influence of four PGPR strains on the degradation of five soil applied pesticides and their effects on bacterial growth. Interactions of Bacillus subtilis GB03, Bacillus subtilis FZB24, Bacillus amyloliquefaciens IN937a and Bacillus pumilus SE34 with two concentrations of acibenzolar-S-methyl, metribuzin, napropamide, propamocarb hydrochloride and thiamethoxam in liquid culture and soil microcosm were studied. The degradation of acibenzolar-S-methyl by all PGPR tested in low and high concentration, was 5.4 and 5.7 times, respectively, faster than that in non-inoculated liquid culture medium. At the end of the 72-h liquid cultured experiments, 8-18, 9-11, 15-36 and 11-22% of metribuzin, napropamide, propamocarb hydrochloride and thiamethoxam, respectively, had disappeared from PGPR inoculated medium. Under the soil microcosm experimental conditions, the half-lives of acibenzolar-S-methyl incubated in the presence of PGPR strains spiked at 1.0 and 10.0 mg kg(-1) were 10.3-16.4 and 9.2-15.9 days, respectively, markedly lower compared with >34.2 days in the control. From the rest pesticides studied degradation of propamocarb hydrochloride and thiamethoxam was enhanced in the presence of B. amyloliquefaciens IN937a and B. pumilus SE34. Acibenzolar-S-methyl, propamocarb hydrochloride and thiamethoxam significantly increased the PGPR growth. However, the stimulatory effect was related to the level of pesticide spiked.

Determination of acibenzolar-S-methyl and its acidic metabolite in soils by HPLC-diode array detection.

A simple and accurate method for the analysis of acibenzolar-S-methyl (benzo[1,2,3]thiadiazole-7-carbothioic acid-S-methyl ester; CGA 245 704; ASM) and its major conversion product, benzo[1,2,3]thiadiazole-7-carboxylic acid (CGA 210 007; BTC), in soils is presented. ASM extraction from soil samples was performed using acetonitrile and BTC was extracted with a mixture of potassium phosphate buffer (0.5 M, pH 3) and acetonitrile (70:30 %, v/v). Both extracts were directly analyzed in a high-performance liquid chromatography-diode array detection (HPLC-DAD) system. Pesticide separation was achieved on a C18 (4.6 mm × 150 mm, 5 µm) analytical column with a isocratic elution of acetonitrile:water 40:60 % (v/v) with 0.6 mL L⁻¹ acetic acid at a flow rate of 1 mL min⁻¹. Linear regression coefficients (r (2)) of the external calibration curves were always above 0.9997. The limits of detection (LOD) and quantification (LOQ) of the method were 0.005 and 0.02 mg kg⁻¹ for ASM, and 0.01 and 0.05 mg kg⁻¹ for BTC, respectively. Recoveries were investigated at six fortification levels and were in the range of 90-120 % for ASM and 74-96 % for BTC with relative standard deviations (RSDs) below 11 % in all cases. The method was also validated by analyzing freshly spiked soil samples with 2.7% organic matter content at 0.5 mg kg⁻¹ level, with slightly lower recovery values only for ASM. Moreover, recoveries for intermediate aged residues of the analytes were similar to fresh residues. This method was also applied to determine ASM half-life (t(½) = 8.7 h) and the rate of the acidic metabolite formation.

Simple determination of 40 organophosphate pesticides in raw wool using microwave-assisted extraction and GC-FPD analysis.

A validated analytical method for the multiresidue analysis of 40 organophosphate pesticides (OPs) and conversion products in raw wool has been developed. The method is based on the selective microwave-assisted extraction (MAE) of raw wool with acetonitrile and analysis of extracts by gas chromatography-flame photometric detector. The optimum MAE conditions were 20 min duration at 80 °C with 30 mL of acetonitrile per gram of wool. A validation study was performed according to the European SANCO guidelines 10684/2009. Limits of detection and quantification for all pesticides tested were from 0.01 to 0.2 mg/kg and from 0.2 to 1.0 mg/kg, respectively. The average recoveries of pesticides spiked at different levels were in the range of 70-120% with relative standard deviations of ≤ 20%. The extraction performance was compared to the one obtained with a reference Soxhlet extraction. The method was also applied in the analysis of real wool (after field application) samples.

Effect of the form of the sesame-based diet on the absorption of lignans.

The effect of different forms of sesame-based diets on the concentration of plasma lignans was assayed by estimating the levels of certain lignans (sesame lignans and enterolignans) in the plasma of experimental animals. In a series of experiments, male Wistar rats were fed either a raw sesame-enriched diet or a tahini-enriched diet. The plasma concentration of the lignans (sesame lignans and enterolignans) was determined at various time intervals over a 24 h period after a single administration. Enterodiol and enterolactone concentration in the tahini-treated group was significantly higher than in the raw sesame-treated group. In another series of experiments, male Wistar rats were fed, for 15 d, diets enriched in raw dehulled sesame, sesame perisperm, sesame oil, tahini and a polyphenolic extract derived from the seed perisperm. Enterodiol and enterolactone plasma concentration was high in the case of the sesame perisperm in spite of its low concentration in the assessed sesame lignans. Overall, the levels of the sesame lignans and enterolignans present in plasma seem to be influenced not only by the amount of lignan intake but also by other factors such as the form of the sesame-based diet.

Determination of alachlor, metolachlor, and their acidic metabolites in soils by microwave-assisted extraction (MAE) combined with solid phase extraction (SPE) coupled with GC-MS and HPLC-UV analysis.

A well-validated analytical method based on microwave-assisted extraction (MAE) and SPE is presented for the combined analysis of alachlor, alachlor-oxanilic acid (OXA), alachlor-ethanesulfonic acid (ESA), metolachlor, metolachlor-OXA, metolachlor-ESA residues in soils. Extraction of solutes by soil sample was carried out by MAE for 20 min at 100 degrees C in the presence of 50 mL solution (methanol/water 50:50), the extract was subsequently passed through C18 cartidges and fractionated into two fractions, the first with parent compounds (PCs) analyzed with GC-MS and the second one containing the metabolites analyzed with HPLC. For the SPE step, various types of sorbents (Environmental C18, tC18, Supelclean ENVI-carb, and LiChrolut EN) have been used, and their respective advantages and disadvantages are discussed. After the method optimization, average recovery values of all solutes were > 71% in the 50-500 microg/kg fortification range with RSD <10%. The LOQ and LOD were 10-50 and 5-10 microg/kg, respectively. The method was validated with two types of soils (1 and 2.4% organic matter) and in fresh (12 h aging), intermediate (1 wk aging), and aged (1 month aging) spiked samples. Moreover, residue levels determined after field application of alachlor or metolachlor were higher when soils were processed using this method than with a comparison method based on an overnight flask shaking (FS) of soil suspension.

Rapid method for the determination of 16 organochlorine pesticides in sesame seeds by microwave-assisted extraction and analysis of extracts by gas chromatography-mass spectrometry.

A method for the multiresidue analysis of 16 organochlorine insecticides in sesame seeds has been developed. The method is based on the microwave-assisted extraction (MAE) of the sesame seeds by the use of a water-acetonitrile mixture followed by Florisil clean-up of the extracts and subsequent analysis by gas chromatography-mass spectrometry (GC/MS) in the selected ion monitoring (SIM) mode. MAE operational parameters (extraction solvent, temperature and time, extractant volume) were optimized with respect to extraction efficiency of the target compounds from sesame seeds with 46% oil content. Recoveries >80% with relative standard deviations (RSD) <12% were obtained for all compounds under the selected parameters. The Florisil clean-up step proved sufficient for the removal of co-extracted substances so that no adverse effect on the chromatographic system was observed. Limit of quantification (LOQ) values were in the range of 5-10 microg/kg. The proposed method was applied in the analysis of sesame seed samples imported to Greece.