Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Identification and quantitative detection of Legionella spp. in various aquatic environments by real-time PCR assay

In this study, a SYBR green quantitative real-time PCR was developed to quantify and detect the Legionella spp. in various environmental water samples. The water samples were taken from watershed, water treatment plant, and thermal spring area in Taiwan. Legionella was detected in 13.6 % (24/176), and the detection rate for river water, raw drinking water, and thermal spring water was 10, 21.4, and 16.6 %, respectively. Using real-time PCR, concentration of Legionella spp. in detected samples ranged between 9.75?×?10⁴ and 3.47?×?10⁵?cells/L in river water, 6.92?×?10⁴ and 4.29?×?10⁵?cells/L in raw drinking water, and 5.71?×?10⁴ and 2.12?×?10⁶?cells/L for thermal spring water samples. The identified species included Legionella pneumophila (20.8 %), Legionella jordanis (4.2 %), Legionella nautarum (4.2 %), Legionella sp. (4.2 %), and uncultured Legionella sp. (66.6 %). The presence of L. pneumophila in aquatic environments suggested a potential public health threat that must be further examined.     

Extraction procedure optimization for perfluorooctane sulfonate and perfluorooctanoic acid in food packaging determination by LC-MS/MS

This research aimed to optimize the extraction method parameters for sample pretreatment and determine the levels of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) contamination in food packaging made of paper. Techniques used were pressurized liquid extraction (PLE) followed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Influence parameters of PLE were carefully evaluated for extracted concentration of samples in low level (ng g^?1). The study found that the optimal conditions for PLE were 30 min static extraction time with a flush volume of 100% cell volume and one extraction cycle at 80°C and 1,000 psi. The extraction technique validated the absolute recovery from PFOS and PFOA fortified control samples at three different levels (5, 50, and 200 ng g^?1), with seven repeats at each fortification level. The average recoveries were 79% or higher, with relative standard deviation (RSD) less than 11%. Optimization of the PLE method was established based on recovery data, accuracy, precision, and repeatability of the method. Using optimal PLE technique, PFOS and PFOA were extracted from 34 food-packaging samples collected in Thailand. PFOS and PFOA were detected in all kinds of collected samples, with average concentrations of 4.89 and 2.87 ng g^?1, respectively. The concentrations of PFOS and PFOA were highest in fast-food container samples: 36.99 and 9.99 ng g^?1, respectively.     

Dissipation of spiromesifen and spiromesifen-enol on tomato fruit,tomato leaf,and soil under field and controlled environmental conditions

Dissipation of spiromesifen and its metabolite, spiromesifen-enol, on tomato fruit, tomato leaf, and soil was studied in the open field and controlled environmental conditions. Sample preparation was carried out by QuEChERS method and analysis using LC-MS/MS. Method validation for analysis of the compounds was carried out as per “single laboratory method validation guidelines.” Method validation studies gave satisfactory recoveries for spiromesifen and spiromesifen-enol (71.59–105.3%) with relative standard deviation (RSD) < 20%. LOD and LOQ of the method were 0.0015 μg mL^?1 and 0.005 mg kg^?1, respectively. Spiromesifen residues on tomato fruits were 0.855 and 1.545 mg kg^?1 in open field and 0.976 and 1.670 mg kg^?1 under polyhouse condition, from treatments at the standard and double doses of 125 and 250 g a.i. ha^?1, respectively. On tomato leaves, the residues were 5.64 and 8.226 mg kg^?1 in open field and 6.874 and 10.187 mg kg^?1 in the polyhouse. In soil, the residues were 0.532 and 1.032 mg kg^?1 and 0.486 and 0.925 mg kg^?1 under open field and polyhouse conditions, respectively. The half-life of degradation of spiromesifen on tomato fruit was 6–6.5 days in the open field and 8.1–9.3 days in the polyhouse. On tomato leaves, it was 7–7.6 and 17.6–18.4 days and in soil 5.6–7.4 and 8.4–9.5 days, respectively. Metabolite, spiromesifen-enol, was not detected in any of the sample throughout the study period. Photodegradation could be the major route for dissipation of spiromesifen in the tomato leaves, whereas in the fruits, it may be the combination of photodegradation and dilution due to fruit growth. The results of the study can be utilized for application of spiromesifen in plant protection of tomato crop under protected environmental conditions.     

Biopesticide and formulation processes based on starch industrial wastewater fortified with soybean medium

Abstract

The aim of this study was to produce Bacillus thuringiensis-based biopesticide using starch-producing industry wastewater (SIW) fortified with soybean medium and optimize the formulated product using different adjuvants. This study was necessary as low endotoxin concentration is obtained in formulated biopesticide when SIW alone is used as fermentation medium. The fermentation runs were conducted using SIW alone and SIW fortified with 25% soybean (w/v) medium in 2000?L and 150?L bioreactor, respectively. SIW supplemented with soybean medium showed an increase in cell count (from 1.95?×?10⁸ to 1.65?×?10⁹ CFU mL^–1), spore synthesis (from 1.5?×?10⁸ to 1.35?×?10⁹ CFU mL^–1) and endotoxin concentration (from 436 to 1170?μg mL^–1) when compared to SIW medium alone. The fermented broth was concentrated using continuous centrifugation and adjuvants were added for biopesticide formulation in order to enhance its resistance against UV rays and rainfastness. Entomotoxicity of the formulation produced using fermented broth of SIW fortified with soybean (38,000?IU μL^–1) was higher than that obtained by SIW medium alone (21,000?IU μL^–1), commercial biopesticide Foray 76B (20,000?IU μL^–1) and Btk sander’s (12,500?IU μL^–1).     

Voltammetric detection of trifluralin in tap water,fruit juice,and vegetable extracts in the presence of surfactants

This study describes a novel electrochemical method to determine the herbicide trifluralin in samples of water, fruit juice, and vegetable extracts in the presence of surfactants, using a glassy carbon electrode (GCE). In acidic media, trifluralin was irreversible on the glassy carbon electrode surface at ?0.5 V vs. Ag/AgCl. Surfactant presence on the electrode–solution interface modified current intensities and shifted the reduction peak potential of trifluralin. Different types of surfactant and their concentrations were investigated. The anionic surfactant significantly enhanced the peak current intensity of trifluralin. Under optimal analytical conditions, an analytical curve was obtained in the concentration range of 0.48–32.20 µM. The limits of detection and quantification were estimated at 0.031 and 0.104 µM, respectively. The method was successfully applied to quantify trifluralin in samples of water, orange and tomato juice, and green pepper, carrot, and onion extracts, with recovery rates of 97.9–102.1%. The results were in good agreement with those obtained using high-performance liquid chromatography, indicating that the proposed electrochemical method can be employed to quantify trifluralin in various types foods, with sensitivity, specificity, selectivity and reproducibility.     

Development of an enzyme-linked immunosorbent assay for atrazine monitoring in water samples

The implementation of the Water Framework Directive (2000/60/EC) requires the establishment of monitoring programs. However, conventional procedures for sample preparation prior to chromatographic analysis are rather expensive and time consuming, being the development of cost-effective and easy tool a necessity. The aim of this work was to develop an enzyme-linked immunosorbent assay (ELISA) able to determine atrazine in water samples. Matrix effects evaluation showed that the increase of humic acid (HA) concentration leads to flattened calibration curves and to the loss of the sigmoidal shape. However, such interference was overcome, by the presence of an environmental sample buffer, incubated together with the samples. Recoveries from 88.5 to 119.2 % were obtained in the presence of HA concentrations up to 20 mg?L^?1. An analytical range from 0.003 to 1 μg?L^?1 was obtained, and atrazine was detected in a sewage treatment plant with concentrations ranging from 14 to 52 ng?L^?1.     

Selenium,total mercury and methylmercury in sardine: Study of molar ratio and protective effect on the diet

The purpose of this work was to evaluate the risk-benefit associated with canned sardine consumption, considering the selenium, the mercury and the methylmercury contents and the Se:Hg molar ratio and the Se-health benefit value (HBV) index. In this study, 63 canned sardine samples were purchased worldwide and for the determination of selenium and mercury species, the inductively coupled plasma optical emission spectrometry and thermal decomposition and amalgamation atomic absorption spectrometry were employed. The mean results obtained for the Brazilian samples varied between 12.6 and 65.5?μg kg^?1 for Hg; <3.7 and 45.4?μg kg^?1 for methylmercury; 310 and 1370?μg kg^?1 for Se. The MeHg/Hg ratio showed that the most toxic forms of Hg (MeHg) is predominant in 52 and 39% of the Brazilian samples conserved in tomato sauce and in oil, respectively. Nevertheless, the Se-HBV index and the Hg:Se and Se:Hg molar ratios indicated that the selenium content in canned sardine samples is enough to provide a protective effect on the Hg species.     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

Occurrence and distribution of trifluralin,ethalfluralin, and pendimethalin in soils used for long-term intensive cotton cultivation in central Greece

In the present study, a soil monitoring program was undertaken in Greek cotton cultivated areas in 2012. Twenty-seven soil samples were collected from the entire Thessaly plain in early summer of 2012, corresponding to approximately three months (current use of pendimethalin), up to one year (for the banned ethalfluralin), and three years (for the also banned trifluralin), after the last dinitroaniline application. Low but not negligible levels of dinitroanilines were detected, ranging from 0.01 to 0.21 μg g^?1 d.w. for trifluralin and 0.01–0.048 μg g^?1 d.w. for pendimethalin, respectively. Trifluralin was the herbicide most frequently detected (44.4%). The high historic application of trifluralin and its high persistence and accumulation potential is in line with the abundance of the detected residues. The present data indicate that soil samples contain extractable residues of banned trifluralin, but based on the comparison of the theoretical PECplateau for trifluralin (0.277 µg g^?1) and the maximum Measured Environmental Concentration, it was concluded that the detected residues should be attributed to previous years’ application. The latter suggested the need for continual monitoring of the dinitroaniline family of pesticides, including the banned substances, aiming thus to an improved environmental profile for agricultural areas.     

Formation potentials of bromate and brominated disinfection by-products in bromide-containing water by ozonation

The ozonation involved in drinking water treatment raises issues of water quality security when the raw water contains bromide (Br^?). Br^? ions may be converted to bromate (BrO₃ ^?) during ozonation and some brominated disinfection by-products (Br-DBPs) in the following chlorination. In this study, the effects of ozone (O₃) dosage, contact time, pH, and Br^? and ammonia (NH₃-N) concentrations on the formation of BrO₃ ^? and Br-DBPs have been investigated. The results show that decreasing the initial Br^? concentration is an effective means of controlling the formation of BrO₃ ^?. When the concentration of Br^? was lower than 100 μg/L, by keeping the ratio of O₃ dosage to dissolved organic carbon (DOC) concentration at less than 1, BrO₃ ^? production was effectively suppressed. The concentration of BrO₃ ^? steadily increased with increasing O₃ dosage at high Br^? concentration (>900 μg/L). Additionally, a longer ozonation time increased the concentrations of BrO₃ ^? and total organic bromine (TOBr), while it had less impact on the formation potentials of brominated trihalomethanes (Br-THMFP) and haloacetic acids (Br-HAAFP). Higher pH value and the presence of ammonia may lead to an increase in the formation potential of BrO₃ ^? and Br-DBPs.     

Development of in-house ELISA for detection of chloramphenicol in bovine milk with subsequent confirmatory analysis by LC-MS/MS

This study was undertaken to develop and validate direct competitive ELISA for the determination of chloramphenicol residues in bovine milk. Antisera and an enzyme-tracer for chloramphenicol were prepared and used to develop an ELISA with inhibition concentrations, IC₂₀ and IC₅₀, of 0.09 and 0.44 ng mL^?1, respectively. Milk samples were spiked with standards equivalent to 0, 0.2, 0.3, 0.5, 1.0 &; 1.5 ng mL^?1 and extracted in methanol. The mean recoveries were found to be 73–100% with coefficient of variance 7–11%. The decision limit (CCα) and detection capability (CCβ) were calculated as 0.10 and 0.12 ng mL^?1, respectively. The results were found comparable with the commercial ELISA, having recoveries of 87 to 100%, CCα 0.09 ng mL^?1 and CCβ 0.12 ng mL^?1. As per Commission Decision 2002/657/EC, in-house ELISA was further validated by using LC-MS/MS. Mass spectral acquisition was done by using electrospray ionization in the negative ion mode applying single reaction monitoring of the diagnostic transition reaction for CAP (m/z 152, 194 and 257). The calibration curve showed good linearity in concentrations from 0.025 to 1.6 ng mL^?1 with correction coefficient 0.9902. The mean recoveries were found to be 88 to 100%. The CCα was calculated as 0.057 ng mL^?1 and CCβ 0.10 ng mL^?1. Since CCα and CCβ are less than half of the MRPL (0.15 ng mL^?1), the test was found suitable for screening and quantification of CAP residues in bovine milk samples. Results of surveillance studies indicated that out of 31 analyzed milk samples, 12.9% samples were found with CAP residues but only 3.2% samples were declared positive with maximum concentration 0.31 ng mL^?1, slightly above the MRPL.     

Development and validation of LC-MS/MS method for the determination of Ochratoxin A and its metabolite Ochratoxin α in poultry tissues and eggs

The objective of this study was to develop a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the determination of Ochratoxin A (OTA) and Ochratoxin α (OTα) in poultry tissues and eggs. The two toxins were extracted by a mixture of acetonitrile/water, purified with a reversed phase C18 solid phase extraction column (SPE) and determined by LC-MS/MS. The LC-MS/MS method performances were evaluated in terms of linearity in solvent and in matrix (ranged from 0.5 to 15.10 µg L^?1 for OTA and from 0.60 to 17.85 µg L^?1 for OTα), limit of detection (LOD), limit of quantitation (LOQ), specificity, accuracy and precision in repeatability conditions. Recovery experiments were performed by spiking poultry liver, kidney, muscle and eggs around 1 µg kg^?1 and 10 µg kg^?1. LODs were 0.27 and 0.26 µg kg^?1 while LOQs were fixed at 1.0 and 1.2 µg kg^?1 for OTA and OTα, respectively. Main recoveries for OTA ranged from 82 to 109% and for OTα ranged from 55 to 89%. The values of within-laboratory relative standard deviation (RSD_r) were equal to or below 20%. Considering the results obtained and that all analytical performance criteria were fulfilled, the new extraction and purification method developed for OTA and OTα determination in animal tissues and eggs was found appropriate for control laboratories and research activities designed to ensure food safety.     

Principal component analysis to assess the efficiency and mechanism for enhanced coagulation of natural algae-laden water using a novel dual coagulant system

A novel dual coagulant system of polyaluminum chloride sulfate (PACS) and polydiallyldimethylammonium chloride (PDADMAC) was used to treat natural algae-laden water from Meiliang Gulf, Lake Taihu. PACS (Al_n(OH)_mCl_3n-m-2k(SO₄)_k) has a mass ratio of 10 %, a SO₄ ^2?/Al₃ ⁺ mole ratio of 0.0664, and an OH/Al mole ratio of 2. The PDADMAC ([C₈H₁₆NCl]_m) has a MW which ranges from 5?×?10⁵ to 20?×?10⁵ Da. The variations of contaminants in water samples during treatments were estimated in the form of principal component analysis (PCA) factor scores and conventional variables (turbidity, DOC, etc.). Parallel factor analysis determined four chromophoric dissolved organic matters (CDOM) components, and PCA identified four integrated principle factors. PCA factor 1 had significant correlations with chlorophyll-a (r?=?0.718), protein-like CDOM C1 (0.689), and C2 (0.756). Factor 2 correlated with UV₂₅₄ (0.672), humic-like CDOM component C3 (0.716), and C4 (0.758). Factors 3 and 4 had correlations with NH₃-N (0.748) and T-P (0.769), respectively. The variations of PCA factors scores revealed that PACS contributed less aluminum dissolution than PAC to obtain equivalent removal efficiency of contaminants. This might be due to the high cationic charge and pre-hydrolyzation of PACS. Compared with PACS coagulation (20 mg L^?1), the removal of PCA factors 1, 2, and 4 increased 45, 33, and 12 %, respectively, in combined PACS–PDADMAC treatment (0.8 mg L^?1?+?20 mg L^?1). Since PAC contained more Al (0.053 g/1 g) than PACS (0.028 g/1 g), the results indicated that PACS contributed less Al dissolution into the water to obtain equivalent removal efficiency.     

Photolysis of atrazine in aqueous solution: role of process variables and reactive oxygen species

Photochemical advanced oxidation processes have been considered for the treatment of water and wastewater containing the herbicide atrazine (ATZ), a possible human carcinogen and endocrine disruptor. In this study, we investigated the effects of the photon emission rate and initial concentration on ATZ photolysis at 254 nm, an issue not usually detailed in literature. Moreover, the role of reactive oxygen species (ROS) is discussed. Photon emission rates in the range 0.87?×?10¹⁸–3.6?×?10¹⁸ photons L^?1 s^?1 and [ATZ]₀?=?5 and 20 mg L^?1 were used. The results showed more than 65 % of ATZ removal after 30 min. ATZ photolysis followed apparent first-order kinetics with k values and percent removals decreasing with increasing herbicide initial concentration. A fivefold linear increase in specific degradation rate constants with photon emission rate was observed. Also, regardless the presence of persistent degradation products, toxicity was efficiently removed after 60-min exposure to UV radiation. Experiments confirmed a noticeable contribution of singlet oxygen and radical species to atrazine degradation during photolysis. These results may help understand the behavior of atrazine in different UV-driven photochemical degradation treatment processes.     

Matrix effect in case of purification of oily waters by membrane separation combined with pre-ozonation

In the present study, oil in water emulsions (c_oil?=?100 ppm; d_{oil droplets}?<?2 μm) was purified with ozonation followed by microfiltration using polyethersulfone (PES) membrane (d_pore?=?0.2 μm). The effects of pre-ozonation on membrane microfiltration were investigated in detail both in case of ultrapure and model groundwater matrices, applying different durations (0, 5, 10, and 20 min) of pre-ozonation. Simultaneously, the effects of added inorganic water components on the combined method were investigated. Size distribution of oil droplets, zeta potentials, fluxes, and purification efficiencies were measured and fouling mechanisms were described in all cases. It was found that the matrix significantly affected the size distribution and adherence ability of oil droplets onto the membrane surface, therefore fouling mechanisms also were strongly dependent on the matrix. In case of low salt concentration, the total resistance was caused mainly by reversible resistance, which could be significantly reduced (eliminated) by pre-ozonation. In case of model groundwater matrix, nearly twice higher total resistance was measured, and irreversible resistance was dominant, because of the higher adhesion ability of the oil droplets onto the membrane surface. In this case, pre-ozonation resulted in much lower irreversible, but higher reversible resistance. Increased duration of pre-ozonation raised the total resistance and reduced the elimination efficiency (due to fragmented oil droplets and water soluble oxidation by-products) in both cases, therefore short pre-ozonation can be recommended both from economic and performance aspects.     

Aquatic biomonitoring of Giardia cysts and Cryptosporidium oocysts in peninsular Malaysia

An aquatic biomonitoring of Giardia cysts and Cryptosporidium oocysts in river water corresponding to five villages situated in three states in peninsular Malaysia was determined. There were 51.3 % (20/39) and 23.1 % (9/39) samples positive for Giardia and Cryptosporidium (oo)cysts, respectively. Overall mean concentration between villages for Giardia cysts ranged from 0.10 to 25.80 cysts/l whilst Cryptosporidium oocysts ranged from 0.10 to 0.90 oocysts/l. Detailed results of the river samples from five villages indicated that Kuala Pangsun 100 % (9/9), Kemensah 77.8 % (7/9), Pos Piah 33.3 % (3/9) and Paya Lebar 33.3 % (1/3) were contaminated with Giardia cysts whilst Cryptosporidium (oo)cysts were only detected in Kemensah (100 %; 9/9) and Kuala Pangsun (66.6 %; 6/9). However, the water samples from Bentong were all negative for these waterborne parasites. Samples were collected from lower point, midpoint and upper point. Midpoint refers to the section of the river where the studied communities are highly populated. Meanwhile, the position of the lower point is at least 2 km southward of the midpoint and upper point is at least 2 km northward of the midpoint. The highest mean concentration for (oo)cysts was found at the lower points [3.15?±?6.09 (oo)cysts/l], followed by midpoints [0.66?±?1.10 (oo)cysts/l] and upper points [0.66?±?0.92 (oo)cysts/l]. The mean concentration of Giardia cysts was highest at Kuala Pangsun (i.e. 5.97?±?7.0 cysts/l), followed by Kemensah (0.83?±?0.81 cysts/l), Pos Piah (0.20?±?0.35 cysts/l) and Paya Lebar (0.10?±?0.19 cysts/l). On the other hand, the mean concentration of Cryptosporidium oocysts was higher at Kemensah (0.31?±?0.19 cysts/l) compared to Kuala Pangsun (0.03?±?0.03cysts/l). All the physical and chemical parameters did not show significant correlation with both protozoa. In future, viability status and molecular characterisation of Giardia and Cryptosporidium should be applied to identify species and genotypes/subgenotypes for better understanding of the epidemiology of these waterborne parasites.     

Multiresidue determination of pesticides in tea by gas chromatography-tandem mass spectrometry

An efficient and reliable GC-MS/MS method for the multiresidue determination of pesticides in tea was developed by modifying the Japanese official multiresidue method. Sample preparation was carefully optimized for the efficient removal of coextracted matrix components. The optimal sample preparation procedure involved swelling of the sample in water; extraction with acetonitrile; removal of water by salting-out; and sequential cleanup by ODS, graphitized carbon black/primary secondary amine (GCB/PSA) and silica gel cartridges prior to GC-MS/MS analysis. The recoveries of 162 pesticides from fortified (at 0.01 mg kg^?1) green tea, oolong tea, black tea and matcha (powdered green tea) were mostly (95–98% of the tested pesticides) within the range of 70–120%, with relative standard deviations of <20%. Poor recovery of triazole pesticides was considered to be due to low recovery from the silica gel cartridges. The test solutions obtained by the modified method contained relatively small amounts of pigments, caffeine and other matrix components and were cleaner than those obtained by the original Japanese official multiresidue method. No interfering peaks were observed in the blank chromatograms, indicating the high selectivity of the modified method. The overall results suggest that the developed method is suitable for the quantitative analysis of GC-amenable pesticide residues in tea.     

Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978?r ²?r ²?-1 level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.     

Transformation of sulfaquinoxaline by chlorine and UV light in water: kinetics and by-product identification

Sulfaquinoxaline (SQX) is an antimicrobial of the sulfonamide class, frequently detected at low levels in drinking and surface water as organic micropollutant. The main goal of the present study is the evaluation of SQX reactivity during chlorination and UV irradiations which are two processes mainly used in water treatment plants. The SQX transformation by chlorination and UV lights (254 nm) was investigated in purified water at common conditions used for water disinfection (pH =?7.2, temperature =?25 °C, [chlorine] =?3 mg L^?1). The result shows a slow degradation of SQX during photolysis compared with chlorination process. Kinetic studies that fitted a fluence-based first-order kinetic model were used to determine the kinetic constants of SQX degradation; they were equal to 0.7?×?10^?4 and 0.7?×?10^?2 s^?1corresponding to the half time lives of 162 and 1.64 min during photolysis and chlorination, respectively. In the second step, seven by-products were generated during a chlorination and photo-transformation of SQX and identified using liquid chromatography with electrospray ionization and tandem mass spectrometry (MS-MS). SO₂ extrusion and direct decomposition were the common degradation pathway during photolysis and chlorination. Hydroxylation and isomerization were observed during photodegradation only while electrophilic substitution was observed during chlorination process.