Simultaneous Determination of Imidacloprid,Thiacloprid, and Thiamethoxam in Soil and Water by High-performance Liquid Chromatography with Diode-array Detection

Abstract

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C₁₈ cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 ± 4.2% for thiamethoxam, 99 ± 4.2% for imidacloprid and 94 ± 1.4% for thiacloprid. The recoveries for water samples ranged from 87 ± 3.4% for thiamethoxam to 97 ± 3.9% for imidacloprid and 97 ± 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5 g), and 2, 2, 0.5 µg/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.     

Effects of the aflatoxins on ATPase activities in mouse and rat liver.

The effects of the aflatoxins on ATPase activities in mouse and rat tissues were investigated in vitro. The hepatic oligomycin-sensitive (O.S.) Mg++ ATPase was inhibited significantly. The order of inhibition was G1 greater than B1 greater than G2 greater than B2. Mouse O.S. Mg++ ATPase was more sensitive than the corresponding rat enzyme. The oligomycin-insensitive (O.I.) Mg++ ATPase activities in rat and mouse liver were not altered. Although aflatoxins G1 and B1 were more potent inhibitors of hepatic O.S. Mg++ ATPase, no concentration-response was observed, whereas aflatoxins G2 and B2 inhibited enzyme activity in a concentration-dependent manner. Spectral analysis of aflatoxin G1 solutions suggested that solubility was not related to the observed effects. In addition, the effects of aflatoxin B1 and G1 on mouse brain microsomal Na+-K+ ATPase were examined. Although aflatoxin B1 was more potent that G1, both mycotoxins significantly inhibited enzyme activity in a concentration-dependent fashion.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Occurrence of aflatoxin M1 in human milk samples in Vojvodina,Serbia: Estimation of average daily intake by babies

The objectives of the study were to determine the aflatoxin M1 content in human milk samples in Vojvodina, Serbia, and to assess the risk of infants' exposure to aflatoxins food contamination. The growth of Aspergillus flavus and production of aflatoxin B1 in corn samples resulted in higher concentrations of AFM1 in milk and dairy products in 2013, indicating higher concentrations of AFM1 in human milk samples in 2013 and 2014 in Serbia. A total number of 60 samples of human milk (colostrum and breast milk collected 4–8 months after delivery) were analyzed for the presence of AFM1 using the Enzyme Linked Immunosorbent Assay method. The estimated daily intake of AFM1 through breastfeeding was calculated for the colostrum samples using an average intake of 60 mL/kg body weight (b.w.)/day on the third day of lactation. All breast milk collected 4–8 months after delivery and 36.4% of colostrum samples were contaminated with AFM1. The greatest percentage of contaminated colostrum (85%) and all samples of breast milk collected 4–8 months after delivery had AFM1 concentration above maximum allowable concentration according to the Regulation on health safety of dietetic products. The mean daily intake of AFM1 in colostrum was 2.65 ng/kg bw/day. Results of our study indicate the high risk of infants' exposure, who are at the early stage of development and vulnerable to toxic contaminants.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Simultaneous determination of pesticides,mycotoxins, tropane alkaloids,growth regulators,and pyrrolizidine alkaloids in oats and whole wheat grains after online clean-up via two-dimensional liquid chromatography tandem mass spectrometry

In this study, a two-dimensional liquid chromatography tandem mass spectrometry method was developed and validated for the determination of pesticide residues and contaminants in whole wheat grains and oats. The samples were extracted with a mixture of acetonitrile and water and were injected into the two-dimensional LC-MS/MS system without any further clean-up or sample preparation. Samples were analyzed with four different matrix matched calibrations. Matrix effects were evaluated by comparing analyte signals in the respective matrix matched standard with the neat solvent standards. The final method was validated according to the current Eurachem validation guide and SANTE document. The number of successfully validated analytes throughout all three validation levels in oats and wheat, respectively, were as follows: 330 and 316 out of 370 pesticides, 6 and 13 out of 18 pyrrolizidine alkaloids and 7 out of 9 regulated mycotoxins. Moreover, both plant growth regulators mepiquat and chlormequat as well as the tropane alkaloids atropine and scopolamine met the validation criteria. The majority of pesticides showed limits of detection below 1?µg kg^?1, pyrrolizidine alkaloids below 0.7?µg kg^?1, tropane alkaloids below 0.2?µg kg^?1, growth regulators below 0.7?µg kg^?1 and mycotoxins below 8?µg kg^?1 in both matrices.     

Genotoxic potential of selected cytostatic drugs in human and zebrafish cells

Due to their increasing use, the residues of anti-neoplastic drugs have become emerging pollutants in aquatic environments. Most of them directly or indirectly interfere with the cell’s genome, which classifies them into a group of particularly dangerous compounds. The aim of the present study was to conduct a comparative in vitro toxicological characterisation of three commonly used cytostatics with different mechanisms of action (5-fluorouracil [5-FU], cisplatin [CDDP] and etoposide [ET]) towards zebrafish liver (ZFL) cell line, human hepatoma (HepG2) cells and human peripheral blood lymphocytes (HPBLs). Cytotoxicity was determined by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay and acridine orange/ethidium bromide staining. All three drugs induced time- and dose-dependent decreases in cell viability. The sensitivity of ZFL and HepG2 cells towards the cytotoxicity of 5-FU was comparable (half maximal inhibitory concentration (IC₅₀) 5.3 to 10.4 μg/mL). ZFL cells were more sensitive towards ET- (IC₅₀ 0.4 μg/mL) and HepG2 towards CDDP- (IC₅₀ 1.4 μg/mL) induced cytotoxicity. Genotoxicity was determined by comet assay and cytokinesis block micronucleus (CBMN) assay. ZFL cells were the most sensitive, and HPBLs were the least sensitive. In ZFL cells, induction of DNA strand breaks was a more sensitive genotoxicity endpoint than micronuclei (MNi) induction; the lowest effective concentration (LOEC) for DNA strand break induction was 0.001 μg/mL for ET, 0.01 μg/mL for 5-FU and 0.1 μg/mL for CDDP. In HepG2 cells, MNi induction was a more sensitive genotoxicity endpoint. The LOEC values were 0.01 μg/mL for ET, 0.1 μg/mL for 5-FU and 1 μg/mL for CDDP. The higher sensitivity of ZFL cells to cytostatic drugs raises the question of the impact of such compounds in aquatic ecosystem. Since little is known on the effect of such drugs on aquatic organisms, our results demonstrate that ZFL cells provide a relevant and sensitive tool to screen genotoxic potential of environmental pollutant in the frame of hazard assessment.     

Ultrasensitive determination of carbendazim in water and orange juice using a carbon paste electrode

A carbon paste electrode was used for the electrochemical quantification of carbendazim in water and orange juice samples. Carbendazim oxidation on the electrode surface was found to be controlled by adsorption. The novel electrochemical procedure for carbendazim quantification employed differential pulse voltammetry using a carbon paste electrode under optimal conditions. Carbendazim oxidation currents were linear at concentrations of 2.84 to 45.44 µg L^?1, with a limit of detection of 0.96 µg L^?1. The proposed method was applied to carbendazim quantification in ultrapurified water, river water, and orange juice. Recovery rates in water and orange juice samples were in the 97%–101% range, indicating that the method can be employed to determine carbendazim in these matrices, with advantages including shorter analysis time and lower cost than routine methods such as chromatography or spectroscopy. The electrode showed good reproducibility, remarkable stability, and especially good surface renewability by simple mechanical polishing. The recovery rates observed were highly concordant with those obtained for high-performance liquid chromatography, having a relative standard deviation of less than 1.3%.     

Simultaneous determination of estrogenic odorant alkylphenols,chlorophenols, and their derivatives in water using online headspace solid phase microextraction coupled with gas chromatography-mass spectrometry

A simple online headspace solid-phase microextraction (HS-SPME) coupled with the gas chromatography-mass spectrometry (GC-MS) method was developed for simultaneous determination of trace amounts of nine estrogenic odorant alkylphenols and chlorophenols and their derivatives in water samples. The extraction conditions of HS-SPME were optimized including fiber selection, extraction temperature, extraction time, and salt concentration. Results showed that divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most appropriate one among the three selected commercial fibers, and the optimal extraction temperature, time, and salt concentration were 70 °C, 30 min, and 0.25 g/mL, respectively. The developed method was validated and showed good linearity (R ²?>?0.989), low limit of detection (LOD, 0.002–0.5 μg/L), and excellent recoveries (76–126 %) with low relative standard deviation (RSD, 0.7–12.9 %). The developed method was finally applied to two surface water samples and some of these target compounds were detected. All these detected compounds were below their odor thresholds, except for 2,4,6-TCAS and 2,4,6-TBAS wherein their concentrations were near their odor thresholds. However, in the two surface water samples, these detected compounds contributed to a certain amount of estrogenicity, which seemed to suggest that more attention should be paid to the issue of estrogenicity rather than to the odor problem.     

Development and validation of HPLC methods for analysis of chlorantraniliprole insecticide in technical and commercial formulations

Effective, selective, precise and accurate liquid chromatographic analytical methods for the analysis of a novel chlorantraniliprole insecticide in technical and formulation (coragen, 20% SC) have been optimized and validated. Eight methods were designed based on different mobile phases, temperature and two HPLC columns. The mobile phase consists of two mixtures (acetonitrile:water, 70:30 and methanol:water, 70:30) with 25 or 40ºC. HPLC analysis of chlorantraniliprole was carried out at a wavelength of 260 nm, with a flow rate of 0.8 mL/min. The calibration curves showed a good linear relationship (R² ? 0.99) in the injected quantities ranged from 0.0125 to 1.00 μg. Limit of detection (LOD) was found to be 3.94 to 14.56 ng and from 5.95 to 12.93 ng using the analytical methods I to IV by MicroPack CN-10 and V-VIII by ZORBAX Eclips Plus C18 columns, respectively, based on SDslope values. ZORBAX Eclips Plus C18 column with method VI was the best one (R² = 1.00 and RSD = 0.30), short retention time (4.936 min), high theoretical plates per column (65457.15) compared to others and LOD = 6.49 ng. The accuracy of the best method was demonstrated by recovery rates of 83.04% to 98.50% for grape samples supplemented with 5, 10 and 50 mg chlorantraniliprole/kg.     

Occurrence of free estrogens,conjugated estrogens,and bisphenol A in fresh livestock excreta and their removal by composting in North China

An efficient pretreatment and analytical method was developed to investigate the occurrence and fate of four free estrogens (estrone (E1), 17β-estradiol (17β-E2), estriol (E3), and 17α-ethinylestradiol (EE2)), four conjugated estrogens (estrone-3-sulfate sodium salt (E1-3S), 17β-estradiol-3-sulfate sodium salt (E2-3S), estrone-3-glucuronide sodium salt (E1-3G), and 17β-estradiol-3-glucuronide sodium salt (E2-3G)), and bisphenol A (BPA) in three livestock farms raising beef cattle, cows, sheep, swine, and chickens in Qi County, which is located in North China. The results demonstrated that one cow and one beef cattle excreted 956.25–1,270.41 and 244.38–319.99 μg/day of total (free and conjugated) estrogen, respectively, primarily through feces (greater than 91 %), while swine excreted 260.09–289.99 μg/day of estrogens, primarily through urine (98–99 %). The total estrogen excreted in sheep and broiler chicken feces was calculated to be 21.64–28.67 and 4.62–5.40 μg/day, respectively. It was determined that conjugated estrogens contributed to 21.1–21.9 % of the total estrogen excreted in cow feces and more than 98 % of the total estrogen excreted in swine urine. After composting, the concentration of total estrogen decreased by 18.7–59.6 %; however, increased levels of BPA were measured. In treated compost samples, estrogens were detected at concentrations up to 74.0 ng/g, which indicates a potential risk of estrogens entering the surrounding environment.     

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

Packed in-tube solid phase microextraction with graphene oxide supported on aminopropyl silica: Determination of target triazines in water samples

On-line in-tube solid phase microextraction (in-tube SPME) coupled to high performance liquid chromatography and tandem mass spectrometry (HPLC-MS/MS) was successfully applied to the determination of selected triazines in water samples. The method based on the employment of a packed column containing graphene oxide (GO) supported on aminopropyl silica (Si) showed that the extraction phase has a high potential for triazines extraction aiming to its physical-chemical properties including ultrahigh specific surface area, good mechanical and thermal stability and high fracture strength. Injection volume and loading time were both investigated and optimized. The method validation using Si-GO to extract and concentrate the analytes showed satisfactory results, good sensitivity, good linearity (0.2–4.0 µg L^?1) and low detection limits (1.1–2.9 ng L^?1). The high extraction efficiency was determined with enrichment factors ranging from 1.2–2.9 for the lowest level, 1.3–4.9 intermediate level and 1.2–3.0 highest level (n = 3). Although the analytes were not detected in the real samples evaluated, the method has demonstrated to be efficient through its application in the analysis of spiked triazines in ground and mineral water samples.     

Study of spatial and temporal distribution of antimicrobial in water and sediments from caging fish farms by on-line SPE-LC-MS/MS

An on-line solid phase extraction liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) method for the determination of 12 antimicrobials in sediment and surface water was developed and validated. Furthermore, the spatial and temporal antimicrobials distributions in the sediment and in the water of four fish farms located in the hydroelectric dam of Ilha Solteira Reservoir in Brazil were investigated over four seasons in three sampling sites: at the fish cages, 100 and 1,000 m downstream far from the cages. The method was performed using an Agilent Zorbax 80 SB-C8 column (9.4 × 15 mm, 5 µm) as the loading column, and the Agilent Zorbax Eclipse Plus C18 column (3.0 × 100 mm, 3.5 µm) as a separation column within a run time of 13 min. The limits of quantification were less than 9 ng·L^?1 for the antibiotics in water and 16 µg·kg^?1 in sediment; the recovery ranged from 80 to 119%, with a variation coefficient less than 11%, and the repeatability was lower than 15%. Oxytetracycline was found in the water in all sample seasons. However, florfenicol was identified in April and October 2013 and January 2014, and tetracycline was present in July 2013. Regarding the sediment, oxytetracycline and tetracycline were found in all sampling periods, but chlortetracycline was only identified in January 2014. The spatial distribution of antimicrobials showed that the main pollution source came from the fish farms. This study demonstrated that the proposed method is reliable for the monitoring of antimicrobials in water and sediments and it showed contamination in both matrices from Ilha Solteira Reservoir.     

Quantification of ionophores in aged poultry litter using liquid chromatography tandem mass spectrometry

Veterinary anticoccidials, biochemically known as ionophores, are widely used in poultry feed at therapeutic levels to treat Coccidiosis and at sub-therapeutic levels for growth- promotion. Commonly used ionophores in the US poultry industry are monensin, salinomycin, lasalocid and narasin. There is an increasing concern regarding the persistence of these anticoccidials in the environment. However, little attention has been directed to methods development for quantitatively measuring ionophores in complex environmental matrices such as poultry litters that are land applied. Here, we describe a rapid and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS)-based method developed for simultaneous quantification of monensin, lasalocid, salinomycin, and narasin in aged poultry litter samples. Results show significant level of monensin (97.8 ± 3.2 μg kg^?1), lasalocid (19.2 ± 6.6 μg kg^?1), salinomycin (70 ± 2.7 μg kg^?1) and narasin (57.3 ± 2.6 μg kg^?1) in poultry litter stored for over three years at < 5°C. Our findings indicate that even after several years of unmanaged storage of poultry litter, ionophores may continue to persist in this matrix, raising the possibility of prolonged release into the environment.     

Urinary concentrations of trichlorophenols in the Korean adult population: results of the National Human Biomonitoring Survey 2009

Trichlorophenols such as 2,4,5-trichlorophenol (2,4,5-TCP) and 2,4,6-trichlorophenol (2,4,6-TCP) are organochlorine compounds to which the general public can be exposed via contaminated food, water, and air. This study assessed exposure to 2,4,5-TCP and 2,4,6-TCP in Koreans age 18–69 years based on the Korean National Human Biomonitoring Survey conducted in 2009. Using data from 1,865 representative Koreans, we found that the geometric mean urinary concentrations of 2,4,5-TCP and 2,4,6-TCP were 83.4 pg/mL [95 % confidence interval (CI)?=?78.6–88.6] and 0.39 ng/mL (95 % CI?=?0.35–0.42), respectively. The creatinine-adjusted geometric mean 2,4,5-TCP and 2,4,6-TCP levels were 78.8 ng/g creatinine (95 % CI?=?73.8–84.1) and 0.36 μg/g creatinine (95 % CI?=?0.33–0.40), respectively. Of the Korean adult population, about 67.5 and 87.5 % had respective urine 2,4,5-TCP and 2,4,6-TCP concentrations >0.05 ng/mL (the limit of detection, LOD). Urine 2,4,5-TCP concentrations were significantly associated with age and place of residence, whereas urine 2,4,6-TCP concentrations were higher in rural residents. These findings suggest that most Koreans had detectable levels of 2,4,5-TCP and 2,4,6-TCP in their urine and that the body burden of 2,4,5-TCP and 2,4,6-TCP varied according to demographic and geographic factors.     

Polycyclic aromatic hydrocarbon contamination in an urban area assessed by Quercus ilex leaves and soil

We investigated the PAH contamination of Naples urban area, densely populated and with high traffic flow, by analyses of environmental matrices: soil and Quercus ilex leaves. Being some PAHs demonstrated to have hazardous effects on human health, the accumulation of carcinogenic and toxic PAHs (expressed as B(a)Peq) was evaluated in the leaves and soil. The main sources of the PAHs were discriminated by the diagnostic ratios in the two matrices. The urban area appeared heavily contaminated by PAHs, showing in soil and leaves total PAH concentrations also fivefold higher than those from the remote area. The soil mainly accumulated heavy PAHs, whereas leaves the lightest ones. Median values of carcinogenic PAH concentrations were higher in soil (440 ng g^?1 d.w.) and leaves (340 ng g^?1 d.w.) from the urban than the remote area (60 and 70 ng g^?1 d.w., respectively, for soil and leaves). Also, median B(a)Peq concentrations were higher both in soil and leaves from the urban (137 and 63 ng g^?1 d.w., respectively) than those from the remote area (19 and 49 ng g^?1 d.w., respectively). Different from the soils, the diagnostic ratios found for the leaves discerned PAH sources in the remote and urban areas, highlighting a great contribution of vehicular traffic emission as main PAH source in the urban area.     

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.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.