A reversed phase high performance liquid chromatography method for the determination of fumonisins B1 and B2 in food and feed using monolithic column and positive confirmation by liquid chromatography/tandem mass spectrometry

The development of a reversed phase high performance liquid chromatography fluorescence method for the determination of the mycotoxins fumonisin B(1) and fumonisin B(2) by using silica-based monolithic column is described. The samples were first extracted using acetonitrile:water (50:50, v/v) and purified by using a C(18) solid phase extraction-based clean-up column. Then, pre-column derivatization for the analyte using ortho-phthaldialdehyde in the presence of 2-mercaptoethanol was carried out. The developed method involved optimization of mobile phase composition using methanol and phosphate buffer, injection volume, temperature and flow rate. The liquid chromatographic separation was performed using a reversed phase Chromolith(?) RP-18e column (100 mm × 4.6 mm) at 30 °C and eluted with a mobile phase of a mixture of methanol and phosphate buffer pH 3.35 (78:22, v/v) at a flow rate of 1.0 mL min(-1). The fumonisins separation was achieved in about 4 min, compared to approximately 20 min by using a C(18) particle-packed column. The fluorescence excitation and emission were at 335 nm and 440 nm, respectively. The limits of detections were 0.01-0.04 μg g(-1) fumonisin B(1) and fumonisin B(2), respectively. Good recoveries were found for spiked samples (0.1, 0.5, 1.5 μg g(-1) fumonisins B(1) and B(2)), ranging from 84.0 to 106.0% for fumonisin B(1) and from 81.0 to 103.0% for fumonisin B(2). Fifty-three samples were analyzed including 39 food and feeds and 14 inoculated corn and rice. Results show that 12.8% of the food and feed samples were contaminated with fumonisin B(1) (range, 0.01-0.51 μg g(-1)) and fumonisin B(2) (0.05 μg g(-1)). The total fumonisins in these samples however, do not exceed the legal limits established by the European Union of 0.8 μg g(-1). Of the 14 inoculated samples, 57.1% contained fumonisin B(1) (0.16-41.0 μg g(-1)) and fumonisin B(2) (range, 0.22-50.0 μg g(-1)). Positive confirmation of selected samples was carried out using liquid chromatography-tandem mass spectrometry, using triple quadrupole analyzer and operated in the multiple reaction monitoring mode.     

Analysis and study of the distribution of polar and non-polar pesticides in wastewater effluents from modern and conventional treatments

The analysis of a wide range of pesticides in wastewaters (WWs) undergoing different treatments (both modern and conventional) has been studied. The need for optimizing specific extraction methods for each WW effluent based on their physico-chemical characteristics has been considered. A distribution study was performed to establish if the filtration step before extraction is a correct procedure since pesticides can be more prone to be in the aqueous or the solid phase, depending on their hydrophobicity. This evaluation demonstrated that pesticides are distributed between the aqueous phase and the suspended particulate matter (SPM; e.g. pyrethroids are only found in the SPM). The proposed methodologies involved the determination of 39 polar and 139 non-polar pesticides using solid-phase extraction (SPE) and pressurized-liquid extraction (PLE) for the extraction of the aqueous phase and the SPM, respectively. Ultra high pressure liquid chromatography and gas chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS, GC-MS/MS) were used in the determination stage. WW samples from four different technologies were evaluated: membrane bioreactor, extended aeration, maturation pond and anaerobic pond. Validation data for the four effluents studied were generated, obtaining adequate precision values (estimated as % relative standard deviation, RSD) in almost all cases (<25%). The methods showed limits of detection at 0.01-0.20μgL(-1) and limits of quantification from 0.02 to 0.50μgL(-1). The proposed methods were applied to the analysis of real samples collected from an experimental WW treatment plant, detecting non-polar and polar pesticides at concentrations in the range 0.02-1.94μgL(-1) and 0.02-0.33μgL(-1), respectively.     

Difficulties in fumonisin determination: the issue of hidden fumonisins

In this paper, the results obtained by five independent methods for the quantification of fumonisins B₁, B₂, and B₃ in raw maize are reported. Five naturally contaminated maize samples and a reference material were analyzed in three different laboratories. Although each method was validated and common calibrants were used, a poor agreement about fumonisin contamination levels was obtained. In order to investigate the interactions among analyte and matrix leading to this lack of consistency, the occurrence of fumonisin derivatives was checked. Significant amounts of hidden fumonisins were detected for all the considered samples. Furthermore, the application of an in vitro digestion protocol to raw maize allowed for a higher recovery of native fumonisins, suggesting that the interaction occurring among analytes and matrix macromolecules is associative rather than covalent. Depending on the analytical method as well as the maize sample, only 37–68% of the total fumonisin concentrations were found to be extractable from the samples. These results are particularly impressive and significant in the case of the certified reference material, underlying the actual difficulties in ascertaining the trueness of a method for fumonisin determination, opening thus an important issue for risk assessment.     

Preparation of magnetic indole-3-acetic acid imprinted polymer beads with 4-vinylpyridine and β-cyclodextrin as binary monomer via microwave heating initiated polymerization and their application to trace analysis of auxins in plant tissues

Auxin is a crucial phytohormone for precise control of growth and development of plants. Due to its low concentration in plant tissues which are rich in interfering substances, the accurate determination of auxins remains a challenge. In this paper, a new strategy for isolation and enrichment of auxins from plant tissues was obtained by the magnetic molecularly imprinted polymer (mag-MIP) beads, which were prepared by microwave heating initiated suspension polymerization using indole-3-acetic acid (IAA) as template. In order to obtain higher selective recognition cavities, an enhanced imprinting method based on binary functional monomers, 4-vinylpyridine (4-VP) and β-cyclodextrin (β-CD), was adopted for IAA imprinting. The morphological and magnetic characteristics of the mag-MIP beads were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy and vibrating sample magnetometry. A majority of resultant beads were within the size range of 80-150μm. Porous surface morphology and good magnetic property were observed. Furthermore, the mag-MIP beads fabricated with 4-VP and β-CD as binary functional monomers exhibited improved recognition ability to IAA, as compared with the mag-MIP beads prepared with the individual monomer separately. Competitive rebinding experiment results revealed that the mag-MIP beads exhibited a higher specific recognition for the template than the non-imprinted polymer (mag-NIP) beads. An extraction method by mag-MIP beads coupled with high performance liquid chromatography (HPLC) was developed for determination of IAA and indole-3-butyric acid (IBA) in plant tissues. Linear ranges for IAA and IBA were in the range of 7.00-100.0μgL(-1) and 10.0-100.0μgL(-1), and the detection limits were 3.9 and 7.4μgL(-1), respectively. The analytical performance was also estimated by seedlings or immature embryos samples from three different plant tissues, pea, rice and wheat. Recoveries were in the range of 70.1-93.5%. The results show that the present imprinting method is a promising approach for preparation of selective adsorbents for sample preparation of auxin analysis in plant tissues.     

Development of a new and environment friendly hollow fiber-supported liquid phase microextraction using vesicular aggregate-based supramolecular solvent

Hollow fiber-based liquid phase microextraction (HF-LPME) using conventional solvents is limited by their relative instability and high volatility. The use of supramolecular solvents as a liquid membrane phase could overcome these inconveniences due to their negligible vapour pressure and high viscosity. In the present study, a novel and highly flexible method was developed based on supramolecular solvents constructed of vesicles of decanoic acid, which were used for the first time as a solvent in HF-LPME. This solvent is produced from the coacervation of decanoic acid aqueous vesicles by the action of tetrabutylammonium (Bu(4)N(+)). In this work, halogenated anilines as model compounds were extracted from water samples into a supramolecular solvent impregnated in the pores and also filled inside the porous polypropylene hollow fiber membrane. The extracted anilines were separated and determined by high-performance liquid chromatography. The technique requires minimal sample preparation time and toxic organic solvent consumption, and provides a significant advantage over conventional analytical methods. The important parameters influencing the extraction efficiency were studied and optimized utilizing two different optimization methods: one variable at a time and the Box-Behnken design. Under the optimum conditions, the preconcentration factors were in the range of 74 to 203. Linearity of the method was obtained in the range of 1.0-100 μg L(-1) with the correlation coefficients of determination (R(2)) ranging from 0.9901 to 0.9986. The limits of detection for the target anilines were 0.5-1.0 μg L(-1). The relative standard deviations varied from 3.9% to 6.0%. The relative recoveries of the three halogenated anilines from water samples at a spiking level of 20.0 μg L(-1) were in the range of 90.4-107.4%.     

Determination of fumonisins B1 and B2 in various maize products by a combined SAX + C18 column and immunoaffinity column

Fumonisins B1 and B2 were determined in 42 samples of different maize products from the Swedish market by 2 different methods based on cleanup steps using an immunoaffinity column and a combination of SAX + C18 columns, respectively. A simple "precipitation step" was included before the samples were added to the main column(s), giving less column clogging, fewer interfering peaks, and better recoveries for the different sample matrixes. Recovery, repeatability, and results from the survey showed comparable results with the methods. The limit of detection for both methods was 5 micrograms/kg for fumonisin B1 and 10 micrograms/kg for fumonisin B2. All 7 maize chips analyzed and 6 of 8 popcorn samples contained fumonisins (B1 + B2) with averages of 180 and 115 micrograms/kg, respectively. All other samples except a maize flour sample contained little or no fumonisins.     

Evaluation of comprehensive two-dimensional gas chromatography with micro-electron capture detection for the analysis of seven pesticides in sediment samples

A GC-μECD and a GC×GC-μECD method were developed for the analysis of pesticides in sediments. For 1D-GC, instrumental LOD and LOQ were found in the range from 0.60 to 2.31μgL(-1) and 1.83 to 5.62μgL(-1), respectively. For GC×GC method development two sets of columns were tested (DB-5/DB-17ms, and HP-50+/DB-1ms), and the best results were obtained with the set of columns DB-5/DB-17ms. Instrumental LOD and LOQ were found in the range from 0.08 to 1.07μgL(-1) and 0.25 to 3.23μgL(-1), respectively. The LOD for the GC×GC was about 36% lower than those obtained for the 1D-GC. Concentrations of 21.18μgkg(-1) through 1D-GC method and 3.34μgkg(-1) for GC×GC for trifloxystrobin were found in a sediment sample which was collected close to an area of rice plantation.     

Evaluating the performance of sampling plans to detect fumonisin B1 in maize lots marketed in Nigeria

Fumonisins are toxic and carcinogenic compounds produced by fungi that can be readily found in maize. The establishment of maximum limits for fumonisins requires the development of scientifically based sampling plans to detect fumonisin in maize. As part of an International Atomic Energy Agency effort to assist developing countries to control mycotoxin contamination, a study was conducted to design sampling plans to detect fumonisin in maize produced and marketed in Nigeria. Eighty-six maize lots were sampled according to an experimental protocol in which an average of 17 test samples, 100 g each, were taken from each lot and analyzed for fumonisin B1 by using liquid chromatography. The total variability associated with the fumonisin test procedure was measured for each lot. Regression equations were developed to predict the total variance as a function of fumonisin concentration. The observed fumonisin distribution among the replicated-sample test results was compared with several theoretical distributions, and the negative binomial distribution was selected to model the fumonisin distribution among test results. A computer model was developed by using the variance and distribution information to predict the performance of sampling plan designs to detect fumonisin in maize shipments. The performance of several sampling plan designs was evaluated to demonstrate how to manipulate sample size and accept/reject limits to reduce misclassification of maize lots.     

Hydrazone-based ligands for micro-solid phase extraction-high performance liquid chromatographic determination of biogenic amines in orange juice

Eight hydrazone-based ligands were synthesized, trapped in a silica sol-gel matrix, and were subsequently used in the micro-solid phase extraction (μ-SPE) of biogenic amines (BAs). The BAs investigated were tryptamine, phenylethylamine, putrescine, histamine, tyramine and spermidine. Prior to the extraction, dansyl chloride was added to the samples which were heated to 70°C for 10 min. The samples were extracted with μ-SPE, after which analytes were desorbed using acetonitrile via ultrasonication. The extracts were analysed by high performance liquid chromatography (HPLC) with ultraviolet detection. Of the eight ligands investigated as sorbents, benzophenone 2,4-dinitrophenylhydrazone was found to be the most promising. The enhanced π-π interaction between the analytes and the ligand facilitated the adsorption process. Under the most suitable extraction conditions, the method demonstrated good linearity with correlation coefficient of more than 0.985 over a concentration range of 1-50 μg L(-1). Satisfactory repeatability with relative standard deviations of 7.43-11.30% (n=3) were obtained. Detection limits ranged from 3.8 to 31.3 ng L(-1). The μ-SPE method exhibited lower recoveries (71.5-87.4%) when compared to the solid phase extraction technique (79.7-95.0%), but enrichment factors of 94-460 were obtained. The proposed μ-SPE-HPLC method was applied to the determination of BAs in orange juice purchased from local supermarkets, with satisfactory results. The orange juices were characterized by the presence of relatively high levels of putrescine (range, 550-2210 μg L(-1)) but tryptamine and phenylethylamine were not detected in any of the tested samples.     

Multipesticide residue analysis in maize combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry

A fast and simple gas chromatography-mass spectrometry (GC-MS) method for determination of forty-one pesticide residues in maize is introduced. The sample preparation involves liquid-liquid partitioning with acetonitrile in presence of anhydrous MgSO(4) and NaCl (QuEChERS) followed by dispersive liquid-liquid microextraction (DLLME) using carbon tetrachloride as extractive solvent and the extract obtained by QuEChERS as dispersive solvent. The main factors influencing DLLME efficiency including extractive solvent type and volume as well as the volume of dispersive solvent were evaluated in this study. The DLLME procedure effectively provides an enrichment of the extract and a cleanup of certain polar matrix components, which can maximize the sensitivity when a single quadrupole MS is used. For validation purposes, recoveries studies were carried out at two concentration levels, yielding recovery rates in the range 70-120% for 82% of the analytes. A good linearity and precision, with relative standard deviations generally below 20% were obtained for all forty-one pesticides. The limits of detection obtained were lower than 19 μg kg(-1) for more than 63% of the analytes. In two of a total of ten samples of maize, residues of lindane, tefluthrin, pirimicarb, folpet and bifenthrin were found, although at levels below the maximum limit established for this kind of samples.     

Design of an imprinted clean-up method for mycophenolic acid in maize

In the present work, the development of imprinted polymers selective towards mycophenolic acid and their application in food analysis are reported for the first time. To synthesize the molecularly imprinted polymer (MIP) 4-vinylpyridine and ethyleneglycol dimethacrylate were applied as functional monomer and cross-linker, respectively. Besides the toxin itself, the implementation of structural analogues as templates was evaluated. A molecularly imprinted solid-phase extraction (MISPE) procedure was designed for the selective clean-up of maize extracts. Binding experiments and Scatchard analysis indicated the presence of specific binding sites in the imprinted polymers. The imprinting effect varied along with the selected template. The dissociation constant (K(D)) of the higher affinity binding sites ranged from 0.8 μmol/l to 15.6 μmol/l, while the K(D) of the lower affinity binding sites was in the range of 138.5-519.3 μmol/l. The performance of the MIPs throughout the clean-up of spiked maize sample extracts was evaluated and compared with the results obtained when applying a non-imprinted polymer. Depending on the polymers and the spiked concentration, recoveries after MISPE and non-imprinted solid-phase extraction varied respectively from 49% to 84% and from 28% to 31%. The imprinted polymers were superior regarding matrix effect, limit of detection (LOD) and limit of quantification (LOQ). LOD ranged from 0.17 μg/kg to 0.25 μg/kg and LOQ varied from 0.57 μg/kg to 0.82 μg/kg. Analysis of 15 maize samples by liquid chromatography tandem mass spectrometry revealed that the MIPs could be excellent sorbents for clean-up of contaminated food samples.     

European intercomparison study for the determination of fumonisins in maize

Fumonisins are mycotoxins occurring largely in maize and maize products, which cause animal diseases, such as equine leukoencephalomalacia and porcine pulmonary edema, and may also induce liver cancer on experimental rats. The European Commission Standards, Measurements and Testing (SMT, formerly BCR) Programme, has sponsored a project to improve analytical methodologies for the determination of the two major fumonisins (fumonisin B1 and fumonisin B2) in maize materials. The project involved the following steps: i) the preparation of a blank and a maize material contaminated with fumonisins Bl and B2; ii) a preliminary study of the -irradiation conditions for sterilization; iii) homogeneity and stability studies of the maize materials; iv) an intercomparison study for fumonisins analysis in the above materials with the involvement of 24 European laboratories, most of which have national or international responsibilities for foodstuff and/or feedstuff quality control. Results of the intercomparison study are presented together with the homogeneity and stability data relevant to the maize materials.     

Development of a screening method for the determination of PCBs in water using QuEChERS extraction and gas chromatography-triple quadrupole mass spectrometry

A new method has been developed and validated for the simultaneous analysis of 11 polychlorinated biphenyls (PCBs), in water samples at trace levels by gas chromatography coupled to triple quadrupole mass spectrometry (GC-QqQ-MS/MS). Water samples were extracted by the QuEChERS (Quick Easy Cheap Effective Rugged and Safe) method. The QqQ analyzer acquired data in multiple reactions monitoring (MRM), permitting both quantification and confirmation in a single injection with a running time reduced up to 11.0 min. The effect of matrix interferences in extracts on analyte quantification and the identification of PCBs in water samples was deeply studied. The results showed that PCBs were prone to strong matrix interactions in water samples, and the quantification and identification of PCBs were highly affected by a matrix enhancement effect. To evaluate the performance of the method, validation experiments were carried out on water samples at three spiking levels (1.6, 8.0, 40.0 μg L(-1)). Recovery was in the range of 95 - 109% at 1.6 μg L(-1), 90 - 95% at 8.0 μg L(-1) and 97 - 102% at 40.0 μg L(-1), respectively. Precision values expressed as relative standard deviation (RSD) were lower than 15%. Linearity in the range of 0.5 - 50.0 μg L(-1) provided determination coefficients (R(2)) higher than 0.999 for all compounds. The limits of detection (LODs) for PCBs were ≤0.1 μg L(-1) and the limits of quantification (LOQs) ranged from 0.04 to 0.3 μg L(-1). The applicability of the proposed method to detect and quantify PCBs has been demonstrated in analyse of 15 real samples.     

Analysis of fumonisins B(1), B(2) and B(3) in corn-based baby food by pressurized liquid extraction and liquid chromatography/tandem mass spectrometry

A sensitive and reliable method using pressurized liquid extraction (PLE) and liquid chromatography (LC)/electrospray ionization (ESI) tandem mass spectrometry with a triple quadrupole (QqQ) analyzer has been developed for the analysis of fumonisin B(1) (FB(1)), fumonisin B(2) (FB(2)) and fumonisin B(3) (FB(3)) in corn-based baby foods. Influence of several extraction parameters that affect PLE efficiency such as temperature, pressure, solvent extraction, number of cycles and dispersant/clean-up agents were studied. The selected PLE operating method was: 3g of sample was packed into 11 ml stainless-steel cell and fumonisins were extracted with methanol at 40 degrees C, 34 atm in one cycle of 5 min at 60% flush. The analytes were ionized in ESI operating with positive ion mode and identified by selecting two monitoring transitions, permitting quantification and confirmation in a single injection. Recoveries ranged from 68% to 83% at fortification levels of 200 microg kg(-1) with relative standard deviation (RSD) from 4% to 12%. The limits of quantification were from 2 microg kg(-1) for FB(1) and FB(2), and 5 microg kg(-1) for FB(3), which are below the maximum residue level established by the European Union legislation in infant formulas. The proposed method was successfully applied to the analysis of twenty seven samples of baby food products collected from different markets, and one positive sample with a content of 15.9 microg kg(-1) for FB(1), 9.2 microg kg(-1)for FB(2) and 5.8 microg kg(-1) for FB(3) was obtained. Given the simplicity and potential of the proposed procedure, its application for safety control is recommended.     

Application of ionic-liquid supported cloud point extraction for the determination of microcystin-leucine-arginine in natural waters

A cloud point extraction method has been developed using an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate, BMiM PF(6)) for the determination of a widely studied cyanotoxin (microcystin leucine-arginine, MCLR) in natural waters. Extraction parameters such as sample pH, extraction temperature, extraction time, the amount of ionic liquid and the amount of extraction volume were investigated and optimized to achieve the maximum extraction efficiency. The results obtained indicated a good linearity with the correlation coefficient of 0.995 over the range of 0.5-50 μg L(-1). The relative standard deviation (RSD) of the method was 7.5% (n=6). The calculated method detection limit was 0.03 μg L(-1) (n=6). The practical applicability of the technique was demonstrated by analyzing water samples (n=9) collected from three different sites in local reservoirs.     

Analytical performances of a DNA-ligand system using time-resolved fluorescence for the determination of ochratoxin A in wheat

The analytical performances of a novel DNA-ligand system using the time-resolved fluorescence (TRF) response of ochratoxin A (OTA)-terbium-DNA aptamer interaction were tested for the quantitative determination of OTA in wheat. Wheat was extracted with acetonitrile/water (60:40, v/v) followed by clean-up through affinity columns containing a DNA-aptamer-based oligosorbent. Then, OTA was detected by TRF spectroscopy after reaction with a terbium fluorescent solution containing the DNA-aptamer probe. The entire procedure was performed in less than 30 min, including sample preparation, and allowed analysis of several samples simultaneously with a 96-well microplate reader. The average recovery from samples spiked with 2.5-25 μg kg(-1) OTA was 77%, with a relative standard deviation lower than 6% and a quantification limit of 0.5 μg kg(-1). Comparative analyses of 29 naturally contaminated (up to 14 μg kg(-1)) wheat samples using the aptamer-affinity column/TRF method or the immunoaffinity column/high-performance liquid chromatography method showed good correlation (r = 0.985) in the range tested. The trueness of the aptamer-based method was additionally assessed by analysis of two quality control wheat materials for OTA. The DNA-ligand system is innovative, simple and rapid, and can be used to screen large quantities of samples for OTA contamination at levels below the EU regulatory limit with analytical performances satisfying EU criteria for method acceptability.     

Voltammetric Determination of Arsenic with Modified Glassy Carbon Electrode

In this study, glassy carbon electrode modified with nano gold‐crystal violet film has been used to detect arsenite (As (III)) in a model system and in groundwater samples. The modified electrode was characterized by scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). Using voltammetric measuring technique, linear response was obtained in a concentration range of 2.0–22.0 μM. The arsenite concentrations in groundwater samples varied between 2.4 μM to 4.8 μM. The sensitivity of the modified electrode for As (III) detection was 5.6 μA/μM cm² and 0.8 μM concentration was found as lower limit of detection (LOD). The accuracy of the method was checked with standard method anodic stripping voltammetry (ASV). Groundwater samples were characterized with dynamic (DLS) and electrophoretic (ELS) light scattering measurements which have shown that particles present in different samples differ in size distribution and zeta potential which did not interfere with As (III) detection.     

Simultaneous determination of bisphenol A, triclosan, and tetrabromobisphenol A in human serum using solid-phase extraction and gas chromatography-electron capture negative-ionization mass spectrometry

This study aimed at optimizing and validating a sensitive method for simultaneous determination of bisphenol A (BPA), triclosan (TCS), and tetrabromobisphenol A (TBBPA) in human serum using solid-phase extraction (SPE) and gas chromatography coupled to electron-capture negative-ionization mass spectrometry (GC-ECNI/MS). Sample preparation involved denaturation of serum proteins with formic acid followed by SPE on an Oasis HLB cartridge. Fractionation was performed on Florisil from which the phenolic compounds were eluted with methanol-dichloromethane (DCM) (5:1, v/v). The phenolic fraction was further derivatized with pentafluoropropionic acid anhydride (30 min at 70 degrees C). Further liquid-liquid partitioning using hexane-DCM (4:1, v/v) and K(2)CO(3) 3% aqueous solution was used to eliminate excess reagent and acidic by-products formed during derivatization. The cleaned extract was injected into a GC-ECNI/MS system operated in selected ion monitoring mode. For thorough method validation, each step of the procedure was rigorously optimized. The method limits of quantitation for BPA, TCS, and TBBPA were 0.28 ng mL(-1), 0.09 ng mL(-1) and 0.05 ng mL(-1), respectively. Furthermore, the method was applied to 21 Belgian human serum samples. The median concentrations obtained for BPA (0.71 ng mL(-1)) and TCS (0.52 ng mL(-1)) in Belgian human serum samples were similar to previously reported data for human fluids. Slightly higher levels of TBBPA (0.08 ng mL(-1)) were found in Belgium samples compared to Norwegian serum.     

Determination of tridemorph and other fungicide residues in fruit samples by liquid chromatography-electrospray tandem mass spectrometry

A rapid and sensitive liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS-MS) method for the determination of tridemorph and other pre- and post-harvest fungicides (carbendazim, thiabendazole, imazalil, propiconazole and bitertanol) in banana and orange samples has been developed and validated. The sample preparation was a simple extraction step with acetone using a high-speed blender prior to the injection of the five-fold diluted extract into the LC system with no other previous sample pre-treatment. Quantification was carried out using a matrix matched calibration curve which was linear in the range of 1-100 ng ml(-1) for all the compounds. The limit of quantification was 0.05 mg kg(-1) for all studied compounds, whereas limits of detection ranged between 0.005 and 0.025 mg kg(-1) (0.01 mg kg(-1) for tridemorph). Recoveries for tridemorph from spiked banana and orange samples at 0.05 and 1 mg kg(-1) were satisfactory, with values between 83 and 99% and relative standard deviations (R.S.D.s) lower than 13% (n = 5). For the other fungicides, recoveries between 75 and 95% with R.S.D.s lower than 12% were obtained. The developed method has been applied to the determination of selected fungicides in real samples of bananas and oranges from different origin. Thiabendazole and imazalil have been detected in almost all orange samples analyzed, and in around of 30% of banana samples. Bitertanol residues exceeded the maximum residue level (0.05 mg kg(-1)) in three banana samples while tridemorph was only detected in one sample.     

Amino modified mesostructured silica nanoparticles for efficient adsorption of methylene blue

In this work, mesostructured silica nanoparticles (MSN(AP)) with high adsorptivity were prepared by a modification with 3-aminopropyl triethoxysilane (APTES) as a pore expander. The performance of the MSN(AP) was tested by the adsorption of MB in a batch system under varying pH (2-11), adsorbent dosage (0.1-0.5gL(-1)), and initial MB concentration (5-60mgL(-1)). The best conditions were achieved at pH 7 when using 0.1gL(-1) MSN(AP) and 60mgL(-1)MB to give a maximum monolayer adsorption capacity of 500.1mgg(-1) at 303K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Harkins-Jura isotherms and fit well to the Freundlich isotherm model. The adsorption kinetics was best described by the pseudo-second order model. The results indicate the potential for a new use of mesostructured materials as an effective adsorbent for MB.