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1.
The search on endocrine disrupting chemicals (EDCs) in non-fatty food was evaluated. A fast, high-throughput, accurate, multiresidue method for the analysis of selected EDC pesticides in fruit and vegetable food samples was developed. The QuEChERS technique was used for sample preparation. Fast GC-MS was performed with a narrow-bore capillary column and a quadrupole benchtop detector with electron ionization (EI) and negative chemical ionization (NCI). A part of the work was devoted to the comparison of NCI versus EI approach concerning the sensitivity of detection and to the study of selectivity enhancement in NCI mode. Matrix-matched standard solutions were utilized for calibration. The methods validation was performed. Fortification studies at 1, 5, 10 and 250?µg?kg?1 for 35 pesticides in EI mode and 0.1, 1, 5 and 250?µg?kg?1 for 28 pesticides in NCI mode were performed. Average recoveries for each fortification level ranged from 70 to 110% with >80% of recoveries between 90 and 110%. Limits of quantification (LOQs) were established at 5?µg?kg?1 for EI and at 1?µg?kg?1 for NCI mode, which is lower than the lowest maximum residue level (MRL) value set by the European Commission in fruit and vegetables. The developed and validated fast GC-MS method was successfully applied to the search of EDC pesticides at ultratrace concentration level in real fruit and vegetable samples in Slovakia. Thirty-four samples of 20 different commodities were analyzed. Seven samples contained residues of three or more EDCs pesticides.  相似文献   

2.
In the present work a new, simple, rapid and environmentally friendly dispersive liquid–liquid microextraction (DLLME) method has been developed for extraction/preconcentration of some triazole pesticides in aqueous samples and in grape juice. The extract was analyzed with gas chromatography–flame ionization detection (GC–FID) or gas chromatography–mass spectrometry (GC–MS). The DLLME method was performed in a narrow-bore tube containing aqueous sample. Acetonitrile and a mixture of n-hexanol and n-hexane (75:25, v/v) were used as disperser and extraction solvents, respectively. The effect of several factors that influence performance of the method, including the chemical nature and volume of the disperser and extraction solvents, number of extraction, pH and salt addition, were investigated and optimized. Figures of merit such as linearity (r2 > 0.995), enrichment factors (EFs) (263–380), limits of detection (0.3–5 μg L?1) and quantification (0.9–16.7 μg L?1), and relative standard deviations (3.2–5%) of the proposed method were satisfactory for determination of the model analytes. The method was successfully applied for determination of target pesticides in grape juice and good recoveries (74–99%) were achieved for spiked samples. As compared with the conventional DLLME, the proposed DLLME method showed higher EFs and less environmental hazards with no need for centrifuging.  相似文献   

3.
Decomposition of endocrine disrupting chemicals (EDCs) in wastewater was investigated by use of 60Co γ-ray. Estrogen activities of wastewaters were estimated by the yeast two-hybrid assay based on human or medaka estrogen receptors. The dose required for the elimination of estrogen activity of wastewater below 1 ng dm−3 was about 200 Gy (J kg−1). The elimination dose of the estrogen activity depended on the amounts of total organic carbons in wastewater. The economic cost of the treatment process of EDCs using electron beam was estimated at 17 yen m−3.  相似文献   

4.
In this study, a method employing ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS) was developed to simultaneously screen for 36 endocrine-disrupting chemicals (EDCs; e.g., estrogens, progestogens, phenols, and their metabolites) both in potable and river water. From the selected compounds, 21 target compounds, for which reference standards were available, were used as model compounds for method development and optimization. The other target compounds, for which reference standards were unavailable, were investigated in post-target analysis on the basis of their theoretical molecular masses. The solid-phase extraction and chromatographic separation steps were optimized. For this method, limits of detection for the target compounds were less than 0.72 ng L? 1, and the overall recoveries varied between 46% and 134% with relative standard deviations ranging from 7% to 35%. The mass errors between theoretical and experimental mass for all resulting precursor and characteristic fragment ions ranged from ? 1.9 to 2.8 mDa. The method developed was successfully used to analyze the composition of potable and river water in Shanghai City; in addition, some compounds of interest (estriol, estrone, and bisphenol A) were identified accurately. Further, a post-target analysis was performed and an estrogen metabolite was hypothesized in the water samples due to the excellent sensitivity of the method in full-spectrum acquisition mode and the valuable accurate mass information in MS and tandem MS mode. Therefore, UPLC-Q-TOF-MS has proven to be a powerful technique for wide-scope screening and identification of relevant EDCs in environmental water sources.  相似文献   

5.
Gas chromatography-mass spectrometry (GC-MS) with electron impact (EI), positive-ion chemical ionization (PCI) and negative-ion chemical ionization (NCI) were applied as confirmatory techniques for residue analysis of chlorotriazine pesticides, their degradation products and organophosphorus pesticides in soil samples. Clean-up was effected using a Florisil column with subsequent analysis by GC with a nitrogen-phosphorus detector. GC-MS with the EI mode of operation is the common mode of confirmation for all the pesticides. Further confirmation by either GC-MS with PCI and NCI for chlorotriazines and organophosphorus pesticides, respectively, is recommended. The method was applied to the determination of residue levels of atrazine, deethylatrazine, deisopropylatrazine, simazine, fenitrothion and tetrachlorvinphos in several soil samples at levels from 5 ng g?1 to 9 μg g?1.  相似文献   

6.
The study of pesticide residues belonging to endocrine disrupting chemicals (EDCs) (23 analytes of different chemical classes – organochlorines, organophosphates, pyrethroids, dicarboximides, phtalamides, dinitroanilines, pyrazole, triazinone) in apple matrix with conventional capillary GC–NCI-MS (with methane as reagent gas) in comparison to EI ionization is presented. For sample preparation QuEChERS method was applied. The lowest calibration levels (LCLs) for all pesticides were determined in both modes. Calibration in the NCI mode was performed at the concentration levels from 0.1 to 500 μg kg−1 (R2 > 0.999) and for EI in the range from 5 to 500 μg kg−1 (R2 > 0.99). From LCLs the instrumental limits of detection (LODs) and quantification (LOQs) were calculated. Chemometric study of pesticide signals in two MS modes was performed. Repeatability of all measurements, expressed by the relative standard deviations of absolute peak areas was better than 10% for the majority of compounds. Significantly lower values were obtained for the NCI mode.  相似文献   

7.
In this work, we present a new complete method using Surface Enhanced Raman Spectroscopy (SERS) and chemometrics for the qualitative and quantitative detection of pesticides by measuring the acetylcholinesterase (ACHE) activity. The Raman SERS is not only used for measuring the ACHE activity, but also for the direct detection of pesticides individually and for their identification. Gold nanoparticles (AuNPs) were used as dynamic SERS substrates for sensitive monitoring of ACHE activity in the presence of very low levels of organophosphate and carbamate pesticides, chemical warfare agents that are known to be ACHE inhibitors. The lowest detectable level for paraoxon was determined at 4.0 × 10−14 M and 1.9 × 10−9 M for carbaryl. The use of the enzyme allowed limits of detection for both pesticides that were much lower than the limits obtained by direct SERS analysis of the pesticides. The system shows a linear relationship between the intensity band at 639 cm−1 and pesticide concentration. These results suggest that this biosensor could be used in the future for the non-selective detection of all ACHE inhibitors at very low concentrations with possible identification of the inhibitor.  相似文献   

8.
Study of degradation of diazinon pesticide by 60Co gamma irradiation in a single aqueous solution was conducted on a laboratory scale and the effect of ionizing radiation on the removal efficiency of diazinon residues was investigated. Distilled water solutions at three different concentrations of targeted compound (i.e. 0.329, 1.643 and 3.286 μmol dm−3) were irradiated over the range 0.1–6 kGy. The initial concentration of contaminant and irradiation doses play a significant role in the rate of destruction; this was evident from the calculated decay constants of diazinon residue. Gamma radiolysis showed that the absorbed doses from 1.5 to 5.6 kGy at a dose rate of 4.79 kGy h−1 achieved 90% destruction for diazinon with initial concentrations over the range 0.329–3.286 μmol dm−3. The radiolytic degradation by-products and their mass balances were qualitative determined with good confidence by using GC/quadrupole mass spectrometry (GC/MS) with EI+ or CI in positive and negative ionization mode and diazinon degradation pathways were proposed. Additionally, the final products of irradiation were identified by ion chromatography (IC) to be acetic and formic acid.  相似文献   

9.
Measurements of (p, ρ, T) for{xNH3 +  (1   x)H2O} at x =  (1.0000, 0.8374, 0.6005, and 0.2973) and at specified temperatures and pressures in the compressed liquid phase were carried out with a metal-bellows variable volumometer between T =  310 K and T =  400 K at pressures up to 17 MPa. The results cover the high-density region from ρ =  345 kg · m  3 for x =  1.0000 to ρ =  878 kg · m   3for x =  0.2973. The experimental uncertainties at a 95 per cent confidence interval in temperature T, pressure p, density ρ, and mole fraction x were estimated to be less than  ± 11 mK,  ± 2.6 kPa,  ± 2.1 · 10   3. ρ, and  ± 1.8 · 10  3· x, respectively. A detailed comparison of the density values with literature data as well as with an equation of state proposed by Tillner-Roth and Friend is also reported.  相似文献   

10.
The analytical performance of a high transmission interface (S mode), inductively coupled plasma-quadrupole mass spectrometer (the VGE Plasma Quad 3) was evaluated for multitrace element analysis of geological and environmental materials. The sensitivity, limits of detection (LODs), effect of Ca and Na and other major elements on mass response, background, percentage 156CeO+/140Ce+, 70Ce++/140Ce+, and long- and short-term variations were compared with those obtained with the conventional mode (normal mode). Normal mode sensitivities varied from 20 MCPS ppm−1 (millions of counts per second per ppm) for 9Be+, 70–80 MCPS ppm−1 for 59Co+, 90 for 115In+ and 40–50 MCPS ppm−1 for the heavy masses. S mode sensitivities were 180 MCPS ppm−1 for 59Co+, 350–380 for 115In+ and 140Ce+, 300 MCPS ppm−1 for 208Pb+, and 150 MCPS ppm−1 for 232Th+ and 238U+, i.e. enhancements amounting to 7. Three σ normal and S mode LODs are mainly in the 1–2 and 0.1 ppt range, respectively. S mode LODs are enhanced relative to the normal mode, for masses >80 amu, by factors ranging from about 10 to 50. S mode LODs are depressed relative to normal mode LODs for masses <50 amu by a factor of 10, and the extent of depression is related linearly to mass. In the high- and mid-mass ranges, backgrounds were about 10. They were not affected by sample composition: at 8 amu the S mode background for real samples amounted to about 20, whereas at 220 amu it amounted to four counts. S and normal mode percentage 156CeO+/140Ce++ and percentage Ce++/Ce+ ratios were about 1.5%, and temporal variations were insignificant. The percentage RSDs of normal and S mode Sr+, Ag+ and Pb+ isotope ratios were about 0.1%, with the exception of S mode 208Pb+ and 208Pb+/206Pb+ ratios in the presence of NaCl, which were degraded by a factor of about 2. Normal and S mode long-term variations for continuous aspiration of 0.1% NaCl for periods of up to 13 h were mass dependent, varying from 2.5–4% for 7Li+ and 9Be+ to about 2% for the mid-mass range, increasing slightly to about 3% for high masses. Most of this variation occurred during the first 100–150 min of the analysis during cone priming. With compensation, normal and S mode long-term percentage RSDs and drift were reduced to 1–2%. These variations indicate that extended periods of S mode analysis can be conducted without periodic recalibration. A calibration procedure, based on spiked HNO3, was validated by analysing spiked NaCl solutions, standard water and geological standard reference material (SRM) solutions with internal standardization using conventional solution delivery and flow injection. The agreement of the S mode data and the certified and literature values for ultratrace elements, including ppt levels of rare earth elements in the water standards, was satisfactory. An important conclusion is that ion sampling effects in the S mode are minimal and that the enhanced ion transmission interface is not only beneficial for microanalysis using laser ablation, but for geological and environmental type solutions as well. Sensitivity enhancements were preserved and matrix effects were approximately ±20% for solutions containing 0.1–0.2% total dissolved salt concentration. These variations were reduced to <5% with internal standards matched in mass and ionization potential.  相似文献   

11.
A rapid, specific and sensitive multiresidue method based on dispersive solid phase extraction sample preparation and gas chromatography with the mass spectrometric detection for the analysis of 234 pesticides in Korean herbs (Acanthopanax senticosus, Morus alba L., Hovenia dulcis) has been developed. Method recoveries were found to be between 62 and 119% with relative standard deviation lower than 21% for all compounds in the concentration range of 0.05 to 0.400 mg kg? 1. Limits of quantification of most compounds are below 0.050 mg kg? 1. The data demonstrate that this method was successfully used for analysis of 234 pesticides in Korean herbs.  相似文献   

12.
Gradient-corrected (BP86) density-functional calculations were used to study the chemical bond between transition-metal complexes and N- and P-heterocyclic carbenes EHC (EHC = imidazolin-2-ylidene; 1,3-dimethylimidazolin-2-ylidene; 1,3-dihydro-1,3-diphosphol-2-ylidene; 1,3-dimethyl-1,3-diphosphol-2-ylidene). Forty two complexes of the type [M]  EHC, [M] = CuCl, AgCl, AuCl, BeCl+, Cu+, Ag+, Au+, have been studied. Both electrostatic contributions as well as π-back-donation are of special importance for the [M]  EHC bond. The metal–ligand bond strengths are comparable for NHC and PHC complexes. Whereas the former undergo stronger electrostatic interactions, the latter show a higher degree of π-bonding. When considering NHC and PHC as ligands for transition-metal-based catalysts, the results of the present study suggest that PHC both compete with NHC – in terms of metal-to-ligand bond strength – as well as complement NHC – in terms of the nature of the metal–ligand bond.  相似文献   

13.
Two clay minerals from the kaolin group, namely well-ordered kaolinite and poorly ordered halloysite, were investigated by terahertz time-domain spectroscopy (THz-TDS). Both clay samples were used for preparation of their respective intercalates using dimethyl sulfoxide (DMSO) and potassium acetate (KAc) with water. The intercalates were also characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The dielectric behaviour of clay samples was investigated in the far-infrared region of 0.2–2.7 THz corresponding to about 6.7–89.9 cm−1. The frequency dependence of the power absorption coefficient revealed clear absorption bands for DMSO intercalates but not for KAc with water. For kaolinite – DMSO intercalate a distinct doublet at 1.70 THz (56.6 cm−1) and 1.88 THz (62.6 cm−1), and for halloysite – DMSO intercalate a single broad band centred around 1.72 THz (57.3 cm−1) were found. These bands are reported for the first time in this type of intercalation substances and indicate the application potential of THz time-domain spectroscopy for use in the investigation and detection of chemical behaviour of molecular species introduced into the interlayer space of layered substances such as clays and clay minerals. Additionally, the qualitative characteristics of observed bands of DMSO intercalates in the THz region reasonably resembled the structural order/disorder of used kaolinite and halloysite samples.  相似文献   

14.
This work introduces the feasibility of using sugar cane bagasse (SCB) – a sugar cane industry waste – as a selective solid phase extractor for Fe(III). The order of metal uptake capacities in μmol g?1 for the extraction of six tested metal ions from aqueous solution using static technique is Fe(III) > Cu(II) > Pb(II) > Zn(II) > Cd(II) > Co(II). Since SCB exhibits remarkable binding characteristics for Fe(III), special interest was devoted for optimizing its uptake and studying its selectivity properties under static and dynamic conditions. In this respect, batch experiments were carried out at the pH range 1.0–4.0, initial concentration of metal ion (10–100 μmol), weight of phase (25, 50, 75, 100, 125 and 150 mg) and shaking time (10, 30, 45, 60, 90, 120 and 150 min). FT-IR spectra of SCB before and after uptake of Fe(III) were recorded to explore the nature of the functional groups responsible for binding of Fe(III) onto the studied natural biosorbent. The equilibrium data were better fitted with Langmuir model (r2 = 0.985) than Freundlich model (r2 = 0.934). Moreover, Fe(III) sorption was fast and completed within 60 min. The adsorption kinetics data were best fitted with the pseudo-second-order type. As a view to find a suitable application of SCB based on its unique property as a benign sorbent, it was found that, Fe(III) spiked natural water samples such as doubly distilled water (DDW), drinking tap water (DTW), natural drinking water (NDW), ground water (GW) and Nile River water (NRW) was quantitatively recovered (>95.0%) using batch and column experiments, with no matrix interferences.  相似文献   

15.
A sensitive and selective liquid chromatographic–tandem mass spectrometric (LC–MS–MS) method was developed to determine pantoprazole sodium (PNT) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C18 column (symmetry 3.5 μm; 75 mm × 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of acetonitrile–water (90:10, v/v). The method was linear over a concentration range of 1–100 ng mL?1. The lower limit of quantitation was 1 ng mL?1. The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was <10.5%. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ng mL?1 PNT) was within ±1.25% in terms of relative errors.  相似文献   

16.
In this paper we report an SFG/DFG investigation of the adsorption of CN? – used as a probe molecule to study the electrochemical double-layer structure – at a polycrystalline Au electrode in 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl) amide ([BMP][TFSA]) room-temperature ionic liquid (RTIL). The adsorption of CN? yielded single SFG and DFG bands in the range from ca. 2125 to 2135 cm?1, exhibiting a Stark tuning of ca. 3 cm?1 V?1. Vibrational resonances – corresponding to modes of the RTIL coadsorbed with CN?, were found in the range from ca. 1200 to 1500 cm?1. The study of the double-layer structure was complemented by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements, from which the differential double-layer capacity (CDL) was estimated.  相似文献   

17.
Dissociative ionization of 1,4-bis(2,5-phenyloxazolyl)benzene (POPOP) molecule by electron impact in gaseous phase is studied. Potentials of appearance of some fragments of the molecule under study are determined from the experimentally measured dependences of ionization cross-section on the ionizing electron energy. A new ion with m/z = 144 [C9H6ON]+ is detected in the mass spectrum of the POPOP molecule, being complementary to the fragment with m/z = 220 [C15H10ON]+. The threshold of appearance of this ion is determined (Eap = 9.51 eV) as well as the first ionization potential of the POPOP molecule and fragment ion appearance potentials.  相似文献   

18.
A 0D numerical approach including a Collisional-Radiative model is elaborated in the purpose of describing the behavior of the nascent plasma resulting from the interaction between a 4 ns/65 mJ/532 nm Q-switched Nd:YAG laser pulse and an aluminum sample in vacuum. The heavy species considered are Al, Al+, Al2+ and Al3+ on their different excited states and free electrons. The translation temperatures of free electrons and heavy species are assumed different (Te and TA respectively). Numerous elementary processes are accounted for as electron impact induced excitation and ionization, elastic collisions, multiphoton ionization and inverse Bremsstrahlung. Atoms passing from the sample to gas phase are described by using classical vaporization theory so that the surface temperature is arbitrarily limited to values less than the critical point one at 6700 K. The laser flux density considered in the study is therefore moderate with a fluence lower than 7 J cm? 2.This model puts forward the major influence of multiphoton ionization in the plasma formation, whereas inverse Bremsstrahlung turns out to be quasi negligible. The increase of electron temperature is mainly due to multiphoton ionization and Te does not exceed 10,000 K. The electron induced collisions play an important role during the subsequent phase which corresponds to the relaxation of the excited states toward Boltzmann equilibrium. The electron density reaches its maximum during the laser pulse with a value  1022, 1023 m? 3 depending highly on the sample temperature. The ionization degree is of some percents in our conditions.  相似文献   

19.
An ultra-preconcentration technique composed of solid-phase extraction (SPE) and dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–flame photometric detection (GC–FPD) was used for determination of thirteen organophosphorus pesticides (OPPs) including phorate, diazinon, disolfotane, methyl parathion, sumithion, chlorpyrifos, malathion, fenthion, profenphose, ethion, phosalone, azinphose-methyl and co-ral in aqueous samples. The analytes were collected from large volumes of aqueous solutions (100 mL) into 100 mg of a SPE C18 sorbent. The effective variables of SPE including type and volume of elution solvent, volume and flow rate of sample solution, and salt concentration were investigated and optimized. Acetone was selected as eluent in SPE and disperser solvent in DLLME and chlorobenzene was used as extraction solvent. Under the optimal conditions, the enrichment factors were between 15,160 and 21,000 and extraction recoveries were 75.8–105.0%. The linear range was 1–10,000 ng L?1 and limits of detection (LODs) were between 0.2 and 1.5 ng L?1. The relative standard deviations (RSDs) for 50 ng L?1 of OPPs in water with and without an internal standard, were in the range of 1.4–7.9% (n = 5) and 4.0–11.6%, respectively. The relative recoveries of OPPs from well and farm water sat spiking levels of 25 and 250 ng L?1 were 88–109%.  相似文献   

20.
We report the world smallest tubular solid oxide fuel cell – needle-type micro SOFCs applicable to micro power devices. The anode-supported cell was prepared using cost effective, conventional extrusion and dip-coating techniques. The diameter of the needle-type cell is 0.4 mm, consisting of NiO-Gd doped Ceria (GDC) for anode (under 100 μm thick), GDC for electrolyte (8 μm thick), and (La, Sr) (Co, Fe)O3 – GDC for cathode. The cell performances of 80, 160 and 300 mW cm−2 at 450 °C, 500 °C, and 550 °C, respectively, were obtained using a simple current collection method with wet H2 fuel. Impedance analysis indicated that the SOFC has a potential to be improved by optimizing the current collection method. Bundle concept using the SOFCs with the packing density of 100 cells in 1 cm3 was also proposed.  相似文献   

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