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1.
In this research, magnetic Fe3O4 nanoparticles were synthesised by co-precipitation method and modified with polythiophene (PT) to produce Fe3O4-PT nanoparticles for preconcentration and determination of cadmium (??) ion followed by electrothermal atomic absorption spectrometry. The results of FT-IR spectroscopy, EDX analysis and SEM images show that Fe3O4-PT nanoparticles were synthesised successfully. Different parameters such as sample pH, amounts of adsorbent, sample volume, extraction time, type and concentration of eluent and desorption time were completely investigated and optimum conditions were selected.

Under the optimum conditions, the calibration curve was linear in the range of 0.01–0.25 µg L?1 of cadmium (??). The relative standard deviation was 4.7% (n = 7, 0.10 µg L?1 Cd2+) and limit of detection was 3.30 ng L?1. The accuracy of the proposed method was verified by the analysis of a certified reference material and spike method. Finally, the proposed method was applied for the determination of ultra-trace levels of cadmium (??) in different water and food samples.  相似文献   

2.
《Analytical letters》2012,45(10):1759-1771
A robust gold-coated solid-phase microextraction fiber was rapidly prepared on an etched stainless-steel wire based on chemical deposition. Gold(III) was reduced to produce a mechanically robust fiber with a stable coating. Subsequently, it was applied for solid-phase microextraction of five polycyclic aromatic hydrocarbons in water samples coupled to high performance liquid chromatography with an ultraviolet-visible detector. The preconcentration conditions were optimized, including extraction and desorption time, temperature, stirring rate, and ionic strength. Under the optimized conditions, the calibration graphs were linear in the range from 1 to 500 µg · L?1 for naphthalene and 0.20–500 µg · L?1 for phenanthrene, anthracene, fluoranthene, and pyrene. Limits of detection were between 0.016 and 0.22 µg · L?1 (signal-to-noise ratio = 3). The analysis of water samples showed that the recoveries ranged from 86.0% to 112.9% with relative standard deviations between 2.03% and 11.7%. The fiber coating was sensitive and suitable for the preconcentration and determination of polycyclic aromatic hydrocarbons in environmental waters. Compared with previously reported solid-phase microextraction methods, this device offered easy preparation, low cost, resistance to organic solvents, good stability, and high durability.  相似文献   

3.
The occurrence of 26 commonly used cytostatic compounds in wastewaters was evaluated using an automated solid-phase extraction (SPE) method with liquid chromatography–high-resolution mass spectrometry (LC–HRMS). Detection was optimized using Oasis HLB SPE cartridges at pH 2. Two hospital effluents and their two receiving wastewater treatment plants were sampled over five days. In hospital effluents, eight cytostatics were detected at levels up to 86.2 μg L?1 for ifosfamide, 4.72 μg L?1 for cyclophosphamide, and 0.73 μg L?1 for irinotecan, the three most relevant compounds identified. Cyclophosphamide and megestrol acetate were found in wastewaters at concentrations up to 0.22 μg L?1 for the latter. The predicted environmental concentrations (PEC) in sewage effluents of ifosfamide (2.4–4.3 ng L?1), capecitabine (11.5–14.2 ng L?1), and irinotecan (0.4–0.6 ng L?1), calculated from consumption data in each hospital, published excretion values for the target compounds, and wastewater elimination rates, were in agreement with experimental values.  相似文献   

4.
A simple method for determination of polycyclic aromatic hydrocarbons (PAHs) in water using headspace solid-phase microextraction (HS-SPME) with gas chromatography-flame ionisation detector (GC-FID) was developed. In order to obtain the convenient experimental conditions for HS-SPME extraction an experimental design with two steps was accomplished. A 26-2 fractional factorial design and central composite design (CCD) considering three significant factors were used. Naphthalene, anthracene and fluoranthene were chosen as representatives of two, three and four aromatic rings, and the global response of three PAHs was used for the results, evaluation. The chosen extraction conditions were: 85 μm polyacrylate fibre; 50 °C temperature; 60 min time; 20 mL-dissolution volume (in 40 mL glass vial); without salt addition; and 2 min desorption time. The procedure was extended to other seven PAHs (acenaphthylene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene and benzo(a)anthracene) and the analytical characteristics were checked. The limit of detection (LOD) was from 0.08 (anthracene) to 0.20 μg L?1 (naphthalene). The precision expressed as relative standard deviation (RSD in %) using 50 μg L?1 of each analyte ranged from 6.8 to 17 %. The method was applied to the analysis of the surface waters and leaching waters of contaminated soils from Gipuzkoa (North Spain). The PAHs were not detected in surface water samples. Most of the PAHs were found in the leachates from contaminated soils showing a maximum global value of 75.5 μg L?1.  相似文献   

5.
We present a method for the separation and determination of transition metals in electrolytes based on ion chromatography (IC) with post-column reaction (PCR) and serial conductivity and spectrophotometric detection. Three IC columns [Metrosep C4—250/4.0 (column A), Metrosep C6—250/4.0 (column B), and Nucleosil 100-5SA—250/4.6 (column C)] with different capacities, and stationary phases were used and compared with each other for method development. All spectrophotometric measurements were carried out with 4-(2-pyridylazo)resorcinol (PAR) as PCR reagent at a wavelength of 500 nm. To characterize the precision of the separation, the selectivity for the analysis of transition metals (nickel, cobalt, copper, and manganese) in the presence of large amounts of lithium and the resolution of the peaks were determined and compared with one another. Furthermore, the limits of detection (LOD) and quantification (LOQ) were determined for the transition metals. The LODs and LOQs determined by column C were as follows: cobalt (LOD/LOQ): 9.4 µg L?1/31.3 µg L?1, manganese (LOD/LOQ): 7.0 µg L?1/23.5 µg L?1, and nickel (LOD/LOQ): 6.3 µg L?1/21.1 µg L?1. Finally, the concentration of transition metal dissolution of the cathode material Li1Ni1/3Co1/3Mn1/3O2 (NCM) was investigated for different charge cut-off voltages by the developed IC method.  相似文献   

6.
A sensitive, economic, rapid and simple method for the determination of four N-methylcarbamate pesticides: methomyl (2.0–80 μg L?1), aldicarb (5.0–50 μg L?1), butocarboxim (2.0–60 μg L?1) and oxamyl (2.0–60 μg L?1); is reported. It relies on the coupling of photoinduced chemiluminescence (PICL) detection with flow injection (FI) methodology. The automation of FI together with the use of light as a reagent decreased the environmental impact of the analysis. The proposed method was based on the oxidation of these pesticides, previously irradiated on-line with UV light, with cerium(IV), using quinine as a sensitiser. Limits of detection below the legal limits (100 ng L?1) established by the European Union for drinking waters were obtained without the need of preconcentration steps. A good inter-day reproducibility (1.6–6.4%, n = 5), repeatability (rsd = 2.7 %, n = 25) and high throughput (123 h?1) were achieved. The method was successfully applied to the determination of methomyl in natural waters with mean recoveries ranging from 90% to 98%.  相似文献   

7.
Seven heavy polycyclic aromatic hydrocarbons (PAHs) of concern on the US Environmental Protection Agency priority pollutant list (benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-c,d]-pyrene) were simultaneously analyzed in extra virgin olive oil. The analysis is based on the measurement of excitation–emission matrices on nylon membrane and processing of data using unfolded partial least-squares regression with residual bilinearization (U-PLS/RBL). The conditions needed to retain the PAHs present in the oil matrix on the nylon membrane were evaluated. The limit of detection for the proposed method ranged from 0.29 to 1.0 μg kg?1, with recoveries between 64 and 78 %. The predicted U-PLS/RBL concentrations compared favorably with those measured using high-performance liquid chromatography with fluorescence detection. The proposed method was applied to ten samples of edible oil, two of which presented PAHs ranging from 0.35 to 0.63 μg kg?1. The principal advantages of the proposed analytical method are that it provides a significant reduction in time and solvent consumption with a similar limit of detection as compared with chromatography.
Figure
The excitation-emission fluorescence spectroscopy on nylon membranes, associated with U-PLS/RBL, is a useful tool for resolving a mixture of PAHs in the presence of a complex matrix such as that of edible oils.  相似文献   

8.
This paper presents a trisolvent ultrasonic extraction and HPLC analysis method for the determination of 11 polycyclic aromatic hydrocarbons in air particulate collected on an air filter by a commercial high volume air sampler. A reverse phase column, Vydac 201 TP, and a gradient mobile phase, acetonitrile/water, were used. The 11 PAHs, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a, h]anthracene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene were completely resolved under experimental conditions. All the PAHs except coronene were monitored by fluorescence with λex=270 nm, λem>389 nm. Coronene was monitored by UV with λ=300 nm. The methodology was evaluated by spiking SRM 1649 with a PAH standard and then going through different extraction procedures and analyzing the PAH concentrations without clean-up. An external standard method was used for quantitation. The recovery yields for fluoranthene, benz[a]anthracene, benzo[a]pyrene, benzo[ghi]perylene and indeno[l,2,3-cd]pyrene were above 90%. The detection limits of PAH with fluorescence at λex=270 nm, λem>389 nm ranged from 5.7 pg to 69.5 pg.  相似文献   

9.
A simple and sensitive method was developed for the determination of three nonsteroidal anti-inflammatory drugs (NSAIDs)—ibuprofen, naproxen and fenbufen in human plasma. The method involved in column liquid chromatographic separation and chemilumenescence (CL) detection based on the CL reaction of NSAIDs, potassium permanganate (KMnO4) and sodium sulfite (Na2SO3) in sulfuric acid (H2SO4) medium. The chromatographic separation was carried out using a reversed-phase C18 column, which allowed the selective determination of the three medicines in the complicated samples. The special features of the CL detector provided lower LOD for determination than that of existing chromatographic alternatives. The results indicated that the linear ranges were 0.01–10.0 μg mL?1 for ibuprofen, 0.001–1.0 μg mL?1 for naproxen, and 0.01–10.0 μg mL?1 for fenbufen. The limits of detection were 0.5 ng mL?1 for ibuprofen, 0.05 ng mL?1 for naproxen and 0.5 ng mL?1 for fenbufen (S/N = 3). All average recoveries were in the range of 90.0–102.3%. Finally, the method had been satisfactorily applied for the determination of ibuprofen, naproxen and fenbufen in human plasma samples.  相似文献   

10.
《Analytical letters》2012,45(9):1430-1441
A new column loaded with modified silica gel-chitosan is proposed as a preconcentration system for adsorption of trace cadmium (II) and copper (II). The optimization steps were performed under dynamic conditions, involving pH, sample flow rate, eluent selection, concentration, volume, and flow rate. Trace Cd(II) and Cu(II) were quantitatively adsorbed by the modified silica gel-chitosan. The metal ions adsorbed on the separation column were eluted with 0.1 M HNO3 and determined by flame atomic absorption spectrometry. Under the optimum conditions, this method allowed the determination of cadmium and copper with limits of detection (LOD) of 20 ng L?1 and 38 ng L?1, respectively. The relative standard deviation values (RSDs) for 1.0 mg L?1 of cadmium and 1.0 mg L?1 of copper were 2.62% and 2.85%, respectively.  相似文献   

11.
This study reported for the first time the use of cholesterol-functionalized magnetic nanoparticles (Fe3O4@SiO2@Chol) for the determination of polycyclic aromatic hydrocarbons (PAHs) in traditional Chinese medicine samples (TCMs) by high performance liquid chromatography (HPLC) coupled with fluorescence detection. The method was efficient, environmentally friendly, and fast. The solvent consumption of the proposed column is only half of the conventional column but with higher efficiency. Influencing factors, including sorbent amount, desorption solvent, sample volume and extraction time, were investigated in detail. Under the optimum conditions, good linearity (R2 > 0.991) was obtained over the range of 5–400 ng g−1, with limits of detection (LOD) 0.75, 0.50, 1.0, 0.56, 0.60, 0.84 and 0.80 ng g−1 for anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene, respectively.  相似文献   

12.
In the present study, the solid–liquid extraction with low temperature purification was validated for the determination of 16 polycyclic aromatic hydrocarbons from sewage sludge by gas chromatography-mass spectrometry. Recoveries ranged 70–114% for naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene and chrysene, while the compounds benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene showed recoveries of between 40 and 70%. The relative standard deviation was less than 13% for all of the compounds. Negative matrix effect was observed on the 10 compounds with less retention time in the chromatographic analysis and positive matrix effect noticed on the others. The limits of quantification were from 2 to 20 μg kg?1, about 30 times less than the maximum residue limit allowed in sludge by the European Union. The validated method produced quantification of 11 PAHs in one sludge sample at concentrations ranging 20–2000 μg kg?1.  相似文献   

13.
《Analytical letters》2012,45(17):2747-2757
Abstract

Brazilian sugarcane spirits were analyzed to elucidate similarities and dissimilarities by principal component analysis. Nine aldehydes, six alcohols, and six metal cations were identified and quantified. Isobutanol (LD 202.9 µg L?1), butiraldehyde (0.08–0.5 µg L?1), ethanol (39–47% v/v), and copper (371–6068 µg L?1) showed marked similarities, but the concentration levels of n-butanol (1.6–7.3 µg L?1), sec-butanol (LD 89 µg L?1), formaldehyde (0.1–0.74 µg L?1), valeraldehyde (0.04–0.31 µg L?1), iron (8.6–139.1 µg L?1), and magnesium (LD 1149 µg L?1) exhibited differences from samples.  相似文献   

14.
A novel non-chromatographic method for the pre-concentration and determination of trace methyl mercury in water samples has been proposed. This method included two main steps: (1) The methyl mercury in sample solution was adsorbed on PDMS of the Fe/SiO2/PDMS bed enrichment column; (2) the analyte was thermally desorbed from the enrichment column and pyrolysed to Hg0 in an iron particle bed pyrolysis column by using electromagnetic induction heating technique, and then detected by an on-line coupled atomic fluorescence detector. Several factors affecting the enrichment column preparation and concentration procedure have been investigated and optimised. Under optimal condition, the detection limit (3σ) was 0.2 ng L–1, along with relative standard deviations of 2.4% (10 ng L–1, N = 11) for the repeatability study. The enrichment factor obtained was 108. The two standard reference materials (GBW08675, GBW10029) were analysed to validate the present method. This method was successfully applied to the determination of ng L–1 methyl mercury in water samples.  相似文献   

15.
《Analytical letters》2012,45(16):2593-2605
A method was developed for the determination of vitamin B12 based on the enhancement of cobalt (II) on the chemiluminescence (CL) reaction between luminol and percarbonate (powerful source of hydrogen peroxide). The release of cobalt (II) from the vitamin B12 was reached by a simple and fast microwave digestion (20 s microwave digestion time and a mix of nitric acid and hydrogen peroxide). A charge coupled device (CCD) photodetector, directly connected to the cell, coupled with a simple continuous flow system was used to obtain the full spectral characteristics of cobalt (II) catalyzed luminol-percarbonate reaction.

The optima experimental conditions were established: 8.0 m mol L?1 luminol in a 0.075 mol L?1 carbonate buffer (pH 10.0) and 0.15 mol L?1 sodium percarbonate, in addition to others experimental parameters as 0.33 mL s?1 flow rate and 2 s integration time, were the experimental conditions which proportionate the optimum CL emission intensity. The emission data were best fitted with a second-order calibration graph over the cobalt (II) concentration range from 4.00 to 300 µ g L?1 (r2 = 0.9990), with a detection limit of 0.42 µ g L?1. The proposed method was successfully applied to the determination of vitamin B12 in pharmaceuticals.  相似文献   

16.
A new solid substrate-room temperature phosphorescence (SS-RTP) quenching method for the determination of trace As(V) has been developed, based on the facts that 9-hydroxy-2,3,4,9-tetrahydro-1,10-anthraquinone (R) can emit intense and stable SS-RTP on solid substrate, and α,α'-dipyridyl can activate As(V) catalysis of the reaction of H2O2 oxidizing R to non-phosphorescence compound R', which can cause the sharp quenching of SS-RTP. Under the optimum condition, the relationship between the ΔIp of the emitting intensity and 1.60-160 fg·spot^-1 As(V) (corresponding concentration: 0.0040-0.40 ng·mL^-1, sample volume: 0.4 μL·spot^-1) conformed to Beer' law. The regression equation of working curve can be expressed as ΔIp= 20.46+0.5492CAs(v) fig·spot^-1) (r= 0.9995, n = 6). The limit detection (LD) is 0.27 fg·spot^-1 [As(V) corresponding concentration: 6.8 × 10^-13 g·mL^-1, n=11]. The samples containing 0.0040 and 0.40 ng·mL^-1 As(V) were repeatedly determined for 11 times. RSD are 3.0% and 2.7% respectively. The SS-RTP mechanism was also discussed. R was synthesized in this paper. Meanwhile, the structure was determined by NMR, IR, mass spectra and elemental analysis.  相似文献   

17.
Four DNA electrochemical biosensors using four types of DNA (calf thymus ssDNA, calf thymus dsDNA, salmon testis ssDNA and salmon testis dsDNA) were constructed using graphite screen printed electrodes. These biosensors were exploited as analytical tool to detect polycyclic aromatic hydrocarbons-DNA interactions using benzo(a)anthracene and phenantrene as model analytes, the guanine oxidation peak variation being the signal revealing the interaction between PAHs and immobilized DNA. The salmon testis ssDNA biosensor resulted as the most promising device and was further evaluated for benzo(a)anthracene, fluorene, indeno(1,2,3-cd)pyrene, anthracene, and phenanthrene in 5–40 ng mL?1 solutions, and for benzo(a)pyrene (5–50 ng mL?1). A concentration dependent variation of the DNA guanine oxidation peak was observed for all compounds. The effect of benzo(a)pyrene ultraviolet (UV) activation on the benzo(a)pyrene (BaP)-DNA interaction was evaluated at concentration levels of 20 and 50 ng mL?1, and a 3.5- and 2.7-fold increases of the guanine oxidation peak was measured respectively. The salmon testis ssDNA biosensor was examined with PAHs contaminated samples of Mytilus galloprovincialis. Upon UV irradiation of three sample extracts exceeding the BaP maximum level, a positive variation of the DNA guanine oxidation was obtained. An average 2.4-fold increase of the guanine oxidation peak was detected demonstrating that the sensor can be used to detect toxic degradation products of PAHs.  相似文献   

18.
A rapid and simple method was optimized and validated for the separation and quantification of anthracene and benzo(a)pyrene, two of the most toxic polycyclic aromatic hydrocarbons, at ultratrace levels in aqueous samples by direct injection. The determination of anthracene and benzo(a)pyrene was performed by reverse-phase high-performance liquid chromatography (HPLC) with fluorescence detection. A fractional factorial matrix and a Box–Behnken design were chosen for screening and optimization purposes, respectively. The optimized parameters that significantly influenced the system were the flow rate (1?mL?min?1), mobile-phase strength (90% acetonitrile:10% deionized water), column temperature (35°C), and excitation wavelength (254 and 267?nm for anthracene and benzo(a)pyrene, respectively). The injection volume and emission wavelength were fixed at 100?µL and 416?nm, respectively. The quantification limits were 75?ng?L?1 for anthracene and 30?ng?L?1 for benzo(a)pyrene. The relative standard deviations for the recovery and intra and interday precision values were lower than 20%. The method allows the analysis of aqueous samples with a good resolution for anthracene and benzo(a)pyrene below values permitted by the recently developed European Directive 2013 Directive. 2013. Directive 2013/39/EU of the European parliament and of the council of 12 August 2013 amending directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. Official Journal of the European Union L 226:117. [Google Scholar]/39/EU for inland surface waters. In addition, this work provides guidelines for the simultaneous optimization of several parameters by experimental design.  相似文献   

19.
A simple, sensitive, precise and accurate reversed phase liquid chromatographic method has been developed for the simultaneous estimation of atorvastatin (AT) calcium, ramipril (RA) and aspirin (AS) from capsule dosage form. The method was developed using a Phenomenex Luna C18 (250 mm, 4.6 mm i.d., 5 µm) column with a mobile phase consisting of 0.1%, orthophosphoric acid buffer:acetonitrile:methanol (45:50:5 v/v/v), pH 3.3, at a flow rate of 1 mL min?1. Detection was carried out with ultra-violet detection at 210 nm. The retention times were about 12.19, 2.35, and 3.95 min for AT calcium, RA and AS, respectively. The developed method was validated for linearity, accuracy, precision, limit of detection, limit of quantitation and robustness. The linearity ranges were 1–6 µg mL?1 for AT calcium, 0.5–3 µg mL?1 for RA and 7.5–45 µg mL?1 for AS with mean recoveries of 100.59 ± 0.68, 100.62 ± 0.83 and 100.49 ± 0.73% for AT calcium, RA and AS, respectively. Limit of detection obtained were 29.85 ng mL?1 for AT calcium, 4.71 ng mL?1 for RA and 85.13 ng mL?1 for AS. Impurity of salicylic acid was found in capsule dosage form at the retention time of about 4.84 min. The proposed method can be used for the estimation of these drugs in combined dosage forms.  相似文献   

20.
Molecular imprinted polymer for determination of malachite green (MG) and fuchsine basic (FU) dyes by spectrophotometry has been used, to develop a novel simultaneous extraction and preconcentration method. Molecularly imprinted layer-coated nano-alumina (MIP@Nano-Al2O3) as adsorbent was prepared by surface molecular imprinting technique, and characterised by FTIR spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis (EDAX) and thermogravimetric analysis (TGA). The method is based on simultaneous extraction of MG and FU dyes from aqueous solution by using molecularly imprinted polymer and measuring the absorbance at 617 and 546 nm for MG and FU, respectively. Parameters which affect the extraction efficiency such as pH, volume of eluent and amount of adsorbent were investigated and optimised. Linear calibration curves were obtained in the range of 2–750 ng mL?1 for MG and 1–240 ng mL?1 for FU under optimum conditions. Detection limit based on three times the standard deviation of the blank (3Sb) was 0.655 and 0.245 ng mL?1 (n = 10) for MG and FU, respectively. The relative standard deviation (RSD) for 100 ng mL?1 of MG and FU was 2.35 and 3.06% (n = 7), respectively. The method was applied to the simultaneous determination of the dyes in different seafood and environmental water samples.  相似文献   

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