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1.
The developed method for trace analysis of volatile components in plasma allows direct injection of up to 150 samples to the GC–MS/MS system without injector cleaning. This method requires no modification of plasma and the working environment does not interfere with the determination of these analytes. The method allows simultaneous quantification of non-polar sevoflurane and its polar metabolite hexafluoroisopropanol (free, unconjugated form). It is characterized by high repeatability and sensitivity with the detection limit of 0.009 mg L?1 for sevoflurane and 0.018 mg L?1 for hexafluoroisopropanol and the linear range 0.050–150 mg L?1. The method was used to determine the concentration of sevoflurane and hexafluoroisopropanol in plasma samples of 7 patients undergoing general anesthesia with sevoflurane. The average concentration of sevoflurane and free hexafluoroisopropanol was 57.2 mg L?1 and 0.39 mg L?1, respectively. The method can be applied for clinical monitoring, as well as for analytical toxicology.  相似文献   

2.
A flow injection on-line displacement solid-phase extraction protocol was employed to minimize mass interferences with determination of palladium by inductively coupled plasma mass spectrometry (ICP-MS). The developed method involved in on-line complexing of Ag+ with pyrrolidine dithiocarbamate (PDC), presorption of the resultant Ag–PDC onto a microcolumn packed with the cigarette filter, displacement sorption of Pd2+ through loading the sample solution onto the microcolumn due to on-line displacement reaction between Pd2+ and the presorbed Ag–PDC, elution of the retained Pd2+ with 50 μL of ethanol for on-line ICP-MS detection. Interferences from co-existing heavy metal ions with lower stability of their PDC complexes relative to Ag–PDC were minimized/eliminated. No interferences from 5 mg L 1 Zn and 3 mg L 1 Pb for 104Pd, 0.4 mg L 1 Cu for 105Pd, 6 mg L 1 Zn and 2 mg L 1 Cd for 106Pd, 6 mg L 1 Zn and 3 mg L 1 Cd for 108Pd, and 2 mg L 1 Cd for 110Pd were observed for the determination of 100 ng L 1 Pd. The enhancement factors of 71–75, sample throughput of 23 samples h 1 and detection limits of 2.8–3.5 ng L 1 were achieved with the consumption of 3.0 mL of sample solution. The precision (RSD) for eleven replicate determinations of Pd at the 100 ng L 1 level was 1.8–2.7%. The developed method was applied to the determination of palladium in rock samples.  相似文献   

3.
This paper reports an electroanalytical method developed for determining the antioxidant tert-butylhydroquinone (TBHQ) in biodiesel, based on the enhancement effect of cetyltrimethylammonium bromide (CTAB). In pH 6.5 Britton–Robinson buffer, a poorly defined oxidation peak was observed for TBHQ at a carbon paste electrode (CPE). In the presence of low concentrations of CTAB, however, the oxidation peak current was markedly increased. Several parameters were studied and optimized for the development of this methodology, and under optimal conditions the oxidation peak current was proportional to TBHQ concentration in the range of (1.05–10.15) × 10−6 mol L−1, with limits of detection and quantification of 7.11 × 10−8 mol L−1 and 2.37 × 10−7 mol L−1, respectively, by linear sweep voltammetry (LSV). The method was applied to TBHQ determination in soybean biodiesel samples. The results were satisfactory in comparison with those obtained using high-performance liquid chromatography (HPLC).  相似文献   

4.
An automated monitoring system for sulfate, nitrite and nitrate based on sequential injection analysis (SIA) was developed. For nitrite determination the modified Griess-Ilosvay method was used, whereas nitrate was previously reduced to nitrite using a cadmium column followed by nitrite determination. A turbidimetric method was carried out in order to determine sulfate. The results showed that the proposed SIA monitoring system constitutes an effective approach for nitrite, nitrate and sulfate determination since it is able to determine levels required by international agencies that regulate these parameters in water. Detection limits of 0.0207 mg N L? 1, 0.0022 mg N L? 1 and 3 mg SO42? L? 1 were obtained for nitrate, nitrite and sulfate, respectively. The developed method offers also typical characteristics of the multicommutated systems, as portability, low reagents consumption and the subsequently minimization of waste generation. The proposed system was successfully applied to drinking water and wastewater samples and validated with a certified river water sample (ION-96.3, LGC Standards).  相似文献   

5.
A simple, rapid and low-cost electroanalytical method is proposed for the determination of acetaminophen (ACP) and codeine (COD) at nanomolar levels in pharmaceutical and biological samples. The analytical procedure is based on a flow injection analysis system coupled to electrochemical detection, which was multiple pulse amperometry (FIA-MPA). Boron-doped diamond was used as the working electrode for electrochemical detection. The electrode was subjected to a cathodic pretreatment and was selected in this work due its good electrochemical performance. By applying the FIA-MPA method, after a number of optimization assays, the analgesics were simultaneously determined at excellent linear concentration ranges. The analytical curves ranged from 80 nmol L−1 to 100 µmol L−1 for ACP and from 50 nmol L−1 to 10 µmol L−1 for COD, and the obtained limits of detection were 30 nmol L−1 and 35 nmol L−1 for ACP and COD, respectively. The practical applicability of the electroanalytical method was evaluated from the ACP and COD determination in two sample matrices: commercial pharmaceutical samples and biological fluids. In the case of pharmaceutical formulation samples, the obtained results were statistically similar to those obtained using a reference chromatographic method. In addition, these drugs were simultaneously quantified in biological fluid samples of urine and human serum with excellent recovery percentages.  相似文献   

6.
A fast and sensitive procedure for extraction and preconcentration of molybdenum in plant samples based on solidified floating organic drop microextraction combined with flame atomic absorption spectrometry and discrete nebulization was developed. 8-Hydroxyquinoline (8-HQ) was used as complexing agent. The experimental conditions established were: 0.5% m v 1 of 8-HQ, 60 μL of 1-undecanol as the extractant phase, 2 min vortex extraction time, centrifugation for 2 min at 2000 rpm, 10 min into an ice bath and discrete nebulization by introducing 200 μL of solution. The calibration curve was linear from 0.02 to 4.0 mg L 1 with a limit of detection of 4.9 μg L 1 and an enhancement factor of 67. The relative standard deviations for ten replicate measurements of 0.05 and 1.0 mg L 1 Mo were 6.0 and 14.5%, respectively. The developed procedure was applied for determining molybdenum in corn samples and accuracy was proved using certified reference materials.  相似文献   

7.
A continuous fixed bed (column) study was carried out by using seed husk of Bengal gram (Cicer arietinum) (SHBG) as a biosorbent for the removal of direct dye, Congo red (CR) from aqueous solutions. The effects of important factors, such as the value of initial pH, the flow rate, the influent concentration of CR, bed depth, particle size of SHBG, foreign ions and regeneration of CR were studied. The effect of similar type of direct dyes like direct turquoise blue 86 (DTB) and direct black 38 (DB) on the adsorption of CR in column containing SHBG is also studied by keeping other parameters constant. The studies confirmed that the breakthrough curves were dependent on flow rate, initial dye concentration, size of SHBG, initial pH of solution of CR and bed depth. The bed depth service time analysis (BDST) model was applied at different bed depths to predict the breakthrough curves. The model is found suitable for describing the biosorption process of the dynamic behaviour of the SHBG column and the data were in good agreement with BDST model. When the flow rate was 0.67 mL/min and the influent concentration of CR was mg L−1, the column capacity was 6.572 mg g−1. The removal capacity of SHBG was more in case of CR (6.572 mg g−1) compared to other similar direct dyes of DTB (1.984 mg g−1) and DB (1.612 mg g−1). The removal of CR was enhanced in the presence of foreign ion potassium (8.308 mg g−1) and decreased in the presence of calcium (5.58 mg g−1). 120 ml of acetone is required for the completion of regeneration of the column and the total amount of CR recovered in this case. All the results suggested SHBG as a potential adsorbent for removal of CR from aqueous solution so that the rate of bio-sorption process is rapid.  相似文献   

8.
Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (II) was then eluted with 10% HNO3 and subsequently reduced by NaBH4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min 1 sample loading rate. The detection limit was 0.2 ng L 1 and much lower than that of conventional method (around 15.8 ng L 1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L 1 of Hg and the linear working curve is from 20 to 2000 ng L 1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.  相似文献   

9.
A new simple method for the spectrophotometric determination of Pb(II) in fly ash leachates was developed. These leachates tend to contain a large amount of Ca(II) and Zn(II); this interferes with spectrophotometric determination of Pb(II) when conventional colorimetric agents are used. A copolymer consisting of protoporphyrin IX disodium salt and acrylamide was synthesized as a colorimetric agent. A measuring reagent containing ethylenediamine-N,N′-dipropionic acid (EDDP) as a masking agent for Zn(II) and an appropriate amount of Ca(II) together with the copolymer was applied to determine Pb(II). The temporal change in the absorption spectrum of the measuring reagent was acquired with a newly developed portable spectrophotometer for this method. The composition of EDDP and Ca(II) in the measuring reagent was optimized to measure leachates contaminated with Ca(II) and Zn(II). The detection limit and relative standard deviation of Pb(II) measured using the optimized method were 0.05 mg L?1 and 2.3%, respectively. The tolerance limits for Ca(II) and Zn(II) contaminants, where errors of less than 10% were allowed at a concentration of 0.5 mg L?1 Pb(II), were 4000 and 4 mg L?1, respectively. The determination of Pb(II) in various samples of actual leachates from incinerator fly ash was examined with this method. The obtained values correlated well with those obtained by flame atomic absorption spectroscopy.  相似文献   

10.
A novel poly(p-xylenolsulfonephthalein) modified glassy carbon electrode was prepared for the simultaneous determination of ascorbic acid (AA), epinephrine (EP) and uric acid (UA). Cyclic voltammetric, chronoamperometric, and differential pulse voltammetric methods were used to investigate the modified electrode for the electrocatalytic oxidation of EP, AA, and UA in aqueous solutions. The separation of the oxidation peak potentials for AA–EP and EP–UA was about 200 and 130 mV, respectively. The calibration curves obtained for AA, EP, and UA were in the ranges of 10–1343, 2–390, and 0.1–560 μmol L−1, respectively. The detection limits (S/N = 3) were 4, 0.1, and 0.08 μmol L−1 for AA, EP and UA, respectively. The diffusion coefficient and the catalytic rate constant for the oxidation of EP at the modified electrode were calculated as 1.40(±0.10) × 10−4 cm2 s−1 and 1.06 × 103 mol−1 L s−1, respectively. The present method was applied to the determination of EP in pharmaceutical and urine samples, AA in commercially available vitamin C tablet, and EP plus UA in urine samples.  相似文献   

11.
The paper presents the preconcentration of trace elements via electrodeposition onto a (micro)aluminum cathode in the presence of ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6] as a supporting electrolyte. The advantages of the proposed method include very simple instrumentation for the preconcentration of trace elements and low-cost reagents. The experiment showed that the use of ionic liquid in the electrodeposition process significantly improves sensitivity, recovery and detection limits for the determination of trace amounts of iron, cobalt, nickel and zinc. The preconcentrated metals were determined using X-ray fluorescence spectrometry. The optimum parameters for electrodeposition such as pH, the volume of the analyzed solution, the voltage and the deposition time were studied. Under the optimized conditions, the detection limits were 5, 2, 3 and 6 μg L 1 for iron, cobalt, nickel and zinc, respectively. The precision and recovery of the method were in the range of 3–5.5%, and 92–103%, respectively. The calibration was performed using aqueous standards of Fe(III), Co(II), Ni(II) and Zn(II) in the range 0.01–0.25 mg L 1. The method was applied successfully in water analysis.  相似文献   

12.
《Microchemical Journal》2011,97(2):337-343
An analytical protocol combining a headspace technique with gas chromatography and detection by photoionization detector and flame ionization detector (HS-GC-PID-FID) was developed. This procedure was used to measure volatile organic compounds (VOCs) in environmental aqueous matrices and was applied in determination of VOCs on the coast of Fortaleza, Brazil. At optimum operating conditions, analytical figures of merit such as linearity (R ranged from 0.9983 to 0.9993), repeatability (5.62 to 9.63% and 0.02 to 0.19% for the quantitative and qualitative analyses, respectively), detection limits (0.22 to 7.48 μg L1) and sensibility were estimated. This protocol favors a fast sampling/sample preparation (in situ), minimizes the use of laboratory material, eliminates the matrix effect from environmental samples, and can be applied to river, estuarine and oceanic waters. The advantage of detectors in series is that a low sensitivity in detection in one is compensated by the other. Toluene was the most abundant VOC in the studied area, with an average concentration of 1.63 μg L1. It was followed by o-xylene (1.15 μg L1), trichloroethene (1.08 μg L1), benzene (0.86 μg L1), ethylbenzene (0.74 μg L1), carbon tetrachloride (0.55 μg L1), m/p-xylene (0.48 μg L1) and tetrachloroethene (0.46 μg L1), compounds which are very commonly detected in urban runoff from most cities. The results of the VOC distribution showed that port activity was not the main source of VOCs along the Fortaleza Coast, but that the contribution from urban runoff seemed more significant.  相似文献   

13.
《Microchemical Journal》2011,97(2):380-385
Basic color data (RGB) obtained from digital images were studied by Factorial Analysis. The results demonstrated that individual RGB data represent different contributions. On the other hand, the total intensity of colors is proposed like a fourth variable in digital colorimetry and can be interpreted as complementary information related to the conditions of image capture in digital cameras. The chemometric study evidences that the analytical information, for quantitative applications, is formed by two parts: deterministic, with valuable analytical interest, and undeterministic or unvaluable analytical information. These results were revealed after variable reduction and data compression, using Principal Component Analysis and Fourier Transform, respectively.The digital colorimetric study was applied to the reaction of Ti(IV) with hydrogen peroxide at 0.09 M sulfuric acid media. They produce a yellow–orange complex solution. And their RGB intensities could be linearly correlated with Ti(IV) concentration in the range of 2.0 to 30.0 mg l 1. In the best conditions, using the intensity of the blue color, a simple and fast method for Ti(IV) determination could be developed. Its detection limit was found to be (criterion 3 s) 0.6 mg l 1 and the rsd for 10.0 mg l 1 of Ti(V) was 4.8%.Calibration by artificial neural nets represents an option that improves the answer to low concentration.Applications of the colorimetric method to the analysis of Ti in representative plastics, with content in mg g 1 level, are presented. Its validity was assessed by ICP-AES with standard addition. Results were in satisfactory agreement. The method is fast and reduces the analysis time.  相似文献   

14.
A novel electrochemical platform was designed and prepared for simultaneous determination of p-acetaminophen (AMP) and p-aminophenol (AP) by combining the excellent conductivity and electrocatalytic activities of tetraaminophenyl porphyrin functionalized multi-walled carbon nanotubes (CNTs-CONH-TAPP) and gold nanoparticles (AuNPs). The as-synthesized CNTs-CONH-TAPP composites were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscope. The incisive oxidation current responses of AMP and AP at the modified electrode promised a sensitive and selective simultaneous determination of AMP and AP. Under optimized conditions, the peak currents were directly proportional to the concentrations of AMP and AP over the ranges of 4.5–500 μmol L−1 and 0.08–60 μmol L−1, respectively, and the limits of detection were 0.44 μmol L−1 for AMP and 0.025 μmol L−1 for AP(S/N = 3) respectively. The proposed modified electrode showed excellent selectivity, reproducibility and long-term stability and could be applied in simultaneous determination of p-acetaminophen and p-aminophenol in real samples.  相似文献   

15.
《Microchemical Journal》2010,94(2):153-158
A method integrating a long waveguide capillary cell with a preconcentration resin in a multi-syringe flow injection analysis (MSFIA) system for iron determination in waters was developed. The determination of iron is based on a colorimetric reaction and two reagents were tested, ferrozine and ammonium thiocyanate. A liquid waveguide capillary cell (1.0 m pathlength, 550 µm i.d. and 250 µL internal volume) with a preconcentration resin were used to improve the sensitivity of the determination. Two different preconcentration resins were also tested, Chelex 100 and NTA Superflow. The developed method employing the NTA Superflow with ferrozine colorimetric reagent provided a detection limit of 0.05 µg L 1 with a linear response up to 8 µg L 1 and a sample throughput rate of 12 per hour. The developed system presents low reagents/sample consumptions. The accuracy was assessed using a certified reference water sample.  相似文献   

16.
Chemical speciation [Sb(V) and Sb(III)] affects the mobility, bioavailability and toxicity of antimony. In oxygenated environments Sb(V) dominates whereas thermodynamically unstable Sb(III) may occur. In this study, a simple method for the determination of Sb(III) in non acidic, oxygenated water contaminated with antimony is proposed. The determination of Sb(III) was performed by anodic stripping voltammetry (ASV, 1–20 μg L−1 working range), the total antimony, Sb(tot), was determined either by inductively coupled plasma mass spectrometry (ICP-MS, 1–100 μg L−1 working range) or inductively coupled plasma optical emission spectrometry (ICP-OES, 100–10,000 μg L−1 working range) depending on concentration. Water samples were filtered on site through 0.45 μm pore size filters. The aliquot for determination of Sb(tot) was acidified with 1% (v/v) HNO3. Different preservatives, namely HCl, L(+) ascorbic acid or L(+) tartaric acid plus HNO3, were used to assess the stability of Sb(III) in synthetic solutions.The method was tested on groundwater and surface water draining the abandoned mine of Su Suergiu (Sardinia, Italy), an area heavily contaminated with Sb. The waters interacting with Sb-rich mining residues were non acidic, oxygenated, and showed extreme concentrations of Sb(tot) (up to 13,000 μg L−1), with Sb(III) <10% of total antimony. The stabilization with L(+) tartaric acid plus HNO3 appears useful for the determination of Sb(III) in oxygenated, Sb-rich waters. Due to the instability of Sb(III), analyses should be carried out within 7 days upon the water collection. The main advantage of the proposed method is that it does not require time-consuming preparation steps prior to analysis of Sb(III).  相似文献   

17.
《Microchemical Journal》2008,88(2):128-131
The present work proposes a direct method based on slurry sampling for the determination of zinc and copper in human hair samples by multi-element sequential flame atomic absorption spectrometry. The slurries were prepared by cryogenic grinding and sonication of the samples. The optimization step was performed using univariate methodology and the factors studied were: nature and concentration of the acid solution, amount sample/slurry volume, sonication time, and particle size. The established experimental conditions are the use of a sample mass of 50 mg, 2 mol L 1 nitric acid solution, sonication time of 20 min and slurry volume of 10 mL. Adopting the optimized conditions, this method allows the determination of zinc and copper with detection limits of 88.3 and 53.3 ng g 1, respectively, and precision expressed as relative standard deviation (RSD) of 1.7% and 1.6% (both, n = 10) for contents of zinc and copper of 100.0 and 33.3 μg g 1, respectively. The accuracy was checked and confirmed by analysis of two certified reference materials of human hair. The procedure was applied for the determination of zinc and copper in two human hair samples. The zinc and copper contents varied from 100.0 to 175.6 and from 3.2 to 32.8 μg g 1, respectively. These samples were also analyzed after complete digestion in a closed system and determination by FAAS. The statistical comparison by t-test (95% confidence level) showed no significant difference between these results.  相似文献   

18.
Membrane-assisted solvent extraction (MASE) coupled to large volume injection was applied to the determination of (gasoline-type) hydrocarbon contamination in water samples. Hexane was used as acceptor phase. 50 μL extract was injected in the programmed temperature vaporizer injector using combined split–splitless evaporation. The extraction conditions were optimized both for MASE with agitation and for MASE with sonication. In the course of optimization the effect of extraction time, extraction temperature, agitation speed, solvent volume, pH, ionic strength and the addition of methanol were tested. Over 75% recovery was accomplished in the range of diesel oil hydrocarbons (n-C9–n-C24). The developed method was validated. Linearity, accuracy and precision were tested. The method showed excellent linearity between 1 and 1000 μg L?1 for n-alkanes and between 0.05 and 50 mg L?1 for gasoline. The method was tested with comprehensive GC × GC as well and found to be non-discriminative to all major compounds of diesel oil.  相似文献   

19.
A thionine modified aligned carbon nanotubes (ACNTs) electrode was fabricated and was used to electrochemically determine nitrite. The thionine modified ACNTs electrode exhibited enhanced electrocatalytic behavior to the oxidation of nitrite. The electrochemical mechanism of the thionine/ACNTs electrode towards the oxidation of nitrite was discussed. The thionine modified ACNTs electrode exhibited fast response towards nitrite with a detection limit of 1.12 × 10−6 mol  L−1 and a linear range of 3 × 10−6 – 5 × 10−4 mol  L−1. The proposed method was successfully applied in the detection of nitrite in real samples.  相似文献   

20.
The determination of chromium (VI) compounds in plants by electrothermal atomic absorption spectrometry (ET AAS) is proposed based on their leaching with 0.1 M Na2CO3. Due to the presence of relatively high amounts of Na2CO3 in the resulting samples, the temperature and time of pyrolysis and atomization stages must be optimized to minimize the influence of the matrix. A limit of detection (LOD) for determination of Cr(VI) in plants by ET AAS was found to be 0.024 μg g−1.The concentration of Cr(VI) and total chromium in plants collected in different geographical areas (South Africa and Russia), grown on soils high in chromium was determined. The concentration of Cr(VI) and total Cr in stems and leaves of plants was in the range of 0.04–0.7 μg g−1 and 0.5–10 μg g−1, respectively. The limited uptake of Cr(III) by plants, in comparison to its concentration in soil, can be explained by the very low solubility of natural Cr(III) compounds.Results for the determination of Cr(VI) were confirmed by the analysis of BCR CRM 545 (Cr(VI) in welding dust) with good agreement between certified (39.5 ± 1.3 μg mg−1) and found (38.8 ± 1.2 μg mg−1) values. The total concentration of Cr in plants has also been determined by ET AAS after dry ashing of samples at 650 °C. Results were confirmed by the analysis of BCR CRM 281 (Trace elements in Rye Grass) with good agreement between the found (2.12 ± 0.16 μg g−1) and certified value (2.14 ± 0.12 μg g−1).  相似文献   

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