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1.
Gas-diffusion microextraction was employed in the extraction of sulphites in wines aiming their electrochemical determination, which was achieved by square-wave voltammetry using screen-printed carbon electrodes. Sulphites are additives commonly used in many produced goods, particularly food products. The developed methodology showed good limits of detection (0.4 mg L 1) and quantification (1.3 mg L 1). The proposed method was also compared with the reference methodology used by the wine industry (the Ripper method, an iodometry) showing no significant differences in the obtained results. Therefore, a simple, cheap and portable alternative for the determination of sulphites in wine is presented.  相似文献   

2.
《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   

3.
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   

4.
Liquid phase extraction with back extraction (LPE-BE) combined with high performance liquid chromatography-diode array detection (HPLC-DAD) was applied for the extraction and determination of erythromycin A, B and C in fermentation broths. According to this procedure, the fermentation broth with the adjustment pH at a fixed value of 10 was first mixed with organic solvent (Vbroth/Vorg = 1.0). After shaking, the mixture was separated into two phases by microfuging at 13,000 rpm for 15 min. Then back extraction was performed into the acidic aqueous phase with pH 5.0 (Vorg/Vaq = 1.0). After centrifugation at 3000, the two phases were separated and 50 μL of the acidic aqueous phase was injected into the HPLC. The effects of different variables such as the nature of extraction solvent and the pH of samples and buffer were investigated. At the most appropriate conditions, dynamic linear ranges of 0.5–8, 0.1–0.9 and 0.1–0.9 mg mL−1 and limits of detection of 0.03, 0.003 and 0.002 mg mL−1 were obtained for erythromycin A, B and C, respectively. Relative standard deviations (RSDs) of the proposed method were less than 9.5%. The mean recoveries were 99.5%. The proposed method is simple and sensitive with highly clean-up effect and it can be used for monitoring the progress of erythromycin fermentation.  相似文献   

5.
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   

6.
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   

7.
A highly sensitive, selective and rapid method for the determination of cobalt based on the rapid reaction of cobalt(II) with 5-(2-benzothiazolylazo)-8-hydroxyquinolene BTAHQ and the solid phase extraction of the Co(II)-BTAHQ complex with C18 membrane disks were developed. In the presence of pH = 6.4 buffer solution and cetylpyridenium chloride (CPC) medium, BTAHQ reacts with cobalt to form a deep violet complex with a molar ratio of 1:1 (cobalt to BTAHQ). This complex was enriched by the solid phase extraction with C18 membrane disks. An enrichment factor of 100 was obtained by elution of the complex from the disks with a minimal amount of isopentyl alcohol. In isopentyl alcohol medium, the molar absorptivity of the complex is 2.42 × 105 L mol−1 cm−1 at 658 nm. Beer’s law is obeyed in the range of 0.01–0.38 μg mL−1 in the measured solution. The relative standard deviation for 11 replicate samples of 0.20 μg mL−1 level is 1.37%. The detection and quantification limits reach 3.1 and 9.7 ng mL−1 in the original samples. This method was applied for the determination of cobalt in biological, water, soil and pharmaceutical preparation samples with good results.  相似文献   

8.
Four inductively coupled plasma mass spectrometric methods: nebulization sample introduction with external calibration; hydride generation with external calibration; isotope dilution with nebulization; and isotope dilution with hydride generation, have been tested and compared. Multimode Sample Introduction System (MSIS™) was employed in either nebulization or hydride generation mode. Best limits of detection (below 0.1 μg L 1) and accuracy were obtained for isotope dilution techniques in hydride generation and sample nebulization mode. A mixture of HNO3 and H2O2 served both for microwave-assisted digestion as well as a medium for subsequent plumbane generation. Optimal reagent concentrations for hydride generation stage were 0.1 mol L 1 HNO3, 0.28 mol L 1 H2O2 and 1.5% m/v NaBH4. Critical effects of acidity, blanks and concomitants have been discussed. Analytical methods were validated by use of plant and water certified reference materials and spiked high-salt solutions (seawater and 20% m/v NaCl) at lead levels in nanograms per gram to micrograms per gram range.  相似文献   

9.
This work reports on a novel chitosan–hematite nanotubes composite film on a gold foil by a simple one-step electrodeposition method. The hybrid chitosan–hematite nanotubes (Chi–HeNTs) film exhibits strong electrocatalytic reduction activity for H2O2. Interestingly, two electrocatalytic reduction peaks are observed at −0.24 and −0.56 V (vs SCE), respectively, one controlled by surface wave and the other controlled by diffusion process. The Chi–HeNTs/Au electrode shows a linear response to H2O2 concentration ranging from 1 × 10−6 to 1.6 × 10−5 mol L−1 with a detection limit of 5 × 10−8 mol L−1 and a sensitivity as high as 1859 μA μM−1 cm−2.  相似文献   

10.
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   

11.
《Microchemical Journal》2011,97(2):194-202
Vertical profiles for total dissolved thallium were obtained at five sites in the western sector of the Ross Sea (Southern Ocean), Antarctica. Thallium is estimated to have a natural mean seawater concentration between 50 and 65 pmol L 1 with higher values in the North Pacific (65 ± 5 pmol L 1) and lower in the Bay of Biscay and Irish Sea (49 ± 3 pmol L 1). Our samples show a concentration varying from 22 to 55 pmol L 1 with a mean value of 46 pmol L 1, depending on depth, dissolved oxygen, salinity and local topographic characteristics. The analyses were performed using an ICP-SFMS that has enabled us to obtain reliable Tl concentration measurements with a relative standard deviation of better than 2.5% and a detection limit, calculated as three times the standard deviation of the “blank signal” of 0.69 pmol L 1 (1.60 pmol L 1, obtained analysing four blank solutions (n = 5) prepared with the same water and acid used for the dilution/acidification steps). Thallium appears to have a nearly conservative distribution in seawater as highlighted also from the comparison with the profiles of two seawater conservative elements: molybdenum and uranium; however it also highlights the presence of a reactive component of thallium, which is more influenced by the presence of particulate matter, oxygen content and fluorescence.  相似文献   

12.
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   

13.
A novel in-situ prepared copper film electrode (CuFE) for anodic stripping voltammetric measurement of trace levels of Hg(II) and Pb(II) is presented. The optimal electroanalytical performance of the CuFE was achieved in electrolyte solution comprising 0.1 M HCl and 0.4 M NaCl. The CuFE exhibited excellent operation in the presence of dissolved oxygen with calculated LoD of 0.1 μg L 1 Hg(II) and 0.06 μg L 1 Pb(II) in combination with 300 s accumulation time, repeatability with RSD of 4.5% for Hg(II) and 0.9% for Pb(II) (n = 12), and favourable linear response in the examined concentration range of 10–100 μg L 1 (R2 = 0.997) for Hg and 5–70 μg L 1 (R2 = 0.999) for Pb after 120 s accumulation. The electrode enabled also simultaneous detection of both investigated metal ions and revealed promising electroanalytical characteristics similar to or in certain cases surpassing those of commonly used gold electrodes.  相似文献   

14.
A simple, sensitive, and cost-effective analytical method was developed for the speciation analysis of inorganic selenium by combining a nano-TiO2 preconcentration with an ion chromatography-conductivity detection (IC-CD) system. The experimental conditions for the simultaneous adsorption and desorption of Se(IV) and Se(VI) were carefully investigated. Under the established optimum condition, the Se(IV) and Se(VI) ions could been simultaneously adsorbed onto the nano-TiO2 surface at pH 4.0, and then effectively desorbed by 0.1 M sodium hydroxide eluent. The adsorption process was fast and reached adsorption equilibrium within 10 min. The nano-TiO2 also exhibited high adsorption capacity with 11.3 mg g? 1 for Se(IV) and 8.34 mg g? 1 for Se(VI). The enrichment factors for Se(IV) and Se(VI) were calculated to be 39 and 30, respectively, with sample volume of 50 mL. The detection limits (3σ) were 0.8 μg L? 1 for Se(IV) and 0.4 μg L? 1 for Se(VI), which were sensitive enough for the routine analysis of water and drink samples. The relative standard deviation was calculated to be < 4% (n = 6) for detection of 30 μg L? 1 Se(IV) and 30 μg L? 1 Se(VI). The results of the present work confirmed that our developed nano-TiO2-IC-CD method could be applied for the detection of inorganic selenium species in tap water and drink samples with good recoveries in the range of 82%–108%.  相似文献   

15.
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   

16.
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   

17.
In this study, dispersive liquid–liquid microextraction (DLLME) combined with ultra-high-pressure liquid chromatography (UHPLC)–tunable ultraviolet detection (TUV), has been developed for pre-concentration and determination of triclosan (TCS), triclocarban (TCC) and methyl-triclosan (M-TCS) in aqueous samples. The key factors, including the kind and volume of extraction solvent and dispersive solvent, extraction time, salt effect and pH, which probably affect the extraction efficiencies were examined and optimized. Under the optimum conditions, linearity of the method was observed in the range of 0.0500–100 μg L?1 for TCS, 0.0250–50.0 μg L?1 for TCC, and 0.500–100 μg L?1 for M-TCS, respectively, with correlation coefficients (r2) > 0.9945. The limits of detection (LODs) ranged from 45.1 to 236 ng L?1. TCS in domestic waters was detected with the concentration of 2.08 μg L?1. The spiked recoveries of three target compounds in river water, irrigating water, reclaimed water and domestic water samples were achieved in the range of 96.4–121%, 64.3–84.9%, 77.2–115% and 75.5–106%, respectively. As a result, this method can be successfully applied for the rapid and convenient determination of TCS, TCC and M-TCS in real water samples.  相似文献   

18.
The present work describes the development of a new strategy to photoelectrochemical detection of L-Dopa at low potential based on oxygen reduction on TiO2 sensitized with iron phthalocyanine (FePc/TiO2). The FePc/TiO2 composite shows a photocurrent 10-fold higher than that of pure TiO2 nanoparticles and it was 4-fold higher than that of FePc exploiting visible light. The band gaps of pure TiO2 nanoparticles, FePc and FePc/TiO2, calculated according to the Kubelka–Munk equation, were 3.22 eV, 3.11 eV and 2.82 eV, respectively. The FePc/TiO2 composite showed a low charge transfer resistance in comparison to the photoelectrode modified with FePc or TiO2. Under optimized conditions, the photoelectrochemical sensor shows a linear response range from 20 up to 190 μmol L 1 with a sensitivity of 31.8 μA L mmol 1 and limit of detection of 1.5 μmol L 1 for the detection of L-Dopa.  相似文献   

19.
《Microchemical Journal》2009,91(2):107-112
A simple and powerful microextraction technique was used for determination of cadmium in water samples using liquid phase microextraction (LPME) followed by graphite furnace atomic absorption spectrometry (GF-AAS). In a preconcentration step, cadmium was extracted from a 2 mL of its aqueous sample in the pH = 6 as cadmium-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) cationic complex into a 4 µL drop of nitrobenzene and ammonium tetraphenylborate as counter ion. In the drop, the cadmium-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) ammonium tetraphenylborate ion associated complex was formed. After extraction, the microdrop was retracted and directly transferred into a graphite tube modified by [Pd(c) + Pd(i)]. Some effective parameters on extraction and complex formation, such as type and volume of organic solvent, pH, concentration of chelating agent and counter ion, extraction time and stirring rate were optimized. Under the optimum conditions, the enrichment factor and recovery were 390 and 78%, respectively. The calibration graph was linear in the range of 0.01–1 µg L 1 with correlation coefficient of 0.9952 under the optimum conditions of the recommended procedure. The detection limit based on the 3Sb criterion was 0.0065 µg L 1 and relative standard deviation (RSD) for eight replicate measurements of 0.1 µg L 1 and 0.4 µg L 1 cadmium was 6.4 and 5.8% respectively. The characteristic concentration was 0.0014 µg L 1 equivalent to a characteristic mass of 5.6 fg. In order to evaluate the accuracy and recovery of the presented method the procedure was applied to the analysis of reference materials and seawater.  相似文献   

20.
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   

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