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At least 163 records · Page 9Linked to original sources

Development of a new hybrid technique for rapid speciation analysis by directly interfacing a microfluidic chip-based capillary electrophoresis system to atomic fluorescence spectrometry.

This paper represents the first study on direct interfacing of microfluidic chip-based capillary electrophoresis (chip-CE) to a sensitive and selective detector, atomic fluorescence spectrometry (AFS) for rapid speciation analysis. A volatile species generation technique was employed to convert the analytes from the chip-CE effluent into their respective volatile species. To facilitate the chip-CE effluent delivery and to provide the necessary medium for subsequent volatile species generation, diluted HCl solution was introduced on the chip as the makeup solution. The chip-CE-AFS interface was constructed on the basis of a concentric "tube-in-tube" design for introducing a KBH4 solution around the chip effluent as sheath flow and reductant for volatile species generation as well. The generated volatile species resulting from the reaction of the chip-CE effluent and the sheath flow were separated from the reaction mixture in a gas-liquid separator and swept into the AFS atomizer by an argon flow for AFS determination. Inorganic mercury (Hg(II)) and methylmercury (MeHg(I)) were chosen as the targets to demonstrate the performance of the present technique. Both mercury species were separated as their cysteine complexes within 64 s. The precision (relative standard deviation, RSD, n = 5) of migration time, peak area, and peak height for 2 mg.L(-1) Hg(II) and 4 mg.L(-1) MeHg(I) (as Hg) ranged from 0.7 to 0.9%, 2.1 to 2.9%, and 1.5 to 1.8%, respectively. The detection limit was 53 and 161 microg.L(-1) (as Hg) for Hg(II) and MeHg(I), respectively. The recoveries of the spikes of mercury species in four locally collected water samples ranged from 92 to 108%.

Electrophoresis, Microchip↗

[Simultaneous determination of trace arsenic and antimony in textile by intermittent flow-hydride generation-atomic fluorescence spectrometry with L-cysteine as a prereducer].

A method for the simultaneous determination of trace arsenic and antimony in textile by intermittent flow-hydride generation-atomic fluorescence spectrometry with L-cysteine as a prereducer was developed. The optimal instrument condition was established. The influence factors such as the acidity of sample solution and carrier liquid, the concentrations of KBH4 and L-cysteine, the flow rate of carrier, and the interference of coexistent elements were investigated. The method was convenient and rapid. Under the optimal condition, the detection limits were 0.35 and 0.22 microg x L(-1), the relative standard deviations were 1.3% and 2.8%, and the recoveries were in the ranges of 93.6% - 98.4% and 92.2% - 103.6% for As and Sb respectively.

English Abstract↗

Determination of element distribution between the symplasm and apoplasm of cucumber plant parts by total reflection X-ray fluorescence spectrometry.

The distribution of Cd, Ni, Pb and Fe between the symplasm (cytoplasm) and apoplasm (cell wall) of cucumber roots and leaves was determined by total reflection X-ray fluorescence spectrometry following a special sample preparation procedure. The plants were grown in modified Hoagland nutrient solution containing Fe in chemical form of Fe(III)-citrate or Fe(III)-EDTA, as well as the heavy metal contaminants, each in concentration of 10 microM. In the roots the larger part of Pb was found in the apoplasm, while Ni and Cd were mostly in the symplasm. In the leaves however, about 50-60% of the Pb content and practically the total amount of Cd were detected in the symplasm. About 30-40% of the translocated Ni remained in the apoplasm of the leaves. The Cd-, Ni- and Pb-treatments resulted in higher total concentration of Fe in the roots, however, the relative amount of Fe in the symplasm decreased in all cases. In the leaves of the control plants the larger part (60-80%) of Fe occurs in the symplasm. Due to the heavy metal effects, the relative amount of Fe in the symplasm decreased except in the Pb-contaminated plants, where in the presence of Fe(III)-EDTA, the Pb treatment resulted in a moderate increment of Fe concentration in the symplasm.

Cucumis sativus↗

Evaluation of a quantitative method for trace impurities in arsenous acids by synchrotron radiation X-ray fluorescence spectrometry and inductively coupled plasma-atomic emission spectrometry.

Thirteen arsenous acid samples of known origins and refining methods were collected. Each sample was subjected to quantitative analysis of any impurity elements present using synchrotron radiation X-ray fluorescence spectrometry (SR-XRF) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). The trace elements selected were Sn, Sb and Bi for the reasons that they were considered not to be changed by their circumstances and that they showed high sensitivity to SR-XRF. These results obtained by both methods were compared and the correlation between these two methods was determined. The quantification of trace impurities obtained by SR-XRF using As as an internal standard showed good agreement with the results obtained by ICP-AES. The discrimination of refining method became possible by the comparison of these impurities' contents measured with non-destructive SR-XRF using several arsenous acid particles.

Journal Article↗

Simultaneous determination of cobalt, copper and zinc by energy dispersive X-ray fluorescence spectrometry after preconcentration on PAR-loaded ion-exchange resin.

A sensitive method for the preconcentration and determination of trace amounts of Co, Cu and Zn by energy-dispersive X-ray fluorescence spectrometry (EDXRF) has been developed. The method is based on the fact that 4-(2-pyridylazo)-resorcinol (PAR) loaded Dowex anion-exchange resin (PAR-resin) can effectively adsorb Co, Cu and Zn at pH 9.0 to form PAR-metal complexes. The detection limits for Co, Cu and Zn were 1.53, 0.31 and 0.21 ppb, respectively. The precisions for five replicate measurements of the three metals were 3.4, 2.7 and 2.1% RSD, and the calibration curves were linear up to 75 microg with correlation coefficients of 0.9975, 0.9980 and 0.9985, respectively. The method was successfully applied for the simultaneous determination of Co, Cu and Zn in seawater samples at ppb levels.

Journal Article↗

Elements in autopsy liver tissue samples from Greenlandic Inuit and Danes. I. Sulphur, chlorine, potassium and bromine measured by X-ray fluorescence spectrometry.

The purpose of this study was to measure the content of the elements Sulphur (S), Chlorine (C1), Potassium (K) and Bromine (Br) in normal liver tissue samples from Greenlandic Inuit using X-ray fluorescence spectrometry, and compare the results with those obtained in normal liver tissue samples from Danes. Liver tissue sample were obtained at autopsy from 50 Greenlandic Inuit (27 men, 23 women) with a median age of 61 years (range 20-83) and from 74 Danes (44 men, 30 women) with a median age of 52 years (range 15-87). In Inuit, the content of elements given as median and (5-95 percentile) was: sulphur, 108.07 mmol/kg dry liver (86.78 - 169.44); chlorine, 92.16 mmol/kg dry liver (45.39-128.42); potassium, 181.66 mmol/kg dry liver (146.41-236.35); bromine, 0.0901 mmol/kg dry liver (0.0563-0.1589). In Danes, the corresponding values were: sulphur, 147.58 mmol/kg dry liver (70.41-236.81); chlorine, 96.95 mmol/kg dry liver (54.01-162.52); potassium, 198.40 mmol/kg dry liver (150.68-256.37); bromine, 0.1101 mmol/kg dry liver (0.0701 - 0.4203). None of the elements displayed any significant gender difference, neither in Inuit nor in Danes. Inuit had a lower liver content of sulphur (p < 0.0001), potassium (p < 0.008) and bromine (p < 0.002) as compared with Danes.

Adult↗

Development of an on-line UV decomposition system for direct coupling of liquid chromatography to atomic-fluorescence spectrometry for selenium speciation analysis.

Speciation analysis of four selenium species (selenite, selenate, selenocystine, and selenomethionine) has been performed by on-line coupling of liquid chromatography (LC), UV decomposition, hydride generation (HG), and atomic-fluorescence spectrometry (AFS). Because only selenite (Se(IV)) can generate hydrides, on-line conversion of organic and inorganic selenium species is discussed. Preliminary study showed that the use of only UV light was not sufficient to reduce selenate, because no absorption is observed for this compound at the main wavelength of the low-pressure mercury lamp (253.7 nm). Thus, new conditions based on addition of a reducing reagent (I-) were developed. Mechanisms of action are proposed to explain selenium species conversions. Because of their compatibility with on-line treatment, phosphate buffers were used for chromatographic separation on an anion exchange column (Hamilton PRP-X100). Detection limits (19-60 pg Se) and repeatability of the technique were close to those obtained by conventional quadrupole ICPMS. Applications to real samples such as water and oysters are presented and emphasize the robustness of the system.

Journal Article↗

Determination of trace elements in suspensions and filtrates of drinking and surface water by wavelength-dispersive X-ray fluorescence spectrometry.

An X-ray fluorescence method (XRF) is presented that allowed low detection limits (at the 0.1-23 ng mL(-1) level) to be obtained for Cr, Mn, Fe, Ni, Zn, Sr, Pb, Bi and Br in water. The samples were prepared using a thin layer method. Trace elements were determined via the calibration curve and standard addition. Absorption effects and inhomogenities in prepared samples were checked for using the emission-transmission method and internal standards, respectively. The results from the XRF method were compared with the results from the inductively coupled plasma atomic emission spectrometry method.

Journal Article↗

Rubidium content in autopsy liver tissue samples from Greenlandic Inuit and Danes measured by X-ray fluorescence spectrometry.

BACKGROUND: The biological function of rubidium (Rb) is unknown, but this alkali metal probably has a normal biologic role. OBJECTIVE: To measure the content of Rb in liver tissue samples from Greenlandic Inuit using X-ray fluorescence spectrometry, and compare the results with those obtained in liver samples from ethnic Danes. STUDY DESIGN: Observational, descriptive survey on environmental pathology. METHODS: The setting was related to forensic medicine and hospitalised care in Nuuk, Ilulissat and Copenhagen. Normal liver tissue was obtained at autopsy from 50 Greenlandic Inuit (27 men) with a median age of 61 years (range 23-83) and from 42 Danes (31 men) with a median age of 38 years (range 16-83). RESULTS: Liver Rb content in Inuit was not significantly different compared with Danes. There was no significant gender difference in liver Rb content either in Inuit or in Danes. The content of Rb given as median (5-95 percentile) was 0.1837mmol/kg dry liver (0.1041-0.3147) in Inuit, and 0.1965mmol/kg dry liver (0.0799-0.2815) in Danes (p=0.6). There was an inverse correlation between liver Rb content and age in Inuit (r(s)=-0.45, p=0.002) but not in Danes. Median hepatic Rb index (Rb content in micromol/kg dry weight divided by age in years) in Inuit was 3.05 and in Danes 4.21 (p=0.02). The correlations between liver Rb and liver potassium content were: Inuit r(s)=0.28, p=0.07; Danes r(s)=0.25, p=0.08; combined series r(s)=0.34, p=0.01. CONCLUSIONS: Inuit have liver Rb levels, which are quite similar to the levels found in Danes. In Inuit, liver Rb content appears to decrease with age.

Adolescent↗

[Determination of RE2O3-Mo-Co in hydrogenation catalyst by X-ray fluorescence spectrometry].

An X-ray fluorescence spectrometer was applied to the determination of Mo-Co-RE2O3 in hydrogenation catalyst. The standard samples were manually synthesized, the powder pellets were used for sample preparation, and the matrix effects were corrected by the empirical coefficients. A series of sampling methods and spectrum conditions were studied. The ranges of the determination are MoO3: 7%-13%, CoO: 2%-7%, and RE2O3: 3%-6%. The results show that the accuracy and precision of this method are satisfactory. The relative standard deviations for MoO3, CoO and RE2O3 are less than 2% for the above analytical ranges. The method has been used in routine analyses. The results agree well with other methods.

Catalysis↗

Determination of trace metals in drinking water using solid-phase extraction disks and X-ray fluorescence spectrometry.

A convenient method is described for monitoring Cd, Ni, Cu, and Pb at trace levels in drinking water samples. These metals are preconcentrated on a chelating solid-phase extraction disk and then determined by X-ray fluorescence spectrometry. The method tolerates a wide pH range (pH 6-14) and a large amount of alkaline and alkaline earth elements. The preconcentration factor is well over 1600, assuming a 1 L water sample volume. The limits of detection for Cd, Ni, Cu, and Pb are 3.8, 0.6, 0.4, and 0.3 ng/mL, respectively. These are well below the federal maximum contaminant level values, which are 5, 100, 1300, and 15 ng/mL, respectively. The proposed method has many advantages including ease of operation, multielement capability, nondestructiveness, high sensitivity, and relative cost efficiency. The solid-phase extraction step can be conducted in the field and then the disks can be mailed to a laboratory for the analysis, eliminating the cost of transporting large volumes of water samples. Furthermore, the color of the used extraction disk provides an initial estimate of the degree of contamination for some transition metals (for example, Ni and Cu). Thus, the overall cost for analysis of metals in drinking water can be minimized by implementing the method, and small water supply companies with limited budgets will be better able to comply with the Safe Drinking Water Act.

Chromatography↗

Rapid screening method for simultaneous determination of four polycyclic aromatic hydrocarbons in water samples by derivative non-linear variable-angle synchronous fluorescence spectrometry.

Derivative non-linear variable-angle synchronous fluorescence spectroscopy (D-NLVASFS) has been developed to improve the selectivity of the fluorescence measurement without loss of sensitivity. We report a simple screening approach for the rapid and simultaneous determination of 1,2.5,6-dibenzoanthracene (DBA), 2,3-benzofluorene (BF), pyrene (Pyr) and 3,4-benzopyrene (BaP) in a mixture by using first-derivative NLVASFS. The method is efficient, fast and straightforward, and the measurement was simply based on a single spectrum via a single spectral scanning of a sample. The linear ranges 0.005-0.30, 0.02-0.30, 0.02-0.40 and 0.005-1.0 microg/mL and the detection limits 0.08, 1.14, 1.64 and 0.12 ng/mL are obtained for DBA, BF, Pyr and BaP, respectively. The method was applied to water samples spiked with the four polycyclic aromatic hydrocarbons (PAHs), with mean recoveries of 103.0% (SD 5.9%) for DBA, 96.4% (SD 4.2%) for BF, 96.2% (SD 4.0%) for Pyr and 98.2% (SD 3.0%) for BaP.

Nonlinear Dynamics↗

Human nails as a biomarker of arsenic exposure from well water in Inner Mongolia: comparing atomic fluorescence spectrometry and neutron activation analysis.

Arsenic (As) is found naturally in the geological strata within the Ba Men Region of Inner Mongolia, China. A study was conducted to compare the total As measurements from two analytical techniques: instrumental neutron activation analysis (INAA) and atomic fluorescence spectrometry (AFS), and to verify nails as an exposure biomarker in this population. In 1999, nail and water samples were collected in a pilot study. Fingernails and toenails were pooled from 32 participants and analysed for total As by both INAA and AFS. Mean nail As values were 14.8+/-2.4 and 19.4+/-2.8 microg g-1 (+/-SEM) for INAA and AFS, respectively. Results from these two methods were significantly correlated (r=0.93, p<0.0001). In 2000, a second study was conducted and INAA was used to measure total As in toenails from 314 Ba Men residents. Well water samples were collected from 121 households and analysed by AFS. A significant correlation was observed between toenail and well water As (r=0.84, p<0.0001). Based on the results, INAA was significantly correlated with AFS and proved to be a reliable measure of nail As levels. In this population, toenail samples are a useful internal As exposure biomarker from drinking water sources.

Adult↗

Characterization of a tunable optical parametric oscillator laser system for multielement flame laser excited atomic fluorescence spectrometry of cobalt, copper, lead, manganese, and thallium in buffalo river sediment.

A pulsed (10 Hz) optical parametric oscillator (OPO) laser system based on beta-barium borate (BBO) crystals and equipped with a frequency-doubling option (FDO) was characterized for use in laser excited atomic fluorescence spectrometry (LEAFS). This all-solid-state laser has a narrow spectral line width, a wide spectral tuning range (220-2200 nm), and a rapid, computer-controlled slew scan of wavelength (0.250 nm s-1 in the visible and infrared, and 0.125 nm s-1 in the ultraviolet). The output power characteristics (15-90 mJ/pulse in the visible, 1-40 mJ in the infrared, and 1-11 mJ in the ultraviolet), laser pulse-to-pulse variability (3-13% relative standard deviation, RSD, of the laser pulses), conversion efficiency of the FDO (2-17%), and spectral bandwidth in the visible spectrum (0.1-0.3 cm-1) were measured. The laser was used as the excitation source for a flame LEAFS instrument for which rapid, sequential, multielement analysis was demonstrated by slew scan of the laser. The instrument allowed about 640 measurements to be made in about 6 h, with triplicate measurements of all solutions and aqueous calibration curves, which yielded accurate analyses of a river sediment (National Institute of Standards and Technology, Buffalo River Sediment, 2704) for five elements with precisions < 5% RSD. Comparable or improved flame LEAFS detection limits over literature values were obtained for cobalt (2 ng mL-1), copper (2 ng mL-1), lead (0.4 ng mL-1), manganese (0.2 ng mL-1), and thallium (0.9 ng mL-1) by flame LEAFS.

Calibration↗

Discrimination of arsenous acids with comparison of trace elements contained by using synchrotron X-ray fluorescence spectrometry.

In the poisonous incident case occurred in Japan, clarification of the identity between seized poisons and retrieved from crime scene is strictly required from the court. In this case, arsenous acid was used as a poisonous material and, seized one from suspect's house was only twenty particles. The synchrotron X-ray fluorescence spectrometry by comparing the intensity ratios of L(alpha) line of four heavy metal, such as Bi, Sn, Sb, Se to K(beta) line of As was performed to overcome this problem. In this paper, the evaluation of this new method using 13 authentic arsenous acid samples, 4 of 13 were refined by Chinese method, 7 of 13 were refined by Japanese method (Sumitomo mining Co. Ltd. method), 2 of 13 were refined by German and Swiss method. As a result, by the comparison of the ratios of these four elements to As, these 13 samples were clearly classified to three products classes produced by different refining methods.

Journal Article↗

Hyphenating multisyringe flow injection lab-on-valve analysis with atomic fluorescence spectrometry for on-line bead injection preconcentration and determination of trace levels of hydride-forming elements in environmental samples.

In this work the third generation of flow injection analysis, that is, the so-called micro-lab-on-valve (microLOV) approach, is proposed for the first time for the separation, preconcentration, and monitoring of metalloids as hyphenated with atomic fluorescence spectrometry (AFS). This was made feasible by interfacing the micromachined LOV-module with AFS by a multisyringe flowing stream network for on-line postcolumn derivatization of the eluate aimed at generation of hydride species. The potential of this new hyphenated technique for environmental assays was ascertained via determination of ultratrace level concentrations of total inorganic arsenic in freshwater. Employing quantitative preoxidation of As(III) to As(V) in the samples by means of permanganate, the method involves preconcentration of arsenate at pH 10 on a renewable anion exchanger, namely, Q-Sepharose, packed in a LOV microcolumn. The analyte species is afterward stripped out and concurrently prereduced by a 300 microL eluent plug containing 6 mol L(-)1 HCl and 10% KI. The eluate is downstream merged with a metered volume of sodium tetrahydroborate (0.3% w/v) for generation of arsine, which is subsequently quantified by AFS. The flow system facilitates on-column reduction of the retained arsenic with no need for application of programmable stopped flow. Yet, the high concentration of reductant and extreme pH conditions for elution hinder the sorbent to be reused due to gradual deactivation of the functional moieties, so that maximum benefit can be taken from the application of the bead renewable strategy. The proposed procedure is characterized by a high tolerance to metal species and interfering hydride-forming elements. In fact, ratios of Se(IV) to As < or = 5000 and Sb(V) to As < or = 500 are tolerated at the 10% interference level. Under the optimized experimental conditions, a detection limit (3sigma) of 0.02 ng mL(-1) As, a dynamic linear range of 0.05-2.0 ng mL(-1) As (by tailoring the AFS gain), an enrichment factor of 8.8 for arsenate, and a precision better than 6.0% at the 0.1 ng mL-1 level were obtained for the bead-injection mode whenever the loading sample volume was affixed at 3.0 mL. The reliability and accuracy of the automated procedure was ascertained by determining total inorganic arsenic in both spiked environmental waters and certified reference materials of variable matrix complexity (TMDA-54.3 and ERM-CA010) at the low ng mL(-1) level. No significant differences were found between the experimental results and the certified values at a significance level of 0.05.

Journal Article↗

Elements in autopsy liver tissue samples from Greenlandic Inuit and Danes. V. Selenium measured by X-ray fluorescence spectrometry.

The content of selenium in normal liver tissue samples from Greenlandic Inuit was measured and the results compared with those obtained in normal liver tissue samples from Danes. Normal liver tissue samples were obtained at autopsy from 50 Greenlandic Inuit (27 men, 23 women) with a median age of 61 years (range 23-83) and from 74 Danes (44 men, 30 women) with a median age of 60 years (range 15-87). Total liver selenium content was measured by X-ray fluorescence spectrometry. The content of selenium (median) was in Inuit 26.6 micromol/kg dry liver (5-95 percentile: 15.2-49.4) and in Danes 17.7 micromol/kg dry liver (5-95 percentile: < 3.8-36.5) (p < 0.0001). Liver selenium content displayed no significant gender difference, either in Inuit or Danes. In Inuit men, there was a negative correlation between liver selenium content and age (rs = -0.39, p < 0.05), whereas Danish men displayed a positive correlation between liver selenium content and age (rs = 0.37, p = 0.02). There was no correlation in Inuit or Danish women. In Inuit, the median hepatic selenium index (liver selenium content divided by age) was 0.48 and in Danes 0.33 (p = 0.001). There was an inverse correlation between hepatic selenium index and age both in Inuit (rs = -0.77, p < 0.0001) and in Danes (rs = -0.47, p < 0.0001). In conclusion, Inuit had a higher liver content of selenium and a higher hepatic selenium index compared with Danes. The more favourable selenium status is due to a higher nutritional selenium intake with fish and meat from sea mammals.

Adolescent↗