Determination of Mercury in Geological Materials by Continuous-Flow,Cold-Vapor,Atomic Absorption Spectrophotometry

Abstract

To determine mercury in geological materials, samples are digested with nitric acid and sodium dichromate in a closed teflon vessel. After bringing to a constant weight, the digest is mixed with air and a sodium chloride-hydroxylamine hydrochloride-sulfuric acid solution and then Hg(II) is reduced to Hg with stannous chloride in a continuous flow manifold. The mercury vapor is then separated and measured using cold vapor atomic absorption spectrophotometry (CV-AAS). For a 100 mg sample the limit of detection is 20 parts per billion (ppb) Hg in sample. To obtain a 1% absorption signal, the described method requires 0.21 ppb Hg solution (equal to 16 ppb in sample). Precision is acceptable at less than 1.2% RSD for a 10 ppb Hg aqueous standard. Accuracy is demonstrated by the results of the analysis of standard reference materials. Several elements do interfere but the effect is minimal because either the digestion procedure does not dissolve them (e.g., Au or Pt) or the; are normally of low abundance (e.g., Se or Te).     

Application of an ETV-ICP system for the determination of elements in human hair

When determining element contents in hair samples without sample digestion it is necessary to analyze large sample volumes in order to minimize problems of inhomogeneity of biological sample materials. Therefore an electrothermal vaporization system (ETV) is used for solid sample introduction into an inductively coupled plasma (ICP) for the determination of matrix and trace elements in hair. This paper concentrates on the instrumental aspects without time consuming sample preparation. The results obtained for optimization tests, ETV operating parameters and ICP operating parameters, are shown and discussed. Standard additions are used for calibration for the determination of Zn, Mg, and Mn in human hair. Studies including reproducibility and detection limits for chosen elements have been carried out on certified reference materials (CRMs). The determination of reproducibility (relative standard deviation (RSD) of n = 10) and detection limits (DLs) of Zn (RSD < 8.5%, DL < 0.8 μ g⁻¹), Mn (RSD < 14.1%, DL < 0.3 μ g⁻¹), and Mg (RSD < 7.4%, DL < 6.6 μ g⁻¹) are satisfactory. The concentration values found show good agreement with the corresponding certified values. Further sample preparation steps, including hair sampling, washing procedure and homogenization for hair, relating to measurements of real hair samples are described.     

Prediction of rizatriptan trace level in biological samples: An application of the adaptive-network-based fuzzy inference system (ANFIS) in assisting drug dose monitoring

Introduction: Solvent bar microextraction technique is a sample preparation method prior to analysis for complicated matrices such as urine, blood, stem cell culture, and wastewater. This method, when coupled with adaptive-network-based fuzzy inference system, can detect and predict the concentration of trace elements and drugs at ultra-trace levels in complicated matrices.

Material and method: Rizatriptan was used as a model drug for validation of this method. Therefore, six parameters (pH of donor and acceptor phase, stirring rate, time, temperature, and salt addition) affecting the preconcentration and determination of this drug were investigated. In this method, pH gradient was applied to transfer the drug into the solvent bar. MATLAB version 2010 was used for data analysis. Construction of an input-output mapping was done based on the results obtained from the experiments. For the simulation, the ANFIS architecture was employed to model nonlinear functions, identify nonlinear components in a control system, and predict a chaotic time series, all yielding remarkable results. Based on the best model chosen, the drug was preconcentrated and analyzed under the optimum condition.

Results and discussion: The figures of merit were as follows: preconcentration factor: 127; limit of detection: 15?ng?mL^?1; limit of quantification: 50?ng?mL^?1; R²:0.999; RSD: 3.0%(interday) and 4.6% interaday. As a result, this method can be employed for preconcentration and microextraction of several elements, drugs, antibodies at trace levels in complicated matrices. After modeling, the optimum condition could be predicted without performing unnecessary and expensive experiments.

Conclusion: Certain biomarkers can also be preconcentrated and detected using the proposed method. It offers high sample clean up, therefore it can be used for clean validation. Prediction of the course of treatment may be possible with the proposed method, therefore it is highly practical, easy and cost-effective.     

Oxidability Determination in Waste Waters Using an Automatic Titrator Based on a Multicommutated Unsegmented Flow System

Abstract

The automatic titrator based on a multicommutated unsegmented flow system was applied to redox titrations and used for oxidability determination in waters analysis. This automatic titrator allows the attainment of complete titration curves, being the determination of titrand concentration performed without requiring any prior calibration. After sample treatment (oxidation step), the oxidability determination in waste water samples was accomplished by the automatic flow titrator (titration step). Repeated determinations of standard solutions gave a 3.5% RSD (n=10, 0.010M) for repeatability and a 3.2% RSD (n=2, 0.057M) for reproducibility. Samples results (n=9) were in good agreement (t-test) with those obtained with a reference procedure.     

The Stability of Precipitation Samples under Field Conditions

Abstract

Eight wet-only samplers. placed in one location were used to sample precipitation. Subsamples were taken from the sample bottles directly after the precipitation event and at regular intervals up to a period of 2100 hours and analysed, while the samples stayed in the samplers under field conditions.

Outliers were deleted by means of conventional statistical techniques. The resulting data base was tested by means of the F-test for consistency and for changes in the chemical composition of precipitation samples directly after sampling or after an extended stay under field conditions. Eighty-one percent of the samples showed consistent results and no clear indication of chemical changes was found.

Regression analysis indicated that the uncertainties for samples analysed after 1 week are less than 5% generally for the bulk elements and less than 14% for the trace elements. After a period of 400 hours the uncertainties for the buld elements increase to a level of 5–10% and 5–30% for the trace elements.

Contamination, as a result of handling the samples to obtain subsamples, seems the main cause for the increase of the concentrations which was observed.

Contamination during sample pretreatment and analysis in the laboratory is probably of minor importance.     

Determination of Trace Metals in Fish Tissue by Flame Atomic Absorption Spectrometry using a Discreet Nebulization Technique

Abstract

Flame atomic absorption spectrometry is applied to the analysis of trace metals in fish tissue after digestion of the sample with nitric acid in a decomposition vessel. The digested sample is analyzed directly using a discreet nebulization technique. Enhancement effects were observed for all elements studied. The method was applied to the analysis of copper, iron and zinc in several species of fish.     

Determination of Rare-Earth Elements in Sulfide Minerals by Inductively Coupled Plasma Mass Spectrometry with Ion-Exchange Preconcentration

A procedure was developed for determining ultratrace rare-earth elements in sulfide minerals by inductively coupled plasma mass spectrometry with ion-exchange preconcentration. The concentration factor was 200. The found concentrations of rare-earth elements were 6–30 times lower than those in chondrites. For lanthanum and praseodymium, RSD < 10%; for other rare-earth elements, RSD < 6%. The accuracy of the results was verified by the addition of known amounts of Eu, Tb, Tm, and Lu to a chalcopyrite sample at the stage of decomposition with HCl and HNO₃. The calculated yield of rare-earth elements was 94–96%. The detection limit was from 0.06 ng/g (6 × 10^–9%) for lutetium to 5 ng/g (5 × 10^–7%) for cerium. The procedure was used for the determination of rare-earth elements in chalcopyrites, pyrites, and sphalerites.     

Method for Determination of Selenium and Arsenic in Human Urine by Atomic Fluorescence Spectrometry

Abstract

The study presents the method for simultaneous determination of selenium and arsenic in human urine by atomic fluorescence spectrometry (AFS). According to the procedure developed, a sample is first digested in the microwave system, then chemically treated in the flow through a hydride generation system, and finally exposed to measurements in a double‐channel atomic fluorescence spectrometer. It has been revealed that selenium and arsenic can be accurately determined with detection limit of 0.13 and 0.16 µg/L and repeatability (RSD) of 1.0 and 1.2%, respectively. The urine samples taken from a control group and from persons subjected to a special diet were analyzed. The obtained results proved that the method developed was capable of controlling reliably even slight changes of both elements in a wide range of their concentrations, and, as such, that it can be recommended to be used for clinical and toxicological purposes.     

The Determination of a New Trifluorinated Quinolone,Fleroxacin, Its N-Demethyl,and N-Oxide Metabolites in Plasma and Urine by High Performance Liquid Chromatography with Fluorescence Detection

Abstract

A liquid chromatographic method is described for the determination of the new fluoroquinolone Ro 23–6240 and its N-demethyl and N-oxide metabolites in plasma and urine. The three substances were extracted from aqueous solution with dichloromethane/isopropanol containing sodium dodecyl sulphate. After evaporation and reconstitution, samples were analysed on a reversed-phase column using ion pair chromatography and fluorescence detection. The limit of quantification was 10–20 ng/ml (RSD 4%) using a 0.5 ml plasma sample, and the inter assay precision was 3–10% over the concentration range 50 ng/ml to 20 μg/ml. Recovery from plasma was 81% (RSD 10%) over the range 10 ng/ml to 5 μg/ml. The method has been applied successfully to the analysis of several thousand samples from human pharmacokinetic studies. Care has to be taken to avoid exposure of samples to direct sunlight, and the use of opaque vessels for sample storage and handling is recommended.     

Ultrasonic Leaching of Bio-Collectors for Heavy Metal Analysis

Abstract

A Bio Collector - Ultrasonic Leaching Method (BC-ULM) was developed for the analysis of heavy metals (Pb, Cd,Cr, Ni, Cu, Fe and Al) on plant sprouts for the assessment of environmental pollution. Fabaceae Rabinia Pseudoacacia L. and Pinaceae Pinus Sylvertris L. sprouts were chosen as bio-collectors. The bio-collector sprouts were leached using 1% HNO₃ solution under ultrasonic effect and the obtained leachate samples were analysed by atomic absorption spectrometry (AAS).

The accuracy of BC-ULM was tested by comparing obtained results with those of deposition plate (DPM) and ashing (AM) methods which both are of practical use. Our findings show that BC-ULM and AM results are in agreement. Average heavy metal pollution factors of BC-ULM and DPM are well comparable with each other. Maximum and minimum heavy metal polluted stations were determined with no difference at all for all three methods. The average RSD % of BC-ULM varied between 5.5–8.4 % for n=13, depending on the analyte and the nature of the sample. Again, average RSD % was obtained between 1.7–8.0 % (n=9) and 3.4–9.8 % (n=11) for AM and DPM, respectively. The precision variance between BC-ULM and AM was not significant at 0.05 probability for all metals except copper.     

Substoichiometric Isotope Dilution Analysis of Sulphur in coal

Abstract

Substoichiometric radioisotope dilution analysis has been applied to the determination of sulfur in coal. The experimental procedure involved the combustion of coal samples labelled with ³⁵S as sodium sulfate in a flowing oxýgen stream, collection of the combustion gases in hydrogen peroxide and substoíchiometric precipitation of barium sulfate. Samples of 0.2–10.0% sulfur were accurately determined with ±2% RSD by measuring the activity of the precipitates thus obtained and with comparison to standard samples carried through the same procedure. Analysis times of 15 minutes per sample were typical.     

Total nitrogen in wastewater analysis: Comparison of Devarda’s alloy method and high temperature oxidation followed by chemiluminescence detection

Two methods for determining total nitrogen (TN) contents of complex wastewaters were compared: Devarda’s alloy method and a method involving high temperature oxidation (HTO) followed by chemiluminescence detection (CLD). In the latter multiple standard additions were used for quantification purposes since the CLD response was found to be dependent on the structure of the analysed nitrogen-containing compounds. For both methods, sample dilution steps were necessary to achieve acceptable accuracy. The accuracies for selected compounds used in tests were within the 65–105% range. In a long-term interlaboratory investigation the HTO-CLD method yielded significantly (p < 0.05) higher results than Devarda’s alloy method and greater precision (within-assay repeatability approximately 1% RSD, while the corresponding within-day repeatability for Devarda’s alloy method was approximately 7% RSD).     

Optimization and validation of a Laser Ablation Inductively Coupled Plasma Mass Spectrometry method for the routine analysis of soils and sediments

A simple, rapid and sensitive method was developed for the routine analysis of trace elements on sediments and soils by UV-ns-LA-ICP-MS. The homogenization procedure that reduces the particle size of the samples to less than 1 µm diameter was found to be a key factor to allow for a representative sampling of the bulk soil at the micro-scale and to improve reproducibility and cohesion of the sample without requiring the use of any binder. The elimination of binders simplified the sample preparation and avoided any undesirable dilution of the sample. SEM/EDX analyses were conducted to evaluate the efficiency of laser to sample interaction. Matrix effects and different quantitation strategies were employed to demonstrate the utility of the analytical technique. Sixteen elements were analyzed on soil and sediment samples and certified reference materials. Analytical results obtained by LA-ICP-MS were comparable to solution ICP-MS analysis in terms of accuracy, precision and limits of detection. Two independent proficiency tests for trace metals in soils were conducted to compare the performance of the method versus conventional digestion ICP and AA methods, obtaining z scores ≤ 3 for all elements measured by LA-ICP-MS. An overall bias between 8 and 15% was found, depending on the sample while the overall precision was found to be better than 5% RSD for all samples. Limits of detection were as low as 0.01 mg kg^− 1.     

Isolation of Ligands of Trace Metals from Plant Samples by Immobilized Metal Affinity Chromatography

Abstract

Isolation of ligands of trace elements from plants by affinity chromatography with a metal immobilised on iminodiacetate resin has been investigated. To simulate various types of bioligands the following compounds were tested: phytic acid, peptides containing Cys and peptides containing Asp. Optimal conditions allowing isolation of the peptides with good efficiency comprise the use of Ga³⁺ ion, sample adsorption at pH = 4 and elution of the compounds by 0.3 mol/l NH₃. Phytic acid was bound too tightly and was not eluted. The procedure was used for purification of extracts of rye flour. The purified sample is suitable for analysis by MALDI-MS.     

Determination of Trace Elements in Different Powdered Samples by Atomic Emission Spectrometry with Spectral Excitation in a Two-Jet Arc Plasmatron

The effects of operating parameters and easily ionized additives on the analytical signal in the region before the confluence of plasmatron jets were studied. It was shown that the effective atomic excitation temperature in this region is independent of the concentration of NaCl (0–50%) in the graphite powder. A method was proposed for the direct atomic emission determination of trace elements in powdered samples. In this method, multielement analysis of various samples, such as graphite concentrates of trace impurities, soils, bottom sediments, plants, and humic acids can be performed under unified conditions using a unified set of reference samples without sample mineralization and dissolution. At the stage of sample preparation, a finely divided sample is mixed with a spectroscopic buffer (graphite powder doped with NaCl). The detection limits for several dozen elements in their direct determination varied from 10^–6 to 10^–4 wt % at a relative standard deviation (RSD) of no worse than 15%.     

Imaging and Quantitation of One and Two Dimensional TLC With a New Radioanalytic Imaging System

Abstract

A new method for the imaging and quantitation of radiolabeled substrates fractionated on one or two dimensional (2D) TLC plates has been developed. The TLC sample is read by a microcomputer-controlled beta- and gamma-sensitive gas proportional counter. The TLC plate is scanned by a 20 × 20 cm array of 952 individual detector elements, and the resulting quantitative image is displayed on a high resolution monitor for analysis. Individual radioactive spots may be quantitated on-screen.     

Anodic Stripping Potentiometric Determination of Cu,Pb, Cd and Zn In Natural Waters on a Novel Combined Electrode System

Abstract

A method is described for the reliable determination of copper, lead, cadmium and zinc in natural waters by anodic stripping potentiometry with the use of a novel combined electrode. The method involves two stripping cycles during which copper is initially determined on its own, followed by simultaneous determination of lead, cadmium and zinc after addition of gallium (III) ions. The optimum conditions include 0.01 M HCl as supporting electrolyte, 10 mg/L Hg (II) as chemical oxidant; E_dep(Cu) -700 mV vs Ag/AgCl; E_{dep(Pb,Cd,Zn)} -1200 mV vs Ag/AgCl; t_dep 10s; 150 μg/L Ga (III); sample rotation rate 5 and rest period 30s. Under these conditions, as low as 0.06 μg/L Cu (0.7% RSD); 0.2 μg/L Pb (13% RSD); 0.04 μg/L Cd (7.8% RSD) and 0.06 μg/L Zn (5.5% RSD) can be determined reliably. A linear concentration range of 0–110 μg/L was obtained for the four metals. The successful application of the method to reference fresh water, creek water and tap water is demonstrated.     

Determination of Trace Elements in Liquid Fuels by Instrumental Neutron Activation Analysis

Abstract

An instrumental neutron activation analysis with Ge(Li) γ -spectrometry and computer-assisted data reduction, has been developed for the determination of more than 20 elements in different liquid fuels. Organo-metallic standard solutions were mixed to obtain suitable standards. Two neutron irradiations and 4 γ-spectrometric measurements are required for each sample. Corrections were taken into account for a few spectrometric and nuclear interferences. The overall standard deviation for nearly all elements is mainly determined by counting statistics. The following elements can be determined : Na, Al, S, Cl, K, Sc, V, Cr, Fe, Co, Ni, Cu, Zn, As, Se, Br and La whereas the concentration of the following elements are mostly near the limit of detection: Mg, Mo, Sb, Ba, Th and Hg.     

Determination of Trace Elements in Super Alloy by ICP-MS

 A method is described for determination of 14 trace elements in super alloy certified reference material. Inconel 718 by ICP-MS. The interferences were investigated in detail. By using appropriate settings of the operational parameters and correcting interferences the elements without interference free isotopes were also analyzed. Non-spectral interference to the analytes was studied. No matrix separation or any other sample pretreatment but acid dissolution was made. 14 trace elements (B, Sc, Ga, Ge, In, Sn, Sb, Te, Hf, Ag, Ce, Tl, Pb and Bi) were analyzed by matrix matched standard solution calibration and using Rh as internal standard. Good agreement was achieved between the found levels and the certified values for most of the elements. The RSD (n = 4) of the determination values of Ce was lower than 20%, and RSD of the other 13 elements was lower than 10%. Received July 21, 2000. Revision May 29, 2001.     

Identification and quantification of main flavonoids in the leaves of Bambusa multiplex cv. Fernleaf

Abstract

The chemical profile of Bambusa multiplex cv. Fernleaf (B. multiplex) leaves was analysed by UPLC-DAD-Q-TOF-MS. Twelve compounds were identified and C-glycosyl flavonoids, including vitexin, isovitexin, isoorientin and its derivatives, are the main constitutes of the plant. Besides, a HPLC method for isoorientin quantification was developed. The RSD of retention time and peak area were 0.05% and 2.04% for six times analysis of isoorientin with concentration of 20?μg/mL. The recovery of isoorientin in real sample was 99.2%. The general trend of isoorientin content in B. multiplex leaves was that it steady increased from Jan. to May, and then quickly decreased. The maximum was found on May with value of 4.7?mg/g. The lowest level of isoorientin was found during Aug. to Nov. with value of about 1.66?mg/g. In different seasons, isoorientin is always the most dominant flavonoid which was accounted for about 50% of total flavonoids in the sample.