Pre-ashing of biological samples — a sample preparation technique for solid sampling ZAAS

Summary A pre-ashing method by a conventional electrothermal furnace was used as a concentration technique for powdered biological samples in the solid sampling technique with GF-ZAAS. A relationship equation between the concentration factors and the concentrations of main inorganic components in biological samples has been established, and it has become possible to calculate the concentration factors, if the total concentration of K, Na, Mg and Ca, or total concentration of K and Mg, or the concentration of K only are known. The proposed method has been successfully applied to the direct determination of Co, Ni, Mn and Pb at the g/kg levels in biological samples.Presented at the 5th International Colloquium on Solid Sampling, with Atomic Spectroscopy, May 18–20, 1992; Geel, Belgium. Papers edited by R.F.M. Herber, Amsterdam     

Design and simulation of neutron radiography system based on 241Am–Be source

Neutron imaging is extended rapidly as a means of non-destructive testing (NDT) of materials. Various effective parameters on the image quality are needed to be studied for neutron radiography system with good resolution. In the present study a portable system of neutron radiography has been designed using ²⁴¹Am–Be neutron source. The effective collimator parameters were calculated to obtain relatively pure, collimated and uniform neutron beam. All simulations were carried out in two stages using MCNPX Monte Carlo code. In the first stage, different collimator configurations were investigated and the appropriate design was selected based on maximum intensity and uniformity of neutron flux at the image plane in the outlet of collimator. Then, the overall system including source, collimator and sample was simulated for achieving radiographic images of standard samples. Normalized thermal neutron fluence of 2.61×10^?5 cm^?2 per source particle with n/γ ratio of 1.92×10⁵ cm^?2 μSv^?1 could be obtained at beam port of the designed collimator. Quality of images was assessed for two standard samples, using radiographic imaging capability in MCNPX. The collimated neutron beam in the designed system could be useful in a transportable exposure module for neutron radiography application.     

Sorbent-excluding sample preparation method for GC–MS pesticide analysis in apple peel

Apple peel is frequently exposed to pesticides, especially in the last stages of the pesticide treatment practice. For a certain period, peel retains most of the applied pesticides, which precisely indicates the presence of pesticide residues. This study was conducted to establish and evaluate the method for the residue analysis of pyrimethanil, cyprodinil, trifloxystrobin, bifenthrin and boscalid by GC–MS in peel of Granny Smith, Golden Delicious and Idared varieties. The method consisted of few steps, without the routine usage of sorbents, and resulted in efficient removal of waxes, targeted as main interferences in GC–MS analysis. The matrix effect, boscalid selectivity issue, trend of lower trueness for bifenthrin in all matrices and for all analytes in Granny Smith matrix were in some way associated with the waxes. Finally, the method was applied to the analysis of three varieties of apple orchard samples, after 9 and 5 months of treatment with commercial formulations that contain pyrimethanil, cyprodinil and boscalid as active ingredients. Since the developed method consisted of few steps and used nontoxic and economic reagents, it could be implemented as a fast, economic and reliable screening method.     

A simple method of target preparation for the bulk analysis of powder samples by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS)

A simple and rapid procedure using a glue technique has been developed for the preparation of stable targets from powder samples for bulk analysis by LA– ICP–MS. The procedure was evaluated for the analysis of trace elements in SiC, of rare-earth elements in different types of silicate (rocks, sediments, and soils), and of Au and platinum-group elements in geological silicates. The test analysis was conducted using an IR laser in combination with a quadrupole mass spectrometer. The recommended preparation procedure offers the possibility of different types of calibration, for example application of certified reference samples in combination with prepared spiked samples on a base of a natural or synthetic matrix, or addition calibration. The resulting calibration functions are linear over a range of several decades. The trueness of the results was evaluated by use of certified reference samples. Analytical concentration ranges, detection limits, and the relative standard deviations are reported. Received: 20 November 2000 / Revised: 13 March 2001 / Accepted: 17 March 2001     

Facile preparation of a cellulose microfibers–exfoliated graphite composite: a robust sensor for determining dopamine in biological samples

A simple and robust dopamine (DA) sensor was developed using a cellulose microfibers (CMF)–exfoliated graphite composite-modified screen-printed carbon electrode (SPCE) for the first time. The graphite-CMF composite was prepared by sonication of pristine graphite in CMF solution and was characterized by high-resolution scanning electron microscopy, Fourier transform, infrared, and Raman spectroscopy. The cyclic voltammetry results reveal that the graphite-CMF composite modified SPCE has superior electrocatalytic activity against oxidation of dopamine than SPCE modified with pristine graphite and CMF. The presence of large edge plane defects on exfoliated graphite and abundant oxygen functional groups of CMF enhance electrocatalytic activity and decrease potential to oxidize DA. Differential pulse voltammetry was used to quantify DA using the graphite-CMF composite-modified SPCE and demonstrated a linear response for DA detection in the range of 0.06–134.5 µM. The sensor shows a detection limit at 10 nM with an appropriate sensitivity and displays appropriate recovery of DA in human serum samples with good repeatability. Sensor selectivity is demonstrated in the presence of 50-fold concentrations of potentially active interfering compounds including ascorbic acid, uric acid, and dihydroxybenzene isomers.     

An241Am−Be source based thermal neutron activation analysis facility at KFUPM

An instrumental thermal neutron activation analysis facility based, on a 16 Ci²⁴¹ Am–Be source, a high resolution -ray spectrometry setup and a PC-based data acquisition system at KFUPM is described. The thermal neutron flux distribution was determined from the induced activities of high purity indium foils. The absolute thermal neutron flux was calculated from the activities of bare and cadmium-covered gold foils at a position of 3 cm from the soource at which the flux reaches a maximum. The facility tests were carried out with the determination of manganese concentrations in six types of industrially important steel samples. The result of 1.33% manganese in SS-304 steel sample was in excellent agreement with the literature value. The method is nondestructive, economical and ideal for bulk analysis.     

Finding a suitable shield for mixed neutron and photon fields based on an Am–Be source

This study aimed to investigate a shielding design against neutron and photon rays from neutron irradiators based on Am–Be sources, using the Monte Carlo simulation. Different shielding materials were studied, including borated polyethylene, DaGa concrete, and epoxy resin with colemanite. The Monte Carlo N-particle code (MCNP) was used to design shielding. A new type of neutron and photon shielding material based on 40 % galena, 55 % polyethylene, and 5 % boric acid is proposed. The results show that the total effective dose of radiation is significantly reduced by the optimum radius of this shielding system.     

Effective liquid–liquid extraction method for analysis of pyrethroid and phenylpyrazole pesticides in emulsion-prone surface water samples

The distribution of pyrethroid and phenylpyrazole pesticides in the water environment has raised public concerns because of their potential risks to ecosystem and human health. However, co-extraction of emulsifier type compounds (by liquid–liquid extraction, LLE) present in environmental samples can present a challenge for quantifying typically low concentrations of pesticides. Several methods were evaluated for breaking emulsions in problematic environmental surface water samples extracted by LLE using methylene chloride. Target pesticides included 11 typical pyrethroid and phenylpyrazole pesticides commonly used in agricultural and landscape insect pest control. The most effective method was selected for validation in fortification studies with GC-ECD analysis. The average recoveries of spiked pyrethroid and phenylpyrazole pesticides were 88.2–123.4% for water samples with moderate emulsions and 93.0–117.4% for water samples with severe emulsions. Recoveries of the pesticides ranged 81.0–126.4% (water samples with moderate emulsions) and 95.9–110.6% (water samples with severe emulsions) for lowest fortification level (5–20 ng L⁻¹), 88.2–123.4% (water samples with moderate emulsions) and 93.0–117.4% (water samples with severe emulsions) for middle fortification level (10–40 ng L⁻¹), and 90.2–119.9% (water samples with moderate emulsions) and 91.2–105.9% (water samples with severe emulsions) for highest fortification level (50–200 ng L⁻¹). Relative standard deviations of pesticide recoveries were usually <10%. Results indicate that this method is a robust and reproducible option for LLE of pyrethroid and phenylpyrazole pesticides from emulsion-prone surface water samples.     

Spectra and dose with ANN of 252Cf, 241Am–Be, and 239Pu–Be

Artificial neural networks have been applied to unfold the neutron spectra and to calculate the effective dose, the ambient equivalent dose, and the personal dose equivalent for ²⁵²Cf, ²⁴¹Am–Be, and ²³⁹Pu–Be neutron sources. The count rates that these neutron sources produce in a Bonner Sphere Spectrometer with a ⁶LiI(Eu) were utilized as input in both artificial neural networks. Spectra and the ambient dose equivalent were also obtained with BUNKIUT code and the UTA4 response matrix. With both procedures spectra and ambient dose equivalent agrees in less than 10%. The Artificial neural network technology is an alternative procedure to unfold neutron spectra and to perform neutron dosimetry.     

HPLC–based methods for the determination of levetiracetam in biological and pharmaceutical samples

Levetiracetam is one of the new generation anti–epileptic agents (also known as anticonvulsants or antiseizure drugs). Following its approval for marketing in 2000, levetiracetam has been widely used in the treatment of epilepsy due to its broad spectrum effects. One of the advantages of this antiseizure drug is its rapid and complete absorption after oral administration. It has also minimal drug–drug and food interactions, and shows more than 95% bioavailability. The determination of levetiracetam in various samples is carried out using several analytical methods including HPLC–based methods. HPLC–based methods are used for different pharmaceutical analyses and play an important role in drug monitoring during patient follow–ups. This review provides a summary of the HPLC–based methods used in the determination and quantification of levetiracetam in biological fluids and pharmaceutical preparations.     

Implementation of the k 0-standardization method for analysis of geological samples at the Neutron Activation Analysis Laboratory, São Paulo, Brazil

The Neutron Activation Analysis Laboratory (LAN-IPEN) has been analysing geological samples for many years with the INAA comparative method, for geochemical and environmental research. This study presents the results obtained in the implementation of the k ₀-standardization method at LAN-IPEN, for geological samples analysis, by using the program k ₀-IAEA, provided by the International Atomic Energy Agency (IAEA). The thermal to epithermal flux ratio f and the shape factor α of the epithermal flux distribution of the IEA-R1 nuclear reactor of IPEN were determined for the pneumatic irradiation facility and one selected irradiation position, for short and long irradiations, respectively. To obtain these factors, the “bare triple-monitor” method with ¹⁹⁷Au–⁹⁶Zr–⁹⁴Zr was used. In order to validate the methodology, the geological reference materials basalts JB-1 (GSJ) and BE-N (IWG-GIT), andesite AGV-1 (USGS), granite GS-N (ANRT), SOIL-7 (IAEA) and sediment Buffalo River Sediment (NIST–BRS-8704), which represent different geological matrices, were analysed. The concentration results obtained agreed with assigned, with bias <10 % except for Zn in AGV-1. The U-score test showed that all results, except Mg in JB-1, are within 95 % confidence interval. These results indicate excellent possibilities of using this parametric method at the LAN-IPEN for geochemical and environmental studies.     

Characterization of an orphan Ra–Be neutron source

Journal of Radioanalytical and Nuclear Chemistry - An orphan radium-beryllium (Ra–Be) neutron source (Nuclear Chicago Corporation) detected inside a scrap metal shipping container, was seized...     

X–ray fluorescent spectroscopy with a focused X–ray beam collimated by a glass capillary guide tube and element mapping of biological samples

Several research groups developed X–ray fluorescent spectroscopic microanalysis systems using focused X–ray beams. Typical examples are reviewed for these systems using conventional and synchrotron radiation light source. Details of the system developed by the present authors are additionally shown. Applications for biological samples done by the present authors are also shown. Focused X–ray beam by a glass capillary guide tube method is useful for non–destructive real–time monitoring of elemental distribution of plants.     

A method for direct,semi-quantitative analysis of gas phase samples using gas chromatography–inductively coupled plasma-mass spectrometry

A new and complete GC–ICP-MS method is described for direct analysis of trace metals in a gas phase process stream. The proposed method is derived from standard analytical procedures developed for ICP-MS, which are regularly exercised in standard ICP-MS laboratories. In order to implement the method, a series of empirical factors were generated to calibrate detector response with respect to a known concentration of an internal standard analyte. Calibrated responses are ultimately used to determine the concentration of metal analytes in a gas stream using a semi-quantitative algorithm. The method was verified using a traditional gas injection from a GC sampling valve and a standard gas mixture containing either a 1 ppm Xe + Kr mix with helium balance or 100 ppm Xe with helium balance. Data collected for Xe and Kr gas analytes revealed that agreement of 6–20% with the actual concentration can be expected for various experimental conditions.To demonstrate the method using a relevant “unknown” gas mixture, experiments were performed for continuous 4 and 7 hour periods using a Hg-containing sample gas that was co-introduced into the GC sample loop with the xenon gas standard. System performance and detector response to the dilute concentration of the internal standard were pre-determined, which allowed semi-quantitative evaluation of the analyte. The calculated analyte concentrations varied during the course of the 4 hour experiment, particularly during the first hour of the analysis where the actual Hg concentration was under predicted by up to 72%. Calculated concentration improved to within 30–60% for data collected after the first hour of the experiment. Similar results were seen during the 7 hour test with the deviation from the actual concentration being 11–81% during the first hour and then decreasing for the remaining period. The method detection limit (MDL) was determined for the mercury by injecting the sample gas into the system following a period of equilibration. The MDL for Hg was calculated as 6.8 μg · m^− 3. This work describes the first complete GC–ICP-MS method to directly analyze gas phase samples, and detailed sample calculations and comparisons to conventional ICP-MS methods are provided.     

Determination of trace elements in quartz glass by use of LINA-Spark–ICP–MS as a new method for bulk analysis of solid samples

The determination of trace elements in pure quartz glass samples has been performed by coupling an ICP quadrupole mass spectrometer with the LINA-Spark-Atomizer, an IR laser ablation system dedicated to direct bulk and surface analysis of solid samples. Linear calibration curves were obtained for nine elements (Na, Al, Ca, Ti, Cr, Mn, Zr, Ba, and Pb) in the ng g^–1 range with detection limits of less than 10 ng g^–1 for Ca, Cr, Mn, Zr, Ba, and Pb and in the range of 120–220 ng g^–1 for Na, Al, and Ti. The distance between the laser focal point and the sample surface has a significant influence on signal intensity and precision, both of which can be improved by a factor of approximately two by focusing the laser 15 mm behind the sample surface. Aerosol moistening reduced the standard deviation of the signal intensity by a factor of 2–4. Signal instability, which resulted from different ablation rates or variations in the transmission of the mass spectrometer, were compensated by use of the simultaneously measured SiAr⁺ ion as an internal standard. Under these conditions precision was usually better than 5% RSD. The results were compared with those obtained by use of a commercial LA–ICP–MS system. With this instrumentation linear calibration curves were achieved for three elements only (Al, Ti, and Pb), showing that LA–ICP–MS is less appropriate for bulk analysis in the ng g^–1 range.     

Hollow fiber-based liquid–liquid–liquid microextraction combined with electrospray ionization-ion mobility spectrometry for the determination of pentazocine in biological samples

A new method based on liquid–liquid–liquid microextraction combined with electrospray ionization-ion mobility spectrometry (LLLME-ESI-IMS) was used for the determination of pentazocine in urine and plasma samples. Experimental parameters which control the performance of LLLME, such as selection of composition of donor and acceptor phase, type of organic solvent, ionic strength of the sample, extraction temperature and extraction time were studied. The limit of detection and relative standard deviation of the method were 2 ng/mL and 5.3%, respectively. The linear calibration ranged from 10 to 500 ng/mL with r² = 0.998. Pentazocine was successfully determined in urine and plasma samples without any significant matrix effect.