Biological Standard Reference Materials Research Articles

Application of NAA standardization methods using a low power research reactor

Two widely used neutron activation analysis (NAA) standardization methods (relative and k0) have been validated at the Ghana Research Reactor-1 (GHARR-1) Centre using environmental and biological standard reference materials (SRMs). The samples were IAEA Soil-7 as an environmental sample, and NIST Orchard Leaves 1571 as a biological sample. The qualitative and quantitative analyses were done using a high resolution Canberra N-type high purity germanium (HPGe) detector. The accuracy and precision were evaluated for the elements analysed. The concentrations of most of the elements were found to be within 10% of the certified values. Precision was calculated from six replicate measurements and was found to be within 15%.

INAA of Trace Elements in Biological Materials Using the SLOWPOKE-2 Reactor in Jamaica

The biological standard reference materials Orchard Leaves SRM 1571 and Oyster Tissue SRM 1566a was analysed by instrumental neutron activation analysis (INAA) at the International Centre for Environmental and Nuclear Sciences, Jamaica at (ICEN) and at the Instituto de Pesquisas Energeticas e Nucleares (IPEN-CNEN/SP), Brazil. The comparison of the results with those obtained with the more powerful reactor are used to evaluate the possibilities of INAA for the analysis of biological samples at ICENS. The detection limits, the precision and accuracy of the results obtained in both laboratories are compared. The advantages and disadvantages of the different irradiation facilities are discussed. Some results obtained for Jamaican biological samples are also presented.

Direct analysis of reference biofluids by coupled in situ electrodeposition-electrothermal atomic absorption spectrometry

The application of coupled in situ electrodeposition-electrothermal atomic absorption spectrometry (ED-ETAAS) to the determination of Pb in biological standard reference materials is described. In situ electrodeposition at a cell voltage of 3.0 V from 25-μl samples onto electrodeposited Pd is used to quantitatively separate the analyte from blood and urine matrices. With subsequent withdrawal of spent electrolyte, this overcomes the atomisation problems inherent with high salt and organic contents. ED-ETAAS is applied with minimal sample pre-treatment (acidification). The electrolysis process aids decomposition of the organic matrix, and the release of trace elements. Evolution of H 2 at the cathode counters fouling of the Pd modifier surface. The palladium deposit is renewed in situ for each determination. For AMI certified lyophilised blood, diluted 1+3 with 0.1 M HCl (18.1 μg/l Pb), the R.S.D. was 3.0% (peak height; n=5) and the detection limit (3 σ blank; n=5) was 1.5 μg/l. Results for certified blood samples were AMI 72.3±4.3 μg/l (certified 76.2±7.6 μg/l) and Seronorm 34.2±2.0 μg/l (36±4 μg/l). The result for NIST SRM 2670 normal urine acidified to 1% HNO 3 was 8.1±0.6 μg/l (recommended value 10 μg/l).

Application of a macrocycle immobilized silica gel sorbent to flow injection on-line microcolumn preconcentration and separation coupled with flame atomic absorption spectrometry for interference-free determination of trace lead in biological and environmental samples.

A simple and highly selective flow injection on-line pre-concentration and separation-flame atomic absorption spectrometric method was developed for routine analysis of trace amounts of lead in biological and environmental samples. The selective preconcentration of lead was achieved in a wide range of sample acidity (0.075 to > or = 3 mol L(-1)HNO3) on a microcolumn (145 microL) packed with a macrocycle immobilized on silica gel. The lead retained on the column was effectively eluted with an EDTA solution (0.03 mol L(-1), pH 10.5). Three kinds of potential interferences, i.e., preconcentration inferences from metal ions with an ionic radius similar to that of Pb(II) due to their competition for the cavity of the macrocyle, elution kinetic interferences from ions which form stable complexes with EDTA due to their competition for EDTA, and interferences in the atomizer from residual matrix, were evaluated and compared in view of the read-out mode of the analyte response (peak area vs peak height), column wash step (with vs without), column capacity (50 vs 145 microL), and column shape (conical vs cylindrical). The results showed that a combination of increase in column capacity, quantitation based on peak area, and use of dilute nitric acid for column wash before elution efficiently avoid the above-mentioned potential interferences. With the use of a 145 microL column the present system tolerated up to 0.1 g L(-1) Ba(II), 1 g L(-1) Sr(II), and at least 10 g L(-1) Fe(III), Cu(II), Ni(II), Zn(II), Cd(II), Al(III), K(I), Na(I), CaII), and Mg(II) in the sample digest. Further improvement of the interference tolerance can be achieved by increasing column capacity if more complicated samples need to be analyzed. At a sample loading rate of 3.9 mL min(-1) with 30-s preconcentration, an enrichment factor of 52, a detection limit (3s) of 5 micrograms L(-1) Pb in the digest and a sampling frequency of 63 h(-1) were obtained. The precision (RSD, n = 11) at the 200 micrograms L(-1) level was 1.9%. The enrichment factor and the detection limit can be further improved by increasing sample loading rate without degradation in the efficiency due to the favorable kinetics and low hydrodynamic impedance of the present system. The analytical results obtained by the proposed method for a number of biological and environmental standard reference materials were in good agreement with the certified and recommended values.

Study on the direct analysis of solid powder biological samples using fluorination assisted electrothermal vaporization inductively coupled plasma atomic emission spectrometry with PTFE slurry modifier

A method has been described for the direct determination of Ti, Cu, Mn, Cr and Cd in solid biological samples without any chemical pretreatment by fluorination assisted electrothermal vaporization inductively coupled plasma atomic emission spectrometry (ETV-ICP-AES) with slurry sampling. A polytetrafluorethylene (PTFE) emulsion was used as a fluorinating reagent to promote the vaporization of the analytes from the graphite furnace. The interface between furnace device and ICP torch and the main factors affecting the analytical signal were investigated systematically. The detection limits for the determination of Ti, Cu, Mn, Cr and Cd are 6.3, 4.7, 10, 13 and 278 ng/mL, respectively; the relative standard deviations are in the range of 1.5 (Mn) ∼4.0% (Cd) after optimization of the operating conditions. The recommended approach has been applied to directly determine the trace elements of interest in the Chinese traditional medicine Loulu and in the solid biological standard reference material (peach leaves, GBW 08501) with satisfactory results.

Flow Injection Hydride Generation Atomic Absorption Spectrometry for Determination of Arsenic in Water and Biological Samples from Arsenic-Affected Districts of West Bengal, India, and Bangladesh

The increasing concern over human exposure to arsenic in West Bengal and Bangladesh has necessitated the development of a rapid method for determination of trace levels of arsenic in water and biological samples. We have developed a simple indigenous flow injection hydride generation atomic absorption spectrometry (FI-HG-AAS) system for the determination of arsenic in parts-per-billion levels in water and biological samples. The technique is fast, simple, and highly sensitive. The accuracy and precision of the method were evaluated by spiking known amounts of arsenic and analyzing different types of environmental and biological standard reference materials. The organic matter in a biological sample was destroyed by acid digestion and dry ashing technique. We analyzed thousands of tubewell water samples from the affected districts of West Bengal and Bangladesh. Most of the water samples contained a mixture of arsenite and arsenate and in none of them could we detect methylated arsenic. We also analyzed thousands of urine (inorganic arsenic and its metabolites), hair, and nail samples and hundreds of skin-scale and blood samples of people drinking arsenic-contaminated water and showing arsenical skin lesions. Quality control was assessed by interlaboratory analysis of hair samples. An understanding of arsenic toxicity and metabolism requires quantitation of individual arsenic species. The techniques we used for the determination and speciation of arsenic are (i) separation of arsenite and arsenate from water by sodium diethyldithiocarbamate in chloroform followed by FI-HG-AAS; (ii) determination of arsenite in citrate/citric buffer at pH 3 and total arsenic in water in 5 M HCl by FI-HG-AAS. Thus, arsenate is obtained from the difference; (iii) for analysis of inorganic arsenic and its metabolites in urine FI-HG-AAS was used after separation of the species with a combined cation-anion exchange column. Total arsenic in urine was also determined by FI-HG-AAS after acid decomposition. The species arsenite and arsenate are present in groundwater in about a 1:1 ratio and about 90% of the total arsenic in urine is present as inorganic arsenic and its metabolites.

Determination of toxic and trace elements in algae by instrumental neutron activation analysis

Instrumental neutron activation analysis has been applied in the determination of toxic and other trace elements in a set of three algae materials provided by the International Atomic Energy Agency, with the aim of environmental preservation through enhanced applications of nuclear analytical techniques. The quality of the analysis method has been evaluated by analyzing a number of biological standard reference materials. By adding mineral nutrients, the cultivation of algae for metals is enhanced, in particular, selected toxic heavy metals such as As, Cd, Cr, Hg, Ni and Pb. It is believed that the level of elemental concentration in algae samples are dependent on environmental conditions due to its biochemical properties. Therefore, algae materials may be useful as an indicator or controller of environmental water pollution.

Elemental analysis of micro-samples of liquids or slurries by coiled-filament in-torch vaporization-inductively coupled plasma atomic emission spectrometry (ITV-ICP-AES)

In coiled-filament in-torch vaporization (ITV) sample introduction for inductively coupled plasma atomic emission spectrometry (ICP-AES), a sample is placed onto a coiled filament (e.g., a Re wire) and the sample carrying filament is inserted into a vaporization chamber which is attached to an ICP torch. In this study, six vaporization chambers were tested using in-situ generated smoke. Of these, a 6.5 cm 3 (internal volume) chamber was chosen. An Ar-H 2 (≈3% v/v) carrier gas was used and the effect of flow rate and filament insertion position was determined for several elements (e.g., Zn, Pb, Cd, Mn, Mg, V, Be and Sr) that covered a range of wavelengths and vaporization characteristics. Analytical performance characteristics were also obtained and calibration graphs were linear over several orders of magnitude. Detection limits were in the pg to sub-pg range. Coiled-filament ITV-ICP-AES was also briefly tested with powdered solids as slurries using a biological standard reference material and Mn and Zn as test elements.

Determination of mercury in biological samples using organic compounds as matrix modifiers by inductively coupled plasma mass spectrometry

A method was developed for the determination of total mercury in biological samples. The effects of aqueous ammonia, ethylenediamine and triethanolamine on Hg signal intensity by inductively coupled plasma mass spectrometry has been evaluated and the possible mechanisms discussed. It has been proved that the signal intensity of Hg significantly increases with adding, in the presence of small amounts of aqueous ammonia, ethylenediamine or triethanolamine. The normalized intensity (the signal intensity ratio with amine and without amine) of Hg increases as the concentration of aqueous ammonia, ethylenediamine or triethanolamine increases, but the degree of enhancement of aqueous ammonia was smaller than that of ethylenediamine and triethanolamine. The normalized intensity of Hg with aqueous ammonia, ethylenediamine and triethanolamine decreases as the nebulizer flow rate increases, but decreasing degree of aqueous ammonia was smaller than that of ethylenediamine and triethanolamine. The higher the RF powers the higher the normalized intensity of Hg at the same nebulizer flow rate. The addition of aqueous ammonia, ethylenediamine and triethanolamine into analytical solutions significantly improved the transport efficiency of Hg. The detection limit of Hg is improved about ten times by the addition of ethylenediamine or triethanolamine under the optimum experimental parameters. The method has been used to determine mercury in biological standard reference materials (SRM). The analytical results are very close to the certified values and the determined values for similar samples.

Minimising the risk of some systematic errors by the use of the single vessel principle for cold vapour atomic absorption spectrometric determination of mercury in biological solids

The suitability of the single vessel principle (performing all steps of an analytical procedure in one vessel) for cold vapour atomic absorption spectrometric determination of mercury in biological solids was evaluated. The single vessel method gave a lower mean blank level with better precision, hence lower detection limits, as compared to the conventional method. The determination of total mercury in biological standard reference materials by the single vessel method also produced significantly higher mercury values and better precision than the conventional method. However, the mercury concentrations obtained in certified reference materials by the use of both methods were close to the mean certified values. Moreover, the use of the single vessel method is cost effective, rapid and environment friendly. The use of the single vessel technique is therefore recommended for accurate and reliable determination of mercury in biological solids.

Microwave-Assisted Vapor-Phase Nitric Acid Digestion of Small Biological Samples for Inductively Coupled Plasma Spectrometry

The applicability of microwave-assisted, vapor-phase nitric acid digestion of small biological samples in closed-vessel microwave systems is examined for the inductively coupled plasma atomic emission spectroscopy (ICP-AES) determination of 10 elements (Al, As, Ca, Cu, Cd, Fe, Mn, Mo, Pb, and Zn). A 1.8 mL quartz sample container geometry was optimized for the successful decomposition of 50 to 90 mg of powdered biological samples. Microwave energy was efficiently coupled by addition of 250 μL of distilled deionized water to the sample. A single microwave-assisted, vapor-phase acid sample digestion was accomplished within 30 min (including cooling time) at ∼1200 psi pressure and 450 W microwave power in a commercial pressurized microwave decomposition (PMD) system. Multiple microwave-assisted, vapor-phase acid digestions were achieved at moderately high pressure (400 to 480 psi) and 230 °C with a second closed-vessel microwave apparatus. The results for 10 elements in biological standard reference materials agree well with the certified values.

A comparison of the performance of a fundamental parameter method for analysis of total reflection X-ray fluorescence spectra and determination of trace elements, versus an empirical quantification procedure

The performance has been compared of two different quantification methods — namely, the commonly used empirical quantification procedure and a fundamental parameter approach — for determination of the mass fractions of elements in particulate-like sample residues on a quartz reflector measured in the total reflection geometry. In the empirical quantification procedure, the spectrometer system needs to be calibrated with the use of samples containing known concentrations of the elements. On the basis of intensities of the X-ray peaks and the known concentration or mass fraction of an internal standard element, by using relative sensitivities of the spectrometer system the concentrations or mass fractions of the elements are calculated. The fundamental parameter approach does not require any calibration of the spectrometer system to be carried out. However, in order to account for an unknown mass per unit area of a sample and sample nonuniformity, an internal standard element is added. The concentrations/mass fractions of the elements to be determined are calculated during fitting a modelled X-ray spectrum to the measured one. The two quantification methods were applied to determine the mass fractions of elements in the cross-sections of a peat core, biological standard reference materials and to determine the concentrations of elements in samples prepared from an aqueous multi-element standard solution.

Selective Extraction and “One-Drop” Flame Atomic Absorption Spectrometric Determination of Silver in Biological Standard Reference Materials

Selective Extraction and “One-Drop” Flame Atomic Absorption Spectrometric Determination of Silver in Biological Standard Reference Materials

Determination of bromine and iodine in biological and environmental materials using epithermal neutron activation analysis

Epithermal neutron activation analysis (ENAA) was applied to the determination of the contents of bromine and iodine in 40 biological and environmental standard reference materials and Chinese diets. Boron nitride (BN) for solid samples and BN+Cd for liquid samples were adopted as shield material. Irradiation was carried out in inner and outer irradiation sites in a Miniature Source Reactor (MNSR) for solid and liquid samples, respectively. The 443 keV photopeak of 128I and the 616 keV photopeak of 80Br were used. The precision of measurement (relative standard deviation) is 2∼6% for contents of iodine of more than 100 ng/g and 8∼12% in the 20∼100 ng/g range in solid samples, and 12∼18% at less than 100 ng/ml in liquid samples. For bromine, the precision of measurement is 2–8% for solid samples and lower than 13% for liquid samples. The detection limits under experimental conditions varied between 10∼30 ng/g, 55∼95 ng/g and 25∼68 ng/g for iodine and 50∼150 ng/g, 200∼450 ng/g and 100∼300 ng/g for bromine in ENAA with BN shield in inner irradiation sites, with Cd shield and BN+Cd shield in outer irradiation sites, respectively.

Flow injection atomic absorption spectrometery for the standardization of arsenic, lead and mercury in environmental and biological standard reference materials

Results of a thorough study and application of flow injection atomic absorption spectrometry for the determination of As, Pb and Hg in parts per million to sub-parts per billion levels in environmental and biological samples have been described. Various standard reference materials from the National Bureau of Standards, USA, the National Institute of Standards and Technology, USA, the Community Bureau of Reference, Brussels, Belgium and the National Institute for Environmental Studies, Japan and Standard Chinese river sediment were used. By flow injection hydride generation AAS the standard reference materials were analyzed for As and Pb. Mercury was determined by cold vapour flow injection AAS from environmental and biological standard reference materials. The technique is fast, simple and highly sensitive. It takes only 30 s for each analysis from the digested solution. The detection limits of As, Pb and Hg are 1.8 μg L–1 and 2.0 μg L–1 and 1.5 μg L–1, respectively. The results show good agreement with the certified values.

Determination of bromine and iodine in normal tissues from Beijing healthy adults.

The contents of bromine and iodine in samples of heart, liver, spleen, lung, muscle, and hair from healthy adults living in Beijing, China, were determined using epithermal neutron activation analysis. The results indicate that the contents of bromine in lung and iodine in liver are higher than those in other tissues, except human hair. The bromine contents in Beijing human tissues are significantly lower than those in other countries. The contents of iodine are slightly lower than those in other countries, but the difference is not significant. Three biological standard reference materials were simultaneously determined with the samples, and our results agree well with the certified values.

Determination of Arsenic and Selenium in River Water by Hydride Generation Inductively Coupled Plasma-Mass Spectrometry with High Resolution

Hydride generated in a mixing coil was separated in a gas-liquid separator which was closed with an electromagnetic pinch valve and then swept continuously into the torch of a high-resolution inductively coupled plasma-mass spectrometer. The system was operated with variable speed-peristaltic pumps by manipulating electromagnetic relays and a timer. Water vapor in the hydride gas was removed by inserting a glass trap immersed in an ice bath. Interference with transition matals was eliminated by using Chelex 100 resin. The detection limits (3 times the signal-to-noise ratio) of arsenic and selenium are 0.03 and 0.06ng/ml, respectively, at a resolution of 10000. The accuracies checked with biological standard reference materials obtained from the National Institute of Science and Technology (NIST), USA, and the National Research Council (NRC), Canada, were within the certified values. The arsenic and selenium contents in river water were determined by the present method.

Application of tertiary amines for arsenic and selenium signal enhancement and polyatomic interference reduction in ICP-MS analysis of biological samples

Water soluble tertiary amines enhance signals and decrease polyatomic chloride interferences in the direct inductively coupled plasma – mass spectrometric (ICP-MS) determination of As and Se in biological samples. Preliminary experiments with amine concentrations and nebulizer flow rates produced element and interference signal intensity changes. Arsenic and Se ICP-MS determination parameters have been optimized by a simplex procedure with amines in an argon plasma or without amines but with addition of N2 to the Ar. Variables include RF (radio frequency) power, nebulizer gas flow rate, intermediate gas flow rate, and amine concentration or nitrogen gas flow rate. Detection limit, minimization of polyatomic ion intensities, and reproducibility have been evaluated as reponse factors. The signal enhancement and element-to-molecular interference ratios differ to some extent with analyte intensity optimum operating conditions. The detection limits with addition of nitrogen (16 pg mL–1 for As and 180 pg mL–1 for Se) or of amines (8 pg mL–1 for As and 120 pg mL–1 for Se) and the extent of chloride interference minimization were compared. Amines addition was more beneficial. Biological standard reference materials and food and fecal samples were analyzed following different sample dissolution procedures.

Determination of Arsenic and Selenium by Hydride Generation Atomic Absorption Spectrometry Using a Gas–Liquid Separator and a Dehydration Trap

Hydride generated in a mixing coil was collected in a gas–liquid separator, dehydrated in a dehydration trap, and swept into an electrically heated furnace by manipulating electromagnetic relays and timers. Interferences from transition metals were eliminated by the Chelex 100 separation. Sharp peaks were recorded on a recorder. Detection limits (signal to noise ratio 3) of arsenic and selenium were 0.6 ng/ml and 1 ng/ml, respectively. Accuracies checked with biological standard reference materials obtained from the National Institute of Standards and Technology (NIST) of USA and the National Research Council (NRC) of Canada were within the certified values except for those of oyster tissue.

Determination of antimony in river water by hydride generation-AAS.

Stibine, generated by mixing a 0.7 M sulfuric acid solution of antimony(III)with a 2% sodium tetrahydroborate solution in a mixing coil for 30 s, was separated from solution in a gas-liquid separator, and then swept into an electrically heated quartz furnace by manipulating electromagnetic relays and timers.Sharp peaks were recorded on a recorder. The detection limit (three times signal to noise ratio) for antimony(III)was 0.6 ng ml-1.It took five minutes for one sample measurement.Interference from transition metals could eliminated by Chelex 100 separation.Antimony(V)was reduced by using a 0.1 M potassium iodide solution. The accuracy, checked with a biological standard reference material obtained from the National Institute of Standard and Technology (NIST) of USA, was within the certified value. Antimony in river water was determined by the present method.