INAA and PIXE for the determination of the contents of extractable sediment

The three-stage BCR sequential step reference extraction procedure was applied to the reference material BCR CRM 601, especially developed for fractionation studies. Extracted fractions were analyzed for Cr, Ni, Zn, Cd, and Pb, by k ₀-standardized instrumental neutron activation (k ₀ INAA) and proton induced X-ray emission (PIXE), and flame atomic absorption spectrometry (FAAS). Sample preparation procedures were developed for both k ₀ INAA and PIXE techniques, related to the evaporation of the solutions in order to get solid samples for neutron and proton irradiation. Quality control was assessed by intercomparison of the analytical results obtained by the applied techniques, which included results for a few certified reference materials. In the extracted fractions, chromium concentration was not determined accurately by both nuclear techniques. Concerning Cd, Ni, Pb, and Zn, the results were in general in good agreement with the certified values and FAAS. Some incomplete separation of the residue might have occurred.     

Neutron activation analysis of extractable organohalogens in milk from China

Instrumental neutron activation analysis (INAA) has been used for the determination of extractable organohalogens (EOX) in milk. The detection limits are 50 ng, 8 ng and 3.5 ng for Cl, Br and I, respectively. The EOX concentrations in milk samples from various regions of China were determined. Meanwhile, organochlorine pesticides residues were detected by gas chromatography. The concentrations of the EOX in the milk samples are decreasing in the order of EOCl >> EOBr > EOI, and EOCl accounts for 95% of the total EOX. The average concentration of EOCl in milk is 4.44 ·g/g expressed as fat weight basis, with the highest value of 17.6 ·g/g from South China. The mean concentrations of total HCH and DDT are 0.038 ·g/g and 0.046 ·g/g, respectively. Organochlorine pesticides account only for 1.6% of the EOCl, indicating the very high proportion of the unknown EOCl in the milk sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of extractable organohalogens in the atmosphere by instrumental neutron activation analysis

Summary Air samples were collected at a downtown site in Beijing from January to July 2004 and analyzed by instrumental neutron activation analysis (INAA) combined with organic solvent extraction method for the concentrations and distributions of extractable organohalogens (EOX), including extractable organochlorinated (EOCl), organobrominated (EOBr) and organoiodinated compounds (EOI). The concentrations of EOX were increasing in the order of EOCl >> EOBr ~ EOI in both gaseous and particulate phase. EOCl accounted for 75.8-100% and 83.7-100% of EOX in particulate and gaseous phase, respectively, suggesting that EOCl was the major component of the organohalogens in the atmosphere. In the plots of the logarithm of the EOX concentrations versus the reciprocal temperature, their linear relations were observed for EOCl (R = -0.9), for EOBr (R = -0.6) and EOI (R = -0.7) in gaseous phase, which indicated that the concentrations of EOCl, EOBr and EOI in gaseous phase exhibited a strong temperature dependence, i.e., their concentrations increased with increasing of temperature.     

INAA determination of major and trace elements in loess,paleosol and precipitation layers in a pleistocene Loess Section,China

Instrumental neutron activation analysis was used for the determination of 31 major and trace elements in 32 samples from the Xinji Loess Section, Shaanxi Province, China. Interferences, including those from uranium fission products, were evaluated and corrections applied where necessary. The 39.7-meter deep section comprises of Lishi Loess of the middle Pleistocene (Q₂) and Malan Loess of the late Pleistocene (Q₃). The section is characterized by the presence of 5 layers of paleosol, and each paleosol is underlain by a precipitation layer. When the elemental abundances are converted to a carbonate-free basis, there is little compositional difference among the carbonate-free fractions of loess, paleosol and precipitation layers. This indicates that dissolution of carbonate minerals by downward-moving surface water was an important process in paleosol formation while other minerals were not severely weathered and elemental fractionation was minimal. The parent materials of the paleosol and precipitation layers closely resemble the loess layers in their elemental abundances, which suggests that all layers in the section have a compositionally similar source.     

Multielement determination in Tillandsia by INAA

Instrumental neutron activation analysis was employed to measure 43 elements, including some macroconstituents, in the leaves of some species of the epiphytic genusTillandsia (Bromeliaceae). The results, confirming the oligotrophyc nature of the genus, are briefly discussed with regard to a possible role as multielemental environmental monitors.     

INAA with gamma-gamma coincidence for selenium determination in food

Selenium detection limits of INAA are normally above its concentration in most biological materials. Gamma-gamma coincidence methodology can be used to improve the detection limits and uncertainties in the determination of selenium. Here, some edible parts of plants were measured using a HPGe detector equipped with a NaI(Tl) active shielding, producing spectra both in normal and coincidence modes. The results presented the reduction of the detection limits of selenium by a factor of 2 to 3 times and improvement in the uncertainty of up to 2 times.     

Rare earth elements determination and distribution patterns in surface marine sediments of the South China Sea by INAA,Malaysia

Results obtained from the analysis of sediments surface samples taken from rivers mouth and polluted marine environment were analyzed for REE contents to determine the concentrations of La, Ce, Sm, Eu, Tb, Dy, Lu and Yb using instrumental neutron activation analysis. Thirty surface samples were collected from ten sites in the coastal marine sediments of the South China Sea along 957 km stretch of the east coast of Peninsular Malaysia. The samples prepared in the powdered form before irradiating them in a neutron flux of ~4 × 10¹² n cm⁻² s⁻¹ at 750 kW power using the TRIGA Mark II research reactor at Malaysian Institute for Nuclear Technology (MINT). Results of the total concentration are used to establish baseline data in environmental pollution assessment and to develop the correlations between the Ce/Ce* anomalies and the distribution patterns of some the light rare earth elements (LREEs) and the heavy rare earth elements (HREEs). The Chondrite-normalized REE pattern from each site examined and used to explain the sedimentation patterns by anthropogenic activities and by natural processes such as shoreline erosion, weathering deposits. Shale-normalized (NASC) patterns suggest enrichment of LREEs relative to the HREEs with a positive Ce/Ce* anomaly. Validation of the used method was done using a Soil-7 SRM.     

A comparison of INAA and ise for the determination of calcium in human hair

The calcium concentration was determined in human hair of several normal individuals and of patients suffering from various bone diseases. A comparison of results achieved with an ion-selective electrode with those obtained with the neutron activation analysis demonstrated a good accuracy of the two methods. The precision of the determination with the ionselective electrode may be characterized by a relative standard error of 8.8%.     

INAA in the determination of the elemental constituents of a natural fluorite

A complementary use of the comparative and the semi-absolute variations of instrumental neutron activation analysis (INAA) has enabled us to determine 22 different elements in a sample of natural fluorite originating from the younger granite province of Nigeria. The mineral has a brownish purple appearance with some veinlets having a deep purple coloration. Of all the 22 elements measured, Fe (851.36 ppm), Sb (7.69 ppm), Ag (87.4 ppm), Hg (2.71 ppm) and Se (1.97 ppm) are found to be exclusive to the veinlets while Au (109.15 ppm), Co (2.15 ppm) and W (173.20 ppm) are concentrated in the main matrix of the fluorite. With the aid of the semi-absolute method, it was possible to measure the Au concentration in the IAEA Soil-7 reference material to be 56.83±5.87% ppm. A qualitative electron microprobe analysis (EMA) showed that the bulk of the matrix is composed mainly of Ca and F, as expected.     

Trace element impurity determination in aspirin tablets by INAA

Instrumental neutron activation analysis (INAA) was applied to assess trace element concentrations in six samples of aspirin tablets acquired in São Paulo city, Brazil. Concentrations of the elements Br, Ca, Co, Cr, Fe, K, La, Na, Sc and Zn were determined. Comparisons were made between the results obtained with published data for aspirins from foreign countries. Certified reference materials, INCT-MPH-2 Mixed Polish Herbs were analyzed for quality control of the analytical results.     

14 MeV INAA nitrogen determination in coal conversion liquids

Fast neutron activation analysis has been used for the direct determination of nitrogen in coal conversion liquids. In our previous work on coals, solid standards such as N-1-naphthylacetamide. NBS SRM 912 urea and NBS SRM 148 nicotinic acid were used for nitrogen determinations. In this work, a set of organic liquids was selected and evaluated for use as nitrogen standards in the analysis of coal-derived liquids. The use of the liquid standards minimizes problems associated with maintaining uniform irradiation and counting geometries and self absorption differences related to varying matrix densities. The standard liquids were selected using criteria of high boiling point, well-defined stoichiometry, high-purity, non-hygroscopic nature and simple C−H−N elemental compositions. Excellent agreement between the 14 MeV INAA data and calculated stoichiometric values has been demonstrated for liquids with nitrogen contents from 1.89 to 39.95%. The liquid standards have been used to determine nitrogen in a set of typical coal conversion liquids and several international standards.     

Validation of methods for the determination of aluminium in fish gills by INAA and ICP-MS

In a European study of fish death in mixing zones of rivers with different acidities a reliable determination of Al and other elements in gills from freshwater fish was required, and both INAA and ICP-MS were studied as candidate reference methods. INAA requires minimum sample handling with a correspondingly small risk of contamination and no blank value; however, a careful study was needed of both nuclear interference from P and the increased detection limit caused by other major elements in the sample, before reliable results for Al could be ascertained. ICP-MS requires dissolution of the sample with a resulting risk of contamination and a significant reagent blank; while sensitivity was good, the interference from N created problems for sample decomposition in the microwave oven. Our experience with actual samples indicates that both methods suffer from considerable contamination problems, requiring that samples be handled in a clean bench with superpure reagents. Nuclear interference was determined experimentally by irradiating stoichiometric P-compounds with and without a Cd-shield; the observed interference of 1 g Al from 50 mg of P was found to require no correction in almost all cases. The accuracy of results was ascertained by analyzing SRM 1577 Bovine Liver.     

A comparison between INAA and ICP-MS for the determination of element concentrations in marine sediments

In this study, instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) were used to compare results obtained by both techniques for sediment samples collected from the Patras Harbour, Western Greece. The accuracy of the methods was tested using reference materials. In total seven elements were measured by both techniques (Zn, Ni, Cr, Ba, As, U, Co). Results obtained by ICP-MS were compared with those obtained by INAA by applying paired t-test. Insignificant differences in mean concentration values were found for Zn, Ni, Cr and Ba, whereas the differences for As, Co and U were significant. Correlations between element concentrations measured by both techniques are also discussed.     

INAA for the validation of chromium and copper determination in copper chromite by infrared spectrometry

Summary Elérhetoség     

The determination of trace elements in active charcoal by INAA

Neutron activation followed by X-ray spectrometry with magnetic deflection of -rays was applied to the nondestructive determination of Co, Cu and Br in active charcoal.     

The use of INAA for the determination of trace elements,in particular cadmium,in plastics in relation to the enforcement of pollution standards

Many plastic products have relatively short life cycles. Upon final destruction, inorganic additives used for pigmentation, as polymer stabilizer or as flame retarding agent are being released to the environment. In a rapidly increasing way governmental authorities are setting limits to the use of inorganic additives, in particular cadmium, in plastics. INAA has attractive characteristics which may make authorities decide to select it for the control programs in relation to the enforcement of pollution standards. In this paper, an evaluation is made of the use of INAA for such analysis; analysis protocols, sensitivities, and observed levels of other trace elements are being discussed.     

Semi-empirical determination of detector absolute efficiency in INAA of voluminous samples

When neutron activation analysis of voluminous samples is performed using the absolute method, the detector absolute efficiency for -ray emiting distributed sources must be known. In this study, a Monte-Carlo program was developed to include the calculation of the effective solid angle subtended by a collimated detector from irregularly shaped voluminous samples. The program cna cope with dififerent sample shapes and geometries provided that the sample covers the view of the detector. Data such as the source and detector dimensions, the source-detector distance, the detector view at a cartain distance, the thickness and the composition of any intervening materials, the -ray energies of interest and the corresponding attenuation coefficients for each material are required. The method adopted for calculating the detector absolute efficiency of the voluminous sample in a certain geometry takes into account the effect by -rays baing emited from different position within the sample and also considers their attenuation in the sample material as well as any intervening materials between the sample and the detector and is compared with a reference point source. The alculations are varified experimentally using a distributed source of 75 mm diameter and 100 mm thickness and two semiconductor detectors. The difference between the calculated and measured absolute efficiencies did not exceed 4%.     

Evaluation of a sequential extraction procedure for the determination of extractable trace metal contents in sediments

The determination of extractable trace metals in sediments using sequential extraction procedures has been performed in many laboratories within the last ten years in order to study environmental pathways (e.g. mobility of metals, bounding states). However, the results obtained by different laboratories could hardly be compared due to lack of harmonized schemes. Owing to the need for standardization and subsequent validation of extraction schemes for sediment analysis, the Measurements and Testing Programme (formerly BCR Programme) of the European Commission has organized a project to adopt a sequential extraction procedure that could be used as a mean of comparison of data of extractable trace metals in sediments. A scheme was designed after a series of investigations on existing schemes and tested in interlaboratory studies. This paper presents the results of two round-robin exercises on extractable trace metals using this sequential extraction protocol and describes the final version of the extraction procedure amended according to the most recent improvements.     

Optimal strategies for determination of free/extractable and total microcystins in lake sediment

The optimization of analytical procedures for the quantification of free and total microcystins (MCs) in natural sediments was systematically examined based on solvent extraction and Lemieux oxidation. In this optimized analytical procedure, a sequential solvent extraction using 50% (v/v) methanol and EDTA-sodium pyrophosphate was selected as the optimal extraction solvent for free MCs analysis, after which the purified extracts and sediment residuals were applied to the optimized Lemieux oxidation for determination of total MCs in lake sediments. The optimized procedures were shown to be efficient and reliable for the routine analysis of both free and total MCs in lake sediment samples, as indicated by the minimal adverse impact of sediment organic matter on the recovery of free MCs and yield of MMPB (2-methyl-3-methoxy-4-phenylbutyric acid). Finally, the developed procedures were applied to field sediment samples collected from Lake Dianchi during a bloom season and seven of thirty samples showed positive results.     

Limit of the INAA procedure for copper determination based on the64Cu 511 keV line

The²³⁵U/²³⁸U ratio is determined by neutron activation analysis counting the ϕ-rays of short half-lives fission products and²³⁹U. The effect of the neutron spectrum hardening using a⁶LiD converter is also demonstrated. The²³⁵U/²³⁸U ratio is determined using short irradiation, waiting and counting times.