Evaluation of concentrations of major and trace elements in human lung using INAA and PIXE

The elemental concentrations of Br, Ca, Ce, Cl, Co, Cr, Cs, F, Fe, Hf, K, Mg, Mn, Na, O, Rb, Sb, Sc, Se, V and Zn in 15 human lung autopsy samples, taken from subjects aged more than fifty years old, were determined by instrumental neutron activation analysis (INAA) using reactor neutrons in conjunction with a high resolution detection system. Two modes of irradiation and counting were applied; namely cyclic neutron activation analysis (CNAA) and conventional neutron activation analysis. Proton induced X-ray emission (PIXE) analysis, using a proton beam emerging from a 2 MV Van de Graff accelerator, was additionally employed and Ge, Ni, P and Ti were also identified in the lung tissue. Detection of the X-ray spectra was performed using a high resolution Si(Li) semiconductor. The relevance of these results, including a comparison between the concentrations of elements measured in a pig's lung using CNAA and those found in the human lung is discussed.     

Trace Analysis by Heavy Ion Induced X-Ray Emission

 Various K-, L- and M-shell X-ray production cross sections are measured for heavy ion impact on elements in the range Z ₂ = 13 to 83. The ion species range from Z ₁ = 10 to 36, and ion energies from 1 to 16 MeV are used. Enhanced cross sections are observed when the projectile K- or L- binding energy is similar to the energy of the target K-, L- or M-shell. This effect is used to improve the analysis sensitivity for selected elements. As an example trace analysis of Fe in glass with V, Mn, Co and Ni ions is investigated. Results are compared with proton induced X-ray emission analysis on the same samples. In these samples Fe-K_α X-ray production is similar for irradiation with 3 MeV protons and 14 MeV Ni ions. However the signal to background ratio is four times higher for the irradiation with Ni ions as compared to irradiation with protons. Advantages and drawbacks of heavy ion induced X-ray emission for quantitative analysis compared to proton induced X-ray emission analysis are discussed.     

Simultaneous determination of low Z elements in barium borosilicate glass samples by in situ current normalized particle induced gamma-ray emission methods

Particle induced gamma-ray emission (PIGE) method using 4 MeV proton beam was utilized to analyze two types of barium borosilicate glass (BaBSG) samples for quantification of concentrations of low Z elements. The in situ current normalization method was applied in the analysis of eight samples containing varying concentration of F along with Si, B and Na. Charge normalized PIGE method was applied to determine concentrations of above low Z elements including Li and Al in samples having simulated nuclear waste from reprocessing of thoria spent fuel. Synthetic samples and NIST SRMs were used for method validation.     

Simultaneous PIXE and PIGME Analysis of a Nigerian Tar Sand Sample from a Deep Borehole

Tar sands from a deep borehole in southwestern Nigeria were subjected to elemental analysis by simultaneous proton induced X-ray emission (PIXE) and proton induced gamma-ray emission (PIGME) techniques. The concentration of 22 major, minor and trace elements, namely Al, Ca, Cr, Cu, F, Fe, Ga, Ge, K, Li, Mg, Mn, Na, P, Pb, Rb, S, Si, Sr, Ti, Zn and Zr were determined. The accuracy and precision of the techniques for chemical analysis were assured by analysing the NBS 278 geological standard.     

Speciation of elements in atmospheric particulate matter by XANES

The atmospheric particulate matter samples were collected in Shanghai, China. The X-ray absorption near-edge structure (XANES) spectra of Cr, Mn, Cu and Zn were measured. The XANES spectroscopy was used as a fingerprint to compare with that of reference materials to obtain speciation information. The oxidation state of these elements and main chemical components in the samples were described using the method. The results show that in our samples the oxidation state of Cr is trivalent, Mn mainly exists in the divalent state, Cu also exists in the divalent state, and Zn mainly exists in the zinc sulfate. For the XANES spectra of samples with different particle size and from different sampling site, we did not find their obvious differences. When we compared the XANES spectra of our samples with those of standard reference material SRM 1648, we found that they are similar in regards to the determined elements. The elemental concentrations in the samples were determined by proton induced X-ray emission (PIXE). The difference of elemental concentrations was observed in the different samples.     

Raman spectroscopic study on archaeological glasses in Thailand: ancient Thai glass

Glasses have been used as ornamental and decorative objects in Thailand for several hundred years as seen in archaeological artifacts, such as glass beads found throughout the regions. Decorative glasses can generally be seen as architectural components in Buddhist temples and old-styled palaces. They came in various colors ranging from transparent to amber, blue, green and red of different shades and tones. Fragments of archaeological glass samples were characterized for the first time using Raman spectrophotometer with the aim of obtaining information that would lead to the identification of the glass samples by means of laser scattering. The samples were also investigated using other techniques, such as proton induced X-ray emission spectroscopy, scanning electron microscopy cooperated with energy dispersive X-ray fluorescence spectrometer and synchrotron radiation to induced X-ray fluorescence. The results showed that they were mostly lead-silica based glasses whose colors were induced by metal ions. The differences in chemical compositions were confirmed by Raman signature spectra.     

Distribution of some major and trace elements in Danube Delta lacustrine sediments and soil

Sediment cores collected from lakes Mesteru and Furtuna (eastern part), Sontea channel and soil samples collected from Caraorman bar, all located in the Danube Delta, were analyzed for 42 elements (Ag, Al, As, Be, Na, Mg, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Y, Mo, Ag, Cd, In, Sn, Sb, Cs, Ce, Hf, Hg, Tl. Pb, Bi, Th. U) by instrumental neutron activation analysis (INAA), thick target proton induced X-ray emission (TT-PIXE) and inductively coupled plasma-mass spectrometry (ICP-MS). The INAA and TTPIXE yielded total concentrations whereas the ICP-MS data reflected the fractions soluble in 14M HNO₃. The ICP-MS data exhibited surface enrichment relative to the lower part of the sediment core of Cu, Zn, As, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb, and Bi, most prominently by Cd and Hg. Their vertical distribution in the investigated cores generally reflected the pollution history of recent sediments in Danube delta, showing a steady increase until the end of the 1980s followed by a slow decrease after 1990. The vertical profiles of most remaining elements were characterized by a relatively uniform distribution along the cores. In some cases, the concentrations of As, Cd, Cu, Cr, Mn, Ni and Pb exceeded minimum thresholds of safety, as defined by the Romanian regulations. The elemental composition of the sediment below 20 cm depth (total concentrations) was similar to that of the upper continental crust (UCC) for most elements. Values distinctly higher than UCC were observed for As, Sb (factor ~5) and Cr, Ni, Cu (factor 2 to 3). The nitric acid soluble element concentrations in the soil samples in some cases showed increased values at the surface as compared to 30 cm depth, either due to air pollution or to the action of plants. In no case a large contribution to the topsoil from atmospheric deposition was evident, indicating that the surface contamination of the sediments was mainly by riverine transport. This revised version was published online in July 2006 with corrections to the Cover Date.     

INAA of ancient glass beads from Sungai Mas archaeological site,Bujang Valley,Malaysia

The multi-elemental content of sixteen glass beads and eight glass samples from archeological site Sg Mas in Bujang Valley (finding from 5 th to 14 th century) were assayed by neutron activation analysis (NAA). Ten beads differed in colour and eight of them were opaque. Contents of twentyfour elements, which might be present in the samples as a flux, stabilizer, colorants or opacifier were examined. The elements Al, Br, Cl, Co, Cr, Fe, Hf, K, Mn, Na, Sc,Th, Zn and Zr were detectable in all samples. On the other hand, concentration of the elements As, Ba, Ca, Cs, Rb, Sb, Ta, Ti, U, and V were below the detection limit in some samples. The concentration of elements found are discussed in terms of color and/or opacity of the glass bead and glass samples. Although the elemental composition does not fully explain the color and opacity of the studied materials, it can still be used as fingerprint of the glass used for the bead making.     

Growth kinetic on the optical properties of the Pb(1-x)Mn(x)Se nanocrystals embedded in a glass matrix: thermal annealing and Mn2+ concentration

Semimagnetic Pb(1-x)Mn(x)Se nanocrystals were synthesized by a fusion method in a glass matrix and characterized by optical absorption (OA), atomic/magnetic force microscopy (AFM/MFM), and photoluminescence techniques. MFM images strongly indicated the formation of Pb(1-x)Mn(x)Se magnetic phases in the glass system. Quantum dot size was manipulated by tuning annealing time. It was shown that Mn(2+) impurity affects nucleation, where Mn(2+)-doped samples present a redshift of the OA peak after a short annealing time and a blueshift after long annealing time compared to undoped PbSe NCs. This behavior was linked to the dependence of band-gap energy and the absorption selection rule on Mn(2+) concentration. Photoluminescence in the Pb(1-x)Mn(x)Se nanocrystals increases as the temperature rises up to a point and then decreases at higher temperatures. Anomalous increases in emission efficiency were analyzed by considering temperature induced carrier-transfer in semimagnetic Pb(1-x)Mn(x)Se quantum dots nanocrystals of different sizes.     

Optimized microwave-assisted decomposition method for multi-element analysis of glass standard reference material and ancient glass specimens by inductively coupled plasma atomic emission spectrometry

A novel microwave-assisted wet-acid decomposition method for the multi-element analysis of glass samples using inductively coupled plasma atomic emission spectrometry (ICP-AES) was developed and optimized. The SRM 621 standard reference glass material was used for this purpose, because it has similar composition with either archaeological glass specimens or common modern glasses. For the main constituents of SRM 621 (Ca, Na, Al, Fe, Mg, Ba and Ti), quality control data are given for all the examined procedures. The chemical and instrumental parameters of the method were thoroughly optimized. Thirteen acid mixtures of hydrochloric, nitric, and hydrofluoric acids in relation to two different microwave programs were examined in order to establish the most efficient protocol for the determination of metals in glass matrix. For both microwave programs, an intermediate step was employed with addition of H₃BO₃ in order to compensate the effect of HF, which was used in all protocols. The suitability of the investigated protocols was evaluated for major (Ca, Na, Al), and minor (Fe, Mg, Ba, Ti, Mn, Cu, Sb, Co, Pb) glass constituents. The analytes were determined using multi-element matrix matched standard solutions. The analytical data matrix was processed chemometrically in order to evaluate the examined protocols in terms of their accuracy, precision and sensitivity, and eventually select the most efficient method for ancient glass. ICP-AES parameters such as spectral line, RF power and sample flow rate were optimized using the proposed protocol. Finally, the optimum method was successfully applied to the analysis of a number of ancient glass fragments.     

ICP-AES analysis of metal content in shell of mussel Mytilus galloprovincialis from Croatian coastal waters

Metal content in samples of shell of mussel Mytilus galoprovincialis was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The efficiency of conversion of crude samples into solution by acid digestion in an open plate and in a microwave oven was examined by use of certified reference material of marine sediment and laboratory made standards of calcite and aragonite. Influence of high Ca content matrix on emission intensities of Al, Ba, Cd, Cu, Fe, Mg, Mn, Na, Ni, Pb, Sr and Zn was observed as depression of emission signal for most of the measuring elements, ranging from 0.8% to 8%. Greater values were noted at Ba and Ni emission lines. Enhancement of signals was observed for Na and Mg lines. The determination of As, Sb, Se and Sn was performed by HG/ICP-AES. The greater abundance of Sn was found in samples collected near the Al-processing industry centre. No detectable concentrations of As, Sb, and Se were found in shell samples. Results of ICP-AES metal analysis showed that samples collected near harbours, city waste or sewage outlets, and chemical industry centres indicate the certain level of contamination. It is shown that shell analysis provides useful data in determination of marine environment status.     

Comparison of nondestructive proton and neutron activation: The case of biological samples

The capabilities of reactor neutron and 12 MeV proton activation were evaluted on samples of orchard leaves, beef liver and bovine liver. Based on γ-ray spectrometry, As, Ca, Cu, Fe, Mo, Pb, Sr, Ti, Zn and Zr at levels ranging from 2 to 20 900 ppm were detected following proton activation of 1 hour. Al, Br, Ca, Cl, Cu, Mg, Mn, Rb and V (ranging from 0.4 to 20 900 ppm) were measured by neutron activation (1 min irradiation). As, Ba, Br, Cr, Co, Fe, Hg, La, Na, Rb, Sb and Zn (ranging from 0.2 to 2400 ppm) were determined following a 14 h neutron irradiation. Although covering different elements, the two techniques are comparable in their scope, i. e. detection limits that can be achieved and number of elements that can be detected simultaneously.     

Proton induced X-ray emission (PIXE) technique for determining multi-element composition of transformed hairy root cultures of Boerhaavia diffusa L.: an important medicinal herb

Therapeutically important inorganic elements in Agrobacterium rhizogenes-mediated genetically transformed hairy root cultures (HRCs) of a pharmaceutically significant herb Boerhaavia diffusa were quantified using proton induced X-ray emission technique. This was compared with that of roots from the naturally grown donor plant. Two macro-elements (Ca & K) and eight different trace elements namely V, Cr, Mn, Fe, Co, Cu Zn, and Ni were detected and their content was determined. In HRCs of a transformed rhizoclone, calcium and potassium had values which were significantly higher than that of in vivo roots. The concentrations of several trace elements, which are known to have a positive implication in human healthcare, were found to be either comparable (Fe) to that in the natural root samples or higher (Mn, Zn, Cr, Cu, Co) in the transformed rhizoclone. The genetically transformed HRCs can thus serve as a fast-proliferating renewable resource of medicinally useful minerals targeting specific diseases.     

Air quality control monitoring at an urban and industrialized area

Air particulate matter analysis has been performed since 1999, within a contract for air quality monitoring of an urban waste incinerator. Air collection was made with Gent samplers, which collect size-fractionated aerosol samples in three sampling sites. Samples were analyzed by instrumental neutron activation analysis (INAA) and proton induced X-ray emission (PIXE). In this study some INAA results are discussed. PM₁₀ mass concentrations are compared with the limit values for human health protection regulated by the European Council Directive 1999/30/CE. Weekend day and weekday samples are compared concerning As, Co, Fe, K, La, Na, Sb, Sc, Se and Zn mean concentrations collected at Bobadela for 1999. Enrichment factors are also presented. Enrichments were found for As, Sb, Se and Zn for both fractions in the three sampling sites. In order to quantify the evolution for the 1999-2001 period, basic statistics was performed for the enriched elements. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characterization of prehistorical glass beads excavated from Khao Sam Kaeo (Chumphon, Thailand) using PIXE and SEM–EDS

It was proved that non-destructive and non-sampling methods were used to analyze the composition of the archaeological glasses. Glass has been used in ornaments and decoration in Thailand for thousands of years. In this study, glass bead fragments found from the archaeological site at Khao Sam Kaeo, Chumphon Province, southern Thailand were analyzed by the proton induced X-ray emission spectroscopy (PIXE) and scanning electron microscope coupled with energy dispersive X-ray fluorescence spectroscopy (SEM?CEDS). The composition analysis showed that copper was mainly presence as the colorant. Titanium, common impurity in sand, was all present in the glass bead samples. Furthermore, this type of glass almost spread over the various sites in this region that demonstrated the long distance or exchange connections. Finally, PIXE and SEM?CEDS have been used to be the efficient techniques to analyze the archaeological objects, especially the glassy materials, to understand their characteristics and how they were produced in ancient times.     

The status of trace and minor elements in pulses: A PIXE measurement

The proton particle induced X-ray emission (proton PIXE) technique has been employed to study the heavy element status (essential and toxic) in five different varieties of pulses commonly cultivated and consumed in Bangladesh. In this analysis, the samples were irradiated in air with 2 MeV protons having 30 nA beam intensity for characteristic X-ray excitation. For 40 μC irradiations, the concentration of ten elements (K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Br, and Rb) was determined by comparison with a calibration obtained from the NBS orchard leaf standard, SRM 1571. In a comparative study with atomic absorption spectrophotometric (AAS) measurements of some elements in lathyrus sativus, the data were found to be in good agreement. The results obtained from the present study are discussed and compared with available data.     

Elemental profile in some common medicinal plants of India. Its correlation with traditional therapeutic usage

Several parts of plants are used in herbal and Ayurvedic medicines of India. The different elemental constituents at trace levels of these plant parts play an effective role in the medicines prepared. Elemental composition of different parts (root, bark, leaf, seed) of some medicinal plants of North Eastern India has been determined by using proton induced X-ray emission (PIXE). A total of 14 elements, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Br, Rb, Sr, Y, Zr and Pb have been measured. Their concentrations were found to vary in different samples. Medicinal properties of these plant samples and their elemental distribution have been correlated.     

On-line redox speciation analysis of antimony using l-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

l-proline was immobilized on controlled pore glass to study the ability of this material for the separation and preconcentration of Sb(III) and Sb(V). The substrate was packed in a minicolumn and incorporated in a flow injection system. The effluents of the on-line solid phase extraction (before and after elution) were directly coupled to the hydride generation inductively coupled plasma optical emission spectrometry system. The effect of pH, sample (and eluent) volume, flow rates of sample loading and elution on separation of Sb(III) e Sb(V) were evaluated. Our experiments demonstrated that Sb(V) was not retained and it was selectively determined during the loading step, while retained Sb(III) was determined after elution. The proposed system was also used for the selective preconcentration of Sb(III). In this case, a preconcentration factor of 11 and a limit of detection of 90 ng L⁻¹ for Sb(III) were achieved when 8 mL of sample were loaded into the column. The speciation analysis of inorganic Sb in river water and effluent samples was performed using the proposed method. The values obtained for total Sb (obtained by sum of Sb(III) and Sb(V)) were in good agreement with expected values. Recoveries of Sb(III) and Sb(V) in the river water Standard Reference Material 1640 (from National Institute of Standard and Technology) and spiked river waters were between 83 and 111%.     

Determination of trace elements in coal and coal fly ash by joint-use of ICP-AES and atomic absorption spectrometry

Microwave-acid digestion (MW-AD) followed by inductively coupled plasma-atomic emission spectrometry (ICP-AES), graphite furnace atomic absorption spectrometry (GFAAS), and hydride generation atomic absorption spectrometry (HGAAS) were examined for the determination of various elements in coal and coal fly ash (CFA). Eight certified reference materials (four coal samples and four CFA samples) were tested. The 10 elements (As, Be, Cd, Co, Cr, Mn, Ni, Pb, Sb, and Se), which are described in the Clean Air Act Amendments (CAAA), were especially considered. For coal, the HF-free MW-AD followed by ICP-AES was successful in the determination of various elements except for As, Be, Cd, Sb, and Se. These elements (except for Sb) were well-determined by use of GFAAS (Be and Cd) and HGAAS (As and Se). For CFA, the addition of HF in the digestion acid mixture was needed for the determination of elements, except for As, Sb, and Se, for which the HF-free MW-AD was applicable. The use of GFAAS (Be and Cd) or HGAAS (Sb and Se) resulted in the successful determination of the elements for which ICP-AES did not work well. The protocol for the determination of the 10 elements in coal and CFA by MW-AD followed by the joint-use of ICP-AES, GFAAS, and HGAAS was established.