On the accuracy of protein determination in large biological samples by prompt gamma neutron activation analysis

A prompt gamma neutron activation analysis (PGNAA) facility has been developed for the determination of nitrogen and thus total protein in large volume biological samples or the whole body of small animals. In the present work, the accuracy of nitrogen determination by PGNAA in phantoms of known composition as well as in four raw ground meat samples of about 1 kg mass was examined. Dumas combustion and Kjeldahl techniques were also used for the assessment of nitrogen concentration in the meat samples. No statistically significant differences were found between the concentrations assessed by the three techniques. The results of this work demonstrate the applicability of PGNAA for the assessment of total protein in biological samples of 0.25-1.5 kg mass, such as a meat sample or the body of small animal even in vivo with an equivalent radiation dose of about 40 mSv.     

Phantom studies of Cd, Hg and Cl by prompt gamma neutron activation analysis using a Pu-Be neutron source

Prompt gamma neutron activation analysis is a means of non-invasive monitoring for occupational exposure to toxic heavy metals such as Cd and Hg. Preliminary kidney detection limits from previous phantom studies at McMaster were 13.6 ± 0.2 ppm for Cd (125 mL phantom) and 315 ± 24 ppm for Hg (125 mL phantom) using the ²³⁸Pu-Be neutron source and 0.88 ± 0.01 ppm for Cd (125 mL phantom) and 16.91 ± 0.05 ppm for Hg (30 mL phantom) using the thermal neutron beam port at the McMaster Nuclear Reactor. The detection limits vary greatly between the two methods due to differences in experimental set-up, neutron energy spectra and a difference in dose by more than a factor of 100. The Hg detection limit from preliminary data is much higher than expected for both neutron source types. In order to explain the apparent detection limit discrepancy, measurements of Hg and Cd phantoms were performed using the ²³⁸Pu-Be neutron source. The results were compared to phantom measurements of Cl, a well-known neutron activation element.     

Effects of the behaviour of the proton-induced isotopes production on the analysis of ancient alloys

The present work concerns non-destructive ion beam analysis carried out by means of proton-beam-induced nuclear reactions in the 10-30 MeV energy range. We focused our attention on the yield distribution of the isotopes produced in the internal region of a metal alloy. This distribution, which defines the analytical region, displays, at incident energy of about 20 MeV in a bronze based alloy, a bell-shaped curve centred at about 600 μm with an average width of about 400 μm. By changing the incident proton energy it is possible to displace the above region in the interior of the metal body. It should be pointed out that if we neglect to take into account the correct behaviour of the isotope yield distribution in samples with surface inhomogeneities we can obtain erroneous analytical results. We describe some experiments based on proton activation analysis (PAA) carried out at the INFN-Laboratori Nazionali del Sud (LNS) in Catania where we verified the bell-shape of the radioactive isotope distribution. The resulting formulas are given for quantitative analysis.It is straightforward that, by choosing the appropriate incident proton energy, it is possible to confine the whole analytical region to the interior of the body, thus eliminating any influence of surface effects. We have called this particular approach deep proton activation analysis (DPAA). Examples of its use on archaeological artefacts are given.     

Microbeam analysis of lateral inhomogeneity in depth penetration of Pd in porous silicon

Porous silicon (PS) is widely utilized in gas sensors. Palladium is a good choice to sensitize the surface of PS to hydrogen. Ideally for highest sensitivity of the sensor, all the pores of PS should be completely covered with palladium. Rutherford backscattering spectroscopy (RBS) technique is routinely used to determine depth profile of elements in thin layers. By using microbeam analysis as a complementary technique, we clearly observed the lateral image of penetrated Pd in depth. In this work, we used electrochemically anodized-silicon wafer doped with Pd by the electroless process. In our analysis, we intentionally characterized both the area of PS where Electric Field is applied during silicon etching (EF area) and the Field Free region (FF area) of the sample. Microbeam analysis show that EF area of the sample is covered with thicker palladium layer, but the pores are rarely filled in this area, while in the FF area of the sample, there is a thin palladium film on the silicon surface, but the pores are partially filled. We used a computational simulation method based on columnar pore structure and linear variation of Pd depth profile in pores and determined the lateral variation of Pd penetration in pores in both parts of the sample. These simulations showed that there are 180 ± 80 nm thick Pd layer with 300 ± 200 nm penetration in pores in EF region and 80 ± 40 nm thin Pd layer with 800 ± 200 nm penetrate in pores in FF region.     

Micro-crystalline inclusions analysis by PIXE and RBS

A characteristic feature of the nuclear microprobe using a 3 MeV proton beam is the long range of particles (around 70 μm in light matrices). The PIXE method, with EDS analysis and using the multilayer approach for treating the X-ray spectrum allows the chemistry of an intra-crystalline inclusion to be measured, provided the inclusion roof and thickness at the impact point of the beam (Z and e, respectively) are known (the depth of the inclusion floor is Z + e). The parameter Z of an inclusion in a mineral can be measured with a precision of around 1 μm using a motorized microscope. However, this value may significantly depart from Z if the analyzed inclusion has a complex shape. The parameter e can hardly be measured optically. By using combined RBS and PIXE measurements, it is possible to obtain the geometrical information needed for quantitative elemental analysis. This paper will present measurements on synthetic samples to investigate the advantages of the technique, and also on natural solid and fluid inclusions in quartz. The influence of the geometrical parameters will be discussed with regard to the concentration determination by PIXE. In particular, accuracy of monazite micro-inclusion dating by coupled PIXE-RBS will be presented.     

Calculation of thermal neutron self-shielding correction factors for aqueous bulk sample prompt gamma neutron activation analysis using the MCNP code

In this work thermal neutron self-shielding in aqueous bulk samples containing neutron absorbing materials is studied using bulk sample prompt gamma neutron activation analysis (BSPGNAA) with the MCNP code. The code was used to perform three dimensional simulations of a neutron source, neutron detector and sample of various material compositions. The MCNP model was validated against experimental measurements of the neutron flux performed using a BF₃ detector. Simulations were performed to predict thermal neutron self-shielding in aqueous bulk samples containing neutron absorbing solutes. In practice, the MCNP calculations are combined with experimental measurements of the relative thermal neutron flux over the sample’s surface, with respect to a reference water sample, to derive the thermal neutron self-shielding within the sample. The proposed methodology can be used for the determination of the elemental concentration of unknown aqueous samples by BSPGNAA where knowledge of the average thermal neutron flux within the sample volume is required.     

Characterisation of an enamelled metallic object found in Guerrero Negro (Baja California) by PIXE and RBS techniques

The coast of Guerrero Negro (Baja California) has been known for a long time by archaeologists for its shipwrecks. Archaeologists are recovering objects that come from sunken Spanish galleons in the colonial period, and reach the American coast in the frontier of the USA with Mexico.An enamelled metallic object was found next to the beach in Guerrero Negro. We have analysed the piece with proton induced X-ray emission (PIXE) and Rutherford backscattering (RBS) in an attempt to establish whether the object could come from one of the colonial shipwrecks and to valuate its cleaning process.Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) have been also performed in three samples taken from the object in order to observe the heterogeneity of the material.The materials found revealed the presence of typical lead-glass enamels from with pigments such as cuprite (red), or lead-tin yellow used in colonial times. The metallic part consisted of brass. As for the cleaning process, the average efficiency considered as the weight% of chlorine removed, was of 83.4% for brass and 100% for enamels.     

Silver surface enrichment controlled by simultaneous RBS for reliable PIXE analysis of ancient coins

Evidence of silver surface enrichment of ancient silver-copper coins has been pointed out in the past years. Surface enrichment can be fortuitous or intentional. In this paper, we have investigated the cleaning procedures usually performed after excavation or in museums. We have shown that chemicals or commercial products routinely used dissolve preferentially the copper phase and consequently contribute to the silver surface enrichment. As a result, surface analyses such as PIXE or XRF can be strongly affected by this effect. By using simultaneously RBS and PIXE, it is possible to check through the silver surface enrichment and then select the reliable measurements, characteristic of the bulk composition. Results on coins recently discovered and mechanically or chemically cleaned are presented.     

Design study of a channel in the moderator on improving C and O measurement in coal

By introducing a channel in the moderator of a coal analysis setup using neutron-induced gamma technique, more fast neutrons can reach the coal. Then the characteristic gamma-rays of C and O are increased due to neutron inelastic scattering (NIS) reaction, and measurement of the two elements is sufficiently improved. Monte-Carlo simulations have been carried out in this work for the setup with different prism channels. These prism channels have different positions and sizes, but their bottom surfaces are all nearby the neutron source. The results show that, it could obtain the optimum improvement of C and O measurement, by selecting a proper position and size for the prism channel.     

Analysis of activation products generated from photoneutron capture reactions inside a linear accelerator used in a cargo inspection facility

Activation products are generated from photoneutron capture reactions inside a linear accelerator (LINAC) used in a high energy X-ray cargo inspection facility. The activation products are estimated using MCNPX, Monte Carlo simulation code, in order to evaluate radiological safety in the facility. The result shows that the maximum radiation dose rate from the saturated activity in LINAC room is about 2.18E−06 Sv/h and 74-W-187 is the most significant radionuclide generated. It is, therefore, recommended that a proper measure to reduce the radionuclide is considered to protect occupational workers against the decay radiations.     

PIXE as a complement to trace metal analysis of sediments by ICP-OES

The adverse effects of metal contamination in sediments require methods that can quickly and accurately assess the extent of environmental pollution. Particle induced X-ray emission spectrometry (PIXE) is demonstrated to be a viable alternative to an established method, which consists of acid digestion and Inductively coupled plasma-optical emission spectrometry (ICP-OES) to measure trace metals in sediment. The analysis of trace metal composition by both techniques on a NIST Standard Reference Material mud gives results that are consistent with the certified values for fourteen measured metals, seven of which are common to both methods. A comparison study conducted on a sediment core from a freshwater lake with a known chromium contamination in Muskegon County, MI also shows a good correlation between the methods for transition metals of environmental interest over a wide range of metal concentrations. Total sample preparation and analysis time for the PIXE measurements is roughly one third that of acid digestion and ICP-OES. Also, the acid digestion step does not elute all the metal, while the nondestructive PIXE approach is a total metals analysis method. However the PIXE method generally has higher limits of detection for many environmental metal contaminants. By combining the two techniques, the acid digestion elution factor can be quantified by running PIXE on an original sample and on the residue resulting from acid digestion.     

Determination of Fe in waste waters of the Krsko nuclear power plant measured simultaneously by liquid scintillation spectrometer (LSC) and X-ray spectrometer (XRS)

This paper presents comparison of two methods for the determination of ⁵⁵Fe activity of waste waters discharged from the Krsko nuclear power plant (KNPP). Research was conducted on 12 composite samples of waste water collected in the waste monitor tank (WMT) during each month as well as on Analytics, Inc. cross-check sample. Results showed that the complicated and time-consuming method proposed by the Environmental Measurements Laboratory (EML) could be successfully replaced with a simple and fast based on the extraction of ⁵⁵Fe from waste water by non-specific chelating agent ammonium-pyrrolidinedithiocarbamate (APDC) at pH 4 after separation from cobalt, and activity measurement by X-ray fluorescence spectroscopy (XRS). Results obtained by the XRS method were approximately 8.6% lower than those obtained by liquid scintillation spectrometer (LSC). The mean deviation of the XRS results from the activity of cross-check sample was 2.47%, which ensures that this method is accurate enough for environmental monitoring.     

The optimization of gamma spectra processing in prompt gamma neutron activation analysis (PGNAA)

The uncertainty of the elemental analysis is one of the major factors governing the utility of on-line Prompt Gamma Neutron Activation Analysis (PGNAA) in the blending and sorting of bulk materials. In this paper, a general method applicable to Gamma spectra processing is presented and applied to PGNAA in mineral industry. Based on the Fourier transform of spectra and their de-correlation in the Fourier space (the improvement of the conditioning of the correlation matrix), processing of overlapping of characteristic peaks minimizes the propagation of random errors, which optimizes the accuracy and decreases the detection limits of elemental analyses. In comparison with classical methods based on the linear combinations of relevant regions of spectra the improvement may be considerable, especially when several elements are interfering. The method is applied to four case stories covering both borehole logging and on-line analysis on conveyor belt of raw materials.     

Quantification of sodium in ancient Roman glasses with ion beam analysis

Concentrations of light elements (Na, Al, Si) in glass have been profiled by comparing the PIGE yields as a function of beam energy to those of a glass standard in combination with PIXE measurements which are used to determine the specific energy loss of protons in the unknown glasses. The technique has been tested on a known sample and applied to a few Roman natron glasses giving results compatible with the morphology of the archaeological samples, as deduced from microscopy. The results have suggested some considerations on the systematic use of the PIGE technique in the determination of bulk sodium concentration in ancient materials.     

Concentration profiles in paint layers studied by differential PIXE

Differential PIXE measurements varying the proton energy were used to probe the concentration profiles of metal-based pigments in paint layers. The algorithms developed earlier for metal targets were improved and enhanced to include light elements; the necessary information on chemical compounds has to be provided by complimentary methods. The de-convolution method employs slicing the target into layers characterized by mean production depths; the matrix inversion is replaced by a min χ² problem. Two different methods of normalization are used: setting the sum of weight fractions of particular compounds to unity, and direct measurements of the projectile number, in our case through the argon line excited in the air. The efficiency of the two methods was compared for paint layers in frescoes, showing that smother concentration profiles are obtained using the measured proton numbers. Conversion of the layer areal densities into geometrical thicknesses is discussed.     

PIXE and RBS analysis of Tl-1223 superconducting phase substituted by scandium

Ion beam analysis techniques (IBA) were performed to determine the elemental stoichiometry of superconducting samples of type TlBa₂Ca_2−xSc_xCu₃O_9−δ, with 0 ? x ? 0.6, prepared via solid-state reaction technique. By combining particle induced X-ray emission (PIXE) with Rutherford backscattering spectrometry (RBS), the stoichiometry of the samples is determined. However, the oxygen content is obtained by using non-Rutherford backscattering cross-section at 3 MeV proton beam. Furthermore, the prepared samples were also characterized using X-ray powder diffraction (XRD) and electrical resistivity measurements. The X-ray data indicate that the partial substitution of Ca²⁺ by Sc³⁺ ions does not affect the tetragonal structure of Tl-1223 superconducting phase. The superconducting transition temperatures T_c, determined from electrical resistivity measurements, was found to be highly correlated to the Sc-content.     

Elemental and topographic characterization of LDPE based copolymeric films obtained by gamma irradiation

The preparation of PE-g-HEMA (polyethylene-grafted-hydroxyethyl methacrylate) films by ⁶⁰Co gamma irradiation has been optimized to produce a new material suitable for bioapplications.This paper reports the elemental and topographic analysis of PE-g-HEMA films with different grafting degrees, obtained under optimized experimental conditions, with the purpose to appraise their possible toxicological risk and their surface roughness properties.In this way a Nuclear Microprobe using PIXE (Proton Induced X-ray Emission) technique was used to assess the elemental analysis of the film samples prepared. Trace contaminations of elements heavier than Si (Ca, Cl, Fe, K, P, S, Si and Zn) were found, but their concentrations do not pose toxicological risk.Atomic Force Microscopy (AFM) and Scanning Electronic Microscopy (SEM) techniques were used to assess the morphological characterization of the films, revealing the roughness and 3D porous structure of their surface, which are ones of essential characteristics for bio-interaction or cell adhesion.     

Possible use of a BGO array for neutron stimulated emission computed tomography by summing adjacent signals

Neutron stimulated emission computed tomography (NSECT) is a new approach for biological spectroscopy and imaging. Since the gamma-ray photons emitted from stimulated element have energies from 100 keV to about 6 MeV, previous reports have proposed that the projection path can be defined by the neutron beam. In this paper, another possible method has been applied and the performance presented through simulations. When using signals from a single BGO crystal it is impossible to achieve good energy resolution for such high-energy photons. When summing additional signals from adjacent crystals, the energy spectrum becomes much better. Using an energy window with energy resolution of 90 keV, an average intrinsic spatial resolution of 3.938 mm FWHM is obtained.     

PIXE and PIGE techniques for the analysis of Antarctic ice dust and continental sediments

An analytical procedure has been implemented in this work for an accurate geochemical characterization and quantitative analysis of the fine dust (particles diameter < 5 μm) trapped in Antarctic ice cores and the fine fraction of potential source areas (PSA) sediments by size selection, filtering and PIXE-PIGE combined measurements. The underestimation of concentrations of the lighter elements, like Na, Mg, Al and Si, due to X-ray self-absorption inside each individual aerosol particle, was also evaluated and the analytical overall accuracy tested by means of measurements performed on size selected certified mineral standards.