International Journal of PIXE

Performance of a micro WDX-PIXE system that consists of position sensitive x-ray spectrometer and the heavy ion microbeam line is described. The influence of the position resolution of the position sensitive proportional counter (PSPC) used in the spectrometer on system energy resolution is discussed based on the measured values for C and O K x-rays. The system has successfully been used for chemical state analysis of various compound materials and small area of the materials (< 3 × 10^-3mm²) can be analyzed.

The X-ray emission spectra have been analyzed by the genetic algorithm. The X-ray peaks are represented by Gaussians or Lorentzians and the best estimates of their parameters are determined with the optimization strategy based on the mechanism of natural selection and natural genetics. The calculated results for artificial, pseudo-experimental, and experimental spectra are compared with those obtained by other methods and the validity of the present method is demonstrated.

The paper presents some preliminary results of PSS performances measured by using various exciting sources. The energy resolution of 25eV for MnKα and of ~ 15eV for TiKα is obtained, respectively, for various exciting sources. The satellite structure of SiKα has been clearly observed. The peak of CrKβ and of MnKα in a stainless steel sample has also been resolved and the detectable amount of Ti has been less than 10^-9 g. The comparisons of these results attempt to find more suitable exciting source for a different application of PSS and to discuss the possibility of application carried out by PSS combined with a new μ-X-ray exciting source.

For more detailed understanding of the line shape of X-ray peaks observed with Si(Li) detectors, a new Monte Carlo code was developed and tested in the range of incident X-ray energy less than 5 keV. In our simulation the individual elastic and inelastic processes in the solid and the charge collection probabilities in the different region of detectors are taken into account. The results of our model calculations are compared with experimental data. In general, good agreement is found between the experimental and calculated line shapes. This fact demonstrates the validity of the present model.

A external microbeam system using polyimide windows has been developed for PIXE (Particle Induced X-ray Emission) analysis in air. A beamline consists of a magnetic quadrupole-doublet lens, cylindrical objective slits and double-deflection scanning coils. Polyimide films with a thickness of 3.5 μm or 7.5 μm were used for the exit windows. Spot sizes in air were measured by beam-induced fluorescence of CsI scintillation plates. A minimum spot size obtained was about 10 μm for a 1.5 MeV proton beam. PIXE-mapping images of a Cu grid were successfully obtained in air.

Since the cellular metabolism has not yet been fully elucidated, it is very useful to get the information of elemental distributions in a single cell. We applied a micro-PIXE camera to obtain a picture presented with density of an element in a cell. Our micro-PIXE camera is on the basis of PIXE analysis using micro ion beams with the spot size of less than 1 μ m and the samples can be analyzed in air, so the size and the state of samples are not limited. Here, we analyzed the spatial distributions of elements in a single cell of animal for a medical application. Bovine aortic endothelial cells(BAECs) were cultured in culture medium containing bromodeoxyuridine(BrdU) which is known to be used in the DNA synthesis. We could take the elemental maps of phosphorus, potassium and sulfur which present well a shape of cell and a position of nucleus in this cell. Moreover, we obtained the picture of Br, that is, BrdU. It was found that BrdU was locally concentrated in two or three regions in the nucleus.

In this review (in continuations) X-ray crystal spectrometers working on ion beams and their applications are surveyed. The present fourth part continues to describe: (i) their use for elemental analysis; (ii) their use for obtaining the information about the chemical effects in the Particle Induced X-ray Emission spectra; (iii) their use in basic research for obtaining information applied in the above relations and their applications on acelerators. We update the data of formerly discussed systems according to the changes in the world.

The properties of gas scintillation proportional counter are investigated for Mn K x-ray spectra. The pulse-height spectra are strongly affected by changing of the value of a potential V₂ in the acceleration region and analyzed by the Gaussian profile fitting method.

The experimental apparatus of X-ray fluorescence (XRF) microprobe analysis at Beijing Synchrotron Radiation Facility (BSRF) is described. Using the bovine liver as the standard reference, the minimum detection limit (MDL) of trace element was measured to determine the capability of biological sample analysis by synchrotron radiation XRF microprobe. The relative change of the content of the major or trace element in the normal and tumor part of human bone tissue slice was investigated. The experimental result relation to the clinical medicine was also discussed.

We have measured elemental concentration of old Japanese copper coins made in the Edo period (1600-1860) by PIXE and XRF to study the availability of elemental concentration analysis for production place identification of copper-based archaeological alloys. We also aimed to compare the effectiveness of these two methods for this purpose. We used 2.5 MeV proton beam for PIXE measurement. For XRF measurement we operated a XRF equipment with rhodium target at 50 kV Since elemental uniformity is indispensable for concentration analysis, we also measured the elemental distributions by SEM at 25 kV. Two dimensional images obtained by SEM showed nearly uniform distribution for iron, tin and antimony but not for lead. Besides of main components, copper and lead, many minor components were measured by PIXE and XRF. The relative concentrations of arsenic, silver, antimony and tin showed clear difference by the place the coins were made.

The simultaneously applied techniques of Particle Induced X-ray Emission (PIXE), Rutherford Backscattering Spectrometry (RBS) and Scanning Transmission Ion Microscopy (STIM), have been successful in mapping and quantifying trace elements during the progression of several human diseases, in particular those degenerative diseases which have a corresponding animal model. In atherosclerosis, iron has been shown to be present in increased concentrations at the early stage of lesion formation, and when the animal model has been kept anaemic, the artery wall shows a reduced uptake of iron and a delay in lesion formation compared with controls. In Parkinson's disease, there is also an increased concentration of iron in the substantia nigra region of the brain. Although the increase in bulk iron appears to lag behind the dopaminergic cell death, we have detected an increase in localized deposits of iron at the onset of cell death. These two results infer that iron may play a role in both diseases, perhaps through the mediation of free radicals. The induction of epilepsy through the injection of kainic acid has shown that the cell death is accompanied by an increase in calcium levels as early as one day after injection. The increase in calcium is consistent with activation of phospholipase A₂ and free radical damage.

The Oxford Scanning Proton Microprobe continues to be used in the field of trace element measurement in biological systems, exploiting the unique advantages of sensitive, quantitative trace element analysis using PIXE, high spatial resolution and the long penetrating power of MeV protons. This paper outlines a number of recent applications which highlight these advantages. These include: (a) Analysing the distribution of metals in the pupae of leaf-cutting ants to determine the storage sites and transport mechanism of metals used to harden the edges of the mandibles. (b) A study of the distribution of zinc in the retina of rats to determine the role of zinc in light and dark adaptation of the eye. (c) The analysis of crystals of proteins and other large organic molecules prepared for structure determination using x-ray diffraction. These often contain metal atoms, and the identity and concentration of the metal is an important diagnostic for determining the nature of the protein and the quality of the crystallisation. The crystals are normally small (~100μm) and so microPIXE is being used to characterise them. This technique has wide ranging applications, including qualitative and quantitative identification of metals in reaction centres, in active sites and in metal binding proteins, and of DNA or RNA bound to proteins.

In TIARA facility of JAERI, a scanning transmission ion microscopy (STIM) technique was introduced to the light ion microbeam system, so as to make direct beam positioning to samples for micro-PIXE analyses in the atmosphere. STIM is a low current (less than fA level) and high efficient sample imaging technique, which does not induce radiation damage even to biological cells for beam positioning before micro-PIXE analysis. The sample (bovine aortic endothelial cells) was prepared using a freeze-dry method on a thin polymer film which act not only as a sample backing foil but also as a beam extraction window to the atmosphere. A Si PIN photodiode (cover glass removed) was set just behind the sample in the atmosphere to measure the energy of proton microbeams passing through the sample and the window. STIM images were obtained in a short time, and corresponded with elemental maps obtained by subsequent micro-PIXE analyses. This paper will describe details of the experimental system and show preliminary results of STIM imaging and micro-PIXE analyses.

The penetration abilities of surfactants need to be known by companies manufacturing hair-care products. In this work three complementary techniques were used simultaneously - PIXE, NRA and RBS - to measure the penetration of a surfactant, which had been deuterated, into permed hair fibres. Using a scanning micro-beam of 2MeV ³He ions 2-dimensional concentration maps were obtained which showed whether the surfactant penetrated the fibre or just stayed on the surface. This is the first report of the use of three simultaneous scattering techniques with a scanning micro-beam.

Nuclear microprobe analysis studies in cancer cell pharmacology and biology carried out at Bordeaux-Gradignan are reported. The cellular pharmacology of two anticancer agents, cis-diammine-dichloroplatinum(II), and 4′-iodo-4′-deoxy-doxorubicin, were investigated, as well as the role of iron in neuroblastoma carcinogenesis, and chromium(III) in trans-generation carcinogenesis. Nuclear microprobe analysis, using PIXE and particle backscattering microanalysis, was able to reveal intracellular and tissue distributions of the elements under investigation. Moreover, the fully quantitative and multi-elemental character of nuclear microprobe analysis offered information on possible mechanisms of drug action, metal carcinogenesis, and interactions with endogenous trace elements in cancer cells.

Comparative study on amyotrophic lateral sclerosis (ALS) and parkinsonism-dementia (PDC) in the Kii Peninsula of Japan and Guam was conducted to evaluate the participatory role of environmental minerals in the pathogenesis of the above neurodegenerative diseases, using particle-induced x-ray emission (PIXE) spectrometry and morphometric-statistical analysis. A significantly high content of Al in the hippocampus and spinal cord of Kii and Guamanian ALS/PD cases was found with a positive correlation for Fe and Cu, and a negative correlation for Zn. The numbers of hippocampal neurons in Guamanian PDC, Alzheimer's disease, and Parkinson's disease were significantly decreased with a high Al content. Al content significantly and positively correlated with the number of Alzheimer's neurofibrillary tangles (NFTs) in the hippocampus of ALS cases and controls in both foci, especially in Guamanian cases. The slope of best linear regression of Guamanian cases was markedly steeper than that of Japanese cases (p < 0.001). Morin staining for Al showed green fluorescence on the nucleolus, cytoplasm, and NFT in the hippocampus of Kii ALS cases. These findings suggest that Guamanian and Kii people have a predisposition to develop ALS/PDC precipitated by their geological/geochemical environmental status, i.e., a prolonged low intake of Ca and Mg together with excess exposure to Al and other environmental minerals.

Normal cell functions of the brain are often impaired by an excess accumulation of metal ions. There have been increasing efforts in recent years to measure and quantify excessive accumulations of biological constituent elements (such as Fe, Zn, Cu, and Ca), as well as the presence and distribution of contaminating elements (such as Al) in the brain tissues. Since Al might be associated with cases of neurodegenerative disorders, such as Alzheimer's disease (AD), Parkinson's disease (PD) and amiotrophic lateral screlosis (ALS), it is very important to measure and quantify Al levels using precise analytical techniques. The aim of this investigation is to measure the Al contents present in the temporal cortises for three cases. The specimens concerned were taken from unfixed autopsy brains, which have been preserved in a deep freezer at -80°C. A tandem type accelerator of 2 MeV energy was used to measure the concentrations of Al in these specimen tissues. In order to increase the sensitivity of the signals in the low energy region of the spectra, the absorber was removed. The results show that peak intensity depends on the site measured. In certain cases, however, an extremely high concentration of Al was observed in PIXE spectra, with an intensity higher than those of the other major elements present in the brain. Samples from the same subjects were also analyzed using EPMA-EDX. X-ray maps produced by EPMA-EDX showed the presence of extremely high concentrations of Al. The results yielded by PIXE analysis was in good qualitative agreement with those from EPMA-EDX.

Two minor and six trace elements (i.e., K, Ca, Mn, Fe, Cu, Zn, Se and Rb) and the wet-to-dry weight ratio were determined in five post-mortem human brains affected by a putaminocapsular hemorrhage. Most elements were "washed away" from the region of the bleeding. Iron, on the contrary, was accumulated, up to a level comparable with that in blood. The trace element alterations in the cortex, white matter and striatum adjacent to the bleeding were compared to those in the respective border areas of recent middle cerebral artery infarcts. The main difference in elemental alterations within the border areas of both hematomas and infarcts is the higher Fe accumulation in the former. The other elemental alterations in the border areas of bleedings are similar, but mostly smaller than those in infarcts. Also the edema formation in cortical and white matter border areas of the hematomas is less than for infarcts. The present findings suggest that in tissues adjacent to putaminocapsular hemorrhages changes occur, but of a milder nature than in border areas of the infarcts.

The interactions between mitochondrial and nuclear Mg concentration for the development of radiation-induced apoptosis were tested IN VIVO in Sarcoma-180 in BALB/c mice.

The frequency of apoptosis was expressed as a percentage of TUNEL reactivity in the 5 microscopic views under 400 times magnification, and Mg concentration in either mitochondria or nucleus was measured by Particle Induced X-ray Emission (PIXE), on 3, 6, 9, 12 and 24 hours after the 10 or 20 Gy of ⁶⁰Co gamma ray radiation, to the mice with or without the 0.01 mMOL MgCl₂ oral administration.

There were proximal increases of apoptosis, which peaked on 9 hours after radiation. The Mg concentration of mitochondria strongly correlated with frequency of apoptosis from 3 to 9 hrs after radiation, and that of the nucleus strongly correlated with frequency of apoptosis from 6 to 24 hours after radiation. The oral administration of MgCl₂ did not change those correlations.

The two steps are considered: 1st) signaling from mitochondria to nucleus involving Mg on induction of apoptosis; and 2nd) removal of apoptosis involving nuclear Mg.

Proton Induced X-ray Emission (PIXE) method is used for the determination of elemental concentration in a cancellous bone of human femoral head from five autopsies and seven patients with femoral neck broken. Specimen preparation and experimental procedure are described in detail. Using t test, the results show that the concentrations of P, Ca, Fe, Cu, Sr in a control group are higher than those in a patient group, but the concentrations of S, K, Zn, Mn are not significantly different. The physiological functions of metal elements in human bone are also discussed.

Alzheimer's, Parkinson's disease and ALS are among major neurodegenerative diseases. The cause of neurodegeneration is unknown, but there are indications that excessive accumulation of essential elements, and sometimes, incorporation of toxic foreign elements in neurons aggravate neurodegeneration. During the past decade, many researchers investigated the causative factors in degenerative diseases to specify genetic or environmental factor. PIXE analysis has been used for these studies because of the sample preparation is easy and detection limit is very low. However, the concentration of matrix elements and foreign elements are extremely low and difficult to detect and to quantify. In this study, specimens from patients with Alzheimer's disease with no chemical treatment, and those with chelating were analyzed. In all analyzed specimens, Na, Al, Si, P, S, Cl, Ca, Ti, V, Cr, Fe and Cu were detected. Each specimen in this study consisted of cerebral cortex and substantia alba. From these experiments we can observe a clear tendency that the accumulation of the metal elements are different depending on the constituent tissues, and the method of sample preparation has a dominant role in the measurement results.

We made a comparative study of the elements in the periosteum on titanium plates and screws for internal bone fixation, normal periosteum, and oral mucosa by the PIXE method. We studied 11 patients, 4 men and 7 women, with mandibular fracture or facial deformity. The implanted time length of the materials in the body was 5 to 16 months. The analyzed samples were 11 periostea on the materials, 11 normal periostea and 4 oral mucosae. The results were as follows. Twenty-four essential and 11 contaminated elements were detected in the periostea on the materials as well as in the normal periostea and the oral mucosae. In the mean values of titanium and aluminum, there were significantly higher values in the periostea on the materials than in the normal periostea. The mean concentration values of the other elements did not differ significantly between that in the periostea on the materials and that in the normal periostea. The concentration of titanium in the periostea on the materials was not correlated with sex, age of the patients, or the implanted time length. However, there was a significantly higher titanium concentration value in the periostea on the plates than on the screws. Our results could indicate that the existence of a titanium element in the periostea on the materials was caused by its dissolution from the materials.

Selenium (Se) concentration-time profiles in plasma and organs including liver, kidney, heart, lung, spleen and brain of rats (Jcl Wister, 9 wks old, n = 32) were investigated after a single intravenous (iv) / oral (po) administration of sodium selenite (dose is equivalent to 2 mg/kg b.w. of Se), The Se concentration was determined by PIXE analysis. Among the investigated biological samples, Se concentration was the highest in the kidney or liver, followed by the heart, lung or spleen, then plasma, and the brain. Se concentrations in these organs were 0.5 to 5 times of plasma Se. The distribution profiles of Se in the organs were dependent on the route of administration. Furthermore, their profiles appeared almost parallel to the plasma Se-concentration in a logarithmic scale. Compared to the Se concentration-time profiles in plasma and organs by the route of administration, po group showed about 1/4-1/2 of the Se concentration in iv group except for kidney. Kidney kept relatively higher concentration of Se, which was similar in the both groups. This may explain our recently published data that urinary excretion was similar in the both groups. The relative oral bioavailability of plasma and each organ was calculated by the ratio of area under the concentration-time curve after oral administration (AUCpo) to AUCiv. Each organ appeared to have their own bioavailability (i.e., liver 39%, kidney 97%, heart 37%, lung 18%, spleen 10%, and brain 72%), where plasma was 46%. These results highly suggested that different Se distribution in organs by the different route of administration was due to the different metabolic profile.

Otoliths and phytoplanktons have been investigated using a nuclear microprobe. A brief description of sample preparation and irradiation conditions is given. The results indicate a great potential of the technique in marine sciences.

Trace elements in a cuttlebone, a buoyant calcified tissue developing simultaneously with the individual growth, of an adult giant cuttlefish originating from the water of Ishigaki Island were measured by PIXE to examine the ontogenetic change of the element concentration. Beside calcium (major element), iron, zinc, manganese, copper, bromine and relatively large amounts of strontium were detected in the cuttlebone. Strontium concentration varied with position along the cuttlebone: it was high near the spine (the portion that deposited at the paralarval stage), then showed some variations at the middle portion of the cuttlebone (the portion that deposited from young stage to sub-adult stage) and became the highest near the locus (the portion that deposited near the catch date, i.e., adult stage). This variation was compared to migration of this species between inshore and offshore waters.

High-resolution nuclear microscopy was used to study the layered structure in the shell of the pacific oyster, Crassostrea gigas. In cross section, the layers appear as opaque white zones and clearer translucent zones. Raman spectroscopy indicates that the zones consist of alternating layers of the aragonite and calcite morphs of calcium carbonate, the mineral constituent of the shell. The chemistry of the shell varies from individual to individual but generally the predominant metal ion is Ca, with varying amounts of Si, Cl, Cr, Mn, Fe, Zn, Sb, Ni, Fe, As and Sr. Two dimensional maps of these major, minor and trace elements were measured in many shells with nuclear microscopy to identify the patterns of Zn and Sr deposition reflecting the calcite and aragonite layers. The significant difference in the patterns identified by ion beam analyses are possibly a result of isostructural exclusion of these metal ions between the different aragonite and calcite polymorphic forms of calcium carbonate.

High Fe concentrations were reported from roots of plants grown in soil. This has been discussed as a possible Fe source for plants, since the concentrations shown in the roots were much higher than in the shoots.

There are, however, also some indications that soil contamination at the root surface of soil grown plants could have led to an overestimation of the Fe concentration in roots.

Fe distribution in root cross sections of barley (Hordeum vulgare L. cv. Alexis) has been studied to investigate this hypothesis.

Micro-PIXE analyses in point and mapping mode were complemented by the STIM technique. Based on the correlation between Fe and soil-related elements (Ti, Al and Si), most of Fe located at the root surface could be attributed to soil contamination. It could also be shown that this soil contamination leads to an overestimation of Fe concentration in roots.

A large fraction of coal extracted from the earth is burnt in thermal power stations. In the combustion process most of the mineral matters in the coal are fused into an fly ash. Fly ash has a great potential for use in agriculture as a provider of major and micro nutrients to plants. Concentrations of some elements in the soil may increase when fly ash is applied to the soil. This paper presents the results on analysis of heavy metals in crops of wheat and paddy grown over last two years on coal ash-applied soils of Bakreswar and Farakka sites as a part of Fly Ash Mission projects on bulk scale utilization of coal ash in agricultural lands by Particle Induced X-ray Emission(PIXE) and Energy Dispersive X-ray Fluorescence(EDXRF) techniques.

The air quality sampling and analysis of airborne particulate matter (APM) in Ljubljana region has been started, recently. The sampler is positioned at around 10 km from the city limits in the direction of the prevailing winds. The aerosol samples were measured by a standard in-vacuum PIXE arrangement. The measured concentrations show the influences of the industry and traffic at the city.

A method of transferring suspended particulate matter (SPM) from the used filter of a beta-absorption mass monitor to a polycarbonate filter for subsequent PIXE analysis has been developed. The method allows determination of the relative elemental composition of SPM. It was demonstrated that PIXE analysis can detect S, Cl, Fe and Zn in SPM sampled over a one-hour period.

Particulate matter (PM-3.9 and PM-15.8) samples were collected in the three zones at the Northeast, Southwest and Southeast suburbs of Mexico City, from July to August 1998, for one week for each sampling site. The concentrations of several elements in the PM-3.9 and PM-15.8 samples were determined by Particle Induced X-ray Emission (PIXE). In the PM-3.9 samples, 21 elements were determined for each zone, and Na, Mg, Al, Si, S, K, Ca, Ti, Fe, Cu, Zn and Pb are found to be the major elemental components. On the other hand, 22 elements including P were determined on the PM-15.8 samples, and the dominant elements were the same as in the PM-3.9. Factor analysis is applied to the 28 variables (14 elements for each PM-3.9 and PM-15.8 groups) and for 21 samples (seven days for three zones) in order to identify possible sources of the particles. The result of factor analysis allows to identify five major sources, being soil the major contributor.

Modern medical procedures, including laser surgery, can generate fine aerosols that may carry biologically active agents. With such procedures becoming more commonplace, it is evident that we need to look at the health implications on hospital staff when dealing with highly contagious patients with bacterial and/or viral infections, such as AIDS. The focus of this study is not to determine what portion that population is actually harmful, only to deduce what segment is still biologically active after vaporization from tissues. We have developed procedures to collect and analyze aerosols by size (from >10 μm to less than 0.07 μm) and by time (from minutes to ~ 4 hour increments). Health relevant size cuts for aerosols in a work environment have been adopted by the International Organization for Standardization and the Comite of European de Normalisation. We examined both the nature of the aerosols generated and the efficiency of hospital masks used by personnel in screening aerosols and simulated conditions under which aerosols might be inhaled. Four sets of data were recorded: Mask filtered physical, mask filtered biological, unfiltered physical and unfiltered biological. A combination of PIXE analyses on impactor and filter samples were matched with filters and strips plated on agarose plates and counted for colony forming units to determine the biologically active subset of the population.

The Chaliyar river, located in Kerala, India has shown preoccupying pollution levels, that constitute a threat to public health and the ecological system. PIXE and PIGE techniques have been employed to measure the elemental concentrations in the river sediment samples. Thick targets were prepared out of the sediment samples collected from various sites along the course of the river. The measurements were carried out using 3 MeV proton beam obtained from 3 MV Tandem pelletron accelerator at Institute of Physics, Bhubaneswar. The elemental concentrations, especially that of heavy metals, at different sites are discussed in detail. Our results show that sediments from a site where the industrial activities are high are significantly high in concentrations of heavy metals (Cr, Ni, Cu, Zn, Hg and Pb) than those collected from non-industrial sites. The measured values are compared with the average composition of unpolluted river sediments and other national and international river sediments.

Fly ash is a major component of solid material generated by the coal-fired thermal power plants. In India the total amount of fly ash produced per annum is around 100 million tonnes. Fly ash has a great potential for utilization in making industrial products such as cement, bricks as well as building materials, besides being used as a soil conditioner and a provider of micro nutrients in agriculture. However, given the large amount of fly ash that accumulate at thermal power plants, their possible reuse and dispersion and mobilization into the environment of the various elements depend on climate, soils, indigenous vegetation and agriculture practices. Fly ash use in agriculture improved various physico-chemical properties of soil, particularly the water holding capacity, porosity and available plant nutrients. However it is generally apprehended that the application of large quantity of fly ash in fields may affect the plant growth and soil texture. Hence there is a need to characterize trace elements of fly ash. The results of trace element analysis of fly ash and pond ash samples collected from major thermal power plants of India by Particle Induced X-ray Emission (PIXE) have been discussed.

This paper reports the chemical compositions of chicken-blood stone Ji Xue Shi measured by Proton Induced X-ray Emission (PIXE). The experimental result show that for the red portion of chicken-blood stone, the concentration of Hg is as high as 20 wt%, and the concentration of S can be above 10 wt%. For the non-red portion the main chemical compositions are Al₂O₃ and SiO₂. The obtained chemical compositions are close to those of kaolinite for Balin chicken-blood stone, and of pyrophyllite for Changhua chicken-blood stone, respectively. So far many Changhua chicken-blood stones and Balin chicken-blood stones were found in China, the PIXE method can be used to explore the provenance of available chicken-blood stones.

Chemical composition of the fluids in the fluid inclusions of quartz from the pegmatite veins of the Yamaguchi W-Cu skarn deposit was measured by a combination of the crush-leach method in deionized water and chemical analysis using PIXE. Chemical composition of the fluids is characterized by a low molar ratio of Na/K and a high Cu concentration. The molar ratio of Cu/(Cu+Fe+Zn) of the fluid inclusions is higher than that of massive sulfide deposits on the seafloor. The molar ratio of Cu/(Cu+Fe+Zn) of the fluid inclusions is similar to the ratios of the vapor-rich fluid inclusions from the quartz-cassiterite veins hosted within the Mole Granite in New South Wales, Australia. The high Cu concentration in fluid inclusions of quartz associated with the pegmatite veins from the Yamaguchi deposit suggests that the fluid emanating from the Miyako granitic melt at the later stage of crystallization had a high Cu content.

Ancient pigments were analyzed using PIXE and XRD methods in the laboratory, which were painted on ancient Egyptian monuments. On the other hand, those on monuments remaining with entire shape were investigated using the hand-held type of an XRF spectrometer and an X-ray diffractometer in the field. For the laboratory experiment, several wall fragments of the Malqata palace in ancient Egypt (18^th Dynasty, ca. 1390 B.C.) were investigated. In the field experiment, the block of Ramesses II (19^th Dynasty, ca. 1270 B.C.), the Wooden Coffin of Neb-sny (18^th Dynasty, ca. 1400 B.C.), the Funerary Stele of Amenemhat (11^th Dynasty, ca. 2000 B.C.), and the painted walls of the Tomb of Userhat (18^th Dynasty, ca. 1400 B.C.) were investigated. From white and blue colored parts, huntite and Egyptian blue were found, respectively, which are a very rare mineral and an artificial pigment prepared only in ancient Egypt, respectively.

In order to classify the Otani Collection's Dunhuang and Turfan manuscripts, their trace elements were analyzed by PIXE. The paper samples of these manuscripts were fallen off when they were photographed for a CD-ROM catalog. These samples were very small and their size was less than several millimeters. In addition, some paper fragments dating from the late Edo-era of Japan and the late Qing Dynasty of China, and modern Japanese handmade paper were analyzed using PIXE and NAA. Quite interesting results were obtained when analyzing the trace elements – Na, Mg, Al, Si, S, Cl, K, Ca, Sc, Mn, Fe, Cu, Zn, As, Br, Sr, Ba, Pb, La, Sm. It was found that Dunhuang and Turfan papers of the Otani Collection were characterized by its highest iron and bromine content. The reason of the highest iron content probably originates in their making process and/or depends on their preservative environment. On the other hand, it became clear as for the highest bromine content that the origin is from fumigation of methyl bromide.

Six types of samples including urushi, urushi tree and black coating films taken from ancient Buddha images were examined by analyses of PIXE, organic element and FT-IR to identify with urushi another material. Based on the results of three analytical experiments above mentioned, the coating materials aging over hundreds of years were identified with weathered urushi films mixed with other material. Further investigation may reveal the urushi coating techniques used in the past.

The Japanese papers, "washi", are made from the plants. Since the elements included in the washi have the informations of the raw material plants, there is potentiality of the identification of the production place by the element analysis of the washi. Three kinds of washi made of kozo, which have different habitats, were prepared. The elements in their washi were measured by the PIXE. It was confirmed that the amount of elements included in the washi depend on the habitats of their raw material plants.

Proton Induced X-ray Emission, PIXE is a very well established analytical method. This technique of analysis can equally be applied both in vacuum, internal PIXE, and in atmosphere, external PIXE. External PIXE has been applied to material analysis in Van de Graaff laboratory at AEOI using filters and funny filters. Advantages of using these filters have been studied when analysing ancient written documents such as envelopes, inks, and newspapers. This technique clearly demonstrated the differences between new and old inks and papers. More data is needed to show other features of this technique.

In this work, external PIXE was applied for the analysis of ancient silver and bronze coins. Turkish and Romanian silver coins, Roman and Byzantine bronze coins were investigated using a 3 MeV proton beam. To evaluate the in-depth distribution of major and minor elements (Cu, Ag, Au, Pb for silver matrix and Cu, Zn, Ag, Sn, Pb for copper matrix), the coins were polished using silicon carbide abrasives. In order to test the homogeneity of the coins, measurements were carried out at three different impact points. Each position of the samples was carefully controlled in order to avoid differences in geometrical factors from one analysis to another. All the analyses were performed on flat external and bright regions so as to exclude the irradiation of possible inclusions or deposits. The calculations of the elemental concentrations in the coins were made by relative to reference standard alloys (Ag-Cu, Cu-Sn, Sn-Pb).

Ancient Iranian silver coins minted in various parts of the ancient Iran from Transoxiana to Mesopotamia over a time span of 460 years (247BC-208AD) during Parthians dynasty were analysed by PIXE with a 2.2 MeV proton beam. Forty seven silver coins owned by Tamashagah-e-Pool (museum of money) in Tehran were examined in this study. The possible correlation between the composition of coins and the minting time or the minting location of coins has been the prime objective of the present study. Elemental analysis of ancient coins could also reveal the direct relation with the political and economical situation and also with the metallurgy of the minting time. Results on the contents of principal component elements (Fe, Ni, Cu, As, Br, Ag, Sn, Sb, Ba, Au and Pb) are presented and discussed.

Human teeth from pre-Columbian and recent population groups have been analyzed by PIXE. Ancient teeth corresponding to children and adults were obtained from archaeological burials located in five geographic areas of Mexico. Inter-specific and inter-site differences in the trace element contents of enamel were compared in order to get some insight into differences in diet, environmental conditions, teeth health, disease state and post mortem alteration among the co-occurring populations. For permanent teeth from adults, small variations in trace element levels were found depending on the collection site or tooth health, but for deciduous teeth from children, the concentration of elements such as Mn, Fe and Sr varied considerably. In this work, the possible sources of variation are discussed.

We report on ion beam investigations of 40 bone samples from the archaeological site Edesheim/Rheinland–Pfalz, Germany, a burial site of a Merowingian population (6–8th century AD).

The samples were prepared as pellets from the so–called WARD'S triangle. This region is an inner part of the femoral neck and one of the areas of high fracture risk in the case of osteoporosis. The experiments were carried out with an 1.5 MeV H⁺ beam at the 2 MV VAN DE GRAAFF accelerator of the University of Leipzig. Simultaneously to the PIXE measurements, PBS and PIGE spectra were recorded.

We will present a correlation matrix for 11 selected elements detected by PIXE, which exhibits trends and dependences from which preliminary information on various diagenetic processes can be derived.