Assessing zinc from a nail clipping using mono-energetic portable X-ray fluorescence.

A mono-energetic X-ray beam from a portable X-ray fluorescence device was used to excite characteristic X-rays from zinc in a series of nail clipping phantoms. Twenty nail clipping phantoms having equal zinc concentrations of ~40 µg/g, but with different physical characteristics, were measured individually for 300 s using a small diameter (~1 mm) X-ray beam. Energy spectra obtained from the measurements were analyzed using PyMca software. Zinc signal size varied widely between the different clippings, with a relative standard deviation of 41% observed in the combined signal from zinc Kα and Kß characteristic X-rays. Three different normalization approaches were introduced to account for variation in the amounts of sample interrogated by the X-ray beam. All three approaches produced similar results, and successfully reduced the relative standard deviation to between 12% and 13%. A clear trend was still observed, however, between the normalized zinc signal and the thickness of clipping measured. To account for this effect, normalized signals were adjusted to calculate "thickness-corrected" values. The relative standard deviation of these thickness-corrected values was 6.2%. Reproducibility of measurement from individual clippings was excellent, with relative standard deviations on the order of 1%, with or without normalization. Overall, this new method of measuring zinc in nail shows promise for the assessment of zinc status in humans using a portable device. The method is sensitive, rapid, and requires only a single nail clipping.

Discrimination of geographical origin of hop (Humulus lupulus L.) using geochemical elements combined with statistical analysis.

Beer is a popular alcoholic beverage worldwide, traditionally made from water, barley and hop (Humulus lupulus L.) strobili. The strobili contain lupulin glands whose components (mostly bitter acids and polyphenols) confer unique and locally different flavours to beer types. It is therefore relevant for brewers and consumers to precisely know the geographical origin of hop plants used for high-quality beer. Hop plants belonging to the variety Hallertau Perle, grown in two locations, Cavalese and Imèr, of the Trentino Region (Italy) were analysed to establish a direct relationship between the chemical elements detected in soil and in plant parts. Chemical elements were determined by X-ray fluorescence and inductively coupled plasma mass spectrometry in soil, leaf and strobili samples from Cavalese and Imèr. The data from the two areas were compared by a nonparametric test (Mann-Whitney) and multivariate statistics (principal component analysis and partial least squares discriminant analysis). The geochemical characterization and the statistical analyses showed different concentrations of major and trace elements in soil and plant parts from the two areas. A reliable correlation could be established between some elements in soil and strobili samples, that is Nb, Fe, Rb and Zr for Cavalese and Mg, Ni, Zn and Zr for Imèr. These elements could therefore be used as geochemical fingerprints to identify the geographical origin of strobili from the two study areas, an approach useful to verify the origin of hop plants for the production of high-quality beer.

A nested multivariate chemometrics based calibration strategy for direct trace biometal analysis in soft tissue utilizing Energy Dispersive X-Ray Fluorescence (EDXRF) and scattering spectrometry.

Compton scatter-modulated fluorescence and multivariate chemometric (artificial neural network (ANN) and principal component regression (PCR)) calibration strategy was explored for direct rapid trace biometals (Mn, Fe, Cu, Zn, Se) analysis in "complex" matrices (model soft tissues). This involved spectral feature selection (multiple fluorescence signatures) normalized to or in conjunction with Compton scatter. ANN model resulted in more accurate trace biometal determination (R2>0.9) compared to PCR. Hybrid nested (ANN and PCR) approach led to optimized accurate biometals' concentrations in Oyster tissue (≤ ± 10%).

Performance comparison of two Olympus InnovX handheld x-ray analyzers for feasibility of measuring arsenic in skin in vivo - Alpha and Delta models.

The Figure-Of-Merit (FOM) performance, a combination of detection limit and dose, is compared between two generations of handheld X-Ray Fluorescence (XRF) spectrometers for the feasibility of in vivo XRF measurement of arsenic (As) in skin. The Olympus InnovX Delta model analyzer (40 kVp using either 37 or 17µA) was found to show improvements in Minimum Detection Limit (MDL) using arsenic As-doped skin calibration phantoms with bulk tissue backing, when compared to the first generation InnovX Alpha model (40kVp, 20µA) in 120s measurements. Differences between two different definitions of MDL are discussed. On the Delta system, an MDL of (0.462±0.002) µg/g As was found in phantoms, with a nylon backing behind to mimic bulk tissue behind skin. The equivalent and effective doses were found to be (10±2) mSv and ~7×10-3µSv respectively for the Alpha and (15±4) mSv and ~8×10-3µSv respectively for the Delta system in 120s exposures. Combining MDL and effective dose, a lower (better) FOM was found for the Delta, (1.7±0.4) ppm mSv1/2, compared to (4.4±0.5) ppm mSv1/2 for the Alpha model system. The Delta analyzer demonstrates improved overall system performance for a rapid 2-min measurement in As skin phantoms, such that it can be considered for use in populations exposed to arsenic.

Assessing arsenic and selenium in a single nail clipping using portable X-ray fluorescence.

The feasibility of measuring arsenic and selenium contents in a single nail clipping was investigated using a small-focus portable X-ray fluorescence (XRF) instrument with monochromatic excitation beams. Nail clipping phantoms supplemented with arsenic and selenium to produce materials with 0, 5, 10, 15, and 20µg/g were used for calibration purposes. In total, 10 different clippings were analyzed at two different measurement positions. Energy spectra were fit with detection peaks for arsenic Kα, selenium Kα, arsenic Kß, selenium Kß, and bromine Kα characteristic X-rays. Data analysis was performed under two distinct conditions of fitting constraint. Calibration lines were established from the amplitude of each of the arsenic and selenium peaks as a function of the elemental contents in the clippings. The slopes of the four calibration lines were consistent between the two conditions of analysis. The calculated minimum detection limit (MDL) of the method, when considering the Kα peak only, ranged from 0.210±0.002µg/g selenium under one condition of analysis to 0.777±0.009µg/g selenium under another. Compared with previous portable XRF nail clipping studies, MDLs were substantially improved for both arsenic and selenium. The new measurement technique had the additional benefits of being short in duration (~3min) and requiring only a single nail clipping. The mass of the individual clipping used did not appear to play a major role in signal strength, but positioning of the clipping is important.

Optimizing detector geometry for trace element mapping by X-ray fluorescence.

Trace metals play critical roles in a variety of systems, ranging from cells to photovoltaics. X-Ray Fluorescence (XRF) microscopy using X-ray excitation provides one of the highest sensitivities available for imaging the distribution of trace metals at sub-100 nm resolution. With the growing availability and increasing performance of synchrotron light source based instruments and X-ray nanofocusing optics, and with improvements in energy-dispersive XRF detectors, what are the factors that limit trace element detectability? To address this question, we describe an analytical model for the total signal incident on XRF detectors with various geometries, including the spectral response of energy dispersive detectors. This model agrees well with experimentally recorded X-ray fluorescence spectra, and involves much shorter calculation times than with Monte Carlo simulations. With such a model, one can estimate the signal when a trace element is illuminated with an X-ray beam, and when just the surrounding non-fluorescent material is illuminated. From this signal difference, a contrast parameter can be calculated and this can in turn be used to calculate the signal-to-noise ratio (S/N) for detecting a certain elemental concentration. We apply this model to the detection of trace amounts of zinc in biological materials, and to the detection of small quantities of arsenic in semiconductors. We conclude that increased detector collection solid angle is (nearly) always advantageous even when considering the scattered signal. However, given the choice between a smaller detector at 90° to the beam versus a larger detector at 180° (in a backscatter-like geometry), the 90° detector is better for trace element detection in thick samples, while the larger detector in 180° geometry is better suited to trace element detection in thin samples.

Characterization of energy response for photon-counting detectors using x-ray fluorescence.

PURPOSE: To investigate the feasibility of characterizing a Si strip photon-counting detector using x-ray fluorescence. METHODS: X-ray fluorescence was generated by using a pencil beam from a tungsten anode x-ray tube with 2 mm Al filtration. Spectra were acquired at 90° from the primary beam direction with an energy-resolved photon-counting detector based on an edge illuminated Si strip detector. The distances from the source to target and the target to detector were approximately 19 and 11 cm, respectively. Four different materials, containing silver (Ag), iodine (I), barium (Ba), and gadolinium (Gd), were placed in small plastic containers with a diameter of approximately 0.7 cm for x-ray fluorescence measurements. Linear regression analysis was performed to derive the gain and offset values for the correlation between the measured fluorescence peak center and the known fluorescence energies. The energy resolutions and charge-sharing fractions were also obtained from analytical fittings of the recorded fluorescence spectra. An analytical model, which employed four parameters that can be determined from the fluorescence calibration, was used to estimate the detector response function. RESULTS: Strong fluorescence signals of all four target materials were recorded with the investigated geometry for the Si strip detector. The average gain and offset of all pixels for detector energy calibration were determined to be 6.95 mV/keV and -66.33 mV, respectively. The detector's energy resolution remained at approximately 2.7 keV for low energies, and increased slightly at 45 keV. The average charge-sharing fraction was estimated to be 36% within the investigated energy range of 20-45 keV. The simulated detector output based on the proposed response function agreed well with the experimental measurement. CONCLUSIONS: The performance of a spectral imaging system using energy-resolved photon-counting detectors is very dependent on the energy calibration of the detector. The proposed x-ray fluorescence technique offers an accurate and efficient way to calibrate the energy response of a photon-counting detector.

Choice of operating voltage for a transmission electron microscope.

An accelerating voltage of 100-300kV remains a good choice for the majority of TEM or STEM specimens, avoiding the expense of high-voltage microscopy but providing the possibility of atomic resolution even in the absence of lens-aberration correction. For specimens thicker than a few tens of nm, the image intensity and scattering contrast are likely to be higher than at lower voltage, as is the visibility of ionization edges below 1000eV (as required for EELS elemental analysis). In thick (>100nm) specimens, higher voltage ensures less beam broadening and better spatial resolution for STEM imaging and EDX spectroscopy. Low-voltage (e.g. 30kV) TEM or STEM is attractive for a very thin (e.g. 10nm) specimen, as it provides higher scattering contrast and fewer problems for valence-excitation EELS. Specimens that are immune to radiolysis suffer knock-on damage at high current densities, and this form of radiation damage can be reduced or avoided by choosing a low accelerating voltage. Low-voltage STEM with an aberration-corrected objective lens (together with a high-angle dark-field detector and/or EELS) offers atomic resolution and elemental identification from very thin specimens. Conventional TEM can provide atomic resolution in low-voltage phase-contrast images but requires correction of chromatic aberration and preferably an electron-beam monochromator. Many non-conducting (e.g. organic) specimens damage easily by radiolysis and radiation damage then determines the TEM image resolution. For bright-field scattering contrast, low kV can provide slightly better dose-limited resolution if the specimen is very thin (a few nm) but considerably better resolution is possible from a thicker specimen, for which higher kV is required. Use of a phase plate in a conventional TEM offers the most dose-efficient way of achieving atomic resolution from beam-sensitive specimens.

Thin and thick target PIXE analyses to assess the mechanism of Cu2+ removal by Egeria densa.

In this work the PIXE technique was used to study the mechanism of metal sorption by dead biomass. Several batch copper-sorption experiments were performed by using Egeria densa biomass. PIXE measurements were performed in solid and liquid samples. Element concentrations in biosorbent samples were determined using the Clara software. Based on the mass balance among the major elements in the liquid and solid phases before and after the Cu-removal experiments, an ion exchange process is suggested as the main mechanism.

The effect of covariance between the K alpha and the K beta lead peak concentrations on the uncertainty in the result of in vivo (109)Cd KXRF bone lead measurement.

The effect of covariance between the K alpha and K beta lead peak concentrations on the uncertainty in the (109)Cd K x-ray fluorescence measurement of lead in bone is addressed here. It is commonly believed that this covariance arises as a result of the mutual dependence of the ratios of x-ray to coherent amplitudes on the same coherent peak amplitude. Previous work assumes statistical independence between spectral quantities of interest, crudely estimates the uncertainties in the lead peak concentrations, and suggests that the effect of covariance on the measurement uncertainty is small and can be ignored. Consequently, the current method followed by most laboratories reports the measurement uncertainty as if the fluctuations in the measured peak concentrations were independent. The robustness of such assumption, however, is undermined by existing epidemiological data. This paper assesses the magnitude of the covariance effect, using a method based on the observed significant correlations between the ratios of x-ray to coherent peak amplitudes in series of repeat phantom measurements. The revised uncertainties following this approach can exceed the uncertainties estimated by the accepted method by as much as 40%, which suggests a much stronger effect of covariance on the measurement uncertainty than previously reported.

X-ray microdiffraction and conventional diffraction from frozen-hydrated biological specimens.

A system for recording microdiffraction patterns from micrometer-sized quick-frozen hydrated biological specimens at the high-flux beamline BL40XU of SPring-8 is described. The optics consists of a pair of pinholes drilled into tantalum substratum, with a defining aperture of diameter 2 microm. The frozen specimens are placed in an in-vacuum cryochamber mounted on a three-axis goniometer, where the specimens are stably held at a liquid-nitrogen temperature ( approximately 74 K). A beam size of 1.5 microm (full width at half-maximum) is attained at the sample position. By using this system, diffraction patterns have been recorded from an isolated single myofibril (diameter approximately 3 microm) of an insect flight muscle in an area equivalent to a single sarcomere (length approximately 3 microm). The technique is potentially applicable to other micrometer-sized hydrated biological specimens, which are more susceptible to radiation damage than dry synthetic polymers or biopolymers. The quick-freezing of biological specimens has also been proven useful in reducing the specimen volume in the beam in conventional diffraction recordings.

Corrections to "How to calculate lead concentration and concentration uncertainty in XRF in vivo bone lead analysis" by Kondrashov and Rothenberg.

Kondrashov and Rothenberg (Appl. Radiat. Isot. 55 (2001) 799) have published "a substantial correction for calculating estimates of lead concentration and uncertainty for in vivo X-ray fluorescent bone analysis with Cd-109 source" (sic). Our paper shows that their correction fails to consider two important points that render it (i) a correction to a superseded method and (ii) of limited effect. Also, their approach to a "crude" estimate produces measurement uncertainties that are implausibly small. In order that they not be propagated in the literature, our paper also corrects several misstatements and errors in Kondrashov and Rothenberg.

Calibration and characterization of a digital X-ray fluorescence bone lead system.

Five different combinations of digital shaping parameters were tested for a newly assembled. 109Cd source, K X-ray fluorescence bone lead system. System calibration results are presented, along with analyses of measurement uncertainty and reproducibility obtained from repeat measurements of a bone phantom and a human tibia. Digital shaping parameters of 2.4 micros for a rise time/fall time and 1.2 micros for a flat top width were identified as superior. The digital system provided significant improvements in overall measurement precision, with gains of at least 25-35% over conventional system results.

A new model for statistical error analysis in XAS: about the distribution function of the absorption coefficient.

Under some general hypothesis, this paper proposes a theoretical model, showing that a gaussian distribution is generally a good approximation of the experimental distribution of the absorption coefficient. This result is confirmed experimentally by usage of appropriate statistical tests.

Matrix effects during potassium and calcium determinations in rice saplings using X-ray spectrometery.

For selectively excited calcium K X-rays in rice saplings, the relations alpha = N(KR)[1 + A gamma + B beta/(1 + alpha)] and 1/N(Ca) = alpha/beta + b + c beta are found to support the enhancement of potassium K X-rays and N(Ca) calcium K X-ray counts during potassium and calcium determinations, respectively. Here alpha, beta and gamma are weight fractions of potassium, calcium and the matrix substrate, respectively, N(KR) is the relative potassium K X-ray counts of the sample to that of pure potassium and A, B, a, b and c are constants. Tests of these relations, using eight known mixtures of CaCO3, KNO3 and Na2B4O7 10H2O (borax), have further supported the findings.

How to calculate lead concentration and concentration uncertainty in XRF in vivo bone lead analysis.

The authors provide a substantial correction for calculating estimates of lead concentration and uncertainty for in vivo X-ray fluorescent bone analysis with Cd-109 source. Based on general principles, they provide mathematical techniques for propagation of uncertainties in XRF analysis. They give additional considerations for lowering the detection limit and improving spectral data quality.

[The methodological characteristics of determining the basic and trace elements in the serum and peripheral blood cells by the x-ray fluorescence method]. / Metodicheskie osobennosti opredeleniia osnovnykh i mikroélementov v syvorotke i kletkakh perifericheskoi krovi rentgenofliuorestsentnym metodom.

Analytical parameters of instrumental methods of the element analysis of biomedical objects are compared and the place occupied by x-ray fluorescent analysis (RFA) among them is demonstrated. The methods for preparing the specimens of liquid media of the organism and the RFA are simple, rapid, involve no disintegration of the sample, and allow measurements of elements at sigma 1 = 0.02 at concentrations of 12 micrograms/ml. The method is preferable and promising for some basic elements (P, S, Cl, K, Ca), which are difficult to measure by other methods. The levels of S, K, Ca, Fe, Zn, and Cu were measured in erythrocytic mass and blood serum of normal subjects, patients with asthma and aplastic anemia, and recipients of allogenic kidneys.

Application of the fundamental parameter method to the in vivo x-ray fluorescence analysis of Pt.

The application of the fundamental parameter method (FPM) to the in vivo x-ray fluorescence (XRF) analysis of Pt has been investigated. The FPM is conventionally used to carry out elemental analysis of samples in vitro without the need to use standard samples of accurately known composition for system calibration. The present work has involved the use of the FPM to calculate the concentration of Pt solutions in phantoms, with concentrations ranging from 25-1000 ppm. The phantoms simulate the measurement of Pt-based chemotherapy drugs in head and neck tumours. The radiation sources were a 150 kV tungsten-anode x-ray tube and the isotope 99mTc. The minimum detection limit measured for Pt was in the range 8-30 ppm (depending on radiation source and geometry), using a narrow (5 mm) diameter beam. Dose rates in the phantom were 0.1-5 mGy h(-1). Average differences between nominal and calculated values of Pt concentration were <8% using the phantoms in air to simulate measurement of Pt in superficial body sites. If the phantoms were placed in a water bath, to simulate measurement at greater depths of overlying tissue, higher systematic differences (15-20%) were observed. This effect is probably due to multiple scattering processes in the surrounding medium.

[The use of emission spectrum analysis in the forensic medical expertise of gunshot wounds (experimental research)]. / Primenenie émissionnogo spektral'nogo analiza pri sudebno-meditsinskoi ékspertize ognestrel'nykh povrezhdenii (éksperimental'nye issledovaniia)]

Presents the methodology of experimental shots from various guns (n = 11) by common cartridges and of emission spectral analysis (ESA) which was used to study the regularities in deposition of "gunshot metals" at the site of gunshot injuries and to detect the characteristic differences in shooting with and without obstacles. Effects of some factors on deposition of metal components of gunshot products at the site of gunshot injuries are studied: type of gun, shell (with/without coating or semicoated), presence of obstacles, distance, and order of the shot. Results of studies are presented for some guns, which may be useful in forensic medical expert evaluations by means of ESA.

Monte Carlo simulation of source-excited in vivo x-ray fluorescence measurements of heavy metals.

This paper reports on the Monte Carlo simulation of in vivo x-ray fluorescence (XRF) measurements. Our model is an improvement on previously reported simulations in that it relies on a theoretical basis for modelling Compton momentum broadening as well as detector efficiency. Furthermore, this model is an accurate simulation of experimentally detected spectra when comparisons are made in absolute counts; preceding models have generally only achieved agreement with spectra normalized to unit area. Our code is sufficiently flexible to be applied to the investigation of numerous source-excited in vivo XRF systems. Thus far the simulation has been applied to the modelling of two different systems. The first application was the investigation of various aspects of a new in vivo XRF system, the measurement of uranium in bone with 57Co in a backscatter (approximately 180 degrees) geometry. The Monte Carlo simulation was critical in assessing the potential of applying XRF to the measurement of uranium in bone. Currently the Monte Carlo code is being used to evaluate a potential means of simplifying an established in vivo XRF system, the measurement of lead in bone with 57Co in a 90 degrees geometry. The results from these simulations may demonstrate that calibration procedures can be significantly simplified and subject dose may be reduced. As well as providing an excellent tool for optimizing designs of new systems and improving existing techniques, this model can be used in the investigation of the dosimetry of various XRF systems. Our simulation allows a detailed understanding of the numerous processes involved when heavy metal concentrations are measured in vivo with XRF.