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.

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.

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.

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.

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.

A K edge filter technique for optimization of the coherent-to-Compton scatter ratio method.

The ratio method involves forming the ratio of the elastic to inelastic x-ray scatter signals from a localized region of a scattering medium to determine its mean atomic number. An analysis is presented of two major error sources influencing the ratio method: firstly statistical (photon) noise and secondly multiple scattering and self-attenuation of the primary and scatter radiations in the medium. It is shown that a forward scattering geometry minimizes errors of both types for substances composed of elements with low and medium atomic number. However, owing to the small energy separation (approximately 100 eV) of coherent and Compton scatter for this geometry, they cannot be distinguished directly with semiconductor (e.g., Ge) detectors. A novel K edge filter technique is described which permits separation of the elastic and Compton signals in the forward-scatter geometry. The feasibility of this method is demonstrated by experimental results obtained with Ta fluorescence radiation provided by a fluorescent x-ray source filtered with an Er foil. The extension of this technique to the "in vivo" measurement of low momentum transfer inelastic scattering from biological tissues, possibly providing useful diagnostic information, is briefly discussed.

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.

In vivo XRF analysis of mercury: the relation between concentrations in the kidney and the urine.

The objective of this study was to determine the concentrations of mercury in organs of occupationally exposed workers using in vivo x-ray fluorescence analysis. Twenty mercury exposed workers and twelve occupationally unexposed referents participated in the study. Their mercury levels in kidney, liver and thyroid were measured using a technique based on excitation with partly plane polarized photons. The mercury levels in blood and urine were determined using atomic absorption spectrophotometry. The detection limit for mercury in the kidney was exceeded in nine of the exposed workers, but in none of the referents. The mean kidney mercury concentration (including estimates below the detection limits) was 24 micrograms g-1 in the exposed workers, and 1 microgram g-1 in the referents. The association between mercury in the kidney and in urine was statistically significant, but it was unclear whether the relation was linear. The measurements on liver (n = 10) and thyroid (n = 8) in the exposed workers showed mercury levels below the detection limit. The study shows that it is now possible to measure the mercury concentrations in kidneys of occupationally exposed persons, using in vivo x-ray fluorescence. The estimated concentrations are in reasonable agreement with the limited human autopsy data, and the results of animal studies.

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.

Soluble metals in the atmosphere and their biological implications. A study to identify important aerosol components by statistical analysis of PIXE data.

Multivariate statistical analysis has been applied to time series measurements of aerosol elemental composition from PIXE analysis of filter samples, and principal components have been resolved that represent distinct particle types in an external mixture in the atmosphere. In this study, it is argued that a combination of chemical and statistical analyses of the data may be more powerful in determining chemical species in atmospheric aerosols than studied that employ mainly direct chemical analysis of chemical species in unresolved mixtures of aerosol particle samples. Sulfur is generally associated with mineral dust elements. It is reasoned that the association may represent sulfuric acid coatings on particles that can lead to mineral dissolution and solubilization of significant amounts of aluminum, iron, and other metals. Upon wet or dry deposition to the surface, the fluxes of these metals in biologically-available form may be sufficient to affect primary productivity in the world ocean and cause ecological damage in lakes. As a consequence, the fluxes of biogenic trace gases to the atmosphere may be changed, possibly leading to changes in the tropospheric concentration of ozone. The inputs to lakes of soluble aluminum, which is toxic to fish, may be partly by deposition directly from the atmosphere, thus not limited to leaching of soils by acid deposition. Human inhalation of soluble aluminum and other solubilized mineral metals may account, in part, for the observed geographic pattern of deaths attributed to chronic obstructive pulmonary disease (COPD) that show high rates in cities of the Western US and the southeast region, but low in most of the midwest and northeast.

Applicability of microwave acid digestion to sample preparation of biological materials for analysis by particle-induced X-ray emission (PIXE).

A microwave acid digestion method for the preparation of biological samples for PIXE analysis is presented. The precision and accuracy of the entire PIXE analytical procedure, including the microwave digestion step, were evaluated by analyzing eight certified reference materials. For elements heavier than K, and for concentration levels from 2 micrograms/g upward, the total random error of a single analysis is in the range of 2-5%. The accuracy is better than 5%. The detection limits are down to 0.3 micrograms/g.

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.

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.

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.

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.

Lead in fingerbone: a tool for retrospective exposure assessment.

Exposure to inorganic lead may cause many adverse health effects. When absorbed, lead is accumulated in large part in bone. In this study, we investigated the relationship between lead concentration in fingerbone, exposure time, and lead in blood. We also sought to design a model that made it possible to use fingerbone lead as an indicator of earlier exposure. The study comprised 137 active workers from a secondary lead smeltery. Workers had undergone regular determinations of blood lead (i.e., up to 6 times/y) for up to 24 y. In addition, during the period 1979-1992, workers underwent up to four fingerbone lead assessments via noninvasive x-ray fluorescence. We calculated cumulative blood lead, adjusted for time-related reduction of bone lead according to a transfer of lead from bone to blood, for each worker. We obtained the best fit of bone lead to cumulative adjusted blood lead when we assumed a 14-y half-time for the transfer coefficient. This half-time was similar to the terminal half-time for lead in bone in retired smelters, whom we studied earlier by longitudinal in vivo measurements. We described models for the accumulation of bone lead on blood lead and exposure time. The combined data on bone lead and exposure time may be used to estimate a mean blood lead during previous exposure. Such estimates will be valuable in epidemiological studies aimed at evaluating the toxic effects of long-term lead exposure in lead workers for whom data on previous blood lead levels are lacking.

[A high-voltage x-ray spectrometer for x-ray apparatus]. / Rentgenospektral'nyi izmeritel' vysokikh napriazhenii dlia rentgenapparatov.

A high-voltage measuring instrument has been developed to be used in medical X-ray equipment. It measures without connection up to the current-carrying circuits. In the device, the limit of the braking spectrum is used to determine the values of X-ray tube-applied voltage, which are calculated to a high precision by the programme put into the analyser and printed out on a printer. The scale of the device is calibrated by the peak reference points of the reference isotopic sources of gamma radiation.

[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.