Abstract
In this work, a non-commercial triaxial geometry energy dispersive X-ray Fluorescence (EDXRF) setup and a benchtop mu-XRF system were used to identify postmortem contamination in buried bones. For two of the individuals, unusually high concentrations of Cu and Pb, but also Zn (in one individual) were observed. The pigments of the burial shroud coverings have been identified as the source of contamination. Accurate and precise quantitative results were obtained by nondestructive process using fundamental parameters method taking into account the matrix absorption effects. A total of 30 bones from 13 individuals, buried between the mid-XVlllth to early XIXth centuries, were analyzed to study the elemental composition and elemental distribution. The bones were collected from a church in Almada (Portugal), called Ermida do Espirito Santo, located near the Tagus River and at the sea neighbourhood. The triaxial geometry setup was used to quantify Ca, Fe, Cu, Zn, Br, Sr and Pb of powder pressed bone pellets (n=9 for each bone). Cluster analysis was performed considering the elemental concentrations for the different bones. There was a clear association between some bones regarding Fe, Cu, Zn, Br and Pb content but not a categorization between cortical and trabecular bones. The elemental distribution of Cu, Zn and Pb were assessed by the benchtop p.-analysis, the M4 Tornado, based on a polycapillary system which provides multi-elemental 2D maps. The results showed that contamination was mostly on the surface of the bone confirming that it was related to the burial shroud covering the individuals.

Abstract

Abstract
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 20 mu g/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 K-alpha, selenium K-alpha, arsenic K-beta, selenium K-beta, and bromine K-alpha 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 Ka peak only, ranged from 0.210 +/- 0.002 mu g/g selenium under one condition of analysis to 0.777 +/- 0.009 mu g/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 (similar to 3 min) 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.

Abstract
Lead is a potent toxicant associated with adverse cardiovascular effects and hypertension in children. Yet, few studies have determined if autonomic dysfunction associated with lead exposure involves brain regions which regulate autonomic responses. Central autonomic nuclei such as the nucleus tractus solitarius (NTS) and hypothalamic defence area (HDA) may be particularly sensitive to lead infiltration because they are adjacent to ventricles and areas with semi-permeable blood-brain-barriers. To understand if autonomic nuclei are sensitive to lead accumulation Wistar rats were exposed to lead from the gestational period and lead levels were quantified in brain regions that regulate arterial pressure: the NTS and the HDA. Energy dispersive X-ray fluorescence (EDXRF) was used to quantify total brain lead levels and revealed no differences between exposed and control tissues; measured values were close to the detection limit (2 mu g/g). Electrothermal atomic absorption spectrometry (ETAAS) was also used, which has a greater sensitivity, to quantify lead. There was similar to 2.1 mu g/g lead in the NTS and similar to 3.1 mu g/g lead in the HDA of exposed rats, and no lead in the control rats. There were greater lead levels in the HDA (similar to 50%) as compared with the NTS. Pathology studies revealed more prominent lead granules in the HDA as compared with the NTS. Increased microglia and astrocyte activation was also noted in the NTS of lead exposed rats as compared with the HDA. Regional differences in neuro-inflammatory responses likely contribute to heterogeneous lead accumulation, with enhanced clearance of lead in the NTS. Future studies will resolve the mechanisms underpinning tissue-specific lead accumulation.

Abstract

Abstract
X-ray fluorescence spectrometry (XRF) is a rapid, non-destructive multi-elemental analytical technique used for determining elemental contents ranging from percent down to the µg/g level. Although detection limits are much higher for XRF compared to other laboratory-based methods, such as inductively coupled plasma mass spectrometry (ICP-MS), ICP-optical emission spectrometry (OES) and atomic absorption spectrometry (AAS), its portability and ease of use make it a valuable tool, especially for field-based studies. A growing necessity to monitor human exposure to toxic metals and metalloids in consumer goods, cultural products, foods and other sample types while performing the analysis in situ has led to several important developments in portable XRF technology. In this study, a new portable XRF analyzer based on the use of doubly curved crystal optics (HD Mobile®) was evaluated for detecting toxic elements in foods, medicines, cosmetics and spices used in many Asian communities. Two models of the HD Mobile® (a pre-production and a final production unit) were investigated. Performance parameters including accuracy, precision and detection limits were characterized in a laboratory setting using certified reference materials (CRMs) and standard solutions. Bias estimates for key elements of public health significance such as As, Cd, Hg and Pb ranged from -10% to 11% for the pre-production, and -14% to 16% for the final production model. Five archived public health samples including herbal medicine products, ethnic spices and cosmetic products were analyzed using both XRF instruments. There was good agreement between the pre-production and final production models for the four key elements, such that the data were judged to be fit-for-purpose for the majority of samples analyzed. Detection of the four key elements of interest using the HD Mobile® was confirmed using archived samples for which ICP-OES data were available based on digested sample materials. The HD Mobile® XRF units were shown to be suitable for rapid screening of samples likely to be encountered in field based studies. © 2016 Elsevier B.V.