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
Childhood lead poisoning remains a significant public health issue, especially in the United States, where the most common source of exposure is lead-based paint (LBP). X-Ray Fluorescence (XRF) analysis is still the most widely used method for detecting LBP in the field. Although portable XRF instrumentation based on excitation from a 57Co radioisotope has been used for more than 30 years, there have been few reports documenting its performance. Here we describe a study that was conducted by the New York State Department of Health's Wadsworth Center laboratory in response to concerns raised by field users of the RMD LPA-1 XRF analyzer (Protec Instrument Corp.) working across the state. The performance issues were investigated for ten field units: five reported as problematic based on user feedback, and 5 that were not. Accuracy was assessed against NIST SRM 2579 lead in paint, which was developed specifically for use with portable XRF analyzers. On average, the absolute bias found was within ±20% at the threshold value for LBP (1.0 mg cm-2) based on the NIST SRM 2579 data. Calibration blocks provided with each analyzer for quality assurance monitoring were evaluated using a different XRF analyzer (Niton XLT 3t 700s GOLDD) operated in painted products mode (µg cm-2). However, when the Niton XRF analyzer was checked against NIST SRM 2579, it was found to have a negative bias. That negative bias was easily corrected using a "calibration" curve with a quadratic fit to the data. NIST-corrected data obtained for the calibration blocks showed assigned values were within the manufacturer's stated tolerance range, albeit with a consistent positive bias. The root cause for 3 of the 5 problematic devices was likely incorrect positioning of the device. A low bias for a fourth device was likely caused by a deteriorated calibration block, and the fifth device, while just within the manufacturer's technical specifications, was the only one confirmed with a low bias. Increased operator training may resolve some of the issues reported in the field; on-going competency assessments may be warranted for this hand-held technology. © 2014 The Royal Society of Chemistry.

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
Portable instruments based on X-Ray Fluorescence Spectrometry (XRF) have the potential to assist in field-based studies, provided that the data produced are reliable. In this study, we evaluate the performance of two different types of XRF instrument (XOS prototype and Thermo Niton XL3t). These two XRF analysers were evaluated in a laboratory setting, and data were reported for 17 elements (As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sn, Sr, Ti, V, and Zn). Samples analysed (n = 38) included ethnic herbal medicine products (HMPs), ethnic spices (ES), and cosmetic products (CPs). Comparison analyses were carried out using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). In general, results reported for Cd, Cu, and Pb by the XOS prototype analyser, using the non-metal mode, were negatively biased (5–95%) as compared to ICP-OES. In contrast, results reported for Pb, As, Cd, Cu and Zn by the Niton, using the soil mode, were positively biased, in some instances (Cd) by up to four orders of magnitude. While the sensitivity of both instruments was insufficient for reliably ‘quantifying’ toxic elements below 15 mg/kg, XRF was still capable of positively ‘detecting’ many elements at the low single-digit mg/kg levels. For semi-quantification estimates of contaminants at higher levels, and with limited sample preparation, both XRF instruments were deemed fit for the purpose. This study demonstrates that modern XRF instrumentation is valuable for characterising the elemental content of food, cosmetic, and medicinal products. The technology is particularly useful for rapidly screening large numbers of products (100’s per day) in the field, and quickly identifying those that may contain potentially hazardous levels of toxic elements. Toxic elements can be confirmed by examining the raw spectrum, and the limitations of factory-based calibration are generally manageable for field-based studies. © 2015 Wadsworth Center, New York State Department of Health.

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.