Mihai R. Gherase

A rapid, high sensitivity technique for measuring arsenic in skin phantoms using a portable x-ray tube and detector

Using a portable x-ray tube and silicon PiN diode detector, an improved approach to the measurement of arsenic in skin phantoms was demonstrated. Skin phantoms of 8 mm thickness were made from polyester resin, with arsenic concentrations ranging from 0 to 30 microg g(-1). The excitation of characteristic arsenic x-rays was performed with the x-ray tube and K(alpha) x-rays were used as an indicator of arsenic concentration. From repeated phantom measurements, an instrumental minimum detection limit of 0.446 +/- 0.006 microg g(-1) was found, using an acquisition time of 120 s (real time). This compares with previously reported approaches having instrumental minimum detection limits of 3.5 +/- 0.2 microg g(-1) (1800 s real time), 2.3 +/- 0.1 microg g(-1) (1000 s live time) and 0.40 +/- 0.06 microg g(-1) (1000 s live time).

Simultaneous assessment of arsenic and selenium in human nail phantoms using a portable x-ray tube and a detector

A novel approach to the measurement of arsenic and selenium in nail phantoms is demonstrated. Two-component nail phantoms of 0.7 mm and 1.5 mm thickness were made from a polyester resin-salt mixture and dosed with equal arsenic and selenium concentrations ranging from 0 to 30 microg g(-1). A backing was made to simulate the soft tissue and bone of the great toe. Characteristic x-rays for arsenic and selenium were recorded using a portable x-ray tube and a silicon PiN diode detector. The minimum instrumental detection limits for arsenic and selenium in 0.7 mm solitary nail samples were as follows: 0.510 +/- 0.018 microg g(-1) and 0.519 +/- 0.026 microg g(-1) respectively; for 1.5 mm solitary nail: 0.465 +/- 0.035 microg g(-1) and 0.561 +/- 0.062 microg g(-1); for 0.7 mm nail with backing: 1.522 +/- 0.038 microg g(-1) and 1.401 +/- 0.049 microg g(-1); for 1.5 mm nail with backing: 1.354 +/- 0.054 microg g(-1) and 1.367 +/- 0.068 microg g(-1).

X-ray fluorescence measurements of arsenic micro-distribution in human nail clippings using synchrotron radiation

Arsenic (As) distribution in nail clippings from three healthy human subjects was investigated using the microbeam experimental setup of the hard x-ray micro-analysis (HXMA) beamline from the Canadian Light Source (CLS) synchrotron. A pair of toenail and fingernail clippings was collected from each of three subjects (one contributed two fingernail clippings). The fingernail and toenail clippings were embedded in polyester resin and cut in cross-sectional slices with an average thickness of 270 µm. Nine nail clipping cross sections were analyzed from the three subjects. The same method was used to produce five cross sections of nail phantom clippings with concentrations of As ranging from 0 to 20 µg g−1, in increments of 5 µg g−1. These samples were used to produce a calibration line for the As Kα peak. The energy of the x-ray beam was set at 13 keV for optimal excitation of As and the beam size was 28 × 10 µm2. Each sample was analyzed using a point-by-point scanning technique in a 45° beam-sample and 90° beam-detector geometry. The dwelling time was set at 30 s for the human nail clippings and 20 s for the nail phantom clippings, using a step size of 50 µm in both the horizontal and vertical directions for all samples. As concentration for each point was calculated based on the calibration line parameters and the fitted amplitude of the observed As Kα peak. As concentration maps were produced for each nail clipping cross section. The maps show that small regions (<0.1 mm2) with higher As concentrations (>1 µg g−1) are located predominantly in the ventral and dorsal layers of the nail. The results are in agreement with findings reported in a recent study and can be linked to nail histology and keratin structure.

A calibration method for proposed XRF measurements of arsenic and selenium in nail clippings

A calibration method for proposed x-ray fluorescence (XRF) measurements of arsenic and selenium in nail clippings is demonstrated. Phantom nail clippings were produced from a whole nail phantom (0.7 mm thickness, 25 × 25 mm(2) area) and contained equal concentrations of arsenic and selenium ranging from 0 to 20 µg g(-1) in increments of 5 µg g(-1). The phantom nail clippings were then grouped in samples of five different masses: 20, 40, 60, 80 and 100 mg for each concentration. Experimental x-ray spectra were acquired for each of the sample masses using a portable x-ray tube and a detector unit. Calibration lines (XRF signal in a number of counts versus stoichiometric elemental concentration) were produced for each of the two elements. A semi-empirical relationship between the mass of the nail phantoms (m) and the slope of the calibration line (s) was determined separately for arsenic and selenium. Using this calibration method, one can estimate elemental concentrations and their uncertainties from the XRF spectra of human nail clippings.

The radiation dose from a proposed measurement of arsenic and selenium in human skin.

Dose measurements following 10 min irradiations with a portable x-ray fluorescence spectrometer composed of a miniature x-ray tube and a silicon PiN diode detector were performed using thermoluminescent dosimeters consisting of LiF:Mg,Ti chips of 3 mm diameter and 0.4 mm thickness. The table-top setup of the spectrometer was used for all measurements. The setup included a stainless steel lid which served as a radiation shield. Two rectangular polyethylene skin/soft tissue phantoms with two cylindrical plaster of Paris bone phantoms were used to study the effect of x-ray beam attenuation and backscatter on the measured dose. Eight different irradiation experiments were performed. The average dose rate values measured with TLD chips within a 1 x 1 cm(2) area were between 4.8 and 12.8 mGy min(-1). The equivalent dose for a 1 x 1 cm(2) skin area was estimated to be 13.2 mSv. The maximum measured dose rate values with a single TLD chip were between 7.5 and 25.1 mGy min(-1). The effective dose corresponding to a proposed arsenic/selenium skin measurement was estimated to be 0.13 microSv for a 2 min irradiation.

K-shell X-ray fluorescence measurements of arsenic depth-dependent concentration in polyester resin discs using the fundamental parameter method

In the realm of X-ray fluorescence (XRF) applications, inhomogeneous distribution of an element can occur as a function of depth within a sample. An example is the measurement of arsenic in skin; arsenic binds with non-uniformly distributed keratin. In this paper, an XRF signal equation based on the fundamental parameter (FP) method, which explicitly takes into account the depth dependence of the elemental concentration, was developed. The formalism was experimentally verified for two-disc resin stacks with different arsenic concentrations.

Evaluation of a novel portable x-ray fluorescence screening tool for detection of arsenic exposure

A new portable x-ray fluorescence (XRF) screening tool was evaluated for its effectiveness in arsenic (As) quantification in human finger and toe nails ([Formula: see text]). Nail samples were measured for total As concentration by XRF and inductively coupled plasma-mass spectrometry (ICP-MS). Using concordance correlation coefficient (CCC), kappa, diagnostic sensitivity (Sn) and specificity (Sp), and linear regression analyses, the concentration of As measured by XRF was compared to ICP-MS. The CCC peaked for scaled values of fingernail samples, at 0.424 (95% CI: 0.065-0.784). The largest kappa value, 0.400 (95% CI:  -0.282-1.000), was found at a 1.3 μg g(-1) cut-off concentration, for fingernails only, and the largest kappa at a clinically relevant cut-off concentration of 1.0 μg g(-1) was 0.237 (95% CI:  -0.068-0.543), again in fingernails. Analyses generally showed excellent XRF Sn (up to 100%, 95% CI: 48-100%), but low Sp (up to 30% for the same analysis, 95% CI: 14-50%). Portable XRF shows some potential for use as a screening tool with fingernail samples. The difference between XRF and ICP-MS measurements decreased as sample mass increased to 30 mg. While this novel method of As detection in nails has shown relatively high agreement in some scenarios, this portable XRF is not currently considered suitable as a substitute for ICP-MS.

Simultaneous detection of As and Se in polyester resin skin phantoms.

It is known that As and Se act as metabolic antagonists. Hence, an improvement in assessing As-related health risks can be achieved by simultaneous quantitative measurements of both As and Se levels in the human body. In this paper, the simultaneous detection of trace concentrations of As and Se in polyester resin skin phantoms was demonstrated. The experiments were performed with a commercial miniature X-ray tube and silicon PiN detector X-ray fluorescence (XRF) system. No significant overlap between the K(alpha) peaks of the two elements was observed. Minimum detection limits of (1.05+/-0.02) microg As g(-1) and (0.88+/-0.02) microg Se g(-1) were found.

Synchrotron X-ray absorption spectroscopy analysis of arsenic chemical speciation in human nail clippings

Environmental context Chronic ingestion of arsenic leads to its accumulation in keratinous tissues, which can represent a risk factor for developing cancer. We use synchrotron X-ray absorption spectroscopy to investigate chemical bonding of arsenic in the keratins from nail clippings of volunteers from areas in Atlantic Canada with low-to-moderate arsenic contamination of drinking water. The study helps our understanding of arsenic metabolism and its role in cancer development. Abstract Drinking water aquifers in many areas of the world have naturally elevated levels of inorganic arsenic exceeding the World Health Organization limit. Arsenic concentrations in human nail clippings are commonly used as a biomarker of exposure to this toxic element. However, the chemical form of arsenic accumulated in nail tissues is not well determined. We employed synchrotron microprobe and bulk X-ray absorption spectroscopy techniques to analyse the concentration and chemical speciation of arsenic in the finger- and toenail clippings of volunteers living in the vicinity of Sackville, New Brunswick, Canada. This area is known to have low-to-moderately elevated levels of arsenic in ground water. Arsenic species in clippings were represented by three main groups, distinguished by the As-K near-edge X-ray absorption fine structure spectra: (1) AsIII type, which can be fitted as a mixture of As bound to thiols, and also to oxygen or methyl groups, with a small contribution from AsV species, (2) AsV type, best represented by fitting arsenate in aqueous solution and (3) The AsIII+AsV mixture type. The high proportion (%) of sulfur-bound arsenic species most likely corresponds to binding between arsenic (in its trivalent and, to a lesser extent, pentavalent forms) and cysteine residues in the sulfur-rich fraction of keratin and keratin-associated proteins. Further work is needed to explore whether these chemical species could be used as toxicity biomarkers of human exposure to elevated levels of As in drinking water.

Detection of lead in bone phantoms and arsenic in soft tissue phantoms using synchrotron radiation and a portable x-ray fluorescence system

The differences and commonalities between x-ray fluorescence results obtained using synchrotron radiation and a portable x-ray fluorescence device were examined using arsenic in soft tissue phantoms and lead in bone phantoms. A monochromatic beam energy of 15.8 keV was used with the synchrotron, while the portable device employed a rhodium anode x-ray tube operated at 40 kV. Bone phantoms, dosed with varying quantities of lead, were made of Plaster of Paris and placed underneath skin phantoms of either 3.1 mm or 3.9 mm thickness. These skin phantoms were constructed from polyester resin, and dosed with varying amounts of arsenic. Using an irradiation time of 120 s, arsenic Kα and Kβ, and lead Lα and Lβ characteristic x-ray peaks were analysed. This information was used to calculate calibration line slopes and minimum detection limits for each data set. As expected, minimum detection limits were much lower at the synchrotron for detecting arsenic and lead. Both approaches produced lower detection limits for arsenic in soft tissue than for lead in bone when simultaneous detection was attempted. Although arsenic Kα and lead Lα emissions share similar energies, it was possible to detect both elements in isolation by using the arsenic Kβ and lead Lβ characteristic x-rays. Greater thickness of soft tissue phantom reduced the ability to detect the underlying lead. Experiments with synchrotron radiation could help guide future efforts toward optimizing a portable x-ray fluorescence in vivo measurement device.