David E.B. Fleming

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).

Characterization of the depth distribution of Ca, Fe and Zn in skin samples, using synchrotron micro-x-ray fluorescence (SμXRF) to help quantify in-vivo measurements of elements in the skin.

In vivo monitoring of trace and biometals in skin is normally quantified using phantoms that assume a constant elemental distribution within the skin. Layered calibration skin phantoms could potentially improve the reliability of in vivo calibration skin phantoms by better representing the actual in vivo distribution. This work investigates the micro-distribution of iron, calcium and zinc in prepared human skin samples taken from a number of locations on the body. Slices (orientation running from the skin surface into the dermis) were extracted from 18 formalin-fixed necropsy samples and scanned using the micro-XRF setup at the VESPERS beamline (Canadian Light Source). Elemental surface maps were produced using a 6×6 μm(2) beam in steps of 10 μm. Microscope images of histology slides were obtained for comparison. Statistically significant differences (p<0.01) were noted between the epidermal and dermal layers of skin for the elements examined (Ca, Fe and Zn), demonstrating the ability to clearly distinguish elemental content in each layer. Iron was consistently noted at the epidermal/dermal boundary. These results would indicate that when using phantoms to quantify elemental levels measured in the skin, note should be taken of the appropriate depth distribution.

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.

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).

In vivo K-shell X-ray fluorescence bone lead measurements in young adults

The (109)Cd K-shell X-ray fluorescence (XRF) technique was used to measure in vivo tibia lead concentrations of 34 young adults living in the state of Vermont (USA) and the province of New Brunswick (Canada). The subjects ranged in age from 18 to 35 years, and had no known history of elevated lead exposure. Measurement parameters were varied, using the same XRF system for both populations. Tibia lead concentrations were low for both groups, with mean values of 0.7 microg lead g(-1) bone mineral (Vermont) and 0.5 microg g(-1)(New Brunswick). No individual measurement exceeded 7 microg g(-1). Mean uncertainty values obtained for the Vermont and New Brunswick subjects were 4.1 microg g(-1) and 2.6 microg g(-1), respectively. Improved measurement uncertainty in the New Brunswick group was attributed to the use of a reduced source-to-skin distance (approximately 5 mm) and a longer measurement time (3600 seconds) using a weaker radioisotope source (< or =0.42 GBq). Measurement uncertainty tended to increase with body mass index. For a given body mass index, female subjects returned a measurement uncertainty approximately 1 microg g(-1) greater than males.

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.

Feasibility of measuring arsenic and selenium in human skin using in vivo x-ray fluorescence (XRF)--a comparison of methods.

In recent years, in vivo measurement systems of arsenic in skin by K-shell x-ray fluorescence (XRF) have been developed, including one which was applied in a pilot study of human subjects. Improved tube-based approaches suggest the method can be further exploited for in vivo studies. Recently, it has been suggested that selenium deficiency is correlated with arsenic toxicity. A non-invasive measurement of both elements could therefore be of potential interest. The main aim of this current study was to evaluate and compare the performance of an upgraded portable XRF system and an advanced version of the benchtop XRF system for both selenium and arsenic. This evaluation was performed in terms of arsenic and selenium Kα detection limits for a 4W gold anode Olympus InnovX Delta portable analyzer (40 kVp) in polyester resin skin-mimicking phantoms. Unlike the polychromatic source earlier reported in the literature, the benchtop tube-based technique involves monochromatic excitation (25 W silver anode, manufactured by x-ray optics, XOS) and a higher throughput detector type. Use of a single exciting energy allows for a lower in vivo dose delivered and superior signal-noise ratio. For the portable XRF method, arsenic and selenium minimum detection limits (MDLs) of 0.59  ±  0.03 ppm and 0.75  ±  0.02 ppm respectively were found for 1 min measurement times. The MDLs for arsenic and selenium using the benchtop system were found to be 0.35  ±  0.01 ppm and 0.670  ±  0.004 ppm respectively for 30 min measurement times. In terms of a figure of merit (FOM), allowing for dose as well as MDL, the benchtop system was found to be superior for arsenic and the two systems were equivalent, within error, for selenium. We shall discuss the performance and possible improvements of each system, their ease of use and potential for field application.