Application of XRF and field portable XRF for environmental analysis

The aim of the present review is to evaluate, on the basis of published papers, the real potential of XRF technique for environmental analysis. Special attention is given for the determination of heavy metal pollution in water. Results of numerous papers for various samples are presented. Some details of the technique and preconcentration methods employed are also discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Development of a palm portable mass spectrometer

A palm portable mass spectrometer (PPMS) has been developed with a weight of 1. 48 kg (3 lb) and a size of 1.54 L (8.2 × 7.7 × 24.5 cm³) that can be operated with an average battery power of 5 W. A miniaturized ion trap has been used as a mass analyzer that consists of four parallel disks with coaxial holes. A rf voltage of 1500 V _p-p at 3.9 MHz has been used for scanning ion mass of up to m/z 300. An ion-getter pump serves for high vacuum of the PPMS. Sample gas was introduced in pulse mode. An embedded microcomputer has been developed for system control. Detection of organic gases diluted in the air has been demonstrated up to 6 ppm for toluene and 22 ppm for dimethyl methylphosphonate (DMMP). Performance results suggest usefulness of the PPMS as a personal mobile device for detection/identification of chemical warfare agents in the field.     

Combined non-destructive XRF and SR-XAS study of archaeological artefacts

We report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as “proto-majolica” pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples’ speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent.     

Development and application of a portable LIPS system for characterising copper alloy artefacts

We report the development of a novel portable and low-cost laser induced plasma spectroscopy (LIPS) system and describe the application method for quantitative characterisation of quaternary copper alloy artefacts. The device was carefully calibrated and phenomenologically characterised using a set of reference samples. The reliability of the quantitative measurement of the depth profile and bulk compositions was assessed through crossed comparisons with traditional analytical techniques. Finally, the LIPS system was applied to investigate a museum figurine of unknown origin composed of several pieces, which is representative of a typical authentication problem.     

Investigation of inherent degradation in cellulose nitrate museum artefacts

Cellulose nitrate was one of the first semi-synthetic plastics to be commercially exploited and as such many museums contain a large number of artefacts illustrating the versatility of this plastic for the creation of a wide variety of functional and aesthetic artefacts. Conservators find themselves faced with the challenge of preserving these ageing artefacts which are showing evidence of significant degradation. The challenge is enhanced by artefacts of similar age and type exhibiting different degrees of degradation. This paper reports the analytical study of selected historical artefacts to explore the origins of these differences. A connection between the durability of the artefacts and the quality of the original synthetic process is identified, indicating the influence of inherent chemical factors on stability. The major contributory factors determining degradation appear to be the sulphate content remaining from the stabilization process and the rate of loss of the camphor plasticizer. A simple swab test is proposed to aid the identification of artefacts which are potentially susceptible to degradation. The test involves analysis of swab extracts by ion chromatography to reveal the presence of oxalate, which is indicative of cellulose nitrate chain scission.     

Accelerated ageing to study the degradation of cellulose nitrate museum artefacts

Cellulose nitrate is susceptible to hydrolysis as well as loss of plasticiser when left in a humid atmosphere. A comparison of the ageing behaviour of cellulose nitrate samples prepared from cotton linters was used to simulate the artefacts studied in a previous study. Certain artefacts were also subjected to accelerated ageing at 12%, 55% and 75% relative humidity at 70 °C. The rate of degradation was observed to vary with the RH, indicating the connection between the absorption of moisture and the hydrolysis process. The effect of varying the sulphate level on the rate of hydrolysis was studied using concentrations similar to those detected in artefacts. The study was carried out using <0.1 mg g⁻¹, 2 mg g⁻¹ and 5 mg g⁻¹ of sulphate and distinct differences were observed which is consistent with the conclusions drawn for a study of a number of artefacts. The observed rates of degradation are consistent with previous studies on cellulose nitrate. The degradation was studied using a combination of infrared spectroscopy, ion chromatography and gel permeation chromatography. The analysis was complemented by a study of the weight changes which occur during ageing.     

A portable, photon analysis spectrometer for the assay of X- and gamma-ray emitting radionuclides

A portable, battery-powered, multichannel analyzer (MCA) for use with Ge spectrometers has been developed for in-field use for the assay of x-and γ-ray emitting radionuclides. The spectrometer is capable of operating to rates greater than 150,000 counts per second. The analyzer is a Canberra InSpector MCA, that is equipped with the INEEL ultra-stable dual-energy pulser, and pulse injection with subsequent removal (PISR) circuitry. PCGAP, a set of MCA control and spectral analysis programs, was developed for use on a PC with a Windows NT Operating System. It includes an interactive peak analysis program as well as automatic spectral analysis programs for the X- and γ-ray regions, and a number of utility programs. The pulser peaks are calibrated with radioactive sources in terms of energy (i.e., their energy equivalents are measured) using the PCGAP spectral analysis package so that energy shifts, including those due to changes in temperature or count rate, do not cause a loss of energy calibration. The number of injected low- and high-energy-equivalent pulses is known so the stored pulser pulses can be used for a dead-time and random summing correction. The pulser peaks are also used to monitor any deterioration in spectral quality caused by noise, ground loops, etc. The results of performance tests to demonstrate the capabilities of this pulser-equipped InSpector are reported.     

便携式质谱仪的研究进展

面对大气、河流、土壤等化学污染,各种突发性爆炸事故和化学泄漏事件,以及生化武器滥用等等社会问题,迫切需要对源头进行现场原位检测分析.质谱(MS)以其检测速度快、灵敏度高、检测样品量少、可对未知物定性定量检测等特点,非常适合应用于这些现场的分析检测.然而实验室用MS的体积、重量、功耗等较大,不便于搬运,无法实现现场的原位...     

Use of electrochemical techniques for the conservation of metal artefacts: a review

Electrochemical techniques like mechanical and chemical ones should be among the panoply of techniques conservators normally use when they conserve metal artefacts. Often though, they are discarded because they are considered as too complicated and dangerous. As a consequence, not much development in the use of these techniques in conservation was observed before the 1990s when their application to marine artefacts once again drew the attention of conservation professionals. More recently, the latter have recognised the importance of these techniques in the understanding of corrosion processes as well as their monitoring and in the solving of specific conservation issues. Furthermore, instruments that were previously only used by corrosion scientists are today entering the conservation field. Portable tools have even been designed so that treatments can be carried out in situ. The current trend is to cluster electrochemical and analytical techniques in parallel in order to fully understand the behaviour of metal artefacts when conserved.     

Optimization of a glancing angle for simultaneous trace elemental analysis by using a portable total reflection X-ray fluorescence spectrometer

By using a portable total reflection X-ray fluorescence spectrometer with a 1 W X-ray tube, a specimen containing nanograms of Ca, Sc, Ti, V, Cr, Mn, Fe, and Ni is measured at several glancing angles of incident X-rays. Continuum X-rays are used as the excitation source. The intensities of the spectral background which degrades sensitivity to trace elements are decreased with a decrease of the glancing angle, and all these elements are detected at the glancing angle of 0.13° smaller than the critical angle for total reflection of the incident X-rays (0.20°). An optimum glancing angle for simultaneously detecting these trace elements is around 0.13°, and detection limits at 0.13° are sub-nanograms to ten nanograms.     

Analysis of archaeological artefacts: PIXE, XRF or ICP-MS?

Elemental analysis of ancient artefacts is of considerable benefit to the field of Archaeology and of general interest to earth scientists. Several techniques are currently available for this purpose, and in this paper the capabilities of PIXE (Particle Induced X-ray Emission), XRF (X-ray Fluorescence) and ICP-MS (Inductively Coupled Plasma - Mass Spectrometry) were evaluated to establish which of these instrumental methods was best suited especially for routine on-line usage. The elements of interest discussed in this paper are useful in archaeological provenance studies.     

Desorption electrospray ionization with a portable mass spectrometer: in situ analysis of ambient surfaces

Desorption electrospray ionization (DESI) is implemented on a portable mass spectrometer and used to demonstrate in situ detection of active ingredients in pharmaceutical preparations, alkaloids in plant tissues, explosives, chemical warfare agent simulants and agricultural chemicals from a variety of surfaces; air monitoring applications using DESI are also introduced.     

The use of a portable total reflection X-ray fluorescence spectrometer for field investigation

A newly developed, portable total reflection X-ray fluorescence (TXRF) spectrometer was tested during a field campaign on Chilean lakes and a German river in January 2002. The field measurements were compared with laboratory measurements carried out on a stationary instrument in the German laboratory. For method validation certified reference material (NIST SRM 1640 Trace elements in natural water) and water samples from different freshwater sources were analyzed with both techniques and evaluated statistically. Based on these preliminary results, it could be concluded that the portable TXRF is a useful technique for the quantitative elemental screening of freshwater samples during field campaigns. Future tests with biological samples (e.g. biofilms and zooplankton), and suspended matter will provide information about the suitability of the portable TXRF for these materials.     

XRF技术在无铅化工艺产品分析中的应用

介绍了XRF技术对无铅化产品和无铅化工艺中铅的快速无损分析的原理及其在实际检测中的应用. 采用自行研制的XRF-1000X射线荧光仪对无铅焊料及镀层进行快速无损分析, 其过程简单、结果准确、精度高.     

Application of INAA and XRF to the analysis of a basic alkaline rock

A study of a basic alkaline rock has been carried out using instrumental neutron activation (INAA), X-ray fluorescence (XRF) and wet chemical analyses techniques. Elemental composition and major oxides have been reported. The rock is found to be rich in K₂O, Na₂O, MgO, CaO, Al₂O₃, and Ti–Fe minerals. The transition elements are also fairly concentrated in the rock. The analyses show the igneous nature of the rock from a high potassic origin.     

Canonical discriminant analysis of cadmium content levels in unpolished rice using a portable near-infrared spectrometer.

Near-infrared analysis (NIRA) was applied to discriminate and determine the cadmium content levels of unpolished rice using canonical discriminant analysis (CDA). The overall correct classification rate was 85.2% for 318 NIR spectra, repeated three times for 106 samples. After a further improvement through decreased misclassification rates, NIRA could be useful as a rapid, nondestructive and convenient analytical method for primary screening and detecting of cadmium-polluted rice.     

Three-dimensional concentration mapping of gases using a portable mass spectrometer system

The visualization of hazardous gaseous emissions at volcanoes using in-situ mass spectrometry (MS) is a key step towards a better comprehension of the geophysical phenomena surrounding eruptive activity. In-situ data consisting of helium, carbon dioxide, sulfur dioxide, and other gas species, were acquired with a quadrupole based MS system. Global position systems (GPS) and MS data were plotted on ground imagery, topography, and remote sensing data collected by a host of instruments during the second Costa Rica Airborne Research and Technology Applications (CARTA) mission. This combination of gas and imaging data allowed three-dimensional (3D) visualization of the volcanic plume and the mapping of gas concentration at several volcanic structures and urban areas. This combined set of data has demonstrated a better tool to assess hazardous conditions by visualizing and modeling of possible scenarios of volcanic activity. The MS system is used for in-situ measurement of 3D gas concentrations at different volcanic locations with three different transportation platforms: aircraft, auto, and hand-carried. The demonstration for urban contamination mapping is also presented as another possible use for the MS system.     

Evaluation of portable XRF instrumentation for assessing potential environmental exposure to toxic elements

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.     

Trace elemental analysis of commercial bottled drinking water by a portable total reflection X-ray fluorescence spectrometer.

A portable total reflection X-ray fluorescence spectrometer was applied to commercial bottled drinking water containing 62 ppb (microg/L) V, 7.5 ppm (mg/L) Ca, and 1 ppm K. A dry residue, prepared by repeated pipetting and drying a 20 microL portion of drinking water on a sample holder six times, and another dry residue, prepared by pipetting and drying a 120 microL portion of the drinking water, were measured. The size of the dry residue of the drinking water was reduced by repeating the pipetting and drying. Calcium and potassium were easily detected in these two dry residues. Vanadium was detected in the dry residue prepared by repeated pipetting and drying. Vanadium, calcium, and potassium were quantified by using an internal standard, and the average quantified concentrations of V, Ca, and K were 91 ppb, 8.2 ppm, and 1.5 ppm, respectively. Although these quantified concentrations deviated from the certified concentrations (62 ppb of V, 7.5 ppm of Ca, and 1 ppm of K), it was possible for this portable spectrometer to estimate approximate concentrations.