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ATOMIC SPECTROMETRY UPDATE

X-ray uorescence spectrometry

Philip J. Potts,*a Andrew T. Ellis,b Peter Kregsamer,c Christina Streli,c Margaret Westd and Peter Wobrauschekc
a

Department of Earth Sciences, The Open University, Walton Hall, Milton Keynes, UK MK7 6AA b Oxford Instruments, Industrial Analysis Group, Wyndyke Furlong, Abingdon, Oxfordshire, UK OX14 1UJ c Atominstitut der Osterreichischen Universitaten, Schuttelstrasse 115, A-1020, Wien, Austria d Materials Research Institute, Shefeld Hallam University, City Campus, Howard Street, Shefeld, UK S1 1WB

Received 20th September 1999

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1 2 2.1 2.2 3 3.1 3.2 4 4.1 4.2 4.3 5 5.1 5.2 6 6.1 6.2 6.3 6.4 6.5 7 8 9 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 10

Reviews Instrumentation General instrumentation and excitation sources Detectors Spectral analysis, matrix correction and calibration procedures Spectral analysis Matrix correction and calibration procedures X-ray optics Optical elements Microuorescence Capillary waveguides Synchrotron radiation Beamlines and optics Applications Total reection XRF spectrometry Instrumentation and quantication Synchrotron radiation-induced TXRF Surface analysis Related techniques Applications Portable XRF On-line XRF Applications Sample preparation Preconcentration techniques Geological Environmental Archaeological and forensic Industrial Clinical and biological Thin lms Chemical state analysis and speciation studies References

applications, including sample preparation, geological, environmental, archaeological, forensic, biological, clinical, thin lms and chemical state analysis, including speciation. Highlights of this year include further work in the development of high resolution detector devices based on both microcalorimeters and superconducting tunnel junction devices. However, there continue to be important developments in capillary X-ray optics, portable XRF, on-line applications, TXRF and synchrotron radiation devices. Furthermore, it is noteworthy that XRF continues to make an essential contribution in a wide range of applications where the nondestructive, high precision, simple sample preparation techniques and well-characterised spectrum interpretation and quantication procedures can be used to advantage.

1 Reviews
XRF continues to go from strength to strength, as indicated by the number of reports covered in the present review. However, almost all developments in science depend on the strength of what has gone on before, and it is a pleasure to report reviews on various aspects of XRF, published as part of the centenary celebrations to mark the discovery of X-rays by a group of distinguished XRF spectroscopists who did much to lay the foundations of modern XRF. Ron Jenkins1 considered the evolution of X-ray instrumentation and techniques emphasizing milestone developments, including the acceptance of XRF and XRD techniques in the 1960s, the inuence of minicomputers in the 1970s and advances related to the introduction of ED detectors. Hans de Vries2 reviewed the early years of XRD and X-ray spectrometry from a historic perspective but included interesting personal reminiscences from early years at Philips in Eindhoven. John Gilfrich3 also looked at the historical development of XRF, giving a personal view of the most important developments in techniques and applications. The complementary biennial review of X-ray spectrometry by Torok and colleagues has been published in Analytical Chemistry.4 This review included sections on PIXE and electron probe microanalysis, techniques not included in the present review, and covers the period from November 1995 to Autumn 1997. Other general reviews of XRF included a wideranging overview of recent developments from the perspective of an individual manufacturer by Uhlig,5 a consideration of basic principles and user benets of WDXRF6 and a wideranging Chinese language review.7 More targeted reviews included the work of Fitton,8 who presented an overview of a range of X-ray techniques in J. Anal. At. Spectrom., 1999, 14, 17731799 1773

This annual review of X-ray uorescence covers papers published over the period 19981999 that are judged to have made a signicant contribution to this branch of the analytical sciences. The review is both comprehensive in scope and selective in the choice of contributions included. The scope includes developments in instrumentation and detectors, matrix correction and spectrum analysis software, X-ray optics and microuorescence, synchrotron XRF, TXRF, portable XRF and on-line applications. Also included is a review of
*Review co-ordinator, to whom correspondence should be addressed and from whom reprints may be obtained.

This Journal is # The Royal Society of Chemistry 1999

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geological applications. Fuentes et al.9 considered the role of various techniques, including XRF, in the determination of the REE, emphasizing the need for chromatographic separation in the analysis of complex matrices. Harada and Sakurai10 described XRF analysis with high energy photons (40 100 keV) and concluded that this approach had some attractive features, particularly in the determination of high-Z elements in medium-z matrices in environmental and materials applications. Important aspects were considered to be the inuence of Compton scattering (especially the effect of double scattering), the provision of quasi-monochromatic excitation to attain reasonable detection limits, and opportunities associated with synchrotron radiation sources and novel developments in X-ray optics and detectors. A Russian language review11 considered the XRF determination of trace elements. One aspect of scientic communication that will become increasingly important in future years is use of the Internet and details of web sites of 31 suppliers of XRF and microanalysis instrumentation were reported by MacRae.12 Standards will also continue to be an important feature of scientic endeavour and Neelmeijer et al.13 reported on results from a paper-based multi-element standard for ED detection using PIXE, XRF and SEM instrumentation. Evaluation of results involved normalizing line intensities of AlCu to that from Zn Ka and comparing ratios with those calculated taking into account known absorbers in the instrument (e.g., detector beryllium window). Limitations included restrictions to lines of v4.5 keV in Rh tube excited XRF, w4.5 keV in XRF with an air path and the need to attenuate K-line emissions from C and O from paper when SEM windowless detectors were used. Buhrke et al.14 also discussed the use and availability of standards (assumed here to mean reference materials) in XRF analysis. Turning now to an aspect that always stimulates a lot of interest, Havrilla15 made a conference presentation addressing the issue of how far can we go in lowering XRF detection limits. Particular instrumental developments considered were TXRF and micro-XRF coupled to the dried spot sample preparation. It is appropriate to end this section by recording the publication of two XRF volumes, namely Volume 39 of Advances in X-ray Spectrometry, edited by Gilfrich and colleagues,16 from which papers have already been cited above, and a special issue of X-ray Spectrometry, edited by Holynska,17 considering X-ray spectrometry in the environment.

2 Instrumentation
2.1 General instrumentation and excitation sources The fast electron-emission phenomenon from Grimm glowdischarge plasmas was introduced by Tsuji and colleagues18 from the Institute for Materials Research, Tohoku University. In this Japanese language paper, the lamp was operated with He gas with an applied potential of up to 5 kV, and the application of the system to the quantitative analysis of FeSi alloys was described. It is pleasing to nd that the authors followed up this interesting work with further publications in English during the review period, describing19 a modication to the lamp by incorporating a 15 mm thick PTFE support to insulate the cathode from the anode body. Stable high voltage discharge plasmas were created in the hollow anode near the cathode with gas pressures of 10100 Pa and discharge currents of 0.110 mA. Transparent lms (0.0150.05 mm thick) were used as X-ray windows and a Si(Li) detector placed behind the end window was used to record X-ray spectra. When operated in side window mode, with electrons impinged on the target at an incident angle of 45 and detected at a take-off angle of 45 through a 0.025 mm thick Be window, higher X-ray intensities were obtained with possible opportunities for use as a portable 1774 J. Anal. At. Spectrom., 1999, 14, 17731799

X-ray tube. Further work by Tsuji et al.20 described the application of a compact XRF instrument with a Grimm tube for the quantitative determination of Mn, Si and Ti in FeMn, FeSi and FeTi alloys. The reader is further enticed with the possibility of observing X-ray diffraction peaks, indicating that the structure of the cathode material may also be determined. Work with this glow discharge device, operated with an Al thin lm target at a discharge voltage of 2.0 kV, a discharge current of 0.1 mA and a He pressure of y0.2 Torr, was also reported by this group from Tohoku University21 to produce characteristic Al Ka X-rays throughout a discharge time of 1.5 h. Stuik et al.22 published a new technique based on the use of a laser plasma X-ray source and spherically curved multilayer optics. The laser light was focused on the sample and a Fe Schwarzschild mirror used to image the uorescence radiation on a 2-D CCD unit. This conguration permitted the detection of C Ka. Recent progress in nickel-like lasers was reported by Zhang et al.23 Korobkin et al.24 described monochromatic Xray sources based on emitters controlled by laser production. Work by Glotin and colleagues25 described the production of tuneable X-rays by optimizing the Compton backscattered photons emitted in an IR free-electron laser. The next generation of large, high power lasers was discussed by Suter et al.26 with prospects for uorescence based imaging of hydrodynamic systems on the National Ignition Facility in the US. Lee et al.27 compared overlapping areas of research in the development of X-ray lasers and third generation radiation sources. Developments in other X-ray excitation sources were published by Sakurai et al.,28 who worked on a high powered X-ray generator equipped with a lanthanum hexaboride cathode for X-ray absorption ne structure experiments. Nasonov et al.29 described a general theory of X-ray coherent bremsstrahlung by low energy electrons moving in a crystal. The possibility of creating a high efciency tuneable source of quasi-monochromatic X-rays was considered. Chesta et al.30 reported a comparison of the efciency of energetic electrons and positrons from low intensity 90Sr and 22Na radioactive sources to produce characteristic radiation. A new experimental conguration for radioisotope excited XRF analysis offering at least a ten-fold increase in intensity of X-rays emitted by the sample when compared with a conventional radioactive source was claimed. Among the advantages claimed for excitation with energetic beta particles was the fact that the radiation yield changed by less than an order of magnitude over the full range of elements investigated. Devan and colleagues31 described their XRF spectrometer with a 20 mCi 109Cd source and a 30 mm263 mm Si(Li) detector, having a resolution of 200 eV at 5.9 keV, coupled to a multichannel analyser for the study of environmental and geological samples in Botswana. Researchers interested in investigating parametric X-ray radiation (PXR) will benet from a review by Shchagin and Maruyama.32 The nature and main properties of this monochromatic, polarized, directed, tuneable radiation arising in the vicinity of Bragg directions of a crystal when relativistic particles pass through were described and possible applications proposed. Several workers published papers on the performance of multilayers during this review period. Chernov et al.33 presented ndings on the effects of X-ray scattering from a NiC multilayer and a NiC multilayer grating. Barbee34 studied the interfacial structure and the atomic interactions between atoms at interfaces in multilayers or nanolaminates. Salashchenko et al.35 described new experimental results for the fabrication and X-ray properties of multilayer X-ray mirrors based on CrSc and WSc for close to normal and Brewster angles of incidence. Holly et al.36 described the design and performance of two new double crystal monochromators (DCM) built at the Madison Physical Sciences Laboratory,

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University of Wisconsin. Aglitskiy et al.37 presented work on the use of mica as a spherically curved crystal in a spectrometer for X-ray measurements on an electron beam ion trap. Andre38 gave the principle of a soft X-ray uorescence spectrometer based on a multilayer interferential transmission plate with illustrations of the Ka emission line of Si and Al samples. Comparison of a mosaic crystal spectrometer to a highperformance solid-state detector for X-ray microuorescence analysis was offered by Chung and colleagues.39 Patent claims for innovation in XRF instrumentation this year included Tifn and Hossain46 for an apparatus and a method for determining the elemental composition and relative locations of particles on the surface of semiconductor wafers. Van de Wal47 described a spectrometer with a double collimator mask to provide a facility to irradiate as large a surface of a specimen as possible whilst eliminating uorescent radiation from the specimen holder by the use of a second collimator mask behind a solar slit. Virshup and Reynolds48 offered methods for the fabrication of rotating anode X-ray targets with a carboncarbon matrix into which high Z material was embedded. In a Japanese language patent, Hiraishi et al.49 claimed an invention related to an anode for a transmission target X-ray tube with metals such as Mo, Re, Th, W and their alloys deposited on a substrate by chemical vapour deposition (CVD). Sipila50 described an invention related to the production of polarized X-ray radiation from a beryllium anode despite its poor effectiveness. An improved EDXRF conguration using total external reection was offered by O'Hara51 for delivering an increased ux of Xrays onto a detector. The optics could also be used as a low energy lter by the incorporation of a stop at or near the aperture. Two German language claims by Schwenke et al.52,53 described an apparatus containing movable multi-layered mirrors for WDXRF. A measuring method and apparatus for time-averaged, uorescent X-ray interferometry was claimed, in Japanese, by Sasaki and Suzuki.54 Similarly, Utaka55 described, in Japanese, an X-ray spectrometer characterized by the incorporation of a UV radiation source to clean the specimen surface prior to analysis. A secondary target device claim, again in Japanese by Terada,56 also provided a facility to switch to direct irradiation of a sample. 2.2 Detectors The cutting edge of detector technology during the review period continued to be forged by high-resolution cryogenic detectors. The advances in this rapidly developing area were reviewed by Kraus57 and Wollman et al.58 Members of the NIST, Boulder, CO, group59,60 reported the best energy resolution to date for a microcalorimeter of 3.1 eV over the energy range 0.12 keV. As anticipated, this group had increased the size of the device itself to 4006400 mm and then added an X-ray polycapillary optic to increase the effective collection area to 4 mm2. The best resolution 3.1 eV versus 4 eV was obtained using a digital pulse processor and the available count rate was 500 cps, rising to 1000 cps with beam blanking. Such an impressive performance enabled the straightforward and direct measurement of chemical shifts in the Fe L series lines from iron compounds and Al K series lines in aluminium and alumina. The exciting potential of these high-resolution devices has led other groups, such as the one at the University of Milan, to fabricate detection systems. Two different detectors, one based on a tin absorber and the other on a germanium thermistor, were reported by this group.61 Both detectors fully resolved the Mn Ka1 and Ka2 lines, providing an energy resolution of around 5 eV. Improvements in the SQUID ampliers for this type of detector were reported by Huber et al.62 and Meier and co-workers,63 whilst the use of an improved SQUID system was found by von Kienlin et al.64 to stabilize the working temperature of the detector. These latter

workers used a 241Am radioisotope source to investigate higher energy performance and measured an impressive energy resolution of 150 eV at 14 keV and 250 eV at 60 keV. Finally, but importantly, arrays of microcalorimeters have been reported by two groups during the review period. Silver and colleagues were awarded a patent65 for a detector system comprising an array of four microcalorimeters delivering an energy resolution of 710 eV over the range 0.27 keV and capable of an input rate, for each of the four detectors, of 10 50 cps. The system incorporated analogue pulse processing and thermal pile-up rejection and was claimed to be compact and portable. A second group, at NASA Goddard Space Flight Center, reported66 the fabrication of a 666 array of silicon microcalorimeters, which delivered an energy resolution of 10 eV over the energy range 0.410 keV. A review by Diebold et al.67 perhaps best indicated the rapid development of this type of device by claiming that the microcalorimeter will replace the traditional Si(Li) detector. Whether and how soon this happens depends upon many factors, but the future bodes well as effective areas and count rates increase and predictions of 0.51 eV energy resolution are made. The second type of high-resolution cryogenic ED detector is based upon superconducting tunnel junctions (STJ). Frank and colleagues, at the Lawrence Livermore Laboratory, reported6870 the best performance so far from this type of detector. Using a 1416141 mm NbAlAl2O3AlNb STJ, an energy resolution of 5.9 eV at 277 eV was achieved at several hundred cps. Upon increasing the count rate, the energy resolution at 277 eV remained below 10 eV up to 10 kcps and degraded to only 13 eV at 23 kcps. Such count rates are substantially higher than those currently available from the high-resolution microcalorimeters. The energy resolution of this device was shown by Le Grand and colleagues at LLNL71 to be within 15% of the theoretically predicted energy resolution. The largest such device thus far was claimed by workers at Kyushi University, Japan.72,73 The device was 2006200 mm against previous devices of 1006100 mm or 1416141 mm and the effect on its operating performance with different magnetic eld ramping speeds was investigated. The energy resolution of the optimized device was 93 eV at 5.9 keV. Kurakado, who has been involved in STJ detectors throughout their short history, reviewed74 series-connected STJs, which offer not only much larger area devices but also the prospect of obtaining positional information from the same detector array. Coupled with the very high resolution, high operating count rate and high detection efciency, the overall characteristics of these devices were claimed to make them particularly attractive. The group working at the European Space Agency, Noordwijk, Holland, reported75 the performance of their tantalum-based 1006100 mm STJ. The energy resolution was 56 eV at 5.9 keV, but this was found to be dominated by spatial non-uniformity in the detecting element itself. When illuminating selectively only a 510 mm spot on their device, its energy resolution was substantially improved to 22 eV, which corresponds to 15.7 eV for the individual Mn Ka1 and Ka2 lines. This still leaves a further factor of two improvement to yield the theoretically predicted energy resolution of 7.3 eV at this energy. Further development by this group included the use of an NbN passivation layer, which was reported by Rando et al.,76 to yield more than a factor of two improvement in detector responsiveness. This device was characterized by Verhoeve et al.,77 who reported the use of this NbAl STJ for photon counting experiments in both the visible and X-ray energy regions. Perhaps the most exciting development by the ESA group was the report by Rando and colleagues78 of a 36-element STJ array detector. The 666 array of tantalum-based STJ detectors exhibited an impressive energy resolution of 2.5 eV at 270 eV and 6.8 eV at 1 keV. The detector energy resolution was reported to be limited by Fano and tunnel noise to about 3 eV at J. Anal. At. Spectrom., 1999, 14, 17731799 1775

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1 keV. Although the performance of all the devices in the array was consistent to within 5%, the individual detectors showed the same spatial non-uniformity of energy resolution reported earlier for a single STJ. A low noise charge sensitive preamplier using a 4-terminal JFET was described by Ukibe et al.79 and their co-workers Katagiri et al.,80 who used it in conjunction with a 1786178 mm STJ. The energy resolution at 5.9 keV was claimed to be 66 eV. In-depth characterization of STJs was also reported by Cristiano et al.81 and Shimizu and co-workers.82 Low-temperature SEM was used by Ohkubo and colleagues83 to investigate the double peaks arising from the different response of the base and counter electrode in the STJ. Clearly, as the volume and advanced nature of the studies on these two types of very high resolution cryogenic detectors demonstrate, the eld continues to advance and much can be expected from it again in the coming year. Although strongly inuenced by a number of papers from a single Materials Research Society symposium on roomtemperature detectors, the review period has seen substantial activity in CdTe and CdZnTe compound semiconductors for room-temperature energy dispersive detectors. Redus and colleagues84 reported the development of a commercially available CdZnTe detector, the construction of which was enabled through improvements in the manufacturing process for CdZnTe detector material. The detector package was Peltier-cooled to 240 C and was capable of an impressive energy resolution of 188 eV at 5.9 keV and 482 eV at 59.5 keV. Improvements in the detector materials were reviewed by Eisen and colleagues,85 who also reported86 on the performance of both single and array detectors using the improved materials. The performance of a new Schottky CdTe detector was reported by a group at ISAS, Kanagawa, Japan.87,88 A 0.5 mm thick high quality 262 mm CdTe crystal with an indium Schottky contact was used to give a low leakage current, which allowed the detector bias to be increased to 400 V, i.e., above that typically used for previous detectors of this type. The leakage current was 0.7 nA at room temperature and less than 1 pA at 270 C, yielding an energy resolution of 1 keV at 122 keV. Hard X-ray performance is typically the major interest for these types of compound semiconductor detector. Work at the ESA, The Netherlands, on CdZnTe and GaAs detectors was reported by Kraft et al.89,90 and Bavdaz et al.,91 who obtained an energy resolution of 700 eV at 14 keV, which is unattractive for terrestrial XRF but of considerable interest for hard X-ray space studies. The performance of a PIN-type CdZnTe detector employing less expensive material, which was produced using either the vertical or high-pressure Bridgman process, was reported by Sudharsanan and coworkers.92,93 Detectors of large volume (w200 mm3) were produced and the new PIN design offered low leakage currents and no charge polarization effects. Ivanov and colleagues,94,95 reported the use of an M-p-N CdTe detector that exhibited a low leakage current and, when operated at 230 C, provided an energy resolution of 420 eV at 5.9 keV. The application of pulse shape discrimination improved the high-energy resolution from 2.4 to 1.5 keV at 662 keV. Matz and Wiedner96 developed a new model for describing charge collection efciency and space charge formation in CdZnTe and CdTe detectors. Ruhter and colleagues at LLNL, Livermore, CA,97 reviewed the application of CdZnTe detectors in nuclear safeguard measurements. The same group was reported by Lavietes and colleagues98 to have produced a working, portable spectrometry system based on a CdZnTe detector, a low power portable MCA and inhouse software. The achievable energy resolution was 2.4 keV at 122 keV and the system was well-suited to portable applications such as nuclear safeguard investigations and onsite high-energy XRF measurements. Although principally targeted at hard X-ray imaging and astrophysics experiments, there has also been considerable activity during the review 1776 J. Anal. At. Spectrom., 1999, 14, 17731799

period into CdZnTe array detectors. A collaboration between a commercial supplier and a group at the Harvard-Smithsonian Center for Astrophysics99102 resulted in a prototype detector comprising a 464 array of PIN CdZnTe detectors, each of 1.561.5 mm and 5 mm thick. The array provided a stopping efciency greater than 80% and energy resolution of 3.5 keV at 122 keV. Workers at NASA, Goddard Space Flight Center,103,104 presented work on prototype CdZnTe strip detectors that they hoped would allow them to construct an array of 580 000 pixels, which will offer a staggering total area of 60 cm2! Yoo et al.105 developed a 16-element linear CdZnTe detector array, which had strong peak tailing and signicant charge sharing for energies less than 60 keV. High energy X-ray imaging CdZnTe detector arrays specically for deployment on space missions were described by Turner et al.106 and Versrand et al.107 An interesting, though ultimately poorly performing, CdZnTe drift detector was reported by Van Pamelan and ButzJorgensen.108 Although the signals could be corrected for hole trapping effects, the energy resolution remained dismal. Finally, Warburton109 described a novel method in which electronic signal processing was used for detectors such as CdZnTe strip detectors in which hole transport is poor. The author claimed that this signal processing would allow subpixel spatial resolution without signicant adverse effects on energy resolution. Turning now to the more conventional area of silicon-based energy dispersive detectors, Allier and co-workers110,111 made a comparison of Si PIN diodes, drift detectors and avalanche photodiodes. Pfaustiel et al.112 reported a comparison, for detectors used in environmental applications in the energy range 10450 keV, of silicon and CdZnTe detectors. The most active section of published research in this area during the review period was that of the silicon drift detector (SDD). Strueder and co-workers113 reviewed the key characteristics and performance of the SDD and reported114,115 their most recent developments in this important new area. In the new devices described, integrated on-chip electronics allowed much larger area devices to be prepared, along with the ability to process maximum count rates in the region of 26106 cps. The energy resolution of 220 eV at 5.9 keV delivered by the new devices at room temperature remained excellent and improved to 140 eV when cooled to 253 K using a simple Peltier cooler. The on-chip electronics employed in these devices were described further by Fiorini et al.116 A new geometry for fabricating SDDs was described by Segal et al.,117 who claimed that the surface leakage current could be substantially reduced, thereby obviating the need for a guard ring. Early results on an 8-mm diameter SDD were promising. The Monte Carlo (MC) simulation of X-ray spectra from large area SDDs was reported by Karvelas and co-workers,118 in which pile-up effects were modelled based upon four key detector parameters. A commercially available Peltier-cooled SDD was used by Fischer et al.119 for energy dispersive texture mapping. Finally, in the search for SDDs with larger active areas, Gauthier and colleagues120 reported the development of a 32-channel SDD with digital signal processing electronics. Two single-channel SDDs with active area of 1 and 10 mm2 were fabricated and tested, as was a monolithic 2 cm2 SDD with eight readout anodes. Energy resolution of the devices remained in the 160170 eV range and the benets of the new digital pulse processing system were described. Interest in silicon charge coupled device (CCD) detectors has remained high during the review period although much of the work is for X-ray imaging on space missions or for the very low X-ray energy region. The European XMM space mission has been the trigger for much work reported in the last year with reports on the technology used in this 36 cm2 monolithic CCD detector by Struder et al.121 and Holl et al.122,123 These reports included details of the fabrication and testing of these impressive devices that offer a detector comprising 12 PN

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CCDs each of 361 cm2 with a total of 768 pixels and each with integrated, on-chip measurement channels. The dimension of each pixel was 1506150 mm2. Measurements and MC modelling reported by Short and co-workers124 determined that the effective depletion depth of this detector was 3035 mm. Meidinger and co-workers125 studied the effects of radiation damage in this detector and found that, although X-ray hardness was excellent, the energy resolution degraded from 135 eV to 175 eV at 5.9 keV after exposure to a 10 MeV proton uence of 26109 cm22. Yoshita and co-workers126,127 and Tsunemi et al.128 at Osaka University presented a careful study into the mechanisms of split events in silicon CCDs. The team used a highly parallel X-ray beam and a mesh in front of the CCD to restrict the positions at which the events interacted and were able to describe the nature of 1-, 2-, 3- and 4-pixel events in the detector. Further characterization of CCD detectors was reported by Hashimotodani et al.,129 who used an electronexcited aluminium source as a calibration source; by Prigozhin et al.130 on the precise measurement of quantum efciency from 60 to 3000 eV and by Dunn and colleagues131 on the absolute calibration of CCD detectors over the energy range 8 98 keV. Finally, Simons and colleagues132 concluded that a deep depletion CCD with a frame rate of a few Hz may be suitable as an ED detector, but if rates greater than 1 kHz were required its use was expected to be very limited. Not to be outdone by the new breed of pixellated detectors based upon CCD technology, Tull and co-workers133 modelled the spectral response from an array of multi-element silicon detectors with multi-channel integrated electronics. Devices were then fabricated on high resistivity silicon and investigated using both conventional 55Fe and 109Cd radioisotope sources and a 5 mm beam of 8.5 keV X-rays. Sellar and co-workers134 reported a novel, pixellated detector in which the 16616 silicon detector array was bump-bonded directly onto a 16616 array of preamplier electronics. The output from the preampliers was fed into two custom-made 128 channel ICs containing the pulse shaping circuitry and pixel address data. The energy resolution of this interesting new detection system was claimed to be 250 eV at 5.9 keV. Aleri et al.135 reported a 2dimensional array of mercuric iodide detectors directly coupled to very low noise ampliers. The authors' interest was mostly for high X-ray energies and the energy resolution at 60 keV was a dismal 15%. Finally, Vilhu et al.136 took the conventional but rather expensive route to an array detector of some 750 cm2 active area for X-ray energies in the range 0.520 keV. The system comprised an array of 19 conventional Si(Li) detectors, each with an active area of 9.2 mm2 and thickness of 3 mm. A radiative cooler was used to reach an operating temperature of 110125 K, which resulted in an energy resolution of 200 eV. There was continuing interest during the review period in non-liquid nitrogen cooling systems for semiconductor detectors. Little137 reviewed the history of Kleemenko cycle coolers, which made use of a new gas mixture and yielded operating temperatures in the range 65150 K. Arai138 was granted a patent for a high purity silicon detector, cooled by a compact gas recycling cooler. A thermoelectric cooling scheme was used by Shen et al.139 for a 28 mm2 Si(Li) detector. A temperature of only 250 C was achieved and the resulting energy resolution of the detector was an abysmal 700 eV at 5.9 keV, which could readily be matched by a good quality gas proportional counter. The Coimbra group continued their work on gas proportional scintillation counters (GPSC) and established the operational parameters needed to operate such detectors, lled with neonxenon gas mixtures, in order to improve low energy performance.140 In a second study141 on large area GPSCs this group demonstrated that a shaped curved grid could retain energy resolution even though the effective detector sensitive area was increased by a factor of six. Work was also reported142 on the good agreement between Monte Carlo (MC) simulation and measured data for the detection of

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X-rays and conversion electrons from a 109Cd radioisotope source in a conventional xenon-lled GPSC. Calculations by Nelson et al.40 showed that signicant transmission improvements may be gained from the use of ultra-thin windows in gas ow proportional detectors. Practitioners who developed skills in changing 1 mm windows in the past will welcome the inclusion of a supporting grid to allow for pressure cycling which the 0.3 mm detector window will undoubtedly experience. Improvements in the performance of spectrometers using gas proportional scintillation counters were offered by Simoes et al.41,42 Pulse integration times of several nanoseconds, necessary to reduce the ballistic decit in the counter, conicted with the requirement of shorter integration times when rise time discrimination was applied. Both requirements were met by a 0.1 ms integration of the pulse in the main amplier for rise time discrimination followed by digital integration with a longer time constant. This combination was reported to improve the resolution and peak-to-background ratio when the pulse-height distribution of X-rays from a109Cd source was processed. Other developments included the performance improvements from a semiconductor X-ray detecting system were reported by Kuwata et al.43 A new time variant pulse processor was described as being able to adapt the weighting function according to detector noise characteristics by the addition of a differentiated signal and an integration of the differentiated signal with the same ratio. Hayakawa and colleagues44 designed a WDXRF spectrometer for small area spectroscopy with energy resolution determined by the spatial resolution of a position sensitive proportional counter. A combination of well designed lters and non-dispersive X-ray detectors was demonstrated by Cazaux45 in various experimental arrangements which used CCD cameras for X-ray imaging in TXRF microscopy.

3 Spectrum analysis, matrix correction and calibration procedures

3.1 Spectral analysis This topic has seen little publication activity during the review period, although Torres and co-workers143 included some novel features to simplify peak tting in their SAX software. The technique used for background correction involved a straightforward peak stripping algorithm, whilst the peak shape model was derived experimentally. A series of samples giving wellseparated XRF peaks was used to build a stored peak shape table whose entries were used in conjunction with parabolic interpolation to derive measured peak intensities. A least squares minimization technique was used to t unknown spectra with the peak models and results of the process were reliable for the classic Mn/Fe K series line overlap. The authors claimed their spectrum processing procedure was faster and less complex than those which use analytical models of a Gaussian peak plus exponential tailing and one or more `shelf' features. The use of measured spectra certainly compensates for some of the non-ideal and variable line shapes seen with some Si(Li) detectors. Smolniakov and Koltoun144 described the use of a special peak deconvolution procedure in which a digital lter was used for background suppression and resolution enhancement in conjunction with a least squares tting procedure for peak tting. Although similar techniques have been in use since the late 1970s, the authors claimed substantial improvements. These improvements resulted in the claim that the effective energy resolution of the EDXRF spectra, using the new technique, approaches that obtained from WDXRF scans. The radiative Auger (RA) X-ray spectrum of Ar was studied by Muhleisen et al.145 using two high-resolution, curved crystal spectrometers at two separate Institutes. The relative intensity of the K-LM RA to the Ka1,2 peak was measured to be 0.18 J. Anal. At. Spectrom., 1999, 14, 17731799 1777

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and 0.25% on the instruments used, which was in strong disagreement with theoretical predictions that are a factor of four greater. This work underlines the importance of the RA effect in some spectra and the need to obtain more-reliable values for the RA peak intensities. Campbell and others associated with the Guelph group continued to make progress in studies of Si(Li) detector line shapes. In one study, Campbell and co-workers146 used highly monochromatized X-ray beams in the energy range 1.8 8.3 keV. The shape and intensity of the longer range, lowenergy shelf was accurately predicted using a Monte Carlo simulation based upon a simple electron transport model. Improved data for silicon escape peak relative intensities were obtained from least squares tting of the spectrum features. However, the authors were unable to identify the physical origin of the exponential tail on the immediate low energy side of the parent peak. The features of the derived detector response models were further investigated147 using XPS of silicon and front contact metals (gold and nickel). Campbell and co-workers148 measured the intensity ratio of the silicon escape peak to the parent peak in the energy range 29 keV in order to determine accurately the K shell uorescence yield of silicon. A value of 0.050 or 0.052 was proposed, which agreed with earlier values from Kreuse and Bambynek, but was signicantly higher than the recent values presented by Hubbell. The detailed evaluation of the spectra obtained took into account the double photo-ionization satellites of the escape peaks. The authors noted that such a detailed study of escape peaks would have been impossible without the signicant improvements to peak tailing delivered through improved crystal processing by one detector manufacturer in particular. Lepy and colleagues149 used heavily monochromatized SR in the energy range 17 keV to calibrate and study the response of a Si(Li) detector. The silicon dead layer was measured experimentally but, interestingly, was claimed to function as a partially active layer. The peak shapes were tted using a Hypermet function similar to that developed by Campbell. Finally, Shima150 reviewed all of the features found in spectra from Si(Li) detectors. An equation describing the efciency of planar germanium detectors was described by Martinez et al.151 The authors concluded that a simple function, which included only the beryllium window absorption and the photoelectric interaction in the bulk, was inadequate, as it did not account for escape peak losses. Their new model was applied to detectors of 5 and 7 mm thick and found to be valid over a wide energy range, although it should be noted that only front-side escape was accounted for. 3.2 Matrix correction and calibration procedures A comprehensive review of inuence coefcient methods was presented by Lachance,152 in which the concordance between the coefcients and the algorithms that use them was carefully examined. The author made the valuable observation that the inuence coefcients can be highly dependent upon the analytical context in which they were determined. Conversely, the algorithms themselves tend to be independent of the analytical context, thus retaining their validity and allowing them to benet from any advances in the denition and determination of the inuence coefcients. The virtues of the fundamental algorithm were once more expounded by Rousseau and Boivin,153 who described how the algorithm brought together the theoretical exactness of the fundamental parameter method with the practical convenience of inuence coefcients and a novel calibration method. In a second paper by Rousseau,154 the theoretical rigour embodied in the fundamental algorithm was used to evaluate three conventional inuence coefcient models in order to identify the main sources of error in each. It must be a source of continuing 1778 J. Anal. At. Spectrom., 1999, 14, 17731799

disappointment to that author as, since the rst introduction of the fundamental algorithm in 1982, few XRF practitioners have adopted it in favour of the widely-used inuence coefcient models, despite the errors identied in them by the fundamental algorithm. A useful systematic procedure was described by OchandioCardo et al.155 for the preparation of sets of calibration standards for XRF spectrometry. A computer program (CALPAT) was developed, which required the user to input only the analyte and the required calibration ranges. The program allowed for the use of pure oxides or salts and certied reference materials and the authors reported that the program was being used successfully in a number of ceramic plants throughout Spain. The use of chemometrics in XRF analysis continues to generate interest despite the large number of inuence coefcient and fundamental parameter (FP) algorithms that are already in use. Taking a particularly novel and interesting approach to determining the light element composition of organic liquids, Molt and Schramm156 used principal component regression (PCR) and backscatter information from EDXRF spectra. Using an yttrium secondary target arranged in Cartesian geometry, the authors were able not only to estimate the overall `dark' matrix, but also to obtain individual concentration values for C, H and O in a wide range of organic solvents and base oils. The analysis of unknown samples gave impressive prediction errors of 4 mg g21 for H, 30 mg g21 for C and 26 mg g21 for O. Overall, the results were impressive and the PCR technique looks promising for use with a wider range of applications in the future. Urbanski and Kowalska157 used PLS regression for the analysis of plating bath solutions and determining the thickness of nickel lms on a steel substrate. The procedure was applied to raw spectral data from low resolution EDXRF instruments and provided reliable data without the need for explicit spectrum processing or matrix correction procedures. Such a method is well suited to simple applications like these, as it requires relatively few analytical standards. A PLS regression approach was also adopted by Luo et al.158 for the analysis of copper alloys. Providing that the top and bottom standards were included in the calibration set, only four standards were required to yield accurate analysis of unknowns. The authors also reported reliable analysis of samples, the analyte concentrations of which lay outside the range of the calibration standards. For more complicated matrices, such as geological samples, the authors advocated combining PLS with an FP approach. Antoniak et al.159 investigated the use of three spectrum smoothing methods prior to the application of PLS regression. An extensive review of the use of expert systems for XRF analysis was presented by Otto and Flock.160 The system took into account all aspects of XRF analysis from the selection of the optimum sample preparation methodology, through selection of instrument parameters to selection of the quantitative model. The inclusion of fuzzy logic in the programs that were developed allowed semi-quantitative analysis of totally unknown samples to be realized. The development of fundamental parameter (FP) programs continued during the review period. The powerful combination of polarized beam EDXRF spectrometry and the FP program TURBOQUANT was presented by Branden161 and Schramm and Heckel.162 The program was set up to cater for many types of sample without the need for calibration by the user and was claimed to provide results for 40 or more major and trace elements in less than 5 min. The performance of the SSQ3000 FP analysis program for use with a high power sequential WDXRF spectrometer was presented by Park.163 Up to 75 elements could be determined in a total measuring time of 23 min, and the author reported, unsurprisingly, that samples of known and declared matrix, such as stainless steels, could be

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determined with higher accuracy than totally unknown samples. Information from the Rh Ka Compton backscatter peak was used to verify the light element (dark matrix) composition and, unless the matrix was correctly dened, the accuracy of the matrix correction and subsequent analysis was signicantly reduced. Angeyo et al.164 used the AXIL-QXAS software (IAEA, Vienna) for the FP determination of trace elements in cellulosic materials such as coffee and tobacco leaves. The authors investigated the effects of geometry in their 109 Cd radioisotope source excited EDXRF system and made use of the emission-transmission method for the estimation of the matrix mass absorption coefcients. For this work, the authors assumed that the dark matrix was cellulose and conrmed the validity of this simplifying approach by the successful determination of many trace elements in samples of dried plant material. A suite of in-house FP analysis programs was developed by Bos and Vrielink.165 Accuracy of analysis was reported to be better than 1% for concentrations greater than 1%. The programs allowed for calculations based upon the following three limitations: all elements measured and the sample mass thickness known; sample mass thickness unknown; or all elements measured and a balance of oxygen assumed. Knowledge of the X-ray tube spectrum energy distribution is of great importance for the majority of FP calculation procedures. An improved model for the tube spectrum was proposed by Finkelshtein and Pavlova.166 The new model addressed the underestimate of the intensity of low energy bremsstrahlung that is inherent to models based solely upon Kramer's law. In addition, the authors took into account the additional target K line uorescence excited by the bremsstrahlung, which can contribute up to 30% of its total intensity. Results from this valuable new model were compared with those from the NIST algorithm and those from careful experimental studies. A comparison of existing algorithms was also made by Schossmann et al.,167 who also proposed a new model. The authors' new model was based upon earlier work by this team at TU Vienna and the improvements made in the new model led to more accurate tting of the characteristic radiation. The provision of high quality experimental data for the testing of tube spectrum algorithms is of prime importance and was the subject of work reported by Aiginger and colleagues168 at the Atominstitut in Vienna. A highly collimated Si(Li) detector was used to measure directly the energy spectrum of X-ray tubes with chromium, molybdenum, rhodium or tungsten anodes. Data were presented for various tube voltages and target take-off angles. The use for matrix correction of scattered radiation remains important for many FP and inuence correction procedures. Bao169 described a new power function that modelled the non-linear inverse relationship between mass absorption coefcients and scattered continuum radiation. The new method was applied to the determination of Sr in pressed pellet samples of geological materials and yielded an accuracy of 2.4% relative compared with 9.7% relative when using the conventional Compton correction procedure. A detailed MC simulation for X-ray single and multiple scattering from bulk samples of linearly polarized photons in the energy range 4080 keV was described by Vincze and co-workers.170 The accuracy of the simulation was conrmed by measurements using a highly monochromatized SR beam on beam line BW5 at Hasylab (Hamburg, Germany). Of particular interest was the novel use of the Rayleigh and Compton scatter peaks to obtain 3-D information on the distribution and composition of the sample dark matrix. A very comprehensive MC simulation for the scattering of polarized X-rays was described by Fernandez et al.171 The validity of the new code (MC-SHAPE) was conrmed by good agreement of its data with those from deterministic calculations and experimental measurements.

4 X-ray optics
Although X-ray microuorescence represents a relatively specialized form of XRF analysis, it is becoming increasingly adopted in specialized applications because of its unique analytical capabilities and the complementary nature of results in comparison with other microprobe techniques. The `big science' end of X-ray microuorescence is based on the synchrotron excitation source, applications of which are also reviewed in Section 5. In this section the characteristics of optical elements and the design and application of both synchrotron and laboratory scale instrumentation are considered. A wide ranging review of this topic, drawing together details of microuorescence, synchrotron and TXRF techniques, was published by Adams et al.172 4.1 Optical elements The transmission and gain of singly and doubly focusing X-ray lenses were investigated by Lengeler et al.173 These devices had focal lengths of 12 m and were capable of focusing hard Xrays to a spot size in the micrometre range. Proposed applications included microdiffraction, microuorescence and coherent imaging. This investigation mainly consisted of a study of the degree of small angle X-ray scattering from a range of low Z materials, since this phenomenon is one of the reasons why lens gain is not as high and the focal spot is not as small as theory. Kawata et al.174 described a new water-cooled doublybent crystal monochromator designed for Compton scatter experiments on a synchrotron beamline at the Photon Factory. The device gave a focused beam of 0.562 mm2 for 60 keV photons and was one order of magnitude higher in brightness than the monochromator it replaced. An overview of X-ray lenses in XRF analysis was presented by Ding et al.175 Kondrashov et al.176 compared the capabilities and properties of an RAP crystal, a nickelcarbon multilayer and a diamondlike carbon X-ray mirror, the properties under consideration being the effects of temperature and radiation on reectivity and resolving power. Multilayer diamond-like carbon structures were found to offer stable performance up to 570 C. A rather specialized imaging device based on a square-pore microchannel plate was described by Martin et al.177 The multichannel plate was used to relay uorescent radiation onto a 2-dimensional charge-coupled device capable of both recording an image and providing energy information, even for low-Z elements such as C, N and O. The picosecond pulsed laser plasma X-ray source at the RutherfordAppleton Laboratory was used as the primary source and, unlike comparable imaging devices, the system had no moving parts. Improvement in the detection sensitivity of EDXRF trace element analysis by means of efcient X-ray focusing based on strongly curved highly oriented pyrolytic graphite (HOPG) crystals was presented at the 1997 Denver Conference by Beckhoff and Kanngiesser.178 These co-workers also presented a paper179 on the excitation of low Z elements by means of a cylindrical graded multilayer which was used as a high energy cut-off in EDXRF analysis. In terms of other developments in instrumentation related to optical elements, Shard et al.180 provided an analysis of the performance of computer controlled piezoceramic electrostrictive actuators with specially designed feedback circuits to provide precise control of the pitch angle of crystals in a double-mirror monochromator. Chen and Wittry181 described a microanalysis instrument based on a small laboratory source from which radiation was monochromatized and focused using a doubly-curved crystal diffractor. Performance of the device tested gave a focused beam of 57643 mm2 and detection limit of 1.6 mg g21. However, partially based on predictions from ray tracing models and improvements in instrumentation, probes of v10 mm diameter offering ng g21 detection limit perforJ. Anal. At. Spectrom., 1999, 14, 17731799 1779

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mance were thought to be possible. Wittry182 also made a patent claim for a simplied system for the monochromatic excitation using a number of focusing diffractors, each prealigned to a source of X-rays excited by an electron beam. 4.2 Microuorescence A number of applications of laboratory microuorescence have been presented, including a paper by Wiess et al.,183 who analysed the ash fraction of plants and peats using an `ED miniprobe multi-element analyser'. A LiF(200) crystal was used as the focusing device for Mo Ka radiation from a conventional X-ray tube. Dry ashing of about 1 g of material yielded about 35 mg of ash for analysis by X-ray miniprobe and results for the element of interest, Pb, were generally in agreement with independent ICP-MS data. Flynn and colleagues184 analysed rearm discharge residues by X-ray microuorescence, results being used to differentiate between different ammunition types and to estimate the shooting distance in comparison with conventional SEMEDX analysis. It was anticipated that this application could be extended with higher specication instrumentation, offering an X-ray tube power of 100 W, rather than 50 W, and a beam diameter of 10 mm, rather than the 100 mm that was available. Gambardella et al.185 used X-ray microuorescence as well as AAS to measure the accumulation of Cu and Fe in the species Idotea baltica after exposure to these elements. Worley and Havrilla186 used m-XRF to measure the distribution of Ga2O3 in a mixed oxide fuel surrogate feed material in a CeO2 matrix. These determinations were required to evaluate the effectiveness with which Ga was removed during fuel processing as Ga can damage the fuel cladding. A rather specialized technique of selected area XRF analysis was described by Hossain and Lowell187 for the determination of light elements on the surface of silicon substrate. The sample surface was excited using a monochromatic beam optimized in energy for the elements of interest. The beam was obtained from a high power laboratory source and formed using collimators, multilayer crystals and a glass capillary waveguide (q.v.) and illuminated an area on the sample from 0.5 to 10 mm in diameter. A perennial problem for almost all forms of microanalysis is the lack of suitable reference materials, certied on a microscale. The problem was reviewed by Zeisler,188 who proposed a remedy in the creation of a new genre of highly homogeneous natural matrix materials. The categories of materials considered were single cell biological materials, nely dispersed suspensions or precipitates derived, for example, from air particulate matter or sediments, or by appropriate pulverization of complex matrices. 4.3 Capillary waveguides No doubt partially stimulated by the introduction of commercial instrumentation as well as the development of a range of applications, X-ray microuorescence using glass capillary waveguides continues to attract a lot of interest. A number of publications continue to model various aspects of the X-ray transmission properties of glass capillaries. Alexandrov et al.189 investigated the `peculiarities of photon transmission through capillary systems' using a numerical solution of a wave equation and offering an explanation for recently discovered interference effects occurring on the multiple reection of Xrays. Parameters such as transmission efciency and intensity gain were calculated by Sanchez and Perez190 for glass capillaries having different geometric shapes and dimensions as a function of photon energy. Calculations were undertaken in two dimensions for monochromatic radiation with synchrotron-like properties (small source with low angular divergence). Refractive index is also important in affecting the transmission 1780 J. Anal. At. Spectrom., 1999, 14, 17731799

properties of glass capillaries and Liang et al.191 reported data for Cs- and Na-glass capillaries in a Chinese-language paper. In what is likely to be an important development in the production of commercial instrumentation, a method of fabricating tapered glass capillaries was described in a patent application by Hirsch.192 The method involved etching a metal or glass wire into a narrowly tapering zone with a shape matching the bore of the desired capillary optics. The wire was then coated either by electroplating, by being built up using electrodeless plating or by encapsulating in a polymer cylinder to increase the diameter for easier handling and greater robustness. The patent also described an apparatus which controlled the rate of removal of the wire from the etching bath in order to control the shape of the taper. An equally inuential contribution was that of Bilderback and Fontes,193 who fabricated a unique computerized glass puller capable of making parabolic or elliptically tapered glass capillaries from hollow glass tubing. Two types of capillary have been made. First, capillaries designed for a single `bounce' of the X-ray beam for imaging diffraction patterns from tiny bundles of carbon and Kevlar bres. Second, capillaries designed for multiple `bounce' for condensing the X-ray beam to create submicrometre beams for m-XRF applications, with the aim of achieving fg sensitivity in the determination of Er and Tb dopants diffused into an optically-active lithium niobate wafer, presumably using a synchrotron X-ray source. A new design of microcapillary lens for X-rays was described by Dudchik and Kolchevsky.194 Details of the fabrication of this device were given, based on a set of microlenses placed inside a glass capillary. Gao and colleagues195 described real and simulated experiments to evaluate the performance of tapered monocapillaries in comparison with straight (i.e., parallel bore) capillaries using a laboratory 16 W X-ray source. Intensities transmitted from tapered capillaries with output diameters of 8 mm and 3.5 mm were 1.4 and 1.5 times, respectively, greater than those observed from parallel bore capillaries of identical output diameter. Tapered monocapillaries were also found to produce a signicantly lower high energy bremsstrahlung and an increased stability in transmitted output when the X-ray source was moved slightly. Janssens et al.196 also investigated properties of ellipsoidal lead-glass capillaries, in this instance for microfocusing high energy synchrotron radiation (0 60 keV). At v30 keV, beam diameters of about 4 mm were produced in which the ux was ten times greater than that of a collimated beam. At 4060 keV, the focused beam diameter was 10 mm. Detection limits for the elements Mn to Gd (Ka lines) in silicate materials were 110 fg for a 1000 s count time. With reference to developments in instrumentation, a desk-top commercial instrument capable of producing a v10 mm diameter X-ray beam using a miniature X-ray tube and an X-ray waveguide tube with a parabolic inner contour was described by Hosokawa et al.197 Samples were mounted on an xy stage and detectors were provided to measure transmitted X-rays as well as uorescence, backscatter and diffracted Xrays whilst scanning the sample. Interesting possibilities were then described in combining images recorded using different signals for the comprehensive analysis of samples such as printed circuit boards. An instrument with some similar analytical capabilities was described by Yamamoto.198 This instrument was also capable of making uorescence and diffraction measurements and incorporated a glass capillary waveguide with a parabolic inner surface which could be coupled to a transmission target tube. The application described in this work was the characterization of the structure of ultra-large-scale integrated circuits which incorporated titanium silicide components and aluminium connections on a silicon substrate. Continuing with the theme of semiconductor components, Fougeres et al.199 developed a new microuorescence instrument comprising an X-ray generator

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coupled to an X-ray focusing capillary with a high resolution CdZnTe detector (225 eV resolution FWHM at 5.9 keV). This instrument was used to control the concentration of Zn and its uctuation in high pressure Bridgman-grown CdZnTe crystals. Features down to 100 mm across could be analysed using an instrument described by Nicolosi200 which incorporated a microfocus X-ray tube and capillary X-ray optics. A particular feature of this instrument was that it was capable of accommodating bulky objects 250 mm in diameter and 100 mm thick. Applications of capillary m-XRF include the work of Kuczumow et al.,201 who analysed petried wood using electron, X-ray and optical microprobes. These techniques offered complementary information and results indicated that some samples of petried wood were the chemical negatives of the primordial living wood. XRF with a focused X-ray beam based on a glass capillary waveguide was also used by Fukumoto et al.202 for the elemental mapping of biological samples. Particular interest was shown in mapping changes in elemental distributions (e.g., Ca, K, Mn) in living leaves after exposure to both high X-ray doses and articial acid rain. The capability of glass capillary m-XRF to characterize glass samples relevant to forensic applications has also been described.203 Holynska et al.204 used an EDXRF microuorescence instrument, which incorporated a 1 mm diameter glass capillary, to analyse air lters, using a special collection device capable of collecting air particulate material on a lter disc, which was progressively exposed over a period of 1 week. Performance of this m-XRF was compared with PIXE and applied to air samples collected from Cracow, Poland. The big brother of the glass monocapillary is the `monolithic polycapillary' lens, usually comprising large numbers (hundreds of thousands) of capillaries bundled together but with each bent to guide the X-ray beam to the same point of focus. Gao et al.205 from the State University of New York evaluated such a device using a 12 W minifocus X-ray source and obtained a 21 mm focused spot (FWHM) at 17.4 keV (Mo Ka) with an intensity of 2400 times greater than that observed from the Xray tube alone, at an equivalent distance of 100 mm. The device was used to analyse and map industrial samples. In a second contribution from the State University of New York, Hofmann and colleagues206 showed the potential of this device to measure diffraction patterns from small lysozyme protein crystals. Some applications require intense parallel X-ray beams and Dozier et al.207 showed how polycapillary devices can be designed to achieve this for use in lithography. The manufacture, measurement of basic characteristics and applications of monolithic polycapillary lenses were described by Xie et al.,208 who reported a 30 mm focal spot diameter using Mo Ka radiation with a gain factor of w2000 compared with an equivalent aperture. Transition element detection limits at the sub-pg level were reported with this device in conjunction with a 1 W X-ray source. Monolithic polycapillary lenses have also found uses in SR applications and Rath et al.209 performed measurements and calculations to show the thermal loading effects when exposed to the white beam from a synchrotron bending magnet. After a time of 1 min, the temperature at the input end of the polycapillary increased by up to 190 C. Cooling in an atmosphere of He or using an air ow would substantially reduce this effect. The focusing properties of polycapillary devices in synchrotron applications were considered in a further contribution from Hofmann et al.210

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aim of this source was to provide 1030 keV X-rays of moderate brilliance for commercial biotechnological and industrial applications. The prototype was being designed for UCLA, California. The status of the world's smallest electron storage ring (50 MeV) for far-IR and incoherent hard X-rays (generated as bremsstrahlung photons) was reported by Yamada.213 The design of a new high brilliance VUV and soft X-ray source for the University of Tokyo was described214 and a grazing incidence reectometer for an undulator beamline at Spring-8 intended for TXRF experiments, for example, was presented.215 Optical components for focusing X-rays were described by Snigirev et al.,216,217 who used compound refractive lenses (of Al, B, Be and C) for sub-micrometre focusing for energies higher than 5 keV at ESRF. A tuneable bent Laue monochromator, where the rst crystal was plane and the second one was bent and its angle kept constant to make the device stable against vibrations, was used at NSLS.218 An article in the Japanese language dealt with a beamline at the Spring-8 facility for high resolution XRF.219 A long-standing problem with monochromators for synchrotron radiation is the high heat load. Two approaches with internal water cooling at wiggler stations at CHESS220 and SSRL, ESRF221 and contact cooling at an undulator insertion device at APS,222 were proved to be effective. An aberration effect observed with bent Laue monochromators in combination with wide fan-shaped synchrotron radiation X-ray beams, referred to as `beam-smiling', was described and a correction involving asymmetric bending of focusing elements proposed.223 In a review article, Chevallier et al.224 discussed hard X-ray microbeam production and applications. Electron microscopes represent the most widely used technique for microanalysis, but the sample must be analysed under vacuum and detection limits are not as low as is required in many applications. Therefore, high brilliance synchrotron radiation is an attractive alternative. As an example of such an instrument, an XRF microprobe system was developed at Spring-8225 and incorporated ED and WD detection. X-ray uorescence correlation spectroscopy was presented as a method for studying particle dynamics in condensed matter.226 5.2 Applications Synchrotron based XRF microprobes have been used in the semiconductor, ceramic and glass industries, as exemplied by the report of McHugo et al.,227 who used an instrument with a 1 mm spatial resolution to detect and map impurities such as Fe and Cu in silicon semiconductor devices using well characterized standard samples. A synchrotron radiation XRF microscope was also used to study multi-metal oxide ceramics that had been designed to sequester radioactive actinides for longterm storage and disposal.228 The correlation of solar cell performance with the distribution of metal impurities in polycrystalline silicon was studied,229 as were unopened inclusions of gas bubbles in an aluminosilicate glass matrix, using a microbeam to determine Mo, Rb and Xe.230 The continuing interest in atmospheric aerosols was shown in several publications, demonstrating that synchrotron excited XRF is a well suited method for this category of sample. By applying principal factor analysis to elemental compositions, the origin of aerosols collected at different Siberian locations was studied.231 Within the framework of an inter-laboratory comparison, SRXRF analyses of aerosols collected on lters were compared232 with results from other techniques (NAA, AAS, OES) and the capabilities and limitations of the SRXRF technique were evaluated. In a further contribution from these authors,233 an evaluation of the use of the SRXRF technique was made in assessing the anthropogenic impact of aerosols in a remote area of northern Siberia. Turning now to biological applications, Janssens et al.234 J. Anal. At. Spectrom., 1999, 14, 17731799 1781

5 Synchrotron radiation
5.1 Beamlines and optics The design of a 1.5 GeV compact storage ring that uses 7 T superconducting magnets was presented by Cline et al.212 The

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determined non-destructively the REE content in fossilized bone by their K-lines with X-ray microuorescence at the Hasylab synchrotron laboratory in Hamburg. The results were discussed and critically compared with those obtained by NAA and laser ablation microprobe ICP-MS. The Sr : Ca ratio in sh otoliths can be used as an indicator of salinity changes and assist in claring the migration history of the eel. Nakai et al.235 collected and analysed samples from the Tone and Elbe rivers (which ow into the East China and North Seas, respectively) to evaluate contrasting migration patterns. Studies were also undertaken of the site-specic lead distribution in scales of carp which had been administered Pb236 and of XRS imaging combined with histochemical staining of the renal section of mercury-treated rats.237 Several publications concerned the analysis of geological samples, one example being bottom sediments from Lake Baikal of relevance to paleoclimatic reconstruction.238 `Warm' and `cold' periods of climate could be distinguished from the corresponding mean contents of elements. Data on some toxic elements associated with the different size fractions in the bottom sediments of Novosibirsk reservoir's tributaries were reported by Sokolovskaya et al.239 Bottom sediment samples were also studied by Bobrov et al.,240 this time from Lake Teletskoy; results revealed the difference between sediment layers associated with rhythmic layer-by-layer oscillations of mineral compositions and grain size. Ferromanganese nodule sections from the Pacic Ocean were statistically characterized by scanning SRXRF to determine the element content of layers.241 A review by Torok et al.242 summarized the principal analytical techniques based on ion and photon beam excitation used for geological materials. Chemical data obtained by mSRXRF on sublimates and incrustations of volcanic gases from Fogo Island volcano (Cape Verde Archipelago) were discussed by Figueiredo,243 a particular feature of this work being the presentation of data for Tl in well identied minerals found in volcanic fumarole sublimates. In highland Lunar rocks (Apollo 16 and Luna 20 missions), six groups of rocks having various aluminium and trace element contents were distinguished on the basis of the distribution of Rb, Sr, Y, Zr and Nb.244 Janssens et al.211 described the XRF analysis of a large number of glass nds from the 15th to 17th centuries resulting from excavations in the centre of Antwerp. Samples were analysed by EPMA and m-SRXRF and could be classied into 4 major compositional types; the implications of these ndings were discussed.

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the excitation energy and distance from anode source to sample. Wegrzynek et al.247 compared the performance of a fundamental parameter method for the quantication of trace elements from TXRF spectrum evaluation with an empirical quantication procedure. The rst method was reported to offer advantages, especially for complex matrices with spectra containing strongly interfering peaks. Hossain et al.248 claimed a patent on an apparatus and method for characterizing particles embedded within a thin lm on an underlying semiconductor wafer. For excitation, a radioisotope source was used, the emitted X-rays impinging upon the sample surface at near grazing angles. The identity and quantity of elements in the thin lm were determined. This is the rst time that a radioisotope source has been used for TXRF, because generally a high brilliance source is required to obtain a reasonable photon ux with a sufciently small divergence for total reection. The TXRF design group at the Ministry of Geology and Mineral Resources, Beijing, published a paper on the development of a high sensitivity TXRF spectrometer249 and applied it to the analysis of trace elements in natural water.250 Also, the group at Yantai University, China,251 developed a TXRF spectrometer with detection limits in the pg range. The Atominstitut group in Vienna published an overview of sources, samples and detectors,252 as well as a paper dealing with the excitation of low Z elements in TXRF.253 In this latter work, a windowless X-ray tube with optimized anode conguration and target material (Al, Si) achieved detection limits of 15 pg for Na. Light elements were also analysed by TXRF by Fukuda et al.,254 using a special spectrometer. 6.2 Synchrotron radiation-induced TXRF The rst SR-TXRF experiments performed at ESRF ID32 were described by Ortega et al.255 using an undulator beamline. Detection limits of 17 fg or 1.86108 atoms cm22 were achieved using a Si(111) double crystal monochromator and measurements were applied to the impurity analysis of Si wafer surfaces. The authors estimated that it would be possible to reduce the detection limits by a factor of 25 by employing optimized optics and detectors. Comin256 also presented at the TXRF conference in Austin future plans for an industrial facility for mapping the distribution of trace impurities on 300 mm silicon wafers. The elements to be detected should range from Na to Hg with routine detection limits of 108 atoms cm22. An update on SR-TXRF was given by Brennan et al.257 concerning the already established routine SR-TXRF beamline at SSRL, with a supplementary presentation by Pianetta258 at the TXRF conference. Detection limits of 36108 atoms cm22 were reported for this facility. Improvements were planned by the use of high count rate electronics and an upgrade of the storage ring to SPEAR 3. Soo et al.259 investigated the heterojunction interface of solar cells and reported measurements of interfacial roughness, interface height uctuations, the effects of heat treatment and the diffusion of Te atoms. These measurements were made by grazing incidence X-ray scattering and the angular dependence of uorescence radiation using synchrotron radiation. Wu et al.,260 from the Chinese Academy of Science, published details of SR-TXRF experiments and the application to preliminary study of several kinds of biological materials (including pig liver and mouse intestine cells),261 unfortunately only in Chinese. 6.3 Surface analysis Hockett262 presented a review article on the current activities of Standards Organisations working in the eld of surface

6 Total reection XRF spectrometry

During the current review period a review article was published by Stoev et al.,245 covering grazing incidence X-ray spectrometry and reectometry. This article gave an overview of recent advances since 1993 on the application to surface and thin lm analysis, both from theoretical and experimental aspects, with 482 references cited. Also, combinations of different grazing incidence techniques were mentioned and their advantages for surface and interface analysis. Furthermore, the 7th Conference on TXRF and Related Techniques took place during the review period in Austin, Texas. A variety of new developments and applications were presented, mainly dealing with semiconductor applications, some contributions being mentioned here. 6.1 Instrumentation and quantication The TXRF group at GKSS published details of the optimization of curved X-ray multilayer mirrors for TXRF.246 Various optical congurations combining focusing and monochromatization were modelled and system parameters such as mirror shape, size of X-ray source, angular divergence and shape of multilayer were varied and the inuence of these design parameters on detection limits studied. Results depended on 1782 J. Anal. At. Spectrom., 1999, 14, 17731799

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analysis using TXRF. In another review, De Gendt et al.263 presented results from the European round-robin assessment of calibration accuracy of TXRF in the analysis of contaminated wafers. A second round-robin assessed vapour phase depositiondroplet collection TXRF techniques, both series of experiments involved the participation of 7 facilities (including industry, research and universities). The vapour phase decomposition (VPD) technique coupled with TXRF was also described as a standard method for the online inspection of surface contamination on silicon wafers in the semiconductor industry264 and a modular system for the fully automated VPD preparation and scanning of 300 mm wafers was described.265 Depth proling of cobalt-implanted silicon wafers was tackled by a new approach by Klockenkamper and von Bohlen,266 where a square section of some cm2 on the wafer was oxidized and precisely etched by HF. The mass of Si in the layer was determined by differential weighing and the Co content in the solution measured by TXRF. By repetition of these steps, the depth prole could be reconstructed. In another approach,267 depth proles were obtained for cobalt-titanium silicide lms by a combination of ex-situ low energy ion beam etching with TXRF. The micro-roughness of polymer thin lms supported on nickel-coated silicon substrates was studied by TXRF and atomic force microscopy.268 Shallow impurity depth proles for As implanted into silicon were established by TXRF and compared to ToF-SIMS by Schwenke et al.269 The authors concluded that SIMS and TXRF provided complementary information. TXRF was used to verify independently the implant doses on a series of reference samples which were used to quantify ToF-SIMS results in the analysis of metal contaminants on UV ozonized GaAs wafer surfaces.270 A comparative study of the As and In implant dose in silicon employed TXRF, SIMS and ToFSIMS271 and claimed a strong correlation between SIMS and TXRF data. 6.4 Related techniques Grazing emission XRF (GEXRF) with 90 degrees incidence and a shallow angle of detection is an alternative to TXRF for the surface characterization of certain samples. Detection is possible with WD methods with consequent benets in the determination of the light element. Typical applications, including the determination of light element contamination on Si and the characterization of TiN and TaN thin layers, were presented by de Bokx et al.272 and Wiener et al.273 For the analysis of trace elements in drinking water the performance of this method and also TXRF were compared with other analytical techniques.274 For this study a natural mineral water was selected, and TXRF was claimed to be suited for the direct analysis of heavy elements. GEXRF was successfully applied to the determination of the low Z elements but results for Mg and Na were systematically low. 6.5 Applications A survey of sampling techniques for solids suitable for TXRF analysis was presented by Klockenkamper et al.275 Several techniques for solid sampling were investigated and one example of each technique was reported, including the direct placing of individual particles, suspensions of powdered material, collection of air dust by impaction, the touchstone technique for metals, laser ablation for local analysis, Q-tip techniques for paintings and inks, freeze-cutting for organic material and direct contamination control of wafers. A comparison of ICP-MS with a microconcentric nebulizer and TXRF for the analysis of small liquid volume samples was performed by Lofthouse et al.276 TXRF was considered to offer the potential of fast effective screening using only 10 ml of solution, and digestion was required prior to the analysis of

polymer samples. ICP-MS offered better detection limits for a wide range of elements but at least 90 ml of sample were required and digestion was essential. Turning now to the TXRF analysis of environmental samples, Zaray et al.277 published a survey on trace element determination in organic environmental matter using TXRF, including the analysis of xylem sap, mussel and algae biomonitoring, and airborne dust analysis. TXRF was applied to the analysis of aerosol samples and compared with other analytical techniques by Ortner et al.278 Neuhauser et al.279 presented results at the 25th Annual Conference of the Federation of Analytical Chemistry and Spectroscopy Societies of on-line monitoring of heavy metals in aerosols which was calibrated with TXRF. Pettersson280 investigated marine periphyton algae communities by TXRF. Algae were directly grown on oat glass, which was used as a sample reector, without sample preparation. The method was evaluated by the analysis of certied plankton reference materials and by comparative analysis of samples using a wet digestion method. In a companion paper, Pettersson and Olsson281 used a digestion method based on nitric acid and hydrogen peroxide, to prepare algae as well as plankton prior to TXRF analysis. Freshwater algae were also investigated by Varga and colleagues,282,283 who compared the TXRF analysis of slurry samples prepared by sonication after freeze drying with solution samples prepared by vapour phase microwave digestion. Good agreement was reported between both techniques and it was concluded that slurry preparation was suitable for TXRF analysis. Experiences in routine food control were presented by Zahlbruckner et al.,284 who used TXRF to determine Ag, Cd, Cu, Fe, Pb, Sr and Zn in water. Chinese tea was investigated by Xie et al.285287 by analysing both digested tea leaves and tea infusions. The main element of interest was Se; the content in the tea leaves ranged from 48 to 570 ng g21 and the extractable portion from 15 to 27%. TXRF is also widely used in medical and biological applications. Indeed, TXRF and PIXE were compared for the analysis of human amniotic uid by Liendo et al.288 to establish correlations between concentrations of certain elements and fetal malformations. An analytical methodology for the analysis of blood plasma was developed by Savage and Haswell,289 where chemical modiers were used to compensate for analyte loss or sample modication during the drying and matrix decomposition stages. The concentration of trace and non-trace elements in Mammalian cultured cells was investigated using TXRF by Gonzalez et al.290 Results could be used to evaluate variations in response to modied concentrations in the extracellular medium. An elemental correlation study in cancerous breast tissue was performed by Majerska et al.,291 who observed an inhibition of enzyme activity caused by variations of trace element concentrations at the clinical stage of cancer. In the eld of industrial applications, TXRF was used for the analysis of radioactive water from a condensed nuclear reactor by Trabuc et al.;292 provided the activity was less than 7000 Bq (alpha emitters) or 107 Bq (beta/gamma emitters), measurements could be undertaken in non-controlled areas. Ferrielectric lms of complex oxides were investigated by Krasnolutskii et al.,293 who reported detection limits of 1021210210 g cm22 in comparison with 10281026 g cm22 by standard XRF. The application of TXRF to cultural and heritage samples includes the non-destructive discrimination between elephant ivory products and mammoth tusk products, which was performed using glancing incidence XRF.294 Results suggested that the integrated intensity ratios of Sr Ka/Ca Ka and Br Ka/P Ka were valuable in discriminating between these two products. Pigments of a late-mediaeval manuscript were J. Anal. At. Spectrom., 1999, 14, 17731799 1783

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investigated by TXRF and micro-Raman spectroscopy by Vandenabeele et al.295 as well as Van Hooydonk.296 A quantitative and qualitative reconstruction of pigments used in the artists' palettes was possible using data from both techniques with the possibility of distinguishing different miniaturists who worked on the manuscript.

7 Portable XRF
When reviewing this year's reports, it is relevant to note that there is a blurring of the distinction between in situ PXRF, which involves direct measurement with the analyser placed against the sample, in comparison with in situ in the sense of mobile laboratory applications, where the PXRF instrument is taken to the site, but where test portions are removed for analysis after some sample preparation. In archaeological applications the former is the only real option, but in applications such as the determination of heavy metals in soil, the latter mode of operation is becoming equally popular. Indeed the analysis of contaminated soil is one of the classical PXRF applications and is illustrated by the work of Rammler et al.,297 who compared three different models of PXRF to monitor and detect pollutants in waste deposits and polluted soil. Muller and Pelzer298 used a mobile XRF spectrometer to analyse dredged materials. Spittler299 described the use of a portable XRF analyser to analyse lead and other toxic heavy metals in soil contaminated by mining and metallurgical activities in the Urals region of Russia. This survey was complemented by gas chromatography measurements on water and soil to determine volatile organic compound residues resulting from spills and leaks. The use of PXRF was described by Schneider,300 again as a eld screening tool for the determination of lead and heavy metals in polluted soil. It was reported that PXRF results did not correlate perfectly with AAS data. Interest continued in the use of PXRF in characterizing contamination at former ring ranges (Hendersen et al.301). In the support of eld remediation operations, Waligora302 used PXRF to monitor the removal of chromium contaminated soil at a hazardous waste site. Samples were prepared and analysed in an on-site laboratory and data were used to conrm that clean-up had been achieved, as well as to determine the average Cr content of a stockpile of excavated soil. Independent analysis of 32 test samples gave a linear correlation coefcient of 0.985 compared with the XRF technique, a comparison in which PXRF presumably beneted from the homogenization of the sample at the preparation stage. The cone penetrometer is a rather more specialized device for evaluating heavy metal contaminants in soil and the preliminary design considerations of such a device, incorporating a miniature X-ray tube and detector, were presented by Elam and Gilfrich.303 Further details of the analytical performance of this device, called by the authors SCAPS (site characterization and analysis penetrometer system), were described by Elam et al.,304,305 including reference to the characterization of Pb within a military establishment. A comparison between XRF data and independent methods of analysis was reported by Shefsky,306 who evaluated the effectiveness of eld screening by XRF under a variety of different site conditions and found, not unexpectedly, that drying, grinding, sieving and homogenizing signicantly improved the quality of data. It was further claimed that in some instances, deciencies in eld methods can be erroneously caused by bias introduced when a sample is split and handled to provide a test portion for independent laboratory analysis. Metals in marine sediments were determined by Kirtay et al.307,308 using PXRF and a manufacturer-supplied fundamental parameter application which was apparently used to correct for particle size effects. Cu, Pb and Zn were measured 1784 J. Anal. At. Spectrom., 1999, 14, 17731799

on samples that were homogenized and analysed wet and a linear correlation was observed with data obtained by a standard method, although PXRF underestimated the true composition, an effect that could have arisen because of discrepancies related to the moisture content. Another classical application of PXRF is in the determination of lead in paint and Afshari et al.309 described a new instrument designed to overcome many of the limitations of earlier instruments. Particular features of this dedicated handheld instrument included optimization of excitation geometry and a mathematical approach which incorporated corrections for both systematic errors such as matrix effects and Compton scatter. In a second contribution, Afshari et al.310 described further aspects of the instrument, which incorporated a 10 mCi 57 Co source and a CdTe detector. Derbin et al.,311 in a Russian language contribution, also described a PXRF instrument for the determination of lead in paint: detection limits of from 0.01 to 0.1% were reported when elements with Zw50 were measured for 15 s. Archaeological applications is another important area for PXRF and Gigante and Cesareo312 continued their many contributions in this area by describing the analysis of ancient metal alloys using an instrument tted with an air-cooled miniature X-ray tube and a high resolution semiconductor detector. A new portable XRF instrument designed for nondestructive analysis of archaeological samples was described by Longoni et al.313 This instrument was based on a Peltier-cooled Si drift detector (offering a resolution of better than 160 eV at 5.9 keV for a shaping time of 2 ms) and a miniature X-ray detector and was used for the analysis of paintings of different ages and for metal alloys. Innovative PXRF applications are also possible in the analysis of air and liquids, the former being demonstrated by the work of Kienbusch et al.314 in the analysis of Pb in high volume air lters in the eld. The specic application concerned sand blasting of steel structures and the consequent possibility of airborne dust containing lead paint. Correlation of XRF results with ICP-AES data indicated that it was feasible to use PXRF instrumentation to provide relatively accurate air quality measurements for Pb. In relation to the analysis of liquids, Allen et al.315 described a lter device designed for the selective extraction of heavy metals down to ng ml21 levels. Extraction efciency was claimed to be 8595% and the detection limit in the determination of Pb in drinking water using a 500 ml sample were 8 ng ml21. Piorek316,317 also described the application of a eld portable instrument designed for the determination of hazardous metals in contaminated soil for the analysis of liquid hazardous waste, described as a mixture of solids suspended in a liquid medium. With minimal sample preparation, detection limits of 10 20 mg kg21 could be achieved in liquid hazardous wastes. All of these applications would not be possible without corresponding developments in instrumentation. Warburton et al.318,319 described a possible extension of `XIA' digital spectrometer technology to XRF devices for portable and remote applications, including a lead paint detector, a remote contamination monitor and a space mission spectrometer. The particular features of this technology were a very high count rate capability (w50 000 cps), low power consumption and digital signal processing technology, all originally developed for multi-detector arrays for use in SR applications. When considering space mission applications, Sarrazin et al.320 described a miniature XRDXRF instrument designed for the in situ characterization of Martian soils and rocks. The instrument incorporated a single CCD detector which was exposed directly to X-rays diffracted and uoresced off the sample. Another combined XRDXRF instrument, claimed to be the rst capable of making measurements in real time, was described by Paglietti and Plescia.321 This instrument used the same miniature detector as was installed on the NASA

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Pathnder mission and X-ray `microtubes' and was capable of the chemical and mineralogical characterization of various types of sample. Russell and Feldmann322 described the use of the `JouleThompson' type cooled detector for eld transportable XRF analysis of heavy metals in contaminated soil. In a Japanese language contribution, Hirai et al.323 described a relatively conventional PXRF instrument incorporating a Si PIN diode and miniature X-ray tube but with a cylindrical crystal to monochromatize and nely focus the primary X-ray beam, yielding advantages in the reduction of the scattered Xray background. Finally, although designed for in situ radioisotope detection, there is some interest in the work of Helmer et al.,324 who compared the performance and efciencies of three types of photon detector, an N-type, thin window germanium semiconductor detector, a plastic scintillator and an array of six CaF2 detectors. Of particular interest was the capability of the latter two detector systems to transfer measurements by telemetry to provide operators with a realtime mapping capability. More details of the Ge detector system were given by Gehrke et al.325 A further prerequisite, if quantitative determinations are to be achieved by PXRF, is an adequate correction model if solid samples with irregular surfaces are to be analysed successfully. Liangquan et al.326 addressed this issue in the analysis of rocks by examining the effect of variations in sample analysis distance, the peak to valley amplitude of the sample surface and the frequency of concave and convex surfaces. These workers describe a correction based on the ratios of the intensities of the characteristic-to-scattered radiation, an approach similar to that proposed by Potts et al.327

layers in ULSI applications. This review included the principles, system requirements and applications for all forms of X-ray metrology for the determination of composition, crystallographic structure and surface roughness. A particular consideration in this application was the need to limit radiation dose to prevent damage to the semiconductor device and it was concluded that both high-speed and damagefree XRF metrology is possible. In another demanding application for XRF, Connolly and Walker336 described a commercial product designed for the on-line monitoring of metals at sub-ng g21 concentrations in waters. The capabilities of this instrument, which incorporates a preconcentration mechanism, were described.

9 Applications
9.1 Sample preparation Practitioners new to XRF may benet from the advice of those who have worked and developed successful applications over the years by consulting papers 338341 that appeared in a review edited by Buhrke et al.337 entitled `A practical guide for the preparation of specimens for XRF and XRD analysis', containing contributions describing all aspects of this topic. Blank and Eksperiandova342 also offered a review of what they considered to be the most suitable preparation procedures published in the period 19871996. Allen343 evaluated the comminuting efciency of Syalon 101 (an AlSioxynitride alloy) for the preparation of geological samples. A system for the automatic preparation of pressed powders of heavy mineral sands using an industrial robot was described by Louw and Pedersen.344 A paper by Malmqvist345 described a semi-low dilution fusion method for oxides and suldes. Originally intended for XRF applications, the method was also offered for the pretreatment of samples for ICP-AES and AAS. Samples with sulfur concentrations of up to 50% m/m were quantitatively converted into sulfate and analysed with an accuracy of about 2%. An algorithm was presented which allowed loss-on-fusion, oxygen content of the non-oxidized components in the sample and also the ratio of FeII to FeIII to be calculated. Shannon346 discussed fusion techniques and the use of alpha coefcients for the analysis of heavy minerals and associated samples. Claisse347 reminded us of the selection criteria for optimizing the composition of lithium borate uxes for bead preparation. Many readers will sympathize with Merkle and colleagues,348 whose platinum ware reached an untimely end whilst attempting to prepare a bead from SiC after pre-oxidation at 1000 C. Concerning the analysis of liquids, Nielson et al.349 offered an order of magnitude improvement in detection limits for trace elements in water by using a new sample support for retaining drops of sample solution in one place and allowing the solution to dry into a single spot. Wolska and Vrebos350 also described the dimpling technique. Menendez-Alonso et al.351 described the direct determination of trace metals in bio-environmental samples by retention with ion-exchange resins. Eksperiandova et al.352,353 proposed methods for making organic glassy and quasi-solid specimens by the introduction of a saccharose thickening agent into aqueous concentrates. Patent claims devoted to sample preparation during this review period included Echi354 who described, in a Japanese language claim, a technique for the rapid detection of elements such as As, Hg, K and Na in food oils. In a German language patent, Neelmeijer et al.355 claimed a technique for metal salt components mounted on a support for use as a secondary multi-element standard. 9.2 Preconcentration techniques Carvalho et al.356 described a sensitive method based on the preconcentration of uranium on powdered foam for the J. Anal. At. Spectrom., 1999, 14, 17731799 1785

8 On-line XRF
A pleasing array of publications is available for this years review, in contrast to the relatively spartan collection in previous years. Cement has been the subject of discussion by Pedersen and Finney,328,329 who described a new commercial on-stream cement raw mix XRF analyser incorporating a windowless powder ow cell. This instrument was claimed to offer increased accuracy and reliability, particularly in the determination of the light elements, Al and Si, avoiding errors associated with abrasion and cross-contamination effects shown by instruments tted with conventional ow cells, and permitting determinations to be made with a 45 min cycle time. Whilst talking of ow cells, Miyoshi330 claimed a patent for a new design. XRF was also used for the on-line control of a La and Nd extraction process by Li et al.,331 and Casarci et al.332 Instrumentation comprised an 241Am excitation source and a hyperpure germanium detector, which was used to measure the La Ka and Nd Kb lines to determine these elements in the rafnate solution from a 16 stage counter-current extraction process. Connolly et al.333 described an on-line system for a pulverized coal feed line. Pulverized coal travelling along the feed line was collected in a recessed chamber, resting against the X-ray transparent window of the XRF analyser. After analysis, pressurized air blew the accumulated sample back onto the feed line, permitting another sample to be collected. Ringo et al.334 described a different sort of on-line application instrumentation in which XRF was used as a detector for capillary electrophoresis. A polyethylene sample cell was inserted between the fused silica capillary segments to permit continuous XRF detection with minimum band broadening and permitting detection down to 1024 mol l21 of metal complexes. Potential applications, particularly with advances in design that would improve detection limits by one to two orders of magnitude, were in the eld of environmental and biological analysis. XRF was also reviewed by ShachamDiamand et al.335 for the on-line analysis of ultra-thin barrier

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determination at ng g21 levels in aqueous samples. The interference levels of various ions and ligands were studied to develop optimum conditions for U in reference materials, waste water, mine drainage and sea-waters. Eksperiandova and colleagues at the National Academy of Science of Ukraine357 offered methods for the determination of small quantities of heavy metals in water-soluble salts and natural water. Necemer and Kump358 described a new approach for the radiochemical separation of 55Fe in waste waters from the Krsko nuclear power plant. The radionuclides were preconcentrated with ammonium pyrrolidinedithiocarbamate (APDC) and separated by ltration through a cellulose nitrate lter prior to analysis. Correjo-Ponce et al.359 proposed a liquidsolid extraction procedure to assist in the determination of Nd, Pr, Sm and Y mixtures using silica gel loaded with 1-(2pyridylazo)-2-naphthol (PAN). 9.3 Geological As has been remarked in previous annual reviews, XRF has become one of the standard techniques used for the routine analysis of geological samples, a theme continued by Potts,360,361 who showed that XRF and ICP-MS was the combination of techniques most widely adopted for routine geochemical analysis, although arguing that microprobe techniques were most likely to have a more signicant impact on advances in geochemistry in future years. The role and capabilities of EDXRF were reviewed by Bacso et al.362 The widespread use of WDXRF in the routine analysis of rocks is not, as might be expected, illustrated by a large number of reports published within the reviewing period, since the method is now well established and few innovations are possible using normal laboratory instrumentation. However, Borkhodoev363 reported on the XRF determination of Nb, Rb, Sr, Y and Zr in rocks to 23 mg g21 detection limits. By contrast, more work has appeared describing the use of radioisotope XRF in geological applications. Puri et al.364 reported the analysis of polymetallic nodules from the Central Indian Basin using 55Fe and 109Cd excitation sources. Samples were diluted with cellulose nitrate before being compressed as powder pellets to reduce matrix effects, although this is not normally necessary in routine silicate rock analysis. Angeyo et al.365 used starch as a binder for rocks from Kenya, before preparing powder pellets for XRF analysis using a 109Cd source. Devan et al.31 described an arrangement, again based on 109Cd excitation, used for the analysis of thin polished slices of ve rocks and three ores and ve air particulates. Reports on the analysis of sediments also featured this year. Majchrak and Pencakova367 described EDXRF in this application (stream sediments), as did Somogyi et al.,368 who employed a radioisotope instrument unusually incorporating a 125 I source. In the latter work, a detailed comparison was undertaken against replicate determinations by ICP-AES with good agreement for Mn, Sr and Zn but disagreement in Fe and Zr data, elements that are normally well-characterized in sedimentary samples. INAA was used as a complementary technique to XRF by Bounakhla et al.369 in the analysis of Moroccan marine sediments in a project designed to understand the mechanisms of sediment transport from coast to sea and assess coastal pollution. A more sophisticated analytical protocol was described by Janssen et al.,370 specically an XRF scanner designed for the semi-quantitative analysis of split sediment cores. This instrumentation was designed for shipboard operation and produced counts for the elements between K and Sr in the Periodic Table. A time of less than 1 h was required to scan a 1 m core section at 2 cm intervals (a resolution of 1 mm was possible), although further developments were planned to improve the calibration procedure and extend the elemental range. Arguably one of the most important geological applications 1786 J. Anal. At. Spectrom., 1999, 14, 17731799
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during the current review period was that of Rieder et al.,371 who presented analytical results for the composition of Martian soil and rock. These data were obtained from the alpha-proton X-ray spectrometer carried on the rover of the Mars Pathnder mission. The rocks had unexpectedly high Si and K contents but low Mg, in comparison with Martian soil and meteorites, and were similar to terrestrial andesites. Suldes are not the easiest sample type to analyse by XRF because sample preparation and matrix effects can be problematic. However, Mihajlovic and Stalov372 determined Tl down to the 0.016% m/m level (0.006% m/m using the method of standard additions). To prepare glass disks, samples (0.5 g) were mixed with KNO3 (0.5 g) and fused with 10 g of Li2B4O7 at 1100 C for 15 min in a Pt5% Au crucible. Other studies included the work of Adams and Allen,373 who described an automated wavelength selection method combined with a calibration procedure incorporating partial least squares regression and applied this method to the analysis of 25 geological reference materials. XRF also contributed to reference material characterization studies of Chinese Pacic Ocean polymetallic nodules and sediments374 and also of four natural soil reference materials.375 Of signicant interest, two conference reports376,377 described the merit of bulk XRF measurements combined with laser ablation ICP-AES/MS on the same glass disk, possibly anticipating full publications of novel applications in next year's review. 9.4 Environmental The performance of EDXRF as a versatile analytical tool for environmental studies was tested in an inter-analytical-method comparison with ICP-MS and GF-AAS in the analysis of seven international biological reference materials by Nguyen et al.378 The same authors379 also published a report on the determination of Hg in environmental samples using EDXRF and CVAAS and found good agreement between these two methods. XRF continues to be a valuable analytical method for the analysis of aerosols and air particle pollution. Braga Marcazzan380 investigated particulate pollution within the framework of a large research programme on air quality in northern Italy. Sampling campaigns were carried out in different areas in the Po Valley and concentration and composition trends in space and time determined as well as main sources of pollution. The main components were found to be crustal elements and sulfur compounds. The investigations were performed with EDXRF and PIXE and both techniques turned out to be of great advantage. A similar study was undertaken in Chile to investigate the chemical characterization and source identication of airborne particulate matter. This study was carried out by Cortes381 under the auspices of IAEA (International Atomic Energy Agency) and showed that several signicant correlations were found between a number of elements (As, Cu and S) and also between the mass of the ne fraction and black carbon, indicating possible sources, including a possible contribution from copper smelters. In Sao Paulo, Brazil, one of the worst air polluted cities, aerosol characterization studies were performed to develop a database on which a control strategy could be developed.382 Particulate matter in the atmosphere was studied in another Brazilian town, Natal, and found to be less than in Rio de Janeiro and Sao Paulo.383 Nejedly et al.384 presented a report about an inter-laboratory comparison of air particulate monitoring data using ion chromatography, PIXE and XRF. The results of an interlaboratory comparison in the multi-element characterization of the atmospheric aerosols was published by Shuvayeva et al.385 using different analytical techniques, including INAA, synchrotron radiation excited XRF, AAS and AES. Talebi et al.386 from Esfahan, Iran, determined the lead associated with airborne particulate matter by FAAS and WDXRF, showed good agreement and pointed out the advantages of WDXRF

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which required no time-consuming sample preparation or the use of environmentally hazardous solvents. KallithrakasKontos and colleagues387 analysed trace elements and the radioactivity in aerosol particles collected near Greek lignite power plants. The monitoring of urban air pollution with EDXRF was performed by Bandhu et al.388 in Chandigarh, India, soil dust, refuse burning, eld burning, automobile exhaust and smelter activity being identied as possible sources. A further important topic for environmental studies with XRF is the eld of water analysis. Ranaweera et al.389 applied XRF to the assessment of pollution by heavy metals of Lunawa Lagoon, Sri Lanka, and the potential of some native plant species to remove heavy metals from the waste waters. Eichhornia crassipes was found to be the most efcient of the species tested in the uptake of As, Cd, Cu, Fe, Pb, Mn, Ni and Zn. The heavy metal content of river water in the Jakarta area of Indonesia was investigated by Surtipanti et al.390 after preconcentration with ammonium pyrrolidine diethyldithiocarbamate. Polukhina and colleagues391 published the results of the determination of heavy metals in water, suspended matter, zooplankton, zoobenthos and bottom sediments of Novosibirsk reservoir by SR-XRF and AAS. The elemental composition of drinking water supplies in three states of Southeastern Nigeria was investigated by Nkono et al.392 They found that the Hg value in public tap water violated the WHO limits of 1 ng g21. Heavy metal assessment in the sediments of the Ave River Basin was performed by Araujo et al.393 Somogyi et al.394 investigated the speciation of elements in lake sediments by XRF and ICP-AES. The feasibility of several EDXRF quantication methods for the multi-element analysis of marine biological and sediment samples from Cienfuegos Bay, Cuba, was studied by Alvarez and colleagues.395 A comparison of trace element concentrations in Asian clams and sediment from the Concho River, Texas, was performed by Webb et al.396 Johnson et al.397 studied contaminated soil samples from 2 industrial sites. Rusell et al.398 analysed hazardous liquid waste for Cd and Cl with EDXRF after mixing the sample with a `matrix-modifying' powder. It was shown that XRF is a suitable method for biomonitoring studies. Cahill et al.399 determined elemental concentrations in feathers using XRF and PIXE. More specically, the geographical differences between two populations of brown pelicans were determined as well as the Hg contamination in birds at Clear Lake, CA. Rautio et al.400 published element concentrations in Scots pine needles on radial transects across a subarctic area. The effect of the emissions from smelters could be assessed in an area within 100 km from the source. XRF was used as a tool for paleoenvironmental investigations by Holynska et al.401 who characterized peat cores from southern Poland by various XRF techniques after dating with the naturally occurring isotope 210Pb. Strong time dependent variations in concentrations of several trace elements were determined, and high concentrations of Pb and Zn indicated an anthropogenic origin. 9.5 Archaeological and forensic Although a relatively specialized eld, the non-destructive analytical capabilities of XRF continue to make an important contribution in the analysis of archaeological and forensic samples. The analysis of pottery, ceramic and porcelain is a case in point. Majolica ceramics from six provenances in Europe were analysed by LaBrecque et al.402 using a simple radioisotope XRF instrument involving count times of 1000 s. These ceramics had previously been classied stylistically, and by thermoluminescence and geographic origin, but the investigators used XRF determinations of Pb, Rb, Sr and

Zr and principal components analysis to conrm their provenance. Conclusions were more consistent when Pb data were omitted from the principal components analysis, probably because clay matrices may have been contaminated when the PbSn enamel was removed. Yu and Miao403 used EDXRF to study the surface of 66 samples of Chinese porcelain for 13 elements. Principal components analysis was undertaken on these data to study the clustering behaviour of data and discriminant analysis used to distinguish the period and origin of the porcelains. Blue and white porcelain was analysed by Yu and Miao,404 using EDXRF to determine elements such as Mn and Co, which were characteristic of the colorant. However, based on critical penetration depths, determinations of Rb, Sr, Y and Zr can originate from the body of the porcelain so that the EDXRF technique is capable of providing data about the glaze, colorant and body for use in attributing samples to different periods and localities. Leung et al.405 used EDXRF to study ancient porcelain bodies from a newly discovered kiln site in China (Linjiang, Jiangxi) and concluded that trace element measurement had considerable potential for sensitive discrimination. Although not strictly an archaeological application, Somogyi et al.406 investigated the dissolution of lead from the surface layer of glazed terracotta pottery vessels using EDXRF and ICP-AES techniques. The aim of this work was to measure the kinematics of lead release from the pottery glaze by varying the pH and temperature of the liquid medium. Although affected by various parameters, the highest lead content was 500 mg ml21 after a 5000 min leach with dilute citric acid, a concentration that is of concern for domestic use. The authentication of paintings is another regular archaeological application of XRF and Newman407 discussed the role of X-ray radiography, X-ray diffraction and X-ray uorescence in this eld (including paintings, sculptures and other objects of art). In another authentication application, Diana et al.408 employed XRF to distinguish genuine works of the painter Caravaggio from replicas and copies from the 17th century. XRF has also been used in a number of other archaeological applications. Milazzo and Cicardi409 reported the analysis of metal alloys from the Corona Ferrea (Iron Crown) of Monza as well as associated glasses and enamels, drawing attention to the problem of quantifying measurements from irregularly shaped objects by XRF. In a Chinese contribution, Mao et al.410 measured Cu, Fe, Pb, Sn and Zn in ancient Chinese bronzes using a dissolution technique in which a portion of the sample solution was spotted onto a lter-paper. In an interesting application Torfs et al.411 investigated decay phenomena on the stonework of the Cathedral of Bari, Italy, using various analytical techniques, including EDXRF. Inside the cathedral, weathering of stone appeared to be mainly associated with marine salts, whereas outside, deterioration was mainly related to pollution effects. Ancient Celtic glasses found in excavation sites in Poland were analysed by Braziewicz et al.,412 who suggested that the measured ratio of Co to Mn may have some chronological signicance. In contrast, Dietrich et al.413 analysed historical (17th century) ferrous ore and slag from the Sternmuehlenthal valley near Chemnitz, Germany, by several complementary techniques, including EDXRF, and found that the iron ore was processed locally. Goldmann et al.414 followed a popular forensic application in the XRF analysis of glass fragments for classication and discrimination. Micro-XRF has an important role to play in this work. Rendle and Taylor415 discussed EDXRF methods for the determination of heavy elements in toxicological samples including foodstuffs and urine samples. Finally, in this section, Hida and Mitsui416 described the application of multivariate analysis to forensic science samples, including the classication of counterfeit coins based on XRF data. J. Anal. At. Spectrom., 1999, 14, 17731799 1787

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9.6 Industrial Once again, the essential contribution made by XRF in industrial laboratories is demonstrated by the wide range of published papers available this year. Beginning with the analysis of raw materials, Arikan et al.417 used EDXRF incorporating a 109Cd source for quality control in the iron ore dressing process, samples being prepared as conventional powder pellets made by mixing the sample with cellulose. A similar procedure, based on WDXRF, was used to determine Nb and Th in ore samples from a benefaction process by Chang and Guan.418 Mzyk et al.419 used XRF to determine Ag and Cu in slags from rening and slimes from copper electro-rening. After dissolving the samples in nitric acid (ammonium acetate solution for high Pb samples), XRF and ICP-AES were used to determine Pb in the ltrate and XRF was used to analyse the residue recovered after ltration. Combined XRFXRD instrumentation is often used in the cement industry, but extending the range of applications, Baumgartner and Yellepeddi420 described its application for process and quality control in the heavy mineral sands industry, in particular in the analysis of samples from the mineral separating plants, titanium slags, through to the nal product, rutile. Turning now to iron and steel, Magallanes and Vazquez421 employed EDXRF for the automatic classication of steels based on the determination of 12 relevant elements and using a data processing technique based on articial neural networks. Unusually, for any branch of science, 100% accuracy in classication was claimed for this technique. Tano and colleagues422 claimed a patent for a sampler designed to offer a rapid analysis capability for steel slugs oating over molten steel. After removal of the sample from the molten steel, the slug was analysed by XRF. Ti and Mo were measured in special steels and alloys using WDXRF by Hasany et al.423 A multivariable regression procedure was employed and the technique had the capability of determining Ti down to 120 mg g21 and Mo down to 350 mg g21. In the analysis of other metallurgical samples, copper alloys were investigated by XRF (Luo et al.158). The authors determined Cu, Fe, Pb and Mo and evaluated three partial least-squares regression procedures for their ability to predict the inuence of noise on the accuracy of results. The conclusion was that partial least squares with single component prediction gave the best accuracy and stability in the analysis of copper alloys. Kitamura et al.,424 in a Japanese language publication, used a combination of XRF and XRD to characterize inclusions in aluminium. A sample of aluminium was melted, then ltered through a porous aluminium lter. Metallic aluminium in the residue was dissolved in a brominemethanol solution and the inclusions retained on the membrane lter and analysed. Corundum, a-quartz and a range of metallic elements at ng g21 levels were all detected. Process control in the cement industry regularly features in this section and this year is no exception. Both Yellepeddi and Bonvin425 and Uhlig et al.426 offered analytical overviews from a manufacturer's perspective and Yellepeddi and colleagues continued to promote the combined XRF/XRD analysis of clinkers (containing about 1.6% m/m free lime), cement and samples from the mining industry, the free-lime content of clinker also being considered in another paper.427 Duer428 described a bench top EDXRF instrument incorporating a Si PIN detector designed for the analysis of the raw material feed of cement kilns and Potgieter and Horne429 evaluated the capabilities of XRF, ordinary and potentiometric titrations and ion selective electrodes for the determination of chloride in cement, although since this paper was written in Afrikaans, it was presumably aimed specically at a South African audience. The reader's attention is also drawn to some interesting cement sampling and analysis developments listed in the on-line section. 1788 J. Anal. At. Spectrom., 1999, 14, 17731799

XRF also has an important role to play in the glass and ceramic industries. Process and quality control in the glass industry were considered in two publications,430,431 the latter describing the role of combined WD/EDXRF instrumentation. The challenging determination of light elements, specically boron in glass, was discussed by Van Sprang and Bekkers,432 who compared the merits of two XRF-based techniques. One method used the direct determination of B Ka with a fundamental parameter quantication. Calibration required some care as the fundamental parameters depended on the chemical environment of B. The second method was based on the use of the Compton scatter intensity to quantify the unanalysed light fraction in an otherwise quantied matrix. Although no matrix-dependent calibration was required for this method, it was not sufciently sensitive for samples below 4% m/m B2O3. A systematic procedure for the preparation of calibration standards for the XRF analysis of ceramics was described by Ochandio-Cardo et al.155 The procedure was designed to optimize the composition of a set of calibration samples, taking into account elements and concentration ranges, potential interference effects and the opportunity to mix metal oxides, salts and certied reference materials. Turning now to the coal, petroleum and nuclear industries, a European Community report433 described the use of ten standard wet chemical methods (principally national methods) for the determination of sulfate, pyrite and total sulfur and/or organic sulfur in 7 coals and 2 cokes. Whereas all methods gave broadly acceptable results, 2 XRF methods based on standard additions proved to be unsatisfactory: a rare failure of the XRF technique? EDXRF was more successful in the analysis of coals using a standard additions procedure, as described by Heimburger et al.434 Lead in gasoline was measured by EDXRF in a Polish contribution from Jelen and Krasodomski435 and the elements Ni, S and V were determined in petroleum by Komine and Tomoike.436 Sulfur in fuels was also an application described by Daucik et al.,437 EDXRF being used to advantage. Considering now the analysis of nuclear fuels, Mudher438 reviewed the use of X-ray methods for the determination of Pu and U. An interesting method for the determination of total U in solution was described by Dewberry.439 The method involved exciting U by adding a mCi quantity of 109Cd to the sample solution and measuring the U L-line uorescence emission. The method was demonstrated on synthetic U samples over the concentration range 115 g l21 and a method for correcting sample self-absorption effects was included. Morel and colleagues440 evaluated methods for measurement of uranium enrichment by recording emissions from 235U, 238U and X-ray uorescence induced within the sample by radiation w100 keV. And nally, the role of several techniques, including XRF, in characterizing plutonium for the purposes of international security, stock-pile stewardship and the characterization of mixed oxide fuels were discussed in a conference presentation by Mahan et al.441 XRF has also contributed to an astonishing variety of other industrial applications including: the analysis of drugs;442 cigarettes widely smoked in Kenya and cigarette ash443 in which it was reported that signicant quantities of As, Ga and Se were ingested during smoking; beauty creams also sold in Kenya,444 where concern was expressed about the Hg content of some of the samples; anionic surfactants and other inorganic ingredients of laundry detergent products,445 where the interest lay in determining alkylbenzene sulfonates, alkyl sulfonates, zeolite, phosphate, silicate and sulfate. XRF was also used in the determination of Mn in a dye, FD&C Blue No 1,446 deposits of aluminium hydroxide and alumsodium aluminate found in the paper-making process,447 iodine in iodized salt448 and wear metals in lubricating oil.449 X-ray uorescence was also applied in the jewellery industry. Marucco and Stankiewicz450 developed an XRF method for the determination of gold in jewellery, the elements determined

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being Ag, Au, Cu, Ni, Pd and Zn. The technique, which incorporated a mathematical matrix correction procedure, was compared with other techniques and considered to offer advantages in the range of jewellery grades that could be analysed against a single calibration. Nguyen and Pham451 applied radioisotope XRF to an analysis of natural rubies from Vietnam and in addition to distinguishing sources, found a correlation between colour of the gemstone and Cr content. A couple of Chinese language publications452,453 described the application of XRF to the analysis of gold-plated jewellery and white carat gold jewellery, respectively. A diverse range of reports has also appeared covering the application of XRF to various inorganic materials of industrial interest. Takahashi and colleagues454 developed a new method for the determination of the REE in REE oxides and single crystals of REE hexaborides from the respective K-line spectra. Instrumentation was based on EDXRF. REE K-lines were also measured by Yan et al.,455 using 241Am excitation and a highpurity germanium detector. The technique was applied to the determination of the REE in HCl solution from separation processes and also REE loaded organic phases. In a similar solvent extraction application, Ravindra et al.456 used XRF to determine Hf in Zr process stream samples. A particular consideration was the choice of a Ge(111) crystal to avoid second order spectral interferences. Franca and colleagues457 determined La and Y in zirconium dioxide ceramic material using HPLC, XRF and INAA techniques, the XRF contribution being the determination of Y. Bai et al.458 published an extensive Chinese language review of REE techniques and Kim et al.459 considered the development of reference materials for the XRF analysis of lead titanate zirconate. In a conference presentation, Posey460 described the benets of WDXRF in a range of applications in the semiconductor industry. Turning now to the XRF analysis of organic-based materials, Van Dalen461 used WDXRF to measure P and S in edible oils and fats. Samples were analysed in disposable liquid cells after solidication with 15% stearic acid and the detection limit for both these elements was reported to be 2 mg kg21. Smagunova et al.462 reviewed the advantages and disadvantages of different XRF methods for the elemental analysis of petroleum and petrochemical products, organometallic and high molecular weight compounds and medicines. Particular attention was paid to sample preparation techniques and methods of calibration. Bledzki and Kardasz463 discussed the role of XRF, as well as X-ray absorption spectrometry and infrared techniques, in the sorting of plastics for recycling of wastes. These and other industrial applications are also covered in the companion comprehensive ASU review of industrial analysis.464 9.7 Clinical and biological During the last two decades, the in-vivo XRF determination of lead in bone has been extensively used for monitoring exposure to leaded gasoline, water, paint and industrial emissions. Skerfving et al.,465 related the accumulation of Pb in nger bone to both time of exposure and blood lead. Similarly, Bergahl et al.466 compared occupational lead exposure in tibial and calcaneal bone with levels in blood plasma and whole blood from active workers. Adolescents living in urban areas were studied by Farias et al.467 Hernandez-Avila et al.468 reported on the contribution of lead mobilized in bone to plasma in environmentally exposed adults. Akyuz et al.469 used radioisotope EDXRF analysis for the determination of other analytes in bone. Calcium, P and Sr levels in a control group were found to be higher than those in tuberculous-arthritis patients, whereas the concentrations of Ba, Ce, La and Zn were no different. O'Meara et al.470 used a 1 mCi 57Co source to excite U in bone. However, the estimated detection minimum of 20 mg g21 may not be sufciently

sensitive for use in monitoring occupational exposures. Cadmium and Pb levels were measured by Gerhardsson et al.471 using in vivo XRF to assess kidney function in active and retired smelter workers. Essential and toxic trace elements in teeth were estimated by Zaichick and Ovchjarenko472 in an in vivo study of Ca, Pb, Sr and Zn in frontal teeth enamel. Bloch et al.473 irradiated shed teeth with 122 and 136 keV gamma rays from a 5 mCi 57Co source to assess the Pb levels in children living in Beijing and industrial sites in the Urals, as compared with those children living in urban locations in the USA. Reiners et al.474 used 241Am to determine the thyroidal iodine content of women between the ages of 20 and 40 years. Other measurements on body tissues included Ali et al.475,476 working at the Swansea In Vivo Analysis and Cancer Research Group, who used a plane polarized XRF conguration for the in vivo determination of Pt in head and neck tumours. A minimum detection limit of 5.6 mg g21 for Pt derived from chemotherapeutic agents was reputed to be the most sensitive in vivo XRF system to date. Sam et al.477 used XRF to determine traces of Ca, Cl, Co, Cr, Cu, Fe, K, Mn, Mo and Zn in human milk. A calibration for the determination of Zn in dry, nely divided hair was developed by Bolormaa et al.,478 based on measurements using synthetic reference samples. Laursen et al.479 reported the analysis of autopsy liver tissue samples from the Greenland Inuit population in comparison with Danes. Part 1 of their work concerned the measurement of Br, Cl, K and S, for which the Inuit data were on average lower than that of the Danes. A comparison between trace levels of Br, Cu, Fe, Rb, Se and Zn in normal and cancer inoculated mice by both XRF and PIXE was reported by Feldstein et al.480 The study was conducted on samples of blood, liver, kidney, colon and skin. Carvalho et al.481 collected human tissues of bone, hair, liver and kidney from 61 individuals (postmortem) to study levels of As, Cu, Fe, Mn, Pb, Rb, Se, Sr and Zn and apply the Pearson correlation matrix to investigate the correlation between the concentrations of these elements with respect to age. Zaichick482,483 compared three methods of estimating extracellular water by the determination of the `corrected bromine space'. The body uids analysed included plasma from venous blood, nger blood and non-stimulated saliva. Olszowy et al.484 related the age, gender, weight, height and locality of donors from measurements of Br in blood. Borjesson et al.485 published a review of in vivo studies using XRF with particular emphasis on the determination of Cd, Hg and Pb. Monte Carlo computer simulation studies for in vivo XRF analysis were reported by a number of workers during this review period. Lewis et al.486 from the Swansea Group used the technique to aid the design and optimization of their polarized source. O'Meara et al.487 applied the Monte Carlo simulation to measurements of Pb and U in bone. Two papers were published by Ao et al.488,489 on the application of the Monte Carlo code CEARXRF, again for the in vivo XRF analysis of Pb in bone. Hugtenburg et al.490 developed a program to model the measurement of cisplatin uptake by in vivo XRF for the `EGS4' Monte Carlo system with extensions to allow for linear polarization and multiple element uorescence. Other biological applications included the work of Angeyo et al.,164 who published a semi-empirical method for improved trace multi-element determination in organic matrices based on 109 Cd radioisotope EDXRF. Akyruz et al.491 studied trace levels of Ba, Br, Ca, Ce, Cu, Fe, I, La, Mn, Rb, Sr and Zn in rainbow trout. Nozaki and Makita99 reported on the detection of various elements in major tissues of silky fowl. Cahill and colleagues492 compared XRF and PIXE for the X-ray analysis of feathers. An investigation of inorganic contents of some diuretic pharmaceutical herbs growing in Turkey was reported by Efe and Yilmaz,493 who used the XRF emissiontransmission technique. Vlachos et al.494 carried out a survey of J. Anal. At. Spectrom., 1999, 14, 17731799 1789

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concentrations of selected metals in seaweeds. The accumulation of Ca, Cu, Fe, K, Mn, Ni, Rb, Sr and Zn in the annual rings of Scots pine trees in the vicinity of a coppernickel smelter was determined by Larsson and Helmisaari.495 Stikans et al.496 reported on an improved technique for quantitative EDXRF analysis of powdered plant materials. Gao et al.498 published a method for the determination of Cu, Fe, Sr and Zn in liquorice by XRF. 9.8 Thin lms Developments in both techniques and their applications are presented in this review to emphasize the increasing use of XRF in the analysis of thin lms, multilayers and coatings. Cesareo et al.499 published some interesting studies in the use of EDXRF for the analysis of thin and intermediate thickness environmental samples. This study included the analysis of algae, microalgae and marine sediments prepared as thin lms as well as the determination of the S concentration on a mural painting in a church in Rome to provide an index of degradation. Lead was also monitored in urban air samples to produce a map of its distribution. Thin layer sample preparation techniques were described by Kyotani and Iwatsuki500 in their method for simultaneous determination of elements in vehicle exhaust particulates and atmospheric dusts. Kaufmann et al.501 reported on attempts to extend the fundamental parameter approach to the analysis of single layer lms made of carbon and silicon nitride, single layer lms of cobalt plus oxygen matrices and complex multilayer structures made of C, Cu and Pd. Composition and thickness determination were the subjects of work by Sammelselg and colleagues,502 who compared different programmes and methods for thin oxide lms. Barrea et al.503 determined the absolute mass thickness of thin foils and Belyaeva et al.504 assessed ion-plasma spray coatings. Other applications included work by Jurczyk et al.505 on the analysis of Cd, Cu, Cr, Ga, Ni, Se and Zn in mono- and polycrystal microsamples by a thin layer method. The team at the University of Sassari506 also published a method for forward EDXRF analysis of thin and intermediate samples with three main advantages identied over normal XRF. Finally, scanning from a variable glancing angle with X-ray photons or accelerated ions for excitation was used by Krasnolutskii and Blokhin507 in a study of sensitivity in thin lm analysis. 9.9 Chemical state analysis and speciation studies A survey of novel X-ray analysis methods was published by Kawai,508 whose research group at Kyoto University has used ve instrument congurations to further their work on chemical state analysis. The Kyoto group509 used monochromatized synchrotron radiation as primary excitation in the study of F Ka spectra of MnF2. A high-resolution X-ray crystal diffraction spectrometer was used by Kuchler et al.510 to study the line width of Ka1,2 in the solid state 3d elements. Xiao et al.511 reported on the possible use of EDXRF to discriminate different chemical states by partitioning the measurement time of the Si(Li) detector into many sub-divisions using a statistical data processing procedure. Work in the soft energy X-ray region included several papers devoted to the K spectrum of carbon. Okotrub and Bulusheva512 studied fullerene compounds using the `PM3' method. Yamada et al.513 measured the C K spectra of mechanically alloyed powders prepared from niobium, tungsten and graphite using EPMA. Kaneyoshi et al.514 used the molecular orbital calculation method in the study of graphite K-V X-ray emission spectra. Kim and colleagues515 calculated the anisotropic C K X-ray emission of carbon (graphite, diamond) and related materials. 1790 J. Anal. At. Spectrom., 1999, 14, 17731799

Studies at Andhra University by Visakhapatnam generated two papers related to satellite spectra for this review. Reddy et al.516 concentrated on the K X-ray satellite spectrum of Mg, whereas Rao et al.517 studied P Ka L1/Ka L0 ratios. Uda et al.518 reported on the theoretical intensity distribution of K X-ray satellite spectra emitted from K and Cr. Photons were used by Murty et al.519 to excite the K X-ray satellite spectrum of Ca in a LiF(200) plane crystal spectrometer. Two papers were published on the L emission spectra and satellites of W by workers in the Institute for Chemical Research, Kyoto University;520,521 the t residuals of La and Lb spectra indicated the presence of satellites in the vicinity of each spectrum which were generated from CosterKronig transitions. Studies by Polasik and colleagues522 were carried out on all 3d transition metals to explain the dependence of Kb to Ka Xray intensity ratios on the changes in congurations of valence electrons. Holzer et al.523 concentrated on Ca, Cr, Cu, Fe, Mn and Ni using a single-crystal diffractometer optimized for minimal instrumental broadening. Buyukkasap524,525 reported on the effect of alloying on the Ka and Kb XRF cross-sections in CrxNi12x and CrxAl12x alloys. Kb to Ka X-ray intensity ratios of Cr, Fe, Ti and V were measured in pure metals and CrB, CrB2, FeB, TiC and VC by Raj et al.526 Using the multiconguration DiracFoch calculation, signicant changes were found in the 3d electron population of Cr in CrB and CrB2 and Ti in TiC from their pure metal values, whereas no change was found for Fe in FeB and V in VC. Raj and colleagues527 also published similar work on Cu and Ni in various silicate compounds. The nature of Mn oxidation states in photosystem II concentrated the minds of Bergmann and colleagues528 in a study of the mechanism of oxygen evolution by photosynthesis. Other applications included work by Leiro and Heinonen530 on Ka1.2 X-ray emission spectra of KCl as well as metallic Ca, Fe and K. A DoniachSunjic type line shape was used to nd Lorentzian tails for the spectra. Chemical effects on La : Lb intensity ratios of Ba, Co and La were studied by Baydas et al.,531 with experimental values compared with theoretical values of pure elements. To complete this paragraph, your reviewer returned to another published work from the Kyoto group,532 where extended ne structure in characteristic XRF was demonstrated for Al. The radiative Auger effect K-LL line at 11001400 eV with an oscillating structure between 1250 and 1350 eV was used to calculate interatomic distance. A timely introduction to speciation studies may be found in a German language paper by Floch et al.533 on the analytical advantages of XRF and soft X-ray spectrometry for speciation studies. Three examples were offered: Zn in scrap from the automotive industry containing Zn, ZnO and ZnFe2O4; the detection of Al2O3 and AlN in low alloy steels and CrVI in solutions using Cr Lb1 and Cr La1,2 lines. Readers with particular interest in the latter example can refer to Pappert's paper,534 this time in English. Speciation and preconcentration of CrIII and CrVI in waters by retention on ion exchange media and determination by EDXRF was presented by MenendezAlonso et al.535 A partnership of EDXRF and ICP-AES was used by Somogyi et al.394 to investigate speciation of elements in lake sediments. The chemical compositions provided information on environmental processes which changed soil and vegetation during sediment accumulation. McDonald et al.536 analysed PM2.5 emissions from residential wood combustion and meat cooking to construct specic proles for use in the chemical mass balance model for the apportionment of ne particle sources. Vanadium speciation by EDXRF was studied by Kallithrakas-Kontos and Moshohoritou537 using the K-L2,3 and K-M2,3 lines. In closing this year's review, we should like to acknowledge the contribution made by Mike Holmes to previous reviews in this series.

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