1、BSI Standards Publication PD ISO/TS 18507:2015 Surface chemical analysis Use of Total Reflection X-ray Fluorescence spectroscopy in biological and environmental analysisPD ISO/TS 18507:2015 PUBLISHED DOCUMENT National foreword This Published Document is the UK implementation of ISO/TS 18507:2015. Th
2、e UK participation in its preparation was entrusted to Technical Committee CII/60, Surface chemical analysis. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provisions of a contract. Us
3、ers are responsible for its correct application. The British Standards Institution 2015. Published by BSI Standards Limited 2015 ISBN 978 0 580 81543 0 ICS 71.040.40 Compliance with a British Standard cannot confer immunity from legal obligations. This Published Document was published under the auth
4、ority of the Standards Policy and Strategy Committee on 31 July 2015. Amendments issued since publication Date Text affectedPD ISO/TS 18507:2015 ISO 2015 Surface chemical analysis Use of Total Reflection X-ray Fluorescence spectroscopy in biological and environmental analysis Analyse chimique des su
5、rfaces Utilisation de rflexion spectroscopie des rayons X de fluorescence totale dans lanalyse biologique et de lenvironnement TECHNICAL SPECIFICATION ISO/TS 18507 Reference number ISO/TS 18507:2015(E) First edition 2015-07-15PD ISO/TS 18507:2015ISO/TS 18507:2015(E)ii ISO 2015 All rights reserved CO
6、PYRIGHT PROTECTED DOCUMENT ISO 2015, Published in Switzerland All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet,
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8、w.iso.orgPD ISO/TS 18507:2015ISO/TS 18507:2015(E)Foreword v Introduction vi 1 Scope . 1 2 Normative references 1 3 Terms, definitions, symbols, and abbreviated terms . 1 3.1 Terms and definitions . 1 3.2 Symbols and abbreviated terms. 2 4 Background 2 4.1 Preliminary remarks 2 5 Instrumentation 4 5.
9、1 Instrumental requirements 4 5.1.1 X-ray sources of radiation 4 5.1.2 Monochromator 5 5.1.3 Detector . 5 5.1.4 Sample station 6 5.1.5 Critical and glancing angle 6 5.2 Quality control of TXRF spectrometer 7 5.2.1 Stability check of X-ray beam 7 5.2.2 Spectroscopic resolution 7 5.2.3 Energy calibrat
10、ion 8 5.2.4 Sensitivity test 8 6 Specimen preparation 8 6.1 Preliminary remarks 8 6.2 Sample carriers . 9 6.2.1 Choice of sample carriers . 9 6.2.2 Cleaning procedure for sample carriers 9 6.3 Sample treatment procedures for chemical analysis by TXRF .10 6.3.1 Liquid samples 10 6.3.2 Solid samples .
11、12 6.3.3 Preparation of the Internal Standard solution 13 7 Data Collection and Storage .14 7.1 Preliminary remarks .14 7.2 Data collection 14 8 Data Analysis .14 8.1 Qualitative analysis 14 8.2 Quantitative analysis .14 8.2.1 Preliminary remarks .14 8.2.2 Background correction 14 8.2.3 X-ray intens
12、ities of each element 15 8.2.4 Experimental derivation of relative sensitivities 15 8.2.5 Quantification by means of internal standard .15 8.2.6 Statistical treatment 16 9 Information required when reporting TXRF analysis 16 9.1 Preliminary remarks .16 9.2 Experimental details .16 9.3 Analysis proce
13、dures 17 Annex A (informative) Comparison of detection limits of TXRF, AAS, and ICP-MS 18 Annex B (informative) Case studies of TXRF analysis for environmental applications .21 Annex C (informative) Case studies of TXRF analysis for biological applications24 ISO 2015 All rights reserved iii Contents
14、 PagePD ISO/TS 18507:2015ISO/TS 18507:2015(E)Annex D (informative) Theoretical derivation of relative sensitivity factors .27 Bibliography .29 iv ISO 2015 All rights reservedPD ISO/TS 18507:2015ISO/TS 18507:2015(E) Foreword ISO (the International Organization for Standardization) is a worldwide fede
15、ration of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that commi
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17、d those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordance with the editorial rules of the ISO/IEC Directives, Par
18、t 2 (see www.iso.org/directives). Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of any patent rights identified during the development of t
19、he document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents). Any trade name used in this document is information given for the convenience of users and does not constitute an endorsement. For an explanation on the meaning of ISO specific t
20、erms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT), see the following URL: Foreword Supplementary information. The committee responsible for this document is ISO/TC 201, Surface chemical an
21、alysis. ISO 2015 All rights reserved vPD ISO/TS 18507:2015ISO/TS 18507:2015(E) Introduction Total Reflection X-Ray Fluorescence (TXRF) spectroscopy is a reliable technique for chemical analysis. TXRF today is employed in electronic industry quality control. TXRF is also a powerful multi-elemental me
22、thod for trace and ultra-trace analysis of different kind of samples that can be grouped as follows: environmental samples (as water, soil, aerosols, deposits, plants), geological and mineralogical samples (as ore, crystals, mineral raw materials), technological samples (as petroleum and petroleum p
23、roducts, thin films, wastes, metals, polymers), biological samples (as blood, serum, urine, human tissue), food samples (as fish, fruit, meat, nuts, mushroom), pharma and biomedical samples (as pharmaceuticals, cell culture media), archaeological, art, and forensic samples. Sample preparation is cri
24、tical for the quantitative analysis and depends on the sample and its aggregate state. Because of its capability to analyse different kinds of samples, TXRF is suitable for chemical metrology at the nanoscale, both for heavy metals and light elements in environmental and biological analysis. The key
25、 advantages of TXRF are the following: a) simultaneous multi-element trace analysis including halogenides; b) analysis of very small sample amounts (lower than nanograms to microgram range depending on sample preparation and condition); c) simple quantification using an internal standard and possibi
26、lity of reference-free quantification; d) suitable for various sample types and applications; e) theoretically low matrix or memory effects; f) relatively short time is required for measurement collection; g) high-sensitivity, low-detection limits depending on sample (elements) matrix, preparation m
27、ethod, and instrumentation.vi ISO 2015 All rights reservedPD ISO/TS 18507:2015Surface chemical analysis Use of Total Reflection X-ray Fluorescence spectroscopy in biological and environmental analysis 1 Scope This Technical Specification provides a framework on the uses of Total Reflection X-Ray Flu
28、orescence (TXRF) spectroscopy for elemental qualitative and quantitative analysis of biological and environmental samples. It is meant to help technicians, biologist, doctors, environmental scientists, and environmental engineers to understand the possible uses of TXRF for elemental analysis by prov
29、iding the guidelines for the characterization of biological and environmental samples with TXRF spectroscopy. Measurements can be made on equipment of various configurations, from laboratory instruments to synchrotron radiation beamlines or automated systems used in industry. This Technical Specific
30、ation provides guidelines for the characterization of biological and environmental samples with TXRF spectroscopy. It includes the following: (a) description of the relevant terms; (b) sample preparation; (c) experimental procedure; (d) discussions on data analysis and result interpretation; (e) unc
31、ertainty; (f) case studies; and (g) references. 2 Normative references No normative references cited in this document. 3 Terms, definitions, symbols, and abbreviated terms 3.1 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1.1 sample carrier fla
32、t substrate where the specimen is deposited Note 1 to entry: The reference surface corresponds to the flat surface of the sample carrier, where the residue lays. The most important feature of the sample carrier is to be a reflector/mirror for X-rays. Surface roughness, matrix, and contamination of t
33、he sample carrier have an impact on TXRF measurements. 3.1.2 residue specimen that lays on the sample carrier to be measured TECHNICAL SPECIFICATION ISO/TS 18507:2015(E) ISO 2015 All rights reserved 1PD ISO/TS 18507:2015ISO/TS 18507:2015(E) 3.2 Symbols and abbreviated terms ppm concentration in part
34、 per million range ppb concentration in part per billion range MW Microwave used to describe the method of digestion (acidic MW digestion) APDC Ammonium pyrrolidine dithiocarbamate MIBK Methyl isobutyl ketone AAS Atomic Absorption Spectroscopy GF-AAS Graphite Furnace Atomic Absorption Spectroscopy I
35、CP-MS inductively coupled plasma-mass spectroscopy IS internal standard INAA Instrumental Neutron Activation Analyses LPME liquid phase microextraction procedure FWHM full width at half maximum IR infrared QC quality control SR Synchrotron radiation XRT X-ray tube XSW X-ray standing wave 4 Backgroun
36、d 4.1 Preliminary remarks TXRF is a surface elemental analysis technique often used for ultra-trace analysis of particles, residues, and impurities on smooth surfaces. TXRF is currently a key tool for wafer surface contamination control in semiconductor chip manufacturing. In the TXRF experiment, th
37、e monochromatic X-ray beam impinges on the sample holder carrying the sample at very small angle, causing total reflection of the beam. The glancing beam angle shall be below the critical angle of X-ray total reflection, differently from XRF method, where both the glancing beam and the detection ang
38、le are at 45. 1Figure 1 shows XRF and TXRF geometries.2 ISO 2015 All rights reservedPD ISO/TS 18507:2015ISO/TS 18507:2015(E) Key 1 X-ray generator 2 energy dispersive detector 3 irradiated sample area Figure 1 a. XRF conventional instrumental geometry: X-ray incident beam angle and fluorescence dete
39、ctor angle are 45 with respect to the sample surface; b. TXRF instrumental geometry: X-ray incident beam angle is near to 0 and detector position is 90 with respect to the sample surface. 2 Due to the low glancing beam angle, in TXRF the detector can be arranged close to the sample leading to a high
40、er fluorescence yield with respect to the conventional XRF geometry. The monochromatic X-ray beam illuminates the sample and it is totally reflected. The great inherent advantage of TXRF is the double excitation of the sample by both the primary and the reflected beams, leading to a doubling in the
41、fluorescence intensity. TXRF detection limits are comparable or better of those that can be obtained by FAAS, while the former technique is more sensitive in terms of total sample amount. 1Table A.1 and Table A.2 show the comparison of the detection limits of TXRF, AAS, and ICP analysis of environme
42、ntal and biological samples, respectively. An advantage of TXRF over AAS and ICP-OES and ICP-MS is the possibility to detect halogenides. TXRF can be used to perform qualitative and quantitative multi-element analysis. For quantitative analysis, an internal standard, i.e. an element absent in the sa
43、mple (for example, V, Sc, Ga, Ge, Se, Y, or Co), is added to the sample aliquot. Reference free TXRF analysis for quantification and qualification is technically possible and has been proposed several times and is employed at some facilities. Resulting benefits of TXRF are significantly reduced back
44、ground noise and matrix effects. In addition, a sample preparation procedure without digestion allows more accurate analysis of some volatile elements, as Hg, As, or Se, which can be reduced by the sample preparation. Table 1 shows a comparison of some characteristics of TXRF, AAS, and ICP-MS. Light
45、 elements (Z 11) are not detected efficiently with commercial spectrometers because their fluorescence signals are absorbed before detection. However, using the vacuum chamber spectrometer, the proper excitation energy (e.g. Cr-Ka, Rh-L.), and the suitable detector with Ultra Thin window, the detect
46、ion down to Carbon is possible. The detection limits for specific element depend on the X-ray tube. For example, by using Mo X-ray tube, only the L-lines of some elements (such as Cd, Sn or Sb) can be detected. Because of the low energy of L-lines and their possible overlapping with K-lines of Cl, K
47、, and Ca, the quantitative analysis for these elements is not reliable. ISO 2015 All rights reserved 3PD ISO/TS 18507:2015ISO/TS 18507:2015(E) Table 1 Comparison between TXRF, AAS, and ICP-MS Property TXRF AAS ICP Technique used Non-destructive technique Destructive technique (digestion required) De
48、structive technique (digestion required) Calibration Single-standard calibration (internal) Multi-standard calibration (external) Multi standard calibration (external) Sample presentation solutions, suspensions, particles, thin films solutions a solutions a Multi-element analysis Yes Sequential only
49、 Yes Digestion procedure Not necessary Yes Yes aGF-AAS and LA-ICPMS allow the analysis of solid samples for special applications. 5 Instrumentation 5.1 Instrumental requirements The TXRF spectrometer consists of the following: sources of X-ray radiation like high-voltage generator and X-ray tubes or synchrotron radiation; a spectral modification element like a monochromator or a cut-off reflector, if necessary; sample station for handling the sample carrier; energy-dispersive detector; data acquisition unit. Wavele
