Analytical atomic spectrometry_with_flames_and_plasmas_-_jose__258___a._c._broekaert

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Analytical atomic spectrometry_with_flames_and_plasmas_-_jose__258___a._c._broekaert

  1. 1. ÂAnalytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic) Â Jose A. C. Broekaert Analytical Atomic Spectrometry with Flames and Plasmas
  2. 2. Â Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic)Analytical Atomic Spectrometry withFlames and PlasmasValeur, B.Molecular Fluorescence. Principles andApplications2001. ISBN 3-527-29919-XGnzler, H. and Williams, A. uHandbook of Analytical Techniques2001. ISBN 3-527-30165-8Hbschmann, H.-J. uHandbook of GC/MS2001. ISBN 3-527-30170-4Welz, B. and Sperling, M.Atomic Absorption SpectrometryThird, Completely Revised Edition1998. ISBN 3-527-28571-7
  3. 3. Â Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic) ÂJose A. C. BroekaertAnalytical Atomic Spectrometry withFlames and PlasmasWeinheim ± New York ± Chichester ± Brisbane ± Singapore ± Toronto
  4. 4.  Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic)  Prof. Dr. Jose A. C. Broekaert Typesetting Asco Typesetters, Hong Kong È Universitat Leipzig Printing betz-druck gmbH, D-64291 È Institut fur Analytische Chemie Darmstadt  Linnestraûe 3 Bookbinding Wilhelm Osswald & Co., 67433 04103 Leipzig Neustadt Germany ISBN 3-527-30146-19 This book was carefully produced. Nevertheless, author and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for A catalogue record for this book is available from the British Library. Die Deutsche Bibliothek ± CIP Cataloguing-in-Publication-Data A catalogue record for this publication is available from Die Deutsche Bibliothek ( WILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany). 2002 All rights reserved (including those of translation in other languages). No part of this book may be reproduced in any form ± by photoprinting, micro®lm, or any other means ± nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not speci®cally marked as such, are not to be considered unprotected by law. Printed in the Federal Republic of Germany. Printed on acid-free paper.
  5. 5. Â Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic)To my wife Paula and our daughters Ilse,Sigrid and Carmen
  6. 6. Â Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic) vii Contents Preface xi Introduction 11 Basic Principles 41.1 Atomic structure 41.2 Plasmas 81.3 Emission and absorption of radiation 91.4 Ionization 181.5 Dissociation 231.6 Sources for atomic spectrometry 271.7 Analytical atomic spectrometry 312 Spectrometric Instrumentation 342.1 Figures of merit of an analytical method 342.2 Optical spectrometers 512.2.1 Optical systems 522.2.2 Radiation detectors 612.2.3 Non-dispersive spectrometers 702.3 Mass spectrometers 722.3.1 Types of mass spectrometers 732.3.2 Ion detection 802.3.3 Ion extraction 822.3.4 Ion optics and transmission 842.4 Data acquisition and treatment 843 Sample Introduction Devices 883.1 Sample introduction by pneumatic nebulization 903.2 Ultrasonic nebulization 1033.3 Hydride and other volatile species generation 1053.4 Electrothermal vaporization 1093.4.1 The volatilization process 1093.4.2 Types of electrothermal devices 111
  7. 7. viii Contents 3.4.3 Temperature programming 114 3.4.4 Analytical performance 115 3.5 Direct solids sampling 117 3.5.1 Thermal methods 117 3.5.2 Slurry atomization 120 3.5.3 Arc and spark ablation 124 3.5.4 Laser ablation 131 3.6 Cathodic sputtering 135 4 Atomic Absorption Spectrometry 148 4.1 Principles 148 4.2 Atomic absorption spectrometers 150 4.2.1 Spectrometers 150 4.2.2 Primary radiation sources 152 4.3 Flame atomic absorption 158 4.3.1 Flames and burners 159 4.3.2 Nebulizers 161 4.3.3 Figures of merit 162 4.4 Electrothermal atomic absorption 164 4.4.1 Atomizers 165 4.4.2 Thermochemistry 168 4.4.3 Figures of merit 169 4.5 Special techniques 172 4.5.1 Hydride and cold-vapor techniques 172 4.5.2 Direct solids sampling 174 4.5.3 Indirect determinations 175 4.5.4 Flow injection analysis 175 4.5.5 Diode laser atomic absorption spectrometry 176 4.6 Background correction techniques 177 4.6.1 Correction for background absorption with the deuterium lamp technique 177 4.6.2 Background correction with the aid of the Zeeman e€ect 179 4.6.3 Smith±Hieftje technique 182 4.6.4 Coherent forward scattering 183 4.7 Fields of application 184 4.8 Outlook 191 5 Atomic Emission Spectrometry 192 5.1 Principles 192 5.2 Atomic emission spectrometers 202 5.3 Flame emission 210 5.4 Arcs and sparks 210 5.4.1 Arc emission spectrometry 210 5.4.1.1 Arc characteristics 210
  8. 8. Contents ix5.4.1.2 Dc arc spectrometry 2115.4.1.3 Ac arc spectrometry 2135.4.2 Spark emission spectrometry 2135.4.2.1 Sparks 2135.4.2.2 Analytical features 2155.5 Plasma source AES 2165.5.1 Dc plasma-jet AES 2175.5.1.1 Types of plasma jets 2175.5.1.2 Three-electrode plasma jet 2185.5.2 Inductively coupled plasma AES 2195.5.2.1 The inductively coupled plasma 2195.5.2.2 Instrumentation 2215.5.2.3 Analytical performance 2235.5.2.4 Applications 2325.5.3 Low-power high-frequency plasmas 2335.5.4 Microwave plasmas 2345.6 Glow discharge AES 2415.6.1 Hollow cathodes for AES 2425.6.2 Furnace emission spectrometry 2435.6.3 Dc glow discharges with a ¯at cathode 2445.6.4 Rf glow discharges 2485.6.5 New developments 2495.7 Laser sources 2516 Plasma Mass Spectrometry 2546.1 ICP mass spectrometry 2556.1.1 Instrumentation 2556.1.2 Analytical features 2576.1.3 Applications 2686.1.4 Outlook 2726.2 Glow discharge mass spectrometry 2756.2.1 Instrumentation 2776.2.2 Analytical performance 2816.2.3 Analytical applications 2827 Atomic Fluorescence Spectrometry 2907.1 Principles 2907.2 Instrumentation 2937.3 Analytical performance 2958 Laser Enhanced Ionization Spectrometry 2978.1 Principles 2978.2 Figues of merit 3008.3 Analytical applications 301
  9. 9. x Contents 9 Sample Preparation for Atomic Spectrometry 302 9.1 Sample preparation in direct compact sample analysis 302 9.2 Grinding, sieving and compaction of powders 302 9.3 Sample dissolution 304 9.3.1 Wet chemical methods 304 9.3.2 Fusion procedures 304 9.3.3 Microwave-assisted methods 305 9.3.4 Combustion techniques 305 9.4 Flow injection analysis 305 9.5 Leaching sample preparation methods 306 10 Comparison with Other Methods 307 10.1 Power of detection 307 10.2 Analytical accuracy 309 10.3 Economic aspects 310 Literature 312 Index 348
  10. 10.  Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic) xiPrefaceSpectrochemical analysis is a powerful instrumental principle for the determina-tion of the chemical elements and their species in a variety of sample types of dif-ferent size, at widely di€erent concentration levels and with very di€ering costperformance ratios and time consumption. In addition, not only monoelement butalso multielement determinations are possible with widely di€ering precision andaccuracy using the various di€erent methods. The basic principles of spectro-chemical analysis are related to the atomic and molecular structure and also to gasdischarge physics as well as to instrumentation and measurement sciences. There-fore, research into spectrochemical analysis requires knowledge of the aforemen-tioned disciplines to enable innovative developments of new methodologies to beachieved in terms of the improvement of power of detection, accuracy and costperformance ratios, these being the driving forces in analytical innovation. Thedevelopment of analytical procedures also requires the analytical chemist to have aknowledge of the theory and the principles of the above mentioned disciplines. It isthe aim of this monograph to bring together the theory and principles of todaysspectrochemical methods that make use of ¯ames and plasma sources. This shouldenable researchers to enter the ®eld of spectrochemical research, where innovationis through the use and development of new sources and the application of newtypes of spectrometers, and also to face challenges from emerging ®elds of appli-cation, which is as straightforward today as it was even in the time of Bunsen andKirchho€. This work should appeal both to chemists and physicists, the coopera-tion of whom is instrumental for progress to be made in this ®eld of analyticalchemistry as well as to users from di€erent areas of science, including the lifesciences, material sciences, environmental sciences, geochemistry, chemical pro-cess technology, etc. This present work could also be viewed as a resume of thetheoretical background, which manufacturers of instrumentation for atomic ab-sorption spectrometry, arc, spark and glow discharge emission spectrometry as wellas ICP emission spectrometry and plasma mass spectrometry with ICPs or glowdischarges and laser based techniques can recommend to their interested users tomake the most ecient use of these analytical methods in their respective ®elds ofapplication. Also research associates entering the ®eld of atomic spectroscopy with¯ames and plasmas should ®nd the necessary basics and references to further litera-ture in this book.
  11. 11. xii Preface The work also describes a number of achievements of over thirty years of re- search performed at the University of Gent (Belgium), the Institute for Spec- trochemistry and Applied Spectroscopy (ISAS), Dortmund, the University of Dort- mund and the University of Leipzig, which have been made possible through many interactions and collaborations with experts in the ®eld, whom I thank thoroughly. A great deal of knowledge gained from my teachers and in interaction with prom- inent senior researchers in the ®eld worldwide and especially at the Council for Scienti®c and Industrial Research and the University of Stellenbosch (South-Africa), the Universitaire Instelling Antwerpen (UIA) (Belgium) and Indiana University, Bloomington (IN, USA) as well as results obtained while collaborating with col- leagues and with students made this book possible, for which all of them are gratefully acknowledged and thanked. Leipzig, June 2001 Â Jose A. C. Broekaert
  12. 12.  Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic)348 Index Index a dc plasma-jet 217 a two-level system 290 glow discharge 241€ AAS 307, 310 hollow cathode 242€ diode laser 148 inductively coupled plasma 219€ AAS with diode laser 156 AFS 310 Abel inversion 29 laser-excited 295 ablation 124 afterglow 216 arc 230 air operated CMP 235 arc and spark 124€ airborne dust 190, 243 spark 230 Al-based alloy 284 laser 230 Al2 O3 132 ablation device Al2 O3 ®lled column 230 spark 127 Al2 O3 powder 286 ablation rate 125, 140, 141, 144, 251 Al2 O3 122, see aluminium oxide abnormal characteristic 144 aluminum 187, 246 abnormal glow discharge 138 ambipolar di€usion 212, 224 absolute intensity 197 ampli®cation 197 absolute measurement 129 analysis absorbance 164 isotopic dilution 266 absorbance signal 163 analysis of microsample 161 absorption 9€, 11, 131 analysis time 126 absorption coecient 13, 181 analyte atom 149 absorption path 159 analyte introduction eciency 109 absorption pro®le 149, 176 analyte line absorption signal 167 physical width 148 absorption transition probability 17 analyte volatilization 113, 169 absorption volume 150, 166 analytical accuracy 309 abundance analytical atomic spectrometry 31 natural 266 analytical evaluation function 35, 197 accelerating voltage 76 analytical ®gures of merit 279 accuracy 201, 282 analytical line 149 acid concentration matching 185 analytical precision 125, 224 acid digestion 289 analytical sensitivity 169, 182 adiabatic expansion 255 anion exchange 271 adsorption 186 anode current 197 adsorption±desorption process 167 anode region 137 aerosol 90 anomalous Zeeman e€ect 154 aerosol droplet 104 Antartic ice 295 aerosol production eciency 104 APDTC complex 227 AES 193, 202 arc 2, 30, 31, 210
  13. 13. Index 349 characteristic 210 background correction 87, 151, 172, 204, disk stabilized 217 205, 222, 224 emission spectrometry 210€ background intensity 258arc ablation 124€ background spectral interference 284arc channel 125 Balmer series 4arc temperature 211 band emission 202, 215arrangement barrier-layer e€ect 82€ Mattauch-Herzog 257 bastnaesite 195ashing step 172 beam-stop 74associative ionization 242 Beer±Lambert law 14Aston dark space 137 Bessel box 256atmospheric particulate matter 286 binder 285, 303atmospheric pressure discharge 126 binning 69atom line bio-medical risk assesment 3 intensity 19 biological material 112, 305atom loss 167 biological sample 123, 168, 266, 270atom number density 241 biological substance 268atom reservoir 141, 291, 294, 299 black body radiation 17atom supply 167 blackening 62, 63atomic absorption 1 blank 47, 106, 200, 201atomic absorption spectrometry 32, 109, 112, sample 200 148€ ``blaze angle b 57 electrothermal atomization 87 blood 270 ¯ame 2 blooming 70 graphite furnace 2 boiling point 116, 229atomic emission 14, 32 Boissel switch 133 glow discharge 309 Boltzmann plot 26atomic emission spectrometry 192€ Boltzmanns law 9 arc 309 bond energy 139 spark 309 box-car integrator 295, 299atomic ¯uorescence 14, 33 brass 134, 252atomic ¯uorescence spectrometry 290€ Bremsstrahlung 18atomic species 4 broadband absorption 151atomic spectra 202 broadeningatomic spectral line Doppler 15€, 16, 157, 170 width 148 Lorentzian 15€, 16atomic spectrometry natural 15€, 16 diode laser 281 pressure 15€atomic structure 4€ resonance 15€atomic term 6 Stark 15€, 21atomic vapor 150 bulk analysis 246atomization step 169 bulk concentrationatomization temperature 166 major 282atomizer 150, 167 minor 282 graphite furnace 165 trace 282 cup 165 burn-in time 141, 245 ®lament 165 burner 159€autocollimation 207 air±acetylene 161axial viewing 227 nitrous oxide 161 multislit 159b burning crater 124, 141, 245background 260 magnetic ®eld 147background absorption 149 burning crater pro®le 143background correction procedure 177 burning gas 159
  14. 14. 350 Index burning gas mixture 159 chemical 188 burning spot 127, 143 chemical hydride generation 107 burning voltage 124, 125, 128, 136, 137, 144, chemical interference 163 241 chemical vapor deposition 115 w 2 test 48€, 49 c chip C, H, N, O analyzer 216 microstructured system 222 calibration chromatography function 34€ gas 230 standard addition 38€ liquid 99, 230 calibration constant 198 chromium 271 calibration curve 149 Cisplatin 288 calibration function 35, 84 clinical analysis 232 calibration function relate 197 clinical chemistry 187 capacity 214 cluster ion 258, 276 carbide 110, 118 CN band 159, 212 carbon arc 211 coated glass 248 carbon deposit 227 Co-based alloy 284 carbon-rod atomizer 111 coecient of variation 36 carbothermal reduction 166 coherent forward scattering 183€ cascade impactor 101 coincidence 224 catalyst 189 cold vapor 108 cathode cold-vapor technique 172, 173 ¯at 281 collector electrode 299 pin form 281 collision cathode current 197 the ®rst kind 138 cathode dark space 137 the second kind 138 cathode fall region 138 collisional decay 298 cathode fall 211 collisional±radiative model 242 cathode layer 137, 211 collisions of the ®rst kind 9€ cathode plume 276 collisions of the second kind 9€ cathodic sputtering 152, 175, 244 column chromatography 190 cavity combined analytical procedure 166 cathode 242 combustion 305 CCD 194, 204, 206, 209, 223, 251 compact ceramic 134 CCD detection 229 compact sample 123, 128 CCD detector 154, 200 compaction 303 CCD spectrometer 199, 213, 225 compromise condition 223 CCD 60, see charge coupled device concentric glass nebulizer 92 cement 188 concomitant 170, 173 ceramic 269 conductive sample 124 ceramic powder 121, 258 con®dence level 36 ceramic sample 286 contamination 186, 304 characteristic 62, 136, 137, 243, 245, 248, 251 continuous mode 133 abnormal 136 continuous sample aspiration 161 current±voltage 211 continuous sample nebulization 162 normal 136 continuous source 153, 183 characteristic concentration 162 continuous source AAS 153, 154 characteristic mass 171 continuum radiation 18, 172 charge coupled device 59, see CCD continuum source 151 charge injection device (CID) 68€ cool plasma condition 262 charge transfer 136, 220 cooled hollow cathode 243 charge transfer device 67, see CTD copper arc 213 charge-coupled device (CCD) 68€, 208 corona discharge 136
  15. 15. Index 351counter electrode 124, 127 detectioncoupling 7 phase-sensitive 294crater diameter 251 detection limit 182, 184, 201, 218, 223, 235,crater pro®le 145 237, 238, 243, 263, 277, 295, 296 rf discharge 146 ¯ame AAS 163, 169crater 133, 246 furnace AAS 169 depth 134 detection of the halogen 243 diameter 133 detectorcritical concentration ratio 224 spectral response 13cross-contamination 130 determinationcross-¯ow nebulizer 227 sequential 202cross section 8, 297 simultaneous 202crossed polarizers 183 deuterium lamp technique 177€crossed-dispersion 206 diatomic molecule 26crossed-dispersion mode 59 di€raction angle 207cryocooling 285 di€raction order 209cryopump 84 di€usion 167, 242CsCl 213 di€usion coecient 167CuaZn alloy 268 digestion under resistance heating 186current-carrying plasma 235 diode 66current modulated 156 diode AAS 149current±voltage characteristic 137, 141, 142 diode array 70cuvette 165, 173 diode-array 66Czerny±Turner monochromator 199 diode laser 154€ diode laser atomic absorption spectrometryd 176, see also diode laser AASD2 -lamp technique 178 dipole 186Daly±Multiplier 277 direct compact sample analysis 302dark current 45, 65 direct insertion probe 279data acquisition and treatment 84 direct sample insertion 89, 228, 229dc arc 10€ direct solids nebulizer 126 stabilized 212€ direct solids sampling 114, 117, 170, 174€,dc arc spectrography 213 230, 268dc discharge 124 discharge 2, 141dc glow discharge dielectric barrier (db) 281 with a ¯at cathode 244€ electrodeless 235dead time 81 hollow cathode 279, 295Debye length 83 restricted 136decay function 109 dc 135degassing 285 rf 135degeneracy 196 single-electrode 235degree of dissociation 160 spark 127degree of ionization 20, 257 di€use spark 127densitometer 62, 63, 254 discharge gap 213departure from LTE 226 discharge lampdepression 164 a ¯oating anode tube 141depth-pro®le 248, 287 ¯at cathode 141depth-pro®le analysis 246 discharge parameter 141depth-pro®ling analysis of steel 287 discharge under reduced pressure 11, 31,depth resolution 287 135€, 152, 297desolvate 104 discharges under reduced pressure 177, 294desolvation 267 discrete sampling 99, 161, 222 membrane 103 dispenser 165detecter noise 148 dispersive element 52
  16. 16. 352 Index displacement energy 139, 140 electrochemical hydride generation 106, 238 dissociation 23€, 168 electrodeless discharge lamp 152, 290, 293 collision-induced 266 electroerosion 89 reaction-induced 266 electrolysis 106 dissociation energy 25, 160 electrolytic hydride generation 106, 107 dissociation equilibrium 168 electromagnet 181 dissociation of oxide 160 electron dissociation reaction 160 charge 197 dissolution eciency 185 electron±ion recombination 242 dissolution speed 185 electron impact 138, 220 dissolved metal 216 electron microprobe 121 divergence 132, 133 electron microprobe line scan 143 Doppler pro®le 158 electron number 18 Doppler spectral width 15 electron number density 220, 221 Doppler-free spectroscopy 158, 301 electron pressure 20€, 211 double arc 109 electron-probe microanalysis 170 double peak 116, 170, 171 electron probe micrograph 243 doubly charged ion 276 electronic energy level 23 drinking water 190 electrostatic analyzer 73, 277 droplet 90, 126, 161 electrothermal AAS 164 droplet diameter 91 electrothermal atomic absorption 164€ droplet distribution 97 electrothermal evaporation 89, 117, 228, 233 droplet size 100, 102 electrothermal vaporization 267, 289 droplet size distribution 100 element Druyvenstein distribution 9 analyte 226 dry solution residue 254, 287 reference 226 drying stage 114, 173 elemental mass spectrometry see ICP-MS dual-beam 150 inductively coupled plasma 3 dual-channel instrument 151 spark source 3 dynode 64 elemental species 116 element-speci®c detection 157, 237, 251 e emission 9€ Eagle mounting 61 emission spectra 4 easily ionized element 211, 224 emission spectrometry Echelle grating 207 furance 243 Echelle monochromator 218 spark 213 dual 153 emulsion 64 Echelle spectrograph 207 end-on 221 Echelle spectrometer 59, 153 energy 8-hydroxyquinoline 270 ion 262 Einstein coecient for spontaneous emission energy distribution 277 11 energy focusing 75 Einstein transition probability 10 energy level 13 einzel lens 256 enriched uranium 158 ``einzel lens 84 entrance collimator 52, 56 elastic collision 136 entrance slit 53 elctrically non-conducting material 131 environmental 3 electric ®eld 135 environmental monitoring 220 electrical discharge 254 environmental sample 186 electrically conducting solid 129 environmental work 270 electrically-conductive sample 281 environmentally-relevant sample 232 electrically-conducting sample 244, see also error of the ®rst kind 47 Grimm lamp error of the second kind 47 electrically non-conducting powder 248, 285 ETV 123
  17. 17. Index 353evaporation 122 ¯ow injection analysis (FIA) 99evaporation stage 114 ¯ow injection analysis 175, see also FIAexcess noise 40 ¯ow injection procedure 162excitation 138, 192, 245 ¯ow-through cell 105excitation condition 225 ¯uorescenceexcited state 156 non-resonance 290, 295excreted oxide 216 resonance 290exit collimator 56 ¯uorescence volume 294extraction of ion 255 ¯uorination 305 ¯ux 131, 196f acid 3041af noise 156 alkali 304FANES (furance atomic non-resonance food 123 emission spectrometry) 243 formation function 109FAPES 272€, see also furnace atomic plasma Fourier transform 79 emission source Fourier transform spectrometry 245€Faraday-cup 277 fractionated volatilization 135Faraday dark space 137 free atom concentration 164, 165Faraday e€ect 183€ free chemical energy 120FIA manifold 162 free sample aspiration 224®eld emission 136 free-running 133®eld ionization 298 freon 118®gure of merit 34, 162, 300, 308 frequency 79, 125 detection limit 199 frequency doubling 133, 156®lament 112 fresh water sample 228®lament plasma 237 fs-laser 252®lament-type MIP 238 full-widths at half maximum 16®ller gas 276 fuming 264®ltering 40 fundamental noise 40®nd use 272 furnace 109, 111, 290¯ame 1, 30, 159€, 290, 299 refractory metal 112 air±acetylene 159 furnace AAS 123, 232 C2 H2 aN2 O 294 fusion 304 carbon rich 164 chemical 294 g emission 210 GaAs 189, see also gallium arsenide high-temperature 160 galvanic detection 299 hydrogen±air 159 gas 289 nitrous oxide±acetylene 159, 210 purging 110 propane±air 159 gas chromatography 190¯ame AAS 150, 158€ gas chromatography¯ame atomic absorption 158€ coupled with ICP-MS 271¯ame temperature 160 multi-capillary 271¯ashlamp 132 gas ¯ow 91¯at cathode 251 aerosol carrier 258¯at Grimm-type glow discharge 147 carrier 262¯icker noise 40 injector 262¯oating restrictor 278 intermediate 220¯ow cell 108, 229 nebulizer 222, 262, 265¯ow-cell 173 outer 220¯ow-cell hydride generation 233, 239 gas ¯ow dynamic 225¯ow-cell type hydride generator 105 gas jet 141¯ow injection 161, 176 gas±liquid separator 107¯ow injection analysis 305 gas-phase reaction 276
  18. 18. 354 Index gas sampling glow discharge 280 mechanically ruled 56 gas temperature 121, 138 plane 58 Gauûian distribution 16 Grimm lamp 244€ Gaussian function 36 Grimm-type discharge 287 GC-MPT-TOFMS 274, 275 Grimm-type source 277 GD grinding 123, 124, 302 dc microsecond-pulsed 279, see glow groove 207 discharge ground state 132 gas sampling 280, see glow discharge ground state atom 148, 296 rf-planar-magnetron 279, see glow discharge h generator Hû line 21 high-frequency 219 halfwidth 203 generation of hydride 108 halogenated hydrocarbon 273 geological 1 halogenation 125 geological sample 232, 269 hard-sphere 139 glass 188, 286 heat gliding spark 130 decomposition 122 glow discharge 68, 125, 137, 175, 193, 275€, latent heat 121 290 heat conductance 135 a planar cathode 144 heated spray chamber 102 gas-sampling 251, 252 heating stage 114 jet-assisted 249 high eciency nebulizer (HEN) 92 microwave assisted 249 high-energy preburn 141, 245 radio-frequency 138 high-frequency discharge 152 rf 145, 248€ high-power nitrogen discharge 272 glow discharge mass spectrometry 255, high-purity Ag powder 286 275€, see GD-MS high-purity Ga 284 glow discharge OES high-purity substance 189, 283 detection limit 216 high-purity Ti 285 glow discharge source 44 high resolution 87 glow emission 136 high-resolution spectrometer 185 gold±platinum gauze 108 high-temperature superconductor 232, 284 gold sponge 173 Hittorf dark space 137 grain size 121, 123 hollow cathode 251, 287 graininess 141 hollow cathode discharge 25 graphite atomizer 113 hollow cathode lamp 14, 152, 177, 290 graphite cup 228 hollow cathode source 293 graphite furnace 118, 228, 295 hop 155 transversally heated 174 hot hollow cathode 243 graphite furnace AAS 150 hot-trapping 107, 173 graphite furnace atomic absorption hydraulic high pressure nebulization system spectrometry 123 102 graphite furnace atomization 237 hydride 89, 105 graphite furnace evaporation 113 hydride forming element 238 graphite platform 165 hydride generation 105€, 229, 289 graphite powder 118 continuous-¯ow 252 graphite tube 111, 112 electrochemical 230 pretreatment 108 hydride technique 150, 172 pyrolytic graphite coated 169 hydrogeological sample 269 grating concave 59 i echelle 59, 209 ICP atomic emission 87 holographically ruled 56 ICP generator 221
  19. 19. Index 355ICP mass spectrometry 255€, see ICP-MS dual 82ICP-AES 87, 232 Faraday collector 81 sequential 226 ion counting 81 simultaneous 226 photographic plate 80ICP-MS 43, 255€, 272, 307, 310 ion energy 259 laser ablation 270€ ion exchange 186 low-resolution 257 ion extraction 82ICP-OES 41, 42, 194, 307 ion intensity 277ICP-optical emission spectrometer 219 ion lens 255ignition pulse 125 ion lineillumination 52€ intensity 19 image on the entrance slit 54 ion optics 83, 84 intermediate image 53 ion sampling 82image 86, 203, 204 ion source 109image dissector tube 67, 68 ionization 18€, 192, 262imaging mirror 52 ionization bu€er 164impact excitation 241 ionization energy 22, 136impact ionization 241 ionization equilibrium 164, 224impactor 286 ionization interference 256impulse theory 139, 144 irradiance 14in-depth resolution 141 isobaric interference 276indirect determination 175 isothermal atomizer 191inductance 214 isothermal furnace 170inductively coupled plasma 2, 193, see ICP isothermic distillation 304inertion of the emulsion 63 isotope ratio 266instrument cost 310 isotope ratio measurement 267instrumental drift 176 isotopic abundance 258integrated absorption 167 isotopic analysis 158integrator 65interference 116, 170, 201, 224, 265€ j additive 85, 224 jet expansion 83 spectral 85 jet-assisted glow discharge 143 calcium-phosphate 163 jet-enhanced sputtering 249 chemical 172 ¯ame AAS 163 isobaric 265 k matrix 269 kerosene 227 multiplicative 85, 86 kinetic energy 136 signal enhancement or depression 86 physical 170 l spectral 202, 205, 258, 260, 261, 264, 265 La- and Sr-compound 164interference noise 40 Lambert±Beers law 184interferogram 71€ laminar-¯ow clean bench 304internal standard 192, 212, 225, 265 lampinternal standardization 85, 125, 135, 212, deuterium 293 225, 264 tungsten halogenide 293ion Langmuir probe 138, 248 cluster 257, 265 laser 2, 30, 31, 131€ doubly charged 265 ablation 131€ doubly charged analyte 258 continous wave 298 ®ller gas 276 Cu-vapor laser-pumped dye 294 polyatomic 260 dye 293ion current 277 excimer 293ion detection 80€ femtosecond 135
  20. 20. 356 Index laser (cont.) linearization 163 gas 133 line-to-background intensity ratio 249 high-power 251 line-to-background ratio 251 Nd:YAG 133, 134, 135, 230 liquid chromatography pulsed dye 294, 299 particle beam 280 rod 132 local thermal equilibrium 20, 28, 220 semiconductor 133 local thermodynamic equilibrium 138 solid state 132 longitudinal ®eld 179, 180 source 131 loop 118, 162 laser ablation 89, 134, 175, 268, 302 Lorentzian distribution 16 laser atomic ¯uorescence 156 low pressure ICPs 280 laser light scattering 122 low pressure MIP 280 laser photoionization 301 low-pressure discharge 30, 88 laser plume 295 low-pressure ICP 273 laser radiation 297 laser source 251 m layered ceramic 248 MacSimion 84, 256 leaching 306 magnetic ®eld 126, 144, 212, 250 least square linear regression 35 magneto-optical e€ect 183 lens 52 magnetron 234 level Marsch method 107 rotational 24 mass analyzer 75 vibrational 24 mass resolution 76, 265 life science 3, 187, 270 mass spectra 258 lifetime 15, 298 mass spectrometer 72€, 84 lifetime of the excited state 11 double-focussing 277€ limit of detection 46€ dual-channel 257 limit of determination 50, 226 ion cyclotron resonance analyzer 79 limit of guarantee of purity 50 ion trap 78 limits of detection 284 multiple-collector magnetic mass analyzer LINA spark 231€ 80 LINA-sparkTM 135 quadrupole 258, 277€ line quadrupole mass ®lter 3 atomic 18 rf-GD-TOF 279 atomic emission 225 sector ®eld 254 hard 23, 223 simultaneous 80 intensity 194 mass spectrometry 254 ion 18 elemental 254 rotational 23, 25 glow discharge 309 soft 23, 223 isotope dilution 267 line coincidence 193 resonance ionization 301 line frequency 196 thermionic 72€ line pair 12 time-of-¯ight 272 line pair selection 225 mass spectrum 280 line pro®le 17, 74 matching unit 221 line source 149 Mathieu equation 74 line spectrum 152 matrix destruction 114, 119 line width 157 matrix e€ect 85, 129, 218, 301, see also line wing 202 interference linear dynamic range 37, 182, 226, 246, 296, matrix interference 215, 309 301 matrix modi®cation 115, 169 linear regression 84 matrix modi®er 114, 115 linearity 182 matrix-free determination 107, 115
  21. 21. Index 357Maxwell distribution 8 molybdenum 187Maxwell velocity distribution 10 momentummean droplet diameter 222 orbital impulse 6medical sample 270 spin 6medium voltage spark 127 monochromatic radiation 14medium voltage spark OES 247 monochromator 149Meinhard nebulizer 92 Czerny±Turner 150, 203melting point 122 Ebert 150, 203melting with ¯uxes 186 monocrystal 139memory-e€ect 104 Monte Carlo model 241mercury 108, 190 Monte Carlo simulation 143mercury cold vapor technique 108 mountingmetal 246, 269 Echelle 60metal alloy 284 Paschen±Runge 60metal argide 282, 284 MSmetal halogenide 160 ICP-TOF 279metal sample 302 quadrupole ion-trap 280metalloprotein 270 MSP 240metallurgical laboratory 215 temperature 240metals analysis 232 excitation 240metals industry 2, 187 gas 240metastable argon 237 MSP miniaturized MIP 240metastable helium 237 multi-CCD system 205metastable level 220 multielement capacity 218, 226metastable state 156 multielement determination 184, 226meteorite 285 multielement method 184MIBK 227 multilayer 287, 288Michelson interferometer 70 multiply charged Ar specie 284microchannel-plate 66microdensitometer 81 nmicrodistributional analysis 134 Na®on membrane 106microsample 112, 117 nascent hydrogen 105microstrip line 240 natural width 15microstructured resonant cavity 240 Nd:YAG laser 251, 268microtechnique 105 nebulizationmicrowave assisted digestion 185 direct injection 222microwave induced plasma 157 high pressure 102, 222, 228microwave induced plasma atomic emission jet-impact 101 detector 273 pneumatic 222microwave-assisted treatment 305 thermospray 228microwave plasma 2, 88, 234€, 255 ultrasonic 103€, 228, 267 capacitively coupled 236 nebulization chamber 90, 96, 101, see spraymicrowave plasma torch 239 chambermill 186 nebulization e€ect 100, 164, 224, 265mini-torch 219 nebulization eciency 92, 102MIP 42 nebulizerMIP torch 238 Babington 94€, 121, 227modelling 241 Babington-type 222modi®er 119 concentric 91, 161Mohs hardness scale 302 cross-¯ow 94, 161, 222, 227molecular band 25, 178, 260 direct injection 96€molecular gas 127, 272 eciency 91molecular species 23, 113, 157, 171 fritted-disk 96, 222
  22. 22. 358 Index nebulizer (cont.) Nuclepore ®lter 95, 121, 122, 128, 303 grid 227 Nukuyama±Tanasawa 100 high-eciency 222, 227 number density jet-impact 222 analyte 196  Áre 227, 239 Lege electron 196 maximum dissolved solid 227 Meinhard 222 o microconcentric high-eciency 271 observation microultrasonic 228 axial 223 oscillating 97€, 222 radial 223 pneumatic 90 observation height 223 nebulizer gas ¯ow 223 observation zone 218 negative glow 137, 243, 245 OES using a Grimm-type glow discharge negative ion 264 247 Nier±Johnson geometry 277 o€-axis 76, 153 niobium 187 oil analysis 189, 216 noble metal 188 on-line matrix removal 176 noise 39, 163, 264, 300 on-line preconcentration 99, 176 ampli®er 47, 200 on-line trace matrix separation 162 background 46 operating stability 93 dark current 200 optical aberration 198 detector 201, 225 optical beam 165 excess 40 optical conductance 59 1af 41, 42, 264 optical emission spectrometry 112 ¯icker 40, 47, 200, 224, 246 optical spectra 8, 112 fundamental 40, 41 optical spectrometer 84 interference 40 optical spectrometry 112 nebulizer 224 optical transmittance 196 non-fundamental 40 optimization maximum 262 photon 200 optimization study 262 pixel-to-pixel 201 optimization 163, 261 random 40 optogalvanic e€ect 297 shot 45 ore 189 type 39 organic matrices 168 white 40, 246, 264 organolead compound 172 noise power spectra 40€, see noise spectrum organolead 190, 271 noise spectra 225 organotin 190 noise spectrum 40 oscillator strength 13, 299 non-absorbed radiation 149 over-ionization 220 non-conducting sample 138 over-population 220 non-conductive sample 286 oxyanions 163, 164 non-element speci®c absorption 168 non-fundamental noise 40 non-LTE 243 p non-LTE plasma 30, 241 P-branch 24 non-metal 156 paint analysis 189 non-resonant AFS 293 particle diameter 128 non-resonant ¯uorescence 292 particle size distribution 104, 122 non-resonant line 250 particle size 121, 123, 303 non-resonant transition 298 partition function 9, 20, 226 non-speci®c absorption 173 Paschen curve 244 norm temperature 211 Paschen series 4 normal distribution 49 Paschen±Runge 203, 206 nucleation 116 peak area 116
  23. 23. Index 359peak height 116 plasmaarray spectrometer 68peak skew 273 platform 115pellet 125, 248, 285 platform technique 113Peltier cooling element 235 plume 251Peltier element 102 pneumatic nebulization 89, 222penetration rate 139, 287 pneumatic nebulizer 161Penning e€ect 220 optimization 100€Penning ionization 138, 242, 275, 276 point to plane 127peristaltic pump 94 Poiseuille law 100permanent magnet 181 Poisson distribution 45Pfund series 4 polarizer 180, 182pharmaceutical 189 polyatomic compound 160photocurrent 64 population inversion 131, 132photoelectric measurement 47, 198 positive column 137photographic detection 2 powder sampling syringe 174photographic emulsion 201 power 223, 263photomultiplier 64€, 150 power detection 215 solar-blind 59, 65, 210 power of detection 46€, 99, 109, 115, 148,photon 196 156, 162, 163, 169, 220, 223, 246, 263,photon ¯ux 197 268, 307photon stop 84 absolute 134photoplate 59 practical resolution 59physical interference 164 precision analysis 125physical line width 149 precision 35, 104, 266physical width 15, 198, 223 preconcentration 107p-component 179, 180 predisperser 56, 153pin-shaped electrode 287 prespark 215pin-shaped sample 277 primary combustion zone 160Plancks constant 196 primary radiation source 152€Plancks law 8, 11 primary source 148, 149, 290, 291, 293plasma 8, 28, 290 prism 1 current-carrying 217 probability 199 current-free 217 pro®le high-frequency 233€ absorption 148, 292 low-power 233€ spectral 292 inductively coupled 219€ pro®le function 17 laser-produced 294 pro®le of spectral line 16 microwave 235 pro®le of the line 76 capacitively coupled 235 protein fraction 270 microwave induced 235 Pt powder 284 stabilized capacitively coupled 233 PTFE vessel 185 toroidal 219 pulse di€erential height analysis 215 transferred 217 pulse length 294plasma discharge pulse width 46 high-frequency 30 pulsed laser 299 microwave 30 pulsed mode 133plasma jet 31 pulverization 123 three-electrode 218 pumping eciency 132plasma mass spectrometry 129, 254€ pumping process 291plasma parameter 248 pyrolytic graphite 112plasma source AES 216€ pyrolytic graphite coated graphite tubeplasma spectrometry 89 170plasma temperature 21 pyrolytically coated 110plasma tomography 29 pyrolytically coated graphite 172
  24. 24. 360 Index q recombination process 110 Q-branch 24 reduced pressure discharge 2, see glow Q-switched 133 discharge quadrupole mass spectra 282 reducing ¯ame 159 quadrupole 256 reduction 112 qualitative analysis 86, 193€ reference element 85, 125, 151 quantitative analysis 192 reference signal 197 quantitative atomic emission spectrometry re¯ectivity 196 194€ re¯ectron 256 quantum eciency 64, 65, 197 refractive index 154 quantum number refractory 110 magnetic 5 refractory carbide 112 main 5 refractory element 164 orbital 5 refractory powder 229, 232, 304 rotational 24 refractory sample 186 spin 6 relative method 197 quarternary ammonium salt 168 relative method of analysis 170 quartz ®ber optics 54€ relative sensitivity factor 281€ quasi-simultaneous measurement of line and relative standard deviation 195 background absorption 177 remote sampling 125 quaternary ammonium salt 114 removal 100 quenching 291 repeatability 36 repeller 76 r residence time 109, 167, 258 R-branch 24 residual gas impurity 276 radial viewing 227 resistance 214 radiance 132 resolution 78, 79, 277 radiant density 179, 198, 290, 292, 293 resolving power 148 radiant ¯ux 51, 151 resonance ¯uorescence 292 radiant intensity 64 resonance line 156, 163, 183 radiation resonance radiation 148 ¯uorescence 294 resonant transition 298 radiation density 11, 150 resonator 132, 234, 236 radiation detector response time 291 photoelectric detection device 61€ restrictor tube con®guration 142 photographic emulsion 61€ Reticon 66 photomultiplier 61 reversed-phase chromatography 271 radiation source 10, 17, 51, 109, 192, 198 rf coil 256 radiation trapping 220 rf discharge 138 radiative 242 rf glow discharge 144 radiative decay 242 rf shielding 278 radiative recombination 220 rf-GD-MS 283, 286 radical 171 rf-powered glow discharge 278 radioisotope 286 rinsing time 222 radiotracer 169 R-L-C-circuit 221 Raman shifting 299 rotating arc 118 random noise 40 rotation mill 302 rare earth element 283 rotation±vibration band spectra 210 raw material 187 rotation±vibration hyper®ne structure 178 Rayleigh scattering 172 rotational energy 24 reciprocal linear dispersion 170 rotational hyper®ne structure 23 recombination 136, 138, 165, 241 RSF 284, 286 recombination continuum 18 Russell and Saunders 7
  25. 25. Index 361Rydberg constant 4 semi-quantitative analysis 254Rydberg state 298, 301 semi-transparent mirror 151 sensitivity 85, 86, 184, 300s sequential 222Saha constant 19 serum 187Saha equation 19€ Seya±Namioka mounting 61Saha-Eggert equation 257 sheathing gas 218sample 88 shock wave 83 ¯at 278 SiC 123, 285, 303, see silicon carbide inhomogeneity 131 side-on 221 pin 278 side-on observation 29sample decomposition 185 sieve 303sample decomposition step 107 sieving 302sample dissolution 302, 304 sifter 125sample feeding 94 s-component 179, 180sample homogeneity 115 signal depression 84, 261sample inhomogeneity 284 signal enhancement 84, 261sample introduction 88€ signal generation 88 pneumatic nebulization 90€ signal-to-background 116sample preparation 302 signal-to-background ratio 112sample solution consumption 161 signal-to-noise 66sample uptake 222 signal-to-noise ratio 44€, 47, 59, 69, 293sample volatilization 88, 126, 246 silicon±boron±carbo±nitride 225sampler 83, 255 Silsbee focussing 140sampler clogging 264 Simplex optimization 223sampling boat 229 simultaneous 222sampling depth 134 simultaneous detection 75sampling eciency 161 simultaneous emission spectrometer 194saturation 291, 293 single beam 150Sauter diameter 100 single-channel instrument 151scanning electron micrograph 129 SIT vidicon 204scanning electron microscopy 96 Skewedness and excess test 48€scanning monochromator 193 skimmer 83, 255scattered radiation 183 cone 279scattering 183 potential 279scintillator 70 slag 189seawater analysis 270 slitsecondary cathode 285, 286 entrance 196secondary electron emission 136 exit 196sector ®eld 256 slope 37 high-resolution 258 slurry 95, 114, 120sediment 286 slurry atomization 120€, 174Seidel 63 slurry nebulization 95, 268selection rule 6 slurry sampling 188selective volatilization 118, 130 small sample 99self biasing 138 Smith±Hieftje technique 182self-absorption 17, 153 SNR value 101, see signal-to-noise ratioself-aspirating 92 soft plasma 272self-reversal 17, 126, 153, 182, 193, 227, 246, soil 285, 286 250, 296 solid sample 211self-sputtering 140 solid state detectorsemi-conductor 189, 281 photodiode array 67semiconductor-grade material 283 SIT vidicon system 67
  26. 26. 362 Index solid state detector (cont.) high-resolution 261 vidicon 67 ICP-MS 258 solid-phase extraction 162 spectral background 203, 220 solids ablation 251 spectral bandwidth 148, 149, 163, 177 solid-state detector 206 spectral dispersion charge injection device 66 angular 57 charge-coupled device 66 reciprocal linear 57 solution 184 spectral interference 144, 163, 193, 282, 296, solvent residue 172 301, 309 source 27, 30€ spectral line 12, 193 continuous 292 spectral line table 193 pulsed 292 spectral line width 155 space angle 196 spectral radiance 152 space charge spectral radiance t 59 positive 136 spectral range 154, 209 space charge e€ect 265 spectral resolution 194 spark 2, 30, 31, 126, 210 spectral scan 87, 202 ac 213 spectral slit width 57, 198 channel 213 spectral stripping 194 condensed 127 spectral term 5 critically damped 215 spectrochemical analysis 192 detection limit 216 spectrograph 2 emission spectrometry 213€ spectrometer generator 214 atomic absorption 150€ high-voltage 126, 128, 215 atomic emission 202€ medium voltage 215 CCD 240 oscillating 215 Czerny±Turner mounting 58 overcritically damped 215 dispersive spectral apparatus 55 repetition rate 127 Ebert mounting 59 single 215 Echelle 206€ unidirectional 215 Fastie±Ebert mounting 59 spark ablated aerosol 239 Fourier transform 70€ spark ablation 88, 128 grating 52 spark ablation coupled with ICP-OES 231€ Hadamard transformation 70€ spark-ablation ICP-MS 282 ICP atomic emission 258 spark chamber 128, 129 mass 73, 74, 76 miniaturized 127 magnetic mass analyzer 74 spark channel 128 quadrupole 73 spark emission spectrometry 88, 131 time-of-¯ight 76€ spark frequency 214 multichannel 151 spark gap 127 non-dispersive 70 spark source mass spectrography 254 non-dispersive spectral apparatus 55 spark source mass spectrometry 254, 284 optical 51 spark train 127 optical mounting 58 sparking Paschen±Runge 61, 223 chamber 127 sequential 203 spatially isothermal graphite furnace 165 simultaneous 203 spatially-resolved measurement 221 two-channel 226 speciation 190, 271, 289 spectrometry species density 143 ac arc 213 spectra 1, 195 dc arc 211€ display 86 laser enhanced ionization 297€ ICP atomic emission 204 spectroscope 192 ICP mass 261 spray chamber 91
  27. 27. Index 363 cyclone 91 rotation 220 single pass 98 rotational 25, 26, 27spray chamber 90, see nebulization chamber spectroscopic measurement 13spray chamber±burner assembly 161 volatilization 168sputter pro®le 250 temperature pro®le 165sputtering 126, 245, 275 temperature program 169 cathodic 135 temperature programming 114€sputtering eciency 144 temperature tuning 155sputtering equilibrium 141 term scheme 7sputtering rate 139 theoretical resolving power 17sputtering yield 139, 140 thermal equilibrium 10, 11stabilized temperature platform furnace 167 thermal evaporation 109, 211stack gas 235 thermal matrix removal 171standard addition 86, 172, 260 thermal method 117standard deviation 36, 199, 200 thermal spray 89statistical weight 19, 22 thermal volatility 130steel 187, 269, 282, 284, 287 thermal volatilization 89, 129 brass-coated 287 thermally stable compound 172 high alloy NiaCr 131 thermally stable oxide 163, 295 low-alloyed 252 thermionic diode 300steel analysis 282 thermochemical aid 211steel mill 303 thermochemical behavior 117, 168stigmatic spectral apparatus 58 thermochemical decomposition 172stimulated emission 131 thermochemical modi®er 119, see matrixstoichiometry 189 modi®erstray-light measurement 100 thermochemical reaction 113, 118stray-radiation 52, 202, 294 thermochemical reagent 114, 119, 168, 229strip line 234 thermochemistry 168structured background 181 thermospray 228student table 37 Thomson scattering 239, 241superalloy 282 three-body collision 242superconductor three-body recombination 276 PbaBiaSraCaaCuaO 225 three-level system 292superconductor material 188 time-of-¯ight 272surface tension 170 time-of-¯ight mass spectrometry 273surfactant 170 time-of-¯ight system 256surfatron 236 time-resolved absorption spectra 154suspension 120 TM010 resonator 237switch TOF-ICP-MS 267 electro-acoustic 133 TOF-MS opto-acoustic 133 plasma 272 torcht Fassel 220tandem source 33 green®eld 220tandem source concept 88 toroidal argon discharge 237tantalum 187 toroidal MIP 238temperature toxic element 187 electron 27, 193, 221, 245, 276 trace-matrix separation 123, 269 excitation 12€, 27, 196, 220, 226 trace-O-mat 305 gas 27 tracer experiment 266 gas kinetic 16 trajectory 75 ionization 28 transfer of free atom 166 norm 22€ transformation equation 63 plasma 223 transformation function 62€
  28. 28. 364 Index transient 116 vesicle mediation 108 transient signal 76, 87, 110, 176, 267 vibrational ®ne structure 23 transition vidicon 59 non-resonant 294 viewing port 165 resonant 294 viscosity 170 transition probability 13, 24, 196, 290, 298 viscosity drag force 121 transmission 62, 84 Voigt e€ect 183€ transmittance 51 Voigt pro®le 16 transport 167 volatile element 164 transport eciency 169 volatile species formation 108 transversally-heated furnace 165 volatile species generation 105€ transverse magnetic ®eld 179 volatilization 128, 165 trapping 107, 173, 238 volatilization e€ect 109 hot 107 volatilization interference 161 trapping hydride 238 volatilization process 27, 109 TTA 162, see also thenoyltri¯uoroacetone volatilization temperature 119 tube furnace 109, 165 VUV wavelength 216 tunable diode laser 191 tunable diode laser source 176 w tunable laser 292, 299 wandering e€ect 126 tuned laser 290 wash-out time 90 tungsten 187 waste water analysis 270 tungsten coil 166 water analysis 190 tungsten ®lament 228, 233 water loading 102 tungsten ®lament atomizer 166 waveguide 234 tungsten furnace 165 wavelength gap 155 tungsten trioxide 174 wavelength modulation laser AAS 157 tuning range 155 WC 123 turbomolecular pump 84, 255 wet chemical dissolution 304 turret 185 wetting agent 121 two-body collision 242 white noise 40 two-line method 21 wire 130 two-photon spectroscopy 301 wire cup 118 wire loop atomization 112 u working coil 219 U3 O8 213 ultrasonic nebulization 89, 123 x ultrasonic stirring 123 xenon lamp 290 uncertainty 38 x-ray ¯uorescence 122 undissociated molecule 171 x-ray spectrometry 311 unidirectional spark 127 xylene 227 urine 270, 288 z v Zeeman AAS 179 vapor 289 Zeeman e€ect 6, 154, 179 vapor cloud 109 anomalous 179 vapor condensation 128 longitudinal ®eld 180 vapor sampling 289 normal 179 vaporization Zeeman splitting 180, 182 electrothermal 109€ Zeeman-e€ect background correction 158 vegetation 286 zero-background 183 velocity of light 13 ZrO2 162, 186, 194, see also zirconium vesicle 174 dioxide
  29. 29.  Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic) 1IntroductionAtomic spectroscopy is the oldest instrumental elemental analysis principle, theorigins of which go back to the work of Bunsen and Kirchho€ in the mid-19thcentury [1]. Their work showed how the optical radiation emitted from ¯ames ischaracteristic of the elements present in the ¯ame gases or introduced into theburning ¯ame by various means. It had also already been observed that the inten-sities of the element-speci®c features in the spectra, namely the atomic spectrallines, changed with the amount of elemental species present. Thus the basis forboth qualitative and quantitative analysis with atomic emission spectrometry wasdiscovered. These discoveries were made possible by the availability of dispersingmedia such as prisms, which allowed the radiation to be spectrally resolved and theline spectra of the elements to be produced. Around the same time it was found that radiation of the same wavelength as thatof the emitted lines is absorbed by a cold vapor of the particular element. Thisdiscovery was along the same lines as the earlier discovery made by Fraunhofer,who found that in the spectra of solar radiation line-shaped dark gaps occurred.They were attributed to the absorption of radiation by species in the cooler regionsaround the sun. These observations are the basis for atomic absorption spectrom-etry, as it is used today. Flames proved to be suitable sources for determinations inliquids, and in the work of Bunsen and Kirchho€ estimations were already beingmade on the smallest of elemental amounts that would still produce an emissionor absorption signal when brought into a ¯ame. From this there was already a linkappearing between atomic spectroscopy and the determination of very smallamounts of elements as being a basis for trace analysis. With industrial developments arose a large need for the direct chemical analysisof solids. This resulted from expansion of production processes, where raw mate-rials are subjected to large-scale processes for the production of bulk materials,from which products of increased value, complying to very strict speci®cations, aremanufactured. The search for appropriate raw materials became the basis for min-ing, which was then developed on a large scale. Geological prospecting with theinevitable analyses of large amounts of samples for many elements, often down tolow concentration levels as in the case of the noble metals, took place. Also tradingof raw materials developed, which intensi®ed the need for highly accurate charac-terization of ores and minerals, a development that today is becoming more strin-
  30. 30. 2 Introduction gent. Accordingly, analytical methodology that allows widely diverse materials to be characterized for many elements became necessary. Because of economic implica- tions this information must frequently be obtained rapidly, which necessitates so-called multielement methods for the direct analysis of solids. Not only is there a need for the characterization of raw bulk materials but also the requirement for process controled industrial production introduced new de- mands. This was particularly the case in the metals industry, where production of steel became dependent on the speed with which the composition of the molten steel during converter processes could be controlled. After World War II this task was eciently dealt with by atomic spectrometry, where the development and knowledge gained about suitable electrical discharges for this task fostered the growth of atomic spectrometry. Indeed, arcs and sparks were soon shown to be of use for analyte ablation and excitation of solid materials. The arc thus became a standard tool for the semi-quantitative analysis of powdered samples whereas spark emission spectrometry became a decisive technique for the direct analysis of metal samples. Other reduced pressure discharges, as known from atomic physics, had been shown to be powerful radiation sources and the same developments could be observed as reliable laser sources become available. Both were found to o€er spe- cial advantages particularly for materials characterization. The need for environmentally friendly production methods introduced new challenges for process control and fostered the development of atomic spectro- metric methods with respect to the reliable determination of elements and their species in both solids, liquids and gaseous samples. The limitations stemming from the restrictive temperatures of ¯ames led to the development of high tem- perature plasma sources for atomic emission spectrometry. Thus, as a result of the successful development of high-frequency inductively coupled plasmas and micro- wave plasmas these sources are now used for routine work in practically all large analytical laboratories. Accordingly, atomic emission spectrometry has developed into a successful method for multielement analyses of liquids and solids as well as for determinations in gas ¯ows. This is due to the variety of sources that are avail- able but also to the development of spectrometer design. The way started with the spectroscope, then came the spectrographs with photographic detection and the strongest development since photoelectric multichannel spectrometers and ¯exible sequential spectrometers, has recently been with array detectors becoming available. In time, the use of ¯ames as atom reservoirs for atomic absorption spectrometry was also transformed into an analytical methodology, as a result of the work of Walsh [2]. Flame atomic absorption spectrometry became a standard tool of the routine analytical laboratory. Because of the work of Lvov and of Massmann, the graphite furnace became popular as an atom reservoir for atomic absorption and gave rise to the widespread use of furnace atomic absorption spectrometry, as o€ered by many manufacturers and used in analytical laboratories, especially for extreme trace analysis. However, in atomic absorption spectrometry, which is essentially a single-element method, developments due to the multitude of atomic reservoirs and also of primary sources available, is far from the end of its development. Lasers will be shown to give new impetus to atomic absorption work and also to make
  31. 31. Introduction 3atomic ¯uorescence feasable as an extreme trace analysis method. They will alsogive rise to new types of optical atomic spectrometry such as laser enhanced ion-ization spectrometry. The sources investigated and that are being used successfully for optical atomicspectrometry are also powerful sources for elemental mass spectrometry. This ledto the development of classical spark source mass spectrometry moving through towhat are today important plasma mass spectrometric methods, such as glow dis-charge and inductively coupled plasma mass spectrometry. The development of ele-mental mass spectrometry started with the work of Aston on the elemental massseparator. Here the ions of di€erent elements are separated on the basis of their de-¯ection in electrical and magnetic ®elds. This development lead to high-resolutionbut expensive instrumentation, with which highly sensitive determinations couldbe performed, as e.g. are necessary for high-purity materials that are required forthe electronics industry. Towards the end of the 1970s, however, so-called quadru-pole mass ®lters developed to such a high standard that they could replace con-ventional mass spectrometers for a number of tasks. The use of mass spectrometryinstead of optical emission spectrometry enabled considerable gains in the powerof detection to be made for the plasma sources developed around that time. Thedevelopment of this ®eld is still proceeding fully, both with respect to the ion sourcesand the types of mass spectrometers used as well as with respect to detector tech-nology. All the items mentioned will ®nally make an impact on the analytical per-formance of plasma mass spectrometry. Certainly the latter is considerably moreadvantageous than optical methods as a result of the possibility of detecting thevarious isotopes of particular elements. The di€erent atomic spectrometric methods with ¯ames and plasmas have to bejudged by comparing their analytical ®gures of merit with those of other methodsfor elemental analysis, a point which has to be seen through a critical eye with respectto the analytical problems to be solved. The scope for plasma spectrometry is stillgrowing considerably, as it is no longer elemental determinations but the deter-mination of the elements as present in di€erent compounds that is becoming im-portant, for problems associated with the design of new working materials, chal-lenges in life sciences as well as for environmental and bio-medical risk assesment.This gives the area of interfacing atomic spectrometry with separation sciences astrong impetus, which needs to be treated in depth, both from the developmentof types of interfaces as well as from the point of view of reshaping existing anddeveloping new sources of suitable size and cost±performance ratios.
  32. 32.  Analytical Atomic Spectrometry with Flames and Plasmas. Jose A. C. Broekaert Copyright > 2002 Wiley-VCH Verlag GmbH & Co. KGaA ISBNs: 3-527-30146-1 (Hardback); 3-527-60062-0 (Electronic)4 1 Basic Principles 1.1 Atomic structure The basic processes in optical atomic spectrometry involve the outer electrons of the atomic species and therefore its possibilities and limitations can be well under- stood from the theory of atomic structure itself. On the other hand, the availability of optical spectra was decisive in the development of the theory of atomic structure and even for the discovery of a series of elements. With the study of the relation- ship between the wavelengths of the chemical elements in the mid-19th century a fundament was obtained for the relationship between the atomic structure and the optical line emission spectra of the elements. In 1885 Balmer published that for a series of atomic lines of hydrogen a rela- tionship between the wavelengths could be found and described as: l ˆ k Á n 2 a…n 2 À 4† …1† where n ˆ 2Y 3Y 4Y F F F for the lines Ha Y Hb Y Hg etc. Eq. (1) can also be written in wavenumbers as: n H ˆ 1al ˆ R…1a2 2 À 1an 2 † …2† where n H is the wavenumber (in cmÀ1 ) and R the Rydberg constant (109 677 cmÀ1 ). The wavenumbers of all so-called series in the spectrum of hydrogen are given by: n H ˆ 1al ˆ R…1an1 À 1an2 † 2 2 …3† where n2 is a series of numbers b n1 and with n1 ˆ 1Y 2Y 3Y 4Y F F F for the Lyman, Balmer, Paschen and Pfund series, respectively. Rydberg applied the formula of Balmer as: n H ˆ R Á Z 2 …1an1 À n2 † 2 2 …4† where Z is the e€ective charge of the atomic nucleus. This formula then also allows calculation of the wavelengths for other elements. The wavenumbers of the atomic
  33. 33. 1.1 Atomic structure 5spectral lines can thus be calculated from the di€erence between two positive num-bers, called terms, and the spectrum of an element accordingly contains a largenumber of spectral lines each of which is related by two spectral terms. The signi®cance of the spectral terms had already been re¯ected by Bohrstheory, where it is stated that the atom has a number of discrete energy levels relatedto the orbits of the electrons. These energy levels are the spectral terms. As long asan electron is in a de®ned orbit no electromagnetic energy is emitted but whena change in orbit occurs, another energy level is reached and the excess energy isemitted in the form of electromagnetic radiation. The wavelength is given accord-ing to Plancks law as: E ˆ h Á n ˆ h Á cal …5†Here h ˆ 6X623  10À27 erg s, n is the frequency in sÀ1 , c ˆ 3  10 10 cm/s is thevelocity of light and l is the wavelength in cm. Accordingly: n H ˆ 1al ˆ Eah Á c ˆ E1 a…h Á c† À E2 a…h Á c† ˆ T1 À T2 …6†T1 and T2 are the Bohr energy levels and the complexity of the emission spectracan be related to the complexity of the structure of the atomic energy levels. For an atom with a nucleus charge Z and one valence electron, the energy of thiselectron is given by: 2 Á p Á Z 2 Á e4 Á m EˆÀ …7† n2h2m ˆ m Á Ma…m ‡ M†, with m being the mass of the electron and M the mass of thenucleus; n is the main quantum number …n ˆ 1Y 2Y 3Y F F F† and gives the order of theenergy levels. Through the movement around the atomic nucleus, the electron hasan orbital impulse moment L of which the absolute value is quantitized as: p jLj ˆ ha…2p† l…l ‡ 1† …8†l is the orbital quantum number and has values of: 0Y 1Y F F F Y …n À 1†. The elliptical orbits can take on di€erent orientations with respect to an externalelectric or magnetic ®eld and the projections on the direction of the ®eld also arequantitized and given by: L z ˆ ha…2p†m l …9†L z is the component of the orbital momentum along the ®eld axis for a certainangle, m l ˆ qlY q…l À 1†Y F F F Y 0 is the magnetic quantum number and for eachvalue of l it may have …2l ‡ 1† values.
  34. 34. 6 1 Basic Principles When a spectral line source is brought into a magnetic ®eld, the spectral lines start to display hyper®ne structures, which is known as the Zeeman e€ect. In order to explain these hyper®ne structures it is accepted that the electron rotates around its axis and has a spin momentum S for which: p jSj ˆ ha…2p† S…S ‡ 1† …10† The spin quantum number m s determines the angles possible between the axis of rotation and the external ®eld as: sz ˆ ha…2p†m s …11† where m s ˆ q1.2 The orbital impulse momentum and the spin momentum are vectors and deter- mine the total impulse momentum of the electron J as: p J ˆL‡S with j Jj ˆ ha…2p† j… j ‡ 1† …12† j ˆ l q s and is the total quantum number. In the case of an external magnetic or electrical ®eld, the total impulse momen- tum also has a component along the ®eld, whose projections on the ®eld are quantized and given by: Jz ˆ ha…2p†  mj with mj ˆ q jY q… j À 1†Y F F F Y 0 …13† This corresponds with possible 2 j ‡ 1 orientations. The atomic terms di€er by their electron energies and can be characterized by the quantum numbers using the so-called term symbols: n m lj …14† Here l ˆ 0Y 1Y 2Y F F F and the corresponding terms are given the symbols s (sharp), p (principal), d (di€use), f (fundamental), etc., originally relating to the nature of di€erent types of spectral lines: n is the main quantum number, m is the multi- plicity …m ˆ 2s q 1† and j is the total internal quantum number. The energy levels of each element can be given in a term scheme. In such a term scheme, also indi- cated are which transitions between energy levels are allowed and which ones are forbidden. This is re¯ected by the selection rules. According to these, only those transitions are allowed for which Dn has an integer value and at the same time Dl ˆ q1, D j ˆ 0 or q1 and Ds ˆ 0. The terms of an atom with one valence electron can easily be found, e.g., for Na …1s 2 2s 2 2p 6 3s 1 †, in the ground level: 3 2 S1a2 [l ˆ 0 (s), m ˆ 2X1a2 ‡ 1 ˆ 2 …s ˆ 1a2† and j ˆ 1a2 … j ˆ jl q sj†]. When the 3s electron goes to the 3p level, the term symbol for the excited level is: 3 2 P1a2Y 3a2 [l ˆ 1 (p), m ˆ 2X1a2 ‡ 1 ˆ 2 as s ˆ 1a2 and j ˆ 1a2Y 3a2]. The terms have a multiplicity of 2 and accordingly the lines have a doublet structure.

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