klaus grasshoff/klaus kremlingl manfred ehrhardt methods ... · preface to the third edition...

Klaus Grasshoff/Klaus Kremlingl Manfred Ehrhardt

Methods of Seawater Analysis

Third, Completely Revised and Extended Edition

With Contribution by:

Leif G. Anderson, Meinrat 0. Andreae, Brigitte Behrends, Constant van den Berg, Lutz Brugmann, Kathryn A. Burns, Gustave Cauwet, Jan C. Duinker, David Dyrssen, Manfred Ehrhardt, Elisabet Fogelqvist, Stig Fonselius, Hans Peter Hansen, Arne Kortzinger, Wolfgang Koeve, Folke Koroleff, Klaus Kremling, Joachim Kuss, Gerd Liebezeit, Willard S. Moore, Thomas J. Miiller, Andreas Prange, Michiel Rutgers van der Loeff, Martina Schirmacher, Detlef Schulz-Bull, Peter J. Statham, David R. Turner, Gunther Uher, Petra Wallerstein, Margareta Wedborg, Peter J. le B. Williams, Bengt Yhlen

8 WILEY-VCH Weinheim . New York . Chichester . Brisbane . Singapore . Toronto

This Page Intentionally Left Blank

Klaus Grasshoff Klaus Kremling Manfred Ehrhardt


8 WILEY-VCH

Klaus Grasshoff/Klaus Kremlingl Manfred Ehrhardt


Third, Completely Revised and Extended Edition

With Contribution by:

Leif G. Anderson, Meinrat 0. Andreae, Brigitte Behrends, Constant van den Berg, Lutz Brugmann, Kathryn A. Burns, Gustave Cauwet, Jan C. Duinker, David Dyrssen, Manfred Ehrhardt, Elisabet Fogelqvist, Stig Fonselius, Hans Peter Hansen, Arne Kortzinger, Wolfgang Koeve, Folke Koroleff, Klaus Kremling, Joachim Kuss, Gerd Liebezeit, Willard S. Moore, Thomas J. Miiller, Andreas Prange, Michiel Rutgers van der Loeff, Martina Schirmacher, Detlef Schulz-Bull, Peter J. Statham, David R. Turner, Gunther Uher, Petra Wallerstein, Margareta Wedborg, Peter J. le B. Williams, Bengt Yhlen

8 WILEY-VCH Weinheim . New York . Chichester . Brisbane . Singapore . Toronto

Prof. Dr. Klaus Grasshoff t Institut fur Meereskunde an der Universitat Kiel Diisternbrooker Weg 20 D-24105 Kiel

Dr. Klaus Kremling Dr. Manfred Ehrhardt Institut fiir Meereskunde an der Universitat Kiel Abt. Meereschemie Diisternbrooker Weg 20 D-24105 Kiel

This book was carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained therein to be free of errors. Readers are advised to keep in mind that state- ments, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Cover Illustration: Dr. Arne Kortzinger

Library of Congress Card No.:

British Library Cataloguing-in-Publication Data:

Die Deutsche Bibliothek Cataloguing-in-Publication Data: Methods of seawater analysis / ed. by Klaus GraRhoff ... With contributions by Leif Anderson; Constant van den Berg. - 3., completely rev. and extended ed. - Weinheim; New York; Chiester; Brisbane; Singapore; Toronto: Wiley-VCH, 1999 ISBN 3-527-29589-5

0 WILEY-VCH Verlag GmbH, D-69469 Weinheim (Federal Republic of Germany), 1999

Printed on acid-free and chlorine-free paper.

All rights reserved (including those of translation in other langauges). No part of this book may be reproduced in any form - by photoprinting, microfilm, or any other means - nor transmitted or trans- lated into machine language without written permission from the publishers Registered names, trade- marks, etc. used in this book, even when not specifically marked as such, are not to be considered unpro- tected by law.

Composition: Kiihn & Weyh, D-79111 Freiburg Printing: Strauss Offsetdruck, D-69509 Morlenbach Bookbinding: Wilh. Osswald, D-67433 Neustadt

Printed in the Federal Republic of Germany.

Dedication

In memoriam Prof. Dr. Klaus Grasshoff 09.06.1932 - 11.03.1981

With this third edition of Methods of Seawater Analysis we (K.K. and M.E.) should like to commemorate the late Klaus Grasshoff, our friend and colleague of many and yet too few years. It was he who, in the foundation years of the 1970s, saw the need to accumulate the analytical expertise of the then small number of marine chemists and to form a common experimental basis for generating reliable data on chemical variables in the sea. In this spirit as guiding principle we strive to cultivate the original seed.

Preface to the third edition

Fifteen years have passed since the second edition of this book was published, a twinkling on the time scale of many oceanic processes, but an eaon if compared with the rapid evolu- tion of analytical techniques needed to describe and measure them. The pace of develop- ment varied; it was most rapid among techniques still immature a decade and a half ago and more sedate among methods such as batchwise nutrient analyses and their automated ver- sions that rightfully bear the epithet classical. Methods to determine trace elements as well as natural radioactive tracers and to analyse the complex assemblages of organic trace constituents of seawater, however, have grown in scope and considerably advanced in refine- ment. Thus, separate and sometimes new chapters are devoted to electrochemical methods, analysis by X-ray fluorescence, and on sampling and analysis of suspended particles. Clean, large scale sample collection at almost arbitrary depths is described providing sufficient material for organic trace analyses at the single compound level, in extreme cases made possible by multi-dimensional gas chromatography. Chapters on pH and total dissolved inorganic carbon determinations were thoroughly revised and expanded. Those interested in material exchange processes between ocean and atmosphere will find detailed instructions for measuring the partial pressure of dissolved carbon dioxide, concentrations of dimethyl sulphide, and how to analyse volatile halocarbons. HPLC analysis of photosynthetic pig- ments is another topic not dealt with in the previous editions. The book does not attempt to include every conceivable aspect of analytical marine chemistry; rather, its authors describe methods they themselves have introduced or refined and that consistently yielded reproduc- ible results in everyday work.

Expanding the scope of the book was made possible thanks to the dedicated efforts of colleagues, who authored ground-breaking publications before yielding to our suggestions to make their abundant expertise available to those looking for advice. Substantial contributions were also made by the technical staff of the Department of Marine Chemistry, Insti- tute for Marine Research at the University of Kiel, Germany. We are specially indebted to - in alphabetical order - Hergen Johannsen, Gert Petrick, and Peter Streu for inspired work and creative ideas.

Compiling a multi-authored book puts considerable strain on the typists. We would have been in dire straits without Ute Weidingers vast skills and unfailing enthusiasm, ably assisted by Annelore Paulsen. Ilona Oelrichs of the Graphic Arts Department spent uncounted hours reproducing the figures many of which needed the helping hands of Maike Heinitz and Reinhold Hellwig.

Kiel, November 1998 Klaus Kremling Manfred Ehrhardt

Contents

List of contributors XXXI

1 Sampling 1 L. Briigmann and K . Kremling

1.1 Introduction 1

1.2 Sampling strategy 2

1.3 1.3.1 1.3.2 1.3.3 1.3.3.1 1.3.3.2 1.3.4 1.3.5 1.3.5.1 1.3.5.2

Sampling techniques 3 Surface water sampling 4 Water samplers for major hydrochemical variables Water samplers for trace constituents Trace elements 12 Trace organic compounds 14 Specific samplers 15 Collection of marine particles 17 Collection of suspended particulate matter (SPM) Collection of sinking particulates 18

6 12

17

1.4 Sampling errors 20

1.5 Quality control 22 1.5.1 Precision 22 1.5.2 Accuracy 22 1.5.3 Limit of detection 23

References to Chapter 1 24

2 Filtration and storage 27 K . Kremling and L. Briigmann

2.1 Filtration 27 2.1.1 General remarks 27 2.1.2 Filters 28 2.1.3 Filtration techniques 30 2.1.3.1 Vacuum filtration 31

x Contents

2.1.3.2 Pressure filtration 31 2.1.3.3 In situ filtration 31 2.1.3.4 Centrifugation 32

2.2 Storage 34 2.2.1 General remarks 34 2.2.2 Storage for the determination of major compounds 34 2.2.3 Storage for the determination of nutrients 36 2.2.3.1 General remarks 36 2.2.3.2 Refrigeration 36 2.2.3.3 Poisoning 37 2.2.4 Storage for the determination of trace elements 38


3 Determination of salinity 41 7: J. Miiller

3.1 Introduction 41

3.2 Symbols and abbreviations 42

3.3 Definition of salinity 42 3.3.1 Early concepts 42 3.3.2 The practical salinity scale of 1978 (PSS78) 44

3.4 Measurement of the conductivity ratio 48

3.5 3.5.1 3.5.2 3.5.3 3.5.4 3.5.5 3.5.6 3.5.7

Salinity from bench salinometers 49 Purpose 49 Standard seawater 49 Sampling 50 The Guildline AUTOSAL Model 8400 B The Beckman Model RSlO 56 Data logging 58 Substandards 60

52

3.6 Salinity from in situ measurements: CTD profilers 62 3.6.1 Principles 62 3.6.2 Operation of CTD-rosette sampler systems 63 3.6.3 Calibration 64 3.6.4 Data processing 68


Contents XI

4 Determination of oxygen 75 H. fl Hansen

4.1 Introduction 75

4.2 Principle of the determination 77

4.3 Error sources and interferences 79

4.4 Reagents 80

4.5 Instruments 81

4.6 4.6.1 4.6.2 4.6.3 4.6.4 4.6.5 4.6.6 4.6.7

Procedure 84 Standardization of the thiosulphate solution 84 Subsampling and fixation of dissolved oxygen 84 Storage 85 Titration 85 Determination of the reagent blank 85 Calculation of the result 86 Accuracy and precision 88


5 Determination of hydrogen sulphide 91 S. Fonselius, D. Dyrssen and B. Yhlen

5.1 Introduction 91

5.2 Units 92

5.3 5.3.1 5.3.1.1 5.3.1.2 5.3.1.3 5.3.1.4 5.3.1.5 5.3.1.6 5.3.1.7 5.3.1.8 5.3.1.9 5.3.2 5.3.2.1 5.3.2.2 5.3.2.3

Analytical methods 92 Method by Fonselius 92 Reagents 93 Special apparatus 94 Sampling 94 Preservation of samples 94 Procedure 94 Analysis 95 Dilution of samples 95 Standardization of the method 95 Calibration of the method 96 Method by Cline 97 Reagents 97 Special apparatus 98 Sampling 98

XI1 Contents

5.3.2.4 Procedure 98 5.3.2.5 Analysis 98 5.3.2.6 Standardization and calibration of the method 98 5.3.3 Titration methods 99 5.3.4 Methods using mercury compounds 100


6 Determination of thiosulphate and sulphur 101 D. Dyrssen, S. Fonselius and B. Yhlen

6.1 Introduction 101

6.2 6.2.1 6.2.2 6.2.3 6.2.4 6.2.4.1 6.2.4.2 6.2.5 6.2.6

Principle of the determination of thiosulphate Apparatus 102 Reagents 102 Sampling and storage 103 Procedure 103 Standardization of the thiosulphate solution Titration of the sample 103 Calculation of the thiosulphate content of the sample Interferences 104

102

103

104

6.3 Principle of the determination of sulphur 104 6.3.1 Apparatus 105 6.3.2 Reagents 105 6.3.3 Sampling and storage 106 6.3.4 Procedure 106 6.3.5 Calculations 106 6.3.6 Interferences 107

6.4 Other methods 107


7 Determination of pH 109 M. Wedborg, D.R. Turner, L.G. Anderson and D. Dyrssen


7.2 List of symbols 109

7.3 Definition of pH 110

7.4 pH scales in seawater 112

Contents XI11

7.5 7.5.1 7.5.1.1 7.5.1.2 7.5.1.3 7.5.2 7.5.2.1 7.5.2.2 7.5.2.3 7.5.3 7.5.4 7.5.4.1 7.5.4.2

8

8.1

8.2

8.3 8.3.1 8.3.2

8.4 8.4.1 8.4.2 8.4.2.1 8.4.2.2 8.4.2.3 8.4.3 8.4.3.1 8.4.3.2 8.4.3.3 8.4.3.4

8.5 8.5.1 8.5.2 8.5.2.1 8.5.2.2 8.5.2.3

Measurement of pH 114 Potentiometry 114 Theory 114 Tris buffers 115 Practical considerations 116 Spectrophotometry 118 Theory 118 Indicator p K values for seawater 120 Measurement procedures 120 Comparison of the various techniques 123 Correction of pH to in situ conditions 123 Empirical equations for correction to in situ temperature Empirical equations for correction to in situ pressure

124 124


Determination of total alkalinity and total dissolved inorganic carbon 127 L.G. Anderson, D.R. Turner, M. Wedborg and D. Dyrssen

Introduction 127

List of symbols 128

Sampling and reference materials 129 Sampling 129 Standard reference materials 129

Total alkalinity 130 Definition 130 Potentiometric titrations 130 Instrumentation 130 Analytical procedure 131 Evaluation procedures 131 Back titration method 135 Reagents 135 Analytical procedure Calculation of results Precision and accuracy

35 35 136

Total dissolved inorganic carbon 136 Potentiometric titrations 136 Coulometric determination technique 136 Instrumentation 137 Analytical procedure 139 Calculation and expression of results 140

XIV Contents

8.6 8.6.1 8.6.2 8.6.3 8.6.3.1 8.6.3.2 8.6.3.3 8.6.3.4 8.6.3.5 8.6.3.6 8.6.4

Thermodynamic calculations of the C 0 2 system in seawater Equations describing the C 0 2 system in seawater 141 Selection of stability constants 142 Calculations with two measured C 0 2 parameters 143 Calculations with pH and AT measured Calculations with pH and f(C02) measured 143 Calculations with pH and CT measured Calculations with AT and CT measured Calculations with AT andf(C02) measured 144 Calculations with CT andf(C02) measured 144 Errors arising from the calculations

141

143

144 144

144


Appendix 8A 147

9 Determination of carbon dioxide partial pressure @(COz)) 149 A. Kortzinger


9.2 Principle of the measurement 149

9.3 Apparatus for continuous mode of operation 150 9.3.1 The equilibrator 150 9.3.2 The analytical system 152

9.4 Reagents 154 9.4.1 Calibration gases 154 9.4.2 Gas purification reagents 155

9.5 Calculation of results 155

9.6 Accuracy 157


10 Determination of nutrients 159 H.P Hansen and E Koroleff

10.1 Introduction 159 10.1.1 Oceanic distributions of nutrients 159 10.1.2 Chemistry of nutrients in the marine environment 160

Contents XV

10.2 Analytical methods 162 10.2.1 Pretreatment of samples 164 10.2.2 The matrix 165 10.2.3 References and standard materials 167 10.2.4 Calibration, blank determination and calculation procedures 168 10.2.5 Determination of dissolved inorganic phosphate 170 10.2.5.1 Principle of the method 170 10.2.5.2 Range and precision 171 10.2.5.3 Interferences 172 10.2.5.4 Reagents 173 10.2.5.5 Analytical procedures 174 10.2.6 10.2.6.1 Principle of the method 175 10.2.6.2 Reagents 175 10.2.6.3 Analytical procedures 175 10.2.7

10.2.7.1 Principle of the method 176 10.2.7.2 Range and precision 176 10.2.7.3 Interferences 176 10.2.7.4 Reagents 176 10.2.7.5 Analytical procedure 176 10.2.8 Determination of nitrite 177 10.2.8.1 Principle of the method 177 10.2.8.2 Range and precision 177 10.2.8.3 Interferences 178 10.2.8.4 Reagents 178 10.2.8.5 Analytical procedures 179 10.2.9 Determination of nitrate 180 10.2.9.1 Principle of the method 180 10.2.9.2 Range and precision 182 10.2.9.3 Interferences 182 10.2.9.4 Reagents 183 10.2.9.5 Preparation of the reductor 183 10.2.9.6 Analytical procedures 185 10.2.10 Determination of ammonia 188 10.2.10.1 Principle of the method 188 10.2.10.2 Range and precision 189 10.2.10.3 Interferences 189 10.2.10.4 Reagents 190 10.2.10.5 Analytical procedures 191 10.2.1 1 Determination of dissolved inorganic silicate 193 10.2.11.1 Principle of the method 193 10.2.11.2 Range and precision 194 10.2.11.3 Interferences 194 10.2.11.4 Reagents 195 10.2.11.5 Analytical procedures 196

Determination of dissolved inorganic phosphate in the presence of arsenic 175

Determination of dissolved inorganic phosphate by an extraction procedure (high-sensitivity method) 175

XVI Contents

10.2.12

10.2.12.1 10.2.12.2 10.2.13

10.2.13.1 10.2.13.2 10.2.14

10.2.14.1 10.2.14.2 10.2.14.3 10.2.15 10.2.15.1 10.2.16 10.2.16.1 10.2.16.2 10.2.16.3 10.2.17

10.2.17.1 10.2.17.2 10.2.17.3 10.2.18 10.2.18.1 10.2.18.2 10.2.18.3 10.2.19 10.2.19.1 10.2.19.2

10.3 10.3.1 10.3.2 10.3.3 10.3.4 10.3.4.1 10.3.4.2 10.3.4.3 10.3.4.4 10.3.5 10.3.6

Determination of nitrogen, phosphorus and silicon in particulate and dissolved organic matter 198 Equipment 199 Calibration and calculation of total and organic nutrients 199 Determination of total and organic phosphorus by acid persulphate oxidation 200 Reagents 200 Analytical procedure 200 Determination of total and organic phosphorus by alkaline persulphate oxidation 201 Reagents 201 Analytical procedure 202 Dilution factors (see Section 10.2.12.2) 202 Determination of polyphosphates 202 Analytical procedure 202 Determination of total and organic nitrogen after persulphate oxidation 203 Range and precision of the method 204 Reagents 204 Analytical procedure 205 Simultaneous oxidation of nitrogen and phosphorus compounds with persulphate 205 Range and precision of the method 205 Oxidizing reagent 206 Analytical procedure 206 Determination of total silicon 206 Principle of the method 206 Reagents 207 Analytical procedure 207 Determination of total silicon by carbonate fusion Reagents 208 Analytical procedure 208

208

Automated nutrient analysis 208 Principle of automated analysis 209 The sampler 211 The proportioning pump 213 The analytical manifold 215 Standard manifold components 216 Heating and cooling 218 Special devices 219 The flow-through spectrophotometer 220 Data acquisition 221 System calibration 223


Contents XVII

11 Determination of the major constituents 229 K. Krernling


11.2 11.2.1 11.2.1.1 11.2.1.2 11.2.1.3 11.2.1.4 11.2.1.5 11.2.1.6 11.2.1.7

11.2.2 11.2.2.1 11.2.2.2 11.2.2.3 11.2.2.4 11.2.2.5 11.2.2.6 11.2.2.7 11.2.3 11.2.3.1 11.2.3.2 11.2.3.3 11.2.3.4 11.2.3.5 11.2.3.6 1 1.2.4 11.2.4.1 11.2.4.2 11.2.4.3 11.2.4.4 11.2.4.5 11.2.4.6 11.25 11.2.5.1 11.2.5.2 11.2.5.3 11.2.5.4 11.2.5.5 11.2.5.6 11.2.6 11.2.6.1 11.2.6.2

Analytical methods 230 Calcium 230 Principle of the method 230 Reagents and equipment 231 Standardization of the EGTA solution 231 Analysis of the sample 232 Calculation of results 232 Precision 232 Spectrophotometric EGTA titration with zincon and Zn-EGTA as indirect indicator 233 Magnesium 233 Principle of the method 233 Reagents and equipment 234 Standardization of EDTA solution 234 Analysis of the sample 235 Calculation of results 236 Precision 236 Ion-exchange separation of magnesium 237 Potassium 237 Principle of the method 237 Reagents and equipment 237 Analysis of the sample 238 Calculation of results 238 Precision 238 Potentiometric method 239 Chlorinity (high precision method) 239 Principle of the method 239 Reagents and equipment 240 Standardization of the silver nitrate solutions 240 Titration of the sample 241 Calculation of the chlorinity 242 Precision 242 Sulphate 242 Principle of the method 242 Reagents and equipment 243 Analysis of the sample 243 Calculation of results 243 Precision 244 Potentiometric back-titration method 244 Bromide 244 Principle of the method 244 Reagents and equipment 244

XVIII Contents

11.2.6.3 11.2.6.4 11.2.6.5 11.2.6.6 11.2.7 11.2.7.1 11.2.7.2 11.2.7.3 11.2.7.4 11.2.7.5 11.2.7.6 11.2.7.7 11.2.8 11.2.8.1 11.2.8.2 11.2.8.3 11.2.8.4 11.2.8.5 11.2.8.6

Standardization of the sodium thiosulphate solution Analysis of the sample 245 Calculation of results 246 Precision 246 Boron 246 Principle of the method 246 Reagents and equipment 247 Analysis of the sample 247 Calibration 247 Calculation of results 248 Precision 248 Mannitol-boric acid method 248 Fluoride 248 Principle of the method 248 Reagents and equipment 249 Analysis of the sample 249 Calibration 250 Calculation of results 250 Precision 250

245


Determination of trace elements 253 12.1-12.2.2 K. Kremling 12.2.3 M.O. Andreae 12.2.4 L. Briigmann 12.3 C.M.G. van den Berg 12.4 12.5 12.6

A. Prange and M. Schirmacher E Koroleff and K. Kremling L. Briigmann and J. Kuss

12.1 Introduction 253 12.1.1 Oceanic concentrations and distributions 253 12.1.2 Analytical options 256 12.1.3 Working environment and sample handling 257 12.1.4 Materials and cleaning procedures 259 12.1.5 Purification of reagents 261 12.1.6 Reference materials 263

12.2 Analysis by atomic absorption spectrometry 263 12.2.1 12.2.1.1 Principle of the method 264 12.2.1.2 Reagents and equipment 267 12.2.1.3 Analysis of the sample 268 12.2.1.4 Calculation of results 270 12.2.1.5 Precision, blank determination and detection limits 271

Cadmium, cobalt, copper, iron, lead, nickel and zinc by ETAAS 263

Contents XIX

12.2.2 12.2.2.1 12.2.2.2 12.2.2.3 12.2.2.4 12.2.2.5 12.2.3 12.2.3.1 12.2.3.2 12.2.3.3 12.2.4 12.2.4.1 12.2.4.2 12.2.4.3 12.2.4.4 12.2.4.5 12.2.4.6 12.2.4.7 12.2.4.8

12.3 12.3.1 12.3.2 12.3.3 12.3.4 12.3.5 12.3.5.1 12.3.6 12.3.6.1 12.3.7 12.3.7.1 12.3.7.2 12.3.7.3 12.3.7.4 12.3.7.5

12.4 12.4.1 12.4.2 12.4.2.1 12.4.2.2 12.4.2.3 12.4.2.4 12.4.2.5 12.4.2.6 12.4.2.7

Determination of manganese 272 Principle of the method 272 Reagents and equipment 272 Analysis of the sample 273 Calculation of results 273 Precision and blank determination 273 Arsenic, antimony and germanium 274 ff. Arsenic 274 Antimony 281 Germanium 286 Mercury 294 Introduction 294 Principle of the method 294 Reagents and equipment 295 Analysis of the sample 297 Calculation of results 299 Precision and determination of blanks Speciation studies 301 Automation 302

300

Analysis by electrochemical methods 302 Introduction 302 Potential scanning methods 303 Cathodic stripping voltammetry 305 Sample pre-treatment 305 Equipment 306 Equipment pre-treatment 306 Reagents 307 Reagent purification 307 Analytical procedures 308 Copper 308 Zinc 311 Nickel 313 Chromium 315 Cobalt 318

Analysis by total-reflection X-ray fluorescence spectrometry (TXRF) 320 Introduction 320 Analytical method 321 Principle of the TXRF technique Analytical features of the instrument 324 Sample pre-treatment 328 Apparatus and reagents 331 Analysis of seawater 334 Analysis of solid samples 337 Blanks, detection limits, precision and accuracy 338

322

XX Contents

12.5 12.5.1 12.5.1.1 12.5.1.2 12.5.1.3 12.5.1.4 12.5.1.5 12.5.1.6 12.5.2 12.5.2.1 12.5.2.2 12.5.2.3 12.5.2.4 12.5.2.5 12.5.2.6

12.6 12.6.1 12.6.2 12.6.2.1 12.6.2.2 12.6.2.3 12.6.2.4 12.6.3 12.6.3.1 12.6.3.2 12.6.3.3 12.6.4 12.6.4.1 12.6.4.2 12.6.4.3 12.6.4.4

12.5 Analysis by spectrophotometry 340 Iron 340 Principle of the method 340 Reagents and equipment 340 Analysis of the sample 341 Calibration 341 Calculation of results 342 Precision and blank determination 342 Manganese 342 Principle of the method 342 Reagents and equipment 343 Analysis of the sample 343 Calibration 34.4 Calculation of results 344 Precision and blank determination 34.4

Analysis of marine particles 345 Introduction 345 Methods of sampling 345 Sampling by pressure filtration 345 Sampling by in situ filtration 347 Sampling by continuous-flow centrifugation 348 Sampling by sediment traps 349 Sample pre-treatment 3.50 Weak acidic leaching 350 Total digestion 351 Sequential extraction 353 Instrumental detection 354 Instrumental detection by AAS 355 Instrumental detection by ICP-AES 356 Calculation of results 358 Accuracy, precision and blank values 358


13 Determination of natural radioactive tracers 365 M . M. Rutgers van der Loeff and W S. Moore


13.2 Sampling 368 13.2.1 Large-volume sampling 368 13.2.2 Particulate fraction 369 13.2.3 Dissolved fraction 369 13.2.3.1 Extraction with MnOz-coated fibres 369 13.2.3.2 Removal of adsorbed elements from Mn-fibre 372

Contents XXI

13.3 Analytical options 372 13.3.1 Radiometry versus mass spectrometry 372 13.3.2 Radioactivity measurements 372

13.4 Special requirements for laboratory 373

13.5 Reagents, spikes and standards 374

13.6 13.6.1 13.6.2 13.6.2.1 13.6.2.2 13.6.3 13.6.3.1 13.6.3.2 13.6.3.3 13.6.3.4

13.7 13.7.1 13.7.2 13.7.3 13.7.4 13.7.5 13.7.6 13.7.7

Instrumental techniques without radiochemical purification 376 Destructive versus non-destructive techniques 376 Particulate matter: direct counting of filters 376 Gamma spectrometry 376 Beta counting 377 Dissolved fraction: counting of fibre or precipitate Mn02-coated cartridges 378 Mn02 precipitate 379 BaS04 380 Fe(OH)3 380

378

Radiochemical methods for the separation of Tl-Po-Pb General analytical considerations 380 Total digestion 381 Fe(OH), precipitation 381 Polonium plating 381 Chloride column 382 Nitrate column 382 Thorium plating 382

380

13.8 Analytical procedures of selected nuclides 383

13.8.1 13.8.2 13.8.3 13.8.4

13.8.5 13.8.5.1 13.8.5.2 13.8.5.3 13.8.5.4 13.8.5.5

234Th 383 210Pb and 'loPo 385 'Be 385 A combined procedure for measurement of dissolved 234Th, 'loPb and 21"Po in 20 L samples Radium and radon measurements in seawater 386 Alpha scintillation measurement of 226Ra and 222Rn Measurement of 228Ra via "8Th ingrowth Gamma spectrometry measurement of 226Ra and 228Ra Delayed coincidence measurement of 223Ra and 224Ra 391 Alpha spectrometry measurement of 226Ra, 228Ra, 223Ra and 224Ra

385

386 388

389

393

13.9 Propagation of errors 394


XXII Contents

14 In situ determination of pH and oxygen 399 H. P Hansen


14.2 In situ determination of pH 399

14.3 In situ determination of oxygen 400


15 Determination of dissolved organic carbon and nitrogen by high temperature combustion 407 G. Cauwet

15.1 Introduction 407 15.1.1 Organic matter or organic carbon analysis 407 15.1.2 DOC and DON in seawater 407 15.1.3 Wet versus dry methods 408

15.2 Methods and instruments 408 15.2.1 Dry combustion or high temperature catalytic oxidation (HTCO) 408 15.2.2 Some instruments 409

15.3 Preparation of samples 409 15.3.1 Contamination problems 409 15.3.2 Sampling 410 15.3.3 Filtration 411 15.3.4 Sample storage 411

15.4 Blanks 412 15.4.1 Water blank 412 15.4.2 Instrument blank 412

15.5 Calibration 414 15.5.1 Carbon calibration 414 15.5.2 Nitrogen calibration 416

15.6 Samples processing 416 15.6.1 Removal of inorganic carbon 416 15.6.2 Determination of DOC 417 15.6.3 Determination of total dissolved nitrogen (TDN) 418 15.6.4 Personal comments 419

15.7 Conclusions 419


Contents XXIII

16

16.1

16.2 16.2.1 16.2.2 16.2.3 16.2.4

16.3

16.4

16.5

16.6 16.6.1 16.6.2 16.6.3 16.6.4

16.6.5 16.6.6

16.7 16.7.1 16.7.2 16.7.3 16.7.4

16.8 16.8.1 16.8.2 16.8.3 16.8.4 16.85

16.9

16.10

16.11

The automated determination of dissolved organic carbon by ultraviolet photooxidation 421 P J. Statham and P: J. le B. Williams

Introduction 421

Analytical strategy 423 Removal of inorganic carbon 423 Oxidation of organic carbon to carbon dioxide Carbon dioxide detection 425 Sampling, filtration and storage 425

424

Sampling 426

Filtration 426

Sample storage 427

Analysis 421 Equipment 427 Initial removal of inorganic carbon 428 The irradiator assembly 428 Removal of carbon dioxide from the irradiated sample, and drying of the gas stream 429 Determination of carbon dioxide in the gas stream by an IRGA 430 The autoanalyser manifold 430

Reagents and standards 431 Low organic carbon content (LOCC) water 431 Analytical reagents 432 Standards 432 Oxygen supply 432

Analytical procedure 433 Pre-analysis steps 433 Analysis 433 Sampling frequency 433 Blanks and calibration 434 System shut-down 434

Data analysis 434

Method performance 435

Identification and solution of common problems 435


XXIV Contents

17 Determination of particulate organic carbon and nitrogen 437 M. Ehrhardt and W Koeve


17.2 The elemental ratio of carbon and nitrogen 438

17.3 Sampling and filtration 438 17.3.1 Filtration of suspended particles 438

17.4 Sample preservation 439

17.5

17.6 Analysis 441 17.6.1 Apparatus 441 17.6.2 Reagents, analytical grade 441 17.6.3 Principle of the analysis 442 17.6.4 Analytical procedure 442

17.7 Calibration 443

Separation of particulate inorganic carbon from particulate organic carbon 440

17.8 Blanks 443


18 Preparation of lipophilic organic seawater concentrates 445 M, Ehrhardt and K.A. Burns


18.2 Outline of the method 446

18.3 Reagents 447

18.4 Apparatus and glassware 448

18.5 Cleaning of the resin 449

18.6 Resin blanks 450

18.7 Storage of adsorption columns 450

18.8 Sample preparation 450

18.9 Sample storage 451


Contents XXV

19 Adsorption chromatography of organic seawater concentrates 453 M. Ehrhardt and K.A. Burns


19.2 Outline of method 453

19.3 Reagents 453

19.4 Apparatus and glassware 454

19.5 Cleaning of silica gel 4.54 19.5.1 Cleaning by Soxhlet extraction 455 19.5.2 Cleaning by continuous extraction 455

19.6 Preparing a separation column 455

19.7 Sample separation 456


20 Clean-up of organic seawater concentrates 459 D.E. Schulz-Bull and J.C. Duinker

20.1 Introduction 459 20.1.1 Particular applications 459 20.1.2 General remarks 460

20.2 Reagents and equipment 460 20.2.1 Cleaning procedures 461 20.2.2 Calibration of the HPLC system 462 20.2.3 Procedural blanks 462

20.3 Compound group separation of seawater samples 463


21 Determination of petroleum residues dissolved and/or finely dispersed in surface seawater 467 M . Ehrhardt and K.A. Burns


21.2 Principle of the method 468

XXVI Contents

21.3 Reagents 469

21.4 Apparatus 469

21.5 Cleaning of glassware 471

21.6 Sampling and sample storage 471

21.7 Column chromatographic clean-up 472

21.8 Blanks 472

21.9 Spectrofluorimetric analysis 472

21.10 Calibration and quantification 473

21.11 Sources of error 474

21.12 Sensitivity and range of the method 475

21.13 Spectral scanning for source identification 475


22 Determination of selected organochlorine compounds in seawater 479 J. C. Duinker and D. E. Schulz-Bull

22.1 Introduction 479 22.1.1 Organochlorines in seawater 479

22.2 Sampling 482 22.2.1 General remarks 482 22.2.2 Sampling and filtration of seawater 482 22.2.2.1 Surface water sampling 483 22.2.2.2 Deep-water sampling 483

22.3 Laboratory procedures 484 22.3.1 22.3.2 Analyte enrichment 486 22.3.3 Volume reduction of organic solvents and solutions 488 22.3.4 Extraction of filters 488 22.3.5 Compound-class separation of extracts by HPLC 488

Cleaning and storage of glassware, filters, chemicals and solvents 485

22.4 Gas chromatographic separation and detection 489 22.4.1 Capillary columns and operating conditions 489

Contents XXVII

22.4.2 22.4.3 22.4.3.1 22.4.3.2 22.4.3.3 22.4.4 22.4.5 22.4.5.1 22.4.5.2 22.4.6 22.4.7 22.4.7.1 22.4.7.2

Single column and multi-dimensional gas chromatography Gases and gas supplies 491 Selection of carrier gas 492 Carrier gas impurities 492 Leaks 493 Sample injection 493 Detectors 494 The Electron Capture Detector (ECD) Mass spectrometry 495 Identification 496 Standards and quantification 497 Standards 497 Calibration 497

490

494

22.5 Interpretation and presentation of results 498


23 Determination of volatile halocarbons in seawater 501 E. hgrlqvist


23.2 Sampling of seawater 503

23.3 23.3.1 23.3.2 23.3.3 23.3.4 23.3.5 23.3.6 23.3.6.1 23.3.6.2 23.3.6.3 23.3.7

Purge and trap (P&T) work-up 505 Materials 506 Volumetric loops 506 Purging of halocarbons from the water Drying the purge gas 507 The valve oven 508 Trapping and desorption 509 Packed trap 510 Open tubular trap 510 Microtraps 510 Automation 51 1

506

23.4 Gas chromatography 511 23.4.1 Separation column 511 23.4.2 Two modes of halocarbon analysis 512

23.5 Detection 514 23.5.1 Electron capture detection 514 23.5.2 Mass spectrometry 515

XXVIII Contents

23.6 23.6.1 23.6.1.1 23.6.1.2 23.6.2 23.6.2.1 23.6.2.2 23.6.3

23.7 23.7.1 23.7.2 23.7.3

23.8

24

24.1

24.2 24.2.1 24.2.2

24.3 24.3.1 24.3.2 24.3.3 24.3.4 24.3.5

24.4

24.5

24.6

24.7

24.8

Calibration 515 Standard mixtures 516 Gaseous standards 516 Liquid standards 516 Calibration curves 516 Linear calibration curves 516 Non-linear calibration curves 517 Determination of extraction efficiency 517

Quality assessment 518 Sensitivity 518 Reproducibility 518 Accuracy 518

Acknowledgements 519


Determination of dimethyl sulphide in seawater 521 G. Uher

Distribution of dimethyl sulphide in seawater 521

Principle of the method 522 The flame photometric detector in the sulphur mode 522 Purge and trap preconcentration 523

Analytical system 524 Purge and trap unit 525 Cryogenic unit 526 Flame photometric detector and gas supply 526 Sampling manifold 527 Control unit 527

Procedure 527

System optimisation and test procedures 528

Calibration 529

Precision 530

Sampling and storage 531


klaus grasshoff/klaus kremlingl manfred ehrhardt methods ... · preface to the third edition...

Documents