Sea Water Analysis

Klaus Grasshoff
Klaus Kremling
Manfred Ehrhardt
Methods of
Seawater Analysis
8WILEY-VCH
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
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
0WILEY-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 specificallymarked 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 con-
stituents 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 pos-
sible by multi-dimensional gas chromatography. Chapters on pH and total dissolved inor-
ganic 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 contribu-
tions 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 Sampling techniques 3

1.3.1 Surface water sampling 4
1.3.2 Water samplers for major hydrochemical variables 6
1.3.3 Water samplers for trace constituents 12
1.3.3.1 Trace elements 12
1.3.3.2 Trace organic compounds 14
1.3.4 Specific samplers 15
1.3.5 Collection of marine particles 17
1.3.5.1 Collection of suspended particulate matter (SPM) 17
1.3.5.2 Collection of sinking particulates 18
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
2.2.2 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 Salinity from bench salinometers 49

3.5.1 Purpose 49
3.5.2 Standard seawater 49
3.5.3 Sampling 50
3.5.4 The Guildline AUTOSAL Model 8400 B 52
3.5.5 The Beckman Model RSlO 56
3.5.6 Data logging 58
3.5.7 Substandards 60
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 Procedure 84
4.6.1 Standardization of the thiosulphate solution 84
4.6.2 Subsampling and fixation of dissolved oxygen 84
4.6.3 Storage 85
4.6.4 Titration 85
4.6.5 Determination of the reagent blank 85
4.6.6 Calculation of the result 86
4.6.7 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 Analytical methods 92

5.3.1 Method by Fonselius 92
5.3.1.1 Reagents 93
5.3.1.2 Special apparatus 94
5.3.1.3 Sampling 94
5.3.1.4 Preservation of samples 94
5.3.1.5 Procedure 94
5.3.1.6 Analysis 95
5.3.1.7 Dilution of samples 95
5.3.1.8 Standardization of the method 95
5.3.1.9 Calibration of the method 96
5.3.2 Method by Cline 97
5.3.2.1 Reagents 97
5.3.2.2 Special apparatus 98
5.3.2.3 Sampling 98
XI1 Contents
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 Principle of the determination of thiosulphate 102

6.2.1 Apparatus 102
6.2.2 Reagents 102
6.2.3 Sampling and storage 103
6.2.4 Procedure 103
6.2.4.1 Standardization of the thiosulphate solution 103
6.2.4.2 Titration of the sample 103
6.2.5 Calculation of the thiosulphate content of the sample 104
6.2.6 Interferences 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 Measurement of pH 114
7.5.1 Potentiometry 114
7.5.1.1 Theory 114
7.5.1.2 Tris buffers 115
7.5.1.3 Practical considerations 116
7.5.2 Spectrophotometry 118
7.5.2.1 Theory 118
7.5.2.2 Indicator p K values for seawater 120
7.5.2.3 Measurement procedures 120
7.5.3 Comparison of the various techniques 123
7.5.4 Correction of pH to in situ conditions 123
7.5.4.1 Empirical equations for correction to in situ temperature 124
7.5.4.2 Empirical equations for correction to in situ pressure 124
8 Determination of total alkalinity and total dissolved inorganic carbon 127

L.G. Anderson, D.R. Turner, M . Wedborg and D. Dyrssen
8.2 List of symbols 128
8.3 Sampling and reference materials 129

8.3.1 Sampling 129
8.3.2 Standard reference materials 129
8.4 Total alkalinity 130

8.4.1 Definition 130
8.4.2 Potentiometric titrations 130
8.4.2.1 Instrumentation 130
8.4.2.2 Analytical procedure 131
8.4.2.3 Evaluation procedures 131
8.4.3 Back titration method 135
8.4.3.1 Reagents 135
8.4.3.3 Calculation of results 35
8.4.3.4 Precision and accuracy 136
8.5 Total dissolved inorganic carbon 136

8.5.1 Potentiometric titrations 136
8.5.2 Coulometric determination technique 136
8.5.2.1 Instrumentation 137
8.5.2.3 Calculation and expression of results 140
XIV Contents
8.6 Thermodynamic calculations of the C 0 2 system in seawater 141

8.6.1 Equations describing the C 0 2 system in seawater 141
8.6.2 Selection of stability constants 142
8.6.3 Calculations with two measured C 0 2 parameters 143
8.6.3.1 Calculations with pH and AT measured 143
8.6.3.2 Calculations with pH and f(C02) measured 143
8.6.3.3 Calculations with pH and CT measured 144
8.6.3.4 Calculations with AT and CTmeasured 144
8.6.3.5 Calculations with ATandf(C02) measured 144
8.6.3.6 Calculations with CTandf(C02) measured 144
8.6.4 Errors arising from the calculations 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

10.1.1 Oceanic distributions of nutrients 159
10.1.2 Chemistry of nutrients in the marine environment 160
Contents XV
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 Determination of dissolved inorganic phosphate in the presence of arsenic 175
10.2.6.2 Reagents 175
10.2.7 Determination of dissolved inorganic phosphate by an extraction
procedure (high-sensitivity method) 175
10.2.7.4 Reagents 176
10.2.8 Determination of nitrite 177
10.2.8.4 Reagents 178
10.2.9 Determination of nitrate 180
10.2.9.4 Reagents 183
10.2.9.5 Preparation of the reductor 183
10.2.10 Determination of ammonia 188
10.2.10.4 Reagents 190
10.2.11 Determination of dissolved inorganic silicate 193
10.2.11.4 Reagents 195
XVI Contents
10.2.12 Determination of nitrogen, phosphorus and silicon in particulate and

dissolved organic matter 198
10.2.12.1 Equipment 199
10.2.12.2 Calibration and calculation of total and organic nutrients 199
10.2.13 Determination of total and organic phosphorus by acid persulphate
oxidation 200
10.2.13.1 Reagents 200
10.2.14 Determination of total and organic phosphorus by alkaline
persulphate oxidation 201
10.2.14.1 Reagents 201
10.2.14.3 Dilution factors (see Section 10.2.12.2) 202
10.2.15 Determination of polyphosphates 202
10.2.16 Determination of total and organic nitrogen after persulphate oxidation 203
10.2.16.1 Range and precision of the method 204
10.2.16.2 Reagents 204
10.2.17 Simultaneous oxidation of nitrogen and phosphorus compounds with
persulphate 205
10.2.17.1 Range and precision of the method 205
10.2.17.2 Oxidizing reagent 206
10.2.18 Determination of total silicon 206
10.2.18.2 Reagents 207
10.2.19 Determination of total silicon by carbonate fusion 208
10.2.19.1 Reagents 208
10.3 Automated nutrient analysis 208

10.3.1 Principle of automated analysis 209
10.3.2 The sampler 211
10.3.3 The proportioning pump 213
10.3.4 The analytical manifold 215
10.3.4.1 Standard manifold components 216
10.3.4.2 Heating and cooling 218
10.3.4.3 Special devices 219
10.3.4.4 The flow-through spectrophotometer 220
10.3.5 Data acquisition 221
10.3.6 System calibration 223

Contents XVII
11 Determination of the major constituents 229
K. Krernling

11.2.1 Calcium 230
11.2.1.2 Reagents and equipment 231
11.2.1.3 Standardization of the EGTA solution 231
11.2.1.4 Analysis of the sample 232
11.2.1.6 Precision 232
11.2.1.7 Spectrophotometric EGTA titration with zincon and Zn-EGTA as indirect
indicator 233
11.2.2 Magnesium 233
11.2.2.3 Standardization of EDTA solution 234
11.2.2.7 Ion-exchange separation of magnesium 237
11.2.3 Potassium 237
11.2.3.6 Potentiometric method 239
1 1.2.4 Chlorinity (high precision method) 239
11.2.4.3 Standardization of the silver nitrate solutions 240
11.2.4.4 Titration of the sample 241
11.2.4.5 Calculation of the chlorinity 242
11.25 Sulphate 242
11.2.5.6 Potentiometric back-titration method 244
11.2.6 Bromide 244
XVIII Contents
11.2.6.3 Standardization of the sodium thiosulphate solution 245

11.2.7 Boron 246
11.2.7.4 Calibration 247
11.2.7.7 Mannitol-boric acid method 248
11.2.8 Fluoride 248
Determinationof 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 A. Prange and M . Schirmacher
12.5 E Koroleff and K . Kremling
12.6 L. Briigmann and J. Kuss

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 Cadmium, cobalt, copper, iron, lead, nickel and zinc by ETAAS 263
12.2.1.5 Precision, blank determination and detection limits 271
Contents XIX
12.2.2 Determination of manganese 272
12.2.2.5 Precision and blank determination 273
12.2.3 Arsenic, antimony and germanium 274 ff.
12.2.3.1 Arsenic 274
12.2.3.2 Antimony 281
12.2.3.3 Germanium 286
12.2.4 Mercury 294
12.2.4.1 Introduction 294
12.2.4.6 Precision and determination of blanks 300
12.2.4.7 Speciation studies 301
12.2.4.8 Automation 302
12.3 Analysis by electrochemical methods 302

12.3.1 Introduction 302
12.3.2 Potential scanning methods 303
12.3.3 Cathodic stripping voltammetry 305
12.3.4 Sample pre-treatment 305
12.3.5 Equipment 306
12.3.5.1 Equipment pre-treatment 306
12.3.6 Reagents 307
12.3.6.1 Reagent purification 307
12.3.7 Analytical procedures 308
12.3.7.1 Copper 308
12.3.7.2 Zinc 311
12.3.7.3 Nickel 313
12.3.7.4 Chromium 315
12.3.7.5 Cobalt 318
12.4 Analysis by total-reflection X-ray fluorescence spectrometry (TXRF) 320

12.4.2 Analytical method 321
12.4.2.1 Principle of the TXRF technique 322
12.4.2.2 Analytical features of the instrument 324
12.4.2.3 Sample pre-treatment 328
12.4.2.4 Apparatus and reagents 331
12.4.2.5 Analysis of seawater 334
12.4.2.6 Analysis of solid samples 337
12.4.2.7 Blanks, detection limits, precision and accuracy 338
XX Contents
12.5 12.5 Analysis by spectrophotometry 340

12.5.1 Iron 340
12.5.1.6 Precision and blank determination 342
12.5.2 Manganese 342
12.5.2.4 Calibration 34.4
12.5.2.6 Precision and blank determination 34.4
12.6 Analysis of marine particles 345

12.6.2 Methods of sampling 345
12.6.2.1 Sampling by pressure filtration 345
12.6.2.2 Sampling by in situ filtration 347
12.6.2.3 Sampling by continuous-flow centrifugation 348
12.6.2.4 Sampling by sediment traps 349
12.6.3 Sample pre-treatment 3.50
12.6.3.1 Weak acidic leaching 350
12.6.3.2 Total digestion 351
12.6.3.3 Sequential extraction 353
12.6.4 Instrumental detection 354
12.6.4.1 Instrumental detection by AAS 355
12.6.4.2 Instrumental detection by ICP-AES 356
12.6.4.4 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 Instrumental techniques without radiochemical purification 376

13.6.1 Destructive versus non-destructive techniques 376
13.6.2 Particulate matter: direct counting of filters 376
13.6.2.1 Gamma spectrometry 376
13.6.2.2 Beta counting 377
13.6.3 Dissolved fraction: counting of fibre or precipitate 378
13.6.3.1 Mn02-coated cartridges 378
13.6.3.2 Mn02 precipitate 379
13.6.3.3 BaS04 380
13.6.3.4 Fe(OH)3 380
13.7 Radiochemical methods for the separation of Tl-Po-Pb 380

13.7.1 General analytical considerations 380
13.7.2 Total digestion 381
13.7.3 Fe(OH), precipitation 381
13.7.4 Polonium plating 381
13.7.5 Chloride column 382
13.7.6 Nitrate column 382
13.7.7 Thorium plating 382
13.8 Analytical procedures of selected nuclides 383
13.8.1 234Th 383

13.8.2 210Pband 'loPo 385
13.8.3 'Be 385
13.8.4 A combined procedure for measurement of dissolved 234Th,'loPb
and 21"Poin 20 L samples 385
13.8.5 Radium and radon measurements in seawater 386
13.8.5.1 Alpha scintillation measurement of 226Raand 222Rn 386
13.8.5.2 Measurement of 228Ravia "8Th ingrowth 388
13.8.5.3 Gamma spectrometry measurement of 226Raand 228Ra 389
13.8.5.4 Delayed coincidence measurement of 223Raand 224Ra 391
13.8.5.5 Alpha spectrometry measurement of 226Ra,228Ra,223Raand 224Ra 393
13.9 Propagation of errors 394

XXII Contents
14 In situ determination of pH and oxygen 399

H. P Hansen
14.2 I n situ determination of pH 399
14.3 I n situ determination of oxygen 400
15 Determination of dissolved organic carbon and nitrogen

by high temperature combustion 407
G. Cauwet

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 The automated determination of dissolved organic carbon

by ultraviolet photooxidation 421
P J. Statham and P: J. le B. Williams
16.2 Analytical strategy 423

16.2.1 Removal of inorganic carbon 423
16.2.2 Oxidation of organic carbon to carbon dioxide 424
16.2.3 Carbon dioxide detection 425
16.2.4 Sampling, filtration and storage 425
16.3 Sampling 426
16.4 Filtration 426
16.5 Sample storage 427
16.6 Analysis 421

16.6.2 Initial removal of inorganic carbon 428
16.6.3 The irradiator assembly 428
16.6.4 Removal of carbon dioxide from the irradiated sample,
and drying of the gas stream 429
16.6.5 Determination of carbon dioxide in the gas stream by an IRGA 430
16.6.6 The autoanalyser manifold 430
16.7 Reagents and standards 431

16.7.1 Low organic carbon content (LOCC) water 431
16.7.2 Analytical reagents 432
16.7.3 Standards 432
16.7.4 Oxygen supply 432
16.8 Analytical procedure 433

16.8.1 Pre-analysis steps 433
16.8.2 Analysis 433
16.8.3 Sampling frequency 433
16.8.4 Blanks and calibration 434
16.85 System shut-down 434
16.9 Data analysis 434
16.10 Method performance 435
16.11 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 Separation of particulate inorganic carbon from particulate organic carbon 440
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
17.8 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

20.1.1 Particular applications 459
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

22.1.1 Organochlorines in seawater 479
22.2 Sampling 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 Cleaning and storage of glassware, filters, chemicals and solvents 485
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
22.4 Gas chromatographic separation and detection 489

22.4.1 Capillary columns and operating conditions 489
Contents XXVII
22.4.2 Single column and multi-dimensional gas chromatography 490

22.4.3 Gases and gas supplies 491
22.4.3.1 Selection of carrier gas 492
22.4.3.2 Carrier gas impurities 492
22.4.3.3 Leaks 493
22.4.4 Sample injection 493
22.4.5 Detectors 494
22.4.5.1 The Electron Capture Detector (ECD) 494
22.4.5.2 Mass spectrometry 495
22.4.6 Identification 496
22.4.7 Standards and quantification 497
22.4.7.1 Standards 497
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 Purge and trap (P&T) work-up 505

23.3.1 Materials 506
23.3.2 Volumetric loops 506
23.3.3 Purging of halocarbons from the water 506
23.3.4 Drying the purge gas 507
23.3.5 The valve oven 508
23.3.6 Trapping and desorption 509
23.3.6.1 Packed trap 510
23.3.6.2 Open tubular trap 510
23.3.6.3 Microtraps 510
23.3.7 Automation 51 1
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
23.6.1 Standard mixtures 516
23.6.1.1 Gaseous standards 516
23.6.1.2 Liquid standards 516
23.6.2 Calibration curves 516
23.6.2.1 Linear calibration curves 516
23.6.2.2 Non-linear calibration curves 517
23.6.3 Determination of extraction efficiency 517
23.7 Quality assessment 518

23.7.1 Sensitivity 518
23.7.2 Reproducibility 518
23.7.3 Accuracy 518
23.8 Acknowledgements 519
24 Determination of dimethyl sulphide in seawater 521

G. Uher
24.1 Distribution of dimethyl sulphide in seawater 521
24.2 Principle of the method 522

24.2.1 The flame photometric detector in the sulphur mode 522
24.2.2 Purge and trap preconcentration 523
24.3 Analytical system 524

24.3.1 Purge and trap unit 525
24.3.2 Cryogenic unit 526
24.3.3 Flame photometric detector and gas supply 526
24.3.4 Sampling manifold 527
24.3.5 Control unit 527
24.4 Procedure 527
24.5 System optimisation and test procedures 528
24.7 Precision 530
24.8 Sampling and storage 531

Contents XXlX
25 Determination of marine humic material 533
G. Liehezeit
25.2 Instrumentation 534
25.3 Dissolved humic substances (DHS) 534

25.3.1 Sampling 534
25.3.2 Fluorimetry 535
25.4 Particulate humic compounds 535

25.4.1 Chemicals 535
25.4.2 Extraction 536
25.4.3 Lipid-associated humic compounds (LHC) 536

25.5.1 Standardization with quinine sulphate 536
25.5.2 DHS and PHC standards 537
25.5.3 Linear range of instrument response 537
25.5.4 Preparation of PHC standards 538
25.6 Synchronous excitation fluorimetry 538
26 Determination of amino acids and carbohydrates 541

G. Liebezeit and B. Behrends
26.2 General remarks 541
26.3 Dissolved free amino acids (DFAA) 542

26.3.1 Compound class reaction 542
26.3.2 Reagents 543
26.3.3 Manual procedure 543
26.3.4 Automatic procedure 543
26.3.5 Flow injection analysis (FIA) 545
26.4 Dissolved combined amino acids (DCAA) 545
26.5 Dissolved carbohydrates 546

26.5.1 Compound class reactions 546
26.5.2 Reagents 546
26.5.3 Procedure 547
xxx Contents

26.5.5 Analytical range 548
26.5.6 Estimation of polysaccharide content (PCHO) 548
26.5.7 Mono- and polysaccharides after aqueous extraction of particulate matter 549
26.6 Chromatographic separation of amino acids 549

26.6.3 HPLC columns 550
26.6.4 Detection 550
26.6.5 Analysis 550
26.6.5.1 Mobile phases 550
26.6.5.2 Gradient conditions 551
26.6.6 Pre-column denvatisation 553
26.6.6.1 Reagents 553
26.6.6.3 Use of internal standard 553
26.7 Chromatographic separation of carbohydrates 554
27 Determination of photosynthetic pigments 557

P Wallersteinand G. Liebezeit
27.2 Sampling 559
27.3 Extraction 559
27.4 Work-up artefacts 560
27.5 HPLC analysis 560

27.5.1 Separation 561
27.5.2 Matrix effects 563
27.5.3 Temperature effects 563
27.5.4 Column ageing 563
27.5.5 Detection 563
27.5.6 Standardization 564
27.5.7 HPLC systems 564
Appendix 567
Index 577
List of Contributors
Meinrat 0. Andreae Jan C. Duinker

Max-Planck-Institut fur Chemie Institut fur Meereskunde
Postfach 3060 an der Universitat Kiel
55122 Mainz Abteilung Meereschemie
Germany Dustembrooker Weg 20
Leif G. Anderson 24105 Kiel
Department of Analytical and Marine Chemistry Germany
Goteborg University David Dyrssen
41296 Goteborg Department of Analytical and Marine Chemistry
Sweden Goteborg University
Brigitte Behrends 41296 Goteborg
Sweden
Zentrum fur Flachmeer-, Kusten- und
Meeresumweltforschung Manfred G. Ehrhardt
Forschungszentrum Terramarc Institut fur Meereskunde
SchleusenstraRe 1 an der Universitat Kiel
26382 Wilhelmshaven Abteilung Meereschemie
Germany Dusternbrooker Weg 20
24105 Kiel
Constant M. G. van den Berg
Oceanographic Laboratory Germany
University of Liverpool Elisabet Fogelqvist
Liverpool L69 3BX Department of Chemistry
United Kingdom Analytical and Marine Chemistry
Lutz Brugmann Goteborg University
Hartkriigen 30 S-41296 Goteborg
Sweden
22559 Hamburg
Germany Stig Fonselius
SMHI Oceanographical Laboratory
Detlef E. Schulz-Bull
Nya Varvet 31
Institut fur Meereskunde
an der Universitat Kiel S-42671 Vastra Frolunda
Abteilung Meereschemie Sweden
Dusternbrooker Weg 20 Hans Peter Hansen
24105 Kiel Institut fur Meereskunde
Germany an der Universitat Kiel
Abteilung Meereschemie
Kathryn A. Burns
Australian Institute for Marine Science Dusternbrooker Weg 20
P. 0. Box 3 24105 Kiel
Germany
Townsville, Qld 4810
Australia Wolfgang Koeve
Institut fur Meereskunde
Gustave Cauwet
Observatoir OcCanologique an der Universitat Kiel
Labortoire d’0cCanographie Biologique Abteilung Planktologie
(CNRS-URA 2071) Dustembrooker Weg 20
BP 44 24105 Kiel
66651 Banyuls sur Mer Germany
France
XXXII List of Contributors
Folke Koroleff Andreas Prange
Institute of Marine Research GKSS-Forschungszentrum
P. 0. Box 33 Postfach 1160
SF-00931 Helsinki 93 21494 Geesthach
Finland Germany
Arne Kortzinger Martina Schirmacher
Institut fur Meereskunde GKSS-Forschungszentrm
an der Universitat Kiel Postfach 1160
Abteilung Meereschemie 21494 Geesthach
Diisternbrooker Weg 20 Germany
24105 Kiel Peter J. Statham
Germany University of Southampton
Klaus Kremling Department of Oceanography
Institut fur Meereskunde Waterfront Campus, European Way
an der Universitat Kiel Southampton SO14 3ZH
Abteilung Meereschemie United Kingdom
Diistembrooker Weg 20 David R. Turner
24105 Kiel Department of Analytical and
Germany Marine Chemistry
Joachim Kuss Goteborg University
Institut fiir Meereskunde 41296 Goteborg
an der Universitat Kiel Sweden
Abteilung Meereschemie Giinther Uher
Diisternbrooker Weg 20 University of Newcastle upon Tyne
24105 Kiel Department of Marine Sciences and
Germany Coastal Management
Gerd Liebezeit Ridley Building (Claremont Road)
Zentrum fur Flachmeer-, Kiisten- und Newcastle upon Tyne NE17RU
Meeresumweltforschung United Kingdom
Forschungszentrum Terramare Bengt Yhlen
SchleusenstraBe 1 SMHI Oceanographical Laboratory
26382 Wilhelmshaven Nya Vervet 31
Germany 42671 Vastra Frolunda
Michiel Ruttgers van der Loeff Sweden
Alfred-Wegener-Institut fiir Polar- und Petra Wallerstein
Meeresforschung Zentrum fur Flachmeer-, Kiisten- und
Postfach 120161 Meeresumweltforschung
27568 Bremerhaven Forschungszentrum Terramare
Germany SchleusenstraBe 1
Willard S. Moore 26382 Wilhelmshaven
Geology Department Germany
University of South Carolina Margareta Wedborg
Columbia SC 29208 Department of Analytical and
U.S.A. Marine Chemistry
Thomas J. Muller Goteborg University
Institut fur Meereskunde 41296 Goteborg
an der Universitat Kiel Sweden
Abteilung Meeresphysik Peter J. le B. Williams
Diistembrooker Weg 20 School of Ocean Sciences
24105 Kiel Menai Bridge
Germ any Gwynedd LL59 5EY
United Kingdom

Sea Water Analysis

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Sea Water Analysis

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Klaus Grasshoff

Dr. Klaus Kremling

Cover Illustration: Dr. Arne Kortzinger

Library of Congress Card No.:

British Library Cataloguing-in-Publication Data:

Die Deutsche Bibliothek Cataloguing-in-Publication Data:

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

Printed on acid-free and chlorine-free paper.

Kiel, November 1998 Klaus Kremling

List of contributors XXXI

1.2 Sampling strategy 2

1.3 Sampling techniques 3

1.4 Sampling errors 20

1.5 Quality control 22

2 Filtration and storage 27

2.1.3.2 Pressure filtration 31

3.2 Symbols and abbreviations 42

3.3 Definition of salinity 42

3.4 Measurement of the conductivity ratio 48

3.5 Salinity from bench salinometers 49

3.6 Salinity from in situ measurements: CTD profilers 62

4.2 Principle of the determination 77

4.3 Error sources and interferences 79

5 Determination of hydrogen sulphide 91

5.3 Analytical methods 92

References to Chapter 5 100

6 Determination of thiosulphate and sulphur 101

6.1 Introduction 101

6.2 Principle of the determination of thiosulphate 102

6.3 Principle of the determination of sulphur 104

6.4 Other methods 107

References to Chapter 6 108

7.1 Introduction 109

7.2 List of symbols 109

7.3 Definition of pH 110

7.4 pH scales in seawater 112

References to Chapter 7 125

8 Determination of total alkalinity and total dissolved inorganic carbon 127

8.1 Introduction 127

8.2 List of symbols 128

8.3 Sampling and reference materials 129

8.4 Total alkalinity 130

8.5 Total dissolved inorganic carbon 136

8.6 Thermodynamic calculations of the C 0 2 system in seawater 141

References to Chapter 8 146

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

9.1 Introduction 149

9.2 Principle of the measurement 149

9.3 Apparatus for continuous mode of operation 150

9.4 Reagents 154

9.5 Calculation of results 155

9.6 Accuracy 157

References to Chapter 9 158

10 Determination of nutrients 159

10.1 Introduction 159

10.2.12 Determination of nitrogen, phosphorus and silicon in particulate and

10.3 Automated nutrient analysis 208

References to Chapter 10 226

11.1 Introduction 229

11.2 Analytical methods 230

11.2.6.3 Standardization of the sodium thiosulphate solution 245

References to Chapter 11 250

Determinationof trace elements 253