Methods of Seawater Analysis [3rd, completely rev. and extended ed] 3527295895, 9783527295890

Table of contents :
Methods of Seawater Analysis......Page 5
Contents......Page 11
List of contributors......Page 33
1.1 Introduction......Page 35
1.2 Sampling strategy......Page 36
1.3 Sampling techniques......Page 37
1.3.1 Surface water sampling......Page 38
1.3.2 Water samplers for major hydrochemical variables......Page 40
1.3.3.1 Trace elements......Page 46
1.3.3.2 Trace organic compounds......Page 48
1.3.4 Specific samplers......Page 49
1.3.5.1 Collection of suspended particulate matter (SPM)......Page 51
1.3.5.2 Collection of sinking particulates......Page 52
1.4 Sampling errors......Page 54
1.5.2 Accuracy......Page 56
1.5.3 Limit of detection......Page 57
References to Chapter 1......Page 58
2.1.1 General remarks......Page 61
2.1.2 Filters......Page 62
2.1.3 Filtration techniques......Page 64
2.1.3.3 In situ filtration......Page 65
2.1.3.4 Centrifugation......Page 66
2.2.2 Storage for the determination of major compounds......Page 68
2.2.3.2 Refrigeration......Page 70
2.2.3.3 Poisoning......Page 71
2.2.4 Storage for the determination of trace elements......Page 72
References to Chapter 2......Page 73
3.1 Introduction......Page 75
3.3.1 Early concepts......Page 76
3.3.2 The practical salinity scale of 1978 (PSS78)......Page 78
3.4 Measurement of the conductivity ratio......Page 82
3.5.2 Standard seawater......Page 83
3.5.3 Sampling......Page 84
3.5.4 The Guildline AUTOSAL Model 8400 B......Page 86
3.5.5 The Beckman Model RS1O......Page 90
3.5.6 Data logging......Page 92
3.5.7 Substandards......Page 94
3.6.1 Principles......Page 96
3.6.2 Operation of CTD-rosette sampler systems......Page 97
3.6.3 Calibration......Page 98
3.6.4 Data processing......Page 102
References to Chapter 3......Page 107
4.1 Introduction......Page 109
4.2 Principle of the determination......Page 111
4.3 Error sources and interferences......Page 113
4.4 Reagents......Page 114
4.5 Instruments......Page 115
4.6.2 Subsampling and fixation of dissolved oxygen......Page 118
4.6.5 Determination of the reagent blank......Page 119
4.6.6 Calculation of the result......Page 120
4.6.7 Accuracy and precision......Page 122
References to Chapter 4......Page 123
5.1 Introduction......Page 125
5.3.1 Method by Fonselius......Page 126
5.3.1.1 Reagents......Page 127
5.3.1.5 Procedure......Page 128
5.3.1.8 Standardization of the method......Page 129
5.3.1.9 Calibration of the method......Page 130
5.3.2.1 Reagents......Page 131
5.3.2.6 Standardization and calibration of the method......Page 132
5.3.3 Titration methods......Page 133
References to Chapter 5......Page 134
6.1 Introduction......Page 135
6.2.2 Reagents......Page 136
6.2.4.2 Titration of the sample......Page 137
6.3 Principle of the determination of sulphur......Page 138
6.3.2 Reagents......Page 139
6.3.5 Calculations......Page 140
6.4 Other methods......Page 141
References to Chapter 6......Page 142
7.2 List of symbols......Page 143
7.3 Definition of pH......Page 144
7.4 pH scales in seawater......Page 146
7.5.1.1 Theory......Page 148
7.5.1.2 Tris buffers......Page 149
7.5.1.3 Practical considerations......Page 150
7.5.2.1 Theory......Page 152
7.5.2.3 Measurement procedures......Page 154
7.5.4 Correction of pH to in situ conditions......Page 157
7.5.4.2 Empirical equations for correction to in situ pressure......Page 158
References to Chapter 7......Page 159
8.1 Introduction......Page 161
8.2 List of symbols......Page 162
8.3.2 Standard reference materials......Page 163
8.4.2.1 Instrumentation......Page 164
8.4.2.3 Evaluation procedures......Page 165
8.4.3.3 Calculation of results......Page 169
8.5.2 Coulometric determination technique......Page 170
8.5.2.1 Instrumentation......Page 171
8.5.2.2 Analytical procedure......Page 173
8.5.2.3 Calculation and expression of results......Page 174
8.6.1 Equations describing the CO2 system in seawater......Page 175
8.6.2 Selection of stability constants......Page 176
8.6.3.2 Calculations with pH and f(CO2) measured......Page 177
8.6.4 Errors arising from the calculations......Page 178
References to Chapter 8......Page 180
Appendix 8A......Page 181
9.2 Principle of the measurement......Page 183
9.3.1 The equilibrator......Page 184
9.3.2 The analytical system......Page 186
9.4.1 Calibration gases......Page 188
9.5 Calculation of results......Page 189
9.6 Accuracy......Page 191
References to Chapter 9......Page 192
10.1.1 Oceanic distributions of nutrients......Page 193
10.1.2 Chemistry of nutrients in the marine environment......Page 194
10.2 Analytical methods......Page 196
10.2.1 Pretreatment of samples......Page 198
10.2.2 The matrix......Page 199
10.2.3 References and standard materials......Page 201
10.2.4 Calibration, blank determination and calculation procedures......Page 202
10.2.5.1 Principle of the method......Page 204
10.2.5.2 Range and precision......Page 205
10.2.5.3 Interferences......Page 206
10.2.5.4 Reagents......Page 207
10.2.5.5 Analytical procedures......Page 208
10.2.7 Determination of dissolved inorganic phosphate by an extraction procedure (high-sensitivity method)......Page 209
10.2.7.5 Analytical procedure......Page 210
10.2.8.2 Range and precision......Page 211
10.2.8.4 Reagents......Page 212
10.2.8.5 Analytical procedures......Page 213
10.2.9.1 Principle of the method......Page 214
10.2.9.3 Interferences......Page 216
10.2.9.5 Preparation of the reductor......Page 217
10.2.9.6 Analytical procedures......Page 219
10.2.10.1 Principle of the method......Page 222
10.2.10.3 Interferences......Page 223
10.2.10.4 Reagents......Page 224
10.2.10.5 Analytical procedures......Page 225
10.2.11.1 Principle of the method......Page 227
10.2.11.3 Interferences......Page 228
10.2.11.4 Reagents......Page 229
10.2.11.5 Analytical procedures......Page 230
10.2.12 Determination of nitrogen, phosphorus and silicon in particulate and dissolved organic matter......Page 232
10.2.12.2 Calibration and calculation of total and organic nutrients......Page 233
10.2.13.2 Analytical procedure......Page 234
10.2.14.1 Reagents......Page 235
10.2.15.1 Analytical procedure......Page 236
10.2.16 Determination of total and organic nitrogen after persulphate oxidation......Page 237
10.2.16.2 Reagents......Page 238
10.2.17.1 Range and precision of the method......Page 239
10.2.18.1 Principle of the method......Page 240
10.2.18.3 Analytical procedure......Page 241
10.3 Automated nutrient analysis......Page 242
10.3.1 Principle of automated analysis......Page 243
10.3.2 The sampler......Page 245
10.3.3 The proportioning pump......Page 247
10.3.4 The analytical manifold......Page 249
10.3.4.1 Standard manifold components......Page 250
10.3.4.2 Heating and cooling......Page 252
10.3.4.3 Special devices......Page 253
10.3.4.4 The flow-through spectrophotometer......Page 254
10.3.5 Data acquisition......Page 255
10.3.6 System calibration......Page 257
References to Chapter 10......Page 260
11.1 Introduction......Page 263
11.2.1.1 Principle of the method......Page 264
11.2.1.3 Standardization of the EGTA solution......Page 265
11.2.1.6 Precision......Page 266
11.2.2.1 Principle of the method......Page 267
11.2.2.3 Standardization of EDTA solution......Page 268
11.2.2.4 Analysis of the sample......Page 269
11.2.2.6 Precision......Page 270
11.2.3.2 Reagents and equipment......Page 271
11.2.3.5 Precision......Page 272
11.2.4.1 Principle of the method......Page 273
11.2.4.3 Standardization of the silver nitrate solutions......Page 274
11.2.4.4 Titration of the sample......Page 275
11.2.5.1 Principle of the method......Page 276
11.2.5.4 Calculation of results......Page 277
11.2.6.2 Reagents and equipment......Page 278
11.2.6.4 Analysis of the sample......Page 279
11.2.7 Boron......Page 280
11.2.7.4 Calibration......Page 281
11.2.8.1 Principle of the method......Page 282
11.2.8.3 Analysis of the sample......Page 283
References to Chapter 11......Page 284
12.1.1 Oceanic concentrations and distributions......Page 287
12.1.2 Analytical options......Page 290
12.1.3 Working environment and sample handling......Page 291
12.1.4 Materials and cleaning procedures......Page 293
12.1.5 Purification of reagents......Page 295
12.2.1 Cadmium, cobalt, copper, iron, lead, nickel and zinc by ETAAS......Page 297
12.2.1.1 Principle of the method......Page 298
12.2.1.2 Reagents and equipment......Page 301
12.2.1.3 Analysis of the sample......Page 302
12.2.1.4 Calculation of results......Page 304
12.2.1.5 Precision, blank determination and detection limits......Page 305
12.2.2.2 Reagents and equipment......Page 306
12.2.2.5 Precision and blank determination......Page 307
12.2.3.1 Arsenic......Page 308
12.2.3.2 Antimony......Page 315
12.2.3.3 Germanium......Page 320
12.2.4.2 Principle of the method......Page 328
12.2.4.3 Reagents and equipment......Page 329
12.2.4.4 Analysis of the sample......Page 331
12.2.4.5 Calculation of results......Page 333
12.2.4.6 Precision and determination of blanks......Page 334
12.2.4.7 Speciation studies......Page 335
12.3.1 Introduction......Page 336
12.3.2 Potential scanning methods......Page 337
12.3.4 Sample pre-treatment......Page 339
12.3.5.1 Equipment pre-treatment......Page 340
12.3.6.1 Reagent purification......Page 341
12.3.7.1 Copper......Page 342
12.3.7.2 Zinc......Page 345
12.3.7.3 Nickel......Page 347
12.3.7.4 Chromium......Page 349
12.3.7.5 Cobalt......Page 352
12.4.1 Introduction......Page 354
12.4.2 Analytical method......Page 355
12.4.2.1 Principle of the TXRF technique......Page 356
12.4.2.2 Analytical features of the instrument......Page 358
12.4.2.3 Sample pre-treatment......Page 362
12.4.2.4 Apparatus and reagents......Page 365
12.4.2.5 Analysis of seawater......Page 368
12.4.2.6 Analysis of solid samples......Page 371
12.4.2.7 Blanks, detection limits, precision and accuracy......Page 372
12.5.1.2 Reagents and equipment......Page 374
12.5.1.4 Calibration......Page 375
12.5.2.1 Principle of the method......Page 376
12.5.2.3 Analysis of the sample......Page 377
12.5.2.6 Precision and blank determination......Page 378
12.6.2.1 Sampling by pressure filtration......Page 379
12.6.2.2 Sampling by in situ filtration......Page 381
12.6.2.3 Sampling by continuous-flow centrifugation......Page 382
12.6.2.4 Sampling by sediment traps......Page 383
12.6.3.1 Weak acidic leaching......Page 384
12.6.3.2 Total digestion......Page 385
12.6.3.3 Sequential extraction......Page 387
12.6.4 Instrumental detection......Page 388
12.6.4.1 Instrumental detection by AAS......Page 389
12.6.4.2 Instrumental detection by ICP-AES......Page 390
12.6.4.4 Accuracy, precision and blank values......Page 392
References to Chapter 12......Page 393
13.1 Introduction......Page 399
13.2.1 Large-volume sampling......Page 402
13.2.3.1 Extraction with MnO2-coated fibres......Page 403
13.3.2 Radioactivity measurements......Page 406
13.4 Special requirements for laboratory......Page 407
13.5 Reagents, spikes and standards......Page 408
13.6.2.1 Gamma spectrometry......Page 410
13.6.2.2 Beta counting......Page 411
13.6.3.1 Mn02-coated cartridges......Page 412
13.6.3.2 Mn02 precipitate......Page 413
13.7.1 General analytical considerations......Page 414
13.7.4 Polonium plating......Page 415
13.7.7 Thorium plating......Page 416
13.8.1 234Th......Page 417
13.8.4 A combined procedure for measurement of dissolved 234Th, 210Pb and 210Po in 20 L samples......Page 419
13.8.5.1 Alpha scintillation measurement of 226Ra and 222Rn......Page 420
13.8.5.2 Measurement of 228Ra via 228Th ingrowth......Page 422
13.8.5.3 Gamma spectrometry measurement of 226Ra and 228Ra......Page 423
13.8.5.4 Delayed coincidence measurement of 223Ra and 224Ra......Page 425
13.8.5.5 Alpha spectrometry measurement of 226Ra, 228Ra, 223Ra and 224Ra......Page 427
13.9 Propagation of errors......Page 428
References to Chapter 13......Page 429
14.2 In situ determination of pH......Page 433
14.3 In situ determination of oxygen......Page 434
References to Chapter 14......Page 439
15.1.2 DOC and DON in seawater......Page 441
15.2.1 Dry combustion or high temperature catalytic oxidation (HTCO)......Page 442
15.3.1 Contamination problems......Page 443
15.3.2 Sampling......Page 444
15.3.4 Sample storage......Page 445
15.4.2 Instrument blank......Page 446
15.5.1 Carbon calibration......Page 448
15.6.1 Removal of inorganic carbon......Page 450
15.6.2 Determination of DOC......Page 451
15.6.3 Determination of total dissolved nitrogen (TDN)......Page 452
15.7 Conclusions......Page 453
References to Chapter 15......Page 454
16.1 Introduction......Page 455
16.2.1 Removal of inorganic carbon......Page 457
16.2.2 Oxidation of organic carbon to carbon dioxide......Page 458
16.2.4 Sampling, filtration and storage......Page 459
16.4 Filtration......Page 460
16.6.1 Equipment......Page 461
16.6.3 The irradiator assembly......Page 462
16.6.4 Removal of carbon dioxide from the irradiated sample, and drying of the gas stream......Page 463
16.6.6 The autoanalyser manifold......Page 464
16.7.1 Low organic carbon content (LOCC) water......Page 465
16.7.4 Oxygen supply......Page 466
16.8.3 Sampling frequency......Page 467
16.9 Data analysis......Page 468
16.11 Identification and solution of common problems......Page 469
References to Chapter 16......Page 470
17.1 Introduction......Page 471
17.3.1 Filtration of suspended particles......Page 472
17.4 Sample preservation......Page 473
17.5 Separation of particulate inorganic carbon from particulate organic carbon......Page 474
17.6.2 Reagents, analytical grade......Page 475
17.6.4 Analytical procedure......Page 476
References to Chapter 17......Page 477
18.1 Introduction......Page 479
18.2 Outline of the method......Page 480
18.3 Reagents......Page 481
18.4 Apparatus and glassware......Page 482
18.5 Cleaning of the resin......Page 483
18.8 Sample preparation......Page 484
References to Chapter 18......Page 485
19.3 Reagents......Page 487
19.5 Cleaning of silica gel......Page 488
19.6 Preparing a separation column......Page 489
19.7 Sample separation......Page 490
References to Chapter 19......Page 491
20.1.1 Particular applications......Page 493
20.2 Reagents and equipment......Page 494
20.2.1 Cleaning procedures......Page 495
20.2.3 Procedural blanks......Page 496
20.3 Compound group separation of seawater samples......Page 497
References to Chapter 20......Page 499
21.1 Introduction......Page 501
21.2 Principle of the method......Page 502
21.4 Apparatus......Page 503
21.6 Sampling and sample storage......Page 505
21.9 Spectrofluorimetric analysis......Page 506
21.10 Calibration and quantification......Page 507
21.11 Sources of error......Page 508
21.13 Spectral scanning for source identification......Page 509
References to Chapter 21......Page 511
22.1.1 Organochlorines in seawater......Page 513
22.2.2 Sampling and filtration of seawater......Page 516
22.2.2.2 Deep-water sampling......Page 517
22.3 Laboratory procedures......Page 518
22.3.1 Cleaning and storage of glassware, filters, chemicals and solvents......Page 519
22.3.2 Analyte enrichment......Page 520
22.3.5 Compound-class separation of extracts by HPLC......Page 522
22.4.1 Capillary columns and operating conditions......Page 523
22.4.2 Single column and multi-dimensional gas chromatography......Page 524
22.4.3 Gases and gas supplies......Page 525
22.4.3.2 Carrier gas impurities......Page 526
22.4.4 Sample injection......Page 527
22.4.5.1 The Electron Capture Detector (ECD)......Page 528
22.4.5.2 Mass spectrometry......Page 529
22.4.6 Identification......Page 530
22.4.7.2 Calibration......Page 531
References to Chapter 22......Page 532
23.1 Introduction......Page 535
23.2 Sampling of seawater......Page 537
23.3 Purge and trap (P&T) work-up......Page 539
23.3.3 Purging of halocarbons from the water......Page 540
23.3.4 Drying the purge gas......Page 541
23.3.5 The valve oven......Page 542
23.3.6 Trapping and desorption......Page 543
23.3.6.3 Microtraps......Page 544
23.4.1 Separation column......Page 545
23.4.2 Two modes of halocarbon analysis......Page 546
23.5.1 Electron capture detection......Page 548
23.6 Calibration......Page 549
23.6.2.1 Linear calibration curves......Page 550
23.6.3 Determination of extraction efficiency......Page 551
23.7.3 Accuracy......Page 552
References to Chapter 23......Page 553
24.1 Distribution of dimethyl sulphide in seawater......Page 555
24.2.1 The flame photometric detector in the sulphur mode......Page 556
24.2.2 Purge and trap preconcentration......Page 557
24.3 Analytical system......Page 558
24.3.1 Purge and trap unit......Page 559
24.3.3 Flame photometric detector and gas supply......Page 560
24.4 Procedure......Page 561
24.5 System optimisation and test procedures......Page 562
24.6 Calibration......Page 563
24.7 Precision......Page 564
24.8 Sampling and storage......Page 565
References to Chapter 24......Page 566
25.1 Introduction......Page 567
25.3.1 Sampling......Page 568
25.4.1 Chemicals......Page 569
25.5.1 Standardization with quinine sulphate......Page 570
25.5.3 Linear range of instrument response......Page 571
25.6 Synchronous excitation fluorimetry......Page 572
References to Chapter 25......Page 574
26.2 General remarks......Page 575
26.3.1 Compound class reaction......Page 576
26.3.4 Automatic procedure......Page 577
26.4 Dissolved combined amino acids (DCAA)......Page 579
26.5.2 Reagents......Page 580
26.5.4 Calibration......Page 581
26.5.6.1 Procedure......Page 582
26.6.1 General remarks......Page 583
26.6.5.1 Mobile phases......Page 584
26.6.5.2 Gradient conditions......Page 585
26.6.7 Calibration......Page 587
References to Chapter 26......Page 588
27.1 Introduction......Page 591
27.3 Extraction......Page 593
27.5 HPLC analysis......Page 594
27.5.1 Separation......Page 595
27.5.5 Detection......Page 597
27.5.7 HPLC systems......Page 598
References to Chapter 27......Page 599
Appendix......Page 601
Index......Page 611