Horst D. Schulz
Matthias Zabel
Editors
Marine Geochemistry
2nd revised, updated and extended edition
With 303 Figures, 49 in color
¥J Springer
Table of Contents
v
;s
Authors
1
ix
xix
The Solid Phase of Marine Sediments
DIETER K. FUTTERER
1.1
1.2
Introductipn
Sources and Components of Marine Sediments
1.2.1
1.2.2
1.2.3
Lithogenous Sediments
Biogenous Sediments
Hydrogenous Sediments
1
1
2
8
10
1.3
Classification of Marine Sediments
11
1.3.1
Terrigenous Sediments
12
1.3.2
1.4
1.4.1
1.4.2
1.4.3
1.4.4
1.5
Deep-Sea Sediments
Global Patterns of Sediment Distribution
Distribution Patterns of Shelf Sediments
Distribution Patterns of Deep-Sea Sediments
Distribution Patterns of Clay Minerals
Sedimentation Rates
Problems
13
16
16
17
19
22
24
2
Physical Properties of Marine Sediments
MONIKA BREITZKE
2.1
2.2
2.2.1
2.2.2
2.2.3
2.2.4
2.3
2.4
2.4.1
2.4.2
Introduction
Porosity and Wet Bulk Density
Analysis by Weight and Volume
Gamma Ray Attenuation
Electrical Resistivity (Galvanic Method)
Electrical Resistivity (Inductive Method)
Permeability
Acoustic and Elastic Properties
Biot-Stoll Model
Full Waveform Ultrasonic Core Logging
28
29
30
31
35
39
42
42
44
47
2.5
Sediment Classification
52
2.5.1
2.5.2
Full Waveform Core Logs as Acoustic Images
P-and S-Wave Velocity, Attenuation, Elastic Moduli and Permeability
54
54
2.6
Sediment Echosounding
57
2.6.1
2.6.2
2.7
Synthetic Seismograms
Narrow-Beam Parasound Echosounder Recordings
Problems
57
64
69
3
Quantification of Early Diagenesis:
Dissolved Constituents in Marine Pore Water
HORST D. SCHULZ
3.1
Introduction: How to Read Pore Water Concentration Profiles
75
3.2
Calculation of Diffusive Fluxes and Diagenetic Reaction Rates
77
3.2.1
3.2.2
3.2.3
3.2.4
3.2.5
3.3
3.3.1
3.3.2
3.3.3
3.4
Steady State and Non-Steady State Situations
The Steady State Situation and Fick's First Law of Diffusion
Quantitative Evaluation of Steady State Concentration Profiles
The Non-Steady State Situation and Fick's Second Law of Diffusion
The Primary Redox-Reactions: Degradation of Organic Matter
Sampling of Pore Water for Ex-Situ Measurements
Obtaining Samples of Sediment for the Analysis of Pore Water
Pore Water Extraction from the Sediment
Storage, Transport and Preservation of Pore Water
Analyzing Constituents in Pore Water, Typical Profiles
77
79
82
87
88
90
90
93
101
102
3.5
3.6
3.7
In-Situ Measurements
Influence of Bioturbation, Bioirrigation, and Advection
Signals in the Sediment Solid Phase
105
112
117
3.7.1
3.7.2
3.7.3
3.8
Analysis of the Sediment's Solid Phase
Interpretation of Element Profiles
Correlation of Sediment Cores by the Contents of Elements
Problems
117
118
119
121
4
Organic Matter: The Driving Force for Early Diagenesis
JORGEN RULLKOTTER
4.1
4.2
4.2.1
4.2.2
4.2.3
4.2.4
4.2.5
4.3
4.3.1
4.3.2
4.3.3
4.3.4
4.3.5
4.3.6
XII
O
The Organic Carbon Cycle
Organic Matter Accumulation in Sediments
Productivity Versus Preservation
Primary Production of Organic Matter and Export to the Ocean Bottom
Transport of Organic Matter through the Water Column
The Influence of Sedimentation Rate on Organic Matter Burial
Allochthonous Organic Matter in Marine Sediments
Early Diagenesis
The Organic Carbon Content of Marine Sediments
Chemical Composition of Biomass
The Principle of Selective Preservation
The Formation of Fossil Organic Matter and its Bulk Composition
Early Diagenesis at the Molecular Level
Biological Markers (Molecular Fossils)
125
126
127
128
130
131
132
134
134
138
142
144
146
146
4.4
4.4.1
4.4.2
4.4.3
Organic Geochemical Proxies
Total Organic Carbon and Sulfur
Marine Versus Terrigenous Organic Matter
Molecular Paleo-Seawater Temperature and Climate Indicators
149
149
150
154
4.5
Analytical Techniques
158
4.5.1
4.5.2
4.5.3
4.5.4
4.5.5
4.6
Sample Requirements
Elemental and Bulk Isotope Analysis
Rock-Eval Pyrolysis and Pyrolysis Gas Chromatography
Organic Petrography
Bitumen Analysis
The Future of Marine Geochemistry of Organic Matter
158
159
159
159
160
161
4.7
Problems
162
5
Bacteria and Marine Biogeochemistry
Bo BARKER J0RGENSEN
5.1
5.1.1
5.1.2
5.2
5.2.1
5.2.2
5.2.3
5.3
5.3.1
5.3.2
5.3.3
5.3.4
5.4
5.4.1
5.4.2
5.4.3
5.4.4
5.4.5
5.4.6
5.4.7
5.5
5.5.1
5.5.2
5.5.3
5.6
Role of Microorganisms
From Geochemistry to Microbiology - and back
Approaches in Marine Biogeochemistry
Life and Environments at Small Scale
Hydrodynamics of Low Reynolds Numbers
Diffusion at Small Scale
Diffusive Boundary Layers
Regulation and Limits of Microbial Processes
Substrate Uptake by Microorganisms
Substrate Limitations in the Deep Sub-surface
Temperature as a Regulating Factor
Other Regulating Factors
Energy Metabolism of Prokaryotes
Free Energy
Reduction-Oxidation Processes
Relations to Oxygen
Definitions of Energy Metabolism
Energy Metabolism of Microorganisms
Chemolithotrophs
Respiration and Fermentation
Pathways of Organic Matter Degradation
Depolymerization of Macromolecules
Aerobic and Anaerobic Mineralization
Depth Zonation of Oxidants
Methods in Biogeochemistry
169
169
171
173
174
174
175
176
177
178
179
180
180
182
182
184
184
185
185
188
189
190
190
192
195
5.6.1
5.6.2
5.6.3
5.6.4
5.6.5
5.7
Incubation Experiments
Radioactive Tracers
Example: Sulfate Reduction
Specific Inhibitors
Other Methods
Problems
196
196
198
198
200
201
XIII
6
Benthic Cycling of Oxygen, Nitrogen and Phosphorus
CHRISTIAN HENSEN, MATTHIAS ZABEL AND HEIDE N. SCHULZ
6.1
Introduction
207
6.2
Distribution of Oxygen, Nitrate and Phosphate in Seawater
208
6.3
The Role of Oxygen, Nitrogen and Phosphorus in Marine Sediments
210
6.3.1
6.3.1.1
6.3.1.2
6.3.1.3
6.3.1.4
6.3.2
6.3.2.1
6.3.2.2
6.3.2.3
6.4
Respiration and Redox Processes
Nitrification and Denitrification
Coupling of Oxygen and Nitrate to other Redox Pathways
Anaerobic Oxidation of Ammonium with Nitrate (Anammox)
Nitrogen Isotopes in Marine Sediments
Input and Redistribution of Phosphate in Marine Sediments
P-Species and Forms of Bonding
Authigenic Formation of Phosphorites
Release of Phosphate by Bacterial Activity
Determination of Consumption Rates and Benthic Fluxes
210
210
215
217
218
219
219
221
221
223
6.4.1
6.4.2
6.4.3
6.5
Fluxes and Concentration Profiles Determined by In-Situ Devices
Ex-Situ Pore Water Data from Deep-Sea Sediments
Determination of Denitrification Rates
Significance and Quantitative Approaches
225
226
226
229
6.5.1
6.5.2
6.6
6.7
Estimation of Global Rates and Fluxes
Variation in Different Marine Environments: Case Studies
Summary
Problems
229
230
234
234
7
The Reactivity of Iron
RALF R. HAESE
7.1
Introduction
241
7.2
Pathways of Iron Input to Marine Sediments
241
7.2.1
Fluvial Input
241
7.2.2
7.3
7.4
7.4.1
7.4.2
7.4.2.1
7.4.2.2
7.4.2.3
7.4.3
7.4.3.1
7.4.3.2
7.4.3.3
7.4.3.4
7.4.3.5
7.4.4
7.4.5
Aeolian Input
B
Iron as a Limiting Nutrient for Primary Productivity
The Early Diagenesis of Iron in Sediments
Dissimilatory Iron Reduction
Solid Phase Ferric Iron and its Bioavailability
Properties of Iron Oxides
Bioavailability of Iron Oxides
Bioavailability of Sheet Silicate Bound Ferric Iron
Iron Reactivity towards S, O2, Mn, NO3", P, HCO3-, and Si-AI
Iron Reduction by HSand Ligands
Iron Oxidation by O2, NO3", and Mn4+
Iron-Bound Phosphorus
The Formation of Siderite
The Formation of Iron Bearing Aluminosilicates
Iron and Manganese Redox Cycles
Discussion: The Importance of Fe-and Mn-Reactivity in Various Environments
242
244
246
247
248
248
249
251
251
251
253
255
255
256
257
260
XIV
7.5
The Assay for Ferric and Ferrous Iron
262
7.6
Problems
264
8
Sulfur Cycling and Methane Oxidation
Bo BARKER J0RGENSEN AND SABINE KASTEN
8.1
8.2
8.2.1
8.2.2
8.2.3
Introduction
Sulfate Reduction and the Degradation of Organic Matter
Geochemical Zonation
Dissimilatory Sul fate Reduction
Sulfate Reduction and Organic Carbon Mineralization
271
272
273
274
275
8.3
Anaerobic Oxidation of Methane (AOM)
278
8.3.1
8.3.2
8.3.3
8.4
8.4.1
8.4.2
8.4.3
8.4.4
8.5
8.6
8.7
8.8
The AOM Zone in Marine Sediments
Energy Constraints and Pathway of AOM
Quantitative Role of AOM
Effects of Sulfate Reduction on Sedimentary Solid Phases
Reactions with Iron
Pyrite Formation
Magnetite and Barite
Non-Steady State Diagenesis
Pathways of Sulfide Oxidation
Determination of Process Rates
The Sulfur Cycle
Problems
279
280
283
285
285
285
288
289
293
298
300
302
9
Marine Carbonates: Their Formation and Destruction
RALPH R. SCHNEIDER, HORST D. SCHULZ AND CHRISTIAN HENSEN
9.1
9.2
Introduction
Marine Environments of Carbonate Production and Accumulation
311
311
9.2.1
9.2.2
9.3
9.3.1
311
315
317
9.4.1
9.4.2
Shallow-Water Carbonates
Pelagic Calcareous Sediments
The Calcite-Carbonate-Equilibrium in Marine Aquatic Systems
Primary Reactions of the Calcite-Carbonate-Equilibrium
with Atmospheric Contact in Infinitely Diluted Solutions
Primary Reactions of the Calcite-Carbonate-Equilibrium
without Atmospheric Contact
Secondary Reactions of the Calcite-Carbonate-Equilibrium in Seawater
Examples for Calculation of the Calcite-Carbonate-Equilibrium in Ocean Waters
Carbonate Reservoir Sizes and Fluxes between Particulate
and Dissolved Reservoirs
Production Versus Dissolution of Pelagic Carbonates
Inorganic and Organic Carbon Release from Deep-Sea Sediments
9.5
Problems
9.3.2
9.3.3
9.3.4
9.4
318
...
320
320
321
324
325
327
334
XV
10
Influences of Geochemical Processes on
Stable Isotope Distribution in Marine Sediments
TORSTEN BlCKERT
10.1
Introduction
339
10.2
10.2.1
10.2.2
Fundamentals
Principles of Isotopic Fractionation
Analytical Procedures
339
339
340
10.3
Geochemical Influences on 18O/16O Ratios
341
18
10.3.1
10.3.2
8 O of Seawater
818O in Marine Carbonates
341
343
10.4
Geochemical Influences on 13C/12C Ratios
346
13
10.4.1
10.4.2
10.4.3
8 CECO2 of Seawater
813C in Marine Organic Matter
813C in Marine Carbonates
346
347
351
10.5
Geochemical Influences on 15N/14N Ratios
353
15
10.5.1
10.5.2
8 N in Marine Ecosystems
815N in Marine Organic Matter
353
355
10.6
Geochemical Influences on 34S/32S Ratios
356
34
10.6.1
10.6.2
10.7
8 S of Seawater and Pore Waters
834S in Marine Sediments
Geochemical Influences on 11B/10B Ratios
356
359
360
10.7.1
10.7.2
10.8
811B of Seawater and Pore Waters
811B in Marine Carbonates
Problems
360
361
362
11
Manganese: Predominant Role of Nodules and Crusts
GEOFFREY P. GLASBY
11.1
11.2
11.3
11.3.1
11.3.2
11.4
11.4.1
11.4.2
11.4.3
11.4.4
11.4.5
11.4.6
11.4.7
11.4.8
XVI
e
Introduction
'*
Manganese, Iron and Trace Elements in Seawater
Sediments
Manganese, Iron and Trace Elements in Deep-Sea Sediments
Diagenetic Processes in Deep-Sea Sediments
Manganese Nodules and Crusts
Deep-Sea Manganese Nodules
Influence of Diagenesis on Nodule Growth
Rare Earth Elements (REE) as Redox Indicators
Co-Rich Mn Crusts
Shallow-Marine Ferromanganese Concretions
Hydrothermal Manganese Crusts
Micronodules
Mineralogy
371
371
375
375
377
380
380
386
388
390
393
395
397
398
11.4.9
11.4.10
11.4.10.1
11.4.10.2
Dating
Mn Crusts as Paleoceanographic Indicators
Recording Hiatuses in Mn Crusts
Application of Isotopic Studies of Co-rich Mn Crusts to the Study of Presentday Deep-ocean Circulation
11.4.10.3 Application of Isotopic Studies of Co-rich Mn Crusts to the Study of Paleocean
Circulation
11.4.11 Economic Prospects
11.4.12 Future Prospects
:
11.5
Problems
12
400
403
403
407
410
411
414
415
Quantification and Regionalization of Benthic Refluxe
MATTHIAS ZABEL AND CHRISTIAN H ENSEN
12.1
12.2
12.2.1
12.2.2
12.2.3
12.2.4
Introduction
Fundamental Considerations and Assessment Criteria
for Benthic Flux Rates
Depth Resolution of Concentration Profiles
Diffusive versus Total Solute Exchange
In-Situ versus Ex-Situ
Time-Dependent Variances and Spatial Variations in the Micro-Environment
430
431
432
433
433
12.3
The Interpretation of Patterns of Regionally Distributed Data
435
12.3.1
12.3.2
12.3.3
Input and Accumulation of Organic Substance
Vertical versus Lateral Input of Particulate Matter
Composition of the Sediment
435
438
440
12.4
Conceptual Approaches and Methods for Regional Balancing
442
12.4.1
12.4.2
12.4.3
Statistical Key Parameters and Regression Analysis
Variograms and Kriging
Geographical Information Systems (GIS)
442
442
443
12.5
12.5.1
445
12.5.3
Applications
Balancing the Diffusion Controlled Fluxof Benthic Silicate in the South AtlanticApplications of Kriging
Global Distribution of Benthic Oxygen Depletion Rates -An Example of Regression
Analysis
°;,4
Use of Numerical Models to Investigate Benthic-Pelagic Coupling
12.6
Concluding Remarks
452
12.7
Problems
452
13
Input from the Deep: Hot Vents and Cold Seeps
12.5.2
429
445
447
450
PETER M. HERZIG AND MARK D. HANNINGTON
13.1
13.2
13.3
13.4
Hydrothermal Convection and Generation of Hydrothermal Fluids
at Mid-Ocean Ridges
Onset of Hydrothermal Activity
Growth of Black Smokers and Massive Sulfide Mounds
Physical and Chemical Characteristics of Hydrothermal Vent Fluids
459
462
462
465
XVII
13.5
T h e Chemical Composition of Hydrothermal Vent Fluids and Precipitates
13.6
13.7
Characteristics of Cold S e e p Fluids at Subduction Z o n e s
Problems
14
. . . 468
472
473
Gas Hydrates in Marine Sediments
GERHARD BOHRMANN AND MARTA E. TORRES
14.1
Introduction
482
14.2
14.2.1
14.2.2
14.2.3
14.3
14.3.1
14.3.2
14.3.3
14.3.4
14.3.5
14.4
482
482
483
484
485
485
487
488
490
492
14.4.1
14.4.2
14.5
14.5.1
14.5.2
Hydrate Crystal Chemistry and Stability of Gas Hydrates
Cages and Three Crystal Structure
Guest Molecules
Stability and Phase Boundaries of Gas Hydrates
Hydrate Occurrence in The Oceanic Environment
Gas Hydrate Stability Zone in Marine Sediments
Seismic Evidence for Gas Hydrates
Generation of Gases for Hydrate Formation
Methane Transport and Hydrate Formation
Gas Hydrate Accumulation in Sediments and Fabric of Natural Gas Hydrates
Pore Water Anomalies Associated with Gas Hydrate Formation and
Decomposition
Gas Hydrate and Chloride Anomalies
Gas Hydrate and Water Isotope Anomalies
Gas Hydrate Carbonate Formation and Anaerobic Oxidation of Methane
Petrographic Characteristics of Clathrites
Carbonate Precipitation through Microbial Activity
14.6
Concluding Remarks
506
14.7
Problems
507
15
Conceptual Models and Computer Models
494
495
502
503
503
504
HORST D. SCHULZ
0
15.1
15.1.1
15.1.2
15.2
15.3
15.3.1
15.3.2
15.3.3
15.4
15.5
Geochemical Models
'?
Structure of Geochemical Models
Application Examples of Geochemical Modeling
Analytical Solutions for Diffusion and Early Diagenetic Reactions
Numerical Solutions for Diagenetic Models
Simple Models with Spreadsheet Software ('Press-F9-Method')
Two-Step Models with Explicit Numerical Solution of Fick's 2" Law
Two-Step Models for Combined Complex Transport/Reaction Processes
Bioturbation and Bioirrigation in Combined Models
Problems
Answers to Problems
XVIII
513
513
517
523
524
525
529
538
543
545