Framboids David Rickard

Visit to download the full and correct content document:

https://ebookmass.com/product/framboids-david-rickard/
Framboids
Framboids
DAV I D R IC KA R D

1
 3
Oxford University Press is a department of the University of Oxford. It furthers
the University’s objective of excellence in research, scholarship, and education
by publishing worldwide. Oxford is a registered trade mark of Oxford University
Press in the UK and certain other countries.

Published in the United States of America by Oxford University Press

198 Madison Avenue, New York, NY 10016, United States of America.

© Oxford University Press 2021

All rights reserved. No part of this publication may be reproduced, stored in

a retrieval system, or transmitted, in any form or by any means, without the
prior permission in writing of Oxford University Press, or as expressly permitted
by law, by license, or under terms agreed with the appropriate reproduction
rights organization. Inquiries concerning reproduction outside the scope of the
above should be sent to the Rights Department, Oxford University Press, at the
address above.

You must not circulate this work in any other form

and you must impose this same condition on any acquirer.

Library of Congress Cataloging-in-Publication Data

Names: Rickard, David, 1943- author.
Title: Framboids / David Rickard.
Description: New York, NY : Oxford University Press, [2021] |
Includes bibliographical references and index.
Identifiers: LCCN 2020058329 (print) | LCCN 2020058330 (ebook) |
ISBN 9780190080112 (hardback) | ISBN 9780197571927 (epub)
Subjects: LCSH: Pyrites. | Ore deposits. | Sediments (Geology) |
Texture (Crystallography) | Aggregation (Chemistry)
Classification: LCC QE390.2.I76 R525 2021 (print) |
LCC QE390.2.I76 (ebook) | DDC 549/.32—dc23
LC record available at https://lccn.loc.gov/2020058329
LC ebook record available at https://lccn.loc.gov/2020058330

DOI: 10.1093/​oso/​9780190080112.001.0001

1 3 5 7 9 8 6 4 2
Printed by Integrated Books International, United States of America
 For Simonne
who has been there since the beginning
 Contents

Synopsis  xiii
Acknowledgments  xxiii
1. Introduction  1
1.1. Definition of Framboids  1
1.1.1. Microscopic Size  1
1.1.2. Spheroidal to Sub-spheroidal Form  2
1.1.3. Discrete Microcrystals  3
1.1.4. Equant and Equidimensional Microcrystals  3
1.2. History of Framboid Research  4
1.2.1. Discovery of Microcrystals in Framboids  4
1.2.2. Advances in Microscopy and Understanding Framboid
Structure  7
1.2.3. Discovering the Nature of Framboids  11
1.3. Distribution of Framboids  11
1.3.1. Framboid Numbers  11
1.3.2. Distribution of Framboids in Sediments and
Sedimentary Rocks  14
1.3.3. Hydrothermal Framboids  17
1.3.4. Cryptic Framboids  18
2. Framboid Sizes  21
2.1. Framboid Size Distributions  22
2.1.1. Log-​normal Distribution  22
2.1.2. Framboid Mean Diameters  24
2.2. Measurement Errors  26
2.3. Framboid Sizes  27
2.3.1. Sedimentary Environments  28
2.3.2. Other Environments  31
2.4. Sedimentary Framboids  32
2.4.1. Framboids in Sedimentary Rocks  32
2.4.2. Framboids in Marine Sediments  34
2.4.3. Framboids in Non-​marine Sediments  34
2.5. Framboids in Other Environments  36
2.5.1. Framboids in Water Columns  36
2.5.2. Framboid Size-​Frequency Distributions and the Oxygenation
State of Paleo-​Water Columns  37
viii Contents

2.6. Hydrothermal Framboids  39

2.6.1. Mineralized Sediments  42
2.7. Polyframboid Sizes  44
2.8. The Maximum and Minimum Sizes of Framboids  44
3. Framboid Shapes  47
3.1. Spheroidal Framboids  48
3.1.1 Sphericity  49
3.1.2. Deviations from Perfect Sphericity  49
3.2. Ellipsoidal Framboids  51
3.2.1. Ellipsoidal Framboids Produced by Deformation  51
3.2.2. Primary Ellipsoidal Framboids  51
3.2.3. Effect of Gravity on Framboid Sphericity  53
3.3. Faceted Framboids  55
3.3.1. Polyhedral Framboids  55
3.3.2. Framboids with Partial Facets  57
3.4. Polyframboids  60
4. Microcrystal Morphology  63
4.1. Microcrystal Sizes  63
4.2. Numbers of Microcrystals in Framboids  64
4.2.1. Packing Densities  67
4.2.2. Ostwald Ripening  69
4.3. Microcrystal Size and Geologic Age  71
4.4. Pyrite Crystal Habits  71
4.5. Framboid Microcrystal Habits  73
4.5.1. Cubic Microcrystals  75
4.5.2. Pyritohedral Microcrystals  76
4.5.3. Octahedral Microcrystals  78
4.5.4. Higher Order Forms  80
4.5.5. Spheroidal Crystals  81
4.5.6. Hollow Microcrystals  83
4.5.7. Incomplete Microcrystals  86
5. Framboid Microarchitecture  90
5.1. Framboid Sections  91
5.2. Single Domain Microarchitectures  92
5.2.1. Cubic Close Packing  92
5.2.2. Close Packed Spheres  95
5.3. Multiple Domain Microarchitectures  98
5.3.1. Pseudo-​icosahedral Domain Structure  99
5.3.2. Other Multiple Domain Microarchitectures  104
5.4. Disordered Framboids  105
5.5. The Microarchitecture of Microcrystalline and Nanocrystalline
Pyrite  108
 Contents ix

6. The Crystallography of Pyrite Framboids  110

6.1. Pyrite Structure  111
6.2. Framboid X-​ray Diffraction  114
6.3. Electron Backscatter Diffraction  119
6.3.1. Accuracy of Pyrite EBSD  121
6.3.2. Framboid Microcrystals Are Single Crystals  122
6.3.3. Microcrystal Orientations  123
6.4. Framboid Crystallography and Self-​Organization  125
6.4.1. Origins of Different Crystallographic Orientations of
Microcrystals in Framboids  127
7. Organic Matter in Framboids  129
7.1. Framboids as Fossilized Microorganisms  130
7.1.1. Schneiderhöhn’s Fossil Bacteria  130
7.1.2. Love’s Microfossils  131
7.1.3. Pyrite Precipitation within Prokaryotic Cells  133
7.1.4. Framboids as Fossil Microbial Colonies  133
7.1.5. Framboids as Fossil Giant Sulfur Bacteria  134
7.1.6. Framboids as Fossil Eukaryotic Microorganisms  134
7.1.7. Polyframboids as Steinkerns  137
7.2. Framboidal Organic Matter  141
7.2.1. Framboids and Biofilms  142
7.2.2. Geopolymers and Framboid Organic Matter  145
7.2.3. The Form of Protokerogen  147
7.2.4. Extrusion of Framboidal Organic Matter  148
7.2.5. Epigenetic Organic Matter  149
7.2.6. Composition of Infilling Materials within Framboids  150
7.3. Organic Matter in Framboids  151
8. Framboid Mineralogy  153
8.1. Non-​pyritic Framboids  153
8.2. Sulfide Minerals, Other Than Pyrite, in Framboids  155
8.2.1. Marcasite Framboids  155
8.2.2. Greigite, Fe3S4, Framboids  156
8.2.3. Copper Sulfide Framboids  159
8.2.4. Sphalerite Framboids  161
8.3. Oxide Framboids  163
8.3.1. Magnetite Framboids  163
8.3.2. Iron and Mn (Oxyhydr)oxide Framboids  165
9. Geochemistry of Framboids  169
9.1. Pyrite Stoichiometry in Framboids  170
9.2. Pyrite Composition  173
9.2.1. Trace and Minor Elements in Sedimentary Pyrite  173
9.2.2. Trace Elements in Pyrite in Coal  175
9.2.3. Trace and Minor Elements in Hydrothermal Pyrite  177
x Contents

9.3. Framboid Composition  179

  9.3.1. Trace and Minor Element Compositions of Framboids  179
  9.3.2. Trace Element Compositions of Hydrothermal Framboids  187
  9.3.3. Sulfur Isotope Compositions of Framboids  187
9.4. Controls on the Trace Element Concentrations in Framboids  189
10. Pyrite Framboid Formation Chemistry  191
10.1. Pyrite Chemistry  191
10.1.1. Pyrite Solubility  192
10.1.2. Pyrite Formation Chemistry  193
10.2. The Polysulfide Reaction  193
10.2.1. Polysulfide Reactants  193
10.2.2. The Polysulfide Reaction Mechanism  194
10.2.3. Aqueous FeS as a Reactant  195
10.2.4. Protonated Iron Sulfide Complexes as Reactants  198
10.2.5. Aqueous Fe(II) as a Reactant  200
10.2.6. Iron Sulfide Minerals as Reactants  203
10.2.7. Nanoparticulate FeS  206
10.3. The H2S Reaction  207
10.3.1. The H2S Reaction Mechanism  208
10.3.2. Microbial Mediation  209
10.3.3. Iron (III) (oxyhydr)oxide  210
10.4. Pyrite Framboid Syntheses  210
10.4.1. Microframboids and Nanoframboids  216
10.4.2. Microspheres  217
10.4.3. Nanoparticulate Pyrite and Pyrite Clusters  218
10.5. Comparison of the Polysulfide and H2S Pathways for
Framboid Formation  220
11. Nucleation of Framboids  222
11.1. Burst Nucleation: The LaMer Theory  222
11.2. Homogeneous and Heterogeneous Nucleation of Framboids  223
11.3. Classical Nucleation Theory  225
11.3.1. Critical Supersaturation  226
11.3.2. Surface Energy of Pyrite Nuclei  228
11.3.3. Pyrite Critical Nucleus Size  229
11.4. Framboid Size and Supersaturation  231
11.5. Nucleation of Framboids  232
11.5.1. Heterogeneous Nucleation of Pyrite  232
11.5.2. Nucleation of Pyrite Framboids  234
12. Framboid Microcrystal Growth  235
12.1. Origin of Pyrite Microcrystal Habits  235
12.1.1. Pyrite Surface Energies  235
12.1.2. Spectator Ions and Adsorption  240
 Contents xi

12.2. Growth Mechanisms and Microcrystal Habit  241

12.2.1. Screw-​Dislocation Growth  241
12.2.2. Surface Nucleation Growth  243
12.2.3. Crystallization by Particle Attachment (CPA)  244
12.2.4. Ostwald Ripening  245
12.2.5. Interrelationship between Monomer Attachment, CPA,
and Ostwald Ripening  246
12.2.6. Supersaturation and Pyrite Framboid Microcrystal
Growth Forms  249
12.3. Origin of Framboid Sizes and the Rate of Pyrite Framboid
Formation  250
12.3.1. Crystal Size Distribution (CSD) Theory  251
12.3.2. Diffusion-​Controlled Growth  252
12.3.3. The Rate of Pyrite Framboid Formation  253
12.3.4. The Rate of Polyframboid and Framboid Cluster
Formation  256
12.4. Molecular Mechanism of Pyrite Crystal Growth  257
12.4.1. Effect of Temperature  258
12.4.2. Effect of pH  260
13. Framboid Self-​Assembly and Self-​Organization  262
13.1. Self-​Assembly: The DVLO Theory  262
13.1.1. Hamaker Constant  265
13.1.2. Electrostatic Interactions  265
13.1.3. The Debye Length and Microcrystal Self-​Assembly  266
13.1.4. Pyrite Surface Charge  268
13.1.5. Net DVLO Forces in Pyrite Framboid Self-​Assembly  269
13.2. Self-​Organization  271
13.2.1. Organic Templates  272
13.2.2. Spatial Constraints: Coacervates  272
13.2.3. Spatial Constraints: Sediment Pores  273
13.2.4. Topotactic Solid Phase Transformations  275
13.2.5. Compaction and Dewatering of Sediments  276
13.2.6. Microcrystal Alignment by Epitaxial Growth and
Secondary Nucleation  276
13.3. The Self-​Organization Process in Framboids  277
13.3.1. The Development of Framboid Shapes  278
13.3.2. The Development of the Framboid Microarchitecture  280

List of Symbols and Abbreviations  283

List of Units  287
Glossary  289
References  301
Index  327
 Synopsis

This book describes what framboids are and how they are formed. It is conse-
quently divided essentially into two sections: Chapters 1–​9 describe framboids
and Chapters 10–​13 discuss how they are formed. This synopsis integrates the
two parts into an integral whole which acts as a vade mecum for the volume.
Section links are listed in parentheses.

The Basic Attributes of Framboids

Generally, framboids are ubiquitous microscopic, sub-​ spherical aggregates

of often, geometrically arranged, pyrite microcrystals. The basic attributes of
framboids are their microscopic size, their sub-spheroidal form, and their mi-
crocrystalline internal structure (1.1).

Framboid Mineralogy

Framboids are predominantly made of pyrite. This is due to the chemical prop-
erties of this mineral and its crystallography, as well as the relative natural
abundances of iron and sulfide. The extreme dominance of pyrite means that
term framboid generally refers to pyrite framboids unless otherwise qualified.
The question of whether other minerals form framboids directly is moot (8.2).
Detailed examination of reports of other mineral framboids reveal microcrystal-
line material within and associated with framboids (e.g., greigite, Fe3S4g) and sub-​
spherical crystalline aggregates (e.g., marcasite, chalcocite-​digenite, magnetite).
In contrast, framboidal aggregates of, for example, polystyrene microspheres,
have been widely synthesized, so there is no a priori reason for other minerals
not forming primary framboids. The limitation is probably the requirements of
crystal habit, solubility, and natural abundances of the constituent elements for
framboid formation.
Framboids are sometimes observed replaced by other minerals. Pyrite
framboids are often formed during the earliest stages of sedimentation or min-
eralization and therefore subject to further reactions with later fluids. Minerals
such as copper, cobalt, zinc, and lead sulfides often display framboidal forms
having replaced original pyrite framboids (8.2.3, 8.2.4). Likewise, oxidation of
xiv Synopsis

pyrite under some conditions can produce iron oxyhydroxide and iron sulfate
framboids (8.3).

Distribution of Framboids in Time and Space

Framboids may be the most abundant mineral texture on Earth. There are
around 1030 framboids on Earth, and they are forming at a rate of about 1021
per year or 1014 per second (1.2.1). They are found throughout the geologic re-
cord; the oldest framboid may be 2.9 Ga. They are abundant in rocks less than
600 Ma old, and decrease through the Proterozoic (>0.6 Ga) until they are rare
in Archean rocks (>2.5 Ga) (1.3.2). Their absence in these ancient rocks may be
related to the low concentrations of sulfate in contemporary seawater, and there
is some suggestion that they tended to occur in systems where sulfate was locally
enriched, such as through hydrothermal activity. They are far more abundant
in sediments and sedimentary rocks than in hydrothermal deposits, and their
presence in igneous rocks appears to be limited to hydrothermal veinlets within
volcanic rocks (1.3.4).

History of the Study of Framboids

Historically, framboids have been known since at least 1885 and were de-
fined in 1935 (1.2). Early interpretations suggested that they were fossilized
microorganisms, and in the 1950s this idea was resurrected by the discovery
of organic matter in some framboids (7.1). The pyrite-​sulfur in sedimentary
framboids is almost wholly sourced through the activities of sulfate-​reducing
microorganisms, so there is a direct relationship between sedimentary framboids
and microorganisms (see p. 129). Subsequently, the limited distribution of or-
ganic matter in framboids, its absence in hydrothermal framboids, and inorganic
framboid syntheses showed that organisms were not necessary for framboid
formation.

Sizes of Framboids

One of the basic attributes of framboids is their microscopic size. Framboid size-
frequency distributions are log-​normal; the geometric mean size of framboids
is 6.0 μm and 95% of framboids range in size between 2.9 and 12.3 μm in di-
ameter (2.3). The largest framboids may be 250 μm in diameter, although
spherical aggregates of framboids, known as polyframboids, may range up to
 Synopsis xv

900 μm in diameter (2.7). Various spherical aggregates of nanoparticles have

been described which are less than 0.2 μm in diameter. These do not form a con-
tinuum with framboids (2.1.1).
There is no evidence for any significant change in framboid diameters with
geologic time (2.4.1), and the differences in mean sizes between hydrothermal
and sedimentary framboids do not, at present, appear to be statistically signif-
icant (2.6). By contrast, it appears that the mean diameters of framboids from
non-​marine sediments are significantly larger (7.6 μm) than marine framboids
(5.7 μm) (2.4.3). There is some evidence that framboids formed in the water
column are smaller than those formed in sediments, but the non-​critical use of
this possible difference as a proxy for paleoenvironmental reconstructions is not
robust (2.5.1).

Microcrystal Size

Framboids are constituted by microcrystals. Microcrystal size distributions are

approximately log-​normal and 95% of framboidal microcrystals are between
0.1 and 3.1 μm (4.1). Packing efficiencies range from cubic and hexagonal close
packings (74 vol %) to random packings (56–​64 vol %) (4.2.1).

Microcrystals Numbers

Framboids contain between less than 100 to over 500,000 microcrystals (4.2).
The ratios of framboid diameters to microcrystal sizes show a clear bimodal
distribution which reflects the populations of close packed ordered framboids
and close packed randomly organized framboids (4.2). The average numbers
of microcrystals in both disordered and ordered framboids are similar, which
suggest that the organization of microcrystals is the result of an additional
process.

Microcrystal Habits

Minerals that do not commonly produce equant crystals forms are unlikely to
display the framboidal texture. This essentially limits the framboid texture to
minerals, like pyrite, displaying isometric symmetry (4.4). The permutations
of pyrite habits result in pyrite displaying the greatest variety of crystal shapes
among the common minerals, which includes approximations to forbidden five-
fold symmetries such as the pyritohedron and pseudo-​icosahedron.
xvi Synopsis

Framboid Sphericity

The original idea that framboids were generally spherical was found to be due to
the limitations of the contemporary optical microscopic methods (1.2.2). Later
scanning microscopic investigations showed that many framboids were at least
partly faceted and some display polygonal icosahedral forms (3.3). This is signifi-
cant since the assumption of framboid sphericity informed earlier explanations of
how they could form. It cannot be assumed that framboids necessarily require a pre-
cursor template, such as a spherical space or spherical organic globule, to develop.

Framboid Microarchitectures

Framboids were originally studied in sections, and this is still a common method
of investigation (5.1.1). Sections through framboids reveal that the microcrystals
in pyrite framboids often show extremely regular arrangements. Framboids
can be classified in terms of whether their constituent microcrystals are regu-
larly arranged (ordered in a single domain), randomly arranged (disordered),
or mixtures of both (partially ordered or multiple domains) (5.1.1). The relative
proportions of these three types are unknown, but there may be a tendency for
the proportion of ordered framboids to increase with geologic age.

Framboid Crystallography

Framboids are not mesocrystals or extreme skeletal varieties of single crystals,

and single crystal X-​ray diffraction analyses of even the most perfectly organ-
ized framboids show ring patterns indicative of dominantly randomly oriented
particles (6.2). Further detailed studies of microcrystal crystallinity by electron
backscatter diffraction showed that the microcrystals within a framboid are
not crystallographically aligned (6.3.3). Both randomly packed and organized
framboids show adjacent framboids with crystallographic orientations rotated
90º. Framboids are formed by the aggregation of pyrite microcrystals rather than
the sequential growth of one microcrystal on another.

Free Energy Minimization and the Development

of Framboid Sphericity

The fundamental driving for the self-​assembly of framboid microcrystals

is reduction in surface free-​
energy (13.1). The self-​
assembly of framboid
 Synopsis xvii

microcrystals to form framboids is consistent with estimations based on the clas-

sical Derjaguin-​Landau-​Verwey-​Overbeek (DVLO) theory, which balances the
attraction between particles due to van der Waals forces against the interparticle
electrostatic repulsive force (13.1).

Entropy Maximization and Self-​Organization

Maximization of entropy is the fundamental process leading to the development

of regular arrangements of microcrystals in framboids (13.3). The formation
of framboids involves two distinct processes. First, pyrite microcrystals aggre-
gate into sub-​spherical groups through free energy minimization. Second, the
microcrystals rearrange themselves into ordered domains through entropy
maximization. Icosahedral symmetry tends to minimize short-​range attractive
interactions and maximize entropy (13.3.2). The physical processes that facilitate
this rearrangement are Brownian motion and surface interactions.

Burst Nucleation

The formation of many thousands of equidimensional and equimorphic

microcrystals in framboids is the fundamental evidence for burst nucleation (11.1).
This is conventionally described by the LaMer model, which is characterized by
(1) a lag phase before nucleation becomes significant, (2) burst nucleation where
the rate of nucleation increases exponentially and may be completed in seconds,
and (3) a short growth phase where nucleation becomes again insignificant (11.1).
The growth phase is dominated by crystal growth, which is limited by the supply of
nutrients, which is not replenished, and growth is rapidly extinguished. The result
of LaMer kinetics is a large number of similarly shaped colloidal particles.

Pyrite Chemistry

The extreme insolubility of pyrite is one of the fundamental reasons for its partic-
ular involvement in framboid formation, as well as for the ubiquity of framboids
(10.1.1). Pyrite solubility is determined by the activities of Fe(II) and S2(-​II).
Aqueous Fe2+ does not appear to react directly with aqueous polysulfide spe-
cies to produce pyrite, and the S-​S bond in aqueous S2(-​II) is normally split by
aqueous Fe2+ to produce aqueous FeS and sulfur (10.2.5). The mechanisms of
pyrite formation include the polysulfide pathway and the H2S pathway. FeS is
the reactant moiety in both processes, either as a dissolved aqueous cluster or a
xviii Synopsis

surface-​bound species. The polysulfide pathway involves the substitution reac-

tion between aqueous S2(-​II) and FeS with [FeS.HS2]– as the reaction interme-
diate (10.2.2). The H2S pathway involves the redox reaction between H2S and FeS
(10.3.1). Both are involved in pyrite nucleation from aqueous solution and pyrite
crystal growth, and both processes have been proven by isotopic tracing. Both
processes have been shown to produce framboids.

Critical Supersaturation

The supersaturation required for pyrite to nucleate is conveniently defined in

terms of the critical supersaturation which defines a point at which nuclei begin
to form at a measurable rate (11.3.1). The critical supersaturation is related to
the solubility via the surface energy. The computed critical saturation for pyrite
varies between 1011 and 1018, which is consistent with experimental estimates.

Classical Nucleation Theory (CNT) and

Framboid Formation

The formation of pyrite nuclei is extremely sensitive to the surface energies of

pyrite nuclei, and small changes in supersaturation lead to changes in the rate of
nuclei formation of several magnitudes. Assuming that the initiation of burst nu-
cleation can be approximated to a rate of one nucleus per second, CNT suggests a
mean surface energy of around 0.6 J m–​2 for pyrite nuclei in aqueous solution at
standard ambient temperature and pressure (SATP) (11.3). The critical radius for
pyrite nuclei under these conditions is between 2.3 and 3.8 Å, which is similar to
the dimensions of the pyrite unit cell (11.3.3).

Framboids and Euhedral Pyrite

By contrast with framboids, euhedral pyrite crystals evidence the formation of

isolated nuclei (11.5.1). These isolated nuclei continue to grow in regimes where
the nutrient supply is not depleted or restricted, resulting in the formation of eu-
hedral pyrite crystals.
Iron (oxyhydr)oxides are the major source of reactant Fe in sedimentary
environments. The reaction between aqueous S(-​II) and Fe(III) (oxyhydr)oxides
produces surface =FeS, polysulfides and surface disulfide. The resulting forma-
tion of surface FeS2 moieties through the reaction between surface =FeS and
S2(-​II) leads to the heterogeneous nucleation of pyrite (11.5.1). This reaction may
the major route for producing individual pyrite crystals, rather than framboids,
 Synopsis xix

especially in sediments. The reaction with surface =FeS is, of course, not limited
to iron (oxyhydr)oxides, but occurs with any iron mineral in a sulfidic environ-
ment, including the relatively scarce iron sulfides mackinawite and greigite, as
well as pyrite itself. The reaction with surface =FeS sites on pyrite is a major route
for euhedral pyrite crystal growth (12.4).

Framboid Crystal Growth

One of the major consequences of the relative insolubility of pyrite is the huge
supersaturations with respect to pyrite that occur widely in low oxygen envir-
onments. The result is that the initial stage of pyrite microcrystal growth occurs
in solutions with large supersaturations, and the less stable octahedral faces de-
velop first (12.2.5). As the pyrite crystals grow, the solution becomes depleted in
nutrients and the supersaturation begins to approach saturation and the most
stable—​or least soluble—​cube faces develop. Truncated cubes and octahedra are
thus common microcrystal habits.
The three basic processes in crystal growth in framboids—​monomer addi-
tion, crystallization by particle attachment (CPA), and Ostwald ripening—​are
neither necessarily successive nor exclusive (12.2.4). End member monomer
growth produces more extreme monodispersed populations of microcrystals. By
contrast, CPA appears to result in quite irregular microcrystals which naturally
lead to more disorganized geometries.

Rate of Framboid Formation

The rate of pyrite crystal growth is unknown. Various qualitative observations

suggest that pyrite crystal growth is rapid and diffusion-​limited. Since pyrite sol-
ubility is so low, diffusion-​controlled growth can be closely modeled by linear
approximations to the diffusion equations (12.3.3). These show that framboids
take between a few hours to a few years to form. The average framboid takes
3–​5 days to form whereas, because of the exponential nature of the relationship
between framboid size and time, there is not much difference in the time taken
for 80 μm (2.2 years) and the maximum observed 250 μm (3 years) diameter
framboids to form.

Effect of Temperature

The effect of temperature on the rate of framboid formation is not well

constrained. As a first approximation, it appears that rate of framboid formation
xx Synopsis

is over a magnitude faster in hydrothermal systems than in sedimentary envir-

onments under similar monomer concentrations. In practical terms this means
that an average 6 μm framboid forms in around 12 hours in hydrothermal sys-
tems rather than 3–​5 days in sediments.

Effect of pH

Pyrite forms mainly through two routes: (1) the reaction between FeS species
and polysulfides (10.2), and (2) the reaction of FeS species and H2S (10.3). Both
of these reactions produce framboidal pyrite. Although pyrite displays extreme
stability in terms of pH space, variations in pH affect the rate of framboid for-
mation through the effect of pH on the solubility of FeSs, which limits the poten-
tial maximum concentration of dissolved Fe(II) and S(-​II) in solution (12.4.2).
At pH <7 the solubility of FeSs is a function of the square of the proton con-
centration and thus its solubility increases rapidly with decreasing pH (10.2.5).
Framboid formation is further constrained by pH since solutions with pH
<5 produce marcasite rather than pyrite (8.2.1, 12.4.2). H2S is the dominant
dissolved sulfide species at pH <7, so the H2S reaction is mainly limited to be-
tween pH 5 and 7. The dominant polysulfide species between pH 4 and 11 is
HS2–​ and this would seem likely to be the major polysulfide reactant.

Organic Matter in Framboids

There is an intrinsic association between organic matter and sedimentary

framboids since the sulfide in sedimentary pyrite is almost wholly the result of
microbial sulfate reduction by mainly heterotrophic organisms (7.2). The exact
nature of this organic material is unknown. However, it appears that microbial
biofilm may be an important contributor (7.2.1). Likewise, the organic residues
from framboids often appear similar to sulfur-​rich organic geopolymers such
as protokerogen (7.2.2). Most of the organic matter in framboids appears to be
syngenetic with the framboids, and framboids seem to have grown in organic
substrates.
The organic relicts tend to take on the form of the pyrite rather than vice versa
(7.1.2). If organisms are involved as templates for framboid formation, they
have not as yet been defined. Generally, known prokaryotic cells, such as giant
sulfur bacteria, are too delicate to provide a scaffold for pyrite framboid forma-
tion (7.1.5). Eukaryotic organisms which might provide an internal template for
framboid formation have not as yet been identified.
 Synopsis xxi

Framboid Geochemistry

At present, the composition of pyrite in framboids is unknown, although it

would be interesting to know its stoichiometry (9.1). The trace element con-
tent of framboids has been widely reported since framboids usually constitute
the earliest pyrite phase in a sediment and therefore are more likely to pick up
trace element variations in contemporary seawater (9.3.1). However, the pro-
cesses leading to trace element contents of framboids are complex and poorly
understood.
No spatial variations in δ34S compositions have been reported within indi-
vidual framboids (9.3.3). This is consistent with the process of burst nucleation
in framboids. It does suggest that framboids pick up a more accurate measure of
the sulfur isotopic composition of the prevailing dissolved sulfide and the trace
element composition of the contemporary environment and are likely to retain
these over geologic time.
 Acknowledgments

The pillars on which this monograph is constructed are three dissertations: my

original undergraduate dissertation in 1965 and the PhD theses of my students
Ian Butler (1994) and Hiroaki Ohfuji (2004). I thank Ian Butler and Hiroaki
Ohfuji for allowing me to reproduce many of the images from their theses. They
also reviewed many of the chapters and were involved in developing many of the
ideas recounted in this book.
This monograph is multidisciplinary and could not have been completed
without the dedicated work of a large number of reviewers. First and foremost
was Rob Raiswell, Emeritus Professor of Sedimentary Geochemistry at Leeds
University, United Kingdom, who read and commented on all 13 chapters. He
also made a series of constructive comments on the structure of the volume
based on his overview.
I thank the following colleagues who reviewed one or more chapters of the
book and whose time and effort in helping to see the work on framboids published
underlines the importance of the topic to a variety of research disciplines.

Ian Butler University of Edinburgh

Michael Engel Friedrich-​Alexander-​Universität
Erlangen-​Nürnberg
Daniel Gregory University of Toronto
Stephen Grimes Plymouth University
Miguel Angel Huerta-​Diaz Universidad Autónoma de Baja California
Ross Large University of Tasmania
George Luther University of Delaware
Hiroaki Ohfuji Tohuko University
Rob Raiswell University of Leeds
Kevin Rosso Pacific Northwest National Laboratory
Zbigniew Sawłowicz Jagiellonian University, Krakow
Nicolas Tribovillard Université de Lille

A number of distinguished researchers also made comments on specific areas

of the book and helped in clarifying particular areas.
xxiv Acknowledgments

David Bond University of Hull

Julia Dshemuchadse University of Michigan
Robert Finkelman University of Texas, Dallas
Dimo Kashchiev University of Sofia
Danlil Kitchaev University of California, Berkeley
Paul Midgley University of Cambridge
Raúl Merino Palomeres University of Madrid
Juergen Schieber Indiana University
Werner Stahel ETH, Zurich
Gregor Trefalt University of Geneva
Richard Wilkin United States Environmental Protection Agency

The subject of framboids cannot be described without the inclusion of many

images and, over the years, many colleagues have sent me images of framboids
they have discovered or synthesized. Many of these images are included in this
monograph and it could not have been completed without these contributions.

Robert Berner † Yale University

Ian Butler University of Edinburgh
Anders Elverhøi Oslo University
Stephen Grimes Plymouth University
Mizela Lay University of Tasmania
George Luther University of Delaware
Peter McGoldrick University of Tasmania
David H. McNeil Geological Survey of Canada
Christopher Morrissey † Hagley, Worcestershire
Indrani Mukherjee University of Tasmania
Edward B. Nuhfer Niwot, Colorado.
Hiroaki Ohfuji University of Tohoku
Heikki Papunen University of Helsinki
Matías Reolid Perez University of Jaén
Zbigniew Sawłowicz Jagiellonian University, Krakow
Heide Schulz-​Vogt Leibniz-​Institut für Ostseeforschung, Rostock
Nicolas Tribovillard University of Lille
Laura A. Vietti University of Wyoming
David Wacey University of Western Australia
 Acknowledgments xxv

Many colleagues, in addition to the ones listed in the previous paragraphs,

have been involved in discussions about framboids during the last 55 years, and
these have helped mold the present volume.

G. Christian Amstutz† Heidelberg University

Hubert Barnes Pennsylvania State University
Dan Bubela† Baas Becking Geomicrobiological Institute, Canberra
Jacques Jedwab † University of Liege
George Kato Kyushu University
Leonard G. Love † University of Sheffield
Anthony P. Millman † Imperial College, London
John Morse† Texas A&M University
Marjorie D. Muir Imperial College, London
Anthony Oldroyd Cardiff University
Richard A. Read Imperial College, London

The list is not complete, and I apologize to those colleagues I have inadvert-
ently missed.
The monograph lists 469 references, often from ancient and esoteric sources.
I thank Jacqueline Roach of the interlibrary loan team of Cardiff University for
her dedicated assistance in sourcing many of these publications.
Finally, I thank my commissioning editor at Oxford University Press, Jeremy
Lewis, for his unflagging support and encouragement.
 1
Introduction

1.1. Definition of Framboids

Framboids are defined as:

Microscopic spheroidal to sub-​spheroidal clusters of equant and
equidimensional microcrystals.

The characteristics of the framboid texture need to be carefully defined since

it is apparent that there are a large number of textures reported in the litera-
ture which are confused with it. This often refers to the more esoteric reports
of framboids. For example, Garcia-​Guinea et al. (1997) described large pyrite
spheres in the remains of ink in the seams of 16th-​and 17th-​century books,
which they described as framboids. In fact, these were smooth spherules of py-
rite with no internal microcrystalline structure.
The key attributes of framboids are the microscopic size, the spheroidal to sub-​
spheroidal outer form, and the internal microcrystalline structure (Figure 1.1).
It is these attributes which have made framboids so interesting to mineralogists,
geologists, and geobiologists, as well as materials scientists. A particularly as-
tonishing feature is the self-​organization displayed by some pyrite framboids.
However, the degree of self-​organization is highly variable, and most framboids
display only limited or even no obvious internal organization.

1.1.1. Microscopic Size

Pyrite framboids found in nature range from <1 to 250 µm in diameter and dis-
play a mean size of around 6 µm. This means that the number of average-​sized
framboids that can be placed on the period at the end of this sentence is 1850.
The aggregates are made up of pyrite microcrystals, rarely more than 500 nm
across, which sometimes display extraordinary ordering. The number of these
microcrystals in any single framboid ranges between 102 and 107 (<0.1 ~20 µm
in diameter). So probably more than 2 billion framboid microcrystals can be
placed on a period. The point is that framboids are exceedingly small and not
usually visible to the naked eye: they occur all around us without our being aware
of them.

Framboids. David Rickard, Oxford University Press. © Oxford University Press 2021.
DOI: 10.1093/​oso/​9780190080112.003.0001
2 Framboids

Figure 1.1. Group of pyrite framboids showing their major attributes: microscopic
size, sub-spheroidal form, and discrete microcrystalline structure consisting of
equant and equidimensional microcrystals.
Scanning electron micrograph by Stephen Grimes.

1.1.2. Spheroidal to Sub-​spheroidal Form

Framboids had classically been assumed to be spherical, and the origin of the
sphericity was a feature of earlier discussions regarding their origin. However,
this proved to be an artifact of the limitations of optical microscopy: framboids
were usually examined in sections under reflected light microscopy. A typical
result is shown in Figure 1.4 later in the chapter. With increasing use of scanning
electron microscope (SEM) techniques, it has become apparent that the outer
surfaces of many framboids are faceted (Figure 1.1). Indeed, framboids may dis-
play polyhedron-​like forms, such as icosahedra (Ohfuji and Akai, 2002). The
original assumption of a spherical form had significant effects on theories re-
garding framboid origins, as discussed later, and the consequences echo in the
literature even today.
 Introduction 3

1.1.3. Discrete Microcrystals

A key feature of the framboidal texture is that they are constituted of discrete
microcrystals varying between approximately 0.1 and 2 µm in size. That is, the inte-
rior of the framboid is not solid, homogeneous pyrite. A number of other spheroidal
pyrite forms are found in which the material is radiating, acicular pyrite, aggregates
of pyrite crystals, and structureless spherules of massive pyrite. These are often
described mistakenly as framboids but have different origins and distributions.
The microcrystals in framboids are often ordered to some degree. This
ordering gave rise to the earlier suggestions that framboids were replacements of
biological forms, as fossilized bacteria or discrete microorganic forms. It is clear,
however, that this is not necessarily the case since framboids are found in high-​
temperature environments and may be synthesized without the involvement of
microorganisms.
In general, the number of ordered framboids appears to be a small fraction of
the total framboid population. However, some form of cryptic or localized, partial
order may occur in a large number of framboids. Ordered or partially ordered mi-
crocrystalline pyrite in irregular, non-​spheroidal, aggregates occurs widely, espe-
cially in recent sediments. But these lack the obvious spheroidal characteristics of
framboids. However, the occurrence of this type of material in nature demonstrates
that microcrystal ordering is unrelated to the outer form of the aggregate.

1.1.4. Equant and Equidimensional Microcrystals

A key feature of the framboid texture is that the microcrystals are all approxi-
mately equant. The microcrystals show a variety of the crystal shapes, including
cubic, cuboidal, cuboctahedral, octahedral, and pyritohedral. The equant form
of the microcrystals is important since it enables close packing arrays. It also
means that minerals that do not commonly form equant habits cannot produce
framboids. This generally limits the framboid texture to minerals that crystallize
in the isometric system and amorphous materials that can form spheres.
Within any single framboid, the individual microcrystals all tend to have the
same size. This enables close packing and contributes to the consequent sta-
bility of the aggregate. They are packed in a variety of ways, including cubic close
packing, icosahedral packing, random packing, and mixtures of these, and con-
sist of 102–​~107 microcrystals (<0.1–​~20 µm in diameter).
4 Framboids

1.2. History of Framboid Research

Framboids were first described when optical microscopes became widespread

in the mid-​19th century. They are usually too small to be seen with the naked
eye and, even with primitive microscopes, their internal structure could not
be resolved. Gabriel Augustus Daubrée (1814–​1891), professor of Mineralogy
at the School of Mines in Paris (and later president of the French Academy of
Sciences) described a potpourri of contemporary occurrences of pyrite in which
he reported microscopic rounded pyrite nodules from the thermal spring at
Bourbonne-​les-​Bains in northeastern France (Daubrée, 1875). He described
one group from a Roman floor as having minute crystal faces. We cannot know
whether these pyrite forms described by Daubrée were framboids, clusters of
framboids, or simple pyrite nodules. However, he noted that his smallest pyrite
crystals were 0.25 mm (250 μm) in size, and this is some 10 times larger than
the normal size range of framboids. Similarly, Jakob Maarten van Bemmelen
(van Bemmelen, 1866), who was to become one of the founders of colloid chem-
istry, described spherical particles of pyrite from polders near Groningen in the
Netherlands, but did not observe their microstructure.

1.2.1. Discovery of Microcrystals in Framboids

Johann Jakob Früh (Figure 1.2) published the first description of framboids in
1885 (Früh, 1885). He found these in a moss peat near Gusev in Kaliningrad,
Russia. At that time, he was a schoolteacher in the idyllic alpine village of Trogon
in northeastern Switzerland. He published his description of pyrite framboids as
part of his Habilitation submission to the University and Polytechnic of Zürich,
which was to become ETH Zürich. Früh was appointed professor of Geography
in Zürich in 1899 and published the monumental Geographie der Schweiz be-
tween 1930 and 1938. Früh’s original contribution has been largely overlooked,
and reference to Figure 1.3 explains why. The framboid illustration is just one
on a page of 39 line drawings of objects he had observed in peat. His discussion
of these objects is also limited: just one paragraph in 49 pages of text. The more
widespread appreciation of framboids in the scientific community had to await
almost 40 years until the work of Schneiderhöhn (1923).

Früh wrote (1885, p. 707):

These spherules are neither spores nor elm-​leaf fungus perithecia. They do not
react to potassium hydroxide or hydrochloric acid. Fungus or lichen spores (Fig. 4
and 29) are lightened by alkalis even if their membrane is highly humic. This is not
the case with the spherules in question. Rather, as I have often convinced myself in
 Introduction 5

Figure 1.2. Johann Jakob Früh (1852–​1938) in 1895.

Image courtesy of ETH Zürich.

various occurrences, they are aggregates of small pyrite crystals. They break down
into numerous particles under pressure (Fig. 30), but spores do not. These particles
are opaque, sharply delimited and, occasionally, show a brownish rim by the light
reflected on their surfaces. Their diameter varies from 0.0007–​0.001 millimeters.
Despite this smallness, they mostly appear in 600 x magnification as sharp squares
or short rectangles, i.e. usually as cubes, which can show Brownian molecular mo-
tion in isolation.1

1 Diese Kügelchen sind weder Sporen noch Ulmus-​kügelchen. Sie reagiren nie auf Kalilauge oder

Salzsäure. Pilz-​oder Flechtensporen (Fig. 4 und 29) werden von Alkalien auch dann aufgehellt, wenn
ihre Membran stark humificirt sein sollte. Mit den in Frage kommenden Kügelchen ist dies nicht der Fall.
Es sind vielmehr, wie ich mich häufig an verschiedenen Vorkommnissen überzeugt habe, Aggregate von
Schwefelkieskryställchen. Durch Druck zerfallen sie in zahlreiche Körnchen (Fig. 30), Sporen hingegen
nicht. Jene Körnchen sind undurchsichtig, scharf begrenzt und höchstens vermöge des an ihren Flächen
reflektierten Lichtes bräunlich umrandet. Ihr Durchmesser variirt von 00007—​0-​001 Millimeter. Trotz
dieser Kleinheit erscheinen sie bei 600/​1 meistens in scharfen Quadraten oder kurzen Rechtecken, d. h.
in der Regel als Würfelchen, welche isolirt die Brown’sche Molekularbewegung zeigen können.
6 Framboids

Figure 1.3. Johannes Jakob Früh’s line drawings of microscopic objects he observed
in peat with framboid images (no. 30) outlined. Früh’s caption reads: 30. Pyrite
spherule. Disintegrating into individual cubes by pressurea (Früh, 1885).
a 30. Schwefelkieskugel, z. Th. durch Druck in einzelne Würfelchen zerfallend.

Früh observed the spherules in a transmitted light microscope at a magnification

of about 600 ×. Even so, he was able to see the framboids themselves and their
constituent microcrystals, which he reported had sizes between 0.7 and 1 mi-
cron. He does not estimate the sizes of the framboids themselves, but they appear
from his figure to be between 10 and 20 μm in diameter. He carried out a series
of chemical tests on these crystals, included demonstrating that they did not dis-
solve in hydrochloric acid but dissolved in nitric acid. Their reaction with carbon
disulfide convinced him that they were constituted of pyrite and not marcasite.
However, Früh was uncertain as to the origin of the sulfide.
 Introduction 7

In 1892 Ludvig Rhumbler, a research assistant at the Zoological Institute at

the University of Göttingen, independently published a description of pyrite
framboids from marine sediments (Rhumbler, 1892). Rhumbler reported that
the spheres fragmented under gentle pressure from the cover glass into micro-
scopic crystals. This was further confirmed by Potonié (1908), who crushed
pyrite framboids from lake sediments between two glass slides to reveal their
constituent microcrystals. In his original report on framboids, Rhumbler sum-
marized most of the essential characteristics of these textures: (1) they are com-
monly pyritic; (2) they are aggregates of microcrystals; and (3) they are formed
in sediments, with the iron being mainly provided from coastal sources and with
the sulfide being produced by the reduction of sulfate. These characteristics have
formed the basic pillars of framboid research over the last century and inform
the structure of the present monograph.

1.2.2. Advances in Microscopy and Understanding

Framboid Structure

The history of understanding of the internal microstructure of framboids is

closely related to technical advances in observing and probing microscopic
objects. It is important to understand this in appraising older work on framboids.
For most of the history of framboid studies, the standard method of observation
was through examining polished blocks of rock. Binocular microscopes gener-
ally did not have sufficient resolution to resolve their internal structure, and py-
rite is opaque to conventional transmitted-​light microscopes. Furthermore, the
observation of materials through thin sections results naturally in some disper-
sion, and the size of the microcrystals approaches the wavelength of light. With
the strictly two-​dimensional surface of the polished blocks used in reflected-​
light microscopy, objects approaching the wavelength of light can be resolved
optically (380 nm (violet) to 750 nm (red)). Normally, white light has been used
to illuminate the specimen with a mid-​wavelength of around 580 nm giving a
maximum theoretical resolution of around 0.2 um with a plan apochromatic ob-
jective with 100 × magnification (Figure 1.4). In other words, bodies separated
by 200 nm can theoretically be observed in reflected-​light microscopy. Since
the usual minimum size of the microcrystals approaches 200 nm, individual
microcrystals can be resolved optically.
The key understanding of the optical properties of the opaque minerals
was the development of the polarizing microscope and its application in re-
flected light microscopy by Koenigsberger (1901), which was systematized by
Schneiderhöhn (1922). The introduction of the polarizing microscope to the
study of opaque minerals was important since it enabled the mineral species to
8 Framboids

Figure 1.4. Reflected-​light microscope image of a polished section of a framboid.

This is imaged in white light and the insert shows the limit of resolution. The
variable sharpness of the microcrystals is due to their varying heights relative to the
plane of focus.
Reichert Zetopan microscope with 100 x oil immersion lens.

be determined and thus pyrite (cubic FeS2), for example, could be distinguished
from marcasite (orthorhombic FeS2).
The first person to record the microarchitecture of pyrite framboids was
Schneiderhöhn (1923) in his studies of the 255 Ma old Kupferscheifer ores
at Mansfeld in Germany (Figure 1.5). Schneiderhöhn was a pioneer in the
application of reflected light microscopy and helped develop the Leitz
Erzmikroscop petrological microscope, which had both transmitted light and
reflected light capabilities. The Leitz had a 95 × oil immersion lens, giving
a linear magnification capability of over 800 × magnification and the possi-
bility of resolving objects <1 μm in size. Schneiderhöhn himself claimed a
resolution of 0.2 μm, which is at the limits of resolution under white light, as
noted earlier. Whatever the actual resolution of his microscope, he was able
to clearly discriminate the individual microcrystalline components of pyrite
framboids.
 Introduction 9

Figure 1.5. The first published image of framboids showing the constituent pyrite
microcrystals in situ. The image was made by Schneiderhöhn (1923) using a 95
x oil immersion objective and the linear magnification was 800 x. The individual
framboids are about 5 μm in diameter and the pyrite microcrystals about 0.5 μm
in size.

The term framboid was first used for these pyrite bodies by American min-
eralogist George W. Rust of the University of Chicago in 1935. In a footnote to
page 407, he explained his choice of the term laconically:

After framboise (Fr.) for “raspberry.”

Rust was an assistant to Professor Edson Sunderland Bastin, professor of

Economic Geology and head of the Department of Geology at the University
of Chicago between 1922 and 1944. Bastin was the author of the paradigmatic
publication Interpretation of Ore Textures (1950), which includes a section on
framboids. Rust’s original photomicrographs of the framboidal texture are
shown, together with his original figure caption, in Figure 1.6. It is significant,
in the light of the later overwhelming interest in framboids in sediments and
sedimentary rocks, that these textures which were first defined as framboidal
were from a hydrothermal copper ore in the Mississippi Valley mining district of
southeastern Missouri.
10 Framboids

Figure 1.6. Rust’s original (1933) microphotographs of framboids. His original

caption read: Cp, chalcopyrite; P, pyrite. 1. X 108. Solid spheroidal masses of pyrite in
chalcopyrite. 2. X r 66. “Framboidal” spheroidal masses of pyrite in chalcopyrite due
to metacolloidal crystallization. 3. X 580. “Framboidal” clusters of pyrite grains due
to crystallization of a gel globule. Secondary minerals separate the discrete crystals of
pyrite. 4. X 450. Same as 3 except that there has been no enrichment of the ore and hence
chalcopyrite still forms the matrix of the pyrite cubes and grains. 5. X 400. Radial “bomb”
type of texture developed in pyrite with a small “framboidal” nest of pyrite grains in the
center of one pyrite area. Chalcopyrite matrix of "bomb" fragments. 6. X 64. Spheroidal
globules of chalcopyrite, with pyrite core, and chalcocite (after bornite) matrix.

Rust provided no details of the microscopic setup he used to prepare these

images, although he probably used a Bausch and Lomb metallographic micro-
scope. In 1931 M. N. Short of the United States Geological Survey (USGS) had
published his account of the microscopic identification of the ore minerals. Since
Bastin had arrived in Chicago from the USGS, it can be assumed that Short’s
techniques, which were state of the art in the United States in the 1930s, were used
at Chicago by Rust. These systems involved huge bellows-​type cameras mounted
on top of metallographic microscopes, or even larger ones mounted horizontally.
The images might require up to 12 minutes exposure time, and Short routinely
developed them as 3.25 × 4.25 inch (8.3 × 10.8 cm) plates. The magnifications
listed by Rust for the images in Figure 1.6 refer to the microscopic magnification
 Introduction 11

of the objective lens multiplied by the eyepiece. The actual size of the framboids in
these images is therefore unknown, and Rust merely refers to them as “tiny.” In his
paper, Rust does not refer to previous reports of occurrences of framboidal pyrite.

1.2.3. Discovering the Nature of Framboids

Framboids may represent the most abundant mineral texture in the natural
world. In this case a texture is defined as the disposition or manner of union of the
particles of a body or substance, using one of Webster’s definitions. It differs from
habit, which specifically refers to a crystal shape. Even with advances in micros-
copy, the question of what framboids actually are was not resolved until the early
years of this century. The details are discussed in Chapters 3–​6. Butler (1994)
originally demonstrated that framboids were not single crystals. This precluded
the idea that framboids were some extreme form of skeletal crystal. Ohfuji et al.
(2006) showed, using enhanced computing techniques, that the microcrystals
in organized framboids were arranged in sub-​domains. Ohfuji et al. (2005) went
further to demonstrate that the individual microcrystals in even the most per-
fectly organized framboids were not crystallographically aligned, even if they
were arranged in regular geometric patterns. This proved that framboids were
simple aggregates of microscopic pyrite crystals. Ohfuji and Akai (2002) dem-
onstrated that some framboids, far from being spherical, showed icosahedral
forms, which is a classically forbidden crystallographic symmetry. More detailed
studies, recounted in Chapter 3, showed that framboids are commonly faceted.
This meant that the problem earlier workers had in accounting for their extreme
spherical shape was a chimera.

1.3. Distribution of Framboids

Framboids are ubiquitous. When the young and eager Polish framboid spe-
cialist Zbigniew Sawłowicz asked the great Professor G. Christian Amstutz of the
University of Heidelberg where he could find some framboids, Amstutz replied,
“Look in the Vistula.” Amstutz’s point was that framboids are all around us, in
local rivers, such as the Vistula, and in your garden soils.

1.3.1. Framboid Numbers

Framboids are almost exclusively made up of pyrite. There are cogent reasons
for this (detailed in Chapters 10–​14), including the abundance of pyrite relative
12 Framboids

to other sulfide minerals, its extreme stability and low solubility, and its mor-
phology. Other minerals also occur in framboids or in framboid-​like forms, as is
described in Chapter 8. However, when framboids are referred to loosely in this
book, the reader can assume that pyrite framboids are being described.
The global quantity of pyrite is relatively well constrained in geochemical
terms (Rickard, 2012b). The total amount of pyrite buried in sedimentary rocks
is between 4 and 6 × 1021 g (Bottrell and Newton, 2004; Holser et al., 1988).
Rickard (2015) estimated that between 1% and 10% of this might be in the form
of framboidal pyrite. This estimate is relatively robust. Vallentyne (1963), for ex-
ample, isolated 450 000 framboids per gram of dried lake sediments. Wilkin et al.
(1996) reported that over 95% of pyrite from the Black Sea sediments occurs as
framboids, irregularly shaped aggregates, and sub-​micron sized microcrystals,
and these textures dominated the pyrite fraction of all the sediments they
examined.
The average framboid diameter is 6 μm (Rickard, 2019a) and the 0.64 packing
density of the dominant randomly packed framboids (section 4.2 in Chapter 4)
suggests that there would be 1.7 × 1030 framboids globally if framboids make
up 10% of the global pyrite and 1.7 × 1029 framboids if they constitute 1%. This
means that there are a billion times more framboids than sand grains on Earth,
and a million times more framboids than stars in the observable universe.
These are minimal estimates since they do not consider pyrite framboids in
igneous and volcanic rocks. The pyrite content of continental crust is <1022 g
assuming all the sulfur is in the form of pyrite, the mass of continental crust is
2.17 × 1025 g (Peterson and Depaolo, 2007), and the average sulfur content is 0.4
wt % (Rudnick and Gao, 2003). The mass of pyrite in the oceanic crust is <1022
g assuming all the sulfur is in the form of pyrite, the mass of the oceanic crust is
0.6 × 1025 g and the average sulfur content is 0.096 wt % (Rickard 2012f). This
suggests that the mass of pyrite in the crust is <2 × 1022 g. There is an element
of double book-​keeping here, since the continental and oceanic crust include a
sedimentary component. However, these constitute a minor fraction (<<10%
according to Peterson and Depaolo, 2007) and the error is insignificant with
respect to the other approximations. The net result is that the mass of pyrite in
the crust is approximately the same as that in sediments and sedimentary rocks.
But the fraction that is in the form of framboids in igneous and volcanic rocks is
relatively small and the contribution of continental crust to the total framboid
inventory is insignificant.
By far the greatest amount of pyrite is contained in sediments and sedimen-
tary rocks, and the pyrite sulfur is microbial in origin. Rickard (2015) estimated
that volcanic sulfur makes up no more than 1% of the global sulfur flux. The esti-
mation was based on a total global sub-​aerial and oceanic volcanic S flux of about
1012 g year (computed from data in Andres and Kasgnoc, 1998; Brimblecombe,
 Introduction 13

2003; Canfield, 2004; Elderfield and Schultz, 1996) and assuming that no more
than 25% of this is fixed as pyrite. This compares with microbial sulfate reduc-
tion which is estimated to be of the order of 30 × 1030 g S a–​1 (e.g. D’Hondt et al.,
2002; Turchyn and Schrag, 2004) with at least 80% of this re-​oxidized (Jorgensen,
1977). This leads to a net burial of 6 × 1013 g S a–​1 as pyrite in sediments. Within
the limits set previously of between 1% and 10% of this pyrite to be framboidal
in form, this suggests that between 3 × 1021 and 3 × 1020 framboids are formed
in sediments every year, or between 1013 and 1014 framboids are formed every
second. Again, the error in ignoring the volcanic and hydrothermal contributions
is insignificant.
Apart from the enormous size of these numbers, the data show that the for-
mation of the framboid texture is facile. It suggests that different pathways lead
to framboid formation and the formation of pyrite microcrystals, their self-​
assembly into spherular forms, and the subsequent self-​organization into or-
ganized internal arrangements are routine chemical and physical processes in
Nature. That is, framboids are not especially remarkable but rather are a result of
routine natural processes.
The strange anvil-​shaped stability area of pyrite in pH-​Eh space, first il-
lustrated by Garrels (1960), is well known and is an artifact of the erroneous
older National Bureau of Standards (NBS) free energy values for aqueous Fe2+
and S2–​ in the calculations. Rickard and Luther (2007) showed that the pyrite
stability region actually extended widely across pH space. A more detailed
rendition is shown in Figure 1.7, where the pyrite stability region is illus-
trated for total dissolved sulfur activities of 10–​3 and 10–​6, which covers the ex-
pected sedimentary concentration range between millimolar and micromolar
sulfide.
Pyrite has an extensive stability region in sediments ranging from pH 2–​10,
both above and below the SO4(-​II) /​S(-​II) redox boundary. This is significant
since this boundary is often used to distinguish “reduced” from “oxidized” envir-
onments. In fact, as pointed out by Rickard and Luther (1997) with respect to
H2S, reduced and oxidized are relative terms relating to electron exchange. Figure
1.7 shows that near the SO4(-​II) /​S(-​II) redox boundary, the calculated ion ac-
tivity product (IAP) in equilibrium with pyrite changes extremely rapidly, up to
1014 within 50 mV (Butler and Rickard, 2000). The effect is significant in that
supersaturations with respect to pyrite vary over very small regions of pH–​
Eh space in this region. Because, as discussed in section 11.3.1 of Chapter 11,
framboid nucleation requires extremely large supersaturations, this IAP gra-
dient may affect whether framboids form or not in a particular sedimentary
environment. The result is that framboid formation can vary over extremely
small distances in a sedimentary or aquatic environment due to local spatial
heterogeneities.
14 Framboids

0.2 0.2
(ΣS) = 10–3 (ΣS) = 10–6
0.1 0.1
Rhombic Rhombic
0 sulfur 0 sulfur
SO4– SO4–
–0.1 –0.1
Eh(V)

Eh(V)
–0.2 –0.2
H2S H2S(aq)
10–15 Pyrite
–0.3 –0.3 10–2
Pyrite –12
10
–0.4 –0.4 HS–
10–2 HS–
–0.5 –0.5
4 6 8 10 4 6 8 10
pH pH

Figure 1.7. Pyrite stability in seawater at 25ºC, 0.1 MPa total pressure and total
dissolved sulfur activities of 10–​3 ((∑S) = 10–​3, left) and 10–​6 ((∑S) = 10–​6, right) for
total dissolved Fe activities between 10–​15 and 10–​2.
Reprinted from Treatise on Geochemistry: Second Edition, Chapter 9, The sedimentary sulfur
system. Copyright (2013) with permission from Elsevier.

1.3.2. Distribution of Framboids in Sediments and

Sedimentary Rocks

The early framboid workers could produce a list of sedimentary localities where
framboids had been observed (e.g., Love and Amstutz, 1969). Such a list today
would run to several volumes.
The distribution of framboids in sediments and sedimentary rocks mirrors
the distribution of pyrite. Since the formation of sedimentary pyrite is a primary
parameter in the biogeochemical cycle of the elements in Earth surface environ-
ments, its distribution through time can be modeled (e.g., Berner, 2006). Secular
variations of pyrite contents of sedimentary rocks were discussed in some de-
tail in Rickard (2012e, 2013) and are shown in Figure 1.8. The general trend is
increasing sulfate in the Proterozoic with a possible peak around 2.0 Ga. Note the
extreme fluctuations in oceanic sulfate concentrations in the Phanerozoic and
the extremely low values in the Archean. The pyrite concentration in sediments
is represented in terms of the balance between burial of reduced sulfur as pyrite
and oxidized sulfur as evaporites. The Phanerozoic generally has seen the bal-
ance skewed toward evaporites in the prevailing oxygenated atmosphere.
The modeling of sedimentary pyrite formation during the Phanerozoic is
more precise because more data are available. The models show that sedimentary
pyrite formation has varied with time, with peaks in the Tertiary, Permo-​Triassic,
Devonian, Silurian, Ordovician, and Cambrian periods. These peak periods are
 Introduction 15

1.5
?
fraction sulfur buried as pyrite
increased pyrite
1.0

increased evaporites

0.5

GOE P
0
30 modern average ocean sulfate concentration
marine sulfate (mmol)

25
20
15
?
10
?
5

0 ?
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0
age Ga

Figure 1.8. Variations in sedimentary pyrite formation with time (see text). GOE
Great Oxidation Event. PЄ Cambrian-​Precambrian boundary. Gray shading
suggests increasing atmospheric O2 during the Proterozoic.
Reprinted from Developments in Sedimentology, Vol. 65, Rickard, D., The evolution of the
sedimentary sulfur cycle. Copyright (2012) with permission from Elsevier.

generally coincident with periods of widespread black shale development and

extensive regions of anoxia in the contemporary oceans. The proportion of pyrite
in the form of framboids may have been greater during these episodes, because
of the prevalence of the stagnant conditions which facilitate framboid forma-
tion. Even so, the chart in Figure 1.9 roughly mirrors the history of sedimentary
framboid formation during the Phanerozoic.
However, a similar relationship between peak sedimentary pyrite formation
and framboid formation cannot be assumed for the Precambrian. Thus, the
peaks in sedimentary pyrite formation relative to evaporites shown in Figure 1.8
at around 1.9 and 1.4 Ga do not appear to coincide with the occurrence of large
numbers of framboids in contemporary sediments.
As described in section 7.1.6 of Chapter 7, in the vast deposits of sedimentary
pyrite in 1.6 Ga Australian mid-​Proterozoic shales, framboids are replaced by
similar sized pyrite spherules and euhedra (Figure 1.10). Etching does not re-
veal any cryptic framboidal texture. The small pyrite euhedra were originally py-
rite spherules which have subsequently been overgrown by euhedral pyrite. The
16 Framboids

sediment pyrite burial

relative to today
1

0 100 200 300 400 500

time Ma

Figure 1.9. Variations in sedimentary pyrite deposition in the Phanerozoic.

Reprinted from Developments in Sedimentology, Vol. 65, Rickard, D., The evolution of the
sedimentary sulfur cycle. Copyright (2012) with permission from Elsevier.

Figure 1.10. Photomicrographs of etched pyrite grains from the 1.6 Ga Mt. Isa
shales showing sub-​spherical forms overgrown with successive generations of pyrite.
These grains represent the material from which the organic sacs were extracted by
Love and Zimmermann (1961).
Published by courtesy of the Society of Economic Geologists.

reason for the general absence of framboids in these sediments is unknown. In

view of the differential nucleation processes leading to pyrite euhedra formation
and framboid formation (section 11.5.1 in Chapter 11), it seems likely that the
extreme supersaturations leading to burst nucleation and framboid formation
were not achieved (except locally; see later discussion) This could be a result of
limited sulfate concentrations in the Proterozoic oceans at this time (Figure 1.8),
which would lead in turn to lower microbial sulfide reduction rates. Low oceanic
sulfate concentrations have been proposed to result from lower atmospheric ox-
ygen concentrations at this time.
Framboids are occasionally reported from Proterozoic and even Archean
rocks. Rickard and Zweifel (1975a) reported framboids from 1.8 Ga massive
 Introduction 17

sulfide ore deposits in Sweden. Guy et al. (2010) reported framboids from 2.9
Ga carbonaceous shales from the Witwatersrand in South Africa (Figure 1.11)
and noted that framboids had also been reported from 2.7 Ga rocks of the Rand
Group. Liu et al. (2020) suggested that framboids formed in Archean sediments
but were subsequently dissolved and the pyrite reprecipitated as nodules and
dispersed fine-​grains. It seems that in these environments, dissolved sulfide
concentrations were locally sufficient to initiate framboid formation. It may be
no coincidence that these environments were all associated with mineralized
sediments, suggesting either a locally enhanced dissolved sulfate concentration
or hydrothermal vents augmenting existing sulfide concentrations.

1.3.3. Hydrothermal Framboids

Framboidal pyrite is also associated with hydrothermal ore deposits, including

many that are known or interpreted to have been formed at, or near, the sea
floor (e.g., Chen, 1978; England and Ostwald, 1993; Halbach and Pracejus,
1993; Honnorez et al., 1973; Pichler et al., 1999; Rickard and Zweifel, 1975b).
Schouten (1946) described framboids from tin veins from Cornwall, United
Kingdom, and from the volcanogenic ores of Rio Tinto, Spain. The framboids at
Rio Tinto, Spain, were the subject of a detailed study by Read (1968). Reedman

Figure 1.11. The oldest framboid? Photomicrograph of a 2.9 Ga framboid from

carbonaceous shale from the Witwatersrand. The white specks are galena grains.
Modified from Guy et al., 2010. Published with permission of the Geological Society of South Africa
(GSSA).
18 Framboids

et al. (1985) described framboidal pyrite in quartz veins from north Wales which
had been formed through hydrothermal processes at an estimated 2 km depth
in the crust. Sassano and Schrijver (1989) described framboids in veins in ca.
490 Ma Cambro-​Ordovician shales from Quebec. Annels and Roberts (1989)
described framboids associated with a ca. 400 Ma old Au deposit. Scott et al.
(2009) described framboids formed from hydrothermal solutions at 175º–​220ºC
in Eocene (ca. 45 Ma) ore veins cutting the ca. 380 Ma sediments in the Carlin
Trend, Nevada. Pyrite framboids have also been reported from probable hydro-
thermal breccias in two andesitic lavas (Love and Amstutz, 1969; Steinike, 1963).
These textures were part of a wide spectrum of sub-​spheroidal pyrite forms
occurring in the andesites, which Love and Amstutz (1969) noted include some
forms which might overlap with the framboidal texture sensu stricto.

1.3.4. Cryptic Framboids

One consequence of the electronic structure and extremely low solubility of py-
rite is that the mineral is extremely tough. Recrystallization of pyrite is difficult to
achieve, and pyrite withstands greenschist-​facies metamorphism (<450 ºC and
<1 GPa). In order for pyrite to be recrystallized, temperatures and pressures in the
amphibolite facies (>450 ºC and <1.2 GPa) are required. At these temperatures
the sulfur fugacity required to maintain pyrite stability becomes extremely high
and pyrite tends to break down to pyrrhotite and sulfur. Depending on the con-
fining pressure, subsequent cooling of the system leads to pyrite reformation. In
these circumstances, pyrite retains no memory of its original state. Otherwise
the original form of pyrite can be revealed by etching. Etching pyrite crystals in
ancient rocks and ores commonly reveals a long and complex history, and no
pyrite should be investigated microscopically without etching or observation of
ultrathin (e.g., 100 nm) sections.
Rickard and Zweifel (1975b) originally showed that pyrite grains within 1.8
Ga massive sulfide ores, which had been metamorphosed to greenschist facies,
contained remnant framboids. Wacey et al. (2015) reported apparently homo-
geneous pyrite grains from 560 Ma turbidites which had been metamorphosed
to 350 ºC and up to 0.7 GPa pressure. These reveal framboidal textures when
ultrathin sections were observed with a transmission electron microscope
(Figure 7.11 in Chapter 7).
The consequence of the cryptic nature of framboids within pyrite crystals in
ancient deposits means that the frequency of framboid occurrences in the geo-
logic record has probably been underestimated.
Since framboids are commonly formed during early diagenesis, the discovery
of these cryptic framboids may also contribute to further understanding of the
Another random document with
no related content on Scribd:
 indistinguishable. They are also commonly taken to
be unities. § 5. Perceptual space and time cannot be
ultimately real, because they involve reference to the
here and now of a finite experience; conceptual
space and time cannot be ultimately real, because
they contain no principle of internal distinction, and
are thus not individual. § 6. The attempt to take
space and time as real leads to the difficulty about
qualities and relations, and so to the indefinite
regress. § 7. Space and time contain no principle of
unity; there may be many space and time orders in
the Absolute which have no spatial or temporal
connection with each other. § 8. The antinomies of
the infinite divisibility and extent of space and time
arise from the indefinite regress involved in the
scheme of qualities and relations, and are insoluble
so long as the space and time construction is taken
for Reality. § 9. The space and time order is an
imperfect phenomenal manifestation of the logical
relation between the inner purposive lives of finite
individuals. Time is an inevitable aspect of finite
experience. How space and time are transcended in
the Absolute experience we cannot say

CHAPTER V
SOME CONDITIONS OF EVOLUTION

§ 1. The concept of 'evolution an attempt to interpret 265

natural processes in terms of individual growth. § 2.
Evolution means change culminating in an end which
is the result of the process and is qualitatively new.
The concept is thus teleological. § 3. Evolution, being
teleological, is essentially either progress or
degeneration. If it is more than illusion, there must be
real ends in the physical order. And ends can only be
real as subjective interests of sentient beings which
 are actualised by the process of change. § 4. Thus
all evolution must take place within an individual
subject. § 5. Further, the subject of evolution must be
a finite individual. All attempts to make “evolution” a
property of the whole of Reality lead to the infinite
regress. § 6. The distinction between progressive
evolution and degeneration has an “objective” basis
in the metaphysical distinction between higher and
lower degrees of individuality. § 7. In the evolutionary
process, old individuals disappear and fresh ones
originate. Hence evolution is incompatible with the
view that Reality consists of a plurality of ultimately
independent finite individuals

CHAPTER VI
THE LOGICAL CHARACTER OF DESCRIPTIVE SCIENCE

§ 1. Scientific description may be contrasted with 279

philosophical or teleological interpretation, but the
contrast is not absolute. § 2. The primary end of all
scientific description is intercommunication with a
view to active co-operation. Hence all such
description is necessarily restricted to objects
capable of being experienced in the same way by a
plurality of individuals. § 3. A second end of scientific
description is the economising of intellectual labour
by the creation of general rules for dealing with
typical situations in the environment. In the course of
evolution this object becomes partially independent
of the former. § 4. From the interest in formulating
general rules arise the three fundamental postulates
of physical science, the postulates of Uniformity,
Mechanical Law, and Causal Determination. § 5. The
mechanical view of physical Nature determined by
these three postulates is systematically carried out
only in the abstract science of Mechanics; hence the
 logical completion of the descriptive process would
mean the reduction of all descriptive science to
Mechanics. That the chemical, biological, and
psychological sciences contain elements which
cannot be reduced to mechanical terms, is due to the
fact that their descriptions are inspired by æsthetic
and historical as well as by primarily “scientific”
interests. § 6. The analysis of such leading concepts
of mechanical Physics as the Conservation of Mass
and of Energy shows them to have only relative
validity

BOOK IV
RATIONAL PSYCHOLOGY—THE INTERPRETATION OF LIFE

CHAPTER I
THE LOGICAL CHARACTER OF PSYCHOLOGICAL SCIENCE

§ 1. The various sciences which deal with the 294

interpretation of human life all avail themselves of the
fundamental categories of Psychology. Hence we
must ask how the concepts of Psychology are related
to actual experience. § 2. Psychology is a body of
abstract descriptive formulæ, not a direct transcript of
the individual processes of real life. It presupposes
the previous construction of the physical order. § 3.
The psychological conception of conscious life as a
succession of “mental states” or “images” is a
transformation of actual experience devised primarily
to account for the experience of other subjects, and
subsequently extended to my own. The
transformation is effected by the hypothesis of
“introjection.” §§ 4, 5. The logical justification of the
psychological transformation of facts is twofold. The
psychological scheme serves partly to fill up the gaps
in our theories of physiological Mechanism, and also,
 in respect of the teleological categories of
Psychology, to describe the course of human
conduct in a form capable of ethical and historical
appreciation. Psychology may legitimately employ
both mechanical and teleological categories. § 6. The
objections sometimes brought against the possibility
of (a) psychological, (b) teleological description are
untenable

CHAPTER II
THE PROBLEM OF SOUL AND BODY

§ 1. The problem of psychophysical connection has to do 313

with the correlation of scientific abstractions, not of
given facts of experience. § 2. The “consciousness”
of Psychology is thus not the same thing as the finite
individual subject of experience, and Reality must not
be said to consist of “minds” in the psychologist’s
sense. Again, we must not assume a priori that there
can be only one working hypothesis of
psychophysical connection. § 3. The possible
hypotheses may be reduced to three,
Epiphenomenalism, Parallelism, and Interaction. § 4.
Epiphenomenalism is legitimate as a methodological
principle in Physiology; it is untenable as a basis for
Psychology because it implies the reduction of
psychical facts to mechanical law. § 5. Parallelism.
The arguments for Parallelism as necessarily valid to
Psychophysics because of its congruity with the
postulates of mechanical Physics, are fallacious. We
cannot assume that Psychology must necessarily
conform to these postulates. § 6. As a working
hypothesis Parallelism is available for many
purposes, but breaks down when we attempt to apply
it to the case of the initiation of fresh purposive
reactions. A teleological and a mechanical series
 cannot ultimately be “parallel.” § 7. We are thus
thrown back on the hypothesis of Interaction as the
only one which affords a consistent scheme for the
correlation of Physiology and Psychology. We have,
however, to remember that what the hypothesis
correlates is scientific symbols, not actual facts. The
actuality represented by both sets of symbols is the
same thing, though the psychological symbolism
affords a wider and more adequate representation of
it than the physiological

CHAPTER III
THE PLACE OF THE “SELF” IN REALITY

§ 1. The “self” is (1) a teleological concept, (2) implies a 334

contrasted not-self (where this contrast is absent
from an experience there is no genuine sense of
self); (3) but the limits which divide self and not-self
are not fixed but fluctuating. The not-self is not a
merely external limit, but consists of discordant
elements within the individual, which are extruded
from it by a mental construction. (4) The self is a
product of development, and has its being in the
time-series. (5) The self is never given complete in a
moment of actual experience, but is an ideal
construction; probably self-hood implies some
degree of intellectual development. § 2. The Absolute
or Infinite Individual, being free from all internal
discord, can have no not-self, and therefore cannot
properly be called a self. § 3. Still less can it be a
person. § 4. In a society of selves we have a more
genuinely self-determined individual than in the
single self. Hence it would be nearer the truth to think
of the Absolute as a Society, though no finite whole
adequately expresses the Absolute’s full nature. We
must remember, however, (a) that probably the
 individuals in the Absolute are not all in direct
relation, and (b) that in thinking of it as a Society we
are not denying its real individuality. § 5. The self is
not in its own nature imperishable; as to the
particular problem of its continuance after death, no
decision can be arrived at on grounds of
Metaphysics. Neither the negative presumption
drawn from our inability to understand the conditions
of continuance, nor the lack of empirical evidence, is
conclusive; on the other hand, there is not sufficient
metaphysical reason for taking immortality as certain

CHAPTER IV
THE PROBLEM OF MORAL FREEDOM

§ 1. The metaphysical problem of free will has been 359

historically created by extra-ethical difficulties,
especially by theological considerations in the early
Christian era, and by the influence of mechanical
scientific conceptions in the modern world. §§ 2, 3.
The analysis of our moral experience shows that true
“freedom” means teleological determination. Hence
to be “free” and to “will” are ultimately the same thing.
Freedom or “self-determination” is genuine but
limited, and is capable of variations of degree. § 4.
Determinism and Indeterminism both arise from the
false assumption that the mechanical postulate of
causal determination by antecedents is an ultimate
fact. The question then arises whether mental events
are an exception to the supposed principle. § 5.
Determinism. The determinist arguments stated. § 6.
They rest partly upon the false assumption that
mechanical determination is the one and only
principle of rational connection between facts; § 7.
Partly upon fallacious theories of the actual
procedure of the mental sciences. Fallacious nature
 of the argument that complete knowledge of
character and circumstances would enable us to
predict human conduct. The assumed data are such
as, from their own nature, could not be known before
the event. § 8. Indeterminism. The psychical facts to
which the indeterminist appeals do not warrant his
conclusion, which is, moreover, metaphysically
absurd, as involving the denial of rational connection.
§ 9. Both doctrines agree in the initial error of
confounding teleological unity with causal
determination

CHAPTER V
SOME METAPHYSICAL IMPLICATIONS OF ETHICS AND
RELIGION

§ 1. If Reality is a harmonious system, it must somehow 381

make provision for the gratification of our ethical,
religious, and æsthetic interests. § 2. But we cannot
assume that ethical and religious postulates are
necessarily true in the forms in which our practical
interests lead us to make them. § 3. Thus, while
morality would become impossible unless on the
whole there is coincidence between virtue and
happiness, and unless social progress is a genuine
fact, “perfect virtue,” “perfect happiness,” “infinite
progress” are logically self-contradictory concepts. §
4. But this does not impair the practical usefulness of
our ethical ideals. § 5. In religion we conceive of the
ideal of perfection as already existing in individual
form. Hence ultimately no part of the temporal order
can be an adequate object of religious devotion. § 6.
This leads to the Problem of Evil. “God” cannot be a
finite being within the Absolute, because, if so, God
must contain evil and imperfection as part of His
nature, and is thus not the already existing realisation
 of the ideal. § 7. This difficulty disappears when we
identify “God” with the Absolute, because in the
Absolute evil can be seen to be mere illusory
appearance. It may, however, be true that religious
feeling, to be practically efficient, may need to
imagine its object in an ultimately incorrect
anthropomorphic form. § 8. The existence, within the
Absolute, of finite “divine” personalities, can neither
be affirmed nor denied on grounds of general
Metaphysics. § 9. Proofs of the “being of God.” The
principle of the “ontological” and “cosmological”
proofs can be defended against the criticism of Hume
and Kant only if we identify God with the Absolute.
The “physicotheological proof” could only establish
the reality of finite superhuman intelligences, and its
force depends purely upon empirical considerations
of evidence

CHAPTER VI
CONCLUSION

§ 1. Can our Absolute Experience be properly called the 408

“union of Thought and Will”? The Absolute is
certainly the final realisation of our intellectual and
our practical ideals. But (1) it includes aspects, such
as, e.g., æsthetic feeling, pleasure, and pain, which
are neither Thought nor Will. (2) And it cannot
possess either Thought or Will as such. Both
Thought and Will, in their own nature, presuppose a
Reality which transcends mere Thought and mere
Will. § 2. Our conclusion may in a sense be said to
involve an element of Agnosticism, and again of
Mysticism. But it is only agnostic in holding that we
do not know the precise nature of the Absolute
Experience. It implies no distrust of the validity of
knowledge, so far as it goes, and bases its
 apparently agnostic result on the witness of
knowledge itself. Similarly, it is mystical in
transcending, not in refusing to recognise, the
constructions of understanding and will. § 3.
Metaphysics adds nothing to our information, and
yields no fresh springs of action. It is finally only
justified by the persistency of the impulse to
speculate on the nature of things as a whole

Index 417

ELEMENTS OF METAPHYSICS
 BOOK I
GENERAL NOTIONS
 CHAPTER I
THE PROBLEM OF THE METAPHYSICIAN
§ 1. The generality and simplicity of the metaphysical problem make it difficult to
define the study. § 2. Problem is suggested by the presence of contradictions
in ordinary experience. § 3. By making a distinction between reality and
appearance the sciences remove some of these contradictions, but
themselves lead to further difficulties of the same sort; hence the need for
systematic inquiry into the meaning of the distinction between the real and the
apparent, and the general character of reality as such. § 4. Metaphysics, as
an inquiry into the ultimate meaning of “reality,” is akin to poetry and religion,
but differs from them in its scientific character, from the mathematical and
experimental sciences in its method, from common scepticism in the critical
nature of its methods as well as in its positive purpose. § 5. The study is
difficult (a) because of the generality of its problems, (b) and because we
cannot employ diagrams or physical experiments. § 6. The objection that
Metaphysics is an impossibility may be shown in all its forms to rest upon self-
contradictory assumptions of a metaphysical kind. § 7. The minor objections
that, if possible, the science is superfluous, or at least stationary, may be met
with equal ease. § 8. Metaphysics is partly akin to the mystical tendency, but
differs from mysticism in virtue of its positive interest in the world of
appearances, as well as by its scientific method. § 9. It agrees with logic in the
generality of its scope, but differs in being concerned with the real, whereas
logic is primarily concerned with the inferrible. §10. The problems of the so-
called Theory of Knowledge are really metaphysical.

§ 1. It is always difficult, in treating of any branch of knowledge, to

put before the beginner a correct preliminary notion of the nature and
scope of the study to which he is to be introduced, but the difficulty is
exceptionally great in the case of the body of investigations
traditionally known as Metaphysics.[1] The questions which the
science seeks to answer are, indeed, in principle of the simplest and
most familiar kind, but it is their very simplicity and familiarity which
constitute the chief difficulty of the subject. We are naturally slow to
admit that there is anything we do not understand in terms and ideas
which we are constantly using, not only in the special sciences, but
in our non-systematised everyday thought and language about the
course of the world. Hence, when the metaphysician begins to ask
troublesome questions about the meaning and validity of these
common and familiar notions, ordinary practical men, and even
intelligent students of the special sciences, are apt to complain that
he is wasting his time by raising idle and uncalled-for difficulties
about the self-evident. Consequently the writer on Metaphysics is
almost inevitably compelled to begin by rebutting the natural and
current prejudice which regards his science as non-existent and its
problems as illusory. The full vindication of metaphysical inquiry from
this charge of futility can only be furnished by such a systematic
examination of the actual problems of the study as will be attempted,
in outline, in the succeeding chapters of this work. All that can be
done in an Introduction is to present such a general description of
the kind of questions to be subsequently discussed, and their
relation to the more special problems of the various sciences, as
may incline the reader to give an impartial hearing to what is to
follow.
§ 2. The course of our ordinary experience, as well as our
education in the rudiments of the sciences, has made us all familiar
with the distinction between what really is or exists and what merely
appears to be. There is no opposition more thoroughly enshrined in
the language and literature of civilised races than the contrast of
seeming with reality, of substance with show. We come upon it alike
in our study of the processes of nature and our experience of human
character and purpose. Thus we contrast the seeming stability of the
earth with its real motion, the seeming continuity and sameness of a
lump of solid matter with the real discontinuity and variety of its
chemical constituents, the seeming friendliness of the hypocritical
self-seeker with his real indifference to our welfare. In all these cases
the motive which leads us to make the distinction is the same,
namely, the necessity to escape from the admission of a
contradiction in experience. So long as our various direct
perceptions are not felt to conflict with one another, we readily
accept them all as equally real and valid, and no question arises as
to their relative truth or falsehood. Were all our perceptions of this
kind, there would be no need for the correction, by subsequent
reflection, of our first immediate impressions about the nature of
ourselves and the world; error would be a term of no meaning for us,
and science would have no existence. But when two immediate
perceptions, both apparently equally authenticated by our senses,
stand in direct conflict with one another,[2] we cannot, without doing
violence to the fundamental law of rational thinking, regard both as
equally and in the same sense true. Unless we abandon once for all
the attempt to reconcile the course of our experience with the
demand of our intellect for consistency in thinking, we are driven to
make a momentous distinction. We have to recognise that things are
not always what they seem to be; what appears to us is, sometimes
at any rate, not real, and what really is does not always appear. Of
our two conflicting perceptions, only one at best can be a correct
representation of the real course of things; one of them at least, and
possibly both, must be mere seeming or appearance, and we are
thus cast upon the problem which every science tries, in its own
sphere and its own way, to solve: what part of our conceptions about
the world gives us reality and what part only appearance?[3] It is
because of the importance of these puzzles of immediate perception
as stimulating to such scientific reflection that Plato and Aristotle
called philosophy the child of Wonder, and it is because the
processes of change present them in a peculiarly striking form that
the problem of change has always been a central one in
Metaphysics.
§ 3. The attempt to harmonise by reflection the contradictions
which beset immediate perception in all its forms is one which is not
confined to a single science; the common task of all sciences is to
say what, in some special department and for special purposes,
must be taken as reality and what as mere appearance, and, by
degrading the contradictory to the level of appearance, to satisfy the
instinctive demand of our intellect for coherency and consistency of
thought. But the development of scientific reflection itself in its turn,
while it solves some of our difficulties, is constantly giving rise to
fresh perplexities of a higher order. Our scientific principles
themselves frequently seem to present us with contradictions of a
peculiarly distressing kind. Thus we find ourselves forced in some of
our geometrical reasonings to treat a curve as absolutely continuous,
in others to regard it as made up of a number of points. Or, again, we
are alternately compelled to regard the particles of matter as inert
and only capable of being moved by impact from without, and yet
again as endowed with indwelling “central forces.” Both the opposing
views, in such a case, clearly cannot be ultimately true, and we are
therefore compelled either to give up the effort to think consistently,
or to face the question, Is either view ultimately true, and if so,
which? Again, the principles of one branch of study may appear to
contradict those of another. For instance, the absolute determination
of every movement by a series of antecedent movements which we
assume as a principle in our mechanical science, appears, at least,
to conflict with the freedom of human choice and reality of human
purpose which are fundamental facts for the moralist and the
historian; and we have thus once more to ask, which of the two,
mechanical necessity or intelligent freedom, is the reality and which
the mere appearance? Finally, the results of our scientific reflection
sometimes seem to be in violent disagreement with our deepest and
most characteristic aspirations and purposes, and we cannot avoid
the question, which of the two have the better title to credit as
witnesses to the inmost nature of reality?
In all these cases of perplexity there are, short of the refusal to
think about our difficulties at all, only two courses open to us. We
may answer the question at haphazard and as it suits our
momentary caprice, or we may try to answer it on an intelligible
principle. If we choose the second course, then clearly before we
formulate our principle we must undertake a systematic and impartial
inquiry as to what we really mean by the familiar distinction between
“seems” and “is,” that is to say, a scientific inquiry into the general
characteristics by which reality or real being is distinguished from
mere appearance, not in some one special sphere of study, but
universally. Now, such an inquiry into the general character of reality,
as opposed to more or less unreal appearance, is precisely what is
meant by Metaphysics. Metaphysics sets itself, more systematically
and universally than any other science, to ask what, after all, is
meant by being real, and to what degree our various scientific and
non-scientific theories about the world are in harmony with the
universal characteristics of real existence. Hence Metaphysics has
been called “an attempt to become aware of and to doubt all
preconceptions”; and again, “an unusually resolute effort to think
consistently.” As we cannot, so long as we allow ourselves to think at
all, avoid asking these questions as to what “is” and what only
“seems,” it is clear that the attempt to dispense with metaphysical
speculation altogether would be futile. We have really no choice
whether we shall form metaphysical hypotheses or not, only the
choice whether we shall do so consciously and in accord with some
intelligible principle, or unconsciously and at random.
§ 4. Our preliminary account of the general character of the
metaphysician’s problem will enable us to distinguish Metaphysics
from some other closely related forms of human thought, and to give
it at least a provisional place in the general scheme of knowledge.
(a) Clearly, Metaphysics, as an inquiry into the meaning of reality, will
have some affinity with religion as well as with imaginative literature,
both of which aim at getting behind mere appearances and
interpreting the reality which lies beneath them. In one important
respect its relation to both is closer than that of any other department
of knowledge,—inasmuch as it, like them, is directly concerned with
ultimate reality, whereas the special sciences deal each with some
one particular aspect of things, and avowedly leave all ultimate
questions on one side. Where it differs from both is in its spirit and
method. Unlike religion and imaginative literature, Metaphysics deals
with the ultimate problems of existence in a purely scientific spirit; its
object is intellectual satisfaction, and its method is not one of appeal
to immediate intuition or unanalysed feeling, but of the critical and
systematic analysis of our conceptions. Thus it clearly belongs, in
virtue of its spirit and method, to the realm of science. (b) Yet it
differs widely in method from the other types of science with which
most of us are more familiar. It differs from the mathematical
sciences in being non-quantitative and non-numerical in its methods.
For we cannot employ the numerical and quantitative methods of
Mathematics except on things and processes which admit of
measurement, or, at least, of enumeration, and it is for Metaphysics
itself, in the course of its investigations, to decide whether what is
ultimately real, or any part of it, is numerical or quantitative, and if so,
in what sense. It differs, again, from the experimental sciences in
that, like Logic and Ethics, it does nothing to increase the stock of
our knowledge of particular facts or events, but merely discusses the
way in which facts or events are to be interpreted if we wish to think
consistently. Its question is not what in detail we must regard as the
reality of any special set of processes, but what are the general
conditions to which all reality, as such, conforms. (Just in the same
way, it will be remembered, Logic does not discuss the worth of the
evidence for particular scientific theories, but the general conditions
to which evidence must conform if it is to prove its conclusion.)
Hence Aristotle correctly called Metaphysics a science of being quà
being, ὄντα ᾖ ὄντα, (as opposed, for instance, to Mathematics, which
only studies existence in so far as it is quantitative or numerical).
Again, as an attempt to discover and get rid of baseless
preconceptions about reality, Metaphysics may, in a sense, be said
to be “sceptical.” But it differs profoundly from vulgar scepticism both
in its method and in its moral purpose. The method of vulgar
scepticism is dogmatic,—it takes it for granted without inquiry that
two perceptions or two speculative principles which conflict with one
another must be equally false. Because such contradictions can be
detected in all fields of knowledge and speculation, the sceptic
dogmatically assumes that there is no means of getting behind these
contradictory appearances to a coherent reality. For the
metaphysician, on the contrary, the assumption that the puzzles of
experience are insoluble and the contradictions in our knowledge
irreconcilable is itself just one of those preconceptions which it is the
business of his study to investigate and test. Until after critical
examination, he refuses to pronounce which of the conflicting views
is true, or, supposing both false, whether one may not be nearer the
truth than the other. If he does not assume that truth can be got and
reality known by our human faculties, he does at any rate assume
that it is worth our while to make the attempt, and that nothing but
the issue can decide as to its chances of success. Again, the
metaphysician differs from the sceptic in respect of moral purpose.
Both in a sense preach the duty of a “suspense of judgment” in the
face of ultimate problems. The difference is that the sceptic treats
“suspense,” and the accompanying mental indolence, as an end in
itself; the metaphysician regards it as a mere preliminary to his final
object, the attainment of determinate truth.
§ 5. We can now see some of the reasons which make the
science of Metaphysics a peculiarly difficult branch of study. It is
difficult, in the first place, from the very simplicity and generality of its
problems. There is a general conviction that every science, if it is to
be anything more than a body of disputes about mere words, must
deal with some definite subject-matter, and it is not easy to say
precisely what is the subject dealt with by the metaphysician. In a
certain sense this difficulty can only be met by admitting it; it is true,
as we have already seen, that Metaphysics deals in some way with
everything; thus it is quite right to say that you cannot specify any
particular class of objects as its exclusive subject-matter. This must
not, however, be understood to mean that Metaphysics is another
name for the whole body of the sciences. What it does mean is that
precisely because the distinction between the real and the apparent
affects every department of our knowledge and enters into every one
of the special sciences, the general problem as to the meaning of
this distinction and the principle on which it rests cannot be dealt with
by any one special science, but must form the subject of an
independent inquiry. The parallel with Logic may perhaps help to
make this point clearer. It is just because the principles of reasoning
and the rules of evidence are, in the last resort, the same for all the
sciences, that they have to be made themselves the subject of a
separate investigation. Logic, like Metaphysics, deals with
everything, not in the sense of being another name for the whole of
our knowledge, but in the sense that it, unlike the special sciences,
attacks a problem which confronts us in every exercise of our
thought. The question of the difference between the two sciences will
be discussed in a later section of this chapter.
There are two other minor sources of difficulty, arising out of the
universality of the metaphysical problem, which ought perhaps to be
mentioned, as they present a serious obstacle to the study of
Metaphysics by minds of a certain stamp. In Metaphysics we have
no such helps to the imagination as the figures and diagrams which
are so useful in many branches of Mathematics; and again, we are,
by the nature of the problem, entirely cut off from the aid of physical
experiment. All our results have to be reached by the unassisted
efforts of thought in the strictest sense of the word, that is, by the
rigid and systematic mental analysis of conceptions. Thus
Metaphysics stands alone among the sciences, or alone with Logic,
in the demand it makes on the student’s capacity for sheer hard
continuous thought This may help to explain why men who are
capable of excellent work in the domain of mathematical or
experimental science sometimes prove incompetent in Metaphysics;
and again, why eminent metaphysical ability does not always make
its possessor a sound judge of the results and methods of the other
sciences.
§ 6. It is now time to consider one or two objections which are very
commonly urged against the prosecution of metaphysical studies. It
is often asserted, either that (1) such a science is, in its very nature,
an impossibility; or (2) that, if possible, it is useless and superfluous,
since the other sciences together with the body of our practical
experience give us all the truth we need; or, again, (3) that at any
rate the science is essentially unprogressive, and that all that can be
said about its problems has been said long ago. Now, if any of these
popular objections are really sound, it must clearly be a waste of
time to study Metaphysics, and we are therefore bound to discuss
their force before we proceed any further.
(1) To the objection that a science of Metaphysics is, from the
nature of the case, impossible, it would be in principle correct to
reply that, as the proverb says, “You never can tell till you try,” and
that few, if any, of those who urge this objection most loudly have
ever seriously made the trial. If any one thinks the task not worth his
while, he is not called on to attempt it; but his opinion gives him no
special claim to sit in judgment on those who think differently of the
matter. Still, the anti-metaphysical prejudice is so common, and
appears in so many different forms, that it is necessary to exhibit its
groundlessness rather more in detail.
(a) It is sometimes maintained that Metaphysics is an impossibility
because the metaphysician’s problems, in their own nature, admit of
no solution. To a meaningless question, of course, there can be no
intelligible answer, and it is occasionally asserted, and often
insinuated, that the questions of Metaphysics are of this kind. But to
call the metaphysician’s question a senseless one is as much as to
say that there is no meaning in the distinction, which we are all
constantly making, between the real and the apparent. If there is any
meaning at all in the distinction, it is clearly a necessary as well as a
proper question precisely by what marks the one may be
distinguished from the other. Our right to raise this question can in
fairness only be challenged by an opponent who is prepared to
maintain that the contradictions which lead us to make the distinction
may themselves be the ultimate truth about things. Now, whether this
view is defensible or not, it is clearly not one which we have the right
to assume without examination as self-evident; it is itself a
metaphysical theory of first principles, and would have to be
defended, if at all, by an elaborate metaphysical analysis of the
meaning of the concepts “truth” and “reality.” Again, the objection, if
valid, would tell as much against experimental and mathematical
science as against Metaphysics. If the self-contradictory can be true,
there is no rational ground for preferring a coherent scientific theory
of the world to the wildest dreams of superstition or insanity. Thus we
have no escape from the following dilemma. Either there is no
rational foundation at all for the distinction between reality and
appearance, and then all science is an illusion, or there is a rational
foundation for it, and then we are logically bound to inquire into the
principle of the distinction, and thus to face the problems of
Metaphysics.[4]
(b) What is essentially the same objection is sometimes put in the
following form. Metaphysics, it is said, can have no place in the
scheme of human knowledge, because all intelligible questions
which we can ask about reality must fall within the province of one or
other of the “sciences.” There are no facts with which some one or
other of the sciences does not deal, and there is therefore no room
for a series of “metaphysical” inquiries over and above those
inquiries which constitute the various sciences. Where there are
facts to investigate and intelligible questions to be put, we are, it is
contended, in the domain of “science”; where there are none, there
can be no knowledge. Plausible as this argument can be made to
appear, it is easy to see that it is fallacious. From the point of view of
pure Logic it manifestly contains a flagrant fallacy of petitio principii.
For it simply assumes that there is no “science,” in the most
universal acceptation of the term—i.e. no body of reasoned truth—
besides those experimental sciences which have for their object the
accumulation and systematisation of facts, and this is the very point
at issue between the metaphysician and his critics. What the
metaphysician asserts is not that there are facts with which the
various special branches of experimental science cannot deal, but
that there are questions which can be and ought to be raised about
the facts with which they do deal other than those which
experimental inquiry can solve. Leaving it entirely to the special
sciences to tell us what in particular are the true facts about any
given part of the world’s course, he contends that we still have to ask
the more general question, what we mean by “real” and “fact,” and
how in general the “real” is to be distinguished from the unreal. To
denounce the raising of this question as an attempt to exclude
certain events and processes from the “province of science,” is
simply to misrepresent the issue at stake. Incidentally it may be
added, the objection reveals a serious misunderstanding of the true
principle of distinction between different sciences. The various
sciences differ primarily, not as dealing with different parts of the
world of reality, but as dealing with the whole of it so far as it can be
brought under different aspects. They are different, not because they
deal with different sets of facts, but because they look at the facts
from different points of view. Thus it would be quite wrong to
suppose that the difference between, e.g., Physics, Physiology, and
Psychology, is primarily that each studies a different group of facts.
The facts studied may in great part be the same; it is the point of
view from which they are regarded by which each of the three
sciences is distinguished from the others. Thus every voluntary
movement may be looked at either as a link in a series of
displacements of mass-particles (Physics), as a combination of
muscular contractions initiated from a centre in the cortex of the
brain (Physiology), or as a step to the satisfaction of a felt want
(Psychology). So Metaphysics does not profess to deal with a certain
group of facts lying outside the province of the “sciences,” but to deal
with the same facts which form that province from a point of view