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Springer Mineralogy

Boris Osovetsky

Natural
Nanogold
Springer Mineralogy
More information about this series at http://www.springer.com/series/13488
Boris Osovetsky

Natural Nanogold

123
Boris Osovetsky
Nanomineralogy Sector, Mineralogy
and Petrography Department
Perm State National Research University
Perm
Russia

ISSN 2366-1585 ISSN 2366-1593 (electronic)

Springer Mineralogy
ISBN 978-3-319-59158-2 ISBN 978-3-319-59159-9 (eBook)
DOI 10.1007/978-3-319-59159-9

Library of Congress Control Number: 2017940584

The book has been published in Russian by the University of Perm. We have received a foreign language
publishing agreement from the copyright holder that entitles us to publishing the English edition.

© Springer International Publishing AG 2017

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
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Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Methods and Objects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2 Mineral–Concentrators of Nanogold . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.1 Sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2.1 Ensembles of Micro- and Nanoparticles . . . . . . . . . . . . . 14
2.2.2 The Morphology of Gold Nanoparticles . . . . . . . . . . . . . 14
2.2.3 The Generations of Nanoparticles . . . . . . . . . . . . . . . . . . 15
2.2.4 Regularities of Nanogold Location on the Surface
of the Matrix Gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.2.5 The Density of Gold Nanoparticles on the Surface . . . . . 21
2.2.6 The Chemical Composition of Gold Nanoparticles . . . . . 21
2.2.7 Nanoscale Particles in the Internal Structure of Gold . . . 22
2.3 Platinum Group Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.4 Goethite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.5 Quartz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2.6 Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.7 Clay Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.8 Magnetite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.9 Carbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.10 Feldspars . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3 Aggregates of Gold Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.1 Some Theoretical Basis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.2 Previous Studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3 Morphological Types of Nanogold Aggregates . . . . . . . . . . . . . . 42

v
vi Contents

3.4 Taxonomy of Aggregates by Their Size and Number

of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.5 Division of Aggregates on the Dimensions of Nanoparticles . . . . 53
3.6 Division of Aggregates on the Density of Space Filling . . . . . . . 53
3.7 Multi-level Structure of Aggregates . . . . . . . . . . . . . . . . . . . . . . . 55
3.8 Regularities of the Location of Aggregates
on the Metal Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.9 Taxonomy of Aggregates on the Chemical Composition of Gold
Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4 “Aggregate” Gold on the Nanoscale . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.1 Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
4.2 The Morphological Features of “Aggregate” Gold . . . . . . . . . . . . 70
4.3 The Structure of Globules in “Aggregate” Gold. . . . . . . . . . . . . . 75
4.4 Structural Features of Interglobular Space . . . . . . . . . . . . . . . . . . 78
4.5 Massive Gold with Growths of Authigenic Metal
on the Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
4.6 Intergrowths of “Aggregate” and Crystal Gold . . . . . . . . . . . . . . 84
4.7 Features of Object Testing on “Aggregate” Gold . . . . . . . . . . . . . 85
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5 Genesis of Natural Nanogold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.1 Nanolayering as a Reflection of the Laws of Crystal Growth . . . 87
5.2 The Origin Processes of Natural Gold Nanoparticles . . . . . . . . . . 89
5.2.1 Crystallization from a Magmatic Melt . . . . . . . . . . . . . . 90
5.2.2 Nanoparticles of Gold in Hydrothermal Ore Bodies . . . . 91
5.2.3 Metamorphic and Metasomatic Transformation of
Rocks with the Release of Nanogold . . . . . . . . . . . . . .. 91
5.2.4 The Release of Nanogold from Sulfides in the
Weathered Rocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 92
5.2.5 Ultra-Dispersive Weathering Processes of Gold-
Bearing Rocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 93
5.2.6 Mechanical Abrasion of Gold During Migration . . . . . .. 94
5.2.7 Metacolloidal Mineral Formation
in Aqueous Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.2.8 Deposition of Nanogold by Ferruginous Substance. . . . . 97
5.2.9 Deposition of Nanogold from Chloride Solutions . . . . . . 97
5.2.10 Sorption of Gold by Carbonaceous Matter . . . . . . . . . . . 98
5.2.11 Concentration of Nanogold in the Life Cycle of
Organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 101
5.3 The Mechanisms of Nanogold Aggregation . . . . . . . . . . . . . . . .. 109
5.3.1 Aggregation Under the Influence of High Surface
Energy of Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . .. 109
5.3.2 Natural Amalgamation . . . . . . . . . . . . . . . . . . . . . . . . .. 111
Contents vii

5.3.3 The Activity of Organisms . . . . . . . . . . . . . . . . ....... 116

5.3.4 Flotation Mechanism. . . . . . . . . . . . . . . . . . . . . ....... 117
5.3.5 “Growing Old” of Colloids . . . . . . . . . . . . . . . . ....... 118
5.4 Geological Formations Conducive to Concentration
of Nanogold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... 118
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ....... 121
6 The Problems of Nanogold Development . . . . . . . . . . . . . . . . . . . . . . 127
6.1 The State of the Theoretical Basis of Gold Nanomineralogy . . . . 127
6.2 Perspective Objects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6.3 On the Methods of Studying of Objects with Nanogold . . . . . . . 130
6.4 Prospecting Value of Nanogold . . . . . . . . . . . . . . . . . . . . . . . . . . 133
6.5 Industrial Technologies of Nanogold Extraction. . . . . . . . . . . . . . 134
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Chapter 1
Introduction

1.1 General

Until the last decade of the previous century, nanogold of natural objects has not
been systematically studied. However, some mentions on the finds of gold
nanoparticles have attracted the attention of researchers. It is believed that for the
first time the gold nanoparticles up to 5 nm in size were found in the Carlin deposit
(Hansen and Kerr 1968). But the study of nano-sized gold has become an important
and widespread task for many scientific centers of the world only at the end of the
previous century.
The exploration of the nanogold objects was preceded by a long period of
research of metal microparticles. Their prevalence in the various ore bodies,
including the largest gold deposits, a variety of occurrence forms and some other
features have been the subjects of detailed analysis (Nikolaeva 1958; Petrovskaya
1973; Lunyov and Osovetsky 1979; Yablokova 1980; Nesterenko 1991; Roslyakov
et al. 1995, etc.). The questions concerning the forms of “invisible” gold in sulfides,
the processes of gold accumulation in sediments, the efficiency of laboratory
methods, the reliable assessment of its content and the industrial extraction are
actively discussed in the second half of the 20th century (Badalov 1972; Cabri et al.
1989; Amosov and Vasin 1995; Tauson et al. 1996; Maddox et al. 1998, etc.).
Petrovskaya (1973) in her classical work among the other problems noted the
specifics of ultra-fine gold and the importance of its research. She possessed
foreknowledge about the presence in deposits of smaller metal that is not known by
the researchers.
The attention of researchers to the study of nanogold in deposits has significantly
increased in recent years. The problem of gold extracting from ores of the largest
deposits with huge reserves of invisible metal needed to be addressed. According to
some scholars, the main difficulties in the development of improved technologies
were due to the extreme fine size of gold particles and complexity of the forms of
gold occurrence.

© Springer International Publishing AG 2017 1

B. Osovetsky, Natural Nanogold, Springer Mineralogy,
DOI 10.1007/978-3-319-59159-9_1
2 1 Introduction

The significant progress in the study of natural nanogold was facilitated by the
discovery of the so-called unconventional deposits (Carlin, Vorontsovskoe,
Svetlinskoe, Olimpiadinskoe, etc.). New gold varieties, the identification of which
required specific methods were found. The improvement of analytical techniques,
especially high-resolution electron microscopy, has created the necessary condi-
tions for penetration into the nano-world of gold, which occurred at the beginning
of the XXI century. At the same time, the experimental methods were developed of
obtaining of gold nanoparticles for use in nanotechnology.
The need for awareness of the nanogold role as a promising resource of the
precious metal is becoming increasingly important. Hopes for the discovery of the
traditional gold deposits with large reserves almost gone. On the contrary, the
possibility of opening the unique reserves with thin-dispersed and nano-sized metal
is becoming more.
The granulometric spectrum of gold particles in the largest deposits based on
available data is characterized by a predominance of grains in tens of micrometers
in size (Witwatersrand, Nom, Tarkwa, Muruntau, etc.). However, the proportion of
nanoscale gold in them is not reliably established. This is due, on the one hand,
difficulties in the use of appropriate analytical methods and, on the other—the loss
of nanogold or even the impossibility of its extracting by the modern technologies.
In recent years the great role of biogenic gold in the formation of the largest
deposits (e.g. Witwatersrand) is established. Such gold formed by microorganisms,
in particular bacteria, to a large extent must be nano-sized in accordance with the
size of the corresponding organisms.
The assumption that a significant portion of mineral resources of gold in the
earth’s crust is in the nanoscale state, is justified by theoretical positions also. In
accordance with the general provisions of geochemistry a low gold clarke deter-
mines noticeable predominance of its fine particles in ore-bearing rocks. It can be
argued that a significant portion of nanogold is captured by the mineral–concen-
trators (primarily sulfides and quartz) during their crystallization in igneous melts
and hydrothermal solutions. This point of view is confirmed in practice. Thus, the
basic reserve of the nanogold resources must be associated with source rock
deposits.
However, similar resources may be found in sedimentary ores of equally
important value. During the processes of weathering, nanogold can be released
from sulfides. Caught in a free state, it enters the composition of colloidal solutions,
migrates in water flows and disperses in sedimentary shell of the earth. However,
the prevailing mass of gold nanoparticles remains in the weathered rocks in a buried
state, and this resource of gold, unlike such primary sources, while almost never
used. Currently it is recognized the fact that the thin-dispersed (invisible) gold is
typical for the rocks of gold-sulfide and gold-sulfide-quartz formations. The con-
clusion is that nanogold should concentrate in weathered rocks (iron hats), formed
on these deposits. For a long time they were the objects of gold excavation.
The above arguments, it would seem, are in conflict with the facts, testifying that
nanogold rarely found in the sedimentary formations. This is due to the following
circumstances. In itself, nanogold in sediments should be quite ephemeral mineral
1.1 General 3

substance. It is subjected to various external influences, is absorbed by the surface

layer of various minerals, can be easily transferred in ionic or atomic forms. The
ephemeral nature of the nanogold existence is confirmed by the experiments on
their receipt in the laboratory. In particular, considerable efforts have been made to
solve the problems of stabilization and preservation of nanogold in a long time
(Egorova 2006).
Even if the sedimentary rock contains appreciable amounts of gold nanoparti-
cles, the problem is how to retain and concentrate them in the processing of samples
in the laboratory. The conventional methods are not applicable in this case due to
the high chemical activity and surface energy of gold nanoparticles. They are not
subjected to gravitational enrichment due to extremely small mass. Determination
of nanogold using precision methods is difficult because of its low melting tem-
perature and volatility.
The most important proof of the nanogold presence in rocks is the direct visu-
alization of particles by electron microscopy of high resolution. However, you must
know the typical places of their concentration. Studies of the surface nano-relief of
placer gold grains extracted from the weathered rocks have allowed establish that
nanogold in large amounts is able to precipitate and accumulate in the hollows of
the matrix metal surface. Even in the placers situated close to source rocks nanogold
is stored in micro- and nanocracks of the gold surface, being protected from the
external influences (Osovetsky 2012b).
The preservation and concentration of nanogold particles in sediments also
contribute to the processes of their aggregation. Some of the formed aggregates of
nanoparticles are quite stable both in chemical and in mechanical respect. Further
consolidation of aggregates and increase of their stability is influenced by the
processes of natural amalgamation and authigenic mineralization, under the influ-
ence of which the gold nanoparticles are cemented by unstructured secondary
(colloidal) metal or amalgams. Such gold can be recovered even by the gravitational
methods of sample enrichment.
Researches of the natural nanogold are currently underway in many laboratories
in the country and abroad. The references to these works are given in the Chapters
of the monograph. The main task set by the author of the monograph is the study of
nanogold occurrences in natural objects and mechanisms of their formation.

1.2 Methods and Objects

To solve these problems at the first stage it is enough to apply the methods of
high-resolution scanning electron microscopy in combination with microprobe
definitions of the chemical composition of gold nanoparticles. The main materials
are obtained when using field scanning electron microscope with cool emission
JSM 7500F (“JEOL”). Determinations of the chemical composition of gold
nanoparticles are performed on energy-dispersive (INCA ENERGY 350) and wave
4 1 Introduction

(INCA Wave) spectrometers by “Oxford Instruments” as the prefixes to a scanning

electron microscope JSM 6390LV (“JEOL”).
Thus, this monograph presents the basics of one of the gold nanomineralogy
areas. It is directly linked with the studies on the nano-relief of gold, the results of
which are given in another monograph by the author (Osovetsky 2012b) and in the
articles devoted to specific nanogold deposits and ore bodies (Osovetsky 2012a, b;
Osovetsky and Barannikov 2012; Barannikov and Osovetsky 2013; Naumov and
Osovetsky 2013). The author acknowledges that the study of nanogold should be
accompanied by other detailed researches of material composition of ores. These
studies were conducted by us with the use of granulometric, mineralogical, pet-
rographic, atomic absorption, mass spectrometer, diffraction analyses, as well as
thermogravimetric and X-ray fluorescence analyses, the results of which were given
in special articles.
Practice shows that there is certain continuity in the study of very small, thin,
powder, dispersed and, finally, nanoscale gold. The transition to the study of
nanogold was prepared by long previous experience of specialists, including
employees of Perm State University. In particular, the study of objects with very
small, fine and powder gold has been becoming the part of the research program of
the Laboratory of Sedimentary Useful Resources (head Lunyov) and Department of
Mineralogy and Petrography of Perm State University for several decades. A team
of Laboratory staff (Blinov, Tyurin, Kositsyna, Fadeev, Bessonov, Utkin, Trushin,
Naumov, Kazymov, Ilaltdinov, etc.) has studied many gold deposits and ore bodies
in the territory of the Urals, Western Siberia, Yakutia, Kuzbass, Transbaikalia,
Pre-Amur region, Ukraine, Uzbekistan, Tadzhikistan, Kazakhstan. New methods
for quick processing of samples with small metal particles were developed and
implemented (Lunyov and Osovetsky 1979; Osovetsky 1979).
Researches on nanomineralogy of gold are performed in the framework of the
development of Perm State National Research University (2010–2019). They are an
integral part of fundamental researches of Nanomineralogy Sector, created in the
structure of the Perm State University (2010). Individual projects are funded from
the grants.
The present study is mainly nanogold in the placer deposits of the Urals
(Andreevskaya, Eleninskaya, Kazanskaya, Kolchinskaya, Shakhmatovskaya,
Mikhailovskaya, Staropoklevskaya, Chernoborskaya placers in the Southern Urals,
Promyslovskaya and Talitskaya in the Middle Urals, Chernorechenskaya and
Vagran in the Northern Urals, Kozhimskaya in the Sub-Polar Urals), as well as
alluvial deposits in Bashkiria (Tarakanny Log), Kuzbass (the Tutuyas and Kitat
Rivers) and Yakutia (the Sololi and Bodaibo Rivers). The paper presents the results
of nanogold study in some foreign objects, for example the placers of the Yukon
Territory (Canada).
Nanogold of black shales studied by the example of Fedotov suite of Basegy
series rocks on the territory of Perm Region. The ore bodies of mercuriferous
nanogold and amalgams, related with the processes of Early Mesozoic
tectono-magmatic activation, were established on the territory of Vyatka-Kama
1.2 Methods and Objects 5

Depression. Gold nanoparticles were also found and described in several primary
deposits and ore bodies (Svetlinskoe in the Southern Urals, Tykotlovskoe in the
Sub-Polar Urals, Paliostrovskiy Klyuch in Khakassia, Vaigul in Kazakhstan).

Acknowledgements The author expresses gratitude to the staff of institutes, universities and
industrial organizations that provided samples and collections of gold particles for research
(Barannikov, Kisin, Suslov, Morozov, Nakaryakova, Konopatkin), colleagues at work for pro-
viding materials for learning and participation in expeditions on the study of gold mineralization in
different regions of Russia (Naumov, Ilaltdinov, Chaikovsky, Kazymov, etc.), as well as for
participation in laboratory processing of samples (Badjanova, Menshikova, Busygina, etc.). The
author is grateful to Iblaminov for helpful comments and advices in preparing the manuscript for
publication.

References

Amosov RA, Vasin SL (1995) Ontogenezis samorodnogo zolota Rossii (The onthogenesis of the
Russian native gold). TsNIGRI, Moscow
Badalov ST (1972) O prichinakh vozniknoveniya kontsentratsii Au v sulfidnykh mineralakh
(About the causes of Au concentrations in sulfide minerals). Geol J Uzbekistan (2): 53–56
Barannikov AG, Osovetsky BM (2013) Morfologicheskie raznovidnosti i nanorelyef poverkhnosti
samorodnogo zolota raznovozrastnykh rossypey Urala (Morphological varieties and surface
nano-relief of native gold of different age placers in the Urals). Lithosphere 3:89–105
Cabri LJ, Chryssoulis SL, de Villiers JPR et al (1989) The nature of “invisible” gold in
arsenopyrite. Canad Miner 27:353–362
Egorova EM (2006) Nanochastitsy metallov: ikh svoistva I vozmozhnaya rol v zhivykh
organizmakh (Metal nanoparticles: their properties and possible role in living organisms). In:
Materials of the scientific conference “Ethics and science of the future”, Moscow: 219–224
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States 1:908–940
Lunyov BS, Osovetsky BM (1979) Metodika poetapnogo izucheniya melkogo rossypnogo zolota
(The technique of step by step studying of fine placer gold). Kolyma 11:36–37
Maddox LM, Bancroft GM, Scaini M et al (1998) Invisible gold: comparison of the Au deposition
on pyrite and arsenopyrite. Am Min 83:1240–1245
Naumov VA, Osovetsky BM (2013) Rtutistoe zoloto i amalgamy v mezozoy-kainozoyskikh
otlozheniyakh Vyatsko-Kamskoy vpadiny (Mercuriferous gold and amalgams in
Mesozoic-Cenozoic sediments of the Vyatka-Kama Depression). Lithol Miner Res 3:256–273
Nesterenko GV (1991) Prognoz zolotogo orudeneniay po rossypaym (The forecast of gold
mineralization on the placer deposits on the example of the southern regions of Siberia).
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Nikolaeva LA (1958) “Novoe” zoloto v rossypaykh Lenskogo rayona (“New” gold in placers of
the Lena area). Proceedings of TsNIGRI 25(2): 19–122, Moscow
Osovetsky BM (1979) O motodike obrabotki prob s melkimi zernami poleznykh iskopaemykh (On
the method of samples’ processing with small grains of useful resources). Proceedings of
higher educational institutions. Geol Prospect, 4: 112–116
Osovetsky BM (2012a) “Novoe” nanozoloto (“New” nanogold). Notes Russ Miner. Soc. 151
(1):88–101
Osovetsky BM (2012b) Nanoskulptura poverkhnosti zolota (Nanosculture of gold surface). Press,
Perm, Perm Univ
Osovetsky BM, Barannikov AG (2012) “Novoe” nanozoloto Chernorechenskoy rossypi (“New”
nanogold of Chernorechenskaya placer). Prob Mineral Petrography Metallogeny 15:36–42
6 1 Introduction

Petrovskaya NV (1973) Samorodnoe zoloto (Native gold). Nauka, Moscow

Roslyakov NA, Nesterenko GV, Kalinin YA et al (1995) Zolotonosnost kor vyvetrivaniay Salaira
(The goldiferousness of the Salair weathered rocks). Novosibirsk
Tauson VL, Mironov AG, Smagunov NV et al (1996) Zoloto v sulfidakh: sostoyanie problemy
form nakhozhdeniay i perspectivy experimentalnykh issledovaniy (Gold in sulfides: state of the
problem on the forms of finding and prospects of experimental studies). Geol Geophys 37
(3):3–14
Yablokova SV (1980) Tipomorfizm i neodnorodnost gipergennogo zolota (Typomorphism and the
heterogeneity of the supergene gold). The inhomogeneity of minerals and crystal growth.
Nauka, Moscow, pp 104–110
Chapter 2
Mineral–Concentrators of Nanogold

2.1 Sulfides

The issue of “invisible” gold in sulfides from hydrothermal deposits has long been
studied by scientists. This gold is the main metal piece produced by mankind, as
prevalent in the reserves of the largest world deposits (Witwatersrand, Tarkwa,
Muruntau, etc.). They account for up to 40% of the total mass of metal in the
deposits.
However, please note that sulfides of hydrothermal genesis do not always
contain gold, and if they are, the latter is characterized by a rather broad grain-size
range of particles. In this spectrum, probably the main place belongs to the gold of
micrometer size, but always visible and possibly predominant proportion to sub-
microscopic particles (smaller than 0.1 lm, i.e. nanoscale).
The role of sulfides as mineral–concentrators of gold indicated by many
researchers (Maslenitskiy 1944, 1948; Kaimirasova 1968; Korobushkin 1970;
Kalitkina 1971; Voitsekhowskiy et al. 1975; Sakharova et al. 1975; Mironov and
Geletiy 1979; Gavrilov et al. 1979, 1982; Kozerenko et al. 1986; Cook and
Chryssoulis 1990; Sazonov et al. 1992; Wilson et al. 1995; Genkin 1998; Simon
et al. 1999b; Bortnikov et al. 2003; Smagunov et al. 2004; Tauson et al. 2005;
Koneev 2006a, b; Meretukov 2006; Zhmodik et al. 2007; Cepedal et al. 2008).
Many sulfides are not only the mineral–concentrators, but the main mineral–
carriers of gold nanoparticles (especially pyrite and arsenopyrite, and to a lesser
extent pyrrhotite, bismuthinite, galena, fahlore, covellite, etc.) (Zagainov 2009).
For example, the main mineral–carriers of gold in the Carlin deposit are arsenic
pyrite and marcasite. In these sulfides free gold of powder in size is present, but the
nanoparticles predominate (Wels and Mullens 1973; Fleet and Mumin 1997; Reich
et al. 2005a, b). Determination of the regularities of gold nanoparticles distribution
in Carlin ores, where they were also found on the surface of the galena and
arsenopyrite grains, is seen as an important step in addressing the issue of invisible
gold in sulfides (Palenik et al. 2004).

© Springer International Publishing AG 2017 7

B. Osovetsky, Natural Nanogold, Springer Mineralogy,
DOI 10.1007/978-3-319-59159-9_2
8 2 Mineral–Concentrators of Nanogold

Gold nanoparticles recorded in the pyrite grains of the Pokrovskiy gold-silver

deposit in the Pre-Amur region (Moiseenko et al. 2010a). The average gold content
in the ore body presented by paleovolcanic rocks is estimated at 44.4 g/t, and
nanogold in pyrite makes up to 9% of the total metal mass in the rock.
The presence of nanogold, in addition to arsenopyrite (especially needle-like
shape) and pyrite, was found in pyrrhotite, chalcopyrite, galena, and sphalerite in
gold ore deposits of Uzbekistan (Koneev et al. 2010). Novgorodova (2004)
revealed nanocrystals of gold in sulfides of the deposits in the Southern Urals.
Ozhogin (2009) when studying the material composition of gold-sulfide ores from
Malomyr in the Pre-Amur region marked the presence of nanogold of 5–10 nm in
size in pyrite and arsenopyrite.
The distribution of gold nanoparticles on the surface of sulfide minerals (pyrite,
galena, pyrrhotite and arsenopyrite) is studied with the use of high-resolution
electron microscopy (Zhmodik et al. 1989; Mikhlin et al. 2006b). The staff of the
Institute of Geology and Nature Management FEB RAS established a presence of
two nanogold types in ore deposits of the Far East: spheroidal from 5–250 nm in
size with high fineness and in the form of monolayers of nano-sized thickness. They
noted that the layers of native gold alternate with films of electrum containing
carbon, uranium, and chlorine (Moiseenko et al. 2010b). The presence of gold
nanoparticles has been established in tiny grains of galena also (Moiseenko and
Kuznetsova 2010).
The main factors determining the concentration of gold in sulfides are their
crystallochemical features (in particular, the presence of certain impurities, defects
of the crystal lattice, etc.) and geochemical parameters of ore-forming environment
(primarily temperature and fugacity of sulfur, etc.) (Badalov 1972; Arehart et al.
1993; Tauson et al. 1996; Zhmodik et al. 2010). The scientists of the Institute of
Geology and Mineralogy SB RAS based the criteria that determined the presence of
gold as isomorphic admixture in sulfide minerals with these features.
Currently the existence of different forms of the gold occurrence in sulfides
assumes: isomorphic, in the form of gold sulfides, as a mechanical admixture of
micro- and nanoparticles of gold and mixed. Isomorphism is observed both in the
cationic positions (lattice sites occupied by iron cations) and anionic (in the place of
the anions of sulfur, arsenic and other elements) (Schweigart 1965). Special studies
have shown that the possible forms of gold occurrence in pyrite are isostructural
compounds of the type AuS2 or Au2S.
However, most scientists believe that finding invisible gold in the pyrite struc-
ture is associated with defects in the crystal lattice. The positions of vacancies are
the most favorable in this respect. This view is based on the endocrypty of trace
elements concept, which theoretically justifies their occurrence in the crystal
structure due to the presence of inherent defects (Urusov and Kravchuk 1978; Cabri
et al. 1989, 2000; Abramovich et al. 1989, 1990; Tauson 1999a, b; den Besten et al.
1999). The application of this concept in relation to gold is fully justified, because it
takes into account important crystallochemical peculiarity of this metal, which is
manifested in his pronounced tendency to endocrypty. The presence of gold
nanoparticles in vacant positions of the crystal lattices of the sulfides accounts for
2.1 Sulfides 9

their relatively rapid movement and the possibility of concentrating in different

structural positions, due to the migration of vacancies. In addition to positions of
vacancies, nanogold may be concentrated in zones of edge dislocations, micro- and
nanocracks, etc.
Large widespread view that invisible gold is mainly concentrated on the surface
of sulfide grains (Bancroft and Jean 1982; Jean and Bancroft 1985; Hyland and
Bancroft 1989; Möller and Kersten 1994; Becker et al. 1997; Maddox et al. 1998).
It is consistent with the known provision that a certain portion of the impurity atoms
located in the vacant positions as a result of migration is to move in the direction of
sub-surface zone. However, the process of adsorption of metal atoms from the
environment plays the main role (Renders and Seward 1989; Widler and Seward
1998, 2002; Laptev and Rozov 2006). The concept of the existence in the
sub-surface zone of sulfides with thickness less than 300 nm of the
non-autonomous phases with a deficit of metals and the presence of specific
chemical bonds, including S–O and S–S, is developed. Considerable number of
them is dimers. Favorable conditions for absorption of trace elements, particularly
nanoparticles, from the environment are created in this zone (Simon et al. 1999a;
Smagunov 2007).
The findings of this conception are confirmed by experimental data (Mycroft
et al. 1995). In particular, the surface properties of the pyrrhotite crystals have
studied at the nanoscale. Pyrrhotite with lots of gold nanoparticles on the surface is
distinguished by a lower ratio of Fe:S. It is assumed that iron deficiency in the
sub-surface layer of pyrrhotite may be associated with the presence of not only
sulfide and sulfur-containing compounds of iron, but also of the oxide and
hydroxide. The latter are characterized by high sorption properties, which are
manifested in the adherence of gold nanoparticles (Smagunov et al. 2004).
An artificial solution was used in one of the experiments. It included gold
nanoparticles of 10–80 nm in size and the fine powder of pyrite particles in the tens
of micrometers. Nanogold was obtained by artificial way, and the size of its par-
ticles was controlled by special methods. It was established experimentally that
nanogold completely deposited on the surface of pyrite particles when its con-
centration in a solution reached about 50 mg/ml. The smallest particles of pyrite
showed the high ability to adsorb gold nanoparticles. At the same time, the process
was also influenced by the size of the gold particles: large nanogold had the higher
adsorption ability (Fu et al. 2012).
Experiments also proved that nanoparticles of gold ranging from 2 to 50 nm in
size and more were absorbed by the surface of sulfides in the process of sponta-
neous precipitation from chloride solutions under reducing conditions. Thus, the
dimensions of the nanoparticles, their location on the surface of sulfide and the total
number depend on the mineral species, surface condition of the grain and the
external environment. By the ability to adsorb nanogold the sulfides are arranged in
the following order: chalcopyrite, sphalerite, galena, arsenopyrite, pyrite, pyrrhotite.
The state of the sulfide surface also affects the morphology of gold nanoparticles.
The deposition of nanogold promotes moderate oxidation with origin thin oxide
films on the mineral surface (Romanchenko 2007).
10 2 Mineral–Concentrators of Nanogold

The possible range of gold occurrence in the crystal structure of sulfides was
calculated by different methods (Tauson et al. 1998a, b). One of them obtained the
limit by almost two orders of magnitude higher than theoretically installed iso-
morphic capacity of the mineral crystal lattice (Smagunov 2007). Thus, it is con-
siderably influenced by the crystallochemical characteristics of the mineral and
geochemical parameters of the environment (temperature, fugacity of sulfur, etc.).
The influence of the energy amount of the metallic bond in the crystals of sulfides in
the presence of invisible gold was experimentally proved also (Mironov et al.
1987). There is a direct correlation between these indicators.
A number of works devoted to the study of the question of particularly mor-
phological aspects of gold nanoforms in sulfides. A detailed study with application
of high-resolution electron microscopy showed that they are frequently the
assemblies of nanoscale globules of gold. Some units can reach quite large sizes.
This conclusion was made by Marchenko (2011) in the study of gold particles up to
20 lm present in the grains of arsenopyrite and arsenical pyrite from the rocks of
black shale formations in Kazakhstan.
Employees of the Amur Scientific Research Institute since 1992 have conducted
systematic research of nanoscale gold. Overall, it was investigated gold from 48
alluvial and three coastal placers, which were located in the eastern areas of the
country. The presence of gold in high quantities in pyrite, hydrogoethite and native
metals (silver, copper, iron) has been determined by precision methods. Gold
nanoparticles of spheroidal shape of 50–100 nm in size with the fineness of 800–
820 were fixed by the methods of high-resolution electron microscopy in these
minerals and kaolinite. Characteristically, nanoparticles of gold in these minerals
formed the “staring” clusters, distributed very unevenly that significantly made
difficulties for their detection. The proportion of nanoscale metal in the total its
weight defined by vacuum filtration methods estimated at an amount of 31%
(Moiseenko 2010).
Nanogold in sulfides in many deposits presents in several morphological types.
For example, the discrete allocations of gold nanoparticles in pyrite and marcasite
and films on the surface of the older sulfides without gold are observed in the Carlin
deposit.
In the gold deposit, confined to the North China Craton, where gold mineral-
ization is hosted by quartz veins in Archean metamorphic rocks of the amphibolite
facies, invisible gold occurs in pyrite, on the one hand, in the form of isomorphic
impurities, and, on the other hand, in the form of nanoparticles of native gold or
electrum, and tellurides of gold. In addition, visible gold is presented hosted by
grain boundaries or filled in microcracks in pyrite (Shi-Jian et al. 2011).
However, sulfides not always perform the role of mineral–concentrators and
especially the mineral–carriers of gold. In this regard, great importance is attached
to the problem of identifying of formation types of deposits, in which sulfides
become the main mineral–carriers of gold.
It is believed that invisible gold in the greatest number concentrates in the
sulfides of the Carlin-type deposits, as well as porphyry copper and pyritaceous
(Vikentyev 2006; Vinokurov and Vikentyev 2009). The significant mass of the gold
2.1 Sulfides 11

is especially concentrated in gold-sulfide disseminated ores. The main mineral–

carrier of gold is arsenopyrite. So, gold-sulfide mineralization in Olimpiadinskoe
deposit is mainly represented by inclusions of nanogold in needle-like arsenopyrite.
The industrial mineralization is presumably formed as a result of crystallization of
gold-arsenic-sulphur complexes that were observed in gas phase by a zone of deep
faults (Savichev 2004).
A more detailed examination reveals a different goldiferousness of separate
generations of mineral–concentrators. The definition of invisible gold contents and
associated elements in pyrite of the four gold-arsenic deposits using laser ablation
ICP-MS (Large et al. 2009) has allowed to establish two phases of pyrite enrich-
ment by gold in every deposit: early (sedimentary) and late (hydrothermal). In the
first stage gold concentrates in arsenic-bearing diagenetic pyrite along with other
trace elements (As, Ni, Pb, Zn, Ag, Te, V, Se), whereas in the second stage gold
occurs as loose particles in the cracks of metamorphic or hydrothermal pyrite, and
thin gold-arsenic edges on the protruding parts of the hydrothermal pyrite grains
(for example, in the Carlin deposit). In hydrothermal pyrite not much Ni, V, Zn, Pb,
Ag, but there are areas with abnormally high contents of Co and As. The increased
contents of cobalt and nickel with low contents of arsenic and gold are also
observed in the marginal edges on the ledges of hydrothermal pyrite grains of some
deposits (Sukhoy Log).
Two generations of arsenopyrite grains are revealed in one of the gold-sulfide
deposits of the Far East. The first of these is represented by large crystals without
gold. The second generation of small arsenopyrite crystals has elongated prismatic
shape. A significant amount of nanogold particles of a few tens of nanometers in
size, forming clusters, is discovered in them by means of transmission electron
microscopy (Ozhogina and Rogozhin 2010).
Thus, mineral–concentrator is capable to include nanogold often in a different
measure in the same mineral deposit. So, one of the main mineral–carriers of gold
in the Witwatersrand deposit is pyrite. However, the gold content in it varies in very
wide limits (9–1440 ppm).
Some geochemical indicators of gold mineralization are revealed for sulfides. In
particular, high arsenic and low iron contents are typical to them. Thus, the arsenic
content in gold-bearing pyrite usually varies from 2 to 8 wt. % (Cline et al. 2005).
The studies of some authors (Reich et al. 2005a, 2006) have shown that when the
ratio Au:As < 0.02 gold is mainly present in pyrite in the form of a monovalent
cation and isomorphically replaces the iron cations. The nanoparticles of native
gold appear when a higher value of this relation is marked. All geochemical signs
indicate that gold is adsorbed by pyrite from ore-bearing fluids, where it was in the
form of complex Au(HS)2.
In Uzbekistan ores especially auriferous arsenopyrite with an increased S:As is
discovered (Koneev et al. 2008). The mineral–carriers of invisible gold are pyrite
and arsenopyrite in the skarn deposit El Valle (Spain). Gold-bearing pyrite (gold
content up to 0.08 wt. %) has a high content of arsenic (up to 9.5 wt. %) and a large
number of other trace elements (Sb, Ni, Tl, Cu, Hg, Se). The abundance of impurity
12 2 Mineral–Concentrators of Nanogold

elements (Cu, Sb, Tl) is also characterized for arsenopyrite (gold content of 0.125–
0.3 wt. %). Invisible gold concentrates on the parts of the surface of pyrite and
arsenopyrite grains, characterized by iron deficiency (Cepedal et al. 2008).
The nature of distribution of gold nanoparticles in the crystal lattices of sulfides
is also studied. In particular, a large amount of gold nanoparticles, the average size
of which is about 4 nm, is detected when observed grains of arsenical pyrite in
high-resolution electronic microscope. Their distribution in the bulk of pyrite grains
is completely chaotic without any signs of a natural orientation.
A detailed study of the distribution of nanogold particles in sulfides is also in the
process of their synthesis. In this case, it is possible to combine different conditions
of mineral formation: the concentration of gold in solutions, their composition,
external parameters, etc. (Bugaeva 2006). These comprehensive studies revealed
the effect of concentration of invisible gold on the border of nanoblocks of pyrite
crystal lattice (planar defects) of 50–100 nm in size. It is manifested at relatively
low temperatures (usually below 300 °C) and leads to the formation of high con-
centrations of gold (up to tens of grams per ton). The implementation of this effect
in natural situations is quite probable in terms of the crystallization of mosaic
structure pyrite from strongly saturated epithermal fluids that has been occurred
during the formation of the Carlin deposit. Some gold-related elements, in particular
arsenic, played the important role in intensifying of this effect. Arsenic ions par-
ticipated in the transport of gold in hydrothermal solutions in the form of
sulfide-arsenide complexes, and then the noble metal was selected from them as an
independent mineral phase in the structures of arsenical pyrite or arsenopyrite.
Arsenic often remains in the haloes of dissipation.
Modeling of the nanogold behavior in pyrite using the molecular dynamics
method shows that from a hypothetical correct location in the matrix of pyrite at a
temperature of 300 °C nanoparticles are rearranged in a random distribution at a
temperature of 900 °C (Reich et al. 2006). During this process gold nanoparticles
approach each other with origin of aggregates (Fig. 2.1).
Experiments have shown that with increasing temperature up to 370 °C the gold
nanoparticles do not react to the state change of the environment. However, the
process of aggregation and consolidation of nanoparticles begins above this tem-
perature, which leads to their instability. By the way, approximately 100 primary
gold nanoparticles smaller than 5 nm in size are transformed into several units of
about 35 nm in size. The reason is melting of small nanoparticles, transition them to
the solution, and then the deposition and aggregation.
The dependence of the melting temperature of free gold nanoparticles from their
size is affected on these processes (Ercolessi et al. 1991). In particular, if you reduce
the size to 4 nm, the melting point of gold is reduced with 1063 to 427 °C. The
temperature limit of the existence of gold nanoparticles in arsenical pyrite was
experimentally determined in the above results of studies. These data emphasized
once again that a favourable condition for conservation of gold nanoparticles in
sulfides is a relatively low temperature.
The behavior of gold nanoparticles in the structure of sulfide minerals depends
significantly on their size that is experimentally proved also. In particular, the
2.1 Sulfides 13

Fig. 2.1 The model of gold nanoparticles location in the structure of pyrite: a—primary at a
temperature of 300 °C, b—redistribution of the nanoparticles at a temperature of 900 °C.
(Reproduced from Reich et al. 2006)

binding energy of gold nanoparticles in the crystal lattice of the sulfide markedly
increases when size decreases from 30 to 3 nm. There are also characteristic
physical phenomena associated with the presence of nanogold (Mikhlin et al.
2006a).
The value of the different mineral species of sulfides as mineral–concentrators of
nanogold is not always consistent with their role as mineral–carriers of metal. The
primary role as the mineral–carrier of gold from sulfide minerals belongs to pyrite
in connection with its significant predominance in gold deposits, although the gold
content in arsenopyrite and sometimes in some other sulfides may be higher than in
pyrite. The proportion of the native nanogold mass in sulfides presumably increases
proportionally to the increase in overall gold grade in ore.

2.2 Gold

The presence of gold nanoparticles in the sub-surface layer of matrix gold grains is
widely common form of their existence in the weathered rocks of deposits and ore
bodies of gold-sulfide and quartz-gold-sulfide formations. They can be found even
on the surface of the grains of placer metal in alluvial deposits near source rocks,
although their surface is subjected to strong mechanical deformations and abrasion
during the transporting process. Gold nanoparticles are often met on the surface of
gold particles in the placers of secondary collectors, re-deposited weathered rocks,
etc.
14 2 Mineral–Concentrators of Nanogold

2.2.1 Ensembles of Micro- and Nanoparticles

Gold nanoparticles typically present together with the microparticles of noble metal
having the size somewhat more than 0.1 lm (Fig. 2.2). The location of the micro-
and nanoparticles is usually dispersed and chaotic within such ensembles, but
sometimes there are clusters of them. However, only particles of nano-sized range
can be distributed on the significant areas of the gold surface (Fig. 2.3).

2.2.2 The Morphology of Gold Nanoparticles

It is theoretically proved that the smallest size nanoparticles, including gold, usually
have a spherical shape (Yushkin 2005). The reason for this phenomenon is the
abundant surface energy of the nanoparticles.
Indeed, electron microscopic study of the gold surface of the numerous gold
objects showed that metal nanoparticles were mainly represented by rounded up to
spherical individuals (see Fig. 2.3). However, there were often other forms also:
worm-like, angular and irregular. Nanoparticles of elongated shape, up to wire-like,
were often presented on the surface of gold particles coated with hydroxides of iron
(Fig. 2.4).
In addition to the above, even more complex morphological types of nanogold
particles (for example, ameboidal) and a geometrically correct triangular, hexago-
nal, etc. are rarely observed (Figs. 2.5, 2.6).
The study of the structure of many nanoparticles under high magnification (up to
300–500 thousand times) does not detect the signs of heterogeneous structure
(Fig. 2.7). Along with this, the complex structure of some nanogold particles,
which represent the aggregates of tightly consolidated nanoparticles of different
shapes and sizes, quite clearly manifests (Fig. 2.8).

1μm 1μm

Fig. 2.2 Ensembles of micro- and nanoparticles of metal on the surface of placer gold grains
2.2 Gold 15

1μm 200 nm

Fig. 2.3 Clusters of gold nanoparticles on the matrix metal surface

1μm 200 nm

200 nm 200 nm

Fig. 2.4 Single and accumulations of gold nanoparticles of elongated shape

2.2.3 The Generations of Nanoparticles

Analysis of electronic microphotographs shows that it is possible to allocate among

single gold nanoparticles the individuals being in different contacts with the surface
of the matrix metal. For example, some nanoparticles barely touch the surface of
matrix gold, the other root in a superficial gold layer to a definite depth (Fig. 2.9).
16 2 Mineral–Concentrators of Nanogold

200 nm 200 nm

Fig. 2.5 Gold nanoparticles of the most common forms (the Vyatka-Kama Depression)

300 nm 300 nm

Fig. 2.6 Gold nanoparticles of various shapes

This fact indicates the time difference from the deposition of nanogold on the
surface of the matrix gold. Probably, individual nanoparticles immerse into the
sub-surface layer over time due to the diffusion of metal atoms. The most “ancient”
of them probably do not differ in the pictures, being completely absorbed in the
sub-surface layer.
In this regard, we can distinguish the generations of different age for gold
nanoparticles. The nanogold of the youngest generation that precipitates immedi-
ately at the nano- or microparticles of the previous one, forming a kind of tandem,
looks especially pronounced in electronic microphotos (Fig. 2.10). It is character-
istic that the particle size of the next generation, as a rule, smaller than the previous
one. These tandems are usually the initial forms that precede the formation of
aggregates.
Sometimes the morphological features of relatively large rounded gold
nanoparticles indicate their concentric zonal structure due, perhaps, layer-by-layer
growth of the shell in the range of some core (Fig. 2.11).
2.2 Gold 17

100 nm 100 nm

100 nm 100 nm

Fig. 2.7 Homogeneous roundish gold nanoparticles

100 nm 200 nm

Fig. 2.8 Nanogold formed by the merging of smaller nanoparticles (the weathered rocks of black
shales)

2.2.4 Regularities of Nanogold Location on the Surface

of the Matrix Gold

Gold nanoparticles are usually not located uniformly on the surface of the matrix
gold. The places of their local concentration are different hollows (cracks, pores,
18 2 Mineral–Concentrators of Nanogold

200 nm 200 nm

200 nm 200 тnm

Fig. 2.9 Nanoparticles of different generations on the gold surface of the Vyatka-Kama
Depression: buried in a surface layer of gold (gray) and the adjacent (light)

200 nm 200 nm

Fig. 2.10 “Tandems” of gold nanoparticles

scratches, etc.) or, on the contrary, the elevated parts of microrelief. In the first case,
they are most often confined to the walls of the negative elements of the surface
microrelief (Figs. 2.12, 2.13).
However, selective localization of gold nanoparticles with distinct boundaries of
“populated” areas is observed even on a relatively flat surface of the matrix metal
2.2 Gold 19

100 nm

Fig. 2.11 Signs of concentric-zonal structure and growth of layered gold nanoparticles

1 μm
1 μm

Fig. 2.12 The location of the nanoparticles on the walls of large hollows in surface microrelief of
the matrix metal grains

1 μm
200 nm

Fig. 2.13 The location of the nanoparticles on the elevated parts of the gold surface microrelief
20 2 Mineral–Concentrators of Nanogold

(Fig. 2.14). Sometimes this is due to the availability of covering films of secondary
substance (usually iron hydroxides). Nanoparticles also concentrate around the
microinclusions on the surface of gold (Fig. 2.15).
On the surface of the matrix metal with ridged or stepped microrelief due to the
projections of microlayers nanogold particles are oriented along the directions of
layering and mainly in the lower zones of microlayers junction (Fig. 2.16). As a
result, there is a linear orientation of the nanoparticles parallel to the projections of
stepped microrelief.

2 μm 1 μm

Fig. 2.14 The boundaries of the concentration zones of gold micro- and nanoparticles on the
matrix surface

200 nm

Fig. 2.15 The location of gold nanoparticles around the microinclusion

2.2 Gold 21

Fig. 2.16 Subparallel

arrangement of gold
nanoparticles on the surface
of layered metal

200 nm

2.2.5 The Density of Gold Nanoparticles on the Surface

Comparative analysis of electron microphotographs of the gold surface covered by

metal nanoparticles shows that the density of the latter is considerably different. It
can be quantified in the value of nanoparticles per unit surface area. Specific
measurements show that the density of the gold nanoparticles on the matrix surface
varies from a few to 150 nanoparticles per 1 mm2. It is controlled by the surface
microrelief, especially the presence of microdefects (scratches, hollows, cracks,
etc.).

2.2.6 The Chemical Composition of Gold Nanoparticles

Microprobe analysis gives the opportunity to determine the chemical composition

of individual microparticles in the one-dimensional cluster with nanoparticles,
which suggests their ordinary genesis. Thus, we can define the average chemical
composition of nanoparticles taking into opinion a sufficiently dense arrangement
of gold nanoparticles.
The results of microprobe analysis have allowed conclude wide variations in the
chemical composition of nano- and microparticles of gold (Table 2.1). The identity
of chemical composition of the matrix metal and particles of gold on its surface is
marked in some cases, too.
Another random document with
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commonly called jockies, and present them to the state of Venice, ‘to
serve in the galleys against the common enemy of Christendom.’
Most of the patriot’s contemporaries probably acknowledged the
existence of the evil which he described—though he probably
exaggerated it to the extent of at least a third—but there is no
appearance of the slightest movement having ever been made
towards the adoption of his remedy. A modern man can only wonder
at such a scheme proceeding from one whose patriotism was in
general too fine for use, and who held such views of the late
tyrannical governments, that he was for punishing their surviving
instruments several years after the Revolution.[257]
At the date noted, the government was revolving more rational
plans for mitigating the evils of the wide-spread mendicancy. The
Privy Council issued a proclamation, 1699.
adverting to the non-execution of the laws
for the poor during the time of the scarcity, but intimating that better
arrangements were rendered possible by the plentiful harvest just
realised. The plan ordered to be adopted was to build correction-
houses at Edinburgh, Dumfries, Ayr, Glasgow, Stirling, Perth,
Dundee, Aberdeen, and Inverness, each for the county connected
with the burgh, into which the poor should be received: no allusion is
made to the other counties. The poor were to be confined to the
districts in which they had had residence for the last three years. It
was ordained of each correction-house, that it should have ‘a large
close sufficiently enclosed for keeping the said poor people, that they
be not necessitat to be always within doors to the hurt and hazard of
their health.’ And the magistrates of the burghs were commanded to
take the necessary steps for raising these pauper-receptacles under
heavy penalties.[258]

It was customary for the Lords of Privy Nov. 9.

Council to grant exclusive right to print and
vend books for certain terms—being all that then existed as
equivalent to our modern idea of copyright. Most generally, this right
was given to booksellers and printers, and bore reference rather to
the mercantile venture involved in the expense of producing the
book, than to any idea of a reward for authorcraft. Quite in
conformity with this old view of literary rights, the Council now
conferred on George Mossman, stationer in Edinburgh, ‘warrant to
print and sell the works of the learned Mr George Buchanan, in ane
volume in folio, or by parts in lesser volumes,’ and discharged ‘all
others to print, import, or sell, the whole or any part of the said Mr
George his works in any volume or character, for the space of
nineteen years.’
In conformity with the same view of copyright, another Edinburgh
stationer, who, in 1684, had obtained a nineteen years’ title to print
Sir George Mackenzie’s Institutes of the Law of Scotland, soon after
this day was favoured with a renewal of the privilege, on his
contemplating a second edition.
Robert Sanders, printer in Glasgow, had printed a large
impression of a small book, entitled Merchandising Spiritualised, or
the Christian Merchant Trading to Heaven, by Mr James Clark,
minister at Glasgow; which, in Sanders’s opinion, was calculated to
be ‘of excellent use to good people of all 1699.
ranks and degrees.’ For his encouragement
in the undertaking, he petitioned the Privy Council (July 13, 1703)
for an exclusive right of publishing the book; and he was fortified in
his claim by a letter from the author, as well as a ‘testificat from Mr
James Woodrow, professor of divinity at Glasgow, anent the
soundness of the said book.’ The Council, taking all these things into
account, gave Sanders a licence equivalent to copyright for nineteen
years.[259]

The abundant harvest of 1699 was Nov. 30.

acknowledged by a general thanksgiving.
But, that the people might not be too happy on the occasion, the
king, in the proclamation for this observance, was made to
acknowledge that the late famine and heavy mortality had been a just
retribution of the Almighty for the sins of the people; as likewise had
been ‘several other judgments, specially the frustrating the
endeavours that have been made for advancing the trade of this
nation.’ [The royal councillors were too good Christians, or too polite
towards their master, to insinuate as a secular cause the subserviency
of the king to English merchants jealous of Scottish rivalry.] For
these reasons, he said, it was proper, on the same day, that there be
solemn and fervent prayers to God, entreating him to look mercifully
on the sins of the people, and remove these, ‘the procuring causes of
all afflictions,’ and permit that ‘we may no more abuse his goodness
into wantonness and forgetfulness.’
The people of Scotland were poor, and lived in the most sparing
manner. When they made an honourable attempt to extend their
industry, that they might live a little better, their sovereign permitted
the English to ‘frustrate the endeavour.’ He then told them to humble
themselves for the sins which had procured their afflictions, and
reproached them with a luxury which they had never enjoyed. The
whole affair reminds one of the rebuke administered by Father Paul
to the starved porter in The Duenna: ‘Ye eat, and swill, and drink,
and gormandise,’ &c.

Notwithstanding the abundance of the Dec. 14.

harvest, universally acknowledged a
fortnight before by solemn religious rites, there was already some
alarm beginning to arise about the future, chiefly in consequence of
the very natural movements observed among possessors of and
dealers in grain, for reserving the stock against eventual demands.
There now, therefore, appeared a 1699.
proclamation forbidding export and
encouraging import, the latter step being ‘for the more effectual
disappointing of the ill practices of forestalled and regraters.’[260]

We have at this time a curious illustration Dec. 7.

of the slowness of all travelling in Scotland,
in a petition of Robert Irvine of Corinhaugh to the Privy Council. He
had been cited to appear as a witness by a particular day, in the case
of Dame Marjory Seton, relict of Lewis Viscount of Frendraught, but
he did not arrive till the day after, having been ‘fully eight days upon
the journey that he usually made in three,’ in consequence of the
unseasonableness of the weather, by which even the post had been
obstructed. The denunciation against him for nonappearance was
discharged.[261]

1700. Jan.
 A case of a singular character was brought before the Court of
Justiciary. In the preceding July, a boy named John Douglas, son of
Douglas of Dornock, attending the school of Moffat, was chastised by
his teacher, Mr Robert Carmichael, with such extreme severity that
he died on the spot. The master is described in the indictment as
beating and dragging the boy, and giving him three lashings without
intermission; so that when ‘let down’ for the third time, he ‘could
only weakly struggle along to his seat, and never spoke more, but
breathed out his last, and was carried dying, if not dead, out of the
school.’ Carmichael fled, and kept out of sight for some weeks, ‘but
by the providence of God was discovered and seized.’
‘The Lords decerned the said Mr Robert to be taken from the
Tolbooth of Edinburgh by the hangman under a sure guard to the
middle of the Landmarket, and there lashed by seven severe stripes;
then to be carried down to the Cross, and there severely lashed by six
sharp stripes; and then to be carried to the Fountain Well, to be
severely lashed by five stripes; and then to be carried back by the
hangman to the Tolbooth. Likeas, the Lords banish the said Mr
Robert furth of this kingdom, never to return thereto under all
highest pains.’[262]
Robert Carmichael was perhaps only unfortunate in some
constitutional weakness of his victim. An energetic use of the lash
was the rule, not the exception, in the old 1700.
school—nay, even down to times of which
many living persons may well say, ‘quæque miserrima vidi, et
quorum pars magna fui.’ In the High School of Edinburgh about
1790, one of the masters (Nicol) occasionally had twelve dunces to
whip at once, ranking them up in a row for the purpose. When all
was ready, he would send a polite message to his colleague, Mr
Cruikshank, ‘to come and hear his organ.’ Cruikshank having come,
Mr Nicol would proceed to administer a rapid cursory flagellation
along and up and down the row, producing a variety of notes from
the patients, which, if he had been more of a scientific musician, he
might have probably called a bravura. Mr Cruikshank was sure to
take an early opportunity of inviting Mr Nicol to a similar treat.

One of the most conspicuous persons at Jan.

this time in Scotland—one of the few,
moreover, known out of his own country, or destined to be
remembered in a future age—was Dr Archibald Pitcairn. He
practised as a physician in Edinburgh, without an equal in
reputation; but he was also noted as a man of bright general talents,
and of great wit and pleasantry. His habits were convivial, after the
manner of his time, or beyond it; and his professional Delphi was a
darkling tavern in the Parliament Close, which he called the Greping
Office (Latinè, ‘Greppa’), by reason of the necessity of groping in
order to get into it. Here, in addition to all difficulties of access, his
patients must have found it a somewhat critical matter to catch him
at a happy moment, if it was true, as alleged, that he would
sometimes be drunk twice a day. It is also told of him that, having
given an order at home, that when detained overnight at this same
Greping Office, he should have a clean shirt sent to him by a servant
next morning, the rule was on one occasion observed till the number
of clean shirts amounted to six, all of which he had duly put on; but,
behold, when he finally re-emerged and made his way home, the
whole were found upon him, one above the other! Perhaps these are
exaggerations, shewing no more than that the habits of the clever
doctor were such as to have excited the popular imagination. It was a
matter of more serious moment, that Pitcairn was insensible to the
beauties of the Presbyterian polity and the logic of the Calvinistic
faith—being for this reason popularly labelled as an atheist—and
that, in natural connection with this frame of opinion, he was no
admirer of the happy revolution government.
He had, about this time, written a letter to his friend, Dr Robert
Gray, in London; and Captain Bruce, a 1700.
person attached to the service of the Duke
of Hamilton, had sent it to its destination under a cover. It fell, in
London, into the hands of the Scottish Secretary, Seafield, who
immediately returned it to the Lord Chancellor in Edinburgh, as one
of a dangerous character towards the government. The Lord
Chancellor immediately caused Dr Pitcairn and Captain Bruce to be
apprehended and put into the Tolbooth, each in a room by himself.
On the letter being immediately after read to the Privy Council
(January 16), they entirely approved of what had been done, and
gave orders for a criminal process being instituted before them
against the two gentlemen.
 Dr Pitcairn.

On the 25th of January, Pitcairn was brought before the Council

on a charge of contravening various statutes against leasing-making
—that is, venting and circulating reproaches and false reports against
the government. He was accused of having, on a certain day in
December, written a letter to Dr Gray in reference to an address
which was in course of signature regarding 1700.
the meeting of parliament. This, he said,
was going on unanimously throughout the nation, only a few
courtiers and Presbyterian ministers opposing it, and that in vain;
‘twice so many have signed since the proclamation anent petitioning
as signed it before.’ ‘He bids him [Dr Gray] take notice that there is
one sent to court, with a title different, to beguile the elect of the
court, if it were possible.’ ‘And all the corporations and all the
gentlemen have signed the address, and himself among the rest; and
it is now a National Covenant, and, by Jove, it would produce a
national and universal ——; to which he adds that he is thinking after
a lazy way to reprint his papers, but hopes there shall be news ere
they are printed, and that he is calculating the force of the musculi
abdominis in digesting meat, and is sure they can do it, une belle
affaire.’
In the letters of charge brought forward by the Lord Advocate, it
was alleged that there were here as many falsehoods as statements,
and the object of the whole to throw discredit on the government was
manifest. One of his allegations was the more offensive as he had
sought to confirm it ‘by swearing profanely as a pagan, and not as a
Christian, “by Jove, it will produce a national and universal ——,”
which blank cannot be construed to have a less import than a
national and universal overturning.’ Seeing it clearly evidenced that
he had ‘foolishly and wickedly meddled in the affairs of his majesty
and his estate, he ought to be severely punished in his person and
goods, to the terror of others to do the like in time coming.’
Dr Pitcairn, knowing well the kind of men he had to deal with,
made no attempt at defence; neither did he utter any complaint as to
the violation of his private correspondence. He pleaded that he had
written in his cups with no evil design against the government, and
threw himself entirely on the mercy of the Council. His submission
was accepted, and he got off with a reprimand from the Lord
Chancellor, after giving bond with his friend Sir Archibald
Stevenson, under two hundred pounds sterling, to live peaceably
under the government, and consult and contrive nothing against it.
[263]

This is the date of a conflagration in Feb. 3.

Edinburgh, which made a great impression
at the time, and was long remembered. It 1700.
broke out in one of the densest parts of the
city, in a building between the Cowgate and Parliament Close, about
ten o’clock of a Saturday night. Here, in those days, lived men of no
small importance. We are told that the fire commenced in a closet of
the house of Mr John Buchan, being that below the residence of Lord
Crossrig, one of the judges. Part of his lordship’s family was in bed,
and he was himself retiring, when the alarm was given, and he and
his family were obliged to escape without their clothes. ‘Crossrig,
naked, with a child under his oxter [armpit], happing for his life,’ is
cited as one of the sad sights of the night. ‘When people were sent
into his closet to help out with his cabinet and papers, the smoke was
so thick that they only got out a small cabinet with great difficulty.
Albeit his papers were lying about the floor, or hung about the walls
of his closet in pocks, yet they durst not stay to gather them up or
take them ... so that that cabinet, and his servant [clerk]‘s lettron
[desk], which stood near the door of the lodging, with some few other
things, was all that was saved, and the rest, even to his lordship’s
wearing-clothes, were burnt.’[264] According to an eye-witness, the
fire continued to burn all night and till ten o’clock on Sunday
morning, ‘with the greatest frayor and vehemency that ever I saw a
fire do, notwithstanding that I saw London burn.’[265] ‘The flames
were so terrible, that none durst come near to quench it. It was a very
great wind, which blew to such a degree, that, with the sparks that
came from the fire, there was nothing to be seen through the whole
city, but as it had been showers of sparks, like showers of snow, they
were so thick.’[266]
‘There are burnt, by the easiest computation, between three and
four hundred families; the pride of Edinburgh is sunk; from the
Cowgate to the High Street, all is burnt, and hardly one stone left
upon another. The Commissioner, the President of Parliament, the
President of the Court of Session [Sir Hugh Dalrymple], the Bank [of
Scotland], most of the lords, lawyers, and clerks were burnt, besides
many poor families. The Parliament House very nearly [narrowly]
escaped; all registers confounded [the public registers being kept
there]; clerks’ chambers and processes in such a confusion, that the
lords and officers of state are just now met in Ross’s tavern, in order
to adjourn the session by reason of the 1700.
disorder. Few people are lost, if any at all;
but there was neither heart nor hand left among them for saving
from the fire, nor a drop of water in the cisterns. Twenty thousand
hands flitting [removing] their trash, they knew not where, and
hardly twenty at work. Many rueful spectacles, &c.’[267]
The Town Council recorded their sense of this calamity as a ‘fearful
rebuke of God,’ and the Rev. Mr Willison of Dundee did not omit to
improve the occasion. ‘In Edinburgh,’ says he, ‘where Sabbath-
breaking very much abounded, the fairest and stateliest of its
buildings, in the Parliament Close and about it (to which scarce any
in Britain were comparable), were on the fourth of February (being
the Lord’s Day), burnt down and laid in ashes and ruins in the space
of a few hours, to the astonishment and terror of the sorrowful
inhabitants, whereof I myself was an eye-witness. So great was the
terror and confusion of that Lord’s Day, that the people of the city
were in no case to attend any sermon or public worship upon it,
though there was a great number of worthy ministers convened in
the place (beside the reverend ministers of the city) ready to have
prayed with or preached to the people on that sad occasion, for the
General Assembly was sitting there at the time. However, the Lord
himself, by that silent Sabbath, did loudly preach to all the
inhabitants of the city,’ &c.[268]
Some of the houses burnt on this occasion, forming part of the
Parliament Square, were of the extraordinary altitude of fourteen
stories, six or seven of which, however, were below the level of the
ground on the north side. These had been built about twenty years
before by Thomas Robertson, brewer, a thriving citizen, who is
described in his epitaph in the Greyfriars’ churchyard as ‘remarkable
for piety towards God, loyalty towards his prince, love to his country,
and civility towards all persons;’ while he was also, by these
structures, ‘urbis exornator, si non conditor.’[269] But Robertson, as
youngest bailie, had given the Covenant out of his hand to be burnt
at the Cross in 1661; and ‘now God in his providence hath sent a
burning among his lands, so that that which was eleven years a-
building, was not six hours of burning. Notwithstanding this, he was
a good man, and lamented to his death the burning of the Covenant;
he was also very helpful to the Lord’s prisoners during the late
persecution.’[270]
There being no insurance against fire in 1700.
those days, the heirs of Robertson were
reduced from comparative affluence to poverty, and the head of the
family was glad to accept the situation of a captain in the city guard,
and at last was made a pensioner upon the city’s charge.[271]
Amongst the burnt out has been mentioned the Bank of Scotland.
‘The directors and others concerned did with great care and diligence
carry off all the cash, bank-notes, books, and papers in the office;
being assisted by a party of soldiers brought from the Castle by the
Earl of Leven, then governor thereof, and governor of the bank, who,
with the Lord Ruthven, then a director, stood all the night directing
and supporting the soldiers, in keeping the stair and passage from
being overcrowded. But the Company lost their lodging and whole
furniture in it.’[272]
Lord Crossrig, who suffered so much by this fire, tells us in his
Diary, that in the late evil times—that is, before the Revolution—he
had been a member of a society that met every Monday afternoon
‘for prayer and conference.’ Since their deliverance, such societies
had gone out of fashion, and profanity went on increasing till it came
to a great height. Hearing that there were societies setting up in
England ‘for reformation of manners,’ and falling in with a book that
gave an account of them, he bethought him how desirable it was that
something of the sort should be attempted in Edinburgh, and spoke
to several friends on the subject. There was, consequently, a meeting
at his house in November 1699, at which were present Mr Francis
Grant (subsequently Lord Cullen); Mr Matthew Sinclair; Mr William
Brodie, advocate; Mr Alexander Dundas, physician, and some other
persons, who then determined to form themselves into such a
society, under sanction of some of the clergy. The schedule of rules
for this fraternity was signed on the night when the fire happened.
‘This,’ says Crossrig, ‘is a thing I remark as notable, which
presently was a rebuke to some of us for some fault in our solemn
engagement there, and probably Satan blew that coal to witness his
indignation at a society designedly entered into in opposition to the
Kingdom of Darkness, and in hopes that such an occurrence should
dash our society in its infancy, and discourage us to proceed therein.
However, blessed be our God, all who then met have continued
steadfast ever since ... and we have had many meetings since that
time, even during the three months that I 1700.
lived at the Earl of Winton’s lodging in the
Canongate.... Likeas, there are several other societies of the same
nature set up in this city.’[273]

The burning out of the Bank of Scotland Feb.

was not more than twenty days past, when a
trouble of a different kind fell upon it. ‘One Thomas M‘Gie, who was
bred a scholar, but poor, of a good genius and ready wit, of an
aspiring temper, and desirous to make an appearance in the world,
but wanting a fund convenient for his purpose, was tempted to try
his hand upon bank-notes. At this time all the five kinds of notes—
namely, £100, £50, £20, £10, and £5—were engraven in one and the
same character. He, by artful razing, altered the word five in the five-
pound note, and made it fifty. But good providence discovered the
villainy before he had done any great damage, by means of the check-
book and a record kept in the office; and the rogue was forced to fly
abroad. The check-book and record are so excellently adapted to one
another, and well contrived; and the keeping them right, and
applying thereof, is so easy, that no forgery or falsehood of notes can
be imposed upon the bank for any sum of moment, before it is
discovered. After discovering this cheat of M‘Gie, the company
caused engrave new copper-plates for all their notes, each of a
different character, adding several other checks; so that it is not in
the power of man to renew M‘Gie’s villainy.’[274]

The glass-work at Leith made a great Feb.

complaint regarding the ruinous practice
pursued by the work at Newcastle, of sending great quantities of
their goods into Scotland. The English makers had lately landed at
Montrose no less than two thousand six hundred dozen of bottles,
‘which will overstock the whole country with the commodity.’ On
their petition, the Lords of the Privy Council empowered the Leith
Glass Company to send out officers to seize any such English bottles
and bring them in for his majesty’s use.[275]

The ill-reputed governments of the last Mar. 14.

two reigns put down unlicensed worship
among the Presbyterians, on the ground that the conventicles were
schools of disaffection. The present government acted upon precisely
the same principle, in crushing attempts at the establishment of
Episcopal meeting-houses. The commission 1700.
of the General Assembly at this time
represented to the Privy Council that the parishes of Eyemouth,
Ayton, and Coldingham[276] were ‘very much disturbed by the setting
up of Episcopal meeting-houses, whereby the people are withdrawn
from their duty to his majesty, and all good order of the church
violat.’ On the petition of the presbytery of Chirnside, backed by the
Assembly Commission, the Privy Council ordained that the sheriff
shut up all these meeting-houses, and recommended the Lord
Advocate to ‘prosecute the pretended ministers preaching at the said
meeting-houses, not qualified according to law, and thereby not
having the protection of the government.’[277]
This policy seems to have been effectual for its object, for in the
statistical account of Coldingham, drawn up near the close of the
eighteenth century, the minister reports that there were no
Episcopalians in his parish. It is but one of many facts which might
be adduced in opposition to the popular doctrine, that persecution is
powerless against religious conviction.

Notwithstanding the many serious and the many calamitous things

affecting Scotland, there was an under-current of pleasantries and
jocularities, of which we are here and there fortunate enough to get a
glimpse. For example—in Aberdeen, near the gate of the mansion of
the Earl of Errol, there looms out upon our view a little cozy tavern,
kept by one Peter Butter, much frequented of students in Marischal
College and the dependents of the magnate here named. The former
called it the Collegium Butterense, as affecting to consider it a sort of
university supplementary to, and necessary for the completion of, the
daylight one which their friends understood them to be attending.
Here drinking was study, and proficiency therein gave the title to
degrees. Even for admission, there was a theme required, which
consisted in drinking a particular glass to every friend and
acquaintance one had in the world, with one more. Without these
possibly thirty-nine or more articles being duly and unreservedly
swallowed, the candidate was relentlessly excluded. On being
accepted, a wreath was conferred, and Master James Hay, by virtue
of the authority resting in him under the 1700.
rules of the foundation, addressed the
neophyte:
Potestatem do tibique
Compotandi bibendique,
Ac summa pocula implendi,
Et haustus exhauriendi,
Cujusve sint capacitatis,
E rotundis aut quadratis.
In signum ut manumittaris,
 Adornet caput hic galerus,
Quod tibi felix sit faustumque,
Obnixe comprecor multumque.

There were theses, too, on suitably convivial ideas—as, for example:

’Gainst any man of sense,
Asserimus ex pacto,
Upon his own expense,
Quod vere datur ens
Potabile de facto....

If you expect degrees,

Drink off your cup and fill,
We’re not for what you please:
Our absolute decrees
Admit of no free-will....

The longer we do sit,

The more we hate all quarrels,
(Let none his quarters flit),
The more we do admit
Of vacuum in barrels. &c.

Or else:
For to find out a parallaxis
We’ll not our minds apply,
Save what a toast in Corbreed[278] makes us;
Whether the moon moves on her axis,
Ask Black and Gregory.[279]

That bodies are à parte rei,

To hold we think it meetest;
Some cold, some hot, some moist, some dry,
Though all of them ye taste and try,
The fluid is the sweetest.

Post sextam semi hora

At night, no friend refuses
To come lavare ora;
Est melior quam Aurorâ,
And fitter for the Muses, &c.

1700.
 A diploma conferred upon George Durward, doubtless not without
very grave consideration of his pretensions to the honour, is couched
in much the same strain as the theses:
To all and sundry who shall see this,
Whate’er his station or degree is,
We, Masters of the Buttery College,
Send greeting, and to give them knowledge,
That George Durward, præsentium lator,
Did study at our Alma Mater
Some years, and hated foolish projects,
But stiffly studied liquid logics;
And now he’s as well skilled in liquor
As any one that blaws a bicker;
For he can make our college theme
A syllogism or enthymeme....
Since now we have him manumitted,
In arts and sciences well fitted,
To recommend him we incline
To all besouth and north the line,
To black and white, though they live as far
As Cape Good-Hope and Madagascar,
Him to advance, because he is
Juvenis bonæ indolis, &c.

We have, however, no specimen of the wit of this fluid university

that strikes us as equal to a Catalogus Librorum in Bibliothecâ
Butterensi; to all external appearance, a dry list of learned books,
while in reality comprehending the whole paraphernalia of a tavern.
It is formally divided into ‘Books in large folio,’ ‘Books in lesser folio,’
‘Books in quarto,’ ‘Books in octavo,’ and ‘Lesser Volumes,’ just as we
might suppose the university catalogue to have been. Amongst the
works included are: ‘Maximilian Malt-kist de principiis liquidorum—
Kircherus Kettles de eodem themate—Bucket’s Hydrostaticks—
Opera Bibuli Barrelli, ubi de conservatione liquoris, et de vacuo,
problematice disputatur—Constantinus Chopinus de philosophicis
bibendi legibus, in usum Principalis, curâ Georgii Leith [described in
a note as a particularly assiduous pupil of the college] 12 tom.—
Compendium ejus, for weaker capacities—Barnabius Beer-glass, de
lavando gutture—Manuale Gideonis Gill, de Syllogismis
concludentibus—Findlay Fireside, de 1700.
circulari poculorum motu,’ &c. One may
faintly imagine how all this light-headed nonsense would please Dr
Pitcairn, as he sat regaling himself in the Greping Office, and how the
serious people would shake their heads at it when they perused it at
full length, a few years afterwards, in Watson’s Collection of Scots
Poems.

The commissioners of the General July 31.

Assembly, considering the impending
danger of a late harvest and consequent scarcity, and the other
distresses of the country, called for the 29th day of August being
solemnised by a fast. In the reasons for it, they mention the
unworthy repining at the late providences, and ‘that, under our great
penury and dearth, whilst some provoked God by their profuse
prodigality, the poorest of the people, who suffered most, and who
ought thereby to have been amended, have rather grown worse and
worse.’

Duncan Robertson, a younger son of the deceased Laird of Struan,

had fallen out of all good terms with his mother, apparently in
consequence of some disputes about their respective rights.
Gathering an armed band of idle ruffians, he went with them to his
mother’s jointure-lands, and laid them waste; he went to a ‘room’ or
piece of land occupied by his sister Margaret, and carried off all that
was upon it; he also ‘laid waste any possession his other sister Mrs
Janet had.’ When a military party, posted at Carie, came to protect
the ladies, he fired on it, and afterwards plainly avowed to the
commander that his object was to dispossess his mother and her
tenants. By this cruel act, Lady Struan and her other children had
been ‘reduced to these straits and difficulties, that they had not
whereupon to live.’
The Privy Council gave orders for the Aug. 2.
capture of Duncan Robertson, and his being
put in the Tolbooth of Edinburgh, and kept there till further orders.
[280]

Nov. 16.
 A band of persons, usually called Egyptians or gipsies, used to go
about the province of Moray in armed fashion, helping themselves
freely to the property of the settled population, and ordinarily
sleeping in kilns near the farmhouses. There seems to have been
thirty of them in all, men and women; but it was seldom that more
than eight or ten made their appearance in 1700.
any one place. It was quite a familiar sight,
at a fair or market in Banff, Elgin, Forres, or any other town of the
district, to see nearly a dozen sturdy Egyptians march in with a piper
playing at their head, their matchlocks slung behind them, and their
broadswords or dirks by their sides, to mingle in the crowd, inspect
the cattle shewn for sale, and watch for bargains passing among
individuals, in order to learn who was in the way of receiving money.
They would be viewed with no small suspicion and dislike by the
assembled rustics and farmers; but the law was unable to put them
entirely down.
James Macpherson, who was understood to be the natural son of a
gentleman of the district by a gipsy mother, was a conspicuous or
leading man in the band; he was a person of goodly figure and great
strength and daring, always carrying about with him—how acquired
we cannot tell—an example of the two-handed swords of a former
age, besides other weapons. He had a talent for music, and was a
good player on the violin. It has been stated that some traits of a
generous nature occasionally shone out in him; but, on the whole, he
was merely a Highland cateran, breaking houses and henroosts,
stealing horses and cattle, and living recklessly on the proceeds, like
the tribe with which he associated.
Duff, Laird of Braco, founder of the honours and wealth of the
Earls of Fife, took a lead at this time in the public affairs of his
district. He formed the resolution of trying to give a check to the
lawless proceedings of the Egyptians, by bringing their leaders to
justice. It required some courage to face such determined ruffians
with arms in their hands, and he had a further difficulty in the
territorial prejudices of the Laird of Grant, who regarded some of the
robbers as his tenants, and felt bound, accordingly, to protect them
from any jurisdiction besides his own.[281] This remark bears
particularly upon two named Peter and Donald Brown, who had
lived for half a year at a place closely adjacent to Castle-Grant, and
 the former of whom 1700.
was regarded as
captain of the band.
Finding Macpherson, the Browns, and
others at the ‘Summer’s Eve Fair in Keith, the
stout-hearted Braco made up his mind to
attack them. To pursue a narrative which
appears to be authentic: ‘As soon as he
observed them in the fair, he desired his
brother-in-law, Lesmurdie, to bring him a
dozen stout men, which he did. They attacked
the villains, who, as they had several of their
accomplices with them, made a desperate
resistance. One of them made a pass at Braco
with his hanger, intending to run him through
the heart; but it slanted along the outside of
the ribs, and one of his men immediately
stabbed the fellow dead. They then carried
Macpherson and [Peter] Brown to a house in
Keith, and set three or four stout men to
guard them, not expecting any more
opposition, as all the rest of the gang were
fled. Braco and Lesmurdie were sitting in an
upper room, concerting the commitment of
their prisoners, when the Laird of Grant and
thirty men came calling for them, swearing no
Duff in Scotland should keep them from him.
Braco, hearing the noise of the Grants, came
down stairs, and said, with seeming
unconcern and humour: “That he designed to
have sent them to prison; but he saw they
were too strong a party for him to contend
Macpherson’s with, and so he must leave them;” but,
Sword. without losing a moment, he took a turn
through the market, found other two justices
of peace, kept a court, and assembled sixty
stout fellows, with whom he retook the two criminals, and sent them
to prison.’[282]
 James Macpherson, the two Browns, and 1700.
James Gordon, were brought before the
sheriff of Banffshire at Banff, on the 7th of November 1700, charged
with ‘being habit and repute Egyptians and vagabonds, and keeping
the markets in their ordinary manner of thieving and purse-
cutting’ ... being guilty also of ‘masterful bangstrie and oppression.’ A
procurator appeared on the part of the young Laird of Grant,
demanding surrender of the two Browns, to be tried in the court of
his regality, within whose bounds they had lived, and offering a
culreach or pledge for them;[283] but the demand was overruled, on
the ground that the Browns had never been truly domiciliated there.
Witnesses were adduced, who detailed many felonies of the
prisoners. They had stolen sheep, oxen, and horses; they had broken
into houses, and taken away goods; they had robbed men of their
purses, and tyrannously oppressed many poor people. It was shewn
that the band was in the habit of speaking a peculiar language. They
often spent whole nights in dancing and debauchery, Peter Brown or
Macpherson giving animation to the scene by the strains of the
violin. An inhabitant of Keith related how Macpherson came to his
house one day, seeking for him, when, not finding him, he stabbed
the bed, to make sure he was not there, and, on going away, set the
ale-barrel aflowing. The jury gave a verdict against all the four
prisoners; but sentence was for the meantime passed upon only
Macpherson and Gordon, adjudging them to be hanged next market-
day.[284]
Macpherson spent the last hours of his life in composing a tune
expressive of the reckless courage with which he regarded his fate.
He marched to the place of execution, a mile from the town, playing
this air on his violin. He even danced to it under the fatal tree. Then
he asked if any one in the crowd would accept his fiddle, and keep it
as a memorial of Macpherson; and finding no one disposed to do so,
he broke the instrument over his knee, and threw himself
indignantly from the ladder. Such was the life and death of a man of
whom one is tempted to think that, with such qualities as he
possessed, he might, in a happier age, have 1700.
risen to some better distinction than that
which unfortunately he has attained.[285]
 At this date one of the most remarkable of 1701. Jan. 25.
the precursors of Watt in the construction
of the steam-engine, comes in an interesting manner into connection
with Scotland. Captain Thomas Savery, an Englishman, ‘treasurer to
the commissioners of sick and wounded,’ had, in 1696, described an
engine framed by himself, and which is believed to have been
original and unsuggested, ‘in which water is raised not only by the
expansive force of steam, but also by its condensation, the water
being raised by the pressure of the atmosphere into receivers, from
which it is forced to a greater height by the expansive force of the
steam.’[286] He had obtained a patent for this engine in 1698, to last
for thirty-five years.
We have seen that there were busy-brained men in Scotland,
constantly trying to devise new things; and even now, Mr James
Gregory, Professor of Mathematics in the Edinburgh University—a
member of a family in which talent has been inherent for two
centuries—was endeavouring to bring into use ‘a machine invented
by him for raising of water in a continued pipe merely by lifting,
without any suction or forcing, which are the only ways formerly
practised, and liable to a great many inconveniences.’ By this new
machine, according to the inventor, ‘water might be raised to any
height, in a greater quantity, and in less space of time,’ than by any
other means employing the same force. It was useful for ‘coal-pits or
mines under ground.’ On his petition, Mr 1701.
Gregory obtained an exclusive right to make
and use this machine for thirty-one years.
Another such inventive genius was Mr James Smith of Whitehill,
who for several years made himself notable by his plans for
introducing supplies of water into burghs. Smith had caught at
Savery’s idea, and made a paction with him for the use of his engine
in Scotland, and now he applied to the Estates for ‘encouragement.’
He says that, since his bargain with Captain Savery, he ‘has made
additions to the engine to considerable advantage, so that, in the
short space of an hour, there may be raised thereby no less than the
quantity of twenty tuns of water to the height of fourteen fathoms.’
Any member of the honourable house was welcome to see it at work,
and satisfy himself of its efficiency; whence we may infer that an
example of it had come down to Edinburgh. In compliance with his
petition, Smith was invested with the exclusive power of making the
engine and dealing with parties for its use during the remainder of
the English patent.[287]
Savery’s steam-engine, however, was a seed sown upon an infertile
soil, and after this date, we in Scotland at least hear of it no more.

It pleased the wisdom of the Scottish July 10.

legislature (as it did that of the English
parliament likewise) to forbid the export of wool and of woolly skins,
an encouragement to woollen manufacturers at home, at the
expense, as usual, of three or four times the amount in loss to the
rest of the community. At this date, Michael Allan, Dean of Guild in
Edinburgh, came before the Privy Council to shew that, in
consequence of the extreme coldness and backwardness of the late
spring, producing a mortality of lambs, there were many thousands
of lambs’ skins, or morts, which could not be manufactured in the
kingdom, and would consequently be lost, but which would be of
value at Dantzig and other eastern ports, where they could be
manufactured into clothing. He thought that property to the value of
about seven thousand pounds sterling might thus be utilised for
Scotland, which otherwise ‘must of a necessity perish at home, and
will be good for nothing;’ and the movement was the more desirable,
as the return for the goods would be in ‘lint, hemp, iron, steel, pot-
ashes, and knaple, very useful for our 1701.
manufactures, and without which the
nation cannot possibly be served.’
The Council called in skinners, furriers, and others to give them
the best advice, and the result was a refusal to allow the skins to be
exported.
Rather more than a twelvemonth before (June 4, 1700), it was
intimated to the Privy Council by ‘the manufactory of Glasgow,’ that
one Fitzgerard, an Irish papist, ‘has had a constant trade these three
years past of exporting wool and woollen yarn to France, and that he
has at this present time combed wool and woollen yarn to the value
of three thousand pounds sterling ready to be exported, to the great
ruin of the nation, and of manufactories of that kind.’ The Council
immediately sent orders to the magistrates of Glasgow to take all