Metamorphic Rock

LITHICS | Manufacture
Harry J. Shafer, in Encyclopedia of Archaeology, 2008
Types of Rocks
The rock family tree begins with volcanic activity and the formation of ‘igneous’ rocks.
These chemically rich rocks break down from weathering, producing gravels, sands, silts, and
clays. As the finer sediments of clays, silts, and sands are deposited on the shallow ocean
floor, they compact and become solidified into ‘sedimentary’ rocks. As sedimentary rocks are
forced deeper into the Earth's crust, pressure and heat alter their structure through
metamorphosis. ‘Metamorphic’ rocks melt through volcanic activity and the cycle begins
again. Finer divisions are made within these three rock categories. For example, there are two
basic types of igneous rocks, intrusive (such as diorite, granite) and extrusive (such
as basalt, andesite, dacite, rhyolite, obsidian). Intrusive rocks are forced upward from molten
rock beneath the surface and cool within the crust; some are later exposed through erosion.
The cooling is slow, allowing crystals to form. These igneous rocks are coarse. Extrusive
igneous rocks are ejected by volcanic activity and cool more rapidly, leading to smaller
crystals and finer structures. All of the extrusive igneous rocks can be shaped by chipping.
Silica content, however, increases from basalt, andesite and rhyolite to obsidian. Obsidian, a
natural glass, has the highest silica content and is rapidly cooled magma, which cools so
quickly that crystalline structure does not have time to form.
Sedimentary rocks are grouped into three classes: clastic, chemical, and biological. Clastic
rocks include sandstone, shale, mudstone, siltstone, and conglomerate. Chemical rocks
include limestone, dolostone (dolomite), and evaporates such as gypsum and salt. Biologic
rocks include coal and chert. Chert and chalcedony are formed by the same process, but
chalcedony has a more fibrous structure and is characteristically semi-translucent. A common
term for chalcedony is agate. Both chert and chalcedony are replacement materials
within fossil casts in sedimentary deposits. An example of replacement is silicified wood
where chalcedony has replaced the cellular structure of the decayed wood.
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Rapid 3D geophysical imaging of aquifers in diverse hydrogeological settings

Subash Chandra, V.M. Tiwari, in Water Security, 2022
3.1 Precambrian crystalline hard rock
The Precambrian crystalline hard rock (i.e., plutonic and metamorphic rocks) that forms
continental basement covers roughly 20% of the Earth’s surface [51] almost 30% of India’s
terrain. The examined case is an over-exploited aquifer in Archaean crystalline hard rock
consists of granite, gneiss and schists (Fig. 2a). The area mainly consists of rock types
belonging to the Peninsular Gneissic Complex, Schistose rocks of Sargur group, Dharwar
super group and Younger intrusive (basic dykes). The gneiss that covers the major portion of
the study area, is divided by the ridge formed by the schistose rocks into two equal halves.
Granite with almost negligible thickness of soil and saprolite covers a small portion of the
study area. The weathered layer of the hard rocks that use to be the principal aquifer is mostly
remains dry and underlying fissures and bedrock fractures controls the groundwater dynamics
in the region. Mapping of the aquifer controlled by the network of the fractures and
associated weathering was the main hydrogeological challenge.
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Fig. 2. (a) Geology adjacent to the profile line AA′; corresponding plot of: (b) HTEM

processed average data- Low moment (LM) and high moment (HM) and altitude of

transmitter; (c) Laterally constrained inversion (LCI) resistivity section; and (d)

transformed lithological model. Gns , Sch and Gns are point locations where id
1 1 2

sounding is extracted.
The HTEM data was acquired at ∼ 145 m flight line spacing. The data was processing on
Aarhus workbench. Fig. 2(b) shows HTEM averaged raw dB/dt data of 22 min’ length, where
the data coupled with noise caused by electric power lines, metallic installations, road, etc.,
are removed. Trapezoidal filter is used to average the data with optimally minimum lateral
averaging i.e. 5 s at 10 micro second (μs) i.e. early usable gate. Thereafter, averaging time
width increases to 8 and 24 s respectively at 100 μs and 1 milli second late gates. The altitude
data of transmitter above the ground records high undulation due to presence of tall trees,
power line, hills, radio towers, etc. The noise coupled data due to power lines, metallic roads
and other installations, fences are removed and marks as data gap. Even the places of exposed
hard and compact sheet rock with negligible soil and weathering cover also become
insensitive to HTEM measurement due to high resistivity and hence dB/dt response falls
below the noise and gets removed after average filter.
An exercise has been performed to create a resistivity section corresponding to the 22 min’
time length HTEM data record and translation into lithological models. Fig. 2c shows
resistivity section where the gridded and interpolated SCI mean resistivity with depth are
imported to the profile. The depth, to which it attains 90% of cumulative sensitivity of total
sensitivity, is taken as depth of investigation (DOI). The resistivity model is taken only above
the line of DOI. The profile shows thin (∼15 m) layer of low resistivity i.e.10–100 Ωm
running all along the profile. Except few small patches, resistivity is dominantly found within
50 Ωm with adequate lateral connectivity, and hence, is inferred as weathered or laminated
layer. The underlying resistivity increases significantly from 100 to 3000 Ωm, which
coincides with the fissured layer of around 10–30 m thickness. Besides this, there are number
of sharp and deep DOI peaks. These deep DOI anomalies or peaks indicate the presence of
deep-seated conductive features. In case of granite and gneiss, there is no other possibility of
deep conductive body than the presence of water saturated bedrock fracture and associated
weathering. Though the fracture thickness compared to host rock remains quite small, but the
presence of cluster of fractures and associated weathering increases the effective thickness of
the conductive structure, and hence become sensitive to the HTEM measurement. In contrary,
the deep DOI peaks in schist belt indicates mineralization. The Fig. 2(d) is the resistivity
transformed lithological section pertaining to the 22 min HTEM data along the profile
running across the gneiss and schist belt.
Fig. 3 shows three typical 1D HTEM resistivity sounding data picked up along resistivity
profile, as shown in Fig. 2, where one sounding (Sch1) is taken from schist zone and two
soundings (Gns1 & Gns2) are picked up from granite gneiss located on either sides the schist
belt. The data is presented in three forms i.e. dB/dt raw data, normalized dB/dt data with their
magnetic moment and the smooth layered inverted model. As explained in eq.2, the dB/dt 1D
data decay with t−5/2 and the noise with t−1/2. The dB/dt response over Sch1 is the strongest and
Gns2 is the weakest one. The normalized dB/dt response is obtained after stacking and
normalization of the LM and HM response by their magnetic moment, where noisy data are
removed. There are significant overlapping gates between low and high moment data. These
two data sets are jointly inverted that provide seamless resistivity models with depth. The
Gns1 and Sch1 data are taken over the DOI peaks, where relatively low resistivity < 1000 Ωm
can be seen extending till around 105 and 130 m depths. In contrary, data and model over
Gns2 is weak and more resistive and hence low DOI i.e. 30 m.
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Fig. 3. (a) HTEM sounding (low and high moment) dB/dt raw data along with the

background noise located in granite gneisses (Gns &amp; Gns ) and schist belt (Sch ).
1 2 1

(b) normalized dB/dt data, and (c) inverted resistivity model marked with depth of

investigation (DOI).
The distribution of such deep DOI patches were systematically analyzed. Spatial distribution
of DOI combined with knowledge of geology, hydrogeology, borehole data, etc., helped in
constructing network of water saturated bedrock fracture at around 100 m depth, which is
termed as Hydrolin in granite gneiss [45]. These results were supported with not only with
the drilling litholog but also validated by the age of the water measured at certain time
interval while pumping as well as the nitrate contents. The deep bedrock fracture horizon
corroborates with associated deep HTEM DOI, higher the well yield and low the age of
water [45]. To further cross check the validity of Hydrolin map, couple of bore wells were
drilled down to 200 m depth in May 2019.
The post drillings also found very well corresponding with the HTEM results, electrical
resistivity tomography and drilling time log (Fig. 4). The ERT data was limited hardly down
to 100 m deep information, but found in corroboration. The drill time log is plotted in terms
of drill time (in minutes) for unit length of rod with depth. The low and high drill time for
unit length rod indicate presence of weak and strong strata respectively. The weakening in the
strata is primarily caused by alteration i.e. weathering and fracturing. Such alteration reduces
the formation resistivity. Thus, there is strong analogy between resistivity and drilling time
log. As expected, the drill time start from 1 min at surface, slowly increasing with depth
except few intermediate abrupt drops and touches to 7 min/m at 60 m depth. However, there
is relative drop in drill time to 5 min/m at 120 m depth, followed by number of drops between
120 m and 160 m depths and thereafter sharp increase indicating touching the bedrock.
HTEM resistivity is found corroborating with drill time log, except marginal shift of low
resistivity peak reflected at 120 m depth compared to the clusters of drill time drops between
130 and 160 m depth. Such marginal difference is an obvious occurrence in highly
heterogeneous terrain. The HTEM derived depth-resistivity distribution is average response
over relatively larger scale than the borehole.

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 Fig. 4. Post heliborne drilling of well over hydrolin and comparison of drill time

profile with 1D resistivity- depth profile of HTEM and ERT. The blue coloured arrow

show water encountered horizon. (For interpretation of the references to colour in this

figure legend, the reader is referred to the web version of this article.)
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Equine petroglyphs in Europe

Robert G. Bednarik, in Journal of Archaeological Science: Reports, 2017
1 Introduction
A review in of the petroglyphs of Siega Verde near Ciudad Rodrigo, far western Spain,
showed that the site's corpus of rock art is mostly less than two centuries old, much of it
dating from the early to the mid-20th century (Bednarik, 2009a). Previously, the equid and
bovid images of the low-grade metamorphics site had been widely attributed to the Upper
Palaeolithic. The report also mentioned, very briefly, that similar circumstances apply to
thousands of other Iberian petroglyphs at open-air sites. There is in fact a large body of
zoomorphic petroglyphs across the Peninsula, consisting almost entirely of horse-like and
bull-like petroglyphs on sites of schist, phyllite or slate that have been ascribed to the
final Pleistocene. Most recently the first such site has been reported from Germany and
assigned to the Aurignacian (Welker, 2015).
What these sites all have in common is their lithology, which excludes the possibility of their
rock art being Palaeolithic because, if exposed to precipitation, these metamorphic
rocks retreat at a rate of 1–10 mm per millennium (Schwegler, 1995; Bednarik, 2007: 61).
Therefore after several thousand years any petroglyphs on such supports tend to become
erased as the schist hydrates and reverts to mud. This is amply demonstrated by rock
inscriptions and dates often found engraved among the rock art, which after a few centuries
become practically unreadable. In addition, at some of the sites, such as Siega Verde and
many of the nearby Côa sites in northern Portugal, petroglyphs are subjected to bombardment
by suspended loads of coarse angular quartz sand during frequent inundations, which
accelerates their erasure.
Zoomorphic petroglyphs, especially of apparently equine figures, occur frequently across
Europe, and not only on schist. Granite, like any rock, also retreats with time, but the rate
varies widely, from 0.05 mm to 2 mm per millennium, depending on the lithology and
environmental conditions. On average it weathers considerably slower than the low-grade
metamorphics. To better understand the effects of weathering on petroglyphs, it is
particularly helpful to calibrate weathering rates from features of known ages. For
instance Bednarik (2009a) utilised engraved dates for this purpose. An alternative approach is
to assess petroglyphs on surfaces of known, or at least approximately known, antiquities. The
methodology of the present review is to begin with such a study of petroglyphs of known age
on granite to provide a context for subsequently considering the generic issue of horse-like
and other petroglyphs at open schist sites in Europe that have so often been assigned to the
Upper Palaeolithic. The corresponding issues in Asia will also be reviewed, albeit very
briefly.
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A Review of Electrical Resistivity Tomography Applications in Underground

Imaging and Object Detection
Jullian Dominic Ducut, ... Elmer Dadios, in Displays, 2022
6.4 Old and ancient structures
In determining the location of the buried ancient structures, misplacement of electrodes and
the topographical profile for inversion must always be observed to avoid incorrect data
analysis [4]. While the presence of metamorphic rocks such as iron-rich minerals and clay
formations in the subsoil exhibits strong attenuation of EM waves from GPRs and KS-700
apparatus, which results in a limit in the depth range and verification of underground
objects [29].
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Petrographic characterization of quartzite tools from the Palaeolithic site of San

Teodoro cave (Sicily): Study on the provenance of lithic raw materials
Gerlando Vita, ... Luca Sineo, in Journal of Archaeological Science: Reports, 2022
1 Introduction
The identification of the raw material used for the production of the prehistoric stone industry
has relevant archaeological and anthropological implications. Studies of raw materials can
shed light on human movements, exchange activities between populations, and the human
spatial organization in prehistory (e.g., Gamble, 1993; Seong, 2004; Andrefsky, 1994; Beck
and Jones, 2011; Crandell et al., 2013; Brooks et al. 2018; Coni, 2019). Also, the
petrographic characterization of the raw material and the definition of its mechanic and
functional features can help in understanding why the prehistoric populations chose a
particular lithotype, and which technics they used for the production of stone tools
(Domanski et al., 1994; Webb and Domanski, 2008). Since the workability of the raw
material depends on the uniformity of the structure (homogeneous) and the physical
properties equal in all directions (isotropic materials), the normally preferred lithic materials
were the most homogeneous and isotropic varieties of siliceous stone such as natural glass.
These, with their sharpness and cleavage, are also scarcer lithic materials (Cotterell and
Kamminga, 1987). Flint and obsidian are the most isotropic and homogeneous lithic groups,
while other lithic materials commonly used for the manufacture of tools during the
Palaeolithic are quartz-arenite and quartzite. One of the most used natural glass in prehistoric
Sicily is obsidian, produced by volcanoes on small islands (Lipari and Pantelleria) at least
since the Early Neolithic (Tykot, 2017). During the early phases of peopling of the island, in
the Upper Palaeolithic, the two main lithic raw materials used by the Epigravettian
communities were chert and quartzite (Tusa, 1999). According to Lo Vetro et al. (2007), the
presence of flint outcrops is known in areas where human presence in prehistoric times is
attested and makes the idea of easy availability of lithic raw materials by groups of
Epigravettian hunter-gatherers plausible. At some stations, alongside the use of flint, the use
of quartzite is recorded; except in rare cases (for example in northeastern Sicily, at the San
Teodoro Cave), the use of this raw material is limited and mainly intended for the production
of generic tools. Exception for Vigliardi (1968), Biddittu and Piperno (1972) and Baldini et
al. (1976), who provided macroscopic information on the lithology of a few stone
assemblages from some Sicilian sites, in-depth, analytical studies of prehistoric lithics from
Sicily and of the origin of raw material and its provenance are lacking. This paper aims to
provide a petrographic characterization of the quartzite lithics that are very abundant in the
late Palaeolithic deposits of the San Teodoro Cave (Vigliardi, 1968). This Palaeolithic site is
one of the most important in Sicily and represents one of the first human settlements on the
largest island in the Mediterranean (D’Amore et al., 2010). The lithic raw material of
quartzite in the European Paleolithic did not receive the same geoarchaeological interest as
flint or obsidian (Prieto et al., 2020), except for some authors (e.g. Straus et al., 1986;
Ebright, 1987). In recent years, numerous studies have been conducted on the
characterization of quartzite in archaeological deposits (Andrefsky, 1994; Pitblado et al.
2008; Blomme et al. 2012; Veldeman et al. 2012; Cnudde et al. 2013; Prieto et al., 2019a,
2021a). There was and remains a certain inhomogeneity between the geological and
archaeological terms, this creates some problems, especially, in the search for the lithotype on
the geological maps. The quartzite in geological literature is a metamorphic rock while in the
archaeological one it is a quartz arenite or quartz-rich sandstone. Howard
(2005) differentiates quartzite into orthoquartzite (sedimentary) and metaquartzite
(metamorphic) respectively due to the presence of clastic and metamorphic micro-textures.
However, the quartzite problem remains as it is not decided to use a univocal terminology
among all archaeologists and geologists. This work characterizes, through petrographic
studies, the lithic industry in orthoquartzite, found very abundantly in the Upper Paleolithic
deposits of the San Teodoro cave (Vigliardi, 1968). This Palaeolithic site is one of the oldest
in Sicily and represents one of the first human settlements on the largest island in the
Mediterranean (D’Amore et al., 2010). We compare the petrographic characterization of the
Palaeolithic tools studied with the geological deposits found in the area of the Nebrodi
Mountains to determine the lithological origin of the raw material and hypothesize its
provenance. We excluded flint artefacts and other materials from our study both because they
are part of an in-depth study of Sicilian flints.
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Laboratory Analyses
Patrick Degryse, in Encyclopedia of Archaeology (Second Edition), 2024
Glossary
Absolute age

The actual number of years that have elapsed from an event until now.
Analytical procedure

Full procedure of analysis, from obtaining the material for analysis and choice of
analytical technique to the full preparation procedure and quality check of the data
obtained.
Atom

Smallest unit of an element in the periodic table of elements that retains the element's
physical and chemical properties.
Atomic mass

The sum of an element's protons and neutrons.

Atomic number

The number of protons in the nucleus of an atom, defining the place and name of the
element in the periodic table of elements.
Bronze
 Metal alloy of copper and tin.
Contamination

Presence of an impurity or undesirable element that may spoil the evaluation of an

object or sample.
Electron

A negatively charged particle, with a charge −1, that moves around the nucleus of an
atom.
Geochronology

Discipline within the geosciences, devoted to the dating of rocks and geological
processes.
Half-life

The time statistically needed to decay half of the parent isotope to the daughter
isotope
Isotope (of an element)

Species of atoms with the same atomic number but with different atomic masses.
Isotopic analysis

Measurement of the ratio of abundance of two isotopes.

Lithification

The process that converts loose sediment to solid rock by compaction and
cementation by chemical processes.
Magma

Molten rock, when above ground called lava.

Magmatic rock

Rock type formed from the cooling and solidification of magma.

Mass spectrometry

Analytical technique separating, measuring and quantifying species (isotopes, atoms

or molecules) of different mass.
Metamorphic rock

Rock type formed from the transformation of pre-existing rocks under the influence of
high (geological) pressure and/or temperature.
Mineral

A naturally occurring, solid, crystalline substance with a specific chemical

composition between certain boundaries.
Neutron

An electrically neutral elementary particle in the nucleus of an atom, having an atomic

mass of 1.
Nucleus
 The center of an atom, comprising protons and neutrons, containing virtually all the
mass of the atom.
Proton

Elementary particle in the nucleus of an atom, having an atomic mass of 1 and a

positive electrical charge of +1.
Provenance

Documentation tracing an object back to its source and owners, or the origin of the
raw materials used to make an object.
Radioactive decay

The process by which an unstable isotope loses energy by radiation, evolving into a
more stable isotope.
Rock

An aggregate of one or more types of minerals.

Sample

Limited amount of a substance or object, fit for analysis and meant to represent the
whole.
Sedimentary rock

Rock type formed from the deposition and possibly lithification of layers of sediment
(such as sand, other rock fragments, fossils).
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Equine petroglyphs in Europe

Robert G. Bednarik, in Journal of Archaeological Science: Reports, 2017
3 Petroglyphs on low-grade metamorphics
The presumed horse images on a schistose outcrop near Gondershausen, Germany (Welker,
2015), are the most recent addition to a long list of percussion petroglyphs at European open
schist and slate exposures that have been attributed to the Upper Palaeolithic (Fig. 2). In this
case, an Aurignacian antiquity (i.e. > 30 ka) has been suggested, based on perceived style.
Although several Palaeolithic art specialists endorsed this assignment, the six zoomorphs
were made < 1000 years ago by a right-handed person with a fairly blunt steel chisel
possessing a 8–9 mm long edge (Bednarik, 2016). The degree of weathering of the
petroglyphs is identical to that of two inscribed characters among them; there are several
metal points lodged in the rock outcrop; and the site is surrounded by extensive evidence of
quarrying for roof tiles in recent centuries. Even the only argument in favour of Aurignacian
age is flawed: equine motifs of similar stylistic parameters, such as those at Castro, are more
common from historical periods across Eurasia than from authentic Pleistocene corpora, nor
were the latter usually produced by percussion. Since there is not a single confirmed open-air
motif of the Pleistocene anywhere in Europe, it is not warranted to conjure up a Palaeolithic
age purely on stylistic basis, when the stylistic parameters of ‘Palaeolithic’ rock art are far
from established (see below).
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Fig. 2. Zoomorphic petroglyphs on schist at Gondershausen, Germany, a few centuries

old.

The Gondershausen claims were preceded by many others to have found ‘Palaeolithic’ rock
art in central Europe, all of which have been refuted. One of the earliest German propositions
of Pleistocene antiquity concerned a ‘stag’ image (with runic inscription) in the Kleines
Schulerloch, Bavaria (Birkner, 1938: Pl. 13; Maringer and Bandi, 1953: 23; refuted
in Bosinski, 1982: 6) and the engraving of an ‘undetermined’ animal figure in the
Kastlhänghöhle (Bohmers, 1939: 40; refuted in Freund, 1957: 55). A black-brown
‘pigmented’ limestone fragment from the Aurignacian of Geißenklösterle was defined as part
of an exfoliated, black-painted rock art motif (Hahn, 1988a, 1988b, 1988c, 1991; Richter et
al., 2000). It is a fire-spalled rock fragment bearing an accretion of partly combusted plant
resin (Bednarik, 2002). A ‘black, yellow and red coloured’ piece from the same site (Hahn,
1986; Müller-Beck and Albrecht, 1987) consists of a rock fragment stained by goethite,
partly converted to haematite by the reducing flame of a hearth; and a more recent carbonate
precipitate containing tiny charcoal flakes. A limestone fragment from Hohle Fels,
interpreted by Conard and Uerpmann (2000) as Germany's only evidence of ‘Palaeolithic art’
was in fact painted after it had fallen from the wall (Bednarik, 2002). Another such assertion
concerns dozens of exfoliated wall fragments of Bärenschliffe (cave bear polishes) bearing
linear incised grooves, which were interpreted as aniconic engravings (Hahn, 1991, 1994;
Scheer, 1994; Conard and Uerpmann, 2000; Holdermann et al., 2001). These markings were
caused by quartz grains embedded in the fur of the cave bears, rubbing their bodies against
the cave walls as they accessed their hibernation lairs (Bednarik, 1994, 2002). A series of
grooves in the Mäanderhöhle at Veilbronn, northern Bavaria, thought to be anthropogenic
and ‘Palaeolithic’, are in fact ‘stretch marks’ formed as the bulging moonmilk ceiling features
expanded (Blumenröther et al., 2015). The supposed engravings in another Bavarian cave, the
Schönsteinhöhle, are clearly animal claw marks, probably of chiroptera (op. cit.), while a
bovid image at Reinhausen near Göttingen is regarded as a recent feature. Thus there is
currently no Pleistocene rock art known in Germany.
Further afield in central Europe, there are several other claims of ‘Palaeolithic art’ that
yielded to refutation. They include those from the Czech Republic, concerning a series of red
markings in Mladeč Cave (Oliva, 1989; refuted in Bednarik, 2006) and black pictograms in
Bycí Skála (refuted in Svoboda et al., 2005). The black rock paintings and torch smears found
in Domica Cave, Slovakia, probably date from the Neolithic Bükk culture, the claimed
presence of Palaeolithic occupation evidence notwithstanding. The Neolithic, Bronze
Age and Iron Age occupation remains in Ardovska Cave provide no support for the
radiocarbon date of about 42,800 years bp from charcoal marks on the cave's wall (as noted
by Sefcakova and Svoboda, 2015). Petroglyphs at two Austrian sites, Kienbachklamm near
Bad Ischl and Stubwieswipfel in the Warschenegg mountains, have been proposed to be of
the Pleistocene (Kohl and Burgstaller, 1992), but some of them were shown to be natural
rock markings, others are part of the extensive corpus of historical rock art in the northern
limestone belt of the Alps (Bednarik, 2009b). Further east, the cave art sites Cuciulat, Kapova
and Ignatiev Caves have been ascribed to Upper Palaeolithic traditions, without evidence.
Three charcoal motifs in the last-mentioned site have yielded radiocarbon results ranging
from 6000 to 8000 years (Steelman et al., 2002). Several claims of Pleistocene rock art have
also been made in England and Wales, beginning with the earliest, by H. Breuil and W. J.
Sollas, that they had found red ochre stripes of the Palaeolithic in Bacon's Hole, Wales. The
markings had been made by a workman only eighteen years previously. Rogers
(1981) reported Palaeolithic cave art in the Wye valley, of petroglyphs with ‘malachite inlay’.
This was found to be natural rock markings covered by green algae (de Sieveking, 1982). The
next claim, from Church Hole in the Creswell Crags refers to three probably recent
engravings (Bahn et al., 2003) from a cave that was soon purported to contain ‘the most
richly carved and engraved ceiling in the whole of cave art’ (Ripoll et al., 2005), with well
over one hundred petroglyphs. However, these were generally natural ceiling features, the
reports lacked scientific detail and presented contradictory interpretations, and a
uranium/thorium date provided was irrelevant to the age of any rock art (Bednarik, 2005).
Most of these assertions were eventually abandoned by the presenters (Bahn and Pettitt,
2007; cf. Montelle, 2008). They were followed by two other postulated Pleistocene rock
markings from British caves, first from Gough's Cave (Mullan et al., 2006), then from
Cathole Cave near Swansea (Nash, 2012, 2015). The first seems to refer to a natural marking;
the second is highly schematised.
There is thus no shortage of claims of Palaeolithic rock art from several parts of Europe,
among which those concerning open schist and slate sites are particularly prominent. Siega
Verde in western Spain is only c. 32 km from the described Castro de Yecla la
Vieja fortifications and is also dominated by equine petroglyphs. The petroglyph site is
divided by a large masonry bridge over the Agueda river, and most of the rock art was
created during its construction period, ending 1924, while other petroglyphs seem related to
the use of a large mill just upstream of the bridge. Both the petroglyphs and hundreds of
inscriptions occurring with them are restricted to the river's flood zone, extending about 6 m
above the thalweg. During these frequent floods, vast quantities of quartz clasts and tons of
coarse angular quartz sand are rafted past the site, heavily impacting on the schist bedrock
and on both the inscriptions and the petroglyphs (Fig. 3). The abrasion coefficient of schist is
40 times higher than that of granite (Attal and Lavé, 2006: 156, 159), and the erasure rate
determined from inscribed dates has been applied to the petroglyphs, showing that almost all
date from the last few centuries (Bednarik, 2009a). The only exception are some higher-lying,
fully patinated filiform engravings that could be of the Iron Age. This is confirmed by the
absence at the site of any Palaeolithic occupation evidence and of any sediments other than
very late Holocene; as well as by the lack of any extinct faunal specimens among the
petroglyph inventory. Another factor confirming the recent age of the rock art is the former
presence of a final Holocene terrace, now almost entirely eroded.
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Fig. 3. Impact of fluvial wear by the suspended load of coarse angular quartz sand on

the schist of Siega Verde, western Spain.

The many petroglyph sites on the lower Côa river, the next southern tributary of the Douro to
the west of the Agueda, have been subjected to the same geomorphological regime. The hard
rocks from upriver have cut a 300 m deep ravine into the schist, and the only river
terraces found near the thalweg are of the late Holocene. An extensive search for Pleistocene
sediments has remained fruitless, and the only petroglyphs found under sediment, virtually
unpatinated, were covered by colluvium and alluvium. Where occupation evidence was
excavated above the river's flood zone it always featured ceramics and microliths down to
bedrock (Zilhão et al., 1997; Aubry et al., 2002). This stands in stark contrast to the Sabor
valley, north of the Douro, where in one excavation 125,000 Upper Palaeolithic stone
artefacts and over 1400 fragments of engraved plaquettes were recovered, but where not a
single petroglyph occurs (Figueiredo et al., 2014). There are no depictions of extinct animals
among the hundreds of zoomorphs on the Côa, most of which feature equine (including
specimens wearing a bridle) and bovid characteristics. The sub-naturalistic animal images
thought to be stylistically Palaeolithic are significantly less weathered and patinated than the
inscriptions of the 18th century next to them, and other zoomorphs, highly schematised, are
much older than the equine and bovine images. Those that occur in the valley's flood zone
show almost no fluvial wear, and numerous petroglyph grooves dissect pre-existing lichen
thalli, while no thalli exceeding 2–3 cm diameter have formed on any grooves. The water
mills found near the petroglyphs of both Gondershausen and Siega Verde are also repeated in
the Côa valley. All petroglyph concentrations are found near the dozens of such ruins or
traces of other economic activities of recent centuries, such as rock quarrying. Moreover, the
four scientific attempts to estimate the ages of the Côa rock art resulted in the unanimous
finding that most of it is of recent centuries (Bednarik, 1995a; Watchman, 1995, 1996).
Gondershausen, Siega Verde and the Côa series of over fifteen sites are only some of the
examples of open schist localities that have been attributed to the Pleistocene on purely
stylistic assumptions, by ignoring that most equine petroglyphs of Europe are of very recent
times. The first of these many sites were Domingo García in central Spain (Martín
Santamaría and Moure Romanillo, 1981) and Mazouco in the Portuguese Douro valley (Jorge
et al., 1981). The first locality features many ‘horse’ images while there is only one equine
zoomorph at the second. However, the Palaeolithicity of the Mazouco petroglyph was soon
refuted (Baptista, 1983). Then, a small series of semi-naturalistic animal heads were reported
from another schist site, Fornols-Haut in the French Pyrenees, and pronounced as Palaeolithic
on the basis of their ‘naturalism’ (Bahn, 1985; Sacchi et al., 1987). The next ‘Palaeolithic
horse’ petroglyph was reported from a schist outcrop at Piedras Blancas near Escullar,
Almería (Martínez, 1986/87). It was followed by the ‘discovery’ of the Siega Verde
petroglyphs (de Balbín Behrmann et al., 1991; de Balbín Behrmann and Alcolea Gonzalez,
1994), which had been known to the local villagers ever since they had been made (Hansen,
1997). By that time, the idea of discovering open-air Pleistocene petroglyphs in schist sites
had become popular, and Ripóll Lopez and Muncio González (1994) offered a series of such
sites near Domingo García, including Carbonero Mayor, Bernardos and Ortigosa. The Côa
reports from 1995 onwards were the first to be responded to by scientific analyses that
refuted a Pleistocene antiquity. In the late 1990s, a headless solitary zoomorph lacking any
diagnostic features at Ocreza, Portugal, was declared to depict a horse, and for that reason
alone was attributed to the Palaeolithic. It was not until 2015 that the next purported
Palaeolithic equine petroglyphs on low-grade metamorphics were reported, from the small
Gondershausen site in western Germany.
The susceptibility of any metamorphic rock substrate to re-equilibration reaction (e.g.
reversal of component minerals to hydrous state) when exposed to precipitation was ignored
in all of these pronouncements. The retreat rates measured on building masonry of natural
stone of known construction dates render the survival of Pleistocene petroglyphs at open sites
highly unlikely, except on the most weathering-resistant rock types, notably quartzite. This
applies especially to deeply pounded petroglyphs on quartzite susceptible to kinetic
energy metamorphosis (Bednarik, 2015a), a conversion process inducing greatly enhanced
survival of petroglyph surfaces. Its products have never been observed on the Iberian schist
petroglyphs, none of which can be assumed to pre-date mid-Holocene times, and most of
which are of the final Holocene.
The tendency of European commentators to place any semi-naturalistic imagery in the
Pleistocene has also influenced pronouncements in Asia, although here the number of such
assertions is considerably smaller than in Europe. Examples are the horse and bull pictograms
at the open site Shishkino in central Siberia (Okladnikov, 1959; refuted in Bednarik and
Devlet, 1993). There is no more a woolly rhinoceros image at nearby Tal'ma as there is one at
Siega Verde or Minateda in Spain. A series of rock art sites on the Kalguty river in Siberian
Altai (Molodin and Cheremisin, 1993, 1994) and others at Delger-Muren and Tes
(Novgorodova, 1983) are not of the ‘Stone Ages’; they are of the Bronze Age or younger
(Kubarev 1997). The pictograms of the Zaraut-Kamar Rockshelter in southern Uzbekistan are
not the ‘earliest known rock art of central Asia’; they are of the late 19th century (Jasiewicz
and Rozwadowski, 2001). Mongolian petroglyphs attributed to the Pleistocene are
superimposed over striae of the final glacial incursion, and the horse and bull images of
Dunde Bulake Site 1 in the Altai of Xinjiang Uygur Autonomous Region, China (Fig. 4), are
not of the Pleistocene, but of the late Holocene (Bednarik, 2015b; Taçon et al., 2016). The
line of anthropomorphs at the same locality are not the ‘earliest known skiers’; nor is the
bone object from Lohanda Nala in India a ‘mother goddess’ (Misra, 1977), being a well-made
but damaged bone harpoon (Bednarik, 1992). And no evidence has been provided for the
putative Pleistocene age of the ‘dynamic’ green anthropomorphs (Wakankar, 1975); they
appear to be preceded by Mesolithic ‘intricate geometric patterns’ (Tyagi, 1988).
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Fig. 4. Semi-naturalistic equines and bovines at Dunde Bulake Site 1, Chinese Altai

region, are not of the Pleistocene, but of the late Holocene.

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Chromium
Julie K. Sueker, in Environmental Forensics, 1964
5.2 PRINCIPAL OCCURRENCE OF CHROMIUM
High amounts of chromium are found naturally in two minerals: chromite (FeCr2O4)
and crocoite (PbCrO4), also known as lead chromate or “red lead.” Crocoite is a brilliant
reddish-orange colored, four-sided crystal mineral that was discovered in 1765 at the Beresof
mine near Ekaterinburg in the Ural Mountains of Siberia. Crocoite is too rare to be useful
commercially, but is prized by mineral collectors for its brilliant color. Notable occurrences
of crocoite are located in the Dundas District of Tasmania, Australia; the Ural Mountains,
Russia; and Inyo and Riverside Counties in California, USA. In 1797, the French chemist
Louis Nicholas Vauquelin produced chromium oxide (CrO3) by mixing crocoite
with hydrochloric acid. In 1978, Vequelin isolated elemental chromium by heating chromium
oxide in a charcoal oven. Vauquelin discovered that chromium compounds can form reds,
brilliant yellows, and deep greens, and that traces of chromium were responsible for the green
color of a Peruvian emerald and the red of rubies.
Chromite is a dark dull mineral that forms in igneous environments and is the primary
commercial chromium ore. In 1798, Lowitz and Klaproth independently discovered
chromium in samples of heavy black rock that is now called chromite, found in a deposit
north of the Beresof Mines. In 1798 a German chemist named Tassaert discovered chromium
in chromite ore in a small deposit in the Var region of South-Eastern France. Chromite forms
in deep ultra-mafic magmas and is one of the first minerals to crystallize from cooling
magma. Because of their density, chromite crystals fall to the bottom of the magma body and
concentrate there. Chromite is also found in metamorphic rocks such as serpentites. As is
indicated by its early crystallization, chromite is resistant to the altering affects of high
temperatures and pressures, thus it is generally unaffected by the metamorphic processes.
This characteristic explains the use of chromites as a refractory component in the bricks and
linings of blast furnaces.
The discovery of chromite ore deposits in the Ural Mountains greatly increased the supplies
of chromium to the growing paint industry and resulted in a chromium chemicals factory
being set up in Manchester, England around 1808. In 1827, Isaac Tyson identified deposits of
chromite ore on the Maryland–Pennsylvania border and the USA became the monopoly
supplier of chromium for a number of years. High-grade chromite deposits were found near
Bursa in Turkey in 1848 and with the exhaustion of the Maryland deposits around 1860, it
was Turkey that then became the main source of supply. The mining of chromium ore started
in India and Southern Africa around 1906. Today, roughly one third to one half of the
chromite ore in the world is produced from South Africa; Kazakhstan, India, and Turkey are
also substantial producers (ATSDR, 2002). Approximately 15 million tons of marketable
chromite ore were produced in 2003 (ICDA, 2005). Untapped chromite deposits are plentiful,
but are geographically concentrated in Kazakhstan and southern Africa. Chromite mining in
the United States ceased in 1961 (ATSDR, 2000).
Native chromium deposits are rare; however, some native chromium metal has been
discovered. The Udachnaya Mine in Russia is a kimberlite pipe rich in diamonds and
produces samples of the native metal. The reducing environment within the kimberlite pipe
helped produce both elemental chromium and diamond.
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LITHICS | Manufacture
Harry J. Shafer, in Encyclopedia of Archaeology, 2008
Glossary
attribute

Any visible characteristic of an artifact.

bending fracture

Fracture caused by bending that exceeds the elastic limits of the material. The flake
characteristically has the remnants of the biface edge at the striking platform and a lip
on the ventral side formed by the bending fracture. It is a common fracture for stone
tools used in cutting, chopping, and piercing. Controlling bending fractures using soft-
hammer and punch techniques was a common method of thinning bifaces.
biface

Artifact chipped or flaked on both faces.

billet

A tubular-shaped implement associated with soft-hammer flaking, usually of antler or

bone, used to create bending fractures to thin bifaces.
bipolar technology
 Applying a force to a stone set on a hard anvil. The stone is subjected to forces from
the initial blow and a rebound force created by the anvil.
blade

Flakes removed from a specially prepared core that are over twice as long as they are
wide, generally have parallel edges, and one or more longitudinal ridges.
blade core

Core especially prepared for the removal of blades.

blank

Term used to describe the beginning or early stage core in stone tool manufacture. A
flake blank may be reduced into a uniface or biface tool, depending on the objectives
of the flintknapper.
bulb of percussion

Pronounced bulb formed on the interior of a flake immediately beneath a direct

impact usually associated with hard-hammer flaking. The bulb is an extension of the
Hertzian cone.
burin-like removal

The removal of a flake from the longitudinal or transverse axis of a flake, uniface, or
biface. The resulting angle created by the platform and flake facet was once regarded
as a burin-like tool for woodworking. This interpretation no longer holds favor since
the spall may have been the objective and used as drill bits. A burin-like facet can also
be produced by direct impact blows on projectile points.
Cryptocrystalline rock (sedimentary rock) formed in limestone.
Cryptocrystalline rock similar to chert but differs by having a fibrous structure.
Chalcedony, also includes agate, is formed under similar conditions as chert and may
be found in the same matrix.
conchoidal

Shell-like characteristics of Hertzian cone fracture. Diagnostic features include cone

initiation, bulb of percussion, and wave characteristics created by fracture
propagation.
cone fracture

See Hertzian cone.

core

The mass from which flakes are removed.

cortex

The outer rind of a pebble or cobble.

A class of rocks that have microscopic crystals not visible to the eye; including chert,
flint, chalcedony, Novaculite, jasper, among others.
debitage

The term used to describe wastage from chipped stone manufacture (flakes, shatter).
Debitage may also include discarded cores and items broken in manufacture.
dorsal
 The exterior side of a flake that may have flake scars or cortex.
edge abrader

Stone, usually quartzite, used to abrade the edges of a blank or preform to facilitate
soft-hammer or punch flaking.
end shock

Snap fracture that occurs near the middle of a biface caused by a blow struck near one
end.
eralliure

Tiny flake scar on the bulb of force created by the force waves of impact.
feather termination

A fracture that terminates at the surface of the core creating a very acute and sharp
angle.
flake

Sliver removed from a mass or core.

flint

Common name for chert. Some argue that the only true flint is that at Dover, England,
used extensively to make gunflints for the British Colonial Empire. Dover flint is a
dark gray to black chert.
flintknapper

An individual who shapes flint or other stone through the process of knapping or lithic
reduction, to manufacture stone tools.
flute

Flake removed from the base to create a longitudinal groove on one or both sides of a
biface, characteristic of Clovis and Folsom projectile point technologies.
formal tool

Tools made to conform to a specific form or design. Example: grooved axes, biface
projectile points.
Hertzian cone

The fracture cone created by a hard hammer striking the surface of cryptocrystalline
stone such as chert, obsidian, or Novaculite.
hard-hammer

Using a stone or other similarly hard material to flake cryptocrystalline rocks.

hinge fracture or termination

A fracture that loses its energy and terminates at the surface of a core by reversing its
fracture path.
igneous

Rocks formed by volcanic activity. Examples are obsidian, basalt, andesite, dacite,
and rhyolite.
lipped flake
 See bending fracture.
mano

(Spanish for hand); in archeology the term for hand stone used with a grinding slab or
metate for grinding seeds and other substances.
metamorphic

Rocks that become melted by heat or pressure. Example: quartzite.

metate

Grinding slab used in conjunction with a hand stone or mano.

novaculite

Cryptocrystalliine rock found in the Ouachita Mountains of Arkansas and in the

Caballos Formation in the Marathon Uplift in the Big Bend region of Texas. These
are the same geological formation and material.
obsidian

Glassy igneous rock that cools so rapidly that a crystalline structure cannot form.
Usually occurs in black or gray, but green, burnt sienna, and speckled deposits also
occur.
overshot or outrepassé

A flake that carries across the core and terminates on the opposite side removing part
of the core edge or end.
preform

A late stage in the manufacturing trajectory of a formal stone tool.

pressure flaking

Applying pressure at the edge of a core by using an antler, bone, or some other
suitable material to create a bending fracture.
quartzite

A metamorphic rock formed under heat or pressure that fuses quartz sand particles
together to form a homogenous mass.
Locality where toolstones outcropped and were procured by prehistoric people.
sedimentary rocks

Sediments such as silts, clays, and sands become compacted in the ocean floor and
become solidified into sedimentary rocks. Example: limestone, siltstone, sandstone.
soft hammer

A percussion tool that is softer than the material being flaked. causing a bending
fracture rather than a cone-initiation fracture characteristics on flakes.
step fracture or termination

Results when a flake detached from the core is pulled away too rapidly; the flake will
bend beyond its elastic limit and snap before it terminates.
striking platform
 The surface from which the blow to remove a flake is struck. Striking platforms on
flakes are described by the nature of this surface, cortex, single faceted, multiple
faceted.
terminations

How the fracture path of a flake ends, includes feature, hinge, step, and overshot.
uniface

Artifact flaked or chipped on only one face.

ventral

The bulbar or interior side of a flake.

wedge fracture (see bipolar)

Created by bi-polar impact where force is generated from two directions, from the
hammer and from the anvil. Fracture may propagate around the cone splitting the core
into multiple pieces.
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Prospects and issues of integration of co-combustion of solid fuels (coal and

biomass) in chemical looping technology
Barnali Bhui, Prabu Vairakannu, in Journal of Environmental Management, 2019
3.2 Iron-based metal oxides
Iron-based oxygen carriers exist in the form of hematite (Fe2O3), magnetite (Fe3O4) and
wustite (FeO). These metal oxides are inexpensive, non-toxic and possess non-agglomeration
characteristics at higher operating temperatures (Cormos, 2010). The reaction between
Fe2O3 and syngas is as follows. Hematite form of iron oxides is reduced to magnetite form.
(26)3Fe2O3+CO→2Fe3O4+CO2

(27)3Fe2O3+H2→2Fe3O4+H2O

Sewage sludge ash was proposed as the oxygen carriers as it mainly contains SiO2, P2O5,
Fe2O3, and Al2O3 (Ksepko, 2014). Iron oxides in sewage sludge can act as metal oxides, and
SiO2, Al2O3 particles present in the ash content could eliminate the agglomeration issues. Xiao
et al. (2010) confirmed that iron-based oxygen carrier is highly suitable for high pressure and
high-temperature operations due to the non-agglomeration property.
3.2.1 Pyrite cinder
Pyrite cinder is a mixture of iron oxides containing calcium and magnesium-based oxides. It
is a waste product of sulfuric acid manufacturing plants. The disposal of this waste to the
environment causes a health hazard to living beings. Hence, the usage of this waste in

composition of pyrite cinder indicates a higher proportion of Fe2O3 of ∼87% by weight (Alp
the CLC process can solve the issues related to the environmental hazard. The chemical

et al., 2009). Zhang et al. (2015) used pyrite cinder as the metal oxides for the CLC process
of coal under an inert and reactive atmosphere. Their results showed that there were no
sintering and agglomeration problems even at higher operating temperatures (950 °C). Thus,
pyrite cinder can be effectively used for the metal oxy-combustion of solid fuel.
3.2.2 Ilmenite
Ilmenite (FeO.TiO2) is one of the cheaper metal oxides, which exhibit the nature of
metamorphic and igneous rocks. Ilmenite does not require any inert support as it inherently
contains unreactive rutile (TiO2). During the oxidation process, ilmenite is converted into
hematite and rutile (Pröll et al., 2009). It was reported that Fe2TiO5 (pseudobrookite) is the
highest oxidation state of the ilmenite (Eq. (26) and (27)). Furthermore, ilmenite exhibits
higher reactivity towards coal than methane (Berguerand and Lyngfelt, 2008). Low
agglomeration tendency, high CO2 capture efficiency, high melting point (1367 °C) and high
mechanical strength are the several advantages of ilmenite that are listed in the literature.
However, ilmenite has low oxygen transfer capacity, which could affect the rate of fuel
conversion (Mendiara et al., 2013a; Linderholm et al., 2011). Furthermore, ilmenite showed
low reactivity at the initial stages of CLC (Cuadrat et al., 2011); however, the reactivity
increased after several cycles of oxidation and reduction process. This could be due to the
production of hematite (Eq. (26)). Ilmenite achieved a solid conversion efficiency of 40%,
89% and 93% using hard coal, bituminous coal, and lignite, respectively (Ströhle et al., 2015;
Abad et al., 2015). This shows that the presence of the higher proportion of volatile matter in
low-rank coal causes higher reactivity of solid fuels in the CLC process.
(28)2FeTiO3+0.5O2→Fe2O3+2TiO2

(29)4FeTiO3+O2→2Fe2TiO5+2TiO

3.2.3 Natural hematite

Natural hematite can be obtained as a waste from steel manufacturing industries. It mainly
contains Fe2O3 as the active phase along with inert metals such as Al2O3 and SiO2. As
discussed earlier, inert components in metal oxides are beneficial for the prevention of
sintering problem that enables long-term usage (Song et al., 2012). This metal oxide
accelerates the rate of char conversion and furthermore, the heat transfer capacity between the
CLC reactors can be enhanced (Ge et al., 2016). Song et al. (2013) reported a higher carbon
capture efficiency using hematite as the oxygen carriers for bituminous coal, compared
to anthracite coal. This might be due to the presence of the higher percentage of volatile
matter in low-rank coals that would be beneficial to the CLC operation.
3.2.4 Red mud metal oxides
Red mud is a mixture of Fe2O3, TiO2, SiO2, CaCO3, and NaOH. It can be obtained as a side
product of Bayer's process during alumina production. It was reported that 55–70% of red
mud could be generated using bauxite as the feed (Mendiara et al., 2012). The reactivity of
red mud oxides with gaseous fuels showed that it could be completely re-oxidized without
any agglomeration problems even at 950 °C (Chen et al., 2015; Ortiz et al., 2011). Also, it
was found that red mud oxides have better reactivity than ilmenite (Mendiara et al., 2013b).