applied

sciences
Review
The Importance of Multidisciplinary Analytical Strategies to
Solve Identification and Characterization Challenges in
Gemology: The Example of the “Green Stones”
Maya Musa 1,2

1 Department of Physics “Giuseppe Occhialini”, University of Milan Bicocca, 20126 Milan, Italy;
[email protected]
2 Department of Earth and Environmental Sciences (DISAT), University of Milan Bicocca, 20126 Milan, Italy

Featured Application: Based on the data and analytical methodologies reported here, this review
can be used as a reference for Green Stones identification and characterization protocols. More-
over, due to the multidisciplinary approach discussed, it can also be considered as an example
useful for similar applications.

Abstract: The present review aims to discuss the importance of a multidisciplinary approach in
cultural heritage and archaeometry investigations. The analytical methods used to identify and
characterize “Green Stones” are discussed as an example. In the present paper, the term Green
Stones is applied but not limited to jade materials, which have considerable importance in cul-
tural heritage studies. In fact, archaeological samples made in Green Stones have been discovered
worldwide, with many dating back to the Neolithic Age. Moreover, these materials represent an
interesting analytical challenge, starting with their nomenclature and, in most cases, the nature
of their polycrystalline samples and their heterogeneity. Indeed, after a brief introduction about
Citation: Musa, M. The Importance the advantages of the non-destructive analytical techniques commonly used for gemstones and
of Multidisciplinary Analytical cultural heritage samples analyses, the limits of the same have been discussed on the basis of Green
Strategies to Solve Identification and Stones applicability. Finally, a multidisciplinary methodology for Green Stones identification and full
Characterization Challenges in characterization, which considers materials’ heterogeneity and information, has been proposed and
Gemology: The Example of the based on different references.
“Green Stones”. Appl. Sci. 2022, 12,
7168. https://doi.org/10.3390/ Keywords: multidisciplinary approach; identification; characterization; green stones; jade; jadeite;
app12147168
nephrite; Fei Cui; maw-sit-sit
Academic Editor: Yosoon Choi

Received: 28 May 2022

Accepted: 14 July 2022
1. Introduction
Published: 16 July 2022
The “multidisciplinary approach” has become very popular in several scientific fields
Publisher’s Note: MDPI stays neutral
in recent decades [1–5]. However, what do we mean by the term “multidisciplinary”? The
with regard to jurisdictional claims in
definition means “across several fields of study” [6]. For our purposes, it can be applied to
published maps and institutional affil-
at least two different levels: The first one is when experts from various fields of disciplines
iations.
are involved in studying a problem that can only be solved by their combined efforts.
The second one is when an analytical problem can be solved only by applying different
diagnostic techniques and combining the results in a typical, so-called multidisciplinary
Copyright: © 2022 by the author.
protocol. In many cases, those two approaches are strictly correlated.
Licensee MDPI, Basel, Switzerland. More generally, it is possible to assert that a multidisciplinary approach must be
This article is an open access article applied every time the object of study presents cross scientific peculiarities. For this reason,
distributed under the terms and the interaction, crossing, and overlapping of scientific fields, apparently very far from each
conditions of the Creative Commons other, is not a surprise if the focus is on cultural heritage.
Attribution (CC BY) license (https:// An example of this concept is found in Pasquarella [7], where the authors demonstrated
creativecommons.org/licenses/by/ the importance of the multidisciplinary approach, combining biological knowledge and the
4.0/). methodology for aerosol particles characterization in relation to monitoring and conserving

Appl. Sci. 2022, 12, 7168. https://doi.org/10.3390/app12147168 https://www.mdpi.com/journal/applsci

 An example of this concept is found in Pasquarella [7], where the authors
demonstrated the importance of the multidisciplinary approach, combining biological
Appl. Sci. 2022,knowledge
12, 7168 and the methodology for aerosol particles characterization in relation to 2 of 30
monitoring and conserving the Palatina historical library in Parma. On the other hand,
archaeometry shows an intrinsic, strong multidisciplinary characteristic, due to the typical
overlapping of many the Palatina historical
analytical library in
techniques Parma. On
required forthe other
this typehand, archaeometry
of study. shows[8]
In Cardoso an intrinsic,
study of the mortars from the town of Ammaia (Lusitania, Portugal) has been performedanalytical
strong multidisciplinary characteristic, due to the typical overlapping of many
techniques
by crossing information requiredby
acquired for several
this typeanalytical
of study. Intechniques:
Cardoso [8] study of the mortars from
stereomicroscopy, X- the town
of Ammaia (Lusitania, Portugal) has been performed by crossing information acquired
ray diffraction, thermal analysis, and scanning electron microscopy coupled with energy
by several analytical techniques: stereomicroscopy, X-ray diffraction, thermal analysis,
dispersive X-ray and spectroscopy. By these cited experiences plus others [9–18], it is possible
scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. By
to highlight that thesecultural heritage plus
cited experiences conservation
others [9–18], studies require
it is possible multidisciplinary
to highlight that cultural heritage
approaches to answer the interdisciplinary nature of the problems
conservation studies require multidisciplinary approaches to answer that must be the
solved.
interdisciplinary
And what about
naturetheof diagnostic
the problemsissues?
that must be solved.
In this scenario, And
it is what about the
interesting to diagnostic
note that issues?
archaeometry, by Wagner’s (2007) [19]
In this scenario, it is
definition, designates the development and applicationinteresting to noteof that archaeometry,
natural scientificbymethods
Wagner’sin(2007) [19]
definition, designates the development and application of
order to contribute to the solution of cultural–historical questions. By this acceptation, fornatural scientific methods in
order to contribute to the solution of cultural–historical questions. By this acceptation, for
Reindel and Wagner (2009) [20], archaeometry becomes the interface between natural and
Reindel and Wagner (2009) [20], archaeometry becomes the interface between natural and
cultural heritage cultural
sciences. On the basis of these considerations, archaeometry shows an
heritage sciences. On the basis of these considerations, archaeometry shows an
intrinsic and significant
intrinsicmultidisciplinary component. component.
and significant multidisciplinary
In Figure 1, a scheme
In Figure 1, a scheme interdisciplinary
showing the aspects of archaeometry
showing the interdisciplinary for
aspects of archaeometry for
archaeological samples identification
archaeological samplesisidentification
reported. is reported.

Figure 1. ArchaeometryFigure requires a multidisciplinary

1. Archaeometry approach to characterize
requires a multidisciplinary archaeological
approach to characterize and
archaeological and
cultural heritage cultural
samples. Gemstones, artefacts, ornaments, and objets d’art, with several
heritage samples. Gemstones, artefacts, ornaments, and objets d’art, with several exceptions,
exceptions, belongbelongto archaeological andand
to archaeological cultural heritage
cultural heritagesamples.
samples. To identifyand
To identify andcharacterize
characterizethese type of
these type of samples, in an archaeometric context, the contributions of different expertise are including
samples, in an archaeometric context, the contributions of different expertise are required,
required, including geologists, mineralogists, etc. Moreover, many analytical techniques are
geologists, mineralogists, etc. Moreover, many analytical techniques are necessary. The acronyms
necessary. The acronyms correspond to: SEM-EDS: Scanning Electron Microscopy with Energy
correspond to: SEM-EDS: Scanning Electron Microscopy with Energy Dispersive Spectroscopy;
Dispersive Spectroscopy; OM: Optical Microscopy; UV-Vis/NIR: Ultraviolet-Visible/Near-InfraRed
OM: Optical Microscopy; UV-Vis/NIR: Ultraviolet-Visible/Near-InfraRed spectroscopy; µ-Raman:
spectroscopy; µ-Raman: micro-Raman Spectroscopy; µ-ATR/FTIR: micro-Attenuated Total
micro-Raman Spectroscopy; µ-ATR/FTIR: micro-Attenuated Total Reflection/Fourier Transform
Reflection/Fourier Transform InfraRed Spectroscopy; ED-XRF: Energy Dispersive X-ray
InfraRed Spectroscopy; ED-XRF: Energy Dispersive X-ray Fluorescence; LA-ICP-MS: Laser Ablation
Fluorescence; LA-ICP-MS: Laser Ablation Inductively Coupled Plasma Mass Spectrometry.
Inductively Coupled Plasma Mass Spectrometry. Imaging techniques: the term “imaging” is com-
Imaging techniques: the term “imaging” is commonly used for diagnostics-per-image systems,
monly used for diagnostics-per-image systems, which typically include multispectral observation
which typically include multispectral observation (i.e., imaging by fluorescence reaction, Wood
(i.e., imaging by fluorescence reaction, Wood lamp, etc.). It is interesting to note that all techniques
lamp, etc.). It is interesting to note that all techniques reported by the green color in the gray boxes
reported by the green color in the gray boxes are typically applied in scientific gemology.
are typically applied in scientific gemology.
It is interesting to note that both levels of multidisciplinary approaches, namely mul-
It is interesting to note diagnostic
tidisciplinary that both protocols
levels ofand
multidisciplinary
interdisciplinary approaches, namely must be
scientific competences,
multidisciplinarycombined
diagnostic protocols
to solve and interdisciplinary
identification scientific
and characterization competences,
issues must
in archaeometry. Indeed, not
Appl. Sci. 2022, 12, 7168 3 of 30

only experts of different disciplines, including mineralogists and petrographers, historians,

anthropologists, material scientists (etc.), but also the application of many different ana-
lytical techniques, such as spectroscopies, chemical analyses, imaging techniques, etc., are
involved in archaeometric studies [17,18,21,22].

2. Cultural Heritage and Gemstones

The use of gem materials as ornaments, art expression, social state indicators, votive
offerings, religious symbols, etc., is as ancient as humanity is old [23–29]. In fact, the
properties able to fascinate humankind, characteristic of the gemstones, are beauty, rarity,
and durability. These three qualities also correspond to the proprieties a material must
have to be defined as a gemstone, even today. Indeed, the term gemstone includes many
different types of materials: inorganic (i.e., diamond, corundum, jadeite, etc.), organic
(i.e., amber, etc.), biogenic (i.e., pearl, coral, etc.), transparent to opaque, single crystal or
polycrystal gemstones, etc., as long as they show beauty, rarity, and durability character-
istics [30]. Therefore, unique objects have been given to us from ancient times, setting
marvellous stones.
For these reasons, several studies have been conducted in collaboration with the
world’s most well-known-international gemological institutes. Among all of these studies,
we can cite the example of the characterization study of the Talisman of Charlemagne,
for which Panczer and co-authors (2019) [31] identified all the gemstones set (nine lateral
stones, eight pearls, and one central stone for each talisman side, plus nine lateral stones
and eight pearls set on the talisman’s border) and hypothesized a Sri Lankan (Ceylon
historical mines) origin for the huge sapphire set on the backside of the talisman, due to
scientific gemological analyses. Another one is the study of the Iron Crown, kept at the altar
of the Teodolinda Chapel in the Cathedral of Monza (Italy). The crown which has uncertain
dating [32] sets a total of 22 gemstones [33], identified by Riccardi [33] as corundum (7),
garnet (7), quartz (4), and artificial glasses (4). In addition, in this second case, a Sri Lankan
origin has been hypothesized by the authors for the corundum gemstones. Regarding
the multidisciplinary protocols, the characterization study of the Chiaravalle Cross can
be considered as an example. Indeed, this cross is a medieval masterpiece belonging to
the Duomo of Milan Museum collection (Italy), where a total of 985 gemstones are set,
including four Trapiche Sapphires representing the first Trapiches found in history, and has
been studied and used to develop a specific multidisciplinary protocol, involving experts
of many different disciplines [34].
The collaboration with the gemological institutes for cultural heritage studies is fo-
cused on the characterization of sample-setting gemstones, but is not only limited to it. In
fact, although it might seem unusual that a gemological institute can help the world of
archaeology/cultural heritage sciences, for more than one reason, those disciplines can
be successfully combined. Indeed, one of the main tasks performed by a gemological
institute is to identify gem materials. To do that in a more modern acceptation of “scientific
gemology”, advanced analytical techniques (i.e., spectroscopic or chemical analyses) are
required, with a specification of analyzing the sample without any preparation. Similar to
that concerning modern gemstone studies, the artworks, archaeological samples, and objets
d’art show the same analytical problems because they cannot be analyzed by destructive
techniques. Thus, similar problems require similar analytical strategies. This is the reason
why the equipment available at the internationally recognized gemological institutes is also
suitable for archaeometric analyses. In fact, all of the high-tech equipment available in such
institutes are equipped with accessories that allow the analysis of tal-quale samples [35–38].
In addition, several other considerations have to be taken into account: the gemological
institutes are experts in gem materials’ treatments, simulants, and imitation identification
which cover, by definition, a huge class of materials (i.e., inorganic, organic, crystals, amor-
phous, biogenic, etc.). It means that it is possible to profit from this expertise; not only for
gemstone identification and characterization, but also to recognize eventual counterfeit-
ing. Indeed, some authors report several issues correlated with the authenticity of objects
Appl. Sci. 2022, 12, 7168 4 of 30

even within collections of museums [20,21,34,39–42]. Since some samples may have no
documented or incomplete provenance, a gap in information and authenticity doubt is
possible [43–45]. Drayman-Weisser (2007) [46] reported an interesting case of a Renaissance
enameled pendant jewel belonging to the collection of the Walters Art Museum: a deep
archaeometry investigation revealed that the Personification of Fortitude pendant represents
an embellishment of the former Renaissance jewellery because none of its parts are original.
Finally, due to the trade demand, in the past two decades, several gemological insti-
tutes have worked hard to increase the knowledge and analytical protocols for geographic
origin determination, including the creation of huge collections of reference stones [47–50].
For all these reasons, gemological competencies can be included in the multidisci-
plinary approaches to cultural heritage and archaeological studies.

3. Analytical Techniques Available

In this paragraph, a brief overview covering the standard gemological tests to the spec-
troscopic and chemical analyses, useful also for archaeometric studies, has been reported.

3.1. Standard Gemological Tools and Analyses

In a gemological laboratory, a sample is firstly described based on its morphological
characteristics, such as weight, shape and cutting style, dimensions, transparency proper-
ties, luster, optical phenomenon (if present), and color. Particularly for the color description,
standard daylight is required, and the observation must be conducted in neutral conditions.
Following international rules [51–53], the color is expressed by tone, hue, and saturation in
the tridimensional colors system [54].
Regarding the other standard gemological tests, applicable also to the cultural heritage
and archaeological samples, a brief discussion related to the main one is reported below.
The refractometer is probably the most important standard gem-testing instrument.
It is used to establish a gem’s refractive index (RI) and birefringence, determine whether
the gem is singly refractive (SR) or doubly refractive (DR), and establish what its optic
character and optic sign are. Using the refractometer along with the correct technique, the
quick identification of a wide range of polished gem materials is possible. The lowest limit
for an RI reading is about 1.35, while the highest is determined by the RI of the contact
liquid used to perform the analyses (it is usually about 1.80) [55–57].
The polariscope can help to determine if a gem is SR, DR, or an aggregate (AGG), and it
can also test for optic character or even detect pleochroism [58]. A gem must be transparent
(TP) to translucent (TL) for testing with the polariscope; opaque (O) and semi-translucent
(STL) stones could give unreliable information.
The dichroscope is a compact, portable instrument and is equally useful on rough and
fashioned gems. It is designed to detect two of the different colors that pleochroic gems
show in most viewing directions, and thus helps to confirm whether a gemstone is SR or
DR [55,59].
Generally, the gemological handheld spectroscope can provide crucial information to
help detect a treatment or identify a synthetic. Indeed, this useful portable small instrument
can show the absorption in the visible light spectrum (400–700 nm), correlated with the
colors’ causes [60]. In addition, it does not require a polished surface, so it can be applied
on rough or mounted gem material and also loose gems.
By the hydrostatic scale, the specific gravity (SG) of a sample can be calculated. To
do that, the scale requires a particular accessory consisting of a holder for a beaker of
water that sits above, but it does not touch the scale’s weighing platform. A wire stand
sits directly on the weighing platform and allows an object to be suspended in the beaker
for weighing. The SG corresponds to the ratio between the object’s weight in air and the
weight in water minus the weight in air [55,61].
Regarding the stone’s hardness, it is not a classical gemological test, due to its micro
destructive nature, but it can occasionally be applied, for example, in rough characterization.
To perform the Mohs scale test, sets of so-called hardness pencils are commercially available
Appl. Sci. 2022, 12, 7168 5 of 30

and, courtesy of optical microscopy observation support, it is possible to determine the

sample’s hardness value [62].

3.2. Optical Microscopy (OM) and Imaging Systems

Regarding imaging and measurements, optical microscopes can be considered a useful
tool for cultural heritage samples and gemstones, as well. A gemological microscope is
a stereo binocular microscope with a good depth of field, generally with magnification
varying between 10× and 80×. A microscope offers many lighting options. Different
types of lighting work best for observing various gem features. The most used lighting
in gemology is the darkfield, but transmitted, reflected, and diffused light can also be
used [55,63].
Not only visible light can be considered, but also the fluorescence imaging systems
can supply information by applying ultraviolet (UV) sources. Indeed, the Wood lamp test,
by exposing the sample to the UV Short Wave (SW), 254 nm, and UV Long Wave (LW),
365 nm, can help separate certain natural gems from their synthetic counterparts, if a stone
is assembled or several impregnation substances are present [56]. Moreover, in the 90s,
the Diamond Trading Company (DTC) (DeBeers Group) developed the DiamondViewTM
instrument with the aim of separating the natural from the synthetic diamonds, on the
basis of the growth patterns shown by the excitation of a shorter UV source (225 nm).
Courtesy of a digital camera, pictures can be acquired in visible and UV modes and at
different magnifications. The application of this instrument also for colored stones analyses
demonstrated its availability to highlight many diagnostic characteristics of this type of
material [64].

3.3. Spectroscopies
Three lines of spectroscopies can be considered, in a complementary way: micro-
Raman (and Raman) spectroscopy, micro-Attenuated Total Reflection/Fourier Transform
Infrared (micro-ATR/FTIR) or classical ATR and FTIR spectroscopy, and Ultraviolet-Visible-
Near-IfraRed (UV-Vis/NIR) spectroscopy. While the first two lines represent very useful
techniques for material identification, based on their characteristic vibrational modes, the
last one is exceptionally suitable for obtaining detailed information about chromophores
elements/groups and/or transitional metals, even if in traces.
Below is a brief description of those techniques and their applicability.
The “Raman” effect was discovered in 1928 by Indian physicist Sir. C. V. Raman,
who observed a faint wavelength shift between a light source (monochromatic) and light
returned after the interaction with a sample. In a typical Raman experiment, monochromatic
radiation (the laser source) is used to excite the sample. The available laser sources belong
to UV, visible, and Near-InfraRed (NIR) spectral regions. Thus, the Raman scattered light
will also be in the visible region if visible excitation is used. No energy is lost for the
elastically scattered Rayleigh light, while the Raman scattered photons lose some energy
corresponding to the specific vibrational modes of the sample [65]. Among the many
advantages of this technique, the main ones are: it is a non-destructive technique and
does not require any sample preparation; the spectrum is characteristic for every mineral
phase, similar to a “fingerprint” [66]; the technique proves to be very suitable for material
identification, by the comparison with reference spectra [67]; and, finally, the spectroscopes
can be coupled with an optical microscope, in order to perform the analysis in a confocal
way [68,69].
The infrared spectrometer uses IR light as a source. These wavelengths can be ab-
sorbed, transmitted, or reflected by the analyzed sample. This instrument is particularly
suitable for material identification in gemology [70], such as epoxy-resins, oils, plastic,
and other substances used for colored gemstone treatments, especially the impregnations
for clarity enhancements. They have distinct features in their infrared spectra and can be
detected by the spectrometer. For gemstones, cultural heritage, and archaeological samples
analyses, the sample preparation required by classical FTIR systems represents a significant
Appl. Sci. 2022, 12, 7168 6 of 30

limitation. This limit can be overpassed due to the development of several accessories,
such as the integration sphere, beam condenser, and ATR [64,71]. The latest evolution
of this technique is represented by the micro-FTIR/ATR system: an integrated module
equipped with an optical microscope, able to combine the classic FTIR analyses in spatially
performing to the sample’s morphology. The main advantages are the increase of spatial
resolution and the analysis performed without sample preparation, especially in the case
of micro-ATR acquisition mode [71–73].
The UV-Vis/NIR spectrophotometer uses a narrow beam of light in the electromagnetic
spectrum between the UV and the NIR, across the visible wavelengths, as a source. A
system of lengths focuses the light beam on the gemstone/sample. Those light wavelengths
not absorbed by the sample are transmitted to the detector. UV-Vis/NIR spectroscopy aims
to observe and characterize several elements present in the samples (i.e., the chromophore
groups, transitions elements, etc.) on the basis of their characteristic absorption bands.
Researchers typically use this information to determine the material’s cause of color [74].
Although this technique traditionally requires sample preparation, courtesy of the latest
generation of accessories (i.e., integration sphere), the instruments allow the analysis of
transparent as well as opaque samples without preparation [75]. Moreover, by applying an
optical fiber system to the spectroscope, it is possible to obtain an adaptable and portable
instrument [76]. In gemology, this technique is usually associated with the classical manual
spectroscope, which shows the gemstone absorption bands limited to the visible range of
the light spectrum.

3.4. Complementary Chemical Analyses

The chemical information is a fundamental test for gemstones, cultural heritage, and
archaeological sample identification and characterization. In fact, parallel to the main
elements constituting the phases, the particular assemblage of trace elements (i.e., those
present and their concentrations) provides a distinctive chemical signature for many gem
materials [21,77]; therefore, different techniques can be considered. The first is Energy
Dispersive X-ray Fluorescence (ED-XRF, or only XRF), due to its more straightforward
applicability. At the same time, in case the sample characterization requires bypassing
the limits of this technique, the chemistry information can be increased based on the
Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) and/or
Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) application.
ED-XRF is a technique whereby a sample is targeted by a high-energy X-ray beam,
causing its chemical elements to fluoresce with a spectrum of lower-energy X-rays, with
each peak being characteristic of a chemical element. The fluorescent X-ray peak intensities
indicate the relative concentrations of the chemical elements. The range of detectable
elements goes formally from sodium (Na) to uranium (U), with different detection limits,
typically higher for the lighter elements and lower for the heavier ones; nevertheless, the
concentration range goes from ppm levels to 100% [78]. The main advantages of this
technique are that it does not require any sample preparation and the relative speed of
the analysis. Because of all these advantages, ED-XRF has become one of the high-tech
routine analyses for gemstone characterization [55]. More recently, Portable XRF (PXRF)
instruments have been developed, with many successful applications in archaeometric
studies among others. Although the PXRF actually cannot substitute in toto the lab-based
counterpart, the possibility of on-site chemical analysis supplies extremely useful infor-
mation in many archaeological and museum applications [79], even if the detection limits
are lower.
On the other hand, by SEM-EDS, the chemical information can be combined with the
sample morphology at very high magnification; moreover, by EDS, several lighter elements
(nominally from boron) can be detected, but this technique generally requires sample
preparation. The one exception to this is the Variable Pressure (VP-SEM) or Environmental
pressure (E-SEM) application. In fact, by the aqueous vapor-controlled injection in the
camera, the metal coating to increase the conductivity of the sample requested by the classic
Appl. Sci. 2022, 12, 7168 7 of 30

SEM-EDS technique can be bypassed. Nevertheless, quantitative chemical data cannot

be collected in VP or E-SEM conditions, but only semi-quantitative information can be
acquired [80].
LA-ICP-MS is a micro-destructive technique able to detect almost all the chemical
elements with detection limits in the range of parts per million (ppm) to even parts per
billion (ppb) levels [64,81,82]. A typical gemological instrument set-up requires a single
quadrupole ICP-MS. However, several laboratories are equipped with the last generation of
a triple-quadrupole instrument, coupled with a 213 nm or 193 nm laser ablation unit. With
the high-performance level of the techniques, as well as a considerable work of protocols
development performed by the different research teams, the diameter of the ablation holes
on the cut and polished stones have been reduced from about 50 µm to 30 µm. This
fact must be considered a crucial goal for the standard application of the technique on
gemstones because usually at least three to five spots are analyzed for each stone, focusing
the laser ablation on the girdle.
It must be noted that all the chemical techniques previously described require suitable
sets of standard samples, not always available and sometimes to be created ad hoc.
The advantages, limits, and complementarity of those techniques will be discussed in
detail in the present review, on the basis of their application to Green Stones.

4. The Example of the Green Stones

Identifying and characterizing “Green Stones” is a complex work due to their con-
siderable heterogeneity. Indeed, “Green Stones” is an “umbrella term” covering different
types of materials, including but not limited to jade. Due to their characteristic attractive
green colors and high toughness, these materials have been very appreciated by humanity
for ornamental purposes since antiquity to modernity.
Considering cultural heritage samples and modern objects made of Green Stones,
another common characteristic must be underlined: this group of gems are not single
crystals (as per many other gemstone qualities) but are massive varieties, constituting
aggregates of minerals. Moreover, these aggregates are rarely mono-mineral but usually
show mineralogical associations. Thus, from the petrographic point of view, we have to
identify rocks.
Compared to a single crystal gemstone, inevitably, this heterogeneity of the materials
affects the identification procedure, at least from three different points of view: the analytical
techniques useful and applicable; the identification and quantification of the minerals, in
terms of relative phases distribution; and the nomenclature. In addition, the origin question
is another discussion point, extremely useful for archaeological studies, but it represents a
delicate analytical issue due to the limits of the characterization of the sources [83].

4.1. The Nomenclature of the Green Stones

One of the main issues related to Green Stones terminology is that the terms used to
identify the materials belong to different disciplines, mixed together: gemology, cultural
heritage, archaeology, mineralogy, and petrography. A brief discussion about the principal
ones is reported below.
“Jade” is a common trade term, and in the gemology field, it is applicable to identify
objects made by only two gemological species: jadeite and nephrite [30,84,85]. This clari-
fication is significant because, by this acceptation, it is possible to individuate the objects
with the highest quality from several points of view within a huge group of materials.
Particularly, nephrite gemological species identifies a rock originated from a solid solution
of the amphibole group minerals actinolite and tremolite, composed of an interlocking
mass of granular and acicular crystals without a preferred orientation. On the other hand,
jadeite is a pyroxene mineral phase, and in gem-quality jadeite, columnar and/or granular
crystals are aggregated. Moreover, in gem-quality jade, jadeite and nephrite are not the
only minerals present: associations are common. For example, in jadeite, the presence of
augite, diopside, aegirine, omphacite, and kosmochlor are expected, but to be defined as
Appl. Sci. 2022, 12, 7168 8 of 30

jadeite-jade, the dominant phase must remain the jadeite with the other phases in traces.
In fact, only a high grade of purity of mineral aggregation is able to guarantee the hard-
ness, toughness, and durability characteristics for which jade has become famous all over
the world.
The modern term jade reflects in its acceptation the antique etymology of the material.
Indeed, these terms come from the old Spanish etymology: jade derives from “piedra de la
ijada”, a Spanish expression meaning “stone of the loins”, from Latin “ilia” (“hip”) [86,87];
and nephrite has its origin in the Spanish “piedra de los riñones” or “stone of the kid-
neys” [88]. It is interesting to note that the conquerors of the New World indicated by
this second term the jade worn used by the indigenous people who believed in its healing
properties [86]. Traces of the same therapeutical application are reported by Salviati [89]
regarding the Medici family of Florence during the Renaissance. Although there are not
previous etymological clues on the western side of the world, and though the Romans did
not appreciate the jades from what we know because they considered them to be unlucky,
it is a fact that objects man-made in “jade” materials, such as ceremonial insignia and
weapons, objects symbolizing the social status of their owners, and ritual and funerary
artifacts, have been found in a different part of the world since the Neolithic Age [85,90–95],
attesting the high level of consideration for this material in ancient civilizations.
On the other side of the world, in China, where a tradition of Green Stones use
is well-documented since Neolithic times, the term “Yù”—literally “the most beautiful
stone”—was used to describe not only jade but also other Green Stones, such as chalcedony
and marble, that were carved into tools and ceremonial objects [87]. In the Chinese under-
standing, the corresponding term of jade was historically split into other two terms: Ying
Yù (hard jade), also known as “Fei Cui”, and Ruan Yù (soft jade), corresponding to the
pyroxene varieties and other Green Stones, respectively.
While the Laboratory Manual Harmonisation Committee (LMHC) and the World
Jewellery Confederation (CIBJO) are very straight for jade definition [30,84], the same
clarity is not always applied. Thus, when the term jade is used as synonymous with
the Chinese “Fei Cui”, or as a direct translation of it, several misunderstandings in the
material identification can occur. Indeed, different eastern countries use the term Fei Cui to
identify different materials. For example, in Japanese, the term Fei Cui is a synonym for
jadeite-jade. However, in the Chinese market, omphacite and kosmochlor “rich members”
of the pyroxene group are often included in the term Fei Cui or, as per the Hong Kong
trades, even “pure” omphacite and/or kosmochlor phases can be included under the Fei
Cui umbrella term [96,97].
This overlapping of historical terminology with modern acceptation can generate
misunderstandings that must be considered when cultural heritage samples and objets d’art
are identified.
Another term used in the Green Stones panorama is Maw-Sit-Sit; it identifies a gem
species corresponding to a green rock constituted by a variable mineralogical association
and described for the first time by E. Gubelin in 1965 [98]. In fact, Maw-Sit-Sit is the name of
the Himalayan village close to Tawmaw (Myanmar), where this gem material is usually ex-
tracted. It must be noted that different authors reported different mineralogical associations
characterizing the Maw-Sit-Sit. Gubelin [99] described the Maw-Sit-Sit as a rock mainly
composed of albite and Cr-jadeite; Manson [100] identified natrolite and kosmochlor as the
main constituents; Hanni and Meyer [101] found chromite, kosmochlor, and Cr-amphibole
as the main minerals, and finally, Colombo [102] demonstrated a composition of albite
and kosmochlore as main phases, with chromite, eckermannite, and natrolite as associated
phases for Maw-Sit-Sit from Myanmar. This heterogeneity in the mineral associations
reflects the variability of the parent rocks, derived from the complex metamorphic system
of the Myanmar area.
Considering the Green Stones, another big family eventually included is the crypto and
micro-crystalline quartz species, such as chalcedony (chromium or chrysoprase varieties),
jasper, and quartzite rocks. Indeed, this species can show several types of colors, including
Appl. Sci. 2022, 12, 7168 9 of 30

green. Although the common basic unit consists of quartz crystals, the relatively significant
heterogeneity of this class of gem materials must be noted. In fact, considering the jasper
and chalcedony species, they are typically in hydrothermal (fluids precipitation product)
and sedimentary environments [103,104], while quartzite is a typical metamorphic product.
As per the variety name, in the Cr-chalcedony variety, the green color is correlated with
the chromium element as chromophore [105]; on the other hand, the characteristic “apple
green” variety of the chalcedony species is the chrysoprase [106].
In addition to these, several other mineral phases are ascribable to Green Stones.
Pyroxenes such as kosmochlor, diopside, and omphacite have been already listed as associ-
ated minerals in jadeite or Maw-Sit-Sit, but they can also be identified as a single phase
or dominant phase, characterizing the material analyzed. Moreover, belonging to Green
Stones, other mineral phases can be listed, i.e., hydrogrossular and grossular, vesuvianite
(californite, variety), or pumpellyite.
Finally, a significant phase belonging to Green Stones is serpentine. By this term,
three different polymorphs (minerals having the same chemical composition but different
crystal structures) are identified: lizardite, antigorite, and chrysotile. While the first two
are typically massive, the last one is of the fibrous variety. Chrysotile is unwillingly quite
famous because it is listed as one of the six fibrous minerals identified by the law as
“asbestos”, and is hazardous to human health [107].
By this short overview of the main materials classified as “Green Stones” and their
definition (summarized in Table 1), underlying their heterogeneity, the importance of
the proper jade and related-to-jade materials identification for archaeological, cultural
heritage studies, and antiquity trades becomes understandable [108]. A proper material
identification represents the base of a good archaeometric work and, consequently, the base
of archaeological or cultural heritage considerations. For example, the discussion about
the origin or the technology applied for artifact creation is strictly related to the materials’
properties and characteristics. Thus, the archaeometric analysis of Green Stones helps
archaeologists to find answers.

Table 1. The nomenclature of “Green Stones”.

Term Definition
Jade Trade name applicable to gem materials made only by jadeite or nephrite.
Gemstone Species–Mineralogical phase; piroxene mineral, columnar and/or granular
Jadeite
crystals are aggregated.
Gemstone Species; a rock originated from a solid solution of the amphibole group minerals
Nephrite actinolite and tremolite, composed of an interlocking mass of granular and acicular crystals
without a preferred orientation.
Fei Cui Trade and historical name; traditionally translated as “hard jade”.
Gemstone Species; green rock constituted by a variable mineralogical association (i.e., albite,
Maw-Sit-Sit
kosmochlor, chromite, eckermannite, natrolite, etc.) found in the Himalayan area.
Chrysoprase Gemstone variety; “apple green” variety of chalcedony species—cryptocrystalline quartz.
Cr-chalcedony Gemstone variety; green variety of chalcedony species—cryptocrystalline quartz.
Green Jasper Gemstone variety; green variety of jasper species—microcrystalline quartz.
Rock (metamorphic), constituting mainly by quartz mineral associated with green phases (i.e.,
Green Quartzite
diopside, etc.).
Gemstone Species—Mineral polymorphic phase; three different polymorphs (minerals
Serpentine having the same chemical composition but different crystal structures) are identified: lizardite,
antigorite, and chrysotile.
Californite Gemstone variety; green massive variety of vesuvianite (idrocrase) species.
Diopside
Omphacite
Gemstone Species–Mineralogical phases; piroxene minerals.
Kosmochlor
Pumpellyite
Hydrogrossular
Gemstone Species–Mineralogical phases; belonging to garnet group.
Grossular

4.2. Classical Gemological and Mineralogical Properties

Beside the terminology discussed in Section 4.1, the main Green Stones materials’
gemological and mineralogical characteristics have been reported in Tables 2 and 3, re-
Appl. Sci. 2022, 12, 7168 10 of 30

spectively. In both tables, the extreme heterogeneity of these materials is underlined. On

the other hand, the presence of similarities cannot be neglected; in addition to the color,
consisting of practically all the green hues and tones, the optical character, reported as
AGG (Table 2) for all of the species, reflects the massive variety of the materials under
discussion. Another common characteristic is hardness, which is reported based on the
Mohs scale and ranges from 5 to 7 12 . The one exception is the hardness of serpentine, which
is lower, but it must be noted that the range reported corresponds to the pure phase, while
the association with other minerals, widespread in serpentine objects, can increase it and
allows the curving cut.

Table 2. Classical gemological and mineralogical properties of Green Stones [56,62,109–112]. Here,
the characteristics of massive varieties have been preferred compared to the single-crystal coun-
terparts, due to the highest diffusion of the first ones in cultural heritage studies, and, according
to the topic, only the green varieties (and not other colors) have been considered. The reported
data correspond to the natural untreated varieties; eventual synthetic, treated, or imitation coun-
terparts have not been considered. RI = Refractive Index; SG = Specific Gravity; AGG = Aggregate
Reaction; DR = Doubly Refractive; STP = Semitransparent; TL = Translucent; STL = Semitranslucent;
O = Opaque; LW = Long Wave (365 nm); SW = Short Wave (254 nm).

Species and RI SG Optical Transparency Mohs

General Description Fluorescence
Variety Character Grade
Light to dark green, often with uneven
coloration, mottling, or root-like markings. 1.666 to 1.680
LW: None to
(+/−0.008) 3.34
Jadeite Vitreous to greasy polish luster with a AGG STP to O Faint White 6
1.66 spot reading (+0.06/−0.09)
dimpled polished surface, granular to SW: None
common
splintery fracture with dull fracture luster.
Light to dark green, possibly with lighter or
darker mottling. Vitreous to greasy polish 1.606 to 1.632
2.95 LW: None
Nephrite
luster, splintery to granular fracture with
1.61 spot reading
(+0.15/−0.05)
AGG TL to O
SW: None 6–6 12
common
dull fracture luster.
Usually yellowish green, green, or greenish 1.560 to 1.570 LW: None to
yellow. Waxy to greasy polish luster, (+0.004/−0.070) 2.57 Med chalky (B,
Serpentine
granular to uneven fracture, with dull to 1.56 spot reading (+0.23/−0.13)
AGG STL to O
W, and G) 2 21 –3 12
waxy fracture luster. common SW: None
Spot readings
around 1.53 to
Opaque saturated green rock with 1.74
(Multiple
characteristic dark green to black veining or 2.77 LW: None
Maw-Sit-Sit readings result AGG O 6
mottling. Waxy to vitreous polish luster, (+0.38/−0.31) SW: None
from
granular fracture with dull fracture luster.
combination of
different
minerals)
Green to bluish green. Might show black 1.720
Hydrogrossular
inclusions. Vitreous polish luster, uneven, (+0.010/−0.050) 3.47 LW: None
(Garnet
granular, or splintery fracture with greasy 1.72 spot reading (+0.08/−0.32)
AGG TL to O
SW: None 6–7 12
Group) common
to vitreous fracture luster.
Vesuvianite Yellowish green, green, brownish green. 1.713 to 1.718
(Idocrase), (+0.003/−0.013) 3.40 LW: None
Californite Vitreous to greasy polish luster, granular 1.70 or 1.71 spot (+0.10/−0.15) AGG TL to O SW: None 6–7
variety fracture with vitreous to dull fracture luster. reading common
Bluish green to yellowish green. Chrome
diopside is intense green. Vitreous polish DR (single
LW: None to
luster, conchoidal to uneven fracture with 1.675 to 1.701 3.29 crystal) TL to O
Diopside
vitreous to resinous fracture luster. Massive (+0.029/−0.010) (+0.11/−0.07) AGG (massive)
Med Green 5 12 –6 12
SW: None
and may show splintery to granular (massive)
fracture.
LW: None to
Green to dark green. Brittle tenancy with 1.662–1.723
Med chalky (B,
Omphacite fracture uneven, conchoidal and luster 1.68 or 1.71 spot 3.16 to 3.43 1 AGG O
W, and G)
5–6
vitreous, silky. reading common
SW: None
DR (single
Pumpellyite Blue–green, dark green to white fibrous to crystal) LW: None
Group
1.674 to 1.764 3.20 to 3.30 1 TL to O
SW: None
5–6
lamellar masses with glassy luster. AGG
(massive)
Chalcedony
Green to slightly bluish green. Greasy to 1.535 to 1.539
(chrome or 2.60 LW: None
chrysoprase
vitreous polish luster, conchoidal fracture (1.53 to 1.54
(+0.10/−0.05)
AGG STP to STL
SW: None 6 12 –7
with dull to waxy fracture luster. spot reading)
variety)
1 SG for omphacite and pumpellyite group has been reported by its range according to the references.
Appl. Sci. 2022, 12, 7168 11 of 30

Table 3. Main mineralogical characteristics of Green Stones species here discussed [96,113,114]. For
the series, the chemical formula of the end member/pure phase has been reported.

Mineral Phase Chemical Formula Group/Family Crystal System

Jadeite NaAl[Si2 O6 ] Clinopyroxene Monocline
Actinolite 1 Ca2 (Mg,Fe)5 [Si2 O6 ](OH)2
Amphibole Monocline
Tremolite 1 Ca2 Mg5 [Si2 O6 ](OH)2
Lizardite 2 Trigonal
Antigorite 2 Mg3 [Si2 O5 ](OH)4 Trioctahedral Phyllosilicate Monocline
Chrysotile 2 Orthorhombic
Tectosilicate, Plagioclase
Albite 3 Na[AlSi3 O8 ] Triclinic
Feldspar
Kosmochlor 3 NaCr[Si2 O6 ] Pyroxene Monocline
Chromite 3 Fe2+ Cr2 O4 Oxides, Spinels Cubic
Eckermannite 3 Na3 Mg4 Al[Si8 O22 ](OH)2 Amphibole Monocline
Natrolite 3 Na16 [Al16 Si24 O80 ]·16H2 O Tectosilicate, Zeolite Orthorhombic
Nesosilicate,
Hydrogrossular Ca3 Al2 (Si3 O12 )·(H2 O)2-6 Cubic
Garnet
(Ca,Na)19 (Al,Mg,Fe)13 (SiO4 )10 (Si2 O7 )4
Vesuvianite Sorosilicate Tetragonal
(OH,F,O)10
Diopside CaMgSi2 O6 Clinopyroxene Monocline
Omphacite (Ca,Na)(Mg,Fe2+ ,Fe3+ )[AlSi3 O8 ] Clinopyroxene Monocline
Pumpellyite Ca2 MgAl2 (Si2 O7 )(SiO4 )(OH)2 ·H2 O Sorosilicate Monocline
Quartz 4 SiO2 Tectosilicate Trigonal
1Main mineral phases (pure end members) constituting nephrite gemological species. 2 Serpentine polymorphs,
particularly the chrysotile is the fibrous variety of the mineral. 3 Main mineral phases constituting Maw-Sit-Sit
variety. 4 Main mineral phase constituting chalcedony species.

In Table 3, the main mineralogical properties of the phases possibly found in Green
Stones are reported. It must be noted that not only silicate minerals but also oxide minerals
have to be considered for Green Stones. Moreover, regarding the silicates, all the families
are represented.
As discussed in depth in the nomenclature section, correctly identifying the green
stone phase represents a crucial point for gemology practice and cultural heritage studies.
Thus, considering the heterogeneity and complexity of the materials, for their identifica-
tion, a mineralogical characterization provides extremely suitable support, as attested by
many archaeometric applications. Moreover, by the characterization of the phase, several
information can be obtained, which could help, for example, in discussions about origins,
colors factors, and mechanical properties considerations.
Despite all of this variability, observing the data reported in Table 3, several similarities
can also be highlighted. Indeed, considering the pyroxene members, jadeite, kosmochlor,
omphacite, and diopside are all minerals showing chemical and crystallographic affinities.
In some cases, they can be found as components of metamorphic rocks, except for diopside,
which can also be found as a component in some magmatic rocks (i.e., alkali olivine
basalts). It is interesting to note that pure jadeite is a colorless mineral: only when a small
amount of chromium (Cr3+ ) goes inside the crystal structure as a substituting element
of aluminium (Al3+ ), jadeite can show its vivid “Imperial Green” color (Figure 2a), so
called in modern and ancient trades. However, green Cr-rich jadeite does not become
a kosmochlor only as a consequence of the substitutions. Indeed, the crystallization of
a phase despite another one is not only a matter of chemical availability but also of the
pressure and temperature conditions involved in the process. Jadeite genesis is such an
example: almost all the known paragenesis involves the albite-jadeite association. If the
metamorphic grade increases, the jadeite component decreases, giving way to omphacite
 paragenesis involves the albite-jadeite association. If the metamorphic grade increases, the
12, 7168 jadeite component decreases, giving way to omphacite crystallization. In this condition 14 of 32
of
regional metamorphism, gabbro rocks can show veins rich in jadeite-pumpellyite
Appl. Sci. 2022,association
12, 7168 (Figure 2b) [114]. 12 of 30
paragenesis involves the albite-jadeite association. If the metamorphic grade increases, the
jadeite component decreases, giving way to omphacite crystallization. In this condition of
regional metamorphism, gabbro
crystallization. rocks
In this can ofshow
condition veins
regional rich in jadeite-pumpellyite
metamorphism, gabbro rocks can show veins
association (Figure
rich2b) [114].
in jadeite-pumpellyite association (Figure 2b) [114].

Figure 2. Jade aspect and texture details: (a) jadeite-jade, imperial green, Photo: M. Musa—
Gemological Education and Certification Institute (GECI) reference stone collection: (b) jadeite-
pumpellyite association (green veins) in albite white matrix (OM Image, 5× magnification, darkfield
light), Photo: M. Musa—GECI reference stone collection; (c) nephrite-jade-polished cabochon
surface, detail of its characteristic texture, where no iso-oriented acicular/columnar crystals are
Figure 2. Jade aspectFigureand2. texture details:
Jade aspect (a) jadeite-jade,
and texture details: (a)imperial green,
jadeite-jade, Photo:
imperial M. Photo:
green, Musa—M. Musa—
evident, but the grains are associated to elongated crystals, oriented in different directions (OM
Gemological Education and Certification
Gemological Education and Institute (GECI)
Certification reference
Institute stone
(GECI) collection:
reference stone (b) jadeite-(b) jadeite-
collection:
Image, 20× magnification, reflected light), Photo: M. Musa—Gulf Institute of Gemology (GIG).
pumpellyite association (greenassociation
pumpellyite veins) in albite
(greenwhite
veins) matrix
in albite(OM
whiteImage,
matrix 5×
(OMmagnification, darkfield darkfield
Image, 5× magnification,
light), Photo: M. light),
Musa—GECI
Photo: M. reference
Musa—GECI stone collection;
reference (c) nephrite-jade-polished
stone collection; cabochon
(c) nephrite-jade-polished cabochon surface,
This
surface, example
detail of its can help to understand
characteristic
detail
why
texture,texture,
of its characteristic where nothe
where
determination
iso-oriented of geographic
acicular/columnar
no iso-oriented acicular/columnar
origin
crystals in
are
crystals are evident,
Green Stones is so
evident, but the grains complex:
but thearegrains not
associatedonly different
to elongated
are associated mines
crystals,
to elongated can produce
oriented
crystals, similar
in different
oriented materials,
directions
in different but
(OM
directions (OM Image,
also differences
Image, in
20×terms
20× magnification, of chemical
reflected
magnification, light), and
Photo:
reflected mineralogical
M.
light), Musa—Gulf
Photo: distribution
Institute
M. Musa—Gulf of can ofbe
Gemology
Institute found
(GIG).
Gemology within
(GIG).
the same vein [90]. Moreover, from a multidisciplinary point of view, the knowledge of
the geological
This example canThis
process helpexample
and to the can
understandhelp to
petrographic
why understand why the determination
identification
the determination of ofthe mining
geographic of geographic
areas
originarein origin in
Green Stones is so complex: not only different mines can produce similar materials, but
necessary
Green information
Stones for thenot
is so complex: geographic originmines
only different hypothesis [115]. similar materials, but
can produce
also differences in terms of chemical and mineralogical distribution can be found within
The same
also differences inconsideration can be applied to amphiboles
terms of chemical and mineralogical distribution and serpentine,
can be found and both
within
the same vein [90]. Moreover, from a multidisciplinary point of view, the knowledge of the
correlate
the same with metamorphic
vein [90]. Moreover,
geological processes.
from
process Serpentines,
a the
and petrographicinidentification
multidisciplinary particular, are
point of view, typical
of thethe products
knowledge
mining areas are ofnecessary
the transformation
geological process of ultramafic
informationandforthe rocks by
the petrographic a hydrothermal
geographic origin identification metamorphic
hypothesis [115]. system,
of the mining areas are while
nephrite requires
necessary information notThe
only
forsame thegeographic
the conditionsorigin
consideration for
canactinolite-tremolite
behypothesis [115]. crystallization
applied to amphiboles and serpentine,but also
and both cor-
the condition
The samefor its characteristic
consideration
relate with can texture
metamorphicbe applied(Figure
processes. 2c). Figure 2c,
to amphiboles
Serpentines, inand in serpentine,
particular, shows
particular, are and both
typical the of the
products
sample detail
correlate transformation
where
with metamorphic of ultramafic
the interlocking
processes. mass rocks by a hydrothermal
of granular
Serpentines, metamorphic
and acicular
in particular, system,
crystalsproducts
are typical without while
ofa nephrite
preferred
the requires
orientation
transformation of arenot only the conditions
well visible.
ultramafic rocks by for
Regarding actinolite-tremolite
a hydrothermalthe nephrite crystallization
genesis, Prokhor
metamorphic but also
system, while [116],condition
the
for its characteristic texture (Figure 2c). Figure 2c, in particular, shows the sample detail
describing
nephrite for example
requires not only thethe ultramafic
conditions complex of East Sayan, reported
for actinolite-tremolite nephrite
crystallization butveins
also
where the interlocking mass of granular and acicular crystals without a preferred orienta-
formation
the at the
condition forbase of the ultramafic
its characteristic members
texture (Figure of 2c).
the ophiolitic
Figure 2c,nappes, as a consequence
in particular, shows the
tion are well visible. Regarding the nephrite genesis, Prokhor [116], describing for example
of the metamorphism
sample detail where and
the metasomatism
interlocking mass resulting
of granular from frictional
and acicular
the ultramafic complex of East Sayan, reported nephrite veins formation heating
crystalsat the atblock-
without the abase of the
matrix contacts.
preferred orientation are members
ultramafic well visible.
of theRegarding the nephrite
ophiolitic nappes, genesis, of
as a consequence Prokhor [116],
the metamorphism and
The hydrogrossular
describing for example and
the grossular
ultramafic (Figure
complex 3a)of are
Eastgarnets
Sayan, crystallized
reported
metasomatism resulting from frictional heating at the block-matrix contacts. typically
nephrite from
veins
the thermal
formation metamorphic
at the base The
of the process members
ultramafic
hydrogrossular applied
and grossular to
of thelimestone.3a) areIn
ophiolitic
(Figure the crystallized
nappes,
garnets case of regional
as a consequence
typically from the
metamorphism,
of the metamorphism thermal
they and metamorphic
can metasomatismprocessresulting
be associated applied
with tofrom
limestone.
vesuviana andIn the
frictional case of regional
diopside
heating and,
at metamorphism,
the finally,
block-
grossular
matrix can be associated with serpentine and found in rhodingite rock (Figure 3b,c).be associated
contacts. they can be associated with vesuviana and diopside and, finally, grossular can
with serpentine and found in rhodingite rock (Figure 3b,c).
The hydrogrossular and grossular (Figure 3a) are garnets crystallized typically from
the thermal metamorphic process applied to limestone. In the case of regional
metamorphism, they can be associated with vesuviana and diopside and, finally,
grossular can be associated with serpentine and found in rhodingite rock (Figure 3b,c).

3. Mineralogical
Figuresamples
Figure 3. Mineralogical samples of (a) grossular/hydrogrossular
of (a) grossular/hydrogrossular and (b) grossular/hydrogrossular
and (b) grossular/hydrogrossular
in rhodingite rock in rhodingite rock
association; association; (c) rhodingite-polished
(c) rhodingite-polished tablet. Photos:tablet. Photos: M. Musa—GIG.
M. Musa—GIG.

Finally, the chalcedony; the green variety can be mainly distinguished between
chromium-chalcedony and chrysoprase (Figure 4). As per the variety name, in the first
Figure 3. Mineralogical samples of (a) grossular/hydrogrossular and (b) grossular/hydrogrossular
in rhodingite rock association; (c) rhodingite-polished tablet. Photos: M. Musa—GIG.
Appl. Sci. 2022, 12, 7168 15 of 3

Appl. Sci. 2022, 12, 7168 Finally, the chalcedony; the green variety can be mainly distinguished 13 of 30between
chromium-chalcedony and chrysoprase (Figure 4). As per the variety name, in the firs
case, the origin of the green color is correlated with chromium naturally present as a trace
on the
case, theother
originhand,
of thethe chrysoprase
green characteristic
color is correlated “apple green”
with chromium colorpresent
naturally is dueastoaa nickel
rich mineral
trace; associated
on the other hand, thewith chalcedony,
chrysoprase typically“apple
characteristic belonging
green” tocolor
the garnierite
is due to a minera
group [106].
nickel-rich The associated
mineral processeswithproducing chalcedony
chalcedony, are still under
typically belonging discussion;
to the garnierite min- typically
eral group [106]. The processes producing chalcedony are still under discussion;
quartz-rich fluid precipitation is hypothesized as a mandatory condition [117], whethe typically,
quartz-rich
the process fluid precipitation is with
is hydrothermal hypothesized as a mandatory
crystallization in geodes condition [117], whether the
or metamorphic.
process is hydrothermal with crystallization in geodes or metamorphic.

Figure4. 4.
Figure (a) Chromium-chalcedony
(a) Chromium-chalcedony mineralogical
mineralogical sample
sample (Photo: (Photo: and
M. Musa—GIG) M. (b)
Musa—GIG)
chrysoprase- and (b
chrysoprase-polished
polished cabochon (Photo:cabochon (Photo:
M. Musa—GECI M. Musa—GECI
reference reference stone collection).
stone collection).

So,
So,starting
startingfrom from general
generalobservations,
observations, how how can these materials
can these be distinguished?
materials be distinguished?
First, a deep investigation of the sample visual characteristics is mandatory. As reported
First, a deep investigation of the sample visual characteristics is mandatory. As reported
previously, applying the OM technique can significantly help the analyst to start several
previously, applying the OM technique can significantly help the analyst to start severa
considerations about, for example, the homogeneity in terms of color, mineral distribution,
considerations
or texture. For these about, for example,
purposes, extremely high the magnification
homogeneity isin notterms
required:of classical
color, minera
distribution,
gemological or texture.
darkfield For these purposes,
stereo-microscopes extremely
are suitable, as well high
as themagnification
last generation isof
nottherequired
classical
digital gemological
portable darkfield (in
optical microscopes stereo-microscopes
case of an on-site analyses are suitable,
section). as well as the las
Observing
generation of the
thedata reported
digital in Tableoptical
portable 1, the importance
microscopes of the(in
RI and
caseSGofasan keyon-site
tests foranalyses
the gemological material identification is evident, among others. Unfortunately, these tests
section).
are sometimes
Observing limited in application
the data reportedor inwith
Table the1,reliability of their results.
the importance of the The RI requires
RI and SG as key test
three operative conditions: the homogeneity of the sample, a polished surface (better if
for the gemological material identification is evident, among others. Unfortunately, these
flat), and the use of the refractometer contact liquid [57]. The first condition is difficult to
tests are sometimes limited in application or with the reliability of their results. The R
apply to rocks, which are a mix of phases. This is the reason, as reported in Table 2, the RI
requires three
technique operative for
is not applicable, conditions:
example, to the homogeneity
Maw-Sit-Sit of the sample,
identification. The same a polished
issue can surface
(better
occur if flat),
if we anda material
analyze the use of madetheby refractometer
jadeite mixed contact
with other liquid [57]. The
pyroxenes firstalbite.
and/or condition i
difficult
The second tocondition
apply toisrocks, which are
more correlated a mix
with of phases.
the surface This is the
characteristics of reason, as reported
the samples. In in
fact,
Table typical
2, theGreen Stones objects
RI technique is notare curved (i.e.,
applicable, fordouble
example, cabochons); therefore,
to Maw-Sit-Sit a lecture
identification. The
on
samethe issue
flat polished
can occur surface
if weisanalyze
extremely rare. Thus,
a material made the by
spot reading
jadeite is usually
mixed the only
with other pyroxenes
possibility
and/or albite. for the
The RIsecond
test, butcondition
it is less accurate
is moreand obtainedwith
correlated by athe
distance observation,
surface characteristics o
without magnification. Moreover, additional limits correlated with the dimension of the
the samples. In fact, typical Green Stones objects are curved (i.e., double cabochons)
objects, often largely sized, must be considered. Finally, the use of the contact liquid, even
therefore, a lecture on the flat polished surface is extremely rare. Thus, the spot reading is
if perfectly safe for gemstones, can be absorbed by a porous object (i.e., serpentine) with
usually
the risk ofthe only possibility
consequent for the
small stains, or itRI test, but
cannot it is lessbyaccurate
be allowed and obtained
the conservation by a distance
institutions
observation,
policies, without
for example, magnification.
in case Moreover,
of museum collections additional limits correlated with the
studies.
dimension
Regarding of the
the SG objects,
test, itoften
allowslargely sized, of
the gathering must be considered.
important informationFinally,
regardingthethe
use of the
contactofliquid,
density even ifbut
the material, perfectly
again it safe for gemstones,
is possible to encounter can be absorbed
limitations of theby a porous objec
technique.
The
(i.e.,most commonwith
serpentine) method the for
risktheofSG test in gemology
consequent corresponds
small stains, to the hydrostatic
or it cannot be allowed by the
weight. In this system, the water temperature, the homogeneity
conservation institutions policies, for example, in case of museum collections of the samples, and their
studies.
dimensions and roughness can affect the precision of the measurement. In cultural heritage,
Regarding the SG test, it allows the gathering of important information regarding the
especially the archaeological samples do not show well-polished surfaces, which can be
density of the material, but again it is possible to encounter limitations of the technique
very rough due to weathering and ageing. Such surface characteristics may easily entrap
Thebubbles,
gas most common
altering the method for the SG test in gemology corresponds to the hydrostatic
SG results.
weight. In this system, the water temperature, the homogeneity of the samples, and thei
dimensions and roughness can affect the precision of the measurement. In cultura
heritage, especially the archaeological samples do not show well-polished surfaces, which
Appl. Sci. 2022, 12, 7168 14 of 30

Thus, considering the limited applicability of the RI and SG, an excellent analytical
protocol for Green Stones samples’ identification and characterization must include the
application of high-tech techniques.

4.3. The Raman Investigation

Among other vibrational spectroscopic techniques, Raman spectroscopy is considered
a powerful tool for identifying minerals and gemstones [66,118–120] (see Section 3.3).
Because of its peculiarity, it represents a very suitable technique to solve the Green Stones
identification problems [96,121].
Table 4 lists the main Raman features for quick identification of the Green Stones. In
fact, considering only the main vibrations, the greater part of the phases constituting Green
Stones can be easily distinguished.

Table 4. Raman main features characterizing Green Stones. The main bands of pure actinolite,
tremolite phases, together with those of nephrite, and antigorite, lizardite, chrysotile phases, together
with those of serpentine, have been reported as references for completeness.

Mineral
Phase/Variety Main Vibrations–Raman Shift (cm−1 ) References

Jadeite 1039, 990 700 [96,120–123]

Nephrite 1060, 1032 674 [90,120,122]
(Actinolite) 1062, 1027 669 [90,124]
(Tremolite) 1062, 1031 676 [90,121]
Serpentine 1044 683, 635 378 [122]
(Antigorite) 1044 683, 635 375 [122,125]
(Lizardite) 1096 b 690 388 [125]
(Chrysotile) 1105 692 389 [125]
Albite1 510, 482 [120,122,123]
(551−) 556,
Kosmochlor 1 950 683 522, 340 [96,126,127]
413 (−418)
Chromite 1 690 b 560 b [126,128]
Eckermannite 1 1025, 992 690 [129]
Natrolite 1 535, 443 [130]
Hydrogrossular 871 361 [131]
Vesuvianite 930, 862 643 [132]
Diopside 1010 666 [120,133]
Omphacite 1024 685 [92,122,123,134]
Pumpellyite 990, 920 697 [135]
Chalcedony 503, 465 [34,136,137]
1 Main phases constituting Maw-Sit-Sit variety. b = Broad band.

The problem in the phase identification may occur only when the phases are char-
acterised by the main vibrational modes within 2 cm−1 Raman shift: jadeite-pumpellyite
(discussed later in this section), nephrite vs. its pure end members, and the serpentine
polymorphs. In fact, ±2 cm−1 is the tolerance commonly accepted for Raman spectrum
interpretation, especially when the analysis is carried out on a natural phase [120,121]. Re-
garding the nephrite, although actinolite is well recognisable, tremolite pure end member
can hardly be detected. To overcome this issue, a deep morphological observation is manda-
tory. Indeed, as already described (see Section 4.1 and Figure 2c), nephrite must show
its characteristic texture, while column-like and/or needle-like habitus, with isoriented
crystals, are typical of actinolite and tremolite pure terms.
Regarding serpentines for gemstone species identification, both of the massive poly-
morphs, antigorite and lizardite, are accepted and both can be easily distinguished on the
basis of their Raman features; nevertheless, the references report spectra more consistent
with the first one [122]. On the other hand, chrysotile polymorph shows the main Raman
bands strictly near to the lizardite ones. In this case, similar to the nephrite, morphological
observation and OM analysis are very helpful because, as already reported, crysotile is the
fibrous polymorph of the serpentine species.
Similar to Table 4, the same can be observed by the reference spectra reported in
Figure 5, where all six spectra reported show relatively strong, sharp, and well-defined
bands, as a consequence of the high crystallinity of the materials analyzed. Only the
 consistent with the first one [122]. On the other hand, chrysotile polymorph shows the
main Raman bands strictly near to the lizardite ones. In this case, similar to the nephrite,
morphological observation and OM analysis are very helpful because, as already
reported, crysotile is the fibrous polymorph of the serpentine species.
Appl. Sci. 2022, 12, 7168 Similar to Table 4, the same can be observed by the reference spectra reported in
15 of 30
Figure 5, where all six spectra reported show relatively strong, sharp, and well-defined
bands, as a consequence of the high crystallinity of the materials analyzed. Only the
omphacite phase shows Raman bands with characteristic Full Width at Half Maximum
omphacite phase shows Raman bands with characteristic Full Width at Half Maximum
(FWHM) of the band amplitude higher than other phases (Figure 5), as diopside or jadeite.
(FWHM) of the band amplitude higher than other phases (Figure 5), as diopside or jadeite.
Generally speaking, by Raman spectroscopy, the higher the crystalline grade of the
Generally speaking, by Raman spectroscopy, the higher the crystalline grade of the sample,
sample, the sharper are the scattered bands [65,119]. Nevertheless, to obtain reliable
the sharper are the scattered bands [65,119]. Nevertheless, to obtain reliable Raman spectra
Raman spectra on Green Stones, the analyst has to pay particular attention to the choice
on Green Stones, the analyst has to pay particular attention to the choice of laser source.
of laser
While forsource. Whileand
inosilicates, for inosilicates, and silicates
silicates generally, generally,
a visible a visible
red source red nm)
(i.e., 632.8 source (i.e.,be632.8
could one
nm) could be one of the best selections, due to the high affinity of the wavelength
of the best selections, due to the high affinity of the wavelength with the silicon tetrahedra with the
silicon tetrahedra
vibration vibration
[120], when the phase[120], when the
is Cr-rich, phasefluorescence
a strong is Cr-rich, aissue
strong
canfluorescence
be generated.issue On
can be generated. On the basis of this consideration, the availability
the basis of this consideration, the availability of a second source, for example, of a seconda source,
visible
for example,
green a visible
(514.5/532 nm)green
or NIR (514.5/532
(785 nm)nm) or NIR
laser, could(785
be nm)
a goodlaser, couldtobesolve
option a good theoption
issue
to solve the issue and complete the characterization. The fluorescence
and complete the characterization. The fluorescence issue is one of the main limits of issue is one of the
the
main limits of the technique [65]. This problem might be solved changing
technique [65]. This problem might be solved changing the source but multi-laser systems the source but
multi-laser
are not alwayssystems are not
available. always
Finally, available.
surface sample Finally,
treatmentssurface sample varnishing,
(i.e., waxing, treatments (i.e., etc.)
waxing, varnishing, etc.) can
can generate Raman fluorescences. generate Raman fluorescences.

Figure 5. Reference
Figure 5. Reference Raman
Raman spectra
spectra ofof several
several Green
Green Stones
Stones samples. Kosmochlor spectrum
samples. Kosmochlor spectrum isis re-
re-
plotted from the RRUFF reference N. R120015 [127]; the
plotted from the RRUFF reference N. R120015 [127]; the other other spectra have been acquired by In-Via
In-Via
Confocal
Confocal micro-Raman
micro-RamanSpectroscope,
Spectroscope,Renishaw,
Renishaw,514.5/632.8 nm sources
514.5/632.8 and elaborated
nm sources using Origin
and elaborated using
Origin
2020 2020 software
software by theonauthor
by the author on GECI Reference
GECI Reference stones collection.
stones collection. Circled
Circled bands bands
in the in the
serpentine
serpentineare
spectrum spectrum arewith
consistent consistent
calcite with
phase calcite phasewith
associated associated with serpentine.
serpentine.

Moreover, as
Moreover, as previously
previously mentioned,
mentioned, a potential difficulty could emerge in jadeite-
pumpellyite identification,
pumpellyite identification, considering
consideringprudential
prudentialtolerance
toleranceofofabout cm−−11 Raman shift
about22cm shift
for the spectrum interpretation, correlated with possible substitutions and/or crystal lattice
defects, which are very common in natural phases [90]. In fact, these two phases diverge for
only a 3 cm−1 Raman shift on the main vibrational bands. In Figure 6, the reference Raman
spectra of the two phases are reported. Despite the Raman shifts of the main vibrational
bands being extremely close (700 vs. 697 cm−1 , see also Table 4), many differences can be
highlighted by observing the trends of the entire spectra. The pumpellyite phase shows not
only a spectrum richer in band numbers, but many of those bands are broader with respect
to the jadeite ones, suggesting the presence of convoluted components [138].
 diverge for only a 3 cm Raman shift on the main vibrational bands. In Figure 6, the
reference Raman spectra of the two phases are reported. Despite the Raman shifts of the
main vibrational bands being extremely close (700 vs. 697 cm−1, see also Table 4), many
differences can be highlighted by observing the trends of the entire spectra. The
pumpellyite phase shows not only a spectrum richer in band numbers, but many of those
Appl. Sci. 2022, 12, 7168 bands are broader with respect to the jadeite ones, suggesting the presence of convoluted
16 of 30
components [138].

Figure6.6. Overlap
Figure Overlap ofof jadeite
jadeite (acquired
(acquired by
by In-Via
In-Via Confocal
Confocal micro-Raman
micro-RamanSpectroscope,
Spectroscope,Renishaw,
Renishaw,
514.5 nm source by the author on GECI Reference stones collection); black line and pumpellyite (re-
514.5 nm source by the author on GECI Reference stones collection); black line and pumpellyite
plotted from RRUFF N. R120172 [135]); red line, Raman spectra with baseline subtraction. The
(re-plotted from RRUFF N. R120172 [135]); red line, Raman spectra with baseline subtraction. The
spectra have been elaborated by Wire 5.5 software. The top-left box shows the OM (5× magnification,
spectra have
darkfield) ofbeen elaborated
a cabochon by Wire
section 5.5 software. The top-left
of jadeite-pumpellyite box shows
association the
in albite OM (5× magnification,
matrix.
darkfield) of a cabochon section of jadeite-pumpellyite association in albite matrix.
Moreover, for the diagnosis, the texture must again be considered; in the top-left box
Moreover,
of Figure 6, thefor
OM theofdiagnosis,
a cabochon the texture
section ofmust again be considered;
jadeite-pumpellyite in theistop-left
association reported, box
of Figure 6, the OM of a cabochon section of jadeite-pumpellyite association
showing the presence of many green elongated crystals of pumpellyite and jadeite in a is reported,
showing the presence
white matrix. of many
This texture, green elongated
not associable crystals ofgem
with jadeite-jade pumpellyite
quality, is and jadeite in a
a consequence
white matrix. This texture, not associable with jadeite-jade
of the specific genesis of the sample and produces higher brittleness. gem quality, is a consequence of
the specific
From an genesis of thepoint
operative sample and produces
of view, higher brittleness.
Raman spectroscopy has several advantages. The
From an operative point of view, Raman spectroscopy
last generation of portable Raman spectrometers, in particular, has several advantages.
exhibit very high The
last generation of portable Raman spectrometers, in particular, exhibit very
versatility and due to optical fiber technology, several models can be easily coupled with high versatility
and due to optical
a portable microscope.fiber These
technology,
set-ups several
allow models
the Raman can characterization
be easily coupledofwith Greena portable
Stones
microscope. These set-ups allow the Raman characterization of Green
“on-site” by a micro-Raman system, which is extremely useful in the case of non- Stones “on-site” by a
micro-Raman system, which is extremely useful in the case of non-homogenous
homogenous samples. In 2017, Gendron et al. [139] reported that a portable Raman samples.
In 2017, Gendron
spectrometer waset al. [139] reported
employed that the
in situ inside a portable RamanVeracruz
Centro-INAH spectrometer wasduring
reserve; employed the
in situ time
short inside the Centro-INAH
available Veracruz
for the analyses, reserve;
several during
El Manatì the short
artifacts time
were available
analyzed withforthe
the
analyses, several El Manatì artifacts were analyzed with the main
main aim of verifying which artifacts were made of jade. By the application of this aim of verifying which
artifacts
technique,werethemade
authorsof jade. By the
proved thatapplication
a total of 11of this technique,
artifacts, 10 axes,theand
authors
1 beadproved
had beenthat a
total of 11 artifacts, 10 axes, and 1 bead had been made by omphacite,
made by omphacite, instead of jadeite. Similarly, Zhao [140] reported the successful instead of jadeite.
Similarly,
combination Zhao of [140] reported
a portable the successful
Raman combination
system, applied with aofportable
a portableXRFRaman
(PXRF) system,
in a
applied with a portable XRF (PXRF) in a complementary way, for nephrite-jade
complementary way, for nephrite-jade artifacts characterization from the Cemetery of the artifacts
characterization
Ying State (Henan from the Cemetery
Province, China).ofCourtesy
the Yingof State
the (Henan Province,
application of the China). Courtesy
two techniques,
of
thethe application
study revealed,ofamongthe two techniques,
other results, thethe study revealed,
interesting presenceamong otherpigment
of cinnabar results, on the
interesting presence of cinnabar pigment on the surface of the two jade artifacts, probably
associated with religious rituals performed during the Western Zhou Period. On the other
hand, a portable system is not able to substitute completely the benchtop counterpart,
especially for the detectors resolution and mapping tools. Indeed, in recent decades, several
micro-Raman mapping systems have been developed, allowing the complete spatially
resolved interpretation of the data, particularly suitable for uneven samples. In other
words, regarding Green Stones, the micro-Raman tool results in a suitable technique
for testing phase distribution and homogeneity [90]. In Figure 7, an example of micro-
Raman mapping on a green stone is reported. In particular, the sample analyzed by
the line map tool comprised mainly quartz and diopside mineral phases. In fact, in
this case, the map elaboration performed by a signal to baseline calculation shows the
 substitute completely the benchtop counterpart, especially for the detectors resolution
and mapping tools. Indeed, in recent decades, several micro-Raman mapping systems
have been developed, allowing the complete spatially resolved interpretation of the data,
particularly suitable for uneven samples. In other words, regarding Green Stones, the
micro-Raman tool results in a suitable technique for testing phase distribution and
Appl. Sci. 2022, 12, 7168 homogeneity [90]. In Figure 7, an example of micro-Raman mapping on a green stone17isof 30
reported. In particular, the sample analyzed by the line map tool comprised mainly quartz
and diopside mineral phases. In fact, in this case, the map elaboration performed by a
signal to baseline calculation shows the relative spatial distribution of the two phases, on
relative spatial distribution of the
the basis of their main Raman
two phases, on the basis of their main Raman bands
bands (Figure 7, top-right): 666 cm−1 for diopside (range
(Figure 7, top-right): 666 cm −1 for diopside (range 662–672 cm−1 ) and 465 cm−1 for quartz
662–672 cm ) and−465
−1 cm for quartz (range 461–471 cm−1). Observing the plot of the blue
−1
1 ). Observing the plot of the blue and red lines, representing the spatial
(range 461–471 cm
and red lines, representing the spatial distribution of the two phases, a complementary
distribution
trend in theofrelative
the twodistribution
phases, a complementary trend
results is evident. in the
This relativetool
powerful distribution
also shows results
the is
evident. This powerful tool also shows the correspondence between
correspondence between the single spectrum acquired (Figure 7, bottom), the spot the single spectrum
acquired
position(Figure 7, bottom),sample’s
on the microscope the spotimage
position on the
(Figure microscope
7, top-left), andsample’s
the phasesimage (Figure 7,
distribution
top-left), and theofphases
by false-colors distribution
the spots. Thus, theby false-colors
line map allowedof the
notspots.
only toThus, the line
identify map allowed
the phases but
not only
also to identify
to highlight the relative
their phases but alsodistribution.
spatial to highlightThetheirmicro-Raman
relative spatial distribution.
mapping systemsThe
micro-Raman
not only allow mapping
the linesystems
maps, not only allow
as already the line
shown, but maps, as already
also the shown,
area maps, whichbutisalso
the area maps,
particularly which
useful is particularly
when poly-phaseuseful
samples when
havepoly-phase samples have to be analyzed.
to be analyzed.

Figure 7. micro-Raman spectroscopy—line map tool applied for a green stone characterization, a
Figure 7. micro-Raman spectroscopy—line map tool applied for a green stone characterization, a
diopside-quartzite rock, reported as an example of the technique’s feasibility. (Top-left) MO image
diopside-quartzite
(20× magnification,rock, reported
reflected light)asshowing
an example of the technique’s
the mapping area on thefeasibility. (Top-left)
sample surface MO the
and also image
(20 ×
analyses spots; (Top-right) data results elaborated by signal to baseline method, considering the the
magnification, reflected light) showing the mapping area on the sample surface and also
two ranges,
analyses corresponding
spots; to theresults
(Top-right) data main vibrational
elaboratedmodes of diopside
by signal (red method,
to baseline line) andconsidering
quartz (blue the
two ranges, corresponding to the main vibrational modes of diopside (red line) andarea
line). Note the complementarity of the main bands’ distribution related to the sample where
quartz (blue
the signals have been detected, highlighted by the graph; (bottom) one of the spot
line). Note the complementarity of the main bands’ distribution related to the sample area whereanalysis results,
corresponding to the cross axes spot in the map image (green): blue and red squares correspond to
the signals have been detected, highlighted by the graph; (bottom) one of the spot analysis results,
the quartz and diopside main vibrational mode ranges, used for the elaboration. The map has been
corresponding to the
carried out using cross
In-Via axes spot
Confocal in the mapSpectroscope,
micro-Raman image (green): blue and514.5
Renishaw, red nm
squares correspond
source, Wire 5.5 to
the quartz and diopside main
software. Data: M. Musa, GIG. vibrational mode ranges, used for the elaboration. The map has been
carried out using In-Via Confocal micro-Raman Spectroscope, Renishaw, 514.5 nm source, Wire 5.5
software. Data: M. Musa, GIG.

4.4. The Fourier Transform InfraRed Spectroscopy (FTIR) Investigation

The infrared spectrometer uses IR light as a source and is a technique belonging to
vibrational spectroscopies. In cultural heritage and archaeometry applications, infrared
spectra can help analysts and researchers to identify functional groups that characterize
the materials or identify eventual gemstone treatments.
Regarding materials characterization, in Table 5, the main vibrational absorption
features of the phases discussed in the present work have been reported.
Appl. Sci. 2022, 12, 7168 18 of 30

Table 5. Infrared main vibrational absorption bands of Green Stones. The IR main bands of the pure
actinolite and tremolite phases, along with nephrite, antigorite, lizardite, and chrysotile phases, along
with serpentine, have been reported as references for completeness.

Mineral
Phase/Variety Main Vibrations–Wavenumbers (cm−1 ) References

Jadeite 582 999 1090 [122,123,141–143]

Nephrite 686, 756 950, 995 1064, 1102 3660, 3676 [122,123,141,144]
(Actinolite) 668, 756 918, 942, 992 1066 b 3675 [144]
(Tremolite) 686, 758 920, 951, 990 1057 3673 [145]
Serpentine 471 990 1080 3671 [122,146,147]
436, 962, 1084 3676
(Antigorite) 449 (−471), 617 (990–) 997 [146,147]
(Lizardite) 442, 621 976 1010, 1084 3687 [146]
(Chrysotile) 439, 609 949 1000, 1080 3649, 3685 [146]
Albite 1 994 1040 [123,148]
Kosmochlor 1 980 1114 [96]
Chromite 1 520 b, 650 b [149]
Hydrogrossular 840, 910 3660 [150]
Vesuvianite 482 900, 980 1011 3570 [151]
Diopside 456 860, 960 1065 [152]
Omphacite 448, 523 956 1060 [122,126,142]
Pumpellyite 440 947 3406, 3556 [153]
Chalcedony 450 780, 796 1067 [154]
1 Several phases constituting Maw-Sit-Sit variety. b = Broad band.

Moreover, Figure 8 shows the absorption spectra of several mineral phases belonging
to Green Stones. It is important to note that, different to what has been shown previously
Appl. Sci. 2022, 12, 7168 21 of 32
for Raman spectroscopy, several bands overlap between the phases, making more complex
the identification, especially for minerals belonging to the same groups.

Figure 8.
Figure 8. Reference
Reference IR
IR absorption
absorption spectra
spectra of
of several
several Green
Green Stones
Stones samples,
samples, re-plotted
re-plotted from
from RRUFF:
RRUFF:
Jadeite N. R050220-1 [143], Actinolite N. R040063-1 [144], Pumpellyite N. R070130-1 [153], Diopside
Jadeite N. R050220-1 [143], Actinolite N. R040063-1 [144], Pumpellyite N. R070130-1 [153], Diopside
N. R040009-1 [152], Antigorite N. R070228-1 [147], and Quartz N. R040031-1 [154]. Powder samples
N. R040009-1 [152], Antigorite N. R070228-1 [147], and Quartz N. R040031-1 [154]. Powder samples
in KBr pellets, transmission mode. Spectra elaboration by Origin 2020 software.
in KBr pellets, transmission mode. Spectra elaboration by Origin 2020 software.

On the
This other hand,isthe
phenomenon specialcorrelated
partially affinities of thethe
with IR characteristic
source with organic compounds
broadening of the
make FTIR
silicate spectroscopy
absorption particularansuitable
bands. Moreover, operativeto consideration
identify jadehasimpregnation
to be made; bythe organic
spectra
substances
reported in treatments (Figure
Figure 8 are 9) [70,155,156].
re-plotted from RRUFF As database
reported by Fritsch
files [156], it is interesting
[143,144,147,152–154], col-
to note that in this modality, none of the fingerprint bands correlated
lected from a powdered sample in transmission mode. In fact, very high-quality with the most
spectra
characteristic vibrational modes of the jadeite are detectable, due to detector saturation,
while the presence of an extraneous compound such as resin, wax, or oil can be easily
highlighted. Since antiquity, the application of oil or waxes has been well-known to
preserve porous gemstone materials, including jades. Since the 1980s, the impregnation
Appl. Sci. 2022, 12, 7168 19 of 30

can be acquired by this method, though unfortunately this procedure shows some lim-
its in cultural heritage or gemology studies. These limits can be partially bypassed: in
recent decades, several accessories and/or modules have been developed to solve the
Figure 8. Reference
problems IR absorption
correlated spectrapreparations
to the sample’s of several Green
(i.e.,Stones samples,
integration re-plotted
spheres, from RRUFF:
Attenuated Total
Jadeite
Reflectance—ATR, etc.). All of these accessories are mandatory in gemological andDiopside
N. R050220-1 [143], Actinolite N. R040063-1 [144], Pumpellyite N. R070130-1 [153], cultural
N. R040009-1
heritage [152], Antigorite
applications. N. R070228-1
As discussed [147],
above, and Quartz
using N. R040031-1
this set-up, the FTIR[154]. Powder samples
characterization can
in KBr pellets, transmission mode. Spectra elaboration by Origin 2020 software.
also be performed without any sample preparation on opaque materials, being extremely
useful for poly-phases and uneven samples such as Green Stones. Unfortunately, although
On the other hand, the special affinities of the IR source with organic compounds
very useful, micro-FTIR is not a portable system.
make FTIR spectroscopy particular suitable to identify jade impregnation by organic
On the other hand, the special affinities of the IR source with organic compounds make
substances treatments (Figure 9) [70,155,156]. As reported by Fritsch [156], it is interesting
FTIR spectroscopy particular suitable to identify jade impregnation by organic substances
to note that in this modality, none of the fingerprint bands correlated with the most
treatments (Figure 9) [70,155,156]. As reported by Fritsch [156], it is interesting to note
characteristic vibrational modes of the jadeite are detectable, due to detector saturation,
that in this modality, none of the fingerprint bands correlated with the most characteristic
while
vibrational modes ofofthe
the presence anjadeite
extraneous compound
are detectable, duesuch as resin,
to detector wax, or while
saturation, oil can
thebepresence
easily
highlighted. Since compound
of an extraneous antiquity, the
suchapplication of oil
as resin, wax, or or
oilwaxes
can behas been
easily well-known
highlighted. to
Since
preserve porous gemstone materials, including jades. Since the 1980s, the
antiquity, the application of oil or waxes has been well-known to preserve porous gemstoneimpregnation
treatment
materials,using artificial
including epoxy
jades. resins
Since the has been
1980s, developed
the and quick
impregnation diffused,
treatment usingdue to its
artificial
higher durability.
epoxy resins has been developed and quick diffused, due to its higher durability.

Figure 9. IR absorption spectra of two Jadeite samples: jadeite with traces of surface waxing or
oiling, which can be typically correlated with polishing and cutting operation, is reported in red [156],
while the black line characterizes jadeite impregnated with epoxy resin [155,156]. The range between
2500 and 3300 cm−1 is the most suitable for organic compound impregnation treatments detection,
due to the strong absorptions correlated with the CH stretching vibrational modes [155,156]. Spectra
have been acquired by Frontier FTIR spectroscope, PerkinElmer, equipped with Harrick reflection
sphere, and analyzed with Spectrum Software. Data: M. Musa, GECI.

In Green Stones modern trade, the so-called “bleaching” treatment applied especially
on jadeite-jade is very common. Using this two-step treatment, less attractive brownish-
grayish jadeite can become whiter, by virtue of removing impurities (causing the brown
and gray colors) by a chemical attack process, followed by a deep polymeric (epoxy resins)
impregnation [155–157]. This procedure originates the “type B” jade [84].
Although this treatment is not common in cultural heritage or archaeological samples,
substances such as oil, wax, and other materials may be used by conservators to protect the
surface of an object instead of the previously used varnishes [55]. Therefore, care must be
taken to determine if it is a treatment or only a conservation measure of the gems [85]. For
Appl. Sci. 2022, 12, 7168 20 of 30

all these reasons, when analyzing Green Stones, taking into account current treatments can
complete the characterization of the samples.
Thus, Raman and FTIR spectroscopies can be considered as complementary techniques.

4.5. The Chromophores Study and the UV-Vis/NIR Spectroscopy Application

A UV-Vis/NIR analysis is suitable for Green Stones to distinguish between natural
color or treated color (Figure 10). Indeed, bleaching and dyeing treatments for modern
jade materials are relatively common [84]. In particular, the dyeing procedure, usually
subsequent to the “bleaching” and impregnation treatment, is a treatment able to increase
the jade colors (in this case, the green is discussed, but the treatment is not limited to
it), due to the addition of artificial pigments [158,159]. In gemology, the terms jade-C,
when it is only dyed, and jade-B + C, when it is impregnated and dyed, are commonly
accepted [84]. As per the polymer impregnation treatment discussed above, the detection
of artificial or enhanced colorations for green jadeite can be evaluated for authenticity. In
Figure 10, two reference absorption spectra of natural green jadeite and dyed green jadeite
are reported, (a) and (b), respectively. In parallel, the spectra acquired by a gemological
handheld spectroscope on the same materials have been reported below the corresponding
Appl. Sci. 2022, 12, 7168 23 of 32
UV-Vis Spectra (Figure 10c,d). The visible range can be considered diagnostic due to the
presence of the Cr3+ characteristic absorptions at about 633, 657, and 692 nm corresponding
to the jadeite-jadeabsorption
A, naturally green,with
correlated or the broad
nickel absorptions
chromophore between
is visible in the600 and
range 700 nm
between 600for
and
dyed green jadeite (jade B + C).
800 nm [106], as an asymmetric band centered at about 645 nm.

Figure 10. (a,b,e,f)Figure

UV-Vis/NIR
10. (a,b,e,f)and (c,d) gemological
UV-Vis/NIR handheldhandheld
and (c,d) gemological spectroscope spectra
spectroscope of Green
spectra of Green
Stones. Spectra acquired by UV-Vis/NIR spectrophotometer Lambda 950, PerkinElmer, equipped
Stones. Spectra acquired by UV-Vis/NIR spectrophotometer Lambda 950, PerkinElmer, equipped
with integration sphere, Spectrum Software. The two “handheld” spectra (c,d) have been reported
with integration sphere,
flippedSpectrum
to highlightSoftware. Theintwo
the similarities “handheld”
the band absorptionspectra (c,d) havetobeen
in correspondence reported
the top spectra. In
flipped to highlightparticular, (a) Natural
the similarities Imperial
in the band Green Jadeite-Jade
absorption A, the sharp absorption
in correspondence at about
to the 633, 657, In
top spectra. and
692 nm, correlated with Cr3+, should be noted; (b) Treated Jadeite-Jade B + C, note the broadening
particular, (a) Natural Imperial Green Jadeite-Jade A, the sharp absorption at about 633, 657, and
of the bands corresponding to orange and red visible ranges (photos and spectra: M. Musa,
692 nm, correlated with Cr3+ , should
gemological handheld bespectroscope
noted; (b) images:
TreatedL.Jadeite-Jade B +(e)
Greggio, GECI.); C,Dyed
noteGreen
the broadening of
chalcedony (Jade
imitation),
the bands corresponding it is interesting
to orange and red to observe
visible the absorptions
ranges (photos and in the same areas
spectra: of the gemological
M. Musa, natural Cr3+ but
showing characteristic broader bands, especially about 710 nm. These impregnations and modern
handheld spectroscope images: L. Greggio, GECI.); (e) Dyed Green chalcedony (Jade imitation), it is
dyeing treatments are performed using chromium-rich pigments; (f) Natural chrysoprase color is
interesting to observe
duethe
to absorptions
nickel-associated in the sameasareas
minerals, shown of by
thethenatural Cr3+ but
characteristic showingspectrum,
UV-Vis/NIR characteristic
with the
absorption centered at about 645 nm. (Data
broader bands, especially about 710 nm. These impregnations and modernand photos: M. Musa, GIG).
dyeing treatments are
performed using chromium-rich pigments; (f) Natural chrysoprase color is due to nickel-associated
Thus, UV-Vis/NIR spectroscopy alone, or combined with gemological handheld
minerals, as shown by the characteristic
spectroscopy UV-Vis/NIR
(if applicable), spectrum,
is a suitable with the
technique absorption
to verify centered
the origin of theatcolors
aboutin
645 nm. (Data and photos:
gemstone M.materials
Musa, GIG).and is particularly useful in determining the source of color for Green
Stones samples.

4.6. Fluorescence Imaging

A diffused and very useful analytical technique for gemstone analysis consists of
fluorescence observation. By the Wood lamp, alternative UVLW and UVSW are applied
to excite the sample and the eventual fluorescence in the visible range can be directly
Appl. Sci. 2022, 12, 7168 21 of 30

Because of Green Stones massive and frequently natural porous textures, dyeing
treatments are very common in the trade, not only for the jades but also applied to other
gemstone materials, such as the chalcedony. By applying UV-Vis/NIR spectroscopy, as
reported in Figure 10e, the identification of the Cr-rich artificial pigment results is less
evident than the jadeite dyeing example. Still, it can be diagnosed because of the broader
absorptions of the band at about 710 nm. Consequently, the visible range is not enough
and must be expanded through the NIR. In spite of this being easily possible by UV-
Vis/NIR digital spectrophotometers (whether benchtop or optical fibers portable system),
the gemological handheld spectroscope does not allow the analysis beyond the visible range
(400–700 nm). Moreover, the digital spectrophotometers are obviously more sensitive than
the handheld gemological spectroscope. In the case of dyeing suspects, a deep OM study is
mandatory: frequently, the dyed samples show characteristic colors concentrations along
the fractures [84,158,160]. Similarly, the analysis of chrysoprase with natural color shows a
diagnostic UV-Vis/NIR spectrum (Figure 10f), where the broad absorption correlated with
nickel chromophore is visible in the range between 600 and 800 nm [106], as an asymmetric
band centered at about 645 nm.
Thus, UV-Vis/NIR spectroscopy alone, or combined with gemological handheld
spectroscopy (if applicable), is a suitable technique to verify the origin of the colors in
gemstone materials and is particularly useful in determining the source of color for Green
Stones samples.

4.6. Fluorescence Imaging

A diffused and very useful analytical technique for gemstone analysis consists of
fluorescence observation. By the Wood lamp, alternative UVLW and UVSW are applied to
excite the sample and the eventual fluorescence in the visible range can be directly observed
or detected by digital systems. For what concerns the application on Green Stones, which
usually show no or only faint fluorescence, this technique can reveal interesting information
regarding the homogeneity of the sample or, eventually, surface treatments. An example
of this is the chalky bluish white strong fluorescence at short wavelength of polished
jadeite, treated with a new generation of polymer coating (not classical epoxy resins). This
fluorescence is not consistent with the natural fluorescence behavior of jadeite, that is,
none to faint white fluorescence at LW and none at SW (Table 2). In this case, Zhang [161]
reported the unusual case of 10 low-quality jades cabochon samples obtained from the
Guangzhou gem market. The samples showed a surface coating more similar to a film
rather than a classic impregnation, identified by the authors as an organic polymeric coating.
In particular, when examined with the DiamondViewTM , the coating fluoresced slightly
blue with alternating brighter spots. Moreover, by this technique, the areas of the sample
covered by the coating versus the areas where the coating had been removed were clearly
evident, strongly assisting the author in the diagnosis.
It must be noted that occasionally surface coatings and/or impregnation substances
can be applied for the maintenance of cultural heritage samples [162,163]. In fact, coatings
are normally applied to gem materials to counterfeit or improve luster and, in some cases,
provide a degree of stability [161,164,165].
For all these reasons, fluorescence imaging can be considered a complementary tech-
nique to the OM study.
The Wood lamp is a typical portable instrument and, of course, it does not require any
sample preparation.

4.7. Chemical Characterization: Elemental Analyses

The final information discussed in the present review consists of the chemistry and
relative analytical techniques.
For the chemical analyses of Green Stones, note the general chemical formula discussed
previously in Table 3. The chemical analysis is not so significant for the phase identification,
which can be easily carried out by other analytical techniques as previously discussed. On
Appl. Sci. 2022, 12, 7168 22 of 30

the other hand, elemental analysis is a deeper and complementary investigation, focusing
on the origin of the color (natural or due to treatment), to be combined with UV-Vis/NIR
information and which is extremely useful for geographic origin determination. This last
factor is a very delicate discussion point, because the origin determination can be made
not on the basis of the main elements common to all gemstones belonging to the same
mineral phases but on trace elements quantification. Another factor which complicates the
analysis interpretation is that Green Stones are typically composed of mineral associations,
as previously discussed. Moreover, due to their characteristic genetic processes, involving
metamorphic alterations, differences can be detected in the chemical traces of samples com-
ing from different points of the same veins. To bypass this issue, or at least collect reliable
information for origin identification, a systematic source characterization is beneficial.
In this scenario, the first choice for elemental analysis is the ED-XRF technique, due to
its non-destructive characteristics and the availability of the portable system, as previously
discussed [78,79]. For example, Delgado Robles et al. [166] described the application of
a portable XRF system (PXRF) for in situ analyses at the Palenque site museum. The
goal of the paper was the characterization (performed with a multidisciplinary approach)
of the green objects belonging to the Palenque Mayan royal burial. PXRF was helpful
in tracking the origin of the minerals constituting the analyzed samples, by taking into
consideration their elemental compositions, calculated from semiquantitative analyses.
In fact, on the basis of the samples’ chemical traces ratios, compared with references
materials analyzed in the same conditions, two different sources can be identified for the
samples’ origin: Montagua and Verapaz. Unfortunately, a set of standards of referent
materials/stones are not always available. Al Kindi [90] reported the study of several
neolithic nephrite axes, discovered in Dhofar governorate (Sultanate of Oman), where
the elemental characterization was performed by ED-XRF. In this second case, the data
obtained for the samples have been compared by a semi-quantitative method, with the
data obtained in one sample collected from the nephrite veins of Lawdar District (Yemen).
Despite reporting a good correlation between the nephrite axes compositions and the
reference (not only for the ratios of the main constituting elements, but also concerning
zinc and potassium traces, probably correlated to secondary minerals), the relationship
between the western Yemen mine and the coastal and interior Dhofar site has been only
hypothesized. Anyhow, the data acquired allowed the foundations to be laid in relation to
interpreting the framework of long-distance exchanges in the area, which can be expanded
by further studies.
Regarding the elemental composition, two other techniques can be considered and
combined in a multidisciplinary approach with standard petrographic analyses: SEM-EDS
and LA-ICP-MS. With the first one, a deep study of the morphology and textures combined
with chemical information at high magnification can be performed.
Considering the second technique, a spot quantitative chemical analysis is possible. It
is interesting to note that with LA-ICP-MS, not only the heavier but also the lighter elements
can be detected and quantified [20,81,82,167]. Both techniques can supply very important
information, complementary to the ones obtained by ED-XRF. The recent (2021) paper
of Zhang et al. [168] can be considered as a good example of LA-ICP-MS’s potentiality
for Green Stones origin determination. In fact, the authors reported the crucial origin
discussion and determination of Sujiacun serpentines samples that were obtained for trace
elements and rare earth elements (REE) using this technique.
Unfortunately, these two techniques are not portable and cannot be applied to all Green
Stones gemstones and cultural heritage samples, due to sample preparation necessities
and micro-destructive applications, respectively. For example, Manrique-Ortega et al. [169]
reported during their study, for a jadeite characterization analytical dissertation for SEM-
EDS analyses, that a 60 µm thick polished section was prepared from each specimen. In
other cases, SEM-EDS analyses can be performed without sample preparation but with
several limitations. Liu [126] reported the use of a variable pressure system to avoid the
metal coating on jade materials. The chemical information in this case can be interpreted
Appl. Sci. 2022, 12, 7168 23 of 30

only as semi-quantitative. Moreover, limitations correlated with the dimensions of the

sample fittable in the SEM camera must also be considered [170].
Similar dimensions problems must also be considered for LA-ICP-MS; nevertheless,
Golitko [171] discussed the advantages and limitations of an open-cell system applicable for
samples with huge dimensions. Another application problem, as previously discussed (see
Section 3.4) is related to the ablation spot dimensions, from which the materials are extracted
for the analysis. Basically, the laser spot size and mass resolution need to be adjusted to
produce signals of comparable intensities for standards and samples. For example, Martin
et al. [172], in their study of boron and lithium isotopic distribution in different mineral
phases, such as mica, pyroxenes, and serpentines, modulated ablation laser spots between
5 and 175 µm. Of course, the cited bigger dimensions are not compatible with cultural
heritage applications, while they can be applied without problems on reference samples
for mine characterization. Generally, when characterizing archaeological and gemstone
samples, 30 to 40 µm are reported for ideal ablation crater dimensions and each sample is
usually from three to five spots [171,173,174]. Typically, ablation sampling spots cannot be
applied to all archaeological samples, objets d’art, museum samples, etc.

5. Conclusions
On the basis of the information discussed, for the identification and characterization
Appl. Sci. 2022, 12, 7168 26 of 3
of Green Stones, it is possible to consider the application of multidisciplinary analytical
protocols (Figure 11).

Figure 11. A summary of the

Figure 11. multidisciplinary
A summary analytical approach
of the multidisciplinary applicable
analytical to the
approach identification
applicable to the of
identificatio
of Green Stones and the characterization
Green Stones and the characterization process. process.

Afterunavoidable
After a deep and a deep andstudy unavoidable studygemological
by the basic by the basic gemological
test, including test,
fluo- includin
rescence, plusfluorescence,
a deep OM plus a deep OM
observation, observation,
the sample must the sample must be
be analyzed byanalyzed by spectroscop
spectroscopic
techniques. micro-Raman
techniques. micro-Raman spectroscopyspectroscopy
is the best toolis the bestphase
for the tool for the phase identification
identification. Al-
Although identifying samples by FTIR spectroscopy is possible, the
though identifying samples by FTIR spectroscopy is possible, the application of this second application of th
second technique should be considered as complementary, especially
technique should be considered as complementary, especially when it is necessary to when it is necessar
to increase related
increase the information the information relatedeventually
to treatments, to treatments, eventually
applied to the applied
sample.to the sample.
Four complementary techniques may be considered
Four complementary techniques may be considered regarding the elemental regarding the elementa
composi-
tion: the ED-XRF for a quick, easy, and “bulk” (with the previously discussed acceptation) discusse
composition: the ED-XRF for a quick, easy, and “bulk” (with the previously
acceptation)
chemical analysis; chemical
then a deeper analysis; then
investigation a deeperthe
combining investigation
gemologicalcombining
handheldthe spec-gemologica
troscope and UV-VIS/NIR spectrophotometer information. Using this combination, theUsing th
handheld spectroscope and UV-VIS/NIR spectrophotometer information.
combination, the sample chemistry can be investigated and detailed informatio
regarding the chromophore groups and/or transition metals becomes available, even if i
traces, based on selective absorptions. The SEM-EDS technique and/or LA-ICP-MS ca
then be used to investigate more deeply the relationship between the chemistry an
morphology/texture of the sample and eventually identify lighter and/or traces element
Appl. Sci. 2022, 12, 7168 24 of 30

sample chemistry can be investigated and detailed information regarding the chromophore
groups and/or transition metals becomes available, even if in traces, based on selective
absorptions. The SEM-EDS technique and/or LA-ICP-MS can then be used to investigate
more deeply the relationship between the chemistry and morphology/texture of the sample
and eventually identify lighter and/or traces elements, not detectable by ED-XRF.
For these reasons, Green Stones are a good example to underline the importance of a
multidisciplinary approach in cultural heritage studies.

Funding: This research received no external funding.

Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The author would like to thank the Special Issue Editors and the Applied Science
Editors for assistance in enhancing the quality of the present paper, as well as the reviewers for their
kind and precious work. The GIG (Gulf Institute of Gemology, Muscat, Sultanate of Oman) and all
of its team is gratefully acknowledged for analytical support. Special thanks also to Lisa Greggio
for her support, availability, and knowledge of Green Stones, developed during our collaboration in
recent years.
Conflicts of Interest: The author declares no conflict of interest.

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