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Journal of Asian Earth Sciences

journal homepage: www.elsevier.com/locate/jseaes

Review

Application of laser Raman micro-analyses to Earth and planetary materials

I-Ming Choua,⁎, Alian Wangb

a CAS Key Laboratory for Experimental Study Under Deep-sea Extreme Conditions, Institute of Deep-sea Science and Engineering, Chinese Academy of Sciences, Sanya,Hainan 572000, Chinab Department of Earth and Planetary Sciences and McDonnell Center for Space Sciences, Washington University, St. Louis, MO 63130, USA

A R T I C L E I N F O

Keywords:Raman spectroscopyEarth and planetary materialsQuantitative analysisPetrogenesis and crustal evolutionRaman mappingPortable Raman systems

A B S T R A C T

Raman spectroscopy contributed greatly in the past 30 years or so for the advances of our understanding of Earthand planetary materials and their associated geological processes. After a brief introduction of the history andbasic theory of Raman spectroscopy, the advantages and disadvantages of this spectroscopic analysis methodwere listed, and examples were given when appropriate. For its applications to the analyses of Earth materials,which include minerals and organic materials, silicate glasses and melts, aqueous solutions, and gases and H2O-gas systems, previous works were discussed and cited. This was followed by a review on “Applications of Ramanspectroscopic studies of minerals and fluids to petrogenesis and crustal evolution”, in which several P-T diagramswere given to show metamorphic evolution of ultra-high pressure units, as well as a schematic cross section ofthe Earth’s outer shells showing recycling of crustal materials in different tectonic regimes.

For its applications to the analyses of planetary materials, which include lunar samples, Martian meteoritesand other extraterrestrial materials, a brief history on the starting and development of Raman spectroscopytechnique was given. We then discussed Raman “point-counting” and “quantitative chemical analysis” methodsdeveloped for obtaining quantitative information on mineral proportions and mineral chemistry in planetarysurface explorations, respectively.

Finally, new developments and future works, which include quantitative analyses, Raman mapping, portableRaman systems, and Raman effects (Resonance Raman Spectroscopy, CARS, SERS), and their associated appli-cations, were discussed.

1. Introduction

Raman spectroscopy provides sensitive photonic information ofmatter at the molecular level in many fields with growing applications,including those concerning Earth and planetary materials. This reviewprovides an overview of its advances and applications, especially thoserelated to Earth and planetary materials. Advances and applicationsachieved before 2012 were summarized in fourteen chapters of thebook “Raman Spectroscopy applied to Earth Sciences and CulturalHeritage” (Dubessy et al., 2012). These chapters were based on thelectures given in the 12th European Mineralogical Union “school” heldat University de Lorraine (Nancy, France) from June 14 to 16, 2012,immediately after the 10th International GeoRaman Conference. Theachievements reached after 2012 were reviewed by Nafie (2013, 2014,2015, 2016). The essential contributions presented in the 11th Inter-national GeoRaman Conference, held at Washington University in St.Louis, USA in June 2014, were summarized in a special volume ofJournal of Raman Spectroscopy (JRS; vol. 46, 2015). Those presented inthe 12th International GeoRaman Conference, held at Novosibirsk,

Russia in June 2016, will be summarized in a special volume of JRS,while some of the accepted papers are already available online.

In addition to the general review of Raman spectroscopy and itsapplications to Earth and planetary materials, emphases of this revieware given to the following items. (1) Quantitative analyses of gases andaqueous solutions, especially for those samples in optical cells at var-ious pressures (P) and temperatures (T); (2) Raman mapping; (3) pet-rogenesis and crustal evolution; and (4) planetary materials, whichwere barely discussed in the book of Dubessy et al. (2012).

2. History, basic theory, and characteristics of laser Raman micro-analyses

2.1. History

“Raman effect”, which explains that wavelength of light changeswhen it is passed through a transparent medium, whether solid, liquid,or gaseous. This effect was predicted theoretically by Smekal (1923)and later proofed experimentally by Raman and Krishnan (1928). His

http://dx.doi.org/10.1016/j.jseaes.2017.06.032Received 8 April 2017; Received in revised form 29 June 2017; Accepted 30 June 2017

⁎ Corresponding author.E-mail address: [email protected] (I.-M. Chou).

Journal of Asian Earth Sciences 145 (2017) 309–333

Available online 04 July 20171367-9120/ © 2017 Elsevier Ltd. All rights reserved.

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ground-breaking work in the field of light scattering, results fromRaman effect, earned Sir Chandrashekhara Venkata Raman (Fig. 1) the1930 Nobel Prize for Physics. However, because Raman signals are veryweak, Raman spectroscopic studies of pure components were verylimited (e.g., Herzberg, 1945). Evolution of Raman instrumentation andincrease of its use have been linked intimately with technological ad-vances of the different components, especially the lasers, which becameavailable in the 1960s and made it possible to provide high irradianceonto the sample to enhance Raman signals (Adar, 2001; Dubessy et al.,2012).

2.2. Basic theory and Raman spectrometer

In a typical Raman scattering measurement, visible light, favorablyfrom a laser source, passes through the solid, liquid or gaseous sample,as shown in Fig. 2 using magnesite crystal as an example (Gillet et al.,1998). About 10−3 of the incoming light is scattered by the crystalatoms, and most of the scattered light exits at the same wavelength(elastic Rayleigh scattering). While about 10−6 of the light interactinelastically with the sample, inducing transitions between vibrationalstates, so that the scattered light contains components at a differentenergy level from that of the incoming radiation (inelastic Ramanscattering) (Long, 1977; McMillan and Hofmeister, 1988; Gillet et al.,1998; Rull, 2012). The energy difference between the incoming lightand the inelastically scattered light corresponds to the energy of thevibrational transition. The inelastically scattered light is analyzed witha spectrometer (to be discussed below), and the obtained Ramanspectrum consists of peaks shifted in energy from the incoming Ray-leigh line (Figs. 2 and 3). The positions of the Raman peaks relative tothe Rayleigh line provide the frequencies of Raman-active vibration,such as those for magnesite (Figs. 2 and 3). In general, the most sym-metric modes give rise to strong Raman peaks, such as the ʋ1 peak

shown in Fig. 3, because they induce the largest change in bond po-larizability (Long, 1977; McMillan, 1985; McMillan and Hofmeister,1988; Gillet et al., 1998).

Fig. 4 is a schematic diagram of a modern Raman spectrometer. Avisible light or UV or IR from a laser source is delivered through a lens and afilter. The light is then reflected by a mirror and a holographic notch filter(function like a mirror in this path) and focused onto the sample through amicroscope objective lens. The backscattered light from the sample is col-lected by the same objective and passed through the same notch filter,which now filters out the dominating Rayleigh component and transmitsthe Raman shifted wavelengths. The Raman scattered light is transported tothe spectrometer, and the beam is deflected by a prism on to the diffractiongrating, which separates the beam into its constituent wavelengths. Theprism deflects the dispersed light through a lens on to a CCD detector,which converts the distribution of light intensity as the function of wave-length to a digital signal to produce a two-dimensional plot of spectral in-tensity vs wavenumber position (Raman shift from laser wavelength, incm−1), a Raman spectrum as shown in Fig. 3.

2.3. Characteristics of laser Raman micro-analyses

2.3.1. Advantages of laser Raman spectroscopyCompare to other analytical tools for Earth and planetary materials,

Raman spectroscopy has the following advantages:

(1) It provides positive identification of solids (including Raman-activeminerals and glasses) and fluids (including melts, aqueous solu-tions, liquids, and gases). For example, typical Raman spectra of S-bearing species that may exist in a planetary sulfur cycle are shownin Fig. 5, and Raman spectra of 10 hydrated and an anhydrous Mg-sulfates are shown in Fig. 6.

Levitan et al. (2009) demonstrated that Raman spectroscopy waseffective in distinguishing among the serpentine-group minerals chry-sotile, antigorite, and lizardite, which have similar XRD patterns (theirFig. 2). Fig. 7 shows the Raman spectra for antigorite and chrysotilefrom their sample 07EM-2 collected from the mine waste at VermontAsbestos Group mine, Belvidere Mountain, Vermont. Peaks that werefound to be particularly diagnostic were the antigorite bands at 1045,686, and 377 cm−1 and the chrysotile bands at 1104, 693, and 388cm−1 (Kloprogge et al., 1999; Rinaudo et al., 2003).

(2) It is non-destructive, except those samples react with laser irra-diation. However, this destructive effect can be minimized by usingrelatively low laser power (e.g., Burlet and Vanbrabant, 2015).

(3) There is essentially no sample preparation needed. Unlike SEMtechnique, analyses of samples beneath the thin section surface ispossible, particularly for solid and fluid inclusions in minerals(Frezzotti et al., 2012).

(4) It is easy to operate and efficient; normally each measurement justtakes a few seconds.

(5) It has excellent spatial resolution (few microns) and therefore, it isan ideal tool for identifying tiny minerals in mineral inclusions andfor the study of fluid or melt inclusions in minerals (Frezzotti et al.,2012). It can also be used to do two- or three-dimensional mapping(see Section 5.2).

The laser spot is calculated with the equation:

=Diameter 1.22(laser wavelength/NA), (1)

where NA is numerical aperture of the objective lens. However, thecollection of Raman signal can be controlled by tuning the size ofconfocal pinhole. The depth of laser excitation depends on laser wa-velength and sample optical property:

=Depth laser wavelength/4πk, (2)

Fig. 1. Bust of Chandrasekhara Venkata Raman, which is placed in the garden of BirlaIndustrial & Technological Museum. (https://en.wikipedia.org/wiki/C._V._Raman).

I.-M. Chou, A. Wang Journal of Asian Earth Sciences 145 (2017) 309–333

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where π = 3.1416, and k is extinction coefficient, which is correlatedwith the sample itself and the laser wavelength. For silicon, laser line633 nm can penetrate around micron while laser line 325 nm can onlypenetrate few nanometers. Again if the sample is transparent for thelaser used, the depth can be controlled by confocal pinhole size. With50 µm confocal pinhole size of LabRam, HR Evolution UV system, thedepth will be 2 µm for UV laser line.

In the study of Korsakov et al. (2010), the excitation laser beam wasfocused on a spheroidal spot of approximately 1 μm × 1 μm × 5 μmusing an Olympus 100× objective lens (NA = 0.95) with a confocalarrangement allowing detection of signals exclusively from the inclu-sions in minerals. They were able to record a 2D Raman map with a stepsize of 1 μm, as shown in their Fig. 12.

(6) It is convenient for in situ measurements in high-pressure opticalcells, such as diamond-anvil cell and fused silica capillary cell. Forexample, Fig. 8 shows Raman spectra collected in situ by Jahn andSchmidt (2010) in a hydrothermal diamond-anvil cell at isochoric(1.33 g/cm3) P-T conditions in the υ1-SO4

2− region of the 2.2 m

Fig. 2. The Raman scattering process. In this example, theincident beam of an Ar laser (λ = 514.5 nm correspondingto an energy (in wavenumber units) of 19435.6 cm−1) isscattered by a magnesite single crystal. 1/103 of the incidentbeam intensity is elastically scattered at the same energyand corresponds to Rayleigh scattering. 1/106 of the in-cident light is scattered inelastically and is accompanied bypositive (anti-Stokes scattering) or negative (Stokes scat-tering) energy changes. These energy modifications resultfrom transitions in vibrational energies related to the in-teraction of the incident beam with crystal vibrations. Theintense peak observed on the Stokes side at an energy of18,431 cm−1 corresponds to a Stokes shift of 1094 cm−1. Asimilar peaks with less intensity is observed on at 20529.6cm−1, with an anti-Stokes shift of −1094 cm−1 The Stokespeaks are more intense than the anti-stokes peaks becausethe ground state is more populated than higher vibrationalstates. Taken from Fig. 2 of Gillet et al. (1998).

Fig. 3. Raman spectrum of magnesite. Unpolarized spectrum recorded with a micro-Raman spectrometer. The atomic motions involved in the Raman-active vibrations areoutlined. The symmetric mode ν1 gives rise to strong Raman peak because the associatedvibration induces a large change in bond polarizability. Taken from Fig. 3 of Gillet et al.(1998).


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MgSO4 solution. Fig. 9 shows the aqueous species of contact ionpair (CIP) and triple ion (TI) become dominant at elevated pres-sures and temperatures. Similarly, these aqueous species were alsoobserved in a fused silica capillary cell in the sulfate-rich fluidphase after the liquid-liquid phase separation of 19.36 mass%

MgSO4 solution along liquid-vapor curve at elevated temperatures(Figs. 10 and 11; Wang et al., 2013a).

(7) It is possible to provide quantitative analyses for both minerals (seeSection 4.3) and fluids (Chou, 2012 and Section 5.1) after calibra-tion of Raman system. Raman spectroscopy can therefore, be ap-plied to the studies of solubilities of gas hydrates in water (Lu et al.,2008), diffusion of gases in aqueous solutions (Lu et al., 2006,2013), and reaction kinetics (Pan et al., 2009; Ou et al., 2016). Ouet al. (2015b) re-evaluated the effects of temperature and NaClconcentration on quantitative Raman spectroscopic measurementsof dissolved CH4 in NaCl aqueous solutions, and applied their re-sults to fluid inclusion analysis. Fig. 12 is a schematic diagramshowing a sample of NaCl homogeneous solution containing CH4

prepared for sample observation, and a collection of Raman spectraof dissolved methane (υ1, symmetric stretching vibrational mode ofCH4) and water (υH2O, OH stretching band of water). Fig. 13 showstheir experimental results on the dependence of PAR/mCH4 ontemperature (T) and NaCl concentration (mNaCl) for dissolved CH4

in NaCl homogeneous solutions with different mCH4 at variouspressures, where PAR is peak area ratio (see Fig. 12).

2.3.2. Disadvantages of laser Raman spectroscopyUnfortunately, there are some disadvantages associated with Raman

spectroscopic analyses, and they are:

(1) No sufficient and systematic Raman data on minerals are available,even though some data are available online (e.g., http://rruff.info/;http://www.dst.unisi.it/geofluids/raman/spectrum_frame.htm)and a catalog of about 140 spectra of minerals, which are of interestin fluid inclusion research, was presented in Tables 2–7 of Frezzottiet al. (2012).

(2) The Raman spectra of solids are not easy to interpret, because boththe symmetry of the molecules and the symmetry of crystal latticehave to be considered.

(3) Raman peak intensities are strongly dependent on the crystal-lographic orientation due to different polarizations of the light indifferent directions.

(4) Direct quantitative information on the composition of the mineral islimited (see Section 4.3).

(5) Some minerals are strongly fluorescent. Fluorescence is the mostserious problem associated with conventional Raman spectroscopy(Panczer et al., 2012). The intensity of fluorescence is at least twoor three orders of magnitude higher than that of Raman scattering,and therefore, for samples exhibit even weak luminescence in therecorded spectral range, the Raman scattering will partially or

Fig. 4. A schematic diagram of a modern Raman spectrometer. Courtesy of Maria Perraki with modifications.

Fig. 5. Typical Raman spectra of S-bearing species that may exist in a planetary sulfurcycle. Taken from Fig. 1 of Wang et al. (2006).


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completely overlapped, as shown in Fig. 14. In their review ofRaman and fluorescence, Panczer et al. (2012) discussed the prin-ciple of Raman and fluorescence, different ways to reject fluores-cence, and taking advantage of simultaneous Raman and lumines-cence measurements, such as the determination of pressure byusing the wavelength-shift of ruby R1 fluorescence line (Piermariniet al., 1975; Mao et al., 1978, 1986). Twenty-eight previous pub-lications were cited.

(6) Some minerals are not or weakly Raman active (e.g., fluorite, ha-lite). However, cryogenic Raman spectroscopic method has beensuccessfully used to identify the presence of NaCl and CaCl2 com-ponents in fluid inclusions (Samson and Walker, 2000; Chu et al.,2016), because hydrates of these and many other salts are Ramanactive (Frezzotti et al., 2012).

3. Laser Raman micro-analyses to Earth materials

3.1. Minerals and organic materials

Raman spectroscopy has been conveniently used to collect vibra-tional spectra of minerals. It is readily coupled with diamond anvil cellsor other types of optical cells with high-temperature furnaces (e.g.,HDAC) or laser heating methods to yield information on minerals dy-namics over the entire range of P-T conditions of the deep interior of theEarth and other planets (Gillet et al., 1998 and references therein;Schmidt and Chou, 2012). As mentioned earlier in Section 2, a total ofabout 140 spectra of minerals, which were of interest in fluid inclusionresearch, was listed in Tables 2–7 of Frezzotti et al. (2012) as a sup-plement to the web Raman mineral library available at: http://rruff.info/. They also reported Raman spectral images of daughter mineraldistribution in an aqueous fluid inclusion (Fig. 15).

Reynard et al. (2012) reviewed previous experimental setups andmethods for obtaining Raman spectra at high pressure and temperaturefor the study of Earth’s mantle and planetary minerals. They gave ex-amples of the use of Raman shifts for calibration of pressure determi-nations in experimental setups and in natural rocks. They also describedthe use of Raman spectroscopy in the study of in situ phase transitions at

Fig. 6. Raman spectra of 10 hydrated and an an-hydrous Mg-sulfates in the spectral regions of SO4

fundamental vibrational modes (right) and waterOH stretching vibrational modes (left). ∗,Tentative spectral assignment; peak of kieserite asimpurity. Taken from Figs. 2 and 3 of Wang et al.(2006).

Fig. 7. Raman spectra of two mineral grains from sample 07EM-2 collected from the minewaste at Vermont Asbestos Group mine, Belvidere Mountain, Vermont. Peaks are labeledby wavenumbers. These spectra were used to establish the presence of two minerals withsimilar composition and XRD peaks. Data were compared with published patterns(Rinaudo et al., 2003), RRUFF database patterns (Downs, 2006), and those of referencesamples. Taken from Fig. 3 of Levitan et al. (2009).


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high pressure or high temperature and gave examples of first-order andhigher-order transitions in major Earth forming minerals or analogues.They finally concluded that further development of Raman spectro-scopy will rely not only on increasing the sensitivity of Raman

spectrometer, but also on systematic coupling of vibrational studieswith first-principles calculations for identification of vibrational fre-quencies with molecular species, which were reviewed by Caracas andBobocioiu (2012).

On their theoretical modeling of Raman spectra, Caracas andBobocioiu (2012) discussed the theoretical basis of lattice dynamics inthe density-functional perturbation theory formalism. Then theyshowed how to compute the Raman spectra, with both peak positionand intensity. They then introduced the WURM project, a freely avail-able web-based repository of computed physical properties for mi-nerals, focused around Raman spectra. The computed data are pre-sented on http://wurm.info website. Fig. 16 shows the comparisonbetween their computed Raman spectrum of topaz with measured onefrom RRUFF. The agreement in peak positions is very good, consideringthe presence of H2O impurity in the measured topaz.

Raman spectroscopy has also been used extensively to characterizeorganic materials in the Earth and planetary sciences. Beyssac andLazzeri (2012) reviewed the theoretical knowledge of the Ramanspectrum of graphitic carbon with emphasis on the defect-activatedpeaks, which they discussed their attributions and spectral properties.They proposed a reference protocol for proper analysis for graphiticcarbons. At the very end, they reviewed the applications of this tech-nique along the themes of graphitization during metamorphism, fluid-rock interactions, fossils and trace of life in the geological record, andcosmochemistry and Earth-surface processes. For example, Ramanspectra of natural graphitic carbons with increasing metamorphic grade(from bottom to top) are shown in Fig. 17 (their Fig. 8).

The application of graphitic carbons as traces of life in the geolo-gical record has been greatly enhanced recently by the use of Ramanmapping method. For example, Dodd et al. (2017) interpreted putativefossilized microorganisms, that are at least 3770 million and possibly4280 million years old in ferruginous sedimentary rocks, as seafloor-hydrothermal vent-related precipitates. This interpretation was mainlybased on their results derived from Raman spectra of carbonaceousmaterial and minerals from maps of granules from jaspers of the Bi-wabik and Nuvvuagittuq supracrustal belt (NSB) in Quebec, Canada(Fig. 18).

In their review of Raman spectroscopy in biogeology and astro-biology, Daniel and Edwards (2012) surveyed the historical bases forastrobiology and the development of Raman spectroscopy techniquesfor the interrogation of relevant biogeological materials.

Because the Coherent anti-Stokes Raman Scattering (CARS) signal ismany orders of magnitude more intense than the conventional Ramansignal, it has been applied for real-time imaging (Daniel and Edwards,2012). For example, the cytochrome distribution in hyphal tip cells ofSchizophyllum commune was visualized using resonance Raman map-ping and CARS microscopy (Fig. 19). (Taken from Fig. 2 of Walter et al.,2010; modified Fig. 2 of Daniel and Edwards, 2012).

Other Raman spectroscopic studies of organic materials were re-ported previously by Chou et al. (2008), Chou (2012), Chou and Pan(2014), and Xu and Chou (2017).

3.2. Silicate glasses and melts

In their review of Raman spectroscopy of silicate glasses and meltsin geological systems, Rossano and Mysen (2012) briefly introduced theglassy state and the relationship between glass and melt. They thendescribed the main steps of Raman spectral analysis, discussing themain approaches and the extent to which this method is quantitative.They finally gave examples of the applications of Raman spectroscopyin the field of Earth science. They demonstrated that Raman spectro-scopy of glasses and melts is a powerful technique for providing in-formation about the silicate network connectivity, other tetrahedrallycoordinated cations (e.g., aluminum, phosphorus, ferric iron, and tita-nium), and speciation of volatile compounds in glasses and melts. Intheir perspectives, in order to interpret complex Raman spectra, they

Fig. 8. Raman spectra in the υ1-SO42− region of the 2.2 m MgSO4 solution at isochoric

(1.33 g/cm3) P-T conditions. Spectra are shifted along the intensity axis for clarity. Thethree dashed lines indicate the shift of Raman bands near 980, 995, and 1005 cm−1. Thenarrow line at 1044 cm−1 is a plasma line from the Ar+ laser. Modified from Fig. 9 ofJahn and Schmidt (2010).

Fig. 9. Relative integrated intensities of components of the υ1-SO42− Raman band region

in 2.2 m MgSO4 solution along the 1.33 g/cm3 isochore shown in (a) for Raman bandsnear 980, 995, and 1005 cm−1 as a function of temperature and pressure. The blackcircles and line are for the species [SO4

2− + SIP (MgH2O(SO4)) + 2SIP (MgH2OH2O(SO4))], the red triangles and line are for the CIP [(MgSO4)], and the blue squares and lineare for the TI [(Mg2SO4

2+)aq]. Modified from Fig. 10 of Jahn and Schmidt (2010).


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suggested the coupling of Raman spectroscopy with other experimentalmethods, such as X-ray absorption spectroscopy, and multiple quantumMAS NMR or cross-polarized MAS NMR methods (e.g., Roiland et al.,2011). They also suggested that calculation of Raman spectra mighthelp to interpret the experimental spectra. Even though they did notcite Mibe et al. (2008), this suggestion was demonstrated in Table 1 andFigs. 3–5 of Mibe et al. (2008). They showed the possible candidates ofchemical species in aqueous fluid, hydrous silicate melt, and super-critical fluid in the system KAlSi3O8-H2O obtained through the ab initiomolecular orbital (MO) calculations using the Gaussian 03 program(Frisch et al., 2004).

3.3. Aqueous solutions

Main Raman vibrations (in cm−1) of 12 major aqueous speciesobserved in fluid inclusions were listed in Table 1 of Frezzotti et al.(2012). Garcia-Baonza et al. (2012) reviewed previous studies onRaman spectroscopy of water and aqueous solution. They discussedhydrogen bonding and water structure, structural vs. spectroscopicmodels of liquid water, temperature and pressure effects on Ramanspectrum of H2O (including liquid water, various forms of ice, amor-phous ices LDA and HAD, low-density water, and high-density water),and aqueous solutions and hydrophobic effects. They also discussedapplications of Raman spectroscopy to the study of fluid inclusions.Because Raman microprobes have spatial resolution in accordance withthe size of fluid inclusions, micro-Raman spectroscopy was consideredto be a main microanalytical technique. They cited several previousreviews, including Dubessy et al. (1989), Burke (2001), and Frezzottiet al. (2012). Mantle fluids from xenolith samples have been studied byFrezzotti and her co-workers (Frezzotti and Peccerillo, 2007; Frezzottiet al., 2009; Frezzotti and Ferrando, 2015). For example, Fig. 20 showsRaman spectra from aqueous fluid inclusions associated with diamondsfrom Lago di Cignana metasediments. Garcia-Baonza et al. (2012) alsocited several studies of polyatomic ionic compounds, such as SO4

2−,HSO4

−, HCO3−, and CO3

2−.Raman spectroscopic studies of aqueous solutions were further ex-

tended to elevated pressures and temperatures by using optical cellswith fused silica (Chou, 2012) and diamond windows (Schmidt andChou, 2012). Chou (2012) described two types of optical cells withfused silica windows, in combination with heating cooling stages, forthe study of aqueous solutions, and other geological fluids, at tem-peratures up to 600 °C and pressures up to 100 MPa. Schmidt and Chou(2012) reviewed the status of the hydrothermal diamond-anvil cell(HDAC), which was specifically designed for experiments on systemswith aqueous fluids to temperatures up to ∼1000 °C and pressures upto a few GPa to tens of GPa, and its applications. These optical cells

permit study of molecules and molecular ions of light elements in fluidsat elevated P and T, including complexation, speciation, phase transi-tions, solubility, and kinetics. For examples, in the optical cells withfused silica windows, Wang et al. (2013a) observed liquid-liquid phaseseparation in MgSO4 solutions and determined polymers in the MgSO4-rich liquid (see Section 2.3(6) above). Similar observations were de-scribed by Wang et al. (2016a) for ZnSO4 solutions, Wang et al. (2016b)for aqueous uranyl solutions, and Wang et al. (2017) for LiSO4 solutions(with either H2O or D2O). In addition, Dargent et al. (2011) collectedRaman spectra related to uranyl chloride complexes in LiCl solution at25 and 200 °C at vapor-saturation pressures (see also Fig. 21 of Chou,2012). In the HDAC, Mibe et al. (2008) examined complexation in H2O+ KAlSi3O8 fluids and associated phase diagram to 900 °C and 2.3 GPa,Mibe et al. (2009) determined speciation of aqueous zinc(II) bromidesolutions to 500 °C and 900 MPa, Zotov and Keppler (2002) studiedsilica speciation and solubility of quartz in H2O to 900 °C and 1.4 GPa.In addition, Lin et al. (2004) determined the melting curve of ice VII to630 °C and 22 GPa, and Schmidt and Watenphul (2010) studied am-monium in aqueous fluids to 600 °C and 1.3 GPa and described silicaand N speciation, silica solubility of Qz-Ky-Kfs/Ms in H2O ± NH4Cl,and kinetics of Kfs to Ms reaction.

3.4. Gases and H2O-gas systems

Main Raman vibrations (in cm−1) of 14 major gaseous species ob-served in fluid inclusions, including those shown in Fig. 21, were listedin Table 1 of Frezzotti et al. (2012). Garcia-Baonza et al. (2012) re-viewed the status of Raman spectroscopic studies of gases and H2O-gassystems. For the Raman spectroscopy of gases, they discussed Ramanscattering cross-section of gases and gas-phase composition calibration,detection limit of gas analysis by Raman spectroscopy, variation ofRaman scattering cross-section with temperature, and density (orpressure). For the H2O-gas systems, they reviewed studies of gas hy-drates and H2O-gas mixture at high temperatures and pressures. Otherexamples related to quantitative analysis and diffusion kinetics weregiven in Section 2.3(7).

3.5. Applications of Raman spectroscopic studies of minerals and fluids topetrogenesis and crustal evolution

Because several of the advantages of Raman spectroscopy mentionedearlier (Section 2.3.), especially its ability to positively identify minerals andfluids, excellent spatial resolution, minimal required sample preparation,and non-destructive nature, its applications in the studies of minerals andfluids have contributed greatly for our understanding as well as formulatingthe models of petrogenesis and crustal evolution. For example, positive

Fig. 10. Photographs showing the phase separa-tion in 19.36 mass% MgSO4 solution along theliquid-vapor curve at elevated temperatures. (a)Homogeneous MgSO4 solution at 250 °C; (b) Atabout 259.5 °C, the original aqueous solution wasseparated into two separated fluid phases, F1 andF2; (c and d) During subsequent heating, thedroplets of scattered F1 tended to coalesce. Takenfrom Fig. 1 of Wang et al. (2013a).


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identifications of high-pressure minerals (e.g., stishovite, TiO2 with the α-PbO2 structure, diamond, coesite, aragonite etc.), as inclusions in mineralsoriginated from lower crust and upper mantle, allow us to assign the originof the rocks to specific P-T regimes (Fig. 22) and/or estimate the depths ofsubduction of crustal materials. In addition, in combination with textural aswell as other pieces of geochemical and geophysical evidence, positiveidentification through Raman spectroscopy of their transformations to re-spective polymorph(s), allow us to formulate the nature of exhumation andthe recycling of the crustal materials (Figs. 23 and 24; Fig. 10 of Perraki andFaryad, 2014). As stated by Ernst and Liou (2008) that metamorphic

conditions required by P-T stabilities of these minerals reflect the operationof plate tectonics, lithospheric subduction, and inferred mantle convection.Therefore, integration of phase equilibria with dynamic tectonic processeshas illuminated the petrogenesis and evolution of the crust (Ernst and Liou,2008; Dobrzhinetskaya and Faryad, 2011; Liou et al., 2014; Frezzotti andFerrando, 2015). It should be emphasized that without the basic foundationestablished mainly based on Raman spectroscopic analyses of minerals andfluids, it is not possible to formulate these big pictures on petrogenesis andevolution of the crust.

Fig. 11. (a) The Raman spectra of the separated F1 and F2 (see Fig. 11) for a solution containing 5.67 mass% MgSO4 at 300 °C. It shows that F1 was characterized by a prominent υ1(SO4

2−) band, whereas this band was very weak in F2, indicating MgSO4(aq) was almost totally concentrated in F1. The weak band at ∼1050 cm−1 was assigned to HSO4− and the peak

at 2992.52 cm−1 is a calibration line from a He–Ne laser (632.817 nm relative to the Nd-YAG line at 532.06 nm); (b) The υ1 (SO42−) band for 5.67 mass% MgSO4 solution (100 and 225

°C) and the unmixed fluid F1(270–350 °C). (c and d) are the fitting results for υ1 (SO42−) bands of homogeneous MgSO4 solution below 267.4 °C, and the unmixed fluid F1 above 267.4 °C,

respectively. The three υ1 (SO42−) bands near 980, 992, and 1003 cm−1 correspond to hydrated SO4

2−, contact ion pair (CIP), and triple ion pair (TI), respectively. The fourth υ1 (SO42−)

band near 1020 cm−1 was only detected in F1 and was considered to be associated with the polymer(s) of MgSO4 (star). Taken from Fig. 3 of Wang et al. (2013a).


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4. Laser Raman Micro-analyses to planetary materials

4.1. Early applications of Raman spectroscopy on extraterrestrial materials

The first set of studies using laser Raman spectroscopy on lunarsamples from Apollo missions 11 and 12 (July and November of 1969)was published in 1971 (White et al., 1971). They were then continuedlater for the samples from Apollo 14–17 missions (Jan. 1971–Dec.1972) (Perry et al., 1972; Estep et al., 1972; Fabel et al., 1972; Sweetet al., 1973; White, 1975; Perry and Lownders, 1975,). Due to the lowefficiency of Raman instrument used during that era (Spex 1401 doublemonochromator Raman system, about f/8), only limited mineralogyinformation was obtained when compared with the yield from mid-Infrared spectroscopy (Perry et al., 1972; Estep et al., 1972). Never-theless, these studies were able to identify the major mineral species oflunar basalt, olivine, pyroxene, feldspar, as well as silicate glasses.Notice in these studies, macroscopic Raman measurements with 90° or180° scattering geometries were used, with sampling sizes in a range ofmm to sub-mm. At that time, Raman spectroscopy was not a commontechnique to study geological samples, mainly because Raman scat-tering is an intrinsic weak physical process.

Actually, it was the birth of micro-probe Raman technology in 1975(Delhaye and Dhamelincourt, 1975; Rosasco et al., 1975) that truly enabledthe geological application of laser Raman spectroscopy. The combination ofa single-mode (longitude and transverse) highly coherent laser with thetraditional optical microscopic technology generated a laser beam that canbe condensed to a spot size at nearly diffraction limit (∼1 µm in diameterfor visible wavelength). This laser beam can be agilely directed to a desiredspot or a depth in a geological sample, as a molecular probe, to makeidentification and characterization of minerals, as well as liquid and gasesspecies in fluid inclusions of minerals. This pinpoint analytic capability isespecially suitable for as is geological samples (rocks and soils)， which areoften heterogeneous in texture, chemically zoned, and sometimes pollutedwith fluorescence. A micro-probe Raman analysis with ∼1 µm spatial re-solution (an order of magnitude higher than that of Mid-IR microscopy, alsoat diffraction limit) was soon demonstrated to be a superior tool for the

laboratory study of meteorites and interstellar dust particles in 1980s’(Heymann, 1987, 1990; Heymann et al., 1988; Makjanić et al., 1988;Wopenka, 1987). At that time, the collecting efficiency of a Raman systemwas still low because of the use of double- and triple-monochromators (f/8)in commercial Raman instrumentation. This often corresponds with theordinary size of a laboratory Raman system to be several cubic meters involume, and using gaseous (Ar or Kr) laser units of>1 m in length asexcitation source. As a result, a good S/N Raman measurement requirestens’ minutes to>10 h (overnight) to accomplish (Wang et al., 1988).

4.2. The starting of planetary Raman spectroscopy

The birth of Planetary Raman Spectroscopy was catalyzed by thesecond revolution in Raman instrumentation. This revolution was fa-cilitated by three great technological advancements in laser, detector,and optics. They are, the diode pumped solid state (DPSS) laser anddiode lasers (to replace gaseous lasers), the 2-D array Charge CoupleDevice (CCD) (to replace single channel photo counting device, i.e.,photomultiplier), and the high performance (OD > 5) filter (to replacethe pre-monochromator) and volume transmissive holographic dif-fractive grating. A group of commercial mid-sized benchtop Ramansystems came into the market in 1990s’, by comprehensive fusion ofthese new technologies. Some benchtop Raman units have exceedinglygood Raman signal strength. For example, on the basis of a filters-plus-monochromator configuration and using a transmissive grating withtransmissive optical configuration, extremely small f-number (f/1.8)system was achieved (KOSI HoloSpec), which has a Raman photonscollection efficiency 38 times of that of state-of-art 1980s’ Ramansystem (Jobin-Yvon U1000 and S3000). The high Raman signalthroughput plus CCD multichannel detection enabled a good S/NRaman spectrum from a mineral grain in a rock (e.g., Martian meteoriteZagami) to be obtained in 5 s (Wang et al., 1999). Furthermore, thesmaller instrument size and simpler optics made the new generationRaman systems to be very robust, demonstrated by their usage for in-dustrial process-control in real-world factories (Tedesco et al., 1993).

The high scientific performance of new generation of Raman

Fig. 12. A schematic diagram showing a sample of NaCl homogeneous solution containing CH4 prepared for sample observation, and a collection of Raman spectra of dissolved methane(υ1, symmetric stretching vibrational mode of CH4) and water (υH2O, OH stretching band of water). The dashed lines between ∼2873 and ∼2937 cm−1 and between 2650 and 3900cm−1 show the base lines for calculating the Raman peak intensities of CH4 and water, respectively (modified from Ou et al. (2015a)). ACH4, AH2O and ACH4+ H2O are the peak area of CH4,peak area of H2O and the sum of them, respectively; HCH4 and HH2O are the peak heights of CH4 and H2O, respectively; PAR is the peak area ratio of CH4 to H2O. Taken from Fig. 1 of Ouet al. (2015b).


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spectrometers, their robust applications in industrial world, and thedemonstrated durability of key components in harsh environments, allindicated a feasibility of developing small, robust, and high qualityRaman system as scientific payload for planetary missions. This ideamotivated two proposals (Wang et al., 1995a, b; Wdowiak et al., 1995)to US NASA on developing flight Raman system for in situ mineralidentification in future landed missions to planetary surfaces, the Moonand Mars.

During the same period, US NASA’s planetary explorations ad-vanced to a new stage. In addition to common fly-by or orbitering aplanet for remote sensing of the planetary surface materials, the en-gineering capability of surface landing and roving on a foreign planetwas demonstrated, i.e., through 1997 US-NASA Pathfinder mission toMars and the sojourner rover. Planetary science entered a new era. Inorder to build the fundamental understanding on the surface materialsof a planet, chemical composition and molecular forms are two types ofkey information. Naturally, the science instrument for obtaining mo-lecular information would be molecular spectroscopy, i.e., mid-IR

spectroscopy and Raman spectroscopy, both have spectra of finger-print-type for the majority of planetary mineral species.

A thermal emission IR spectrometer (TES) was developed and in-stalled on Mars Global Surveyor (MGS, launched November 1996) fororbital remote sensing based on mid-IR absorption features of minerals.A miniaturized version MiniTES was under development for stand-offsensing from rover or lander. However, when making a mid-IR mea-surement of a rock or a soil, as mineral mixtures, we would see ex-tensive spectral band overlap (Fig. 25b). Therefore, spectral deconvo-lution is an absolutely necessity, which brought in uncertainties inmineral identifications and quantifications. In comparison, the Ramanpeaks of major basaltic minerals (olivine, pyroxene and feldspar) havemuch narrow peak widths, and are well separated in the spectra ofmixtures, thus direct and unambiguous mineral phase identificationscan be achieved from raw spectra of lunar soil samples. Fig. 25a showsa Raman spectrum of a lunar soil (and the spectra from individualmineral grains), in comparison with Fig. 25b of TES spectra andFig. 25d of VIS-NIR spectra of major basaltic mineral phases, and

Fig. 13. Dependence of PAR/mCH4 on temperature (T) and NaCl concentration (mNaCl) for dissolved CH4 in NaCl homogeneous solutions with different mCH4 at various pressures.Taken from Fig. 3 of Ou et al. (2015b).


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Fig. 25c of Mössbauer spectrum of a lunar soil). Considering the rocksand soils (i.e., mineral mixtures) are the most common targets in anyrobotic planetary surface explorations, Raman spectral characters ofminerals have made Planetary Raman Spectroscopy very attractive pathfor in situ, definitive, mineralogical characterization of planetary sur-face materials. This is the reason behind the supports of US NASA (andlater European Space Agency, ESA) for flight Raman instrument de-velopments and related instrumental sciences.

4.3. Two important methods in planetary Raman spectroscopy developedusing lunar samples

At the beginning, Raman spectroscopic study of Apollo lunar sam-ples was merely the technical demonstrations (Wang et al., 1995b;Korotev et al., 1998). Those studies intended to show, for example, howwell the Raman peaks of four major lunar minerals (olivine, pyroxene,feldspar, and ilmenite) and silicate glass were separated from each

other in a spectrum taken directly (in situ) on as is lunar soils or lunarrock chips.

A methodology development on Raman point-counting (Haskinet al., 1997) occurred later, following the development of a flightRaman system (Wang et al., 1998), with a goal to quantify the pro-portions of mineral phases in a rock or soil from an in situ Ramananalysis during a planetary surface mission. We would wish that therelative Raman peak intensities of each mineral could be related in astraightforward way to the fraction of that mineral within the volume ofthe target excited by the laser beam (aka, Raman sampled volume). Thisis not possible because, in addition to Raman cross section of a mineral(relevant to the excitation laser wavelength) as the major factor de-termining its Raman peak intensity, there are too many uncontrollableand uncorrectable factors affecting Raman peak intensities. For ex-ample, mineral grain size and surface roughness; the crystal orientationof a mineral grain against the laser beam polarization; the long-rangechemical and structural ordering in its crystal lattice; mineral trans-parency to both incident beam and scattered Raman photons; density ofgrain boundaries in Raman sampled volume; reflection and refractionassociated with grain boundaries; etc. All these properties of the targetare unknown (thus uncorrectable) during a Raman analysis at planetarysurface. Furthermore, to use a broad beam Raman system to analyzerandomly oriented fine-grain mixture (i.e., soil or prepared rockpowder) will end up with the Raman spectra with poor S/N. This isbecause, similar to those shown by the first set of Raman studies oflunar samples in 1970s’ (Perry et al., 1972; Estep et al., 1972; Fabelet al., 1972; Sweet et al., 1973), the intrinsic weakness of Raman signalsfrom minerals.

The Raman point counting (Haskin et al., 1997), i.e., the quantifi-cation of mineral proportions in rocks and soils by Raman spectroscopyon a planetary surface is best done by taking many spectra using highlycondensed laser beam from different locations on a target, with eachspectrum yielding peaks from only one or two minerals. The propor-tions of each mineral in the rock or soil can then be determined fromthe fraction of the spectra that contain its peaks, in analogy with thestandard petrographic technique of point counting. Raman pointcounting measurements were conducted on realistic planetary mate-rials, including lunar samples 14161, 7062, 15273, and 7039 (Haskinet al., 1997), Martian meteorites Zagami (Wang et al., 1999) andEETA79001 (Wang et al., 2004a), and four lunar soil samples 14163,

Fig. 14. Schematic representation of identical Raman spectra of the same compoundrecorded at different laser excitation and of the broad intense structured fluorescence(note that the horizontal scale is in wavelength; taken from Fig. 2 of Panczer et al.(2012)).

Fig. 15. Raman spectral images of daughter mi-neral distribution in an aqueous fluid inclusion.(a) Optical microphotograph of analyzed fluidinclusion in garnet from ultra-high pressure me-tamorphic rocks, western Italian Alps, reportingthe grid of single point measurements. (b) Singlepoint Raman spectrum showing the selected wa-venumber intervals for daughter mineral mapping[diamond (red), rutile (blue), and calcite (green)].(c–e) Spectral images of diamond, rutile, andcalcite distribution in the fluid inclusion. Thecolor intensity of the mineral phases (from blackto white) reflects the increase in the intensity ofthe Raman band. The aqueous fluid in the inclu-sion has no significant Raman signal in the in-vestigated region, and thus does not interfere withthe measurement; modified from Frezzotti et al.(2011). Taken from Fig. 4 of Frezzotti et al., 2012.


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15271, 67511, and 71501 (Ling et al., 2011). Quantitative informationon mineral proportions in these materials was extracted, and it wascompared with similar information obtained from other methodologies(Wang et al., 1999; Ling et al., 2011).

The second method developed for Planetary Raman Spectroscopyinvolves the extraction of mineral chemistry information. Since basalt isthe most common rock type in terrestrial planet (Moon, Mars, Venus,Mercury, etc.), and the major basaltic silicates (olivine, pyroxene,feldspar) are all solid solutions of their chemical endmembers. Theexact chemistry of a type of mineral grains in a rock, i.e. the range of Fovalues (=Mg/(Mg + Fe)) in olivine, the range of Mg# values (=Mg/(Mg + Fe + Ca)) in pyroxene, the K, Na, Ca contents in feldspar, canprovide information on crystallization history of that rock, as well asthe effects of secondary processes they experienced. However, during arealistic planetary surface exploration mission, the co-registration ofanalysis spots by different science payloads (e.g., that for chemicalcomposition and that for mineralogy) is not always easy to achieve, dueto many mission constrains and the difference in field of view (FOV) ofpayloads. Because of this reason, it is desirable to extract mineralchemistry information, in addition to mineralogy, from the Ramanmeasurements on each sampled spot of a target during the mission. Inan early Raman study of lunar samples (Perry et al., 1972), it had beennoticed that the major Raman peak position of some silicates shifts withcation ratio.

Using Apollo samples, Martian meteorites, and the mineral standardof terrestrial rocks, the calibration formulae for extracting Mg/(Mg+ Fe + Ca) and Ca/(Mg + Fe + Ca) cation ratios in quadrilateralpyroxene and for extracting Mg/(Mg + Fe) cation ratio in olivine werepublished in two papers (Wang et al., 2001a; Kuebler et al., 2006). Inthese publications, the cation ratios in pyroxene and olivine were basedon the Raman peak positions near ∼1000, ∼670, and ∼325 cm−1 forpyroxene and doublet in 820–860 cm−1 for olivine. The effect of Fe, Ti,Cr ratio change in the Raman spectra of Fe-Ti-Cr-oxides was studied(Wang et al., 2004b). The conclusion was that although they producerelatively weak Raman signals than oxyanionic minerals (silicates,carbonates, etc.), sufficient information can be extracted from theirspectra (especially the A1g peak position in 660–780 cm−1) to identifythe end-member minerals phases as well as some information aboutcompositional variations in solid solutions. Feldspar, being a morecomplicate type of silicates, has solid solutions in K-Na join (miscible athigh T), Na-Ca join, and K-Na-Ca ternary join and the changes instructural ordering caused by formation temperature. Because K, Na, Cacations locate in the large crystallographic sites quite far from

Fig. 16. Comparison between computed, in WURM (verticalbars), and measured, in RRUFF (continuous), Raman spectraof topaz, Al2SiO4F2. The agreement in peak positions be-tween WURM and RRUFF is very good. Slight peak anddifferences in intensity recorded at high frequency aremostly due to the presence of OH in the experiment, whilethe calculation are for water-free composition. Taken fromFig. 4 of Caracas and Bobocioiu (2012).

Fig. 17. Raman spectra of natural graphitic carbons with increasing metamorphic grade(bottom to top). All the samples come from the western Alps, including the SchistesLustrés and Dora Maira (Beyssac et al., 2002) and the Glarus area (Lahfid et al., 2010).The detailed comment on the evolution of the spectra may be found in Lahfid et al. (2010)and Beyssac et al. (2002). Indicative metamorphic facies and peak-metamorphic tem-perature are given. Taken from Fig. 8 of Beyssac and Lazzeri (2012).


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coordination oxygen in TO4 tetrahedra (T = Si, Al), it was found(Freeman et al., 2008) that the peak position of major Raman peak offeldspar (T-O vibrations in 500–520 cm−1) cannot be used to extractquantitative information regarding the cation compositions. This is si-milar to the cases of olivine and pyroxene. Instead, using a small Ramanspectra database of variety of feldspar plus careful visual inspection, tentypes of feldspar can be classified according to their structure, crystal-linity, and chemical composition solely based on their Raman spectra.The above sets of calibration formulae and classification criteria for

major basaltic mineral chemistry were used in later study of four lunarsoils 14163, 15271, 67511, and 71501 (Ling et al., 2011), and in thestudy of Martian meteorite EETA79001 (Wang et al., 2004b).

As an example, Fig. 26 shows that by identifying olivine and pyr-oxene grains in four Raman-point-counting scans on EETA79001 Mar-tian meteorite, and by calculating the Mg/(Mg + Fe) ratio of theseolivine and pyroxene grains from their Raman peak positions, the au-thors found three compositional groups of olivine and two of pyroxenethat may represent three stages of crystallization of EETA79001 rock.

Fig. 18. Granules from the Biwabik and NSB jaspers. (a) Cross-polar image of granules in Biwabik jasper. IF, iron formation. (b) Ramanmap of area shown with dotted outline in a. CM,carbonaceous material. (c) Cross-polar image of granule in the NSB. (d) Raman map of area shown with dotted outline in c. (e and f) Selected average Raman spectra of carbonaceousmaterial and minerals from maps. Taken from Fig. 4 of Dodd et al. (2017).

Fig. 19. (A) Representative Raman spectra of a hyphal tip cell of S. commune (microscopic picture is depicted in the inset) at the two different locations a1 and a2, the difference spectrum(a1–a2) and the cytochrome b reference spectrum. (B) Intensity distribution of the Raman band representing matrix content by the central peak position at 1652 (1) and cytochromemarker bands with the central peak position at 1573 (2), 1114 (3), 735 cm−1 (4). The relative cytochrome to matrix content is depicted by the relative intensity ratio of the bandscentered at 1573 and 1652 cm−1 (5) and the overlay of the microscopic picture and the relative intensity ratio of 1573–1652 cm1 (6). The plotted intensity distributions are smoothenedby the LabSpec software. Bar: 2 mm for B1–5 and 5 mm for B6. Taken from Fig. 2 of Walter et al. (2010); modified Fig. 2 of Daniel and Edwards (2012).


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Coarse, Mg-rich (∼Fo77) olivine xenocrysts [scan #2 in Fig. 26]formed before the crystallization of pyroxene (scan #1 in Fig. 26). Therims of these xenocrysts reacted with the more ferroan host basalt orimpact melt and attained equilibrium with the surrounding pyroxene.The second type of olivine [scan #3 in Fig. 26] (∼ Fo60) is in equili-brium with the bulk of the pyroxene in the rock. The third type ofolivine [scan #4 in Fig. 26] (∼Fo21] is ferroan and appears to haveformed sparingly from late-stage, residual magma, along with ferroanpyroxene [Mg/(Mg + Fe) ∼0.43, scan#4 in Fig. 26], phosphates, andopaque phases.

4.4. Raman studies of Martian meteorites

The peer-reviewed journal articles on Raman studies of Martianmeteorites occurred in 1990s’ and continue to publish until today, firstusing sophisticated micro-probe Raman spectrometers and recentlyusing Raman imaging technology. These studies can be classified into6–7 fields.

There are studies using the Raman molecular probe capability toreveal the full-blow mineralogy of a Martian meteorite (Cooney et al.,1999; Wang et al., 1999, 2004b; Beck et al., 2006; Steele et al., 2007;Walton et al., 2014). Much more studies combined that capability withthe Raman detection of crystal structural disorders to investigate theimpact-caused mineral amorphization, such as plagioclase to maskely-nite in meteorites (Fritz et al., 2005; Gillet et al., 2005). Furthermore,Raman spectroscopy was used to identify pressure induced structuraltransformations, such as quartz to stishovite and other polymorphous ofSiO2 (Aoudjehane et al., 2005; El Goresy et al., 2008, 2013). Otherexamples include olivine and pyroxene relevant phase transformations

(Van de Moortèle et al., 2007a,b; Bläβ et al., 2010; Imae and Ikeda,2010; Miyahara et al., 2011; Greshake et al., 2013; Baziotis et al., 2013;Walton, 2013), and recrystallization from plagioclase-melt (Wang andChen, 2006). Many new minerals formed by impact in Martian me-teorites. Raman spectroscopy was used to help the confirmation of theiroccurrences (Beck et al., 2004; Fritz and Greshake, 2009), including thetwo new minerals found recently in Tissint meteorite: Tissinite (a va-cancy-rich high-pressure clinopyroxene with a composition essentiallyequivalent to plagioclase) and Ahrensite (γ-Fe2SiO4) (Ma et al., 2015,2016).

Secondary mineral phases have always been an important part ofRaman investigations of Martian meteorites, especially after the findingof evidence of past aqueous activities on Mars by recent Mars ex-ploration rovers, Spirit, Opportunity, and Curiosity. The earliest findingwas an amphibole phase (kaersutite) in Zagami and LEW 88516(Mikouchi and Miyamoto, 2000), then Fe-rich hydrous phase of smec-tite family in NWA817 (Gillet et al., 2002), using Raman spectroscopy.Recently, the searching of secondary phases was concentrated inNakhlites type of Martian meteorite, in which iddingsite-like alterationzone and veins containing clays/salts were observed. Noguchi et al.(2009) first used micro-Raman spectroscopy, with synchrotron XRDand TEM, studied laihunite and jarosite in Yamato 00 nakhlites, andsuggested fluid-assisted high-T oxidation. Hallis et al. (2011), Hallis(2013) made extensive Raman studies on MIL03346 (and its paired rockchips) meteorite, including the iddingsite-like alteration veins, Fe-oxidealteration veins and Ca- and K,Fe-sulfate veins, suggested weakly acidicbrine responsible for some alterations, but posted a question on ter-restrial contamination while this meteorite residing at Miller Range of

Fig. 20. Raman spectra from aqueous fluid inclusions associated with diamonds fromLago di Cignana metasediments. Modified from Frezzotti et al. (2011). (a) Silica in so-lution within a fluid inclusion. The 773 cm−1 peak corresponds to the Si-O symmetricstretch of the Si(OH)4 monomer, and the peak at 1017 cm−1 to the deprotonatedmonomers [SiO(OH)3−, SiO2(OH)22−, and so on]. The aqueous fluid also contains SO4

2−,with Mg-calcite (MgCc) and quartz (Qtz). (b) HCO3

− and CO32− in solution within a fluid

inclusion, containing Qtz. Asterisks indicate host-garnet Raman bands. Taken fromFig. 13 of Frezzotti and Ferrando (2015).

Fig. 21. Raman spectra and relative wavenumbers of most common gaseous fluid speciesin fluid inclusions. Note that the hypothetical CO2 Raman band at 1340 cm−1 is reallytwo bands at 1285 and 1388 cm−1, see text of Frezzotti et al. (2012). Taken from Fig. 5 ofFrezzotti et al. (2012).


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Antarctica. Kuebler (2013) used EMPA and micro-Raman analysis onMIL03346, also identified laihunite, jarosite, Ca-sulfates, and stilpno-melane (with the later three being hydrous), then suggested acid al-teration followed by depositions from neutral solution. More recently,Ling and Wang (2015) used Raman imaging on a thin section ofMIL03346, thoroughly studied the spatial distributions of secondarymineral phases, and the spatial correlations among them as well as withprimary phases. This study revealed calcium sulfates with three hy-dration degrees, a series of K- and Na-jarosite solid solutions, and twogroups of hydrated species with low crystallinity in veins and mesos-tasis. They found that the most abundant Ca-sulfates are bassanite(CaSO4·1/2H2O) and γ-CaSO4 (with a same tube-like structure but no

H2O), while gypsum (CaSO4·2H2O) mainly found at the outer-edge ofmeteorite grain (Fig. 27a). These occurrences suggest the direct pre-cipitation of bassanite from CaeS-H2O brine at low water activity onMars, thus support the Martian origin of most Ca-sulfates in the veinsystem of this meteorite, with the remaining possibility that somebassanite rehydrated to gypsum near the surface of this meteorite in-duced by Antarctica melting ice. In addition, they found a full rangeand continuous solid solutions of K- and Na-jarosite with less amountsof endmembers (Fig. 27b), which implies mainly a precipitation at re-latively high temperature (∼140 °C). The excellent spatial correlations(Fig. 27c) between jarosite grains and the fine-grained low-crystallinityfeldspar and Fe-bearing phases (laihunite, Ti-magnetite, ferrihydrite,

Fig. 22. (A) P–T regimes at different scales assigned to various me-tamorphic types: (1) ultrahigh-P, (2) high-P, (3) low-P and (4) ‘‘for-bidden zone’’ and stabilities of coesite and diamond (modified afterLiou et al. (2004, 2009)). Path A and B represent P-T paths of small/thin UHP terranes and large/thick terranes, respectively (modifiedafter Kylander-Clark et al. (2012)). (B) P–T stabilities of additionalUHP index minerals including pseudomorphic stishovite, majoriticgarnet, high-P clinoenstatite and TiO2 II (α-PbO2 structured TiO2) areshown (modified from Fig. 1 of Liou et al. (2009) and Fig. 1 of Schertland O'Brien (2013)). Taken from Fig. 2 of Liou et al. (2014).

Fig. 23. P-T diagram showing metamorphic evolution of UHP unitsdiscussed in the text of Frezzotti and Ferrando (2015). P-T path for theLago di Cignana Unit is simplified from Groppo et al. (2009). P-T pathfor the Dora-Maria (Brossasco-Isasca Unit) is inferred combining datafrom different lithologies [whiteschist, marble, eclogite, calc-silicaterocks: Rubatto and Hermann (2001), Hermann (2003), Castelli et al.(2007), Ferrando et al. (2009)]. P-T path for quartzite and eclogitefrom South Sulu is simplified from Ferrando et al. (2005) and Frezzottiet al. (2007). P-T path for the high-T (dashed line) UHP zones ofDabie-Sulu is simplified from Zheng et al. (2011). The colored squareson the P-T paths represent the trapping conditions of the fluid inclu-sions reported in Table 1 of Frezzotti and Ferrando (2015). Thecompilation of melting reactions in mafic rocks (thick gray lines) andpelites (dashed gray lines) is revised after Schmidt and Poli (2003) andZheng et al. (2011). The gray-shaded zones representing the solidi forH2O-saturated crustal rocks and the phengite dehydration melting arefrom Bebout (2007, 2013). Mineral abbreviation after Whitney andEvans (2010) and Krbrz (1983). Taken from Fig. 11 of Frezzotti andFerrando, 2015.


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and rasvumite KFe2S3) indicates an apparent easy and short path forchemical alteration and ion-exchanges. Both evidences support the insitu formation (i.e., Martian origin) of these jarosites.

Another emphasis of Raman spectroscopic study of Martian me-teorites is the identification of the carbon/carbonaceous phases, theirspatial distribution and the spatial correlations with other minerals.Carbonates nodules (Cooney et al., 1999) were found in the matrix of

famous ALH84001, the oldest, unique, orthopyroxenite meteorite fromMars. The occurrence of carbon in this meteorite has been questionedsince claim of potential bio-signatures. The first report of graphite inALH84001 was published in American Mineralogists (Steele et al.,2012a), using confocal Raman imaging and TEM. It was found that thegraphite occurs as hollow spheres (nano-onions), filaments, and highlycrystalline particles in intimate association with magnetite in the

Fig. 24. A schematic cross section of the Earth’s outer shells showing recycling of crustal materials in different tectonic regimes (modified after Liou and Tsujimori (2013)). Taken fromFig. 1 of Liou et al. (2014).

Fig. 25. Raman spectra of silicates of lunar soil and mineral grains, compared with thermal emission Mid-IR spectra, Mössbauer spectrum, and Vis-NIR spectra of similar materials. Itdemonstrated that Raman peaks of major basaltic minerals have much narrow peak widths, and are well separated in the spectra of mixtures, thus direct and unambiguous mineral phaseidentifications can be achieved on the basis of raw spectra of mineral mixture (lunar soil).


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carbonate globules. The presence of graphite morphologies that formedat high temperatures indicates that ALH84001 carbonate globules un-derwent a transient heating possibly> 350 °C, thus supports its abioticorigin. On the other hand, this work suggests an inventory of reducedcarbon phases in Martian meteorites should be thoroughly studied. Afollow-up study published in Science magazine (Steele et al., 2012b)presented confocal Raman imaging data on 11 Martian meteorites,spanning about 4.2 billion years of Martian history. Ten of the

meteorites contain abiotic macromolecular carbon (MMC) phases de-tected in association with small oxide grains included within high-temperature minerals. Polycyclic aromatic hydrocarbons were detectedalong with MMC phases in Dar al Gani 476. This study implies thatprimary organic carbon is nearly ubiquitous in Martian basaltic rocks. Itformed through igneous, not biological, processes and was deliveredover most of Martian geologic history to the surface as recently as thelate Amazonian. It calls for cautions for the positive detection of

Fig. 26. Results of mineral phase ID and Mg/(Mg + Fe) ratios of olivine and pyroxene grains in four Raman-point-counting scans on Martian meteorite EETA79001 rock chips. Threecompositional groups of olivine and two of pyroxene were found that may represent three stages of crystallization of EETA79001 rock (Wang et al. (2004b)).

Fig. 27. Raman image of MIL03346 (Ling and Wang, 2015). (a) Spatial distribution of three Ca-sulfates in studied thin section Global distributions of secondary hydrated minerals in MIL03346,168. The most abundant Ca-sulfate is bassanite (CaSO4·1/2H2O) and γ-CaSO4 (with a same tube-like structure but no H2O), while gypsum (CaSO4·2H2O) mainly found at the outer-edge of meteorite grain. (b). Mineral chemistry of jarosites. A full range and continuous solid solutions of K- and Na-jarosite with less amounts of endmembers. (c) Spatial correlationsbetween Jarosite and Fe-bearing species.


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organics (especially PAHs) on Mars by later missions that may be de-tecting this abiotic reservoir. In 2013, MMC phases were detected in anewly found Martian meteorite, The Black Beauty, NWA7034 (Ageeet al., 2013). Karogen-like carbon was identified by micro-Ramanspectra (Lin et al., 2014) in another new Martian meteorite, Tissint,whose δ13C values are significantly lighter than those of Martian at-mospheric CO2 and carbonate. The authors suggested that this karogen-like carbon provided a tantalizing hint for a possible biotic process.

4.5. Raman studies of other extraterrestrial materials

We have to emphasize that using Raman spectroscopy to study stonymeteorites was started very early, right after the birth of micro-probeRaman technology (Michel-Levy and Lautie, 1981). The studied me-teorites cover all varieties, ordinary chondrite, carbonaceous chon-drites, achondrites, and Martian and lunar meteorites.

It is worth to mention that maturation of Raman imaging in-strumentation has greatly increased the overall science value of Ramanspectroscopy for meteorite study (Wang et al., 2015a). Raman spec-troscopy is not only a pinpoint probe to provide mineral identificationand mineral chemistry of individual species any more. The spatialdistribution in a meteorite entity and the spatial correlations among themineral grains in the meteorite can offer important information to an-swer the big questions. For example, it can be used to identify the bioticand abiotic origins of the carbon in Martian meteorites (Steele et al.,2012b), and the Martian or terrestrial origins of secondary phases in ameteorite collected in Antarctica (Ling and Wang, 2015).

Although we cannot cover all major studies of this area publishedduring past 40 years in this short section, some good papers in severaldifferent research fields are worth to mention. In the field of shock-induced mineral structural changes, Heymann (1990) described aRaman study of olivine in 37 heavily and moderately shocked ordinarychondrites, and a similar study was given by Miyamoto and Ohsumi(1995). In the field of carbonaceous materials, there was an extensivestudy using micro-Raman spectroscopy to characterize insoluble or-ganic matter in primitive meteorites by Busemann et al. (2007), andtwo papers using the maturity of carbon as a metamorphic tracer tostudy the petrologic type of chondrites (Bonal et al., 2006, 2007). Apaper by (Fries and Steele, 2008) reported the finding of GraphiteWhiskers (GW) in CV3 meteorites. The GW has a set of Raman spectralfeatures quite different from ordinary carbon phases, which might beindication of high-temperature processing relevant to young solarsystem and supernouvae. In the field of presolar grain study, Wopenkaet al. (2013) studied 103 presolar “graphite” grains in famous Murch-ison meteorite, which established a correlation between the Ramanspectral features (i.e. structural disorder of carbon) with both mor-phology and isotopic data that can be linked to different stellar sources.A newly published paper (Haenecour et al., 2016) used the character-istic Raman features (Fig. 28), with Auger and NanoSIMS, confirmedthe presolar origin of a unique grain, LAP-149, with the lowest 12C/13Cratio ever measured and a high 14N/15N ratio. The characters of thisgrain matched with a low-mass CO Nova ejecta, thus provided the firststrong evidence for graphite condensation in nova ejecta.

5. New developments and future works

5.1. Quantitative analyses and applications

The introduction of high-pressure optical cell (Chou et al., 2005),make reliable quantitative Raman spectroscopic analyses of gases andaqueous solutions possible without the need of cross-section informa-tion for the interested species. As described previously (Chou et al.,1990, and references therein; Chou and Burruss, 2002; Lu et al., 2006),for Raman active species a and b in a fluid phase, their relative con-centrations, C’s (e.g., mole or mol%), are related to their Raman peakareas, A’s, by the formula:

= =A /A (C /C )(σ /σ )(η /η ) (C /C )(F /F )a b a b a b a b a b a b (3)

where σ, η and F are the Raman scattering cross-section, instrumentalefficiency and Raman quantification factor, respectively. Since theRaman scattering cross-sections are related to the specific Raman activespecies and may be affected by molecular interactions, and instru-mental efficiency is varying with the instrumental setting, it is neces-sary to calibrate Raman quantification factor of the interested gas orsolute in water at a wide P–T range with the same instrumental settingfor new quantitative analyses. For example, the relationship betweenpeak-area ratio of methane and water and the dissolved methane con-centration in pure water at temperatures from 274.15 to 373.15 K wasestablished in Lu et al. (2006), as shown in Fig. 29 for 295.3 K. Asdemonstrated by Lu et al. (2006) that this relationship can be applied toobtain concentration of dissolved methane at any spot in the watersection in a capillary tube at any time after a known methane pressurewas applied to the water at specific temperature, and therefore diffu-sion coefficient of methane in water at that temperature can be ob-tained. This method has been applied to other systems, as discussed inChou (2012).

It should be emphasized that the calibrated Raman quantificationfactor (F) shown in Eq. (3), which combines Raman scattering cross-section (σ) and instrumental efficiency (η), can only be applied to thespecific “calibrated” Raman spectroscopic system. Fortunately, cali-bration standards of known composition or fluid density can be pre-pared in fused silica capillaries (Chou et al., 2008) as discussed in Chou(2012), and some of these standards are commercially available.Quantitative analyses of solid solutions in minerals were already dis-cussed in Section 4.3.

5.2. Raman mapping and applications

The newly developed Raman mapping technique not only replacedthe point-counting method (Haskin et al., 1997), described in Section4.3 for quantifying the proportions of mineral phases in a rock or soilfrom an in situ Raman analysis. It also provided detailed information formany geological processes, as discussed earlier in Section 3.1, andshown in Figs. 15, 18 and 19.

5.3. Portable Raman systems and applications

Making a google search on “portable Raman spectrometer”, one canget> 100,000 hits with some 500–600 images. This fact demonstrateshow popular the Portable Raman System becomes these days. Manyportable Raman systems are built to analyze man-made chemicals (purechemicals, pharmaceutical products, industry products, explosive, andeven food products), and were designed to be used in laboratories,manufactures, and airports. Some of them can measure materials invisible-light-transparent containers, such as glass bottles, plastic bagsetc.

However, a few portable Raman systems (e.g., DeltaMu RockHound™,http://www.labwrench.com/?equipment.view/equipmentNo/14461/DeltaNu/RockHound/) were built specifically for the application in geo-logical field, to characterize rocks and soils. Since this review paper em-phasizes on Raman application to Earth and planetary materials, we wouldnot dwell on overall portable Raman units in the current commercialmarket. Instead, we would present the lessons learned, based on the ac-cumulated experiences in Raman instrumentation for planetary surfaceexplorations (applicable for terrestrial geo-field as well) through past 20years, for the building of efficient portable GeoRaman system.

5.3.1. Lesson learned # 1 – definitive mineralogical and petrologiccharacterization is the goal

Needless to say that all targets in a field campaign, on Earth or on aplanetary surface, are mineral mixtures, i.e., rocks and soils formedthrough variety of geological processes. Some planetary explorations


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(e.g., missions to Mars) desire the detection of biomarkers, which (ifexist) might be at ppm-ppb level, it means> 99.99% components in thetargets of a geo-field to be minerals (some with glasses). Therefore, togenerate a comprehensive petrologic picture of the rocks and soils inthe field (through definitive mineralogy), with a purpose to understandtheir formation conditions and evolution history, is the central andindispensable task for a portable Geo-Raman system.

Rocks and soils in geo-field have complex physical textures, in-cluding differences in mineral grain size, petrographic configurations,veins, fractures, porous spaces, surface coatings, as well as clusters ofparticles (in soils). In addition, many natural rock-forming mineralsoccur as solid solutions of endmembers (i.e., Mg/(Mg + Fe) = 0–100 inolivine), and sometimes appear as chemical zoning. These textural de-tails and relevant mineralogical information will be lost when using aportable Raman unit with a large laser beam size for excitation. Forexample, the obtained Raman spectrum would contain peaks frommultiple mineral phases. In order to derive quantitative mineral pro-portions to support petrologic characterization of targeted rock (or soil)from such a spectrum, one will need to know not only the Raman crosssection of each mineral, but also other information. This includes mi-neral grain size, crystal orientation, chemical and structural ordering,mineral transparency to both incident laser beam and scattered Ramanphotons, reflection and refraction associated with grain boundaries.

The few later types of information are impossible to get in a roboticplanetary exploration (and hard to get in terrestrial geo-field).Therefore, for complete and detailed mineralogical and petrologiccharacterization of those targets, an in situ Raman system with tightlycondensed laser beam and line-scan capability (Raman point counting,Haskin et al., 1997, Section 4.3) would be a necessity.

On the other hand, if large xenocrysts, mineral fillings, or minerallayers in a cross-section are clearly visible during a field campaign,direct deployment of a hand-held Raman unit, even with large beamsize, can generate good information for mineral identification (Jehličkaet al., 2008).

Rocks and soils in geo-field have rough uneven surface. Unless asample preparation was made, a portable Raman unit needs to havelarge “Raman sampling depth” to tolerance the surface roughness ofthese samples, i.e. to collect Raman photons from above and beneaththe focus plane of its laser beam. Depends on the optical design and thecolor of targeting mineral, a portable Raman unit can have “Ramansampling depth” of a few mm to cm (Wang et al., 2003a, 2016c). Inother words, the confocal optical design of laboratory Raman systemwould not be suitable for such field applications.

Most soils, and some rocks, in terrestrial geo-field are mixed withbio-genetic species. The best example is clay minerals, which have ex-tremely fine grain sizes and have experienced extensive sedimentary

Fig. 28. Results from Raman spectroscopy (left diagram) and isotope study (right diagrams a and b) on presolar grain LAP-149 (Haenecour et al., 2016).


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processes, thus the input from biological processes was not avoidable.The bio-genetic species in terrestrial clays can generate extremely highfluorescence emission that often obscures the detection of their Ramansignals, which are ∼1010 times weaker. Note the clays (belong tophyllosilicate group, a type of median strength Raman scatterer) haveintrinsically very weak Raman signals due to their fine grain sizes (< 2µm in diameter) and frequently low crystallinity (Wang et al., 2015b).

Some basaltic rocks contain Rare Earth Elements (REE). When using785 nm as excitation line on basaltic rocks, an REE generated broadfluorescence band (850–890 nm) frequently appear in 1000–1500cm−1 Raman spectral range that obscures some Raman peaks of mi-nerals.

5.3.2. Lesson learned # 2 – the top priority of a portable Raman unit isRaman signal strength

Because Raman scattering is an intrinsically weak physical process,and the complexity of geology samples, the two great expansions ofgeological applications of laser Raman spectroscopy occurred only afterthe two instrumentation revolutions (Section 4.1) that tremendouslyincreased Raman signal strength in new Raman systems. In 1975′s, it wasfirst done by using a highly condensed laser beam to interrogate µm-sized sampling area and a microscopic objective (NA ≥ 0.95) to in-crease the Raman photon collectivity, by over 20 times, relative to amacroRaman system. In 1990′s, the second revolution was done byusing high quality laser-reject filters and single low f-number (f/1.4–1.8) spectrometer to reduce the overall loss of Raman photons inoptical path. The result of above instrumentation advances was thatRaman signals of unprepared geo-samples can be easily detected inseconds, which enabled the broad applications of Raman spectroscopyin terrestrial and planetary geology, petrology, mineralogy, gemology,archeology, etc.

Learning from above lessons, to strive for the highest Raman signalstrength should bear the highest priority in developing a portable Ramansystem for geo-field deployment (terrestrial or planetary). Among allaspects, the selection of laser wavelength and the f-number of Ramancollecting optical path are the two most critical parameters to ensurehigh Raman signal strength, for any field-Raman spectrometer.

Theoretically, Raman signal strength is proportional to 1/λ4 (whereλ is excitation laser wavelength), thus it seems the shorter wavelength(deep UV), the more Raman photons. Nevertheless, this rule applies

only to free molecule, i.e. in dilute gases. In real geological world withsolid rock and soil as samples, the penetration depth of a laser beaminto the sample is a decisive factor. The penetration depth determinesthe number of molecules in a sample that to be excited by laser photons,thus directly related to Raman photon generation. The longer laserwavelength has a deeper penetration depth. In this sense, a UV laserwould excite less molecules in a solid sample. In addition, high-energyUV photon (E = hc/λ) would burn the thin layer of sampled solid moreeasily.

The laser wavelength selection also control the overall efficiency ofa Raman system, which is a combination of the efficiencies of all opticalcomponents (filters, lens, mirrors), and the quantum efficiency (QE) ofdetectors. Ordinary CCD detectors are suitable for Raman system usingvisible laser lines with high efficiency (back-illuminated, QE ∼90–95%in 500–700 nm). When selecting UV or IR laser lines for excitation, UV-enhanced CCD detector or IR detector will have to be used, both havinglower QE.

For a portable Raman system targeted broad scope geo-field appli-cations, a clever choice would be to select the most commonly usedlaser line by geo-Raman application community. Fig. 30 shows a his-togram on the laser lines used in over 400 studies, published as ab-stracts during seven International GeoRaman Conferences (2004–2016,only abstracts with listed laser line were counted). Obviously, the greenexcitation (514.5 nm and 532 nm) has been the mostly used excitationlines in past decade for geological applications; 785 nm is the secondpopular excitation line, which has been increasingly used in portableRaman unit because of its small size (a diode laser), by helping to re-duce overall volume of Raman unit. This fact demonstrated the im-portance of engineering consideration.

The effective f-number of Raman collection optical path is thesecond most critical parameter that controls the Raman signal strengthof a portable Raman system. It is a combination of collection effi-ciencies of multiple components (Raman probe, optical fiber, slit,spectrometer, detector) in the collection path, for which the éntendue-match among the components are essential (McCreery, 1996). Inprinciple, an increase of f-number by two times would decrease theRaman photon collection by four times. Therefore, a KOSI HoloSpecwith f/1.8 was claimed to have 38 times Raman photons collectingefficiency than a f/8 Czerny-turner spectrometer (http://www.kosi.com/na_en/products/raman-spectroscopy/imaging-spectrographs/holospec-f1.8.php). The Mars Microbeam Raman Spectrometer (MMRS)and its upgraded version Compact Integrated Raman Spectrometer(CIRS) with f/2 Raman collecting optics (Wang et al., 2014; Wei et al.,2015) would have 100 times Raman photons collecting efficiency thana f/18 stand-off Raman system with a 11-cm diameter collection

Fig. 29. Experimental results showing the linear relation between dissolved methaneconcentrations in water (in mole fraction, X(CH4)) and the peak-area ratios for aqueousmethane and water at 295.3 K and different pressures (up to 47 MPa). The plotted dataare from Table 1 of Lu et al. (2006). The straight line represents the linear regression ofthe experimental data. Taken from Fig. 4 of Lu et al. (2006).

Fig. 30. A histogram on the laser lines used in over 400 studies published as abstractsduring seven International GeoRaman Conferences (2004–2016, only abstracts with listedlaser line were counted).


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telescope for a target one meter away (Maurice et al., 2012).Note if a laboratory Raman system has a low Raman signal strength,

the spectra with acceptable S/N ratio can still be obtained through along duration (hours) measurement on a geological sample, as was donein laboratories before 1990′s. However, a portable Raman system withlow Raman signal strength would be hardly useful in a geo-field cam-paign, since long duration put high requirement on resources, e.g.,power, time, and deploying mechanism that are often restricted.

Field tests of portable Raman systems were made in various Marsanalog sites on Earth in recent years by several teams. For examples, theteams led by Prof. Jan Jehlicka of Charles University in Prague, CzechRepublic (Jehlicka et al., 2008, 2011; Vítek et al., 2012; Kosek et al.,2014), Prof. F. Rull of University of Vallodolid, Spain (Sansano et al.,2014; Gazquez et al., 2014; Rull et al., 2010), and Prof. Alian Wang ofWashington University in St. Louis, USA (Wang et al., 2013b; Wei et al.,2015), and also the team from Jet Propulsion Laboratory, USA.

5.3.3. Lessons learned # 3 – Fluorescence interference, a threat or not?In terrestrial geo-field applications of laser Raman spectroscopy, one

of the major threats is the fluorescence interference from the analyzedsamples. The fluorescence emission can be produced from bio-geneticspecies that were trapped in porous rocks or soils (e.g., clays). They canalso be generated from the electronic transition modes of rare earthelements (e.g., REE–enriched minerals), or in some cases from transi-tion metals.

However, several reports, including two mission observations onMars and many observations on extraterrestrial materials, showed thatfluorescence interference did not cause any detectable threat for Ramanspectroscopic analysis of planetary materials. These observations in-clude: (1) A detailed data analysis (Goetz et al., 2012) of optical mi-croscope results for the Phoenix Mars Lander reported no detection ofUV (360–390 nm)-stimulated luminescence from the soil grains at thePhoenix landing site. (2) A similar analysis of a UV (365nm)-stimulatedluminescence image of Sayunei at Yellowknife Bay taken by MAHLI onthe Curiosity rover reported no detected fluorescence (Minitti et al.,2014). (3) Two UV (365nm)-fluorescence studies (Wang et al., 2003b;Minitti and McCoy, 2012) on five Martian meteorites (Lafayette, LosAngeles, Nakhla, EETA79001, and Zagami) show no detected fluores-cence, except those from epoxy and from a merrillite (a phosphate,known to be enriched in Rare Earth Elements in some lunar samplesthat emits sharp fluorescence peaks) grain in Zagami. (4) Good qualityRaman spectra (using cw 532-nm excitation), without obvious fluor-escence interferences, were obtained in the study of four Martian me-teorites (Zagami (Wang et al., 1999), Los Angles (Wang et al., 2001b),EETA79001 (Wang et al., 2004b), and MIL03346 (Ling and Wang,2015; Wang et al., 2015a). (5) A quantitative study (Wei et al., 2015) onthe fluorescence emitting properties of a variety of extraterrestrialmaterials (lunar and Martian meteorites, achondrites, carbonaceouschondrites, and H, L, and LL type ordinary chondrites) found an averageof 10–100 times weaker fluorescence emitting strength than four ter-restrial clay samples from the Clay Mineral Society (SWx-1, WWy-1,KGa-1, and KGa-2). These studies revealed that the fluorescence inter-ference did not occur in almost all extraterrestrial materials that hadbeen examined, hitherto, by Raman spectroscopy and by UV-stimulatedfluorescence microscopy. Therefore, fluorescence interference wouldnot be a major threat for planetary Raman spectroscopy.

Overall, laser Raman spectroscopy is a highly flexible technology. Onecan select different excitation laser lines, using continuous wave or pulsedlasers, using ordinary or gated detection, using reflective or transmittanceor even Fourier Transfer optical configurations. On the other hand, sam-ples in geo-field (terrestrial and planetary) are complicated and tough tomeasure. There is no best solution for all cases. Based on the scientific goalin a geo-field campaign, one may select (or develop) a different portableRaman system. Among the selections, we believe an essential rule thateveryone will have to follow is to strive for the highest Raman signal strength.A second rule, used in space exploration engineering that would be quite

adequate for geo-field campaign, is the KISS rule, i.e., Keep It Simple,Stupid. Apparently, manufactures of many commercial portable Ramansystems are following these rules.

5.4. Raman effects (resonance Raman spectroscopy, CARS, SERS)

Rull (2012) gave brief discussions on Resonance Raman Spectro-scopy, CARS, and SERS. He stated that most applications of ResonanceRaman Spectroscopy concerned organic molecules and could be inter-esting for their identification, in either environmental research or pla-netology in the quest for life or its precursors. As shown in Fig. 19,CARS is often used as an imaging method under physiological

Fig. 31. (A) Bright-field transmitted light image of collapsed z-stack of field of view withone-phase CH4-rich inclusions and two-phase water-methane inclusions. (B) Coherentanti-Stokes Raman scattering (CARS) image of A. Methane is red and water is green. Inthis field of view we can identify CH4-rich inclusions (incl 2) and methane in vaporbubble of two-phase aqueous inclusions (incl 3). Small volume of water visible in A in tipof inclusion 2 produced weak CARS signal that was lost during signal processing. Three-dimensional rendering of B is shown in rotation in Video DR3 (Data Repository item2012310; doi:10.1130/G33321.1), and CARS spectra of inclusion 2 and aqueous phase ofinclusion 3 are shown in Figure DR1. Taken from Fig. 3 of Burruss et al. (2012).


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environment (Daniel and Edwards, 2012). Burruss et al. (2012) appliedCARS microscopy to the study of fluid inclusions in deeply buried se-dimentary basins (Fig. 31). This allowed them to identify separate gassources, timing of generation, migration, and mixing, as well as po-tential contributions from the deep crust or upper mantle. There aresignificant implications for other broad areas of geosciences includingmineralogy, paleobiology, and geochemistry. These broadly applicableimaging methods will potentially transform the characterization ofEarth and planetary materials.

In Earth science, SERS is mainly for detection of small quantities oforganic molecules in mineral samples, as biomarkers, and mineralogicalanalysis on rock and soils when the signal-to-noise ratio is inadequateor the fluorescence emission is more than Raman scattering (Rull,2012). Note that recent studies (after 2012) on Resonance RamanSpectroscopy, CARS, and SERS were reviewed by Nafie (2016).

6. Conclusion

Raman spectroscopy has been developed as a relatively easy tech-nique for in situ characterization of Earth and planetary materials insolid, liquid (including melt), and gaseous states in a wide P-T range.Gas or aqueous solution standards, which can be easily prepared infused silica capillary optical cell, have been used to calibrate Ramanspectroscopic system for quantitative analyses without the need toobtain the cross-section information. Consequently, in situ quantitativeanalyses have been applied to the study of dynamic systems, such as thediffusion of dissolved gas in aqueous solution at various P-T conditions.

Because of the inherent advantages of Raman spectroscopy, it hasbeen widely used in the studies of either solid or fluid inclusions inminerals. Being able to identify small-sized high-pressure minerals andtheir transformed polymorphs without destroying the samples, togetherwith other geochemical and geophysical evidence, we were able torecognize ultra-high pressure metamorphism and formulate models forpetrogenesis and evolution of the crust. The needs for quantitativeanalyses of lunar samples and meteorites promoted the advances ofRaman spectroscopy, and the needs for future planetary explorationsenhanced the development of portable Raman system. Recent devel-opments in 1D, 2D, and 3D Raman mapping made it possible to viewthe distribution of materials in space and allow us to reveal or for-mulate models for the related geological processes, either biogenic orabiogenic. Despite of remaining challenges (e.g., improving the detec-tion limit and spatial resolution and minimizing the fluorescence andtime needed for Raman mapping), it is clearly shown that Ramanspectroscopy continues to be a rapidly expanding field that providesrelatively simple and non-destructive method for the identification andanalysis of Earth and planetary materials.

Acknowledgments

We would like to dedicate this paper to late Prof. Bor-ming Jahn(National Taiwan University) for his significant contributions to Earthscience, in both academic research and community service. We thankProf. Juhn Guang Liou (Stanford University) for his invitation to makethis contribution, Prof. Jill D. Pasteris (Washington University at St.Louis) for her guidance since 1990 in Raman spectroscopy. We alsothank Prof. Jean Dubessey (University de Lorraine) for organizing andhosting the 10th International GeoRaman Conference at Nancy, France,and editing and publishing the book “Raman Spectroscopy applied toEarth Sciences and Cultural Heritage”. IMC would like to thank Prof.Maria Perraki (National Technical University of Athens, Greece) forsharing her lecture note on“Raman spectroscopy: a useful tool in thestudy of mineral phases in HP/UHP metamorphic rocks”, Dr. Jing Shen(HORIBA, Beijing) for discussions on the size of sample volume inRaman spectroscopic analyses, and his former colleague at U.S.Geological Survey (USGS), Dr. Robert C. Burruss, for his guidance andcontinuous support. He also acknowledges the support of the Mineral

and Energy Programs of USGS, the Knowledge Innovation Program(SIDSSE-201302), the Hadal-trench Research Program (XDB06060100),and the Key Frontier Science Program (QYZDY-SSW-DQC008) ofChinese Academy of Sciences (CAS). AW would like to thank the sup-ports provided by US NASA PIDDP, MIDP, ASTEP, ASTID, MatISSE,MFRP, MoO, PME programs and the supports of McDonnell Center forSpace Sciences at Washington University in St. Louis, in past 25 yearsfor developing the planetary Raman spectroscopy and planetary Ramaninstrumentation. We thank the Guest Editor, Prof. Sun-Lin Chung, andtwo anonymous reviewers for their comments and suggestions, whichgreatly improved the quality of presentation. We also thank Mr. JingFang (Institute of Deep-sea Science and Engineering, CAS) for preparingand finalizing the references and some of the figures in this manuscript.

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