Rocks, Minerals, & Gems

Cathodoluminescence (CL) microscopy reveals the real structure of solids based on a crystal’s intrinsic properties and trace-element chemistry. Although CL is useful for the identification of minerals (and their distribution), researchers more frequently employ this technique to reveal the typomorphic properties and features of minerals that characterize the conditions of formation and alteration to reconstruct geological processes.

The table below shows a diverse range of minerals that may be examined using CL. Note that iron minerals and iron-rich phases are generally non-luminescent.

Class Examples
Elements Diamond
Sulfides Sphalerite
Oxides Corundum, cassiterite, periclase
Halides Fluorite, halite
Sulfates Anhydrite, alunite
Phosphates Apatite
Carbonates  Calcite, aragonite, dolomite, magnesite
Silicates Feldspar, quartz, zircon, kaolinite

Experimental briefs and application notes

Major, minor, and trace element distributions in a meteorite revealed by energy dispersive spectroscopy and cathodoluminescence spectroscopy Streamlined microanalysis in the SEM High-speed, hyperspectral (spectrum) imaging for all with the Monarc detector
 
Observation of crystal structure orientation by cathodoluminescence (CL) polarization-filtered spectrum imaging Cathodoluminescence techniques for the geosciences  

Webinar

Cathodoluminescence Explained. Episode 3: Analysis Modes for Geoscience Applications 

Meteorites

Meteorites can reveal fragments of the history of the evolution of the solar system. With many long-term asteroidal sampling missions, petrographic investigations of meteorite specimens will assist in the study of asteroid samples. These rocky carbonaceous aggregates include snapshots of the early solar system and can contain calcium aluminum inclusions (CAI's) and corundum grains which can be among the first solids to condense from the solar nebula. Understanding their complex history of formation and subsequent thermodynamic events is critical in resolving early planetary stages. The growth patterns, grain boundaries, and subtle zonation from crystallization can indicate formation from nebular gasses. Cathodoluminescence investigation of a meteoritic specimen can reveal and map the presence of trace elements, grain boundaries and assist with mineralogical identification.

Major, minor, and trace element distributions in a meteorite revealed by energy dispersive spectroscopy and cathodoluminescence spectroscopy

Sedimentary Rocks

Sedimentologists use cathodoluminescence (CL) in clastic and carbonate petrography to reveal textural information that is not apparent with other (imaging) techniques. By studying grain provenance, sediment, and cement growth fabrics, CL studies provide insight to understand the diagenetic history better.

Cementation and diagenesis

Depositional grains and cement in carbonate and quartz minerals form under very different conditions that result in clear differences in their trace element chemistry. CL maps are useful to reveal the detail of the growth fabric zonation, dissolution, and micro-fracturing, including successive cement generations.

In sandstone, detrital (of various origins) and authigenic quartz overgrowths enable quantification of cement abundance and determination of porosity-loss processes.

Provenance

CL is a valuable technique to monitor the provenance of feldspars, mudrocks, and quartz (plutonic, volcanic, hydrothermal, and metamorphic). Specifically, maps can detect changes in crystal texture that correlate with impurity distributions and concentrations that approach parts per million levels.

References

Götze, J. M.; Plötze, M.; HaberMann, D., Mineral Petrol 71 (2001) p225 – 250

Scholonel, C.; Augustsson, C., Sedimentary Geology 336, 1 May 2016, p36 – 45

Color cathodoluminescence images captured using a ChromaCL2™ detector and provided courtesy of Prof. J Schieber, Indiana University Shale Research Lab.

Carbonate Rocks


Color cathodoluminescence image of a dolomite thin-section captured using a ChromaCL2™ detector utilizing the carbonate imaging optical filter to observe the blue-green luminescence only.

Petrography of carbonate rocks

Cathodoluminescence (CL)  is particularly useful in discriminating diagenetic relationships in carbonates, especially dolomite. CL can reveal complex growth histories of calcite and dolomite crystals as well as replacement relationships. Phosphorescence of the dominant (orange-red) luminescence of the manganese cation prevents the use of certain acquisition modes. However, wavelength-filtered imaging or spectrum imaging approaches can be useful to visualize texture apparent at other wavelengths.

Economically Important Minerals and Gems


CL spectra of a zircon grain containing a variety of rare earth elements (concentration 0.1 – 100 parts per million). Wavelength spectra were recorded with a MonoCL4™ detector and provided courtesy of Rolla Zanetti, Washington University in St. Louis, and the McDonnell Center for the Space Sciences.

Reservoir rock

The oil and gas industry frequently uses cathodoluminescence (CL) to characterize reservoir rocks.

Rare earth elements (REEs)

The last 20 years have seen an explosion in demand for REEs due to their use in rechargeable batteries, magnets, military-grade metal alloys, and many optoelectronic devices. Minable concentrations of REE-bearing minerals, such as apatite and monazite, are uncommon with sometimes restricted market availability.

CL can reveal the presence of, and identify, REE within a mineral. Their distribution(s) may be mapped even at concentrations lower than ten parts per million based on the distinct emission spectrum of each REE.

Porphyry

Porphyry deposits are one of the world's most important repositories of copper, gold, and molybdenum. High-resolution, scanning electron microscope CL mapping allows the detailed interpretation of the crystallization history within porphyry copper ore deposits to be understood.

Gems

Many gemstones, including diamond and corundum (sapphire or ruby), exhibit strong CL and are widely studied. The inhomogeneous internal structure can reflect changes that occur both during growth as well as post-crystallization. This allows, for example, natural and synthetic diamonds to be distinguished based on their spectrum and a detailed understanding of the various colors they exhibit.

Quartz

One of the most important applications of cathodoluminescence (CL) in geosciences is the possibility to reveal internal structures, growth zoning, and lattice defects in quartz crystals that are not discernible by other analytical techniques. During quartz crystallization, variations of the physicochemical conditions result in crystal zoning. Revealing these features using CL enables geoscientists to reconstruct the specific growth conditions or to reveal multiphase processes. The zoning in quartz can relate either to variations in trace-element uptake or intrinsic defects caused by the effects of growth conditions. ​


Color CL image of a quartz bridge formed from three wavelength-filtered images recorded using a MonoCL3™ detector.

Provenance

The dependence of the CL spectrum (color) of quartz from different origins permits the recognition of specific conditions of formation (e.g., temperature and pressure). Qualitative studies encompassing a wide array of quartz forms has enabled a general provenance classification to be built based on the CL color with guidelines in place for the classification as volcanic, plutonic, hydrothermal, and metamorphic quartz fabrics. However, in combination with other analytical methods such as trace-element analysis, isotope, or inclusion studies is often beneficial. ​

The concentration of titanium in quartz is widely demonstrated as a useful tool for determining the temperature and pressure of quartz crystallization (the so-called TitaniQ method). Qualitative studies show that blue wavelengths could be associated with titanium concentration. However, more recently, it has been noted that spectrum imaging (hyperspectral imaging) approaches are necessary for accurate quantitative analysis. ​

Diagenesis 

CL maps are useful to reconstruct diagenetic processes in reservoir quartz since authigenic and detrital quartz can be distinguished; as well as secondary overgrowths, ghosts of the original fabric, and cementation sequences. Such observations are important to discern various geological and mineralogical aspects, particularly in the field of oil exploration. ​

Metamorphism

CL is useful to unravel deformation features (e.g., microfractures) or fluid migration pathways in crystalline as well as in sedimentary rocks. For instance, it has been demonstrated that CL is an excellent tool to distinguish brittle or ductile deformation processes during sandstone diagenesis. On the other hand, CL can reveal fluid migration due to hydrothermal alteration or pro- and retrograde metamorphic conditions which are often not recognized by conventional polarizing microscopy​.

Zircons

Geochronology

Zircons are frequently used as a geological clock because they include small amounts of radioactive uranium isotopes and their decay products incorporate into the crystal structure during crystallization. In old inherited zircon cores, younger igneous zircons, or ones that have undergone more than one crystallization event, the U/Pb isotope ratio in each crystallization period will differ based on the time elapsed (uranium is immobile in the zircon crystal). This polyphase structure is often not recognizable by conventional imaging methods, such as light microscopy, but necessary for accurate dating results. However, zircons can be selected for dating purposes using cathodoluminescence (CL) in the scanning electron microscope. In essence, an unfiltered CL image is useful to identify zircon phases of different ages that appear as bright regions (e.g., presence of late rims) at the grain perimeter. Moreover, conclusions on the origin and development of the inherited phases can be drawn by comparison with detrital zircons.


An unfiltered CL image of a collection of polished zircon grains that reveal internal texture related to (re-)crystallization. Some zircons exhibit ‘late rims’ (indicated by arrows) where the grain exteriors date to a later geological period than the core. Images captured using the MiniCL™ detector.