Since the first developments of anthropogenic lime materials radiocarbon (14C) dating in the 1960s, numerous studies have been undertaken and developed to investigate the topic further. Historic mortars are complex composite and open system materials that can incorporate a large range of components. Due to the complexity of the historic lime mortars composition, they are not part of a routine protocol in most radiocarbon laboratories and reliable dating is not always achieved. A thorough characterization needs to be performed and different preparation methods can be considered as a function of their compositions. A vast range of terms are employed to qualify the lime mortars components and alterations that can possibly have an influence on the dating result. Here, a detailed description of these components and the various terms used is listed. To illustrate this, images obtained by thin-section petrography and cathodoluminescence are presented in addition to radiocarbon results using stepwise acid hydrolysis on Belgian mortars having different provenance, state, age and composition. Depending on the type of aggregate used, the type of binder and its conservation state, the eventual presence of weathering carbonates and the assumed speed of the carbonation process, the reliability of radiocarbon measurements using the stepwise acid hydrolysis technique is discussed and confronted with presumed historical constraints.

Quicklime samples were collected from six vertical layers (L1–L6) of a feedstock calcined in a traditional single-batch wood-fired kiln and assessed. Three samples were well-burned and three under-burned. The quicklime was slaked in an excess of water and the presence of unburned particles was investigated after settling it into putty. The putty was assessed as bulk and also at three depth levels. Thermal analysis determined the CO2 residua in the quicklime samples. Cathodoluminescence detected individual unburned particles and image analysis was used for their quantification. Settling of the putties led to a considerable reduction of geogenic particles in the layers above the bottom. This was also confirmed by the stable isotope analysis. In the case of the putties made from well-burned quicklime, the δ13C values of samples L4 and L5 ranged from –25.5‰ to –20.5‰ VPDB, and the δ18O values ranged from –17.5‰ to –16.5‰ VPDB. The fractionation was likely affected by the division according to the particle size during the sedimentation. The results of the 14C analysis correlate with the quantified percentage of cathodoluminescent particles.

Algae like diatoms are widely studied as a means to remediate anthropogenically contaminated sites. In the present study, CL (cathodoluminescence) and EDX (energy-dispersive X-ray) spectroscopy in an SEM (scanning electron microscope) were optimized for the detection of Eu(III) sorbed on diatom biosilica. The required stability of biosilica under a focused electron beam was extensively investigated. Using experimentally determined data of thermal properties, the temperature increase within biosilica exposed to an electron beam was simulated by finite element calculations based on results from Monte Carlo simulations of electron scattering. Complementary thermogravimetric studies substantiated a chemical stability of biosilica in a wide temperature range, confirming its suitability for long-lasting SEM investigations. In subsequent EDX measurements, characteristic Eu lines were detected. Eu was found to preferentially accumulate and aggregate on silica fragments. CL spectra were obtained for the Eu(III) reference material, EuCl3. For Eu-loaded biosilica, even parts without detectable Eu signal in the EDX spectra show significant Eu(III) signals in the CL spectra. This highlights the sensitivity of CL in studying f-element sorption. CL data showed that Eu(III) was distributed on the entire surface. In conclusion, this work demonstrates the merit of CL and EDX methods for sorption studies on biogenic materials.

Determining free lime content in steelmaking slag is crucial for its safe reuse in road construction. A simple method has been recently developed to rapidly derive this value via cathodoluminescence (CL) imaging of steelmaking slag, previously quenched from 1,000°C to room temperature, according to the illuminated areas corresponding to free lime (luminescence peak at 600 nm). This quenching is required to obtain intense CL from free lime, but the mechanism of such signal enhancement is still unknown. Therefore, the present study investigated the mechanism by comparing the microstructures, CL images, and CL spectra of free lime in quenched and unquenched steelmaking slag. Large amounts of defects, including dislocations, were observed in the free lime emitting intense luminescence at 600 nm, whereas the samples without clear CL exhibited only a few defects. These results and previous studies suggest that the luminescence at 600 nm from free lime is enhanced by the CL originating from oxygen vacancies (380 nm); therefore, the enhancement of the intensity of the free lime CL peak could be attributed to the increase in the oxygen vacancies via quenching from 1,000°C to room temperature.

Zircon crystals from diamondiferous kyanite gneisses of the Barchi-Kol area (Kokchetav massif, Northern Kazakhstan) have been investigated by a combined application of cathodoluminescence (CL), Raman spectroscopy and electron probe microanalysis (EPMA). The zircon crystals exhibit up to four distinct domains characterised by significantly different CL signatures and parameters of the ν3(SiO4) (1008 cm–1) Raman band (i.e. full width at half maximum, position and intensity). Extremely metamict zircon cores (Domain I) host inclusions of low-pressure minerals (quartz and graphite) and the outer mantles (Domain III) are populated by ultrahigh-pressure relicts (diamond and coesite), whereas inner mantles (Domain II) and overgrowth rim zones (Domain IV) are inclusion free. Both the zircon cores and rims have very low Ti concentrations, implying formation temperatures below 760°C. The Ti content in the inner mantles (up to 40 ppm) is indicative of temperatures in the 760–880°C range. The temperature estimates for the outer mantles are 900–940°C, indicating a pronounced overlap with the peak metamorphic values yielded by the Zr-in-rutile geothermometer for the same rocks (910–950°C). The internal textures of the zircons and the occurrence of index minerals within the distinct domains allow us to unravel the stages of the complex metamorphic history recorded in the zircon. Our data show that the zircon cores are inherited seeds of pre-metamorphic (magmatic?) origin, the inner mantles were formed on the prograde metamorphic stage, the outer mantles record ultrahigh-pressure metamorphism and the outermost rims mark the retrograde metamorphic stage. The observed zircon internal textures are thus clearly correlated with distinct growth events, and in some examples reflect a major part of the metamorphic history. It is concluded that the combined application of the CL, Raman spectroscopy and EPMA techniques to zircon offers significant potential for deciphering the metamorphic evolution of deeply-subducted rocks.

The excitability of local surface plasmon modes in radial trimers composed of gold nanorods was mapped using hyperspectral cathodoluminescence (CL) in the scanning electron microscope. In symmetric trimers, the local plasmon resonances could be excited most effectively at the ends of individual rods. Introducing asymmetry into the structure breaks the degeneracy of the dipole modes and changes the excitability of transverse dipole modes in different directions. CL in the scanning electron microscope has great potential to interrogate individual nanophotonic structures and is a complement to electron energy loss spectroscopy and optical microscopy.

Accurate radiocarbon (14C) dating of lime mortars requires a thorough mineralogical characterization of binders in order to verify the presence of carbon-bearing contaminants. In the last 20 years, cathodoluminescence (CL) has been widely used for the identification of geologic calcium carbonate (CaCO3) aggregates and unreacted lime lumps within the particle size fraction selected for carbon recovery. These components are major sources of older and younger carbon, respectively, and should be removed to obtain accurate age determinations. More recently, laser-induced fluorescence (LIF) has provided another means of investigating the preservation state and composition of CaCO3 binders. Considered the growing interest of the mortar dating community in the latest advancements of these analytical methods, here we review the principles of CL and LIF of CaCO3, their instrument setup, and their application to the characterization of ancient lime mortars used for 14C dating. In addition, we provide examples of SEM-CL and LIF analyses using high-resolution instrumentation, we discuss current issues and propose future lines of research.

Hyperspectral soft X-ray emission (SXE) and cathodoluminescence (CL) spectrometry have been used to investigate a carbonaceous-rich geological deposit to understand the crystallinity and morphology of the carbon and the associated quartz. Panchromatic CL maps show both the growth of the quartz and the evidence of recrystallization. A fitted CL map reveals the distribution of Ti4+ within the grains and shows subtle growth zoning, together with radiation halos from 238U decay. The sensitivity of the SXE spectrometer to carbon, together with the anisotropic X-ray emission from highly orientated pyrolytic graphite, has enabled the C Kα peak shape to be used to measure the crystal orientation of individual graphite regions. Mapping has revealed that most grains are predominantly of a single orientation, and a number of graphite grains have been investigated to demonstrate the application of this new SXE technique. A peak fitting approach to analyzing the SXE spectra was developed to project the C Kα 2pz and 2p(x+y) orbital components of the graphite. The shape of these two end-member components is comparable to those produced by electron density of states calculations. The angular sensitivity of the SXE spectrometer has been shown to be comparable to that of electron backscatter diffraction.

Kinematic indicators, including certain strain fringes, represent an important group of structures related to the progressive deformation in rocks. The evolution of these fibrous textures can be explained by the combination of multiple mechanisms of deformation and fluid flow, mainly controlled by the orientation of the strain field and the morphology of the grains. In general, the observations are done with an optical microscope and compared with computational models of growth. This work proposes a combination of crystallographic and cathodoluminescence data obtained in rocks from banded iron formations of the Iron Quadrangle in Brazil to represent an example of how complementary analytical techniques can be useful to understand geological problems. The chosen sample exhibits a strain fringe structure of quartz around a clast of magnetite partially transformed into goethite and hematite. Through the crystallographic data it was possible to identify the grain boundary morphology and domains of low deformation areas. On the other hand, the cathodoluminescence signal evidenced the occurrence of grains with a higher concentration of crystalline defects.

Agates with spectacular micro-structural features were found in volcanic rocks at several occurrences in the Saar-Nahe region (Germany). These agates include spirals of several tens up to several hundreds of μm in size within zones lacking the characteristic structural agate banding. A combined mineralogical study by polarising microscopy, scanning electron microscopy, cathodoluminescence microscopy and spectroscopy, and electron backscatter diffraction provided evidence that the spirals consist of well-ordered trigonal α-quartz, whereas the surrounding matrix is composed of strongly disordered or amorphous SiO2 phases. The quartz micro-crystals show a systematic rotation of the crystal orientation perpendicular to the direction of the spiral loops indicating helical growth.

It is assumed that the spiral growth is initiated by dislocations with a screw component. The lacking symmetry of the strongly disordered or amorphous matrix initiated a curved development by a screw dislocation in a system far from equilibrium. The atoms/molecules are packed into spiral layers, which is energetically favoured in comparison with the incorporation into plane crystal faces. Such self-organisation growth and polymerisation initiated by a screw dislocation can produce variable spiral morphologies sometimes resembling living forms.

Cathodoluminescence (CL) petrography of nepheline syenites of the Igaliko complex, Gardar province, South Greenland shows that sodalites possess embayed contacts against nepheline, and have formed by a process of metasomatic replacement. This texture is demonstrated clearly by CL, since sodalite luminesces bright orange and nepheline is poorly luminescent. The transformation from nepheline to sodalite results in a volume change which leads to a network of fractures in which deep-blue luminescent fluorite is precipitated. Fluorite is formed since the chlorination process involved in the transformation causes localised reductions of the salinity of the fluid and therefore a decrease in the solubility of fluorite. Sodalite-fluorite textures observed using CL allow sodalites of secondary origin in alkaline igneous rocks to be identified.

Nephelines and sodalites, when observed using scanning electron microscopy, possess small micropores. By analogy with recent work on alkali feldspars, pervasive alteration of nephelines may occur by fluid flow assisted by a permeable micropore network.

Cathodoluminescence (CL) imaging and spectroscopy are outstanding methods in several fields of geosciences. Cathodoluminescence can be examined using a wide variety of electron-beam equipment. Of special interest to geologists are optical microscopes (OMs) equipped with an electron gun. scanning electron microscopes (SEMs) and electron microprobes. Despite the similar kind of excitation, the results obtained may show marked differences. These are related to the use of focused or defocused as well as a scanned or stationary electron beam and the kind of signal acquisition. Images obtained by OM-CL (hot or cold acceleration) and SEM-CL differ due to different spatial resolution, true colour, grey-scale, or monochromatic detection, contrast inversion, phosphorescence effects, etc.

Instrumentation used for spectroscopic studies may differ in sequential or parallel signal acquisition, wavelength range, spectral resolution, and the kind of analytical spot limitation. This is particularly important when investigating transient CL, rare earth element (REE) emissions, or luminescence in the near UV and IR regions as well as samples with small grain sizes and contrasting CL behaviour of adjacent mineral phases.

In the present study, the influence of analytical parameters is demonstrated for certain mineral examples including zircon, fluorite, apatite, feldspar, quartz, corundum, kaolinite, and dickite.

The cathodoluminescence (CL) of cassiterite (SnO2) from the paragenetic sequence in the lodes at South Crofty Mines has been used in the interpretation of the processes which govern mineral deposition. Luminescence is controlled by the substitution of Ti, Fe and W for Sn in the cassiterite lattice. Ti and W behave as luminescence activators whereas Fe quenches luminescence. The observed colours and intensity of the luminescence are believed to result from the interplay between these effects. Successive generations of cassiterite formed during the separate stages of paragenetic evolution show different luminescence colours. These are believed to reflect changes in bulk composition of the fluid, which is indicated by the systematic variation in the composition of tourmaline in the associated gangue.

CL also reveals details of growth and deformation in individual crystals. Growth textures observed in CL are broad concentric growth banding, oscillatory zoning and sector zoning. Sector boundaries often show a zig-zag form which is indicative of competitive growth of adjacent crystal faces. Interpretation of CL textures is used to support the hypothesis that cassiterite growth took place under two main regimes. These are, firstly, conditions in which fluid pressure decreased abruptly when tectonic reactivation caused dilation of parts of the lode fracture system and secondly, conditions of sustained hydraulic pressure within fractured vein fill. In tectonically induced fractures the crystals are stubby, have non-equivalent growth faces and are commonly tetragonal bipyramidal forms in which sector zoning is invariably present. In hydraulic fractures crystals take a predominantly tetragonal prismatic form. Thus, it is believed that growth under these contrasting conditions leads to distinctive morphology and zoning in cassiterite, providing a basis for typomorphic characterisation.

Apatite samples from rare-metal mineralization were investigated by a combination of cathodoluminescence (CL) microscopy and spectroscopy, microchemical analysis and trace element analysis. Internal structures revealed by CL can be related to variations in the crystal chemistry and may sometimes reflect changes in the composition of the mineralizing fluids.

Apatite from mineralization related to alkaline rocks and carbonatites (Type 1) typically exhibits relatively homogeneous blue and lilac/violet CL colours due to activation by trace quantities of rare earth element ions (Ce3+, Eu2+, Sm3+, Dy3+ and Nd3+). These results correlate with determined trace element abundances, which show strong light rare earth element (LREE) enrichment for this type of apatite. However, a simple quantitative correlation between emission intensities of REE3+/2+ and analysed element concentrations was not found.

Apatite from P-rich altered granites, greisens, pegmatites and veins from Sn-W deposits (Type 2) shows strong Mn2+-activated yellow-greenish CL, partially with distinct oscillatory zoning. Variations in the intensity of the Mn2+-activated CL emission can be related either to varying Mn/Fe ratios (quenching of Mn activated CL by Fe) or to self-quenching effects in zones with high Mn contents (>2.0 wt.%). The REE distribution patterns of apatite reflect the specific geological position of each sample and may serve as a “tracer” for the REE behaviour within the ore system. Although the REE contents are sometimes as high as several hundred parts per million, the spectral CL measurements do not exhibit typical REE emission lines because of dominance of the Mn emission. In these samples, REE-activated luminescence is only detectable by time-resolved laser-induced luminescence spectroscopy.

Both types of apatite (Type 1 in the core and Type 2 in the rim) were found in single crystals from the Be deposit Ermakovka (Transbaikalia). This finding proves the existence of two stages of mineralization within this deposit.

Cathodoluminescence (CL) microscopy and spectroscopy combined with SHRIMP ion probe measurements were carried out on detrital zircons from the Cretaceous Weferlingen quartz sand (Germany) to distinguish and characterize different zircon populations.

Investigations by CL microscopy, SEM-CL and BSE imaging show that there are three main types of zircons (general grain sizes of 100–200 µm): (1) apparently weakly zoned, rounded grains with relict cores, (2) well rounded fragments of optically more or less homogeneous zircon grains showing CL zoning predominantly parallel to the z-axis, and (3) idiomorphic to slightly rounded zircon grains typically showing oscillatory euhedral CL zoning. A fourth type of low abundance is characterized by well-rounded grain fragments with an irregular internal structure showing bright yellow CL.

High-resolution CL spectroscopic analyses reveal that blue CL is mainly caused by an intrinsic emission band centered near 430 nm. Dy3+ is the dominant activator element in all zircons, whereas Sm3+, Tb3+, Nd3+ have minor importance. Yellow CL (emission band between 500 and 700 nm) is probably caused by electron defects localized on the [SiO4] groups (e.g. related to oxygen vacancies) or activation by Yb2+ generated by radiation. Variations of the integral SEM-CL intensity are mainly controlled by the intensity of the broad bands and the Dy3+ peaks.

SHRIMP analysis provides in situ high-resolution U-Pb dating of single zircon grains and confirms different ages for the evaluated different zircon types. The measurements show that the U-Pb ages of the zircons from Weferlingen scatter over a wide range (340 to 1750 Ma), backing up earlier conclusions that the quartz sand from Weferlingen is quite heterogeneous in terms of provenance.

A recent investigation of sphalerite from Akoluk deposit, Ordu, NE Turkey, revealed the possible presence of a new activator element in the sphalerite structure. The sample was studied under a reflected light microscope coupled with a cold-stage cathodoluminescence (CL) system which revealed a unique banding in the sphalerite. The same sample was subsequently examined using the backscattered electron and luminescence modes in an electron microscope, the results of which were later confirmed in terms of chemical composition by electron probe microanalyses (EPMA). Detailed evaluation of the EPMA data indicated the presence of a new CL activator element in the sphalerite structure. The data also indicate that Hg2+ in the sphalerite crystal structure substitutes for Zn in a simple manner and for Cd and Cu in a coupled manner. Spectral analysis indicated a bright yellow and orange-red blend (more like brown) CL colour with λmax centred at 580 nm, probably due to Cd and Mn ions, and relatively broad emission bands ranging from 525 to 690 nm with λmax centred at 580 and 700, due probably to Cu, Cd and Hg. This study reports that Hg in the sphalerite crystal lattice behaves as an activator and/or co-activator element resulting in emissions of CL colours that range from yellow with purple shades to shades of brown, based on their varying contents.

Zircon frequently occurs as a minor mineral in kimberlites, and is recognised as a member of a suite of mantle-derived megacryst minerals. Cathodoluminescence (CL) microscopy and laser ablation ICPMS analysis were used to study the internal structure and chemical composition of zircon crystals from southern African kimberlites. Zoning revealed by CL ranges from fine oscillatory to broad homogeneous cores and overgrowths. The ICPMS data show that kimberlite zircons have distinctive trace element contents, with well defined ranges for REE, Y, U, Th, P and some other trace elements. Both low REE contents (ΣREE < 50 ppm), and distinctive chondrite-normalised REE patterns with low and flat HREE are characteristic of kimberlite zircons. Samples or zones with yellow CL have higher Th, U, Y, and REE than those with blue-violet CL. Variations in the concentrations of a range of trace elements lead to different amounts of lattice defects, creating the possibility for different levels of direct excitation of luminescence centres, and therefore different CL colours. The distinctive CL and compositional features described here can rapidly identify kimberlite zircons in prospecting samples taken during exploration for kimberlite bodies.

The North Qôroq syenite centre forms part of the Gardar Province of South Greenland. Extensive metasomatism, associated with the evolution of syenitic magmas, has resulted in redistribution of the rare-earth elements (REE), originally concentrated by magmatic processes, in both the syenites and surrounding granite-gneiss and quartzite country rocks. An important host for REE is apatite which can occur in significant quantities. Metasomatic apatites show complex, concentric, but irregular patterns of zonation, clearly seen using CL and BSE imaging. This zonation is related to successive pulses of metasomatising fluids. Electron microprobe analysis confirms the presence of significant quantities of REE in the apatites. The dominant cation exchange mechanism proposed is Ca2+ + P5+ ⇌ REE3+ + Si4+. In contrast to apatites from the nearby Ilímaussaq intrusion, there is no significant Na present in the structure and exchange reactions involving Na+ and REE3+ for Ca2+ have not occurred.

Apatites from the quartzite are fluor-apatites, while those from the granite-gneiss are more Cl-rich. These differences reflect the fact that granite-gneiss apatites are original and modified by metasomatism, whereas, those in the quartzite are metasomatic in origin. REE were probably transported as carbonate, fluoride or fluor-carbonate complexes, and reflect the activity of a F−-rich, CO2−3-rich fluid phase.

Cathodoluminescence emission spectra and luminescence excitation spectra of Mn2+ in calcites, dolomites, magnesites, a manganocalcite and a rhodochrosite have been measured at both room temperature and 77 K. Ligand-field parameters have been calculated from the excitation spectra which reflect the size of the metal cation site in which the Mn2+ ion resides. The technique of luminescence excitation spectra has enabled the absorption profile of Mn2+ in Mg and Ca sites in dolomite to be separately determined. The variation of the distribution of Mn2+ between Mg and Ca sites in dolomites is demonstrated and discussed in terms of a simple model. It is concluded that the distribution of Mn2+ in dolomites may well provide information about its conditions of formation and/or subsequent alteration.

Kutnohorite with moderate and bright orange-red cathodoluminescence (CL) was studied by CL microscopy and spectroscopy. This mineral was found in fossiliferous concretions composed mainly of rhodochrosite from the Mn-carbonate mineralization at Úrkút, Hungary. The CL microscopy reveals that kutnohorite occurs as impregnations, layers and veinlets. X-ray diffraction, infrared spectroscopy and electron microprobe studies indicate that the luminescent kutnohorite has excess Ca (72.9–80.0 mol.% CaCO3, 16.3–20.5 mol.% MnCO3, 3.3–5.6 mol.% MgCO3 and 0.0–0.5 mol.% FeCO3). Transmission electron microscopy shows that the luminescent carbonate has a dolomite-type structure, with modulated and mosaic microstructures. The CL spectra of this Ca-rich kutnohorite have a single emission band at 630 nm that is characteristic of Mn2+ substitution in the structure. Our results provide evidence for moderate-to-bright cathodoluminescence of Mn-rich natural carbonates even at 8–10 wt.% Mn and up to 2400 ppm Fe. The self-quenching of Mn appears incomplete in the case of Ca-rich kutnohorite from Úrkút.