Orientation dependence of luminescence in plagioclase

The orientation dependence of the luminescence of a well-characterized plagioclase crystal at room temperature and 40 K is reported. A beam of H ⁺ ions was used to provide the excitation. Ion beam luminescence provides emissions effectively from the bulk of the material, and therefore minimizes the contribution to the luminescence from atypical regions. The intensity of the luminescence is strongly orientation-dependent. The intensity and photon energy, particularly of the red/infrared and yellow emission bands, vary significantly. We interpreted this as resulting from Fe ³⁺ and Mn ²⁺ activator ions, respectively, on crystallographic sites with low point symmetry. An emission at 860 nm was also significantly orientation-dependent. The blue luminescence showed the least variability. At room temperature, a 350 nm near-UV emission was noted, whereas at 40 K, emissions were at 240, 260, 300 and 340 nm. UV emissions may result from Na ⁺ diffusion along interfaces within the plagioclase, notably albite-law (010) twins. This variability has significant consequences for the use of single-crystal quantitative luminescence techniques. We have also studied the dependence of the peak intensities and profiles during prolonged ion beam bombardment with heavier (He ⁺) ions. Broadening of the red-infrared emission is interpreted as reflecting growing amorphization of the sample.     

The red luminescence emission of feldspar and its wavelength dependence on K, Na, Ca – composition

Summary ?Feldspar specimens covering the whole Or–Ab–An ternary have been investigated by cathodoluminescence (CL), photoluminescence (PL), radioluminescence (RL) and radiophosphorescence (RP) spectrometry. A red luminescence emission, which is commonly explained by Fe³⁺ lattice defects, is a characteristic feature of all the spectra. Different shifts of the peak-wavelength between ∼680–750 nm (1.82–1.65 eV) were observed with varying feldspar composition. Despite the dependence of the peak position on the Ca/Na ratio, initially described for CL in the 1970s, there is also a shift induced by changing NaK composition. The observed effects can be explained by known relations that the peak position of the red luminescence emission in feldspars can be affected both by the structural state of the feldspar and the site occupancy of the trivalent iron. In the case of alkali feldspars another factor may influence the peak-shift. The incorporation of the larger potassium ion causes non-linear variations of the cell dimensions and therefore Fe–O bond distance. The behaviour of the red peak-shift dependent on the feldspar composition is not equal for all types of luminescence investigated. This is most likely caused by the different luminescence excitation mechanism. Received December 3, 2001; revised version accepted March 25, 2002     

Multiple luminescent spectroscopic methods applied to the two related minerals,leucophanite and meliphanite

The photo-, cathodo-, radio- and ionoluminescence of two related beryllium minerals, leucophanite and meliphanite, have been determined. Meliphanite is an efficient luminescent mineral and has similar luminescence to leucophanite. Both leucophanite and meliphanite efficiently transfer energy to all activators in the sample either from the conduction or through a charge transfer band. We infer that coupling of the luminescence centre and lattice is important for interpreting rare earth element (REE) luminescence. Furthermore, changes in the relative intensity between REE emissions during sample degradation by CL demonstrate that each REE interacts differently with the host. Conversely, when a specific energy level of one REE is targeted in photoluminescence, no energy transfer to other REEs is observed despite many REEs having similarly spaced energy levels. This demonstrates that absorption and luminescence within an individual REE can be considered as intra-ion energy cascades, with little or no energy transfer to other REEs. Anomalous behaviour in the temperature dependence of IL in one leucophanite sample is interpreted as phase transitions in ice hosted in fluid inclusions. A comparison of luminescence of powder and cleavage fragment reveals that some emissions in the UV–blue region are surface related and do not represent bulk luminescence.     

Polarized luminescence spectra of kunzite

Kunzite, the pink, manganese-bearing variety of spodumene, is strongly luminescent under UV or electron beam excitation. Laser excitation of an oriented kunzite single crystal has been used to determine the polarization dependence of the luminescence. The emission spectrum, assigned to an Mn²⁺ center, can be fitted by two Gaussian bands with maxima at 16 568 and 15 679 cm^–1. Analysis of the temperature dependence of emission intensity and band width give estimates of the frequency of the phonons assisting the luminescence transitions. These appear to be bond stretching modes of the octahedral site. Analysis of the polarization dependence of emission intensity allows determination of the orientation of the emission dipole. Comparison of the polarization dependence of excitation and emission radiation shows that coupling between absorption dipole and emission dipole is incoherent.Work supported by the National Science Foundation under Grant No. DMR-74-00340     

He+ ion implantation and electron irradiation effects on cathodoluminescence of plagioclase

Cathodoluminescence (CL) spectra of unirradiated, He⁺ ion-implanted and electron-irradiated plagioclase minerals contain the following emission bands: (1) below 300 nm due to Pb²⁺, (2) at ~320 and ~350 nm to Ce³⁺, (3) at 380–420 nm to Eu²⁺, Ti⁴⁺ and/or Al–O^?–Al/Ti defects, (4) at 560–580 nm to Mn²⁺ and (5) at 720–760 nm to Fe³⁺. During the implantation of He⁺ ion, much of their energy may be dissipated by partial destruction and strain of the feldspar framework, resulting in quenching of CL. Deconvolution of CL spectra acquired from albite and oligoclase reveals an emission component at 1.86 eV (666 nm) assigned to a radiation-induced defect center associated with Na⁺ atoms. As its intensity increases with radiation dose, this emission component has potential for geodosimetry and geochronometry. Electron irradiation causes Na⁺ migration in plagioclase, and then a considerable reduction in intensity of emissions assigned to impurity centers, which is responsible for an alteration in the energy state or a decrease in luminescence efficiency following the change of activation energy. Emission intensity at 1.86 eV positively correlates with electron irradiation time for unimplanted and He⁺ ion-implanted albite and oligoclase, but negatively for the implanted albite above 1.07 × 10^?4 C/cm². It implies that radiation halo produced by α-particles should not be measured using CL spectroscopy to estimate β radiation dose on albite in the high radiation level.     

The nature of red luminescence of natural benitoite BaTiSi3O9

Summary This work examines the red luminescence of benitoite studied by laser-induced time-resolved luminescence spectroscopy. This method allows the differentiation between luminescence centers of similar emission wavelengths, but different decay times. We have also examined the luminescence intensity and decay time as a function of temperature. We found that the red emission of benitoite consists of two individual bands and one line and suggest that the activators of luminescence in benitoite system are Ti³⁺ and a d³ element, namely Cr³⁺ or Mn⁴⁺.     

The causes and petrological significance of cathodoluminescence emissions from alkali feldspars

The cathodoluminescence (CL) of a variety of alkali feldspars from South Greenland has been examined in an attempt to understand the causes of the CL and its petrological significance. Analytical methods have included CL spectroscopy, secondary ion mass spectrometry (SIMS) and electron paramagnetic resonance (EPR) to correlate the presence of certain CL emissions to the presence of certain trace element and point defects. Where possible, blue and red luminescent fractions of the same rock samples have been separated and analysed separately. Blue CL appears to relate to the presence of electron holes on bridging oxygens, particularly on the Al-O-Al bridge, as determined from EPR studies. No correlation with other proposed activators for blue CL such as Eu²⁺, Ga³⁺ or Ti⁴⁺ was observed. Some blue luminescent feldspars also have an emission in the infra-red (IR), invisible during normal visible CL petrography. The red and IR CL emissions correspond to features in EPR spectra attributed to Fe³⁺ and support previous suggestions that Fe³⁺ is related to this emission. However, our studies indicate that the visible red CL relates specifically to Fe³⁺ on the T1 site, whereas the equivalent CL from disordered feldspars lies in the IR. The difference between red and IR CL emissions therefore relates to the state of Fe³⁺ order across the tetrahedral sites. These data allow more meaningful interpretations of CL as a petrographic tool in alkali feldspar-bearing rocks. Received: 5 March 1998 / Accepted: 23 November 1998     

Photoluminescence properties of green and red luminescence from natural and heat-treated sodalite

The sodalite sample used in this investigation did not exhibit the characteristic orange-yellow luminescence due to the $ {\text{S}}_{ 2}^{ - } $ center, because there was no trace of sulfur impurity. The heat-treated samples exhibited green and red luminescence with maximum intensity at 496 and 687 nm, respectively, under 264 nm excitation at room temperature. Their luminescence intensities were extensively dependent on the treatment temperature. The green luminescence efficiency of the sample heat-treated at 900 °C was 6.5 times higher than that of unheated natural sodalite. At 8.5 K, the green luminescence showed a vibronic structure. After heating at 1,300 °C, the crystal structure of sodalite was transformed to NaAlSiO₄ (carnegieite), and the intense red luminescence was exhibited in the NaAlSiO₄ sample. The peak wavelength of the red luminescence shifted from 687 nm at 300 K to 726 nm at 8.5 K. The luminescence lifetimes of the green and red luminescence at room temperature were 2.1 and 5.1 ms, respectively. It was proposed that the origin of the green luminescence is Mn²⁺ replacing Na⁺, and that of the red luminescence is Fe³⁺ replacing Al³⁺ in sodalite or NaAlSiO₄ (carnegieite).     

Strain-driven disordering of low microcline to low sanidine during partial phase separation in microperthites

Microperthitic feldspar crystals containing low microcline in a braid intergrowth often have distinctive microtextures including coarse semi- to in-coherent grain-boundary pleated rims and fine coherent intracrystalline Ab- and Or-rich pleats (Lee et al. 1997). The coarser pleated rims are generally separated from the braid microtexture in the crystal interior by a coherent to semi-coherent transitional zone. Partial phase separation has occurred in the transitional zone in step with that in the Ab- and Or-rich pleats at the grain boundaries, such that Ab-rich lamellar film micro-antiperthite alternates along (010) with more Or-rich lamellar film microperthite; the microtextures and phases are those expected for the respective local bulk compositions. Lamellar microtextures contain tweed orthoclase, whereas low microcline is the only K-feldspar in the fine coherent pleats and braid microperthite. We propose that the small coherent pleats developed from the braid microtexture by interaction of the spontaneous coherency strains with discontinuities within or at the surface of the crystal, and that their initial spacing is guided by that of the braid microperthite. We infer that the transitional zone formed by straightening of the zig-zag braid microtexture above the pleat heads during coarsening and partial phase separation. We further infer that the resulting coherency shear strains induced a reversal of the K-feldspar phase transformation, involving Si, Al disordering of low microcline into low sanidine, now tweed orthoclase, although the crystal was at a T within the hydrostatic T-stability of microcline. Received: 10 June 1996 / Accepted: 12 December 1996     

独居石、磷钇矿显微阴极射线发光研究

独居石、磷钇矿的显微阴极射线发光观察表明,独居石的发光颜色为酱红色,发光较弱,发光强度分布不均匀,受杂质Fe_O_3影响明显。其中有相当数量零星分布的绿色强发光点。发光谱测定表明,这些绿色发光点来自Tb~(3+)、Dy~(3+)的非均匀分布。而独居石的基本发光色来自Sm~(3+)、Eu~(3+)和Tm~(3+)跃迁线。磷钇矿发光色为豆绿色,发光强度大,分布均匀,不受杂质Fe_2O_3影响。两者发光机理也不同,独居石发光直接来自Ce~(3+)的f-d跃迁和它对某些离子的能量传递,而磷钇矿则以[PO_4]~(4-)阴离子团为敏化中心,实现能量向Dy~(3+)等离子传输。     

Mineralogical indicators of volatile loss and alkali metasomatism in roof zones of the biotite granite in the Kwandonkaya Complex, Nigeria

The plutonic rocks in the Kwandonkaya complex, located within the NYG province of Nigeria, have some hypersolvus granites composed mainly of orthoclase microperthite and interstitial annite. These are inferred to have formed from a relatively F-poor, and relatively dry felsic melt. During cooling, Al–Si order was not completely achieved when the inversion of sanidiness to orthoclase and exsolution occurred. A majority of the granites contain intermediate to low microcline with annite to siderophyllite. The samples were incipiently modified in the subsolidus at very low fluid–rock ratios. Drusy granites result from resurgent boiling and volatile loss, which produced orthoclase-dominant feldspar and zoned zinnwaldite, with microcline lining cavities, whereas late loss of volatiles resulted in low microcline and zinnwaldite and metasomatism associated with cassiterite-topaz mineralization. Mica composition in both types of drusy granite is similar and seems to have been fluid-buffered. Albitization was rock-buffered and resulted in variable degree of Al–Si order in K-feldspar and mild modification of mica composition. Key factors affecting both the degree of Al–Si order of K-feldspar and mica compositions at Kwandonkaya seem to be the degree of volatile build-up and loss, and extent of fluid–rock interactions.     

An investigation of cathodoluminescence in albite from the A-type Georgeville granite,Nova Scotia

Cathodoluminescence (CL) reveals red and blue colors within single, non-turbid albite (Ab_98–99) grains from the Georgeville granite, Nova Scotia. A 720 nm X-ray excited optical luminescence (XEOL) peak characterizes red CL regions, while a 280 nm XEOL feature dominates blue CL regions. Synchrotron X-ray fluorescence results indicate that red CL and the 720 nm XEOL peak intensities relate to total Fe concentrations. The relationship between red CL and Fe content is confirmed by electron microprobe (EMPA) and laser ablation-inductively coupled mass spectrometry (LA-ICP-MS). The XEOL technique is used to exclude the Fe K-edge as the cause of red CL. X-ray absorption spectroscopy results indicate that Fe in both the red and blue CL regions is Fe³⁺, and that red CL activation may relate to the Si–Al order of the feldspar and to the distribution of Fe on tetrahedral sites. The CL textures, combined with EMPA and LA-ICPMS analyses, indicate that blue CL albite (Ab₉₈) regions contain higher concentrations of Ca, Ti, Pb and rare earth elements, and were replaced, in part, by a more Fe-rich, trace element depleted albite (Ab₉₉) which displays red CL. Complex diffraction contrasts and amorphous deposits identified in transmission electron microscope images suggest that aqueous fluids have reacted with both red and blue CL regions. Fluid inclusion homogenization temperatures of up to 430 °C provide a lower estimate of the fluid temperature.     

Ultraviolet-blue ionic luminescence of alkali feldspars from bulk and interfaces

Laboratory driven ionic thermal exchange of alkali feldspars from K to Na produces samples which are strongly luminescent in the ultraviolet region near 320 nm. The sites providing this luminescence are suggested as being correlated with the motion of Na atoms along interface-interphases of the material (i.e. with Na-O bond fracture). The thermoluminescence peaks show multi-order kinetics. Thermal preheatings of low albite sensitize the feldspar lattice with respect to thermoluminescence generated by exposure to UV irradiation and heating produces a strong blue luminescence spread over the range 350 nm to 500 nm band in feldspars. The upper temperature for thermoluminescence in feldspars is ∼300 °C, which is also the point where ionic conductivity of albite (010) begins, but the 300 °C region is also the starting point of a large second glow peak in adularia. Whilst it seems appropriate to link the Na motion to the 350–500 nm emission, it is unclear whether these changes are the result of the large anisotropic thermal vibration of Na atoms or the massive Na jumps that occur when the lattice reaches 300 °C. A speculative model is considered in which the UV TL emissions of natural minerals are linked to different interface-interphases (grain boundaries, exsolution limits, twinning planes, antiphase domains). Increased interface coherency energies are related to the kinetic order and the spectral position of luminescence emission peaks. Received: 3 December 1998 / Revised, accepted: 17 April 1999     

A room-temperature phase transition in maximum microcline

A type of hysteresis, similar to that observed in the heat capacity measurements (Openshaw et al., 1979), has been found in the room temperature unit cell parameters of a microcline sample 71104 and likewise indicates the existence of two forms of this microcline. The A-form (obtained on cooling the sample to approximately 80 K) has significantly different values of b, β and V to the B-form which is the more stable form above 300±10 K. The transition from the A- to the B-form occurs over a period of months and has an associated ΔV of ?0.0011 nm³. The cell parameters of the B-form have been measured up to 1278 K and show significant changes: a and V increase, b constracts, and c is unchanged on increasing temperature. The calculated thermal expansion ellipsoid is nearly uniaxial and similar in shape to that for sanidine. Below room temperature the isobaric thermal expansion coefficent α_p, for a natural microcline is nearly four times as large as that for sanidine. Above room temperature α_p for 71104 microcline decreases markedly with increasing temperature. This implies a rapid change in the thermal expansion behavior of microcline which has been correlated with the proposed phase transition.     

Leaching of quartz from precambrian hypabyssal rhyolite porphyry,Llano County,Texas

A Precambrian hypabyssal rhyolite porphyry in central Texas has retained its original texture, although alkali feldspar phenocrysts have inverted and unmixed from zoned, single-phase high-temperature feldspar to zoned microperthite with an intermediate microcline host.Blue quartz phenocrysts owe their color to dispersion by zircon inclusions. Neutron activation analysis reveals substitution of tetravalent cations for silicon in the quartz.In two outcrops, quartz and albite have been completely leached from the rock and K-feldspar added, leaving the texture intact. The leaching was most likely accomplished by residual brine from an overlying Lower Cretaceous evaporite deposit subsequently removed by erosion.     

A cathodoluminescence and petrographical study of marbles from the Pohorje area in Slovenia

Marbles from the Pohorje area in Slovenia are investigated by mineralogical-petrographical analyses of thin sections as well as by cathodoluminescence in order to detect their local variability in texture and mineral assemblages. The CL colours observed in a cold cathode device are related to the manganese contents. An attempt is made to relate the textures seen under CL to mineral reactions during the process of metamorphism. The predominantly calcite marbles from Pohorje exhibit orange luminescence with some dolomite lenses with red luminescence. The typical mineral assemblages are calcite+tremolite+phlogopite or calcite+dolomite+tremolite+phlogopite. Therefore, the estimated temperature from the stability of mineral assemblage is assumed at approximately 500 °C.     

Review of effects of radiation damage on the luminescence emission of minerals, and the example of He-irradiated CePO4

The accumulation of structural damage that is created in minerals upon corpuscular irradiation, has two apparently contrarious effects on their luminescence behaviour. First, irradiation may cause the generation of luminescent defect centres, which typically results in broad-band emissions. Such defect emissions are characteristic of low levels of radiation damage. Second, radiation damage depletes in general the luminescence of minerals, which is associated with broadenings and intensity losses of individual emission lines. Minerals that have suffered elevated levels of irradiation hence tend to be virtually non-luminescent. This review paper aims at giving an overview of the possible correlations of radiation damage and emission characteristics of minerals. After a brief, introductory summary of the damage-accumulation process and its causal corpuscular radiation, an array of examples is presented for how internal and/or external irradiation may change appreciably the emission of rock-forming and accessory minerals. As a detailed example for the complexity of changes of emissions upon damage accumulation, preliminary results of a case study of the photoluminescence (PL) of synthetic CePO₄ irradiated with 8.8 MeV He ions are presented. Irradiation-induced spectral changes include (i) the initial creation, and subsequent depletion, of a broad-band, defect-related PL emission of orange colour, and (ii) gradual broadenings and intensity losses of PL lines related to electronic transitions of rare-earth elements, eventually leading to gradual loss of their splitting into multiple Stark levels (shown for the ⁴F_3/2 → ⁴I_9/2 transition of Nd³⁺).     

Thermoluminescence and radioluminescence in aragonite

Summary Thermoluminescence (TL) and radioluminescence (RL) wavelength spectra of aragonite have been investigated. Despite the different origin of the samples used, a number of common luminescence features emerges. The spectra for TL peaks appearing near 50, 70 and 170 K are identical with a prominent and broad band centered near 400 nm. In the case of TL peaks appearing at about 350, 380, 420 and 455 K, the onset of new emission bands is due to the characteristic emission of some cation impurities (i.e., Mn²⁺, Pb²⁺). Below 200 K, all emission bands encountered for a given TL peak are also present in the RL spectrum obtained at the temperature of the glow peak. The electron-hole recombination mechanisms involved in aragonite appear to be related with those found in rhombohedric carbonates.

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Thermolumineszenz und Radiolumineszenz in Aragonit

Zusammenfassung Wellenlängen-Spektra der Thermolumineszenz (TL) and der Radiolumineszenz (RL) von Aragonit wurden untersucht. Trotz des unterschiedlichen Ursprungs der verwen-deten Proben zeigte die Lumineszenz eine Reihe gemeinsamer Züge. Die bei ungefähr 50, 70 und 170 K auftretenden TL-Spektra sind ident und zeigen eine dominierende und breite Bande mit Zentrum bei ca. 400 nm. Die TL-Maxima, die bei ungefähr 350, 380, 420 und 250 K auftreten, gehören zu Spektren, deren wesentliche Züge Kationen-Verunreinigungen wie Mn²⁺ und Pb²⁺ zugeordnet werden können. Die TL- und RL-Spektra sind ident, wenn die Temperatur des Kristalls kleiner als 200 K ist. Die Elektron-Loch Rekombinationsmechanismen in Aragonit scheinen mit jenen in den rhomboedrischen Karbonaten verwandt zu sein.

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Resumen Dos aragonitos de distinta procedencia se han investigado con et fin de analizar espectralmente sus respectivas emisiones de termoluminiscencia (TL) y radioluminiscencia (RL). A pesar de su distinto origen, ambos aragonitos presentan caracteristicas luminiscentes comunes. Los mâximos de TL que aparecen a 50, 70 y 170 K presentan espectros idénticos. Su principal caracteristica común es la presencia de una prominente y ancha banda cuyo máximo se situa cerca de 400 nm. Los máximos de TL que aparecen alrededor de 350, 380, 420 y 450 K presentan espectros cuya principal caracteristica es la de contener bandas asignables a iones-impureza tales como Mn y Pb. Los espectros de TL y RL son coincidentes siempre que la temperatura del cristal sea inferior a 200 K. Los mecanismos de recombination electron-hueco en et aragonito presentan una cierta similitud con los de los carbonatos romboédricos.

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With 6 figures     

福建碧田Au-Ag-Cu矿床含金石英脉中磷灰石的阴极发光研究

碧田Au Ag Cu矿床含金石英脉中的磷灰石在阴极射线激发下发明亮的黄绿色光 ,特征峰波长为 5 70～5 80nm。阴极发光 (CL)图像揭示了磷灰石的内部环带结构 ,不同环带微量和稀土元素含量具有明显的差异。发光带w(MnO) >0 .4%、n(Mn) /n(Fe) >2、n(Mn) /n(La+Ce) >4;Mn2 + 为CL的主要激发元素。磷灰石晶体结构中以LREE3 + +Si4+ =Ca2 + +P5+ 为主要的元素替代形式。磷灰石微量与稀土元素的分布特征表明 ,该矿床形成于近地表的低温热液体系 ,成矿流体在矿物共沉淀的晚期向富Si、Na方向演化。