Towards single grain ESR dating of sedimentary quartz: first results

In optically stimulated luminescence dating, apparent ages of individual grains are thought to reflect a wide distribution of initial bleaching levels in hard to bleach sediments. Although having a larger age range (up to 1 Ma and beyond), this approach has not been used yet in electron spin resonance (ESR) dating. Here we report on the first results of ESR measurements on single sedimentary quartz grains. Initial bleaching levels are evaluated for two different River Meuse deposits in Limburg, NE Belgium. Measurements were done with a Q-band ESR spectrometer on transparent quartz grains of sufficiently large diameter (0.5–0.7 mm). Single crystal ESR properties were used to identify different ESR active centres. In about 50% of the selected grains an Al and/or Ti–Li signal was detected and the latter has been selected for further measurements. Artificial bleaching experiments show a strong signal decrease with UV light exposure. After gamma-ray irradiation, a number of different signal intensity vs. artificial dose curves could be observed: exponential growth, exponential saturation, linear, with inflexion points, and unclear ones. Many grains show increasing ESR signals with doses up to 1000 Gy, suggesting that the age range could be extended over 1 Ma, covering the Middle Pleistocene and part of the Early Pleistocene. Accumulated doses of individual grains were calculated using the additive dose method. The results show a large dose distribution of individual grains for both deposits. It is concluded that insufficiently bleached grains can be detected using single grain ESR measurements of sedimentary quartz in a fluvial environment.     

石英ESR测年信号衰退特征研究进展

电子自旋共振(ESR)测年法是第四纪地质年代学的重要测试方法之一,其测年范围广,特别是对于20万年至百万年尺度的第四纪样品有着重要意义.准确测量古剂量是影响ESR测年法精度和可信度的重要因素之一,而掌握ESR信号衰退特征及机制是获得准确、可信古剂量的重要前提.ESR测年法适用的地质样品种类较多,如热液石英脉、地质断层泥、水系沉积物等,不同样品的ESR信号衰退特征和机制有较大差异.近年来,国内外学者针对不同地质样品中石英ESR信号的衰退特征和机制深入开展了一系列的实验室模拟和野外观测研究,取得了诸多新认识.回顾了近年来在石英ESR信号衰退特征领域取得的进展,特别是水系沉积物石英ESR信号的衰退特征,并展望了这一领域的未来工作重点.     

Titaniferous magnetite–ilmenite thermometry and titaniferous magnetite–ilmenite–orthopyroxene–quartz oxygen barometry in granulite facies gneisses, Bamble Sector, SE Norway: implications for the role of high-grade CO2-rich fluids during granulite genesis

Oxygen fugacities have been estimated for a wide distribution of samples from the granulite facies terrane (region C) of the Bamble Sector, SE Norway using both the titaniferous magnetite–ilmenite and orthopyroxene–titaniferous magnetite–quartz oxygen barometers. These oxygen fugacities are estimated using temperatures calculated from the titaniferous magnetite–ilmenite thermometer of Ghiorso and Sack (1991) and are both internally consistent with each other as well with the thermometer. In samples for which the estimated temperature is high, the two oxygen barometers show good agreement whereas agreement is poor for low temperature samples. In these low temperature samples, oxygen fugacities estimated from titaniferous magnetite–ilmenite are considerably less than those estimated from orthopyroxene–titaniferous magnetite–quartz. An increase in this discrepancy with decrease in temperature appears to reflect preferential resetting of the hematite component in the ilmenite grains without significant alteration of the more numerous titaniferous magnetite grains. This is due, in part, to greater re-equilibration of the ilmenite grains during retrograde interoxide resetting between the ilmenite grains and the titaniferous magnetite grains. The mean temperature for the non-reset samples, 791?±?17?°C (1σ), is in good agreement with temperatures obtained from garnet–orthopyroxene K_D exchange thermometry in the same region, 785–795?°C (1σ) (Harlov 1992, 2000a). Most non-reset oxygen fugacities range from log₁₀?f?O₂=?14 to ?11.8 or approximately 0.5–1.5?log units above quartz–fayalite–magnetite at 7.5?kbar. Both these temperatures and the range of oxygen fugacities are in good agreement with those estimated using the titaniferous magnetite–ilmenite thermometer/oxygen barometer of Andersen et?al. (1991). The QUIlP equilibrium (quartz–ulvöspinel–ilmenite–pyroxene) is used to project self-consistent equilibrium temperatures and oxygen fugacities for samples reset due to hematite loss from the ilmenite grains. These projected temperatures and oxygen fugacities agree reasonably well with the non-reset samples. The mean projected QUIlP temperature is 823?±?6?°C (1σ). This result supports the conclusion that low titaniferous magnetite–ilmenite temperatures (down to 489?°C) and accompanying low oxygen fugacities are the result of hematite loss from the ilmenite grains. Non-reset oxygen fugacities lie approximately 1.5?log₁₀ units above the upper graphite stability curve indicating that the stable C–O–H fluid phase interacting with these gneisses, whether regionally or locally, was CO₂. This is borne out by the presence of numerous CO₂-rich fluid inclusions in these rocks.     

冰川沉积类型识别与ESR测年样品采样规范

电子自旋共振(ESR)技术是一种确定物质成分和结构的顺磁性质的分析方法,也能够用于沉积物定年。该方法的测量技术和测年的物理机制等还处于发展阶段。冰川作用过程十分复杂,形成各种类型的冰川沉积物,其顺磁信号的归零机制有显著差异,ESR测年的实验方案也有所差异。因此,识别冰碛物类型,采集合适的样品对于ESR测年的准确性十分重要。冰下融出碛和滞碛经过了冰下磨蚀过程,结构致密,细颗粒基质含量高,石英砂中的一些杂质芯的ESR信号能够衰退。许多冰上融出碛,结构疏松,但细颗粒基质含量高,不但经过了搬运过程中的冰下磨蚀过程使ESR信号衰退,又经历了沉积时的冰上阳光直射过程使信号衰退,一些样品的ESR信号能够完全晒退。冰水湖泊和冰水河流沉积的细砂和粉砂来源于冰下研磨的产物,信号会衰退;在搬运沉积过程中又可能被阳光直射,信号进一步衰退。其它类型的冰碛物的ESR信号衰退机制不明,或粒径不适合用ESR方法测年。采集冰碛物ESR年代样品时,最好同时采集信号衰退机制相同的现代冰碛物样品,以便对照,并用于扣除可能的残留信号。     

Quartz chemistry – A step to understanding magmatic-hydrothermal processes in ore-bearing granites: Cínovec/Zinnwald Sn-W-Li deposit,Central Europe

Quartz from granites, greisens and quartz veins from a 1596 m long vertical section through the Cínovec/Zinnwald Li-Sn-W deposit (Czech Republic) was studied using cathodoluminescence (CL) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP MS). The trace contents of Al, Ti, Li and the Ge/Ti and Al/Ti values in quartz reflect the degree of fractionation of parental melt from which primary quartz crystallized. From the biotite granite to the younger zinnwaldite granite, quartz is characterized by increasing contents of Al (from 136–176 to 240–280 ppm) and decreasing Ti (from 16–54 to 6–14 ppm), while the contents of Li and Ge are similar (15–36 and 0.8–1.7 ppm, respectively). Quartz of the greisen stage and vein stage is poor in all measured elements (26–59 ppm Al, 0.5–1.6 ppm Ti, 2–13 ppm Li, 0.8–1.6 ppm Ge). The youngest low-temperature quartz forming thin coatings in vugs in greisen and veins differs in its extreme enrichment in Al (>1000 ppm) and Li (∼100 ppm) and very low Ti (<1 ppm). Within the greisen, remnants of primary magmatic quartz should be distinguished from metasomatic greisen-stage quartz in their higher intensity of CL and relatively higher Ti contents. A part of primary magmatic quartz may by secondarily purified via infiltration of hydrothermal fluids and dissolution–reprecipitation processes. Such quartz parallels newly formed greisen-stage quartz in its chemical and CL properties; the share of greisen-stage quartz may by therefore overestimated.     

The effect of deformation on the TitaniQ geothermobarometer: an experimental study

We performed high strain (up to 47 %) axial compression experiments on natural quartz single crystals with added rutile powder (TiO₂) and ~0.2 wt% H₂O to investigate the effects of deformation on the titanium-in-quartz (TitaniQ) geothermobarometer. One of the objectives was to study the relationships between different deformation mechanisms and incorporation of Ti into recrystallized quartz grains. Experiments were performed in a Griggs-type solid-medium deformation apparatus at confining pressures of 1.0–1.5 GPa and temperatures of 800–1,000 °C, at constant strain rates of 1 × 10^?6 or 1 × 10^?7 s^?1. Mobility of Ti in the fluid phase and saturation of rutile at grain boundaries during the deformation experiments are indicated by precipitation of secondary rutile in cracks and along the grain boundaries of newly recrystallized quartz grains. Microstructural analysis by light and scanning electron microscopy (the latter including electron backscatter diffraction mapping of grain misorientations) shows that the strongly deformed quartz single crystals contain a wide variety of deformation microstructures and shows evidence for subgrain rotation (SGR) and grain boundary migration recrystallization (GBMR). In addition, substantial grain growth occurred in annealing experiments after deformation. The GBMR and grain growth are evidence of moving grain boundaries, a microstructure favored by high temperatures. Electron microprobe analysis shows no significant increase in Ti content in recrystallized quartz grains formed by SGR or by GBMR, nor in grains grown by annealing. This result indicates that neither SGR nor moving grain boundaries during GBMR and grain growth are adequate processes to facilitate re-equilibration of the Ti content in experimentally deformed quartz crystals at the investigated conditions. More generally, our results suggest that exchange of Ti in quartz at low H₂O contents (which may be realistic for natural deformation conditions) is still not fully understood. Thus, the application of the TitaniQ geothermobarometer to deformed metamorphic rocks at low fluid contents may not be as straightforward as previously thought and requires further research.     

ESR dating of quaternary tephra from Mt. Osore-zan using Al and Ti centres in quartz

Quaternary tephra of Mt. Osore-zan was dated by electron spin resonance. Quartz grains were separated from the tephra and ESR signals of Al and Ti centres were measured at 77 K. The signals of Al and Ti centres which have a complicated hyperfine structure were simplified by using wider field modulations width (5 gauss) than usually used (0.5–1 gauss). The influence of 5 gauss modulation width on the measurement of the signal intensity of Al and Ti centres was investigated. The intensity of the signal increases linearly with gamma irradiation and total doses obtained were 178 to 273 Gy and ESR ages were 0.19 to 0.32 Ma. These ages agree with the estimated age of about 0.3 Ma from the correlation of volcanic ash and terrace level.     

Applicability of ESR dating using multiple centres to fault movement — The case of the Itoigawa-Shizuoka tectonic line, a major fault in Japan

No direct method for dating the fault movement has been hitherto established, except ESR dating whose applicability is disputed however. The most serious question in ESR dating is whether accumulated ESR signals are completely reset at the time of fault movement. When the defect centres are partially preserved at the time of previous faulting, the date obtained is uncertain. We have shown (Fukuchi et al., 1985, 1986), however, that we can judge correctly whether ESR signals were completely reset or not when the ESR signal counting is done for multiple ESR centres of different stabilities for resetting. From the data for completely reset centres, actual date of fault movement can be calculated.This multiple centre method was tested with samples whose ESR signal intensities are judged to be about zero at the time of fault movement. The result, which confirms the applicability for the fault movement dated back to 100 ka BP, is presented in this paper.     

Trace element incorporation into quartz: A combined study by ICP-MS, electron spin resonance, cathodoluminescence, capillary ion analysis, and gas chromatography

Pegmatite quartz from different occurrences in Norway and Namibia was investigated by a combination of ICP-MS, Electron Spin Resonance (ESR), Capillary Ion Analysis (CIA) and Gas Chromatography (GC) to quantify trace elements in very low concentrations and to determine their position in the quartz structure.The studied quartz samples show similar geochemical characteristics with low contents of most trace elements. Remarkable are the elevated concentrations of Al (36-636 ppm), Ti (1.6-25.2 ppm), Ge (1.0-7.1 ppm), Na (5.2 to >50 ppm), K (1.6 to >100 ppm) and Li (2.1-165.6 ppm). These elements are preferentially incorporated into the quartz lattice on substitutional (Al, Ti, Ge) and interstitial (Li, Na, K) positions. Li⁺ was found to be the main charge compensating ion for Al, Ge and Ti, whereas some ppm of Na and K may also be hosted by fluid inclusions. Ti may be incorporated as substitutional ion for Si or bound on mineral microinclusions (rutile). The results of the ESR measurements show that there may be a redistribution of alkali ions during irradiation. The diamagnetic [AlO₄/M⁺]⁰ center transforms into the paramagnetic [AlO₄]⁰ center, whilst the compensating ions diffuse away and may be captured by the diamagnetic precursor centers of [GeO₄]⁰ and [TiO₄]⁰ to form paramagnetic centers ([TiO₄/Li⁺]⁰, [GeO₄/Li⁺]⁰).In general, fluid inclusions in pegmatite quartz can be classified as H₂O-CO₂-NaCl type inclusions with water as the predominant volatile. Among the main elements hosted by fluid inclusions in quartz are Na, K, NH₄, Ca, Mg and the anionic complexes Cl⁻, NO₃⁻, HCO₃⁻ and SO₄²⁻. Gas analysis of trapped fluids shows volatile components in the following order of abundance: H₂O > CO₂ > N₂(+) ≥ CH₄ > COS > C₂ and C₃ hydrocarbons. Additionally, traces of Co, Ni, Zn, Pb, and Cu were detected by CIA in fluid inclusions of some samples. There are indications that the REE and Rb are also bound in fluid inclusions, however, the concentrations of these elements are too low to be measured by CIA. Assuming that the REE preferentially occur in fluid inclusions, the typical chondrite normalized REE distribution patterns with tetrad effects and a distinct negative Eu anomaly would reflect the composition of the mineralizing fluid.For a number of elements, especially those with extremely low concentrations, the “type” of incorporation in quartz could not directly be determined. We conclude that these ions either are too large to substitute for the small Si⁴⁺ ion or they are not soluble in the mineralizing fluids to be hosted by fluid inclusions. Some of these elements, which are concentrated in the specific mineralization of certain pegmatites, are not present in elevated concentrations in the paragenetic pegmatite quartz itself. This was observed, for instance, for Be, Cs and Rb in the Li (Be-Cs-Rb) pegmatites of Rubicon or for Nb and Ta for Nb-Ta bearing pegmatites from Norway. It may be concluded that the concentrations of these trace elements in quartz do not reflect the mineralization and that these elements thus, cannot be used as petrogenetic indicator.     

Optically stimulated luminescence (OSL) dating of quartzite cobbles from the Tapada do Montinho archaeological site (east‐central Portugal)

The burial age of an alluvially deposited cobble pavement at the Tapada do Montinho archaeological site (east‐central Portugal) is investigated using optically stimulated luminescence (OSL) dating. Measurements on the cobbles (quartzite clasts) were carried out on intact slices and large aliquots (～8 mm) of quartz grains (63–300 μm), both recovered from the outer 1.5‐mm surface of the cobbles. The recycling ratio, recuperation and dose‐recovery tests show that the single‐aliquot regenerative‐dose (SAR) protocol is applicable to both rock slices and quartz grains; both have similar luminescence characteristics. The variation in the natural OSL signal with depth below the cobble surface using intact slices from two different cobbles shows that both were bleached to a depth of at least ～2 mm before deposition. A model of the variation of dose with depth fitted to data from one of the cobbles gives a burial age of ～19 ka and also predicts the dose‐depth variation at the time of deposition. Ages based on rock slices suggest that one cobble surface, and the inner parts of two other cobbles experienced a resetting event at ～45 ka, consistent with the age control. However, the surfaces of the other cobbles all record light‐exposure events in the range 26 to 14 ka, suggesting that some of the cobbles were exposed to daylight perhaps more than once in this period. Given the shallow burial depth and unexpectedly young ages of the surrounding and overlying finer‐grained sediment, it is suggested that phases of light exposure following surficial erosion are probably responsible for this underestimate. Nevertheless, it is remarkable that we can identify and quantify four events (two light exposures of different durations and two sequential burial periods) in the dose record contained within a single clast, and this suggests that the luminescence dating of rock surfaces may prove, in the future, to be at least as important as sand/silt sediment dating.     

Testing polymineral post-IR IRSL and quartz SAR-OSL protocols on Middle to Late Pleistocene loess at Batajnica,Serbia

The loess–palaeosol sequence of Batajnica (Vojvodina region, Serbia) is considered as one of the most complete and thickest terrestrial palaeoclimate archives for the Middle and Late Pleistocene. In order to achieve a numerical chronology for this profile, four sets of ages were obtained on 18 individual samples. Equivalent doses were determined using the SAR protocol on fine (4–11 μm) and coarse (63–90 μm) quartz fractions, as well as on polymineral fine grains by using two elevated temperature infrared stimulation methods, pIRIR₂₉₀ and pIRIR₂₂₅. We show that the upper age limit of coarse quartz OSL and polymineral pIRIR₂₉₀ and pIRIR₂₂₅ techniques is restricted to the Last Glacial/Interglacial cycle due to the field saturation of the natural signals. Luminescence ages on coarse quartz, pIRIR₂₂₅ and pIRIR₂₉₀ polymineral fine grains are in general agreement. Fine quartz ages are systematically lower than the coarse quartz and pIRIR ages, the degree of underestimation increasing with age. Comparison between natural and laboratory dose response curves indicate the age range over which each protocol provides reliable ages. For fine and coarse quartz, the natural and laboratory dose response curves overlap up to ~150 and ~250 Gy, respectively, suggesting that the SAR protocol provides reliable ages up to c. 50 ka on fine quartz and c. 100 ka on coarse quartz. Using the pIRIR₂₂₅ and pIRIR₂₉₀ protocols, equivalent doses up to ~400 Gy can be determined, beyond which in the case of the former the natural dose response curve slightly overestimates the laboratory dose response curve. Our results suggest that the choice of the mineral and luminescence technique to be used for dating loess sediments should take into consideration the reported limited reliability.     

Application of the titanium-in-quartz thermometer to pelitic migmatites from the Adirondack Highlands, New York

The 'TitaniQ' (Ti-in-quartz) solubility thermometer was applied to migmatitic metapelites from the southern and western Adirondack Highlands, New York, to examine the effect of granulite facies metamorphism on the distribution of Ti in quartz. Both cathodoluminescence imaging and quantitative traverses revealed that individual grains of Adirondack quartz are highly zoned with respect to Ti, and that core-to-rim decreases of Ti are common. Large ranges in calculated temperature were observed within each sample. One sample, not considered to be saturated with respect to TiO₂, gave maximum temperatures more than 100 °C lower than previously estimated peak temperatures. Rutile-saturated southern and western Adirondack samples yielded peak estimates of ≥803 ± 11 °C and ∼860–870 °C, respectively, which are similar to previous estimates from major phase thermometry. Minimum Ti-in-quartz matrix temperatures from rutile-saturated samples are 630 °C, which is interpreted as the closure temperature for Ti diffusion in quartz in these samples. This study demonstrates that Ti-in-quartz thermometry can yield details of rock evolution if the textural setting and reaction history of the quartz is clear, and can yield near-peak metamorphic temperatures in some cases, if care is taken to test for post-peak diffusional resetting.     

Optically stimulated luminescence dating of fluvial deposits: a review

Optically Stimulated Luminescence (OSL) dating allows age determination of sediments deposited during the last glacial-interglacial cycle. This relatively new technique therefore enables chronological frameworks to be established for fluvial deposits that often cannot be dated by other means. The OSL signal of quartz and feldspar minerals is reset by light exposure during fluvial transport, and builds up as a result of ionizing radiation after burial of the minerals. Incomplete resetting of the OSL signal because of inadequate light exposure in the fluvial environment can result in age overestimations, especially for relatively young samples. Methods used for the detection of incomplete resetting, or poor bleaching, are reviewed. It is argued that technique s measuring the OSL signal from small subsamples (aliquots) are most promising for detecting poor bleaching and for obtaining the true age for a sample in which not all grains had their OSL signal completely removed at deposition. Quartz should be the mineral of choice, because it has been shown to yield the most reliable results and because its OSL signal is more rapidly reset than that of feldspar. Aliquot size should be small, with aliquots ideally consisting of a single grain of quartz for samples in which the majority of grains are poorly bleached. Using single-aliquot dating of coarse-grain quartz, age offsets between zero and a few thousand years have been found for modern fluvial deposits. The validity of single-aliquot quartz OSL dating has been demonstrated by application to known-age samples, but for the older age range (>˜13 ka) further proof of the accuracy of the method is essential. The application of quartz OSL dating to investigations of fluvial deposits opens a new realm of possibilities to be explored, as is highlighted by some examples of geological applications.     

A combined EMPA and LA-ICP-MS study of Li-bearing mica and Sn–Ti oxide minerals from the Qiguling topaz rhyolite (Qitianling District,China): The role of fluorine in origin of tin mineralization

The Sn-rich Qiguling topaz rhyolite dike intrudes the Qitianling biotite granite of the Nanling Range in southern China; the granite hosts the large Furong Sn deposit. The rhyolite dike is typically peraluminous, volatile-enriched, and highly evolved. Whole-rock F and Sn concentrations attain 1.9 wt.% and 2700 ppm, respectively. The rhyolite consists of a fine-grained matrix formed by quartz, feldspar, mica and topaz, enclosing phenocrysts of quartz, feldspar and mica; it is locally crosscut by quartz veinlets. Lithium-bearing micas in both phenocrysts and the groundmass can be classified as primary zinnwaldite, “Mus-Ann” (intermediate member between annite and muscovite), and secondary Fe-rich muscovite. Topaz is present in the groundmass only; common fluorite occurs in the groundmass and also in a specific cassiterite, rutile and fluorite (Sn–Ti–F) assemblage. Cassiterite and rutile are the only Sn and Ti minerals; both cassiterite and Nb-rich rutile are commonly included in the phenocrysts. The Sn–Ti–F assemblage is pervasive, and contains spongy cassiterite in some cases; cassiterite also occurs in quartz veinlets which cut the groundmass. Electron microprobe and LA-ICP-MS compositions were used to study the magmatic and hydrothermal processes and the role of F in Sn mineralization. The presence of zinnwaldite and “Mus-Ann”, which are respectively representative of early and late mica crystallization during magma differentiation, also suggests a significant decrease in f(HF)/f(H₂O) of the system. Cassiterite included in the zinnwaldite phenocrysts is suggested to have crystallized from the primary magma at high temperature. Within the Sn–Ti–F aggregates, rutile crystallized as the earliest mineral, followed by fluorite and cassiterite. Spongy cassiterite containing inclusions of the groundmass minerals indicate a low viscosity of the late fluid. The cassiterite in the quartz veinlets crystallized from low-temperature hydrothermal fluids, which possibly mixed with meteoric water. In general, cassiterite precipitated during both magmatic and hydrothermal stages, and over a range of temperatures. The original fluorine and tin enrichments, f(HF)/f(H₂O) change in the residual magma, formation of Ca,Sn,F-rich immiscible fluid, decrease of the f(HF) during groundmass crystallization, and mixing of magma-derived fluids with low-saline meteoric water during the late hydrothermal stage, are all factors independently or together responsible for the Sn mineralization in the Qiguling rhyolite.     

Studies on the lattice distortion and substructures of shocked lamellae in naturally shocked quartz

One unshocked and 9 naturally shocked single quartz crystal grains with 1–6 sets of shock lamellae from the Ries, West Germany, and the Lake Lappajärvi, Finland, covering a range from unshocked quartz withNo = 1.544 to nearly completely glassy quartz withNo = 1.461 have been used for X-ray precession and Laue investigations. Four of the shocked grains have preliminarily been studied under a transmission electron microscope. It is found that quartz havingNo less than 1.539 shows intensive anisotropic cell expansion and lattice disordering which gradually increase asNo decreases. Shock-induced lattice distortion of quartz is clearly shown on both precession and Laue photographs. For the weakly shocked quartz (p < 200 kb) slight to pronounced spreading of spots is observed. When the pressure reaches 200 kb, both concentric spreading of spots having long ‘tails’ and concentric rings (powder pattern) are revealed on the same photograph, which means that besides a part of single crystal there also exist randomly oriented tiny ‘fragments’ of quartz in this shocked quartz grain. As pressure increases from 230 to 315 kb, more and more crystalline puases in the quartz grains have transformed from solid state into silica glass, and the concentric rings and the long ‘tails’ disappear and the spot spreading becomes slight again, but reflection intensities become much lower in comparison with those of weakly shocked quartz. TEM investigations show three kinds of substructures of shock lamellae. The glass contents of two of the four grains (73% and 84% respectively) were measured on TEM photographs with the help of an image analysis system. On the basis of above investigations a six-terminal-state model for the mechanism of deformation in shock metamorphosed quartz is presented.     

Minor elements in quartz from hydrothermal-metamorphic veins in the Nether Polar Ural Province

Vein quartz from the Nether Polar Ural Province was examined by atomic emission spectrometry, gas chromatography, electron paramagnetic resonance, and electron microscopy. According to atomic emission spectrometric analysis, the total concentration of Al, Fe, Mg, Ti, Ca, Na, K, and other minor elements in the quartz varies from 8 to 47 ppm. The lowest concentrations of minor elements were detected in the granulated quartz. Giant-crystalline milk-white quartz is noted for higher concentrations of minor elements, including Na, K, and Ca, because it contains gas-liquid inclusions. The fine-grained quartz contains very small mineral inclusions and is thus noted for elevated concentrations of Ca, Fe, K, Mg, and Ti. Gas chromatographic data on the gas phase separated from the quartz at its heating indicate that this phase contains H₂O, CO₂, and other components. The H₂O concentration reaches 429 ??g/g, while the CO₂ content is commonly no higher than 20 ??g/g. Gas separation is at a maximum at temperatures of 100?C600°C, when gasliquid inclusions decrepitate, as is typical, first of all, of the giant-crystalline milk-white quartz. Gas separation continues at higher temperatures (below 1000°C) but is much less intense. The electron microscopic examination of quartz grains after their acid treatment indicates that the surface of these grains is covered by caverns of various morphology and size, which were produced by the partial dissolution of the quartz and the opening of its gas-liquid and mineral inclusions occurring near the surface; the inclusions were not, however, completely removed. The crystal structure of the quartz contains minor Al, Ge, Na, Li, Ti, and Fe. The lowest concentrations of Al and Ge paramagnetic centers are typical of the granulated (recrystallized) and fine-grained quartz. The giant-crystalline quartz, including its transparent varieties, and individual quartz crystals, first of all their smoky-citrine varieties, contain higher concentrations of minor elements. In the Nether Polar Ural Province, granulated quartz is potentially promising for producing especially pure quartz concentrates. The quality of the translucent coarse-to giant-crystalline quartz, which predominates in the resources and reserves, is deteriorated by gas-liquid inclusions in it and requires deep processing of the raw minerals.     

Caractérisation par résonance paramagnétique électronique (RPE) de quartz naturels issus de différentes sources

Natural quartz crystals coming from Madagascar, Angola, Brazil, and Spain were studied by EPR after β irradiation in order to characterise the paramagnetic centres due to impurities, and examine in which way their relative proportion could constitute a useful criterion for origin researches. In all our samples, EPR experiments revealed germanium centres [GeO₄/M⁺]° with M = Li or Na, aluminium ones [AlO₄/h]° and two titanium centres ([TiO₄/H⁺]° and [TiO₄/M⁺]°) also appeared, except for samples coming from Spain. The comparison of the relative concentrations of paramagnetic species led us on to draw diagrams that allowed distinguishing the origins of the studied samples using only EPR spectra. To cite this article: M. Duttine et al., C. R. Geoscience 334 (2002) 949–955.     

OSL ages and possible bioturbation signals at the Upper Paleolithic site of Lagoa do Bordoal,Algarve, Portugal

Three sediment samples were collected from a soil profile at the Lagoa do Bordoal site, Algarve, Portugal. Quartz extracted from soil horizons within the profile, was optically dated using the single-aliquot regenerative-dose (SAR) protocol outlined by Murray and Wintle (Radiation Measurements 5 (2000) 523). The optically stimulated luminescence (OSL) emitted by quartz within the 90–150 μm size range was measured using three aliquot sizes. The equivalent doses (D_E) that were obtained show an asymmetric distribution. As the numbers of grains in each aliquot are reduced, the distribution of doses is clearly shifted to lower D_E values including zero doses on single grain aliquots. This shift is accompanied by an increase in the asymmetry of the distribution. These patterns indicate that as the aliquot size decreases, the distributions are increasingly characterized by aliquots with lower D_E's. With respect to the present day modern surface, this shift is most evident in the sample collected from a depth of 37 cm, within an ancient B-horizon. It is least evident in the sample located only 10 cm below it, within a sand unit. An asymmetric distribution of D_E's can be a result of a large number of grains that were well bleached at burial being mixed with a small number of grains that were partially bleached at that time (Radiation Measurements 30 (1999) 207). However, the shift in D_E's that is seen in the Lagoa East samples is most likely due to the postburial downward movement of fully and partially bleached grains from the surface, with possible contributions from the downward movement of grains that received low doses while buried in overlying horizons. The simplest explanation for our results is that grains carrying zero or small D_E's have been moved downward during bioturbation events. These results suggest that downward bioturbation in ancient soil profiles can be identified based on the OSL characteristics of quartz grains. We are also able to provide a minimum age of 24.4±3.2 ka for the Upper Palaeolithic lithic assemblage at the site.     

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.     

Research Advances in ESR Provenance Tracing Methods of Quartz in Sediments

The ESR (Electron Spin Resonance) signals of quartz is a newly developed sediment provenance tracing method. In this paper, the various ESR signals in quartz, historical development of quartz ESR signals in sediment provenance tracing, thermal stability characteristics of heat treated E’ center, the potential use of quartz nature E’ center and the irradiated Al/Ti center, as well as successful applications in aeolian sediments, river sediments and marine sediments provenance tracing, were briefly reviewed. The most useful ESR centers of quartz include the heat treated E’ center, the nature E’ center, the Al center and the Ti center. According to recent application researches, the heat-treated E’ center is the most commonly practiced among them while the significance of provenance tracing by Al and Ti centers are still in experimental and theoretical stage. Moreover, nature signal intensities of quartz E’ center not only show a significant dependence on lithology both in bedrocks and deposits, but also can reflect the mixture ratio of deposits with different types of sourced bedrocks. As for the study objects, this method has been successfully used in the studies of provenance area of East Asian dust, the temporal and spatial changes of Loess Plateau provenance, the provenance change of aeolian sediment over time and space on Japanese Islands, as well as sediment provenance tracing of Japan Sea sediments. In addition, the ESR provenance tracing of quartz has promising application prospect in quantitative and semi-quantitative analysis of fluvial sediment provenance tracing. Along with the development of ESR dating, this method can significantly reflect and reconstruct the relationship among regional tectonic movements, geomorphic evolution, and climate evolution. In future work, the combination of trace elements provenance tracing and ESR signals provenance tracing in quartz will help improve and promote the development of sediments provenance tracing methods.