Hydrothermal precious opals of the Raduzhnoe deposit,north Primorye: The nature of the opalescence

This paper reports the results of the study of hydrothermal precious opals. It was established that, in terms of their nanostructure and formation conditions, the hydrothermal opals differ from exogenic precious opals. They are made up of small globules and do not show any structuring of their nanoparticles on the basis of closest packing, which is typical of exogenic precious opals. During their formation, these opals were subjected to pneumatolytic annealing—they experienced the impact of a high-temperature vapor under elevated pressure. The influence of the thermal effect led to the formation of two-dimensional photonic band gaps in the chaotic opal matrix. These bands are composed of sheets whose cells were formed owing to the thermal effects according to the principle of “Benard cells.” Precisely these structured blocks and thin films are responsible for the spectral dispersion of light and iridescence.     

Soil-to-dwelling radon isotope ratio in the Baikal region

Relations between indoor and soil gas radon were experimentally studied in villages of the Baikal region. On the basis of the obtained data, the soil-to-indoor radon ratio was calculated, which can be used for prediction of radon pollution in buildings of the same kind.     

矿物氧同位素模式温度计算

根据对现遥氧扩散模型的解析分析,通过模拟矿物之间的氧同位素交换轨迹进行模式温度计算,改进了常规矿物对氧同位素地质温度计方法。将模式温度计算与矿物氧－扩散封闭次上结合,建立了一个系统独立的同位素温度计算方法,因此所得到的同位素温度能够更好地反映矿物在高温岩石冷却过程中,的氧同位素交换行为;模式温度计算有如下优点：（１）考虑到了矿物之间扩散引起的同位素交换;（２）遵循质量守恒原理,更严格地适用于有限封     

Empirical calibration of oxygen isotope fractionation in zircon

New empirical calibrations for the fractionation of oxygen isotopes among zircon, almandine-rich garnet, titanite, and quartz are combined with experimental values for quartz-grossular. The resulting A-coefficients (‰K²) are:

	Zrc	Alm	Grs	Ttn
Qtz	2.64	2.71	3.03	3.66
Zrc		0.07	0.39	1.02
Alm			0.32	0.95
Grs				0.63

Full-size table

     

Calculation of oxygen isotope fractionation in magmatic rocks

The increment method is applied to calculation of oxygen isotope fractionation factors for common magmatic rocks. The ¹⁸O-enrichment degree of the different compositions of magmatic rocks is evaluated by the oxygen isotope indices of both CIPW normative minerals and normalized chemical composition. The consistent results are obtained from the two approaches, pointing to negligible oxygen isotope fractionation between rock and melt of the same compositions. The present calculations verify the following sequence of ¹⁸O-enrichment in the magmatic rocks: felsic rocks>intermediate rocks>mafic rocks>ultramafic rocks. Two sets of internally consistent fractionation factors are acquired for phenocryst–lava systems at the temperatures above 1000 K and rock–water systems in the temperatures range of 0–1200 °C, respectively. The present calculations are consistent with existing data from experiments and/or empirical calibrations. The obtained results can be used to quantitatively determine the history of water–rock interaction and to serve geological thermometry for various types of magmatic rocks (especially extrusive rocks).     

An Experimental Study of Oxygen Isotope Fractionation in the Quartz—Wolframite—Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water system from 200 to 420 °C. The starting wolframite was synthesized in aqueous solutions of Na₂WO₄ · 2H₂O + FeCl₂ · 4H₂O or MnCl₂ · 4H₂O. The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl. Experiments were conducted in a gold-lined stainless steel autoclave, with filling degrees of about 50%. The results showed no significant difference in equilibrium isotope fractionation between water and wolframite, ferberite and huebnerite at the same temperature (310 °C ). The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370 °C, but to increase significantly with decreasing temperature below 370 °C: 1000 ln α_wf-H₂o= 1.03×10⁶T−2-4.91 (370 °C ±200 °C ) 1000 ln α_wf-H₂o = 0.21×10⁶T −2-2.91 (420 °C -370 °C ±) This projects was financially supported by the National Natural Science Foundation of China.     

Intra-shell oxygen isotope ratios in the benthic foraminifera genus Amphistegina and the influence of seawater carbonate chemistry and temperature on this ratio

Using secondary ion mass spectrometry (SIMS) we looked at the natural variability in the oxygen isotope ratio of the shallow water, symbionts-bearing foraminiferan Amphistegina lobifera. Live foraminifera were collected in February 2005 in the Gulf of Eilat, Israel. Vertical section exposing the knob area of this species represents the growth history of this species from August 2004 to February 2005. SIMS profile at a resolution of ∼15 μm (representing about 2 weeks considering the size of the knob area and the life span of ≈6 months of this foraminifera species) yielded δ¹⁸O changes of ∼1.5‰ that are compatible with the known temperature changes for the Gulf of Eilat for this period (21-27 °C). Natural variability between primary and secondary calcite at the knob area were obtained on horizontal section of the upper knob area. This section is semi-tangential to the growth lines and exposes relatively wide belts of the primary calcite which could be analysed using the SIMS (beam size of 10 × 20 μm). The primary calcite δ¹⁸O value is on average more than 3‰ lower than the secondary calcite that represents the bulk of the skeleton (more than 95% by weight). A vertical profile at the knob was obtained by rastering an area of 50 × 50 μm at vertical steps of roughly 1 μm. The profile revealed a narrow zone of lower δ¹⁸O compared to the higher values above and below it. The difference between the lowest δ¹⁸O and the highest one was also close to 2‰. The δ¹⁸O in the margin - keel area of A. lobifera is also lower compared to the bulk secondary calcite. Specimens that were cultured in the laboratory at a constant temperature and inorganic carbon but at different pH have increased their CaCO₃ weight by roughly a factor of 8. Single specimen from each pH (ranging between 7.90 and 8.45) were investigated with the SIMS at the knob area. While there is some variability within each specimen (perhaps related to the primary calcite), the general trend was a decrease in δ¹⁸O with increasing pH (or CO₃²⁻ concentration), in agreement with previous studies on planktonic foraminifera. Some other specimens grown at different temperatures (between 21 and 33 °C) were also measured with the SIMS at the knob area. For each temperature, we observed also some variability, nevertheless the trend of −0.2‰/°C in δ¹⁸O is observed.     

Timescales for the evolution of oxygen isotope compositions in the solar nebula

We review two models for the origin of the calcium-, aluminum-rich inclusion (CAI) oxygen isotope mixing line in the solar nebula: (1) CO self-shielding, and (2) chemical mass-independent fractionation (MIF). We consider the timescales associated with formation of an isotopically anomalous water reservoir derived from CO self-shielding, and also the vertical and radial transport timescales of gas and solids in the nebula. The timescales for chemical MIF are very rapid. CO self-shielding models predict that the Sun has Δ¹⁷O_SMOW ∼ −20‰ (Clayton, 2002), and chemical mass-independent fractionation models predict Δ¹⁷O_SMOW ∼0‰. Preliminary Genesis results have been reported by McKeegan et al. (McKeegan K. D., Coath C. D., Heber, V., Jarzebinski G., Kallio A. P., Kunihiro T., Mao P. H. and Burnett D. S. (2008b) The oxygen isotopic composition of captured solar wind: first results from the Genesis. EOS Trans. AGU 89(53), Fall Meet. Suppl., P42A-07 (abstr)) and yield a Δ¹⁷O_SMOW of ∼ −25‰, consistent with a CO self-shielding scenario. Assuming that subsequent Genesis analyses support the preliminary results, it then remains to determine the relative contributions of CO self-shielding from the X-point, the surface of the solar nebula and the parent molecular cloud.The relative formation ages of chondritic components can be related to several timescales in the self-shielding theories. Most importantly the age difference of ∼1-3 My between CAIs and chondrules is consistent with radial transport from the outer solar nebula (>10 AU) to the meteorite-forming region, which supports both the nebular surface and parent cloud self-shielding scenarios. An elevated radiation field intensity is predicted by the surface shielding model, and yields substantial CO photolysis (∼50%) on timescales of 0.1-1 My. An elevated radiation field is also consistent with the parent cloud model. The elevated radiation intensities may indicate solar nebula birth in a medium to large cluster, and may be consistent with the injection of ⁶⁰Fe from a nearby supernova and with the photoevaporative truncation of the solar nebula at KBO orbital distances (∼47 AU). CO self-shielding is operative at the X-point even when H₂ absorption is included, but it is not yet clear whether the self-shielding signature can be imparted to silicates. A simple analysis of diffusion times shows that oxygen isotope exchange between ¹⁶O-depleted nebular H₂O and chondrules during chondrule formation events is rapid (∼minutes), but is also expected to be rapid for most components of CAIs, with the exception of spinel. This is consistent with the observation that spinel grains are often the most ¹⁶O-rich component of CAIs, but is only broadly consistent with the greater degree of exchange in other CAI components. Preliminary disk model calculations of self-shielding by N₂ demonstrate that large δ¹⁵N enrichments (∼ +800‰) are possible in HCN formed by reaction of N atoms with organic radicals (e.g., CH₂), which may account for ¹⁵N-rich hotspots observed in lithic clasts in some carbonaceous chondrites and which lends support to the CO self-shielding model for oxygen isotopes.     

The oxygen isotope geochemistry of igneous rocks

Oxygen isotope analyses have been obtained for 443 igneous rock and mineral samples from various localities throughout the world. Detailed studies were made on the Medicine Lake, Newberry, Lassen, Clear Lake, S. E. Guatemala, Hawaii and Easter I. volcanic complexes and on the Bushveld, Muskox, Kiglapait, Guadalupe, Duluth, Nain, Egersund, Lac St. Jean, Laramie, Skaergaard, Mull, Skye, Ardnamurchan and Alta, Utah plutonic complexes, as well as upon several of the zoned ultramafic intrusions of S. E. Alaska. Basalts, gabbros, syenites and andesites are very uniform in O¹⁸/O¹⁶, commonly with δ-values of 5.5 to 7.0 per mil. Many rhyolite obsidians, particularly those from oceanic areas and the Pacific Coast of the United States, also lie in this range; this indicates that such obsidians are differentiates of basaltic or andesitic magma at high temperatures (about 1,000° C). They cannot represent melted sialic crust. The only plutonic granites with such low δ-values are some of the hypersolvus variety, suggesting that these also might form by fractional crystallization. Obsidians from the continental interior, east of the quartz-diorite line, have higher δ-values. This is compatible with their having assimilated O¹⁸-rich sialic crust. A correlation generally exists between the O¹⁸/O¹⁶ ratios of SiO₂-rich differentiates and the chemical trends in volcanic complexes. High O¹⁸/O¹⁶ ratios accompany those trends having the lower Fe/Mg ratios, while ferrogabbro trends are associated with depletion in O¹⁸. Variations in oxygen fugacity may be responsible for these effects, as abundant early precipitation of magnetite should lead to both O¹⁸-enrichment and Fe-depletion in later differentiates. Plutonic granites have higher O¹⁸/O¹⁶ ratios than their volcanic equivalents, because (a) their differentiation occurred at much lower temperatures, or (b) they are in large part derived from O¹⁸-rich sialic crust by partial melting or assimilation. Also, the oxygen isotope fractionations among coexisting minerals are distinctly larger in plutonic rocks than in volcanic rocks. This is in keeping with their lower crystallization temperatures and their longer cooling history, which promotes post-crystallization oxygen isotope exchange. Hydrated obsidians and perlites have δO¹⁸-values that are much different from their primary, magmatic values. A correlation exists between D/H and O¹⁸/O¹⁶ ratios in hydrated volcanic glass from the western U.S.A., proving that the isotopic compositions are a result of exchange with meteoric waters. The O¹⁸ contents of the glasses appear to be about 25 per mil higher than their associated waters; hence, these hydrated glasses have not simply absorbed H₂O, but they have exchanged with large quantities of it. The igneous rocks from Mull, Skye, Ardnamurchan and the Skaergaard intrusion are all abnormally depleted in O¹⁸ relative to “normal” igneous rocks. This is a result of their having exchanged at high temperatures with meteoric water that was apparently abundant in the highly jointed plateau lavas into which these igneous rocks were intruded. In part, this exchange occurred with liquid magma and in part with the crystalline rock; in the latter case the feldspar was more easily exchanged and has become much more depleted in O¹⁸ than has coexisting quartz or pyroxene. The later differentiates of the Muskox intrusion are markedly O¹⁸-rich, but this is not a result of fractional crystallization. It is in large part a result of deuteric exchange between feldspars and an oxygen-bearing fluid (H₂O ?) that was either O¹⁸-rich or had a relatively low temperature. This phenomenon was also observed in a number of granophyres from other localities, particularly those containing brick-red alkali feldspar. The exchanged feldspars in all these examples are turbid or cloudy, and may be filled with hematite dust. It is concluded that most such feldspar in nature is the result of deuteric exchange and is probably drastically out of oxygen isotopic equilibrium with its coexisting quartz.     

岩浆岩体系氧同位素分馏系数的理论计算

The increment method is applied tocalcuation of oxygen isotope fractionation factors for common magmatic rocks by usingoxygen isotope indices for known minerals.The results show that there are some differencesin the degree of 18O-enrichment for the different types of magmatic rocks,andtheir sequence of 18O-enrichment is reckoned as follows acid rocks >neutral rocks > basic rocks > ultrabasic rocks.Two sets of internally consistentfractionation factors for phenocryst-lava systems at temperacture above 1000K and forrock-water systems in the temperature range of 0 to 1200℃ are acquired, respectively.Thetheoretical calibrations are consistent with the data from hydrothermal experiments andempirical estimates.The present results can be used to quantitatively determine thehistory of water-rock exchange and to serve geological thermometry for various magmaticrocks (especially extrusive rocks containing phenocryst).     

亚洲树轮稳定氧同位素研究进展

树轮稳定氧同位素作为一种高精度的古气候代用指标,在亚洲地区的发展起步晚进步快。树轮稳定氧同位素比率（δ¹⁸O）对区域气候信息有较强的记录能力,且与水汽循环关系密切,对于理解复杂的亚洲气候起着重要作用。亚洲地区树轮δ¹⁸O对温度的响应主要出现在高纬度地区,中低纬度树轮δ¹⁸O主要记录与水分（降水、相对湿度、PDSI等）有关的信号。对亚洲地区已发表的树轮δ¹⁸O与气候要素（温度、降水、相对湿度）的相关分析显著性统计显示,生长季气候对树轮δ¹⁸O至关重要,树轮δ¹⁸O 与温度的显著相关关系呈正相关,与降水和相对湿度的呈负相关,温度和降水通过降水δ¹⁸O影响树轮δ¹⁸O,但各自的信号强度存在区域差异,而相对湿度信号则广泛记录在不同区域不同树种之中。亚洲树轮稳定氧同位素研究集中于中低纬度地区,因而对大气水文循环的响应主要侧重于对亚洲夏季风和ENSO的研究,对季风降水的记录反映了季风活动的变化特征以及与之有关的环流信息;季节分辨率的树轮稳定氧同位素研究限于低纬热带亚热带区域,但对于理解区域气候和季风活动的年内变化、挖掘年轮不清晰树种的树轮学研究潜力具有重要的意义。     

方解石—橄榄石—流体三相体系氧同位素交换的实验研究

在６８０℃和５００ＭＰａ以及岩石学相平衡条件下,首次对方解石与镁橄榄石之间在大量超临界ＣＯ２－Ｈ２Ｏ流体存在的条件下进行了氧同位素交换实验。结果发现,在实验刚刚开始的一段时间内氧同位素交换很快,主要是以溶解／重结晶的机制进行的;而在以后的时间里氧同位素交换要慢得多,变成以扩散机制为主。进一步,反应产物方解石相对于镁橄榄石亏损＾１８Ｏ,指示方解石的溶解／重结晶速率大于镁橄榄石。流体相的存在导致具有不     

The implication of the oxygen isotope records in coexisting cherts and phosphates

δ¹⁸O values have been determined for 53 coexisting chert-phosphate pairs from the Phanerozoic and Precambrian. In addition, δ¹⁸O values were also determined for 18 biogenic phosphates from the Phanerozoic.The oxygen isotope data for the chert-phosphate pairs permit the calculation of the temperatures of formation of the chert-phosphate pairs as well as the δ¹⁸O of the waters in which they equilibrated. In turn the calculated δ¹⁸O of the waters permit the calculation of temperatures from the isotopic data of the biogenic phosphates. The temperatures for the Tertiary and Mesozoic samples are compatible with the literature values determined from oxygen isotope data for well-preserved calcareous marine skeletal remains. The temperatures calculated from the chert-phosphate pairs of the Paleozoic are usually higher and vary in cycles of about a 150 million year period. The early Precambrian temperatures are as high as 80°C and decrease with time. The use of chert-phosphate pairs for temperature determinations are sufficiently promising to warrant further investigations of this type on well preserved chert-phosphate or carbonate-phosphate pairs.     

Antiphase hydrogen and oxygen isotope periodicity in chert nodules

Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ¹⁸O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ¹⁸O line with δD values that are almost 50‰ lower. The δD-δ¹⁸O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.     

Theoretical calculation of oxygen isotope fractionation factors in carbonate systems

Using established methods of statistical mechanical calculation and a recent compilation of vibrational frequency data, we have computed oxygen isotope reduced partition function ratios (β values) for a large number of carbonate minerals. The oxygen isotope β values of carbonates are inversely correlated to both the mass and radius of the cation bonded to the carbonate anion but neither correlation is good enough to be used as a precise and accurate predictor of β values. There is an approximately 0.6% relative increase in the β values of aragonite per 10 kbar increase in pressure. These estimates of the pressure effect on β values are broadly similar to those deduced previously for calcite using the methods of mineral physics. In comparing the β values of our study with those derived recently from first-principles lattice dynamics calculations, we find near-perfect agreement for calcite and witherite (<0.3% deviation), reasonable agreement for dolomite (<0.9% deviation) and somewhat poorer agreement for aragonite and magnesite (1.5-2% deviation). In the system for which we have the most robust constraints, CO₂-calcite, there is excellent agreement between our calculations and experimental data over a broad range of temperatures (0-900 °C). Similarly, there is good to excellent correspondence between calculation and experiment for most other low to moderate atomic mass carbonate minerals (aragonite to strontianite). The agreement is not as good for high atomic mass carbonates (witherite, cerussite, otavite). In the case of witherite and cerussite, the discrepancy may be due, in part, to our calculation methodology, which does not account for the effect of cation mass on the magnitude of vibrational frequency shifts associated with heavy isotope substitution. However, the calculations also reveal an incompatibility between the high- and low-temperature experimental datasets for witherite and cerussite. Specifically, the shapes of fractionation factor versus 1/T² curves in the calcite-witherite and calcite-cerussite systems do not conform to the robust constraints on the basic shape of these curves provided by theory. This suggests that either the high- or low-temperature datasets for both minerals is in error. Dolomite-calcite fractionation factors derived from our calculations fall within the wide range of fractionations for this system given by previous experimental and natural sample studies. However, our compilation of available low-temperature (25-80 °C) experimental data reveal an unusual temperature dependence of fractionations in this system; namely, the data indicate an increase in the magnitude of fractionations between dolomite (or proto-dolomite) and calcite with increasing temperature. Such a trend is incompatible with theory, which stipulates that fractionations between carbonate minerals must decrease monotonically with increasing temperature. We propose that the anomalous temperature dependence seen in the low-temperature experimental data reflect changes in the crystallinity and degree of cation ordering of the dolomite phase over this temperature interval and the effect these changes have on the vibrational frequencies of dolomite. Similar effects may be present in natural systems at low-temperature and must be considered in applying experimental or theoretical fractionation data to these systems. In nearly all cases, carbonate mineral-calcite fractionation factors given by the present calculations are in as good or better agreement with experimental data than are fractionations derived from semi-empirical bond strength methods.     

氧同位素在高分辨率古气候研究中的应用探讨

高分率古气候研究成为近年来全球变化研究的热点，随着稳定同位素理论的不断完善和分析测试技术的迅速提高，沉积物中氧同位素(δ^18O)日益成为一项重要的环境替代指标，引起了国内外学者的关注。论述了氧同位素在冰岩心，黄土-古土壤以及洞穴沉积物中的应用，指出了其影响因素和在应用中存在的问题及发展方向。     

A laser fluorination method for oxygen isotope analysis of biogenic silica and a new oxygen isotope calibration of modern diatoms in freshwater environments

An empirical calibration for the oxygen isotope fractionation between biogenic silica and water was determined for diatom frustules sampled from living diatom communities in the Jemez Mountains of northern New Mexico, USA. Over a temperature range from 5.1 to 37.8 °C, the silica-water fractionation is defined by the equation 1000 ln α_{(silica-water)} = 2.39(±0.13) × 10⁶T⁻² + 4.23(±1.49). This relationship is in close agreement with other published silica-water fractionation factors for laboratory cultured diatom samples; however, it is as much as 8‰ lower than equilibrium quartz-water fractionations and 3-4‰ lower than observed silica-water fractionations in diatomaceous silica collected from sediment traps and sediment cores. There are three possible explanations for the disparate silica-water fractionation factors observed in diatom silica: (1) silica does not precipitate in equilibrium with ambient water, (2) silica does precipitate in equilibrium with ambient water, but the silica-water fractionation factor for diatom silica is considerably less than the equilibrium fractionation factor for quartz-water, or (3) silica precipitation is influenced by a ‘vital’ effect, where the δ¹⁸O value of the water inside the diatom cell walls is lower than the δ¹⁸O values of ambient water.Post-mortem loss of organic material results in an alteration or ‘maturation’ of diatom silica in which silica reequilibrates with a silica-water fractionation closer to the equilibrium quartz-water fractionation. Alteration is likely to occur rapidly after the diatom frustule loses its organic coating, either as it settles through the water column or at the sediment-water interface; δ¹⁸O values recorded by paleo-diatom silica therefore do not record growing conditions but more likely record conditions at the sediment-water interface. In the case of lacustrine environments, where the bottom water remains at a nearly constant 4 °C, the reequilibration of diatom silica with bottom conditions could reduce or remove the conflating effects of temperature on δ¹⁸O values recorded by paleo-diatom silica and provide direct information on the δ¹⁸O value of the lake water.     

乌鲁木齐河流域不同水体中的氧稳定同位素

采用乌鲁木齐河流域历年采集的降水、表层粒雪、冰川融水和河川径流等水样资料,分析了取样期间不同水样中氧稳定同位素的变化,揭示了降水中氧稳定同位素变化存在着明显的温度效应,而温度效应又与海拔高度有关;表层粒雪和冰川融水中氧稳定同位素则无明显的高度效应;冰川融水中的氧稳定同位素比率小于河川径流中的氧稳定同位素比率。评估了不同影响因子对水循环过程中稳定同位素变化的影响及相互作用,为稳定同位素技术在水循环研究中的应用提供了实例。