Diffusion of helium in zircon and apatite     

D.J. Cherniak  E.B. Watson  J.B. Thomas 《Chemical Geology》2009,268(1-2):155-166

Diffusion of helium has been characterized in natural zircon and apatite. Polished slabs of zircon and apatite, oriented either normal or parallel to c were implanted with 100 keV ³He at a dose of 5 × 10^{15 3} He/cm². Diffusion experiments on implanted zircon and apatite were run in Pt capsules in 1-atm furnaces. ³He distributions following experiments were measured with Nuclear Reaction Analysis using the reaction ³He(d,p)⁴He. For diffusion in zircon we obtain the following Arrhenius relations:Although activation energies for diffusion normal and parallel to c are comparable, there is marked diffusional anisotropy, with diffusion parallel to c nearly 2 orders of magnitude faster than transport normal to c. These diffusivities bracket the range of values determined for He diffusion in zircon in bulk-release experiments, although the role of anisotropy could not be directly evaluated in those measurements.In apatite, the following Arrhenius relation was obtained over the temperature range of 148–449 °C for diffusion normal to c:In contrast to zircon, apatite shows little evidence of anisotropy. He diffusivities obtained in this study fall about an order of magnitude lower than diffusivities measured through bulk release of He through step-heating, and within an order of magnitude of determinations where ion implantation was used to introduce helium and He distributions measured with elastic recoil detection.Since the diffusion of He in zircon exhibits such pronounced anisotropy, helium diffusional loss and closure cannot be modeled with simple spherical geometries and the assumption of isotropic diffusion. A finite-element code (CYLMOD) has recently been created to simulate diffusion in cylindrical geometry with differing radial and axial diffusion coefficients. We present some applications of the code in evaluating helium lost from zircon grains as a function of grain size and length to diameter ratios, and consider the effects of “shape anisotropy”, where diffusion is isotropic (as in the case of apatite) but shapes of crystal grains or fragments may depart significantly from spherical geometry.  相似文献   

Ti in zircon from the Boggy Plain zoned pluton: implications for zircon petrology and Hadean tectonics     

R. B. Ickert  I. S. Williams  D. Wyborn 《Contributions to Mineralogy and Petrology》2011,162(2):447-461

The understanding of zircon crystallization, and of the Ti-in-zircon thermometer, has been enhanced by Ti concentration measurements of zircon from a small, concentrically zoned pluton in south-eastern Australia, the Boggy Plain zoned pluton (BPZP). Zircon crystals from rocks ranging in composition from gabbro to aplite were analysed for U–Th–Pb dating and Ti concentrations by an ion microprobe. Geochronological data yield a ²⁰⁶Pb/²³⁸U age of 417.2 ± 2.0 Ma (95% confidence) and demonstrate the presence of older inherited or xenocrystic zircon. Titanium measurements (n = 158) yield a mean Ti concentration of 11.7 ± 6.1 ppm (2SD) which corresponds to a mean crystallization temperature of 790°C for an α-TiO₂ = 0.74 (estimated using mineral equilibria), or 760°C for an α-TiO₂ = 1.0. Apparent zircon crystallization temperatures are similar in all intrusive phases, although the gabbro yields slightly higher values, indicating that crystallization occurred at the same temperature in all rock types. This finding is consistent with previous work on the BPZP, which indicates that liquid–crystal sorting (crystal fractionation) was the dominant control on chemical differentiation, and that late, differentiated liquids were similar in composition for all rock types. A simple forward model approximately predicts the range of crystallization temperatures, but not the shape of the distributions, due to sampling biases and complexities in the cooling and crystallization history of the pluton. The distribution of Ti concentrations has a mode at a higher Ti (higher temperature) than the sample set of Hadean detrital zircon. This is consistent with the hypothesis that the skew to low-T in the Hadean dataset is due to the presence of zircon that crystallized from wet anatectic melts.  相似文献   

Trace-element composition of hydrothermal zircon and the alteration of Hadean zircon from the Jack Hills,Australia     

《Geochimica et cosmochimica acta》2005,69(3):637-648

Hydrothermal zircon can be used to date fluid-infiltration events and water/rock interaction. At the Boggy Plain zoned pluton (BPZP), eastern Australia, hydrothermal zircon occurs with hydrothermal scheelite, molybdenite, thorite and rutile in incipiently altered aplite and monzogranite. The hydrothermal zircon is texturally distinct from magmatic zircon in the same rocks, occurring as murky-brown translucent 20–50 μm-thick mantles on magmatic cores and less commonly as individual crystals. The hydrothermal mantles are internally textureless in back-scatter electron and cathodoluminescence images whereas magmatic zircon is oscillatory zoned. The age of the hydrothermal zircon is indistinguishable from magmatic zircon, indicating precipitation from a fluid evolved from the magma during the final stages of crystallization. Despite indistinguishable U-Pb isotopic compositions, the trace-element compositions of the hydrothermal and magmatic zircon are distinct. Hydrothermal zircon is enriched in all measured trace-elements relative to magmatic zircon in the same rock, including V, Ti, Nb, Hf, Sc, Mn, U, Y, Th and the rare-earth elements (REE). Chondrite-normalized REE abundances form two distinct pattern groupings: type-1 (magmatic) patterns increase steeply from La to Lu and have Ce and Eu anomalies—these are patterns typical for unaltered magmatic zircon in continental crust rock types; type-2 (hydrothermal) patterns generally have higher abundances of the REE, flatter light-REE patterns [(Sm/La)_N = 1.5–4.4 vs. 22–110 for magmatic zircon] and smaller Ce anomalies (Ce/Ce* = 1.8–3.5 vs. 32–49 for magmatic zircon). Type-2 patterns have also been described for hydrothermally-altered zircon from the Gabel Hamradom granite, Egypt, and a granitic dyke from the Acasta Gneiss Complex, Canada.Hadean (∼4.5–4.0 Ga) zircon from the Jack Hills, Western Australia, have variable normalized REE patterns. In particular, the oldest piece of Earth—zircon crystal W74/2-36 (dated at 4.4 Ga)—contains both type-1 and type-2 patterns on a 50 μm scale, a phenomenon not yet reported for unaltered magmatic zircon. In the context of documented magmatic and hydrothermal zircon compositions from constrained samples from the BPZP and the literature, the type-2 patterns in crystal W74/2-36 and other Jack Hills Hadean (JHH) zircon are interpreted as hydrothermally-altered magmatic compositions. An alteration scenario, constrained by isotope and trace-element data, as well as α-decay event calculations, involving fluid/zircon cation and oxygen isotope exchange within partially metamict zones and minor dissolution/reprecipitation, may have occurred episodically for some JHH zircon and at ∼4.27 Ga for zircon W74/2-36. Type-2 compositions in JHH zircon are interpreted to represent localized exchange with a light-REE-bearing, high δ¹⁸O (∼6–10‰ or higher) fluid. Thus, a complex explanation involving “permanent” liquid water oceans, large-scale water/rock interaction and plate tectonics in the very early Archean is not necessary as the zircon textures and compositions are simply explained by exchange between partially metamict zircon and a low volume ephemeral fluid.  相似文献   

Ti site occupancy in zircon   总被引：1，自引：0，他引：1  

N.D. Tailby  A.M. Walker  J. Hermann  J.A. Mavrogenes  I.S. Rodina  D. Rubatto 《Geochimica et cosmochimica acta》2011,75(3):905-921

Ti site occupancy in zircon (ZrSiO₄) is fundamental to thermobarometry because substitution mechanisms control Ti content-temperature relations. Here we describe the results of three independent methods used to demonstrate that Ti substitutes for Si and not Zr in zircon. Zircon grains were synthesized from oxide powders held in a Na₂WO₄ flux at 1 bar and 1300 °C. Zircon grains equilibrated with rutile + cristobalite show Ti contents (1201 ppm) nearly half that of zircon grains equilibrated with srilankite ((Ti,Zr)O₂) + tetragonal zirconia (2640 ppm). The lower Ti content of zircon grains produced at silica-saturated conditions indicates that Ti substitution predominately occurs on the Si site. Moreover, the higher Ti contents of silica-saturated experiments at 1 bar (1201 ppm), relative to those at 1 GPa (457 ppm, Ferry and Watson, 2007), indicates a substantial pressure effect on Ti solubility in zircon. Measured Ti K-α edge X-ray Absorption Near Edge Structure (XANES) spectra of synthetic zircon grains show energies and normalized intensities akin to those seen among tetrahedrally coordinated Ti-bearing standard minerals, strongly suggesting that Ti occupies the Si site. Density functional theory (DFT) calculations confirm that Ti substitution is most likely to occur on the Si site and predict a Ti-O bond length of 1.797 Å (compared to an average of 2.160 Å for substitution on the Zr site), in excellent agreement with X-ray Absorption Fine Structure (EXAFS) spectra of experimentally grown zircon grains which indicate a value of 1.76(1) Å. The software FEFF 8.4 was used to simulate XANES spectra from the defect structures determined by DFT for Ti substituting on both the Si and Zr sites. The predicted spectrum for Ti on the Si site reproduces all the key features of the experimental zircon spectra, whereas Ti on the Zr site is markedly different. All applied methods confirm that Ti substitutes for Si in zircon. Consequently, the Ti content of zircon at a given pressure is not only a function of temperature, but will increase with decreasing silica activity. Because elements that activate or quench cathodoluminescence (CL) in zircon are incorporated into the Zr site, a decoupling of CL from Ti contents - incorporated on the Si site in zircon is expected. This hypothesis has been verified by a systematic CL-trace element study of natural and experimental zircon.  相似文献   

变质岩中锆石U—Pb计时问题评述——兼论大别造山带锆石定年   总被引：44，自引：8，他引：44  

陈道公  李彬贤等 《岩石学报》2001,17(1):129-138

锆石是U－Pb计时的首选对象，对于地质历史复杂的变质岩地区，如大别碰撞造山带的年代学研究，具有不可替代的重要性。变质岩中锆石经历了Pb的扩散丢失作用；晶格损伤导致的蜕晶化作用；增生－混合作用和重结晶作用。这些过程对锆石计时的准确性和有效性带来不同程度的影响。为了使测定的年龄有确定的地质意义，在进行锆石U－Pb定年前，必需对锆石进行成因矿物学和矿物内部结构研究，特别是阴极荧光和背散射电子成像研究，通过内部结构特征确定锆石成因过程。在化学U－Pb法定年时注意普通铅校正和^204Pb测定值对年龄的影响，尽量选择单一成因锆石。特别强调在大别造山带年代学中引入锆石微区离子探针定年技术。  相似文献