Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

<Superscript>10</Superscript>Be, <Superscript>18</Superscript>O and radiogenic isotopic constraints on the origin of adakitic signatures: a case study from Solander and Little Solander Islands,New Zealand

Subduction-related Quaternary volcanic rocks from Solander and Little Solander Islands, south of mainland New Zealand, are porphyritic trachyandesites and andesites (58.20–62.19 wt% SiO₂) with phenocrysts of amphibole, plagioclase and biotite. The Solander and Little Solander rocks are incompatible element enriched (e.g. Sr ~931–2,270 ppm, Ba ~619–798 ppm, Th ~8.7–21.4 ppm and La ~24.3–97.2 ppm) with MORB-like Sr and Nd isotopic signatures. Isotopically similar quench-textured enclaves reflect mixing with intermediate (basaltic-andesite) magmas. The Solander rocks have geochemical affinities with adakites (e.g. high Sr/Y and low Y), whose origin is often attributed to partial melting of subducted oceanic crust. Solander sits on isotopically distinct continental crust, thus excluding partial melting of the lower crust in the genesis of the magmas. Furthermore, the incompatible element enrichments of the Solander rocks are inconsistent with partial melting of newly underplated mafic lower crust; reproduction of their major element compositions would require unrealistically high degrees of partial melting. A similar argument precludes partial melting of the subducting oceanic crust and the inability to match the observed trace element patterns in the presence of residual garnet or plagioclase. Alternatively, an enriched end member of depleted MORB mantle source is inferred from Sr, Nd and Pb isotopic compositions, trace element enrichments and εHf ? 0 CHUR in detrital zircons, sourced from the volcanics. ¹⁰Be and Sr, Nd and Pb isotopic systematics are inconsistent with significant sediment involvement in the source region. The trace element enrichments and MORB-like Sr and Nd isotopic characteristics of the Solander rocks require a strong fractionation mechanism to impart the high incompatible element concentrations and subduction-related (e.g. high LILE/HFSE) geochemical signatures of the Solander magmas. Trace element modelling shows that this can be achieved by very low degrees of melting of a peridotitic source enriched by the addition of a slab-derived melt. Subsequent open-system fractionation, involving a key role for mafic magma recharge, resulted in the evolved andesitic adakites.     

Metasomatism and the crystallization of zircon megacrysts in Archaean peridotites from the Lewisian complex,NW Scotland

Zircon megacrysts are locally abundant in 1–40 cm-thick orthopyroxenite veins within peridotite host rocks in the Archaean Lewisian gneiss complex from NW Scotland. The veins formed by metasomatic interaction between the ultramafic host and Si-rich melts are derived from partial melting of the adjacent granulite-facies orthogneisses. The interaction produced abundant orthopyroxene and, within the thicker veins, phlogopite, pargasite and feldspathic bearing assemblages. Two generations of zircon are present with up to 1 cm megacrystic zircon and a later smaller equant population located around the megacryst margins. Patterns of zoning, rare earth element abundance and oxygen isotopic compositions indicate that the megacrysts crystallized from crustal melts, whereas the equant zircon represents new neocryst growth and partial replacement of the megacryst zircon within the ultramafic host. Both zircon types have U–Pb ages of ca. 2464 Ma, broadly contemporaneous with granulite-facies events in the adjacent gneisses. Zircon megacrysts locally form?>?10% of the assemblage and may be associated to zones of localized nucleation or physically concentrated during movement of the siliceous melts. Their unusual size is linked to the suppression of zircon nucleation and increased Zr solubility in the Si-undersaturated melts. The metasomatism between crustal melts and peridotite may represent an analog for processes in the mantle wedge above subducting slabs. As such, the crystallization of abundant zircon in ultramafic host rocks has implications for geochemistry of melts generated in the mantle and the widely reported depletion of high field strength elements in arc magmas.     

银额盆地哈日凹陷油气成藏条件及成藏模式

近年来,银额盆地哈日凹陷的油气勘探呈现出良好的态势,但对于哈日凹陷油气成藏条件相关研究甚少,已不能满足目前油气勘探开发的需求。本研究基于钻录井、地球物理、分析化验等资料,系统分析哈日凹陷油气成藏的烃源岩、储层、圈闭等条件,总结油气成藏条件配置关系,以期为哈日凹陷的后续油气勘探及地质研究提供依据。哈日凹陷主要发育三套烃源岩,其中银根组烃源岩有机质丰度极高,成熟度较低,有机质类型为Ⅰ-Ⅱ1型;巴二段烃源岩有机质丰度较高,成熟-高成熟,有机质类型为Ⅱ1-Ⅱ2型;巴一段烃源岩有机质丰度中等,成熟-高成熟,有机质类型为Ⅱ1-Ⅱ2型。储层类型为砂（砾）岩常规储层、碳酸质泥岩非常规储层和火山岩储层,且均属于特低孔超低渗储层,其中砂、砾岩储层和灰质泥岩储层物性最好,白云岩储层和火成岩储层次之,目前主力油藏主要集中在砂、砾岩储层和灰质泥岩储层这两种类型中。哈日凹陷主要发育两套岩性圈闭,即巴一段砂岩岩性圈闭和巴二段泥岩岩性圈闭,形成了源内（准）连续成藏模式和近源不连续成藏模式。     

Authigenic sericite record of a fossil geothermal system: the Offenburg trough,central Black Forest,Germany

A fossil geothermal area is hosted by the Carboniferous, Permian and Bunter sandstones of the Offenburg intramontane trough in the central Black Forest. The hydrothermal alteration is identified on the basis of newly formed sericites, which appear as pseudomorphs after feldspar and filling of pore spaces. According to K–Ar dating of sericite, serititization occurred about 145 Ma ago (Jurassic). On the basis of ¹⁸O analyses of sericite, sericite composition and vitrinite reflectance, the hydrothermal fluids had temperatures of 150–210 °C. Because their electrolyte content was low, these fluids are assumed to have derived from meteoric water. A second pulse of electrolyte-rich hydrothermal fluids resulted in quartz overgrowths. Fluid mobilization seems to be linked to the disintegration of Pangaea and to reactivated fault systems extending from the crystalline basement into the intramontane sediments.     

甘肃龙首山岩带西井镁铁质岩体成因及其构造意义

西井岩体位于北祁连造山带以北,阿拉善地块西南缘的龙首山隆起带。以往的研究多以沿龙首山断裂分布的镁铁-超镁铁质岩带作为和金川岩体相关的岩浆事件进行,而本次选择西井镁铁质岩体进行了精确的地质年代学和地球化学研究,确定了西井岩体岩性主要为橄榄辉石岩和辉长岩,成岩时代为 (421.0±9.0) Ma,可以和北祁连高压变质带榴辉岩年龄相对应;ε_Nd(t)为4.06~5.52,(⁸⁷Sr/⁸⁶Sr)_i为0.704 548~0.707 575,具有地幔岩石圈特征;微量元素及其同位素计算表明西井岩体经历了约10%的下地壳物质混染。据此得出西井岩体及其龙首山岩带早志留世镁铁质侵入岩体成因模式为:祁连洋壳连续俯冲过程中洋壳与陆壳分离,热的软流圈物质持续冲击地幔岩石圈的底部;由于热传导效应,大地热流沿着地幔岩石圈上升,使得80 km深度的湿的橄榄岩层发生熔融,产生玄武质岩浆作用,玄武质岩浆上升过程中与下地壳物质发生约10%混染,形成西井岩体及其龙首山镁铁超镁铁质岩带。     

Continuous zircon growth during long-lived granulite facies metamorphism: a microtextural,U–Pb,Lu–Hf and trace element study of Caledonian rocks from the Arctic

Microtextural, U–Pb, trace element and Lu–Hf analyses of zircons from gneisses dredged from the Chukchi Borderland indicate a long-lived, Cambrian–Ordovician, granulite facies metamorphism. These results reveal a complete prograde, peak and cooling history of zircon growth during anatexis. Early increasing temperatures caused modification and Pb-loss of Precambrian zircons by recrystallization and dissolution/re-precipitation of existing grains. Small variations in initial ¹⁷⁶Hf/¹⁷⁷Hf results (0.282325–0.282042) and flat HREE patterns of these zircons indicate that they grew by dissolution/re-precipitation in the presence of garnet. Zircons subsequently crystallized from a partial melt during peak to post-peak metamorphism from 530 to 485 Ma. A broad range of initial ¹⁷⁶Hf/¹⁷⁷Hf ratios (0.282693–0.282050) and mineral inclusions within zircons suggest that this phase of growth incorporated Zr and Hf obtained from the breakdown of Zr-enriched phases. Microtextural evidence along with trace element and isotopic data suggests that final growth of metamorphic rims on zircon occurred during slow cooling and crystallization of residual partial melts during the early Ordovician (485–470 Ma). Younger, late Ordovician–Silurian (420–450 Ma) euhedral, oscillatory-zoned, trace element-enriched zircons crystallized within leucocratic veins that intrude the gneisses. Their age corresponds to granitoids dated from this same dredge. The intrusives and veins provide evidence that the Chukchi Borderland rifted from a position near Pearya and northwest Svalbard, which represent the northern continuation of the Caledonian orogen. Evidence for earlier Cambrian metamorphism has not been reported from this region. The age of granulite facies metamorphism reported here represents the earliest phase of deformation in the Arctic Caledonides.     

Iron isotope fractionation in subduction-related high-pressure metabasites (Ile de Groix,France)

Characterisation of mass transfer during subduction is fundamental to understand the origin of compositional heterogeneities in the upper mantle. Fe isotopes were measured in high-pressure/low-temperature metabasites (blueschists, eclogites and retrograde greenschists) from the Ile de Groix (France), a Variscan high-pressure terrane, to determine if the subducted oceanic crust contributes to mantle Fe isotope heterogeneities. The metabasites have δ⁵⁶Fe values of +0.16 to +0.33‰, which are heavier than typical values of MORB and OIB, indicating that their basaltic protolith derives from a heavy-Fe mantle source. The δ⁵⁶Fe correlates well with Y/Nb and (La/Sm)_PM ratios, which commonly fractionate during magmatic processes, highlighting variations in the magmatic protolith composition. In addition, the shift of δ⁵⁶Fe by +0.06 to 0.10‰ compared to basalts may reflect hydrothermal alteration prior to subduction. The δ⁵⁶Fe decrease from blueschists (+0.19 ± 0.03 to +0.33 ± 0.01‰) to eclogites (+0.16 ± 0.02 to +0.18 ± 0.03‰) reflects small variations in the protolith composition, rather than Fe fractionation during metamorphism: newly-formed Fe-rich minerals allowed preserving bulk rock Fe compositions during metamorphic reactions and hampered any Fe isotope fractionation. Greenschists have δ⁵⁶Fe values (+0.17 ± 0.01 to +0.27 ± 0.02‰) similar to high-pressure rocks. Hence, metasomatism related to fluids derived from the subducted hydrothermally altered metabasites might only have a limited effect on mantle Fe isotope composition under subsolidus conditions, owing to the large stability of Fe-rich minerals and low mobility of Fe. Subsequent melting of the heavy-Fe metabasites at deeper levels is expected to generate mantle Fe isotope heterogeneities.     

Differences in grain growth of calcite: a field-based modeling approach

Normal grain growth of calcite was investigated by combining grain size analysis of calcite across the contact aureole of the Adamello pluton, and grain growth modeling based on a thermal model of the surroundings of the pluton. In an unbiased model system, i.e., location dependent variations in temperature-time path, 2/3 and 1/3 of grain growth occurs during pro- and retrograde metamorphism at all locations, respectively. In contrast to this idealized situation, in the field example three groups can be distinguished, which are characterized by variations in their grain size versus temperature relationships: Group I occurs at low temperatures and the grain size remains constant because nano-scale second phase particles of organic origin inhibit grain growth in the calcite aggregates under these conditions. In the presence of an aqueous fluid, these second phases decay at a temperature of about 350 °C enabling the onset of grain growth in calcite. In the following growth period, fluid-enhanced group II and slower group III growth occurs. For group II a continuous and intense grain size increase with T is typical while the grain growth decreases with T for group III. None of the observed trends correlate with experimentally based grain growth kinetics, probably due to differences between nature and experiment which have not yet been investigated (e.g., porosity, second phases). Therefore, grain growth modeling was used to iteratively improve the correlation between measured and modeled grain sizes by optimizing activation energy (Q), pre-exponential factor (k₀) and grain size exponent (n). For n=2, Q of 350 kJ/mol, k₀ of 1.7×10²¹ mⁿs^–1 and Q of 35 kJ/mol, k₀ of 2.5×10^-5 mⁿs^–1 were obtained for group II and III, respectively. With respect to future work, field-data based grain growth modeling might be a promising tool for investigating the influences of secondary effects like porosity and second phases on grain growth in nature, and to unravel differences between nature and experiment.Editorial responsibility: J. Hoefs     

胶东邢家山矽卡岩型钼矿床成矿流体与成矿机制

邢家山矿床是胶东地区发现的大型矽卡岩型钼多金属矿床。通过野外调研,将成矿过程划分为四个阶段:早矽卡岩阶段、晚矽卡岩阶段、石英硫化物阶段和石英-碳酸盐阶段。对不同阶段流体包裹体研究表明,存在液体包裹体(L)、气体包裹体(V)和含子矿物包裹体(S)三类。激光拉曼探针显示流体的气体分类型为H_2O-H_2S,早和晚矽卡岩阶段均一温度集中在375～450℃,盐度存在14%～15%NaCleqv和大于30%NaCleqv两个端元;石英-硫化物阶段均一温度集中在260～340℃,盐度存在8%～12%NaCleqv和大于50%NaCleqv两个端元;石英-碳酸盐阶段流体包裹体均一温度集中在170～200℃,盐度小于10%NaCleqv。该矿床成矿流体具有高温高盐度的特征,且富含H_2S等还原性气体,从矽卡岩阶段到碳酸盐阶段成矿温度和盐度总体有降低的趋势。邢家山钼矿δ~(18) O_(H_2O)值为0.04‰～8.18‰,δ~(13) C_(V-PDB)值为-3. 35‰～-0.73‰,δ~(18) O_(V-SMOW)值为5. 93‰～8. 42‰,δ~(34)S值为6.5～10. 8‰。邢家山矿床成矿流体主要来源于岩浆,后期有大气降水的加入,流体沸腾是成矿的主要机制。