Coupled Ge/Si and Ge isotope ratios as geochemical tracers of seafloor hydrothermal systems: Case studies at Loihi Seamount and East Pacific Rise 9°50’N

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behaviour in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54’N, 155°15’W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50’N. Loihi offers the opportunity to understand contrasting Ge and Si behaviour in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Ge fluid-basalt up to 1.15 ‰ at EPR 9°50’N and 1.64 ‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater-rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of -2.0 ± 0.6 ‰ (2sd), and a maximum value of -3.6 ± 0.6 ‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50’N also demonstrates that Ge isotopes are fractionated by approximately -5.6 ± 0.6 ‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

氟、氯对热液钨、铜成矿的制约-以江西德兴铜矿、大吉山钨矿为例

矿化剂在热液矿床成矿过程中的重要作用一直为人们所关注，矿化剂地球化学行为直接影响成矿元素的富集成矿，不同的矿化剂元素可能对金属成矿具有一定的专属性。本文以著名的江西德兴铜厂超大型斑岩铜矿床和大吉山钨矿床作为研究对象，研究F、Cl与W、Cu成矿的关系。主要的认识如下：（1）F在花岗质岩浆中，可以降低岩浆的粘度、密度、固液相线温度、改变熔体结构，而Cl对熔体结构没有多大的影响。F在流体一花岗质熔体相间，绝大多数配分系数小于1.0，趋向于熔体相中配分，DF随体系中F浓度的升高而增加。Cl在流体一花岗质熔体相间的配分系数均大于1.0，且Dc1 随体系中Cl浓度的升高而增大·Cl强烈地趋向富集于流体相中。（2）Cu在流体一花岗质熔体作用过程中，铜总趋向于流体相中分布（DCu都大于1）。特别是在富Cl流体中Cu浓度较高，说明在富含Cl的热液流体能够从共存的熔体中活化迁移出大量的 Cu，S的加入DCu有降低的趋势。钨趋向于熔体相中富集，其配分系数大多小于1.0。（3）德兴铜厂花岗闪长斑岩属钙碱性系列岩石属I型花岗岩类，具有埃达克岩的特征。岩浆来源于深部，在结晶演化过程中发生了围岩物质的混染，这种高铜含量围岩的混染使成矿物质在岩浆中得到富集，有利于铜的活化、迁移。在铜厂岩体不同的蚀变带中，SiO2、K2O、Cu、Mo等从新鲜斑岩甚至弱蚀变带中带出，而在强蚀变带强烈富集，Cl同样有在强蚀变岩石中富集的趋势；而Na2O、Fe从斑岩体中带出，进入流体相中，流体中大量Fe的存在，有利于铜的沉淀、富集成矿。（4）德兴铜厂斑岩体微量元素和稀土元素地球化学特征表明，该岩体发生了流体一熔体作用，分异出来的流体是一种相对富氯的流体，同时成矿流体的流向是从岩体中心向接触带方向流动。（5）大吉山花岗岩具有高SiO2、A/CNK值，显示过铝质特点。黑云母花岗岩是壳源花岗岩但又受到慢源岩浆或慢源流体的影响。随着花岗岩的演化（从I→II→III）SiO2、K2O＋Na2O逐渐增加，ΣFe、Al2O3、CaO、F含量降低，为成矿提供了大量的矿化剂（F）和沉淀剂（Fe、Ca）。Eu负异常从I至III阶段花岗岩逐渐加强，表明该岩浆经历了高度的分异演化。（6）大吉山花岗岩类稀土元素具有“四重效应”配分的特点以及微量元素对玲Rb、Y/Ho、Zr/Hf以及Nb／Ta发生明显分异，暗示在花岗岩岩浆的演化过程中，经历了充分的流体一熔体作用，同时分异出大量富含F、W等矿化剂元素和成矿元素的热液流体，致使钨矿的形成。大吉山石英脉型钨矿的成矿年龄大约在155 Ma。（7）通过对成矿流体和花岗质岩石黑云母、白云母中卤素相对逸度的研究（log(H2O/fHCl）fluid、log（fHF/fHCl）fluid）发现，铜厂斑岩型铜矿床的成矿体系是相对富氯体系，而大吉山石英脉型钨矿床成矿体系相对富氟，同时氟可能主要迁移W、Sn、Nb、Ta等金属元素。（8）结合斑岩型铜矿床成矿流体特征，铜主要以C1的络合物形式存在和迁移，迁移形式主要是CuCl0、CuCl2等。石英脉型钨矿床中，钨主要以钨酸、钨酸盐及其离解形式存在和迁移，如WO42-、HWO4-、NaHWO4、Naw伍．等；在高度富氟的成矿流体中，钨的氟氧络合物（如WO3F-，WO2F42-等）对钨迁移也具有重要的作用。因此，不同矿化剂类型具有一定的成矿专属性，热液铜矿床主要与Cl、S有 关，而热液钨矿床大多与F有关。

Caracterização petrográfica dos alvos Hidrotermalitos Norte e Sul, Suruca e porção NW da Mina de Chapada - Alto Horizonte, GO

Main occurrence of Cu-Au in Goias Magmatic Arc, the Chapada mine fits into the geological context of the Brasilia Fold Belt, specifically in the Mara Rosa Magmatic Arc. Four targets, named Hidrotermalito Norte and Sul, NW Chapada Mine Portion and Suruca, are situated in this context, which includes ortogneisses and rocks from the Mara Rosa volcanic-sedimentary sequence. All these targets have been studied due to the possibility of presenting a great potential in Cu-Au, as well as the Chapada mine. Hidrotermalitos Norte and Sul targets presents four lithological sequences, which were identified as: quartz-muscovite schist; muscovite quartzites and kyanite quartzites; quartz-biotite-amphibole schist with pyrite and epidote-amphibole-biotite gneisses with muscovite; muscovite-biotite gneisses. They are metamorphosed to amphibolites facies and retrogressive greenschist facies. Sulfetation represented mainly by pyrite. In the NW Chapada Mine Portion, three main lithological groups were identified and classified as biotite gneisses; honblende-quartz-biotite-schist; amphibolites, with the first group metamorphosed in greenschist facies (low grade), and the other two groups metamorphosed in amphibolites facies, with subsequent retrogressive metamorphism in greenschist facies. Sulfetation is represented by chalcopyrite and pyrite. Finally, also three main lithological groups were identified in the Suruca target, classified as garnet-chlorite-epidote-eiotite gneiss; biotite gneiss and chlorite-biotite gneiss with epidote and muscovite; muscovite-quartz schist, all them metamorphised in amphibolites, with retrometamorphism in greenschist facies. Sulfetation represented by pyrite and sphalerite

(Table 1) Uranium and Thorium concentrations, activity ratios and calcium carbonate content of DSDP Site 54-424

The geochemical behaviour of uranium and thorium in metalliferous sediments and hydrothermal deposits has been widely studied and the main results have been summarised by Boström and Rydell. These isotopes may be used to clarify how the metal-rich solutions are introduced into sediment cover and seawater. Using radiochemistry followed by alpha spectrometry, we have measured uranium concentrations as high as several hundred p.p.m., which must clearly be associated with ocean ridge thermal activity, in sediments interbedded between the basaltic basement and the green hydrothermal mud at DSDP Site 424. These high uranium concentrations indicate the path followed by the hydrothermal fluid which, debouching at the sediment-water interface, formed the green mud.

Chemical composition of bottom sediments from the Discovery Deep, Red Sea rift zone

Hot brines in depressions of the central Red Sea contain thousands of times more iron, manganese and other metals than . After removal of salts, approximately half of sediments from these depressions consists of iron hydroxides and they are enriched in zinc, copper, lead and molybdenum. Hydrothermal deposits with the same complex of metals, located along the coast of the Red Sea, are correlated with faults and may be due to occurrences of Tertiary volcanism. Brines of similar composition are known in the Cheleken Peninsula. Certain geological and geochemical data indicate that such brines are of relatively deep origin.