Failed genesis of a Fe-skarn deposit caused by redox states of intrusion and wall rocks (Torre di Rio, Island of Elba, Italy)

IF 3.6 2区 地球科学 Q1 GEOLOGY Ore Geology Reviews Pub Date : 2025-02-01 Epub Date: 2025-01-06 DOI:10.1016/j.oregeorev.2025.106446
Paolo S. Garofalo , Daniele Redi , Nikita Malafeevskiy , Gunnar Schwarz , Christoph Neff , Peter Keresztes Schmidt , Detlef Günther
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Abstract

The Torre di Rio skarn (Island of Elba, Italy) is a pyroxene-ilvaite-epidote skarn that hosts a Fe-oxide mineralization and is the type locality of the mineral ilvaite. In contrast with other Fe deposits of the island, it belongs to a group of subeconomic skarns. We combine surface mapping, petrographic data, scanning electron microscope and electron probe microanalyses, fluid inclusion microthermometry, elemental imaging by Laser Ablation-Inductively Coupled Plasma - Time of Flight Mass Spectrometry (LA-ICP-TOFMS), and fluid-mineral equilibria to compare the genesis of this skarn with that of typical economic skarns.
Fieldwork shows that Torre di Rio consist of ilvaite-, ilvaite-pyroxene, and pyroxene-epidote zones. The epidote-rich zone is in contact with the wall rocks, i.e., a sequence of pelites, marls, marbles, and other sedimentary lithologies. The 6.53–5.9 Ma Porto Azzurro monzogranite is the reduced (ilmenite-bearing) causative intrusion of the skarn, which induced contact metamorphism in the wall rocks at 6.7–6.2 Ma. Torre di Rio formed within the biotite-white mica-chlorite metamorphic zone, a few hundred meters from the contact with Porto Azzurro.
Within the skarn, ilvaite and pyroxenes are both euhedral and arranged in rosettes and spheroids. Ilvaite has a consistent chemical composition with a significant Mn enrichment close to the wall rocks, and pyroxene is hedenbergitic. The epidote is euhedral and occurs as epidote s.s. and allanite-(Ce). Late phases are albite, annite, phengite, chlorite, quartz, calcite, and chalcedony. Magnetite and hematite form spheroid textures or are finely mixed. Euhedral pyrrhotite and pyrite host native Bi and Pb.
Seventeen calcite- and quartz-hosted fluid inclusion assemblages from the ilvaite skarn zones are associated with the magnetite and hematite aggregates. At room temperature, all assemblages are two-phase (L-V). Fourteen of them show constant phase proportions and three show variable proportions. The assemblages with constant phase proportions have salinities between 0.8 and 17.0 mass% NaCleq and homogenize by bubble disappearance between c. 150 and 300 °C. The assemblages with variable phase proportions homogenize by bubble and liquid disappearance between 280 and 330 °C.
Element imaging by LA-ICP-TOFMS of ilvaite and quartz from skarn spheroids shows that several lithophile (e.g., Al, Mg) and siderophile (e.g., As, Ge, Ga, In, Sb) trace elements occur at concentrations between c. 20 μg/g and 1 wt%.
We interpret our dataset as a product of a shallow skarn that formed under extremely reducing conditions, which were controlled by the redox nature of both Porto Azzurro and wall rocks. At these conditions, supersaturation of pyroxenes and ilvaite within the skarn was achieved as a result of phase separation, cooling, and mixing of batches of heterogeneous and homogeneous ore fluids at about 350–150 °C. A Fe-skarn deposit failed to form at Torre di Rio because the supersaturation of Fe-oxides from the ore fluid was inhibited, but the presence of the typical siderophile elements of geothermal-epithermal deposits indicate that the ore environment was transitional between skarn and epithermal. Similar conditions are found in other deposits of the Island of Elba and of the Northern Apennine belt.

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侵入岩和围岩氧化还原状态导致的铁夕卡岩矿床成因失败(Torre di里约热内卢,意大利厄尔巴岛)
Torre di里约热内卢矽卡岩(位于意大利厄尔巴岛)是一种含铁氧化物矿化的辉石-伊云母-绿帘石矽卡岩,是伊云母矿物的类型产地。与岛上其它铁矿床相比,它属于亚经济矽卡岩群。结合地表填图、岩石学数据、扫描电镜和电子探针显微分析、流体包裹体显微测温、激光烧蚀-电感耦合等离子体-飞行时间质谱(LA-ICP-TOFMS)元素成像和流矿平衡,将该矽卡岩的成因与典型经济矽卡岩的成因进行了比较。野外考察表明,托尔迪里约热内卢由依尔辉岩带、依尔辉岩-辉石带和辉石-绿帘岩带组成。富绿帘石带与围岩接触,即泥岩、泥灰岩、大理岩和其他沉积岩性。6.53 ~ 5.9 Ma Azzurro二长花岗岩为夕卡岩的还原(含钛铁矿)成因侵入,在6.7 ~ 6.2 Ma围岩中发生接触变质作用。Torre di里约热内卢形成于黑云母-白色云母-绿泥石变质带内,距离阿祖罗港接触点几百米。在夕卡岩内,辉石和辉石均为自面体,呈玫瑰花状或球状排列。铁辉石化学成分一致,靠近围岩富集明显,辉石为辉石质。绿帘石为自面体,以绿帘石s.s和蓝帘石-(Ce)的形式出现。晚期为钠长石、铝长石、辉长石、绿泥石、石英、方解石和玉髓。磁铁矿和赤铁矿形成球状结构或精细混合。自形磁黄铁矿和黄铁矿中含有原生铋和铅。来自伊云母矽卡岩带的17个方解石和石英流体包裹体组合与磁铁矿和赤铁矿聚集体有关。在室温下,所有的组合都是两相的(L-V)。其中14个为恒相比,3个为变相比。相比恒定的组合的盐度在0.8 ~ 17.0 naleq之间,在150 ~ 300℃之间气泡消失而均匀化。在280 ~ 330℃之间,变相比例的组合通过气泡和液体消失实现均匀化。用LA-ICP-TOFMS对矽卡岩球体中的钛矿和石英进行元素成像,结果表明,几种亲石元素(如Al、Mg)和亲铁元素(如As、Ge、Ga、In、Sb)的浓度在0.20 ~ 1 wt%之间。我们将数据集解释为在极还原条件下形成的浅层矽卡岩的产物,这是由Porto Azzurro和围岩的氧化还原性质控制的。在这些条件下,矽卡岩内的辉石和铁长石的过饱和是由于相分离、冷却以及在约350-150°C下混合了一批非均质和均质矿流体。由于矿石流体中铁氧化物的过饱和作用被抑制,在Torre di里约热内卢未能形成铁夕卡岩矿床,但地热-浅成热液矿床中典型的亲铁元素的存在,表明成矿环境处于夕卡岩-浅成热液过渡阶段。在厄尔巴岛和北亚平宁带的其他沉积物中也发现了类似的情况。
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来源期刊
Ore Geology Reviews
Ore Geology Reviews 地学-地质学
CiteScore
6.50
自引率
27.30%
发文量
546
审稿时长
22.9 weeks
期刊介绍: Ore Geology Reviews aims to familiarize all earth scientists with recent advances in a number of interconnected disciplines related to the study of, and search for, ore deposits. The reviews range from brief to longer contributions, but the journal preferentially publishes manuscripts that fill the niche between the commonly shorter journal articles and the comprehensive book coverages, and thus has a special appeal to many authors and readers.
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