硫化鐵礦物生成於海洋沉積物早成岩、晚成岩或變質作用，常為探討流體氧化還原條件和鐵硫循環與反應的重要指標，硫複鐵礦為其中硫化反應過程中常見之重要攜磁產物，前人X光繞射、磁學性質和有限電子顯微分析顯示早成岩硫複鐵礦形成富含缺陷之次微米晶體集合體；菱硫鐵礦亦具亞鐵磁性，罕見於文獻報導，多數經由低溫熱液礦化作用生成，可由硫複鐵礦、四方硫鐵礦、磁黃鐵礦或菱鐵礦轉變生成，但亦見於富含有機質黏土岩成岩作用，惟其生成模式與意義尚待探索。本研究以高解析度掃描式電子顯微鏡，配合Ｘ光能量分散光譜及電子背向散射繞射，分析臺灣南部二重溪層泥質粉砂至極細砂岩中之硫化鐵礦物，探討硫複鐵礦與菱硫鐵礦的成岩生長機制及其意義。
硫化鐵礦物充填植物炭屑孔隙、生痕孔洞或岩層裂隙，膠結矽酸鹽碎屑物及有孔蟲殼體，形成數毫米至數公分之粒狀、棒狀或板狀結核，以硫複鐵礦和菱硫鐵礦為主要組成。炭屑硫化鐵結核局部含有直徑＜10 μm黃鐵礦莓狀體和些微氧化之次微米細粒硫複鐵礦，構成塊狀集合體，其孔隙邊緣生成粒徑數微米至20 μm之罕見粗粒硫複鐵礦晶粒，多與菱硫鐵礦交錯生長，形成粒徑約50 μm之集合體，生痕化石棒狀及裂隙充填板狀結核與炭屑結核相同地以此種集合體為主要組成。Ｘ光能量分散光譜定量分析顯示彼等硫複鐵礦及菱硫鐵礦成分分別符合Fe3S4及Fe9S11，電子背向散射繞射分析亦分別顯示符合兩礦物之等軸和六方晶胞特徵，單一硫複鐵礦－菱硫鐵礦集合體內之硫複鐵礦具有單晶特性，菱硫鐵礦以四個不同晶體方位與之交生，其板狀晶束呈約120度交角向外延伸，於試片呈現特殊切面外形，與相鄰集合體構成鑲嵌組織；菱硫鐵礦〈001〉及〈100〉分別平行於硫複鐵礦單晶之〈111〉及〈110〉，證實兩礦物順構衍生關係。結核內部之片狀矽酸鹽解理間隙、有孔蟲殻體孔隙和石英及鈉長石晶粒裂隙常見為硫複鐵礦及菱硫鐵礦所充填或取代，結核內部孔隙外緣和硫複鐵礦－菱硫鐵礦集合體邊界和孔隙亦常見蔓生菱硫鐵礦晶簇，板狀晶體延伸生長數微米至25 μm，局部呈現六方板狀晶形。此外，亦可見硫複鐵礦－菱硫鐵礦集合體局部為塊狀黃鐵礦或白鐵礦或細粒含砷黃鐵礦所取代。
上述結果暗示硫複鐵礦－菱硫鐵礦集合體乃取代早成岩硫化鐵結核細粒單硫化鐵礦物之產物，菱硫鐵礦與之順構磊晶交互生長或蔓生於集合體外緣和填隙。此種成岩硫複鐵礦－菱硫鐵礦集合體尚少見於文獻，推測其生成可能侷限於保存有早成岩硫化鐵結核之沉積物，提供局部微觀化學條件，與後期還原性流體作用。本研究以顯微分析實證增進瞭解硫複鐵礦和菱硫鐵礦之晚成岩生成特性、機制與條件，所呈現不同成岩階段產物共存之現象，可為後續解讀硫化鐵礦物分布及其指標意義的重要參考。

Iron-sulfide nodules in siltstones from the Tsengwen-chi section of Erchungchi Formation, southern Taiwan were analyzed by scanning electron microscopy including backscattered electron imaging (BEI), x-ray energy-disperive spectroscopy (EDS) and electron backscatter diffraction (EBSD) techniques in order to identify growth relationships and formation modes of iron-sulfide minerals. BEI-EDS data showed that greigite and smythite are the main constituents of iron-sulfide minerals occupying pore spaces of charcoal debris, burrows, and rock fissures. Greigite and smythite crystals up to 20 μm in size were found to form rossete-like intergrowths with jigsaw-like contacts and occur with EBSD-verified topotaxial and/or epitaxial relationships having smythite 〈001〉 and 〈100〉 parallel to greigite 〈111〉 and 〈110〉, respectively. Partial replacement of aggregates of submicron-sized greigite by coarse-grained greigite-smythite intergrowths and overgrowth of smythite druses on both types of sulfide aggregates sporadically occurred in iron-sulfide nodules. Greigite-smythite intergrowths were locally replaced by pyrite and macarsite. In addition, silicate debris enclosed within iron-sulfide nodules were locally fractured with fissures infilled by greigite-smythite aggregates. The result implies that the unusally coarse-grained Tsengwen-chi greigite-smythite aggregates were formed by interactions between reducing fluids and early diagenetic monosulfide nodules that had provided chemical microenvironments favorable for greigite recrystallization and smythite crystallization at low temperatures. The finding of two different stages of diagenetic iron sulfides in single nodules may provide an important clue for subsequent geological interpretations of iron-sulfide formation and distribution in the region.

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