付勇，郭川

1)貴州大學資源與環(huán)境工程學院，貴陽，500025； 2)貴州大學喀斯特地質(zhì)資源與環(huán)境教育部重點實驗室，貴陽，500025

內(nèi)容提要: 南華盆地成冰系大塘坡組錳礦是我國最重要的錳礦產(chǎn)出層位之一，它形成于成冰紀Sturtian冰川事件之后，其成礦背景及形成機理一直是研究的重點。在系統(tǒng)總結Sturtian冰川事件起始與結束時間、南華裂谷盆地結構演化及古氣候演變等重大地質(zhì)事件的最新研究進展的基礎上，綜合分析了南華盆地大型沉積型錳礦成礦作用過程與這些重大地質(zhì)事件之間的聯(lián)系。揭示了南華盆地Sturtian冰期的啟動和結束與全球其他地區(qū)基本一致，分別發(fā)生在～717 Ma和～660 Ma之前。同時，對南華系大塘坡錳礦成礦時代進行了約束，大約形成于～660 Ma之前。在新元古代中期Rodinia超大陸裂解作用的影響下，南華裂谷盆地內(nèi)部發(fā)育一系列由同沉積斷層控制的地壘—地塹次級盆地。沿同沉積斷層運移的熱液流體為大塘坡錳礦的形成提供了大量的成礦物質(zhì)，并控制著大塘坡錳礦的發(fā)育分布?；瘜W蝕變指數(shù)(CIA)、鋰同位素(δ7Li)及鋨同位素組成[n(187Os)/n(188Os)]等風化指標顯示，南華盆地Sturtian冰期晚期至間冰期大塘坡期早期的氣候為寒冷干燥，隨后轉(zhuǎn)為溫暖濕潤并很快變?yōu)楹涓稍铩Ｖ链筇疗轮型砥?，氣候逐漸由寒冷干燥恢復至溫暖濕潤，并一直保持至大塘坡晚期。整體來看，Sturtian冰期結束后，南華盆地表層海水逐漸氧化，深部沉積水體出現(xiàn)局部間歇式氧化環(huán)境，裂陷階段熱液和陸源輸入的Mn2+被氧化為MnO2發(fā)生沉淀，并在底部伴隨著有機質(zhì)的埋藏及早期成巖作用而最終形成菱錳礦。

新元古代是地球演化過程中的一個重要時期，伴隨著強烈和廣泛的冰川作用(Hoffman et al., 1998)、真核生物擴張(Sahoo et al., 2016)及條帶狀鐵建造(BIF)的再現(xiàn)(Cox et al., 2013)等。這些重大地質(zhì)事件與當時的氣候、海水化學性質(zhì)及板塊構造運動等密切相關，長期以來一直是地球科學研究的重點。其中成冰紀發(fā)生了兩次全球范圍的冰川事件(即Sturtian和Marinoan冰期)，分別對應著華南地區(qū)的江口冰期和南沱冰期(趙彥彥等，2011; 張啟銳等，2016)，這兩次冰期事件很大程度上改變了當時的大陸風化作用，并進一步造成了海洋的化學性質(zhì)和氧化還原狀態(tài)的顯著變化(Hoffman et al., 2017)。華南地區(qū)的這兩次冰期之間發(fā)生了大塘坡間冰期，對應著我國重要的成錳期，在此期間華南地區(qū)形成了豐富的沉積型錳礦床。多年勘探顯示，華南地區(qū)南華系地層中發(fā)育多個大中型沉積型錳礦床(付勇等, 2014)，如貴州大塘坡(周琦等, 2013; Yu Wenchao et al., 2019; 張予杰等, 2020)、重慶秀山(凌云等, 2016; Ma Zhixin et al., 2019; 趙志強等, 2019)、湖南湘潭(史富強等, 2016)等，其中錳礦石主要賦存在大塘坡組第一段(或相當層位)的黑色巖系中，使得黔、湘、渝等地區(qū)成為我國最重要的錳礦產(chǎn)地之一。由于大塘坡組錳礦具有重要的經(jīng)濟價值和科學意義，使得南華紀時期與其形成密切相關的Sturtian冰川事件、盆地演化、古氣候及海洋氧化還原狀態(tài)等內(nèi)容一直是研究的熱點(Li Chao et al., 2012; 杜遠生等, 2015; 齊靚等, 2015; 周琦等, 2016; Lan Zhongwu et al., 2020)。

1 南華盆地Sturtian冰期時限及南華 系錳礦成礦時代

目前Sturtian冰期時限及沉積礦床的形成年齡主要通過一系列的間接定年方法(如Rb-Sr、Sm-Nd、鋯石U-Pb法等)，主要通過對冰期地層、含礦層系或相鄰地層中的火山灰或成巖礦物來實現(xiàn)，但這些間接定年方法受其測試對象稀缺性和自身性質(zhì)的制約，而使其應用存在很大的局限性(Rasmussen, 2005)。相比之下，Re-Os定年方法能直接限定富有機質(zhì)沉積巖(如黑色頁巖)的沉積年齡(Cohen et al., 1999; Kendall et al., 2004; 李超等, 2014; Fu Yong et al., 2016; 王富良等, 2016)。近期研究顯示，在后期成巖作用(如熱成熟、低變質(zhì)作用等)過程中，黑色頁巖中的Re-Os體系仍能保持封閉，即不會發(fā)生Re和Os元素的丟失或獲取(Creaser et al., 2002; Rooney et al., 2010; 李超等, 2014)，這使得Re-Os定年方法被廣泛用來限定前寒武系沉積地層的沉積年齡(Rooney et al., 2010; Zhu Bi et al., 2013; Tripathy and Singh, 2015)。

1.1 Sturtian冰期啟動時間

Sturtian冰期地層在全球范圍內(nèi)廣泛分布，但典型的冰期沉積主要發(fā)育在澳大利亞、納米比亞、加拿大、中國南部、阿曼和蒙古等地區(qū)(Hoffman and Li, 2009; 趙彥彥和鄭永飛, 2011; Hoffman et al., 2017)。這次冰期對應著華南地區(qū)的江口冰期，代表沉積為江口群(長安組+富祿組)或兩界河組與鐵絲坳組(Lan Zhongwu et al., 2014; 汪正江等, 2015)。近年來，針對成冰紀冰川事件的期次、起始與結束時間及全球?qū)Ρ?，前人通過冰期沉積或相鄰地層中的火山灰等開展了大量的研究工作，并取得了一系列的進展(圖1和表1)。其中，Lan Zhongwu 等(2014)獲得了桂北地區(qū)丹洲群頂部凝灰質(zhì)粉砂巖和湖北宜昌地區(qū)蓮沱組頂部凝灰?guī)r的SIMS U-Pb年齡，分別為716.1 ± 3.4 Ma和715.9 ± 2.8 Ma；Lan Zhongwu 等(2015)獲得的湖北宜昌地區(qū)蓮沱組頂部凝灰?guī)rSIMS U-Pb年齡為714 ± 8 Ma；覃永軍等(2015)獲得的黔東南地區(qū)下江群頂界U-Pb年齡為717 Ma；Jiang Zhuo-Fei等(2016)獲得的川西地區(qū)開建橋組頂部凝灰?guī)r夾層的SHRIMP和LA-ICP-MS U-Pb年齡分別為715.0 ± 9.8 Ma和718.8 ± 9.4 Ma；Song Gaoyuan 等(2017)獲得的湘西地區(qū)板溪群頂部碎屑鋯石的LA-ICP-MS U-Pb年齡為714.6 ± 5.2 Ma；蔡娟娟等(2018)獲得的桂北地區(qū)長安組底部冰成雜礫巖碎屑鋯石的LA-ICP-MS U-Pb最小加權平均年齡為719.6 ± 6.1 Ma；Lan Zhongwu 等(2020)獲得的長安組之下拱洞組頂部的CA-ID-IRMS鋯石U-Pb年齡(720.16 ± 1.42 Ma)，并通過Monte Carlo模擬將華南地區(qū)Sturtian冰期的發(fā)生時間限定在717.61 ± 1.65 Ma。因此，華南地區(qū)Sturtian冰期的發(fā)生時間應為～717 Ma。

表1 新元古代Sturtian冰期起始和結束年齡匯編Table 1 Compilation of chronometric dates for the onset and termination of the Neoproterozoic Sturtian glaciation

針對Sturtian冰期的起始時間，國外學者也開展了大量的研究。其中，F(xiàn)anning 和Link(2004)獲得的勞倫西亞Grand Canyon地區(qū)Pocatello組Scout Mountain段之上冰磧巖斑狀流紋巖中巖漿鋯石的SHRIMP U-Pb年齡為717 ± 6 Ma；Bowring等(2007)獲得的阿曼Ghubrah冰磧巖中火山碎屑凝灰?guī)r中的鋯石TIMS U-Pb年齡為713.7 ± 0.5 Ma，這代表了最接近阿曼斯圖特冰期起始時間的年齡數(shù)據(jù)，但由于取樣點位于混積巖之中，因此阿曼斯圖特冰期的起始時間應早于713 Ma。Macdonald等(2010，2018)獲得了加拿大西北部地區(qū)Mount Harper群底部及其之下地層火山灰高分辨率鋯石TIMS年齡，將加拿大地盾斯圖特冰期的起始時間限定在717.4 ± 0.1 Ma和716.9 ± 0.4 Ma。因此，這些年齡數(shù)據(jù)顯示，不同緯度不同大陸上的Sturtian冰期可能是一次同時啟動的、快速的全球性事件，其發(fā)生的時間應為 ～ 717 Ma(圖1；Macdonald et al., 2010; Lan Zhongwu et al., 2020)。

圖1 新元古代Sturtian冰期起始和結束年齡分布圖Fig. 1 The ages of the onset and termination of the Neoproterozoic Sturtian glaciation 數(shù)據(jù)來源：1—蔡娟娟等，2018；2—Lan Zhongwu et al., 2020；3, 17—Fanning and Link, 2004；4, 5—Macdonald et al., 2010；6, 7—Lan Zhongwu et al., 2014；8—Song Gaoyuan et al., 2017；9—Allen et al., 2002；10—Bowring et al., 2007；11—Lund et al., 2003；12—Ferri et al., 1999；13, 29—Fanning and Link, 2008；14, 15—Evans et al., 1997；16—尹崇玉等，2006；18—余文超等，2016b；19—Cox et al., 2018；20—Zhou Chuanming et al., 2004；21—Yu Wenchao et al., 2017；22—Rooney et al., 2014；23—高林志等，2013；24, 25 32, 37—Rooney et al., 2020；26—裴浩翔等，2017；27—Semikhatov, 1991；28—Zhou Chuanming et al., 2020；30—Wang Dan et al., 2019；31—Rooney et al., 2015；33—Zhou Chuanming et al., 2019；34—Fanning and Link, 2006；35—李明龍等，2021；36—Kendall et al., 2006；38—Zhang Sihong et al., 2008 Data are compiled from: 1—Cai Juanjuan et al., 2018&; 2—Lan Zhongwu et al., 2020; 3, 17—Fanning and Link, 2004; 4, 5—Macdonald et al., 2010; 6, 7—Lan Zhongwu et al., 2014; 8—Song Gaoyuan et al., 2017; 9—Allen et al., 2002; 10—Bowring et al., 2007; 11—Lund et al., 2003; 12—Ferri et al., 1999; 13, 29—Fanning and Link, 2008; 14, 15—Evans et al., 1997; 16—Yi Chongyu et al., 2006&；18—Yu Wenchao et al., 2016b&; 19—Cox et al., 2018; 20—Zhou Chuanming et al., 2004; 21—Yu Wenchao et al., 2017; 22—Rooney et al., 2014; 23—Gao Linzhi et al., 2013&; 24, 25 32, 37—Rooney et al., 2020; 26—Pei Haoxiang et al., 2017&; 27—Semikhatov, 1991; 28—Zhou Chuanming et al., 2020; 30—Wang Ping et al., 2019; 31—Rooney et al., 2015; 33—Zhou Chuanming et al., 2019; 34—Fanning and Link, 2006; 35—Li Minglong et al., 2021&; 36—Kendall et al., 2006; 38—Zhang Shihong et al., 2008

1.2 Sturtian冰期結束時間及南華盆地南華系 錳礦成礦時代

(1)Sturtian冰期結束時間。由于華南地區(qū)Sturtian冰期地層(如富祿組、鐵絲坳組或古城組)中尚未發(fā)現(xiàn)用于高精度定年的同沉積火山巖，因此Sturtian冰期結束的時間通常由上覆間冰期地層大塘坡組底部的凝灰?guī)r層限定。Zhou Chuanming 等(2004)獲得的華南貴州東部松桃地區(qū)大塘坡組底部凝灰?guī)r中鋯石的ID-TIMS U-Pb年齡為662.9 ± 4.3 Ma，之后通過CA-ID-IRMS U-Pb法將之修正為659.96 ± 0.46 Ma(Zhou Chuanming et al., 2020)，但由于其采樣部位處于大塘坡組底部位，說明Sturtian冰期結束時間應發(fā)生于之前。隨后，尹崇玉等(2006)也獲得了貴州東部松桃地區(qū)黑水溪剖面大塘坡組底部凝灰?guī)rSHRIMP U-Pb年齡為667.3 ± 9.9 Ma。之后，不同學者進一步開展了一系列Sturtian冰期結束時間的定年工作。例如，Zhang Shihong等(2008)獲得的華南湖北西部地區(qū)緊鄰南沱組下部湘錳組(大塘坡組相當層位)凝灰?guī)r層中鋯石的SHRIMP U-Pb年齡為654.5 ± 3.8 Ma；余文超等(2016b)和Yu Wenchao等(2017)獲得的華南貴州東部松桃地區(qū)將軍山剖面和寨浪溝剖面大塘坡組底部含錳頁巖層鋯石的LA-ICP-MS U-Pb年齡分別為664.2 ± 2.4 Ma和662.7 ± 6.2 Ma；Zhou Chuanming 等(2019)獲得的華南云南東部地區(qū)大塘坡組底部蓋帽白云巖凝灰?guī)r層鋯石的CA-ID-TIMS U-Pb年齡為658.8 ± 0.5 Ma。最近，Rooney 等(2020)獲得了貴州東南部地區(qū)和湖南西部地區(qū)大塘坡組底部含錳頁巖層凝灰?guī)r中鋯石的CA-ID-TIMS U-Pb年齡，分別為660.98 ± 0.74 Ma、658.97 ± 0.76 Ma、657.17 ± 0.78 Ma，其中660.98 ± 0.74 Ma為最接近大塘坡組底界的年齡。同時，Rooney等(2020)還獲得了貴州東北部距鐵絲坳組頂部3 m的黑色頁巖的Re-Os年齡為660.6 ± 3.9 Ma，也進一步證實了富有機質(zhì)沉積巖Re-Os年齡方法的可靠性。在華南湖北恩施地區(qū)，李明龍等(2021)獲得的大塘坡組底部凝灰?guī)r鋯石的LA-ICP-MS U-Pb年齡為658.1 ± 2.6 Ma。這些年齡數(shù)據(jù)在誤差范圍內(nèi)完全一致，因此華南Sturtian冰期結束應發(fā)生在～660 Ma前。

世界其他地區(qū)也獲得了與華南地區(qū)類似的年齡，也進一步限定了Sturtian冰期結束的時間。例如，勞倫大陸獲得的Mackenzie Mountains地區(qū)Hay Creek群Twitya組底部黑色頁巖的Re-Os年齡為662.4 ± 3.9 Ma(Rooney et al., 2014)；前蘇聯(lián)烏拉爾地區(qū)Laplandian冰磧巖之下火山灰層鋯石的TIMS U-Pb年齡為660 ± 15 Ma(Semikhatov, 1991)；澳大利亞南部地區(qū)緊鄰Appila (Sturt) 組冰磧巖之上Wilyerpa組中火山灰層鋯石的CA-ID-TIMS U-Pb年齡和SIMS U-Pb年齡分別為663.03 ± 0.11 Ma(Cox et al., 2018)和659.7±5.3 Ma(Fanning and Link, 2008)；澳大利亞Adelaide Rift Complex地區(qū)Appila (Sdturt) 組冰磧巖之上的Tapley Hill組底部Tindelpina段黑色頁巖的Re-Os年齡為657.2 ± 5.4 Ma(Kendall et al., 2006)；蒙古Tuva—MongoliaTaishir組底部黑色頁巖的Re-Os年齡為659.0 ± 4.5 Ma(Rooney et al., 2015)。這些年齡與華南地區(qū)獲得的年齡在誤差范圍內(nèi)完全一致(圖1)，因此，全球范圍內(nèi)Sturtian冰期的結束可能也是一個等時事件，其應發(fā)生在～660 Ma之前，其持續(xù)時間約為57 Ma(Rooney et al., 2014; Zhou Chuanming et al., 2019; Rooney et al., 2020)。

(2)南華盆地南華系錳礦成礦時代。由于Sturtian冰期結束的時限主要通過上覆大塘坡組底部凝灰?guī)r和富有機質(zhì)沉積巖(如黑色頁巖)獲得，這些年齡也對南華盆地南華系錳礦成礦時代進行了限定。近期，裴浩翔等(2017)獲得的貴州東部道坨錳礦大塘坡組一段含錳黑色頁巖的Re-Os同位素等時線年齡為660.6 ± 7.5 Ma；Wang Dan等(2019)獲得的貴州東部松桃將軍山剖面大塘坡組底部含錳頁巖層凝灰?guī)r中鋯石的SIMS U-Pb年齡為659.3 ± 2.4 Ma。這些年齡數(shù)據(jù)在誤差范圍內(nèi)是一致的，因此結合前人報道的年齡數(shù)據(jù)可將南華盆地南華系錳礦限定在～ 660 Ma，該年齡可對該時期南華盆地甚至全球范圍內(nèi)的成礦地質(zhì)事件提供很好的年齡約束，同時能為全球?qū)Ρ妊芯矿w統(tǒng)很好的年齡框架。

2 南華紀南華裂谷盆地結構演化

已有研究顯示，南華裂谷盆地的形成與演化與Rodinia超大陸的裂解密切相關(王劍等, 2001; 杜遠生等, 2018)。其中，Rodinia超大陸的形成于中元古代末期(1300～900 Ma)的全球范圍造山運動，這次構造運動幾乎波及所有的大陸板塊 (Hoffman, 1991; Li et al., 2008)。隨后，新元古代時期(～750 Ma)發(fā)生了全球性的裂谷作用，導致Rodinia超大陸發(fā)生裂解，并最終在600 Ma完全解體(Li et al., 2008; Zhao Guochun et al., 2018; Wang Wei et al., 2020)。在Rodinia超大陸的形成—裂解過程中，揚子板塊和華夏板塊在830 Ma發(fā)生碰撞形成華南板塊和江南造山帶(王自強等, 2012; 孫海清等, 2013; 趙軍紅等, 2015; Li Qiwei and Zhao Junhong, 2020)，并自820 Ma開始發(fā)生多次幕式大陸裂解作用(Wang Jian and Li Zhengxiang, 2003)。在此背景下，揚子板塊內(nèi)形成了以南華裂谷盆地為代表的沿東南方向展布的裂谷系統(tǒng)(王孝磊等, 2004; 杜遠生等, 2015; Zhao Guochun et al., 2018)，同時南華裂谷盆地內(nèi)部也發(fā)育一系列由同沉積斷層控制的地壘—地塹次級盆地(圖2；周琦等, 2016)。

由于青白口紀(～800 Ma)第一次裂陷活動的作用，在湘西、黔東、桂北地區(qū)(江南構造帶西段)分別沉積了一系列以深水沉積組合和火山巖及凝灰?guī)r沉積為特征的板溪群、下江群、丹洲群(杜遠生等, 2015)。隨后，南華紀(～725 Ma)發(fā)生了第二次裂陷活動，在湘黔邊界地區(qū)沉積了大塘坡組以黑色泥質(zhì)巖系為特征的深水沉積(圖3；Zhang Shihong et al., 2008)。而震旦紀(～635 Ma)發(fā)生了第三次裂陷活動，在江南構造帶東側形成了以硅質(zhì)泥質(zhì)巖系等深水沉積為特征的震旦系—奧陶系地層。整體來看，揚子地塊東南緣裂谷盆地(I級)可劃分為武陵次級裂谷盆地、天柱—懷化隆起及雪峰次級裂谷盆地3個II級結構單元，它們可進一步識別出間隔分布的III級地塹與地壘結構，如溪口—小茶園次級地塹盆地、松桃—石阡次級地塹盆地、萬山—岑鞏次級地塹盆地及黎平—從江次級地塹盆地(圖2；周琦等, 2016)。在這些地塹盆地內(nèi)，大塘坡組沉積厚度自盆地中心向盆地邊緣逐漸降低(圖3)。另一方面，由黔東地區(qū)向鄂西地區(qū)大塘坡組厚度逐漸降低，巖相組合在區(qū)域上也表現(xiàn)出明顯的差異性，二分性逐漸消失(曠紅偉等, 2019)。

圖2 揚子地塊東南緣裂谷盆地結構示意圖及主要錳礦(剖面)分布圖(修改自杜遠生等, 2015)Fig. 2 The tectonic architecture of rift basin of southeastern Yangtze Block and distribution map of Mn deposits (modified from Du Yuansheng et al. 2015&) 1—重慶秀山小茶園錳礦；2—重慶秀山鹽井溝剖面；3—重慶秀山筆架山錳礦；4—貴州松桃道坨錳礦；5—貴州松桃兩界河錳礦；6—貴州松桃西溪堡錳礦；7—貴州江口桃映剖面；8—貴州銅仁萬山石竹溪錳礦床；9—貴州新晃板橋剖面；10—貴州從江八當錳礦點；11—湖南花垣民樂錳礦；12—湖南湘潭錳礦床。 ① 溪口—小茶園次級地塹盆地；② 松桃—石阡次級地塹盆地；③ 萬山—岑鞏次級地塹盆地；④ 黎平—從江次級地塹盆地 1—Xiaochayuan Mn deposit, Xiushan, Chongqing; 2—Yanjinggou Section, Xiushan, Chongqing; 3—Bijiashan Mn deposit, Xiushan, Chongqing; 4—Daotuo Mn desposit, Daotuo, Guizhou; 5—Liangjiehe Mn Deposit, Songtao, Guizhou; 6—Xixibao Mn deposit, Songtao, Guizhou; 7—Taoying Section, Jiangkou, Guizhou; 8—Shizhuxi Mn deposit, Wanshan, Tongren, Guizhou; 9—Banqiao Section, Xinhuang, Guizhou; 10—Badang Mn deposit, Congjiang, Guizhou; 11—Minle Mn deposit, Huayuan, Hunan; 12—Xiangtan Mn deposit, Hunan. ① Xikou—Xiaochayuan sub-graben basin; ② Songtao—Shiqian sub-graben basin; ③ Wanshan—Cenggong sub-graben basin; ④ Liping—Congjiang sub-graben basin

圖3 南華裂谷盆地南華紀兩界河—大塘坡期盆地結構圖(a，據(jù)周琦等, 2016修改)和大塘坡期早期盆地結構圖 (b，據(jù)鄒光均等, 2020修改)Fig. 3 The architecture of the Nanhua rift basin during the Lianghejie—Datangpo Age of the Nanhua Period (a, modified from Zhou Qi et al., 2016&) and during the early Datangpo Age (b, modified from Zou Guangjun et al., 2020&)

3 南華紀南華盆地風化作用記錄

“雪球地球”假說認為，新元古代成冰紀冰川事件之后，地球迅速轉(zhuǎn)為溫室氣候條件，并同時伴隨著強烈的化學風化作用過程(Hoffman et al., 1998; Hoffman and Schrag, 2002)。前人研究顯示，大陸風化作用對海洋營養(yǎng)物質(zhì)的輸入有著非常重要的影響，并進一步制約著海水的氧化還原狀態(tài)，如高營養(yǎng)物質(zhì)輸入會導致海洋表層海水高的初始生產(chǎn)力和富有機質(zhì)頁巖的沉積(Yeasmin et al., 2017; Huang Taiyu et al., 2019; Li Chao et al., 2020)。已有研究顯示，南華盆地大塘坡組底部(或一段)錳礦的形成受沉積水柱氧化還原狀態(tài)的制約(何志威等, 2014; Wu Chengquan et al., 2016; 余文超等, 2020)。為了明確大塘坡組(或相當層位)下部含錳巖系及黑色頁巖形成時期海洋南華盆地的氧化還原狀態(tài)，前人采用一系列地球化學指標開展了大量的研究工作，如元素地球化學(朱祥坤等, 2013; 何志威等, 2014; Wu Chengquan et al., 2016; 趙志強等, 2019)、碳同位素(Chen Xi et al., 2008; 裴浩翔等, 2020)、硫同位素(Li Chao et al., 2012; 張飛飛等, 2013; Wang Ping et al., 2019)、鐵組分(Li Chao et al., 2012; Ma Zhixin et al., 2019)、氮同位素(Wei Wei et al., 2016)、鍶-釹同位素(Yu Wenchao et al., 2016; 余文超等, 2016a)、鉬同位素(Cheng Meng et al., 2018; Ye Yuntao et al., 2018; Tan Zhaozhao et al., 2021)、鋰同位素(Wei Guangyi et al., 2020)等。結果顯示，南華盆地沉積水體的氧化還原狀態(tài)大致經(jīng)歷了3個階段：① 冰期階段主要為缺氧環(huán)境；② 成錳階段主要為表層海水氧化、深部水體缺氧的分層海洋結構；③ 含錳巖系上覆黑色頁巖沉積時期主要為缺氧環(huán)境(Li Chao et al., 2012; Cheng Meng et al., 2018; Tan Zhaozhao et al., 2021)。近期研究表明，冰期向間冰期轉(zhuǎn)換階段，大陸風化作用強度并非是迅速升高的，而是存在著多次短期的波動(Huang Kangjun et al., 2016; Li Chao et al., 2020)。針對南華紀南華盆地的大陸風化強度變化，前人已開展了化學蝕變指數(shù)(CIA；齊靚等, 2015; 李明龍等, 2019; Wang Ping et al., 2020)、鋰同位素(δ7Li)(Wei Guangyi et al., 2020)及鋨同位素組成[n(187Os)/n(188Os)；裴浩翔等, 2017]等方面的研究，并取得一定的認識。

3.1 化學蝕變指數(shù)(CIA)和鋰同位素(δ7Li)

大陸化學風化作用過程主要受控于濕度和溫度(Nesbitt and Young, 1982; Sheldon and Tabor, 2009)。在熱帶—亞熱帶潮濕氣候背景下，高沉淀、高氣溫及高產(chǎn)率的酸性表層水體有利于強烈風化作用(Schoenborn and Fedo, 2011)，可將砂質(zhì)顆粒中的鉀長石有效的轉(zhuǎn)化為粘土礦物(Johnsson et al., 1991)。相比之下，在干旱和極地氣候背景下，有限的沉淀作用及低溫條件通常導致弱的化學風化作用，而且物理風化作用比化學風化作用更為有效，從而會形成化學上不成熟和相對欠風化的沉積物(Nesbitt and Young, 1989)。因此，Nesbitt和Young(1982)提出的化學蝕變指數(shù)(Chemical index of alteration；CIA)可作為評估土壤和沉積物化學風化強度的指標，并具有古氣候意義(Sheldon and Tabor, 2009; Zhai Lina et al., 2018; Wang Ping et al., 2020)。在不同氣候條件下，風化搬運之后形成的沉積物具有不同的CIA值(Nesbitt and Young, 1989；馮連君等，2006)。例如，炎熱濕潤氣候條件下形成的沉積物的CIA值通常為80～100；溫暖潮濕氣候條件下一般為70～80；寒冷干燥氣候條件下形成的沉積物的CIA值為55～70(馮連君等，2006)。但需要注意的是，沉積物的CIA值可能會受到物源組成、搬運過程中的水動力顛選作用及成巖期鉀交代作用等因素的影響(McLennan, 1993; Bahlburg and Dobrzinski, 2011; 李明龍等, 2021)。相比之下，鋰(Li)元素在自然界中主要以Li+離子形式存在，而且無化合價變化(茍龍飛等, 2017)。已有研究顯示，大陸風化作用可造成Li同位素的最大分餾，但生物作用幾乎不會造成Li同位素的分餾(茍龍飛等, 2017；Wei Guangyi et al., 2020)。在風化搬運過程中，輕的Li同位素(6Li)會在次生粘土礦物中優(yōu)先富集，而重的Li同位素(7Li)則會被搬運至海洋中，從而導致海相自生粘土礦物通常具有比陸源風化產(chǎn)物更高的δ7Li值(茍龍飛等, 2017；Wei Guangyi et al., 2020)。因此，海相細粒碎屑沉積巖中的Li同位素組成主要受控于其中陸源碎屑物質(zhì)及海相自生粘土礦物的比例及其Li同位素組成。

李明龍等(2021)開展了鄂西走馬地區(qū)鉆孔ZK701南華系大塘坡組及相鄰層段(下覆古城組和上覆南沱組)的CIA分析(圖4)。古城組頂部較低的CIA值(平均值為57.6；n=2)指示南華盆地Sturtian冰期晚期的氣候條件仍為寒冷干燥，并一直持續(xù)至間冰期大塘坡期早期(CIA平均值=59.1；n=2)。隨后，氣候發(fā)生短暫的波動變化，先由寒冷干燥轉(zhuǎn)為溫暖濕潤并很快變?yōu)楹涓稍铩Ｖ链筇疗轮型砥?，氣候逐漸由寒冷干燥恢復至溫暖濕潤，并一直保持至大塘坡晚期。之后，可能受Marinoan冰期的影響，氣候緩慢向寒冷干燥轉(zhuǎn)變。這種變化趨勢與鄂西走馬地區(qū)鉆孔ZK701(李明龍等, 2019)及黔東地區(qū)鉆孔ZK4207與ZK1408 (齊靚等, 2015)南華系的CIA值反映的氣候演化基本一致(圖4)。由于大塘坡組底部錳礦層礦物相主要為碳酸錳，可能會對CIA計算產(chǎn)生較強的影響。為了消除這種影響，Wang Ping 等(2020)對黔東地區(qū)鉆孔ZK2115錳礦層做了去碳酸鹽組分處理。盡管處理前后的CIA值存在差異(處理過的樣品值偏高)，但在大塘坡組底部均存在一個低值區(qū)域，達到一個高值之后，再轉(zhuǎn)為振蕩的低值，并逐漸升高，指示氣候變化與ZK701類似的趨勢(圖4)。這種趨勢在黔東地區(qū)道坨剖面大塘坡組的δ7Li也有很好的響應(Wei Guangyi et al., 2020)。整體來看，δ7Li值自大塘坡組底部表現(xiàn)出升高→降低→再升高的趨勢，指示在大塘坡期早期寒冷干燥氣候背景下大陸風化作用逐漸減弱，然后在氣候轉(zhuǎn)為溫暖潮濕氣候背景下大陸風化作用增強，并在氣候再次轉(zhuǎn)為寒冷干燥狀態(tài)下大陸風化作用隨之減弱(圖4)。隨后，大塘坡期中晚期在溫暖潮濕背景下大陸風化作用振蕩變化，但維持一個較高的強度。

3.2 鋨同位素組成[n(187Os)/n(188Os)]

在氧化性海水中，Re和Os通常以ReO-4和HOsO-5等高價態(tài)的穩(wěn)定形式存在，在還原性海水中則會被還原成較難遷移的低價離子(Peucker-Ehrenbrink and Ravizza, 2000; Yamashita et al., 2007)。由于Re、Os的親有機性，富有機質(zhì)沉積巖在沉積過程中會吸附一定數(shù)量的低價Re、Os離子。另一方面，富有機質(zhì)沉積巖(如黑色頁巖)中Os元素主要為水成成因，從而導致富有機質(zhì)沉積巖具有與同時期海水相同的Os同位素比值[即初始n(187Os)/n(188Os)值；李超等, 2014]。因此，可通過Re-Os等時線年齡法獲得富有機質(zhì)沉積巖(如黑色頁巖)的初始n(187Os)/n(188Os)值，以此來約束同時期海水的Os同位素比值(Cohen et al., 1999; Peucker-Ehrenbrink and Ravizza, 2000; Cohen, 2004; Fu Yong et al., 2016; Wei Shuaichao et al., 2017; Rotich et al., 2020)。與Sr同位素一樣，地質(zhì)歷史時期海水中的Os同位素組成并非保持不變，其變化非常劇烈(Cohen, 2004)。海水中的Os同位素組成主要有3個物源：①河流輸入的高放射性的古老地殼風化Os[現(xiàn)今河流的n(187Os)/n(188Os)：1.4～1.6；Peucker-Ehrenbrink and Ravizza, 2000]；②洋中脊熱液蝕變輸入的非放射性Os[n(187Os)/n(188Os)約為0.127；Esser and Turekian, 1993; Cohen, 2004]; ③宇宙塵埃帶來的非放射性Os[n(187Os)/n(188Os)約為0.127；Shirey and Walker, 1998; Cohen, 2004]。整體來看，海水中的Os同位素主要是這3項來源的綜合結果，地質(zhì)歷史時期突發(fā)性地質(zhì)事件通常會改變不同端元的供給通量，從而可能造成海水Os同位素的相應波動(Ravizza and Turekian, 1989; Finlay et al., 2010)?，F(xiàn)今正常海水的n(187Os)/n(188Os)為1.05～1.06，反映氧化風化狀態(tài)下海水中的Os同位素組成主要來源于放射性陸殼的風化作用(Levasseur et al., 1998; Peucker-Ehrenbrink and Ravizza, 2000)。而太古宙海水的n(187Os)/n(188Os)僅為0.1～0.15(Anbar et al., 2007; Yang et al., 2009)，則指示缺氧背景下海水中的Os同位素組成主要來源于洋中脊的熱液蝕變作用(Hannah et al., 2004; Kendall et al., 2009)。因此，海水中Os同位素特征的變化可很好的用來示蹤地質(zhì)歷史時期海洋和氣候環(huán)境的演化特征(van Acken et al., 2013; Gibson et al., 2019; Rotich et al., 2020)。

盡管前寒武紀海水的Os同位素組成數(shù)據(jù)較少，其n(187Os)/n(188Os)值整體表現(xiàn)出階梯式增大的趨勢(圖5)，可能反映了大氣氧氣含量的幕式增加過程(Li Chao et al., 2012; Pufahl et al., 2014; Fan Haifeng et al., 2018; Cole et al., 2020; Uahengo et al., 2020; Wei Guangyi et al., 2021)。裴浩翔等(2017)獲得的貴州道坨錳礦大塘坡組底部黑色頁巖的初始n(187Os)/n(188Os)值為0.781，該值明顯低于現(xiàn)今正常海水的n(187Os)/n(188Os)值(圖5)，指示大塘坡組底部沉積時期海水中Os同位素組成來源以海底洋中脊熱液蝕變?yōu)橹?，這也與當時南華盆地廣泛發(fā)育的裂谷活動相一致(杜遠生等, 2015; 周琦等, 2016)。另一方面，較低的初始n(187Os)/n(188Os)值也揭示了當時相對寒冷干燥氣候背景下相對較弱的風化強度。Rooney 等(2020)總結了華南、蒙古及加拿大Sturtian冰期地層的Os同位素化學地層(圖6)，可見n(187Os)/n(188Os)值從Sturtian冰磧巖頂部的～1.4逐漸降至距冰磧巖～2.5 m的～0.4，隨后逐漸升高。n(187Os)/n(188Os)值的變化特征揭示了大陸風化作用強度的變化趨勢，即Sturtian冰期結束階段大陸風化作用相對較強，進入間冰期之后，大陸風化作用可能明顯減弱，隨后再次增強(Li Chao et al., 2012)。Sturtian冰期至間冰期大陸風化作用強度的變化特征與Marinoan冰期非常類似(Huang Kangjun et al., 2016)。

圖5 前寒武紀富有機質(zhì)沉積巖和準同生—早期成巖黃鐵礦的初始n(187Os)/n(188Os)值Fig. 5 The initial n(187Os)/n(188Os) of the Precambrian organic-rich sedimentary rocks and syndepositional—early diagenetic pyrite 引用數(shù)據(jù)來源于Kendall et al., 2009、Rooney et al., 2010, 2011、裴浩翔等, 2017 Data are compiled from Kendall et al., 2009, Rooney et al., 2010, 2011 and Pei Haoxiang et al., 2017&

圖6 Sturtian冰期結束后海水的Os同位素化學地層(修改自Rooney et al., 2020)Fig. 6 The composite Os isotope chemostratigraphy of the post-Sturtian successions (modified from Rooney et al., 2020) 引用數(shù)據(jù)來源于/Data from: Peucker-Ehrenbrink and Ravizza, 2000、Meisel et al., 2001、Rooney et al., 2014, 2015

4 錳礦床成礦模式及南華盆地南華系 錳礦成礦機理

4.1 錳礦床成礦模式

根據(jù)賦礦巖石類型的不同，我國錳礦床大致可分為有海相沉積型、火山—沉積型、碳酸鹽巖中熱水沉積型(或“層控”型)、與巖漿作用有關的熱液型、受變質(zhì)型及表生型6種類型(付勇等, 2014)。其中前3種類型主要為沉積型，中國與全球錳礦的分布和儲量數(shù)據(jù)顯示，這類錳礦床的工業(yè)價值最大，具有巨大的工業(yè)儲量(付勇等, 2014；Maynard, 2010, 2014)，其成礦過程與大氣氧氣含量、海洋氧化還原狀態(tài)及盆地類型等密切相關(Roy, 2006；付勇等, 2014)。針對沉積型錳礦床，目前國內(nèi)外學者基于大量的實例研究提出了兩種較為流行的錳礦成因模式：① 富錳缺氧海水中直接沉淀成礦(圖7a)；② 成巖孔隙水中轉(zhuǎn)化成礦(圖7b, c, d；董志國等, 2020)。

圖7 沉積型錳礦床主要成礦模式圖Fig. 7 The main metallogenic models of sedimentary manganese deposits 修改自/modified from: Force and Cannon, 1988; Huckriede and Meischner, 1996; Roy, 2006; Maynard, 2014

(1)富錳缺氧海水中直接沉淀成礦。錳是一種對氧化還原敏感的變價元素，其存在的形式主要受體系的Eh—pH條件控制(Roy, 2006)。在氧化水體中，錳主要以氧化物(Mn2O3)沉淀的形式存在；在還原性水體中，則主要以溶解態(tài)Mn2+離子形式存在(Krauskopf, 1957)。在現(xiàn)代海洋缺氧水體(如開放海洋的最小含氧帶或局限海洋分層水體的深部缺氧帶)中Mn2+相對集中，但大量實例研究和實驗模擬顯示，現(xiàn)代海洋缺氧水體的Mn2+濃度并不足以沉淀出碳酸錳(MnCO3)礦物(Mucci, 2004; 王霄等，2018)。另一方面，雖然鐵與錳的化學性質(zhì)比較類似，由于Mn2+/Mn(OH)3的還原電位比Fe2+/Fe(OH)3高(Lu Zunli et al., 2010)，在適當?shù)倪€原條件下鐵和錳可發(fā)生分離(Krauskopf, 1957)。但大量的研究實例顯示，沉積型錳礦床中并不存在明顯的鐵錳分帶現(xiàn)象(Maynard, 2010)。因此，富錳缺氧海水中直接沉淀成礦模式還有待進一步的論證。

(2)成巖孔隙水中轉(zhuǎn)化成礦。這種成礦模式主要包括3個階段：① Mn2+離子在還原性缺氧水體中的富集；② 在氧化還原界面之上，運移過來的Mn2+離子被氧化形成錳氧化物(或氫氧化物)發(fā)生沉淀；③隨著上覆沉積物的堆積，沉積物—水界面之下逐漸演變?yōu)橐粋€還原的微環(huán)境，早期沉積的錳氧化物(或氫氧化物)被微生物還原成Mn2+離子，其與孔隙水中的碳酸根(CO32-)離子結合形成碳酸錳(即菱錳礦)發(fā)生沉淀(Roy, 2006; Maynard, 2014)。大量的研究實例顯示，這種成礦模式主要發(fā)生在具氧化還原分層結構的盆地中(Roy, 2006; Maynard, 2014; 董志國等, 2020; 余文超等, 2020)。其中海洋的化學性質(zhì)分層結構可形成于多種環(huán)境，如與極端地質(zhì)事件(如冰川事件等；圖7b)有關的水體循環(huán)受限、最小氧化帶的擴張(圖7c)及季節(jié)性富氧底流的輸入(圖7d)等(Force and Cannon, 1988; Li Chao et al., 2012; Maynard, 2014)。近年來，越來越多的學者認為，在沉積型錳礦床形成過程中微生物可能也起著非常重要的作用(Fan Delian et al., 1999; Yu Wenchao et al., 2019)。

4.2 南華盆地南華系錳礦成礦機理

在元古宙時期，地球大氣圈逐漸發(fā)生氧化，并對地球表層環(huán)境、海洋化學條件和元素循環(huán)過程等產(chǎn)生了深遠的影響(Kump, 2008; Lyons et al., 2014; Cole et al., 2020)。大量的研究顯示，大氣圈氧氣含量的增加并不是一個漸進的過程，而是在兩次快速的增氧之后才達到現(xiàn)今的水平(Canfield, 2005; Lyons et al., 2014)。它們分別為2.1～2.4 Ga左右的大氧化事件(Great Oxidation Event；GOE)和0.75～0.58 Ga左右的新元古代氧化事件(Neoproterozoic Oxygenation Event；NOE)(Kump, 2008; Lyons et al., 2014)。在大氣圈增氧過程中，新元古代成冰紀地球上發(fā)生了幾次全球性的冰川事件，冰雪甚至覆蓋率中低緯度和磁道地區(qū)(即“雪球地球”；Hoffman et al., 1998)。其中可進行全球?qū)Ρ鹊膬纱伪跒镾turtian冰期和Marinoan冰期，分別對應華南地區(qū)的江口冰期和南沱冰期(趙彥彥和鄭永飛, 2011; 張啟銳和蘭中伍, 2016; 曠紅偉等, 2019)。在兩次冰期之間的間冰期期間，華南地區(qū)南華盆地沉積了深水相大塘坡組(或相當層位)，主要分布在黔—湘—渝等地區(qū)。

5 結論

(1)南華盆地Sturtian冰期的啟動和結束與全球其他地區(qū)基本一致，分別發(fā)生在～717 Ma和～660 Ma之前，持續(xù)時間約為57 Ma；且南華盆地南華系大塘坡錳礦大約形成于～660 Ma之前。

(2)在Rodinia超大陸裂解作用的影響下，南華裂谷盆地內(nèi)部發(fā)育一系列由同沉積斷層控制的地壘—地塹次級盆地，為錳質(zhì)的沉淀提供了可容空間；同時，深部熱液為大塘坡錳礦的形成提供了大量的成礦物質(zhì)，并對大塘坡錳礦的發(fā)育具有明顯的控制作用。

(3)南華盆地Sturtian冰期晚期至間冰期大塘坡期早期的氣候主要為寒冷干燥，隨后轉(zhuǎn)為溫暖濕潤并很快變?yōu)楹涓稍?。至大塘坡期中晚期，氣候逐漸由寒冷干燥恢復至溫暖濕潤，并一直保持至大塘坡期晚期。

(4)Sturtian冰期結束后，南華盆地表層海水逐漸氧化，深部沉積水體出現(xiàn)局部間歇式氧化環(huán)境，熱液和陸源輸入的Mn2+被氧化為MnO2發(fā)生沉淀，并在早期成巖階段在微生物的作用下最終形成菱錳礦。

致謝：感謝評審專家和責任編輯對本文修改提出的寶貴建議。

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