張志超 李楠 戢興忠 韓忠 郭耀宇 李在春
ZHANG ZhiChao1,LI Nan1,JI XingZhong1,HAN Zhong2,GUO YaoYu1 and LI ZaiChun1
1. 中國(guó)地質(zhì)大學(xué)地質(zhì)過(guò)程與礦產(chǎn)資源國(guó)家重點(diǎn)實(shí)驗(yàn)室,北京 100083
2. 中國(guó)人民武裝警察部隊(duì)黃金第三總隊(duì),成都 610000
1. State Key Laboratory of Geological Processes and Mineral Resources,China University of Geosciences,Beijing 100083,China
2. No.3 Gold Geological General Party of Chinese Armed Police Force,Chengdu 610036,China
2015-02-10 收稿,2015-06-04 改回.
在熱液蝕變作用過(guò)程中,流體與圍巖進(jìn)行化學(xué)成分的置換導(dǎo)致礦物種類的變化(Putnis,2002)。其中主量元素的變化可以體現(xiàn)出巖石礦物組合的變化,微量元素的變化則可以反映熱液交代過(guò)程中的微觀作用(Whitbread and Moore,2004)。因此,蝕變巖石的元素含量異常值可用于識(shí)別肉眼通常無(wú)法觀察到的礦物成分的變化,并用于進(jìn)一步分析熱液蝕變機(jī)制、以及厘定蝕變與礦化的關(guān)系(Christie and Brathwaite,2003;Chinnasamy and Mishra,2013)。目前,許多學(xué)者運(yùn)用巖石地球化學(xué)手段厘定熱液礦床蝕變過(guò)程中礦物組合特征,研究熱液蝕變強(qiáng)度和元素遷移規(guī)律,以揭示各種蝕變過(guò)程與成礦作用的關(guān)系(Klemm and Kr?utner,2000;Craw,2002;Dugdale et al.,2006;Putnis,2009;袁峰等,2012;王翠云等,2012;張炳林等,2014)。
西秦嶺造山帶位于揚(yáng)子與華北板塊之間,記錄了大規(guī)模的構(gòu)造-巖漿活動(dòng)和成礦事件,是理解構(gòu)造演化和復(fù)合造山過(guò)程中成礦作用的理想選區(qū)(鄧軍等,2010,2011,2013;Deng et al.,2013b,2014b,c;邱昆峰等,2014;Yang et al.,2015d,e,f)。陽(yáng)山金礦帶位于西秦嶺造山帶南緣,從西到東主要有泥山、葛條灣、安壩、高樓山、觀音壩和張家山6 個(gè)金礦床,目前已發(fā)現(xiàn)含金礦脈100 余條,金總資源量超過(guò)300t(圖1b)。金礦帶內(nèi)各礦床發(fā)育的蝕變類型主要有硅化、絹云母化、碳酸鹽化、綠泥石化、綠簾石化和粘土化等。金儲(chǔ)量最大的安壩金礦床(閻鳳增等,2010),蝕變非常發(fā)育,是該金礦帶內(nèi)研究熱液蝕變?cè)诔傻V過(guò)程中作用的理想選區(qū)。李楠(2013)對(duì)陽(yáng)山金礦帶熱液蝕變特征進(jìn)行了研究,在系統(tǒng)地總結(jié)其野外地質(zhì)特征的基礎(chǔ)上,運(yùn)用質(zhì)量平衡的方法對(duì)礦區(qū)千枚巖中三種不同蝕變過(guò)程中元素遷入和遷出情況進(jìn)行了分析,認(rèn)為硅化與成礦的關(guān)系最為密切,碳酸鹽化和粘土化與成礦關(guān)系不大。前人研究未考慮斷裂帶和巖漿巖對(duì)蝕變空間分帶的影響,也未厘清蝕變?cè)诔傻V過(guò)程中的作用。
Yang and Badal(2013)、Yang et al. (2014b,2015c,2016a)和楊立強(qiáng)等(2014a,2015a)通過(guò)對(duì)成礦系統(tǒng)的研究,強(qiáng)調(diào)構(gòu)造-流體耦合成礦作用機(jī)制在成礦系統(tǒng)中的重要性,并認(rèn)為多期次復(fù)合造山作用、構(gòu)造體制轉(zhuǎn)換與金成礦密切相關(guān)(楊立強(qiáng)等,2003,2010,2011a,b;邱昆峰和楊立強(qiáng),2011;鄧軍等,2012;Wang et al.,2014;Deng et al.,2014a;Yang et al.,2016a)。流體在金成礦過(guò)程中起到非常重要的作用(鄧軍等,2001;Yang et al.,2008,2009),尤其在熱液礦床中,流體與金的成礦和熱液蝕變作用關(guān)系密切(邱昆峰等,2015;熊伊曲等,2015),然而,熱液蝕變作用尚缺乏系統(tǒng)的研究,這在一定程度上制約了安壩金礦床的成因研究的深入和進(jìn)一步找礦勘探的工作部署。本文通過(guò)野外及手標(biāo)本觀察,了解不同蝕變的野外特征,并結(jié)合野外斷裂帶及巖漿巖的出露情況,分析蝕變的空間分布規(guī)律;通過(guò)顯微鏡下的詳細(xì)觀察,理清了不同蝕變的礦物組合特征,并分析了不同蝕變礦物形成的先后順序;通過(guò)元素地球化學(xué)的方法和質(zhì)量平衡的計(jì)算,討論元素的遷移規(guī)律,理清了蝕變與金礦化的關(guān)系。
西秦嶺陽(yáng)山金礦帶位于西秦嶺勉略斷裂帶內(nèi)的文縣弧形構(gòu)造帶(杜子圖和吳淦國(guó),1998;閻鳳增等,2010),它由一系列近東西向的逆沖斷裂構(gòu)造(松柏-梨坪斷裂、馬家磨-魏家壩斷裂和白馬-臨江斷裂)及其相關(guān)褶皺構(gòu)成(圖1a)。
陽(yáng)山金礦帶地層主要有中晚元古界碧口群、上古生界的泥盆系、石炭系、二疊系和中生界的三疊系及侏羅系,新生界主要為第四系黃土和陸相沖積物。泥盆系是安壩金礦床的主要賦礦地層,出露的巖性為鈣泥質(zhì)千枚巖、炭質(zhì)千枚巖、灰?guī)r和砂巖。
陽(yáng)山金礦帶內(nèi)巖漿巖的巖性主要為斜長(zhǎng)花崗斑巖脈,且普遍發(fā)育硅化、絹云母化、碳酸鹽化、硫化、綠泥石化、綠簾石化和粘土化蝕變。巖漿巖在礦區(qū)范圍內(nèi)走向NEE 向,分布廣泛且零散,多沿區(qū)域性斷裂分布,與區(qū)域構(gòu)造線平行,明顯受區(qū)域構(gòu)造控制(Yang et al.,2015b;王宏偉,2012;華北,2013)。鋯石SHRIMP U-Pb 測(cè)年結(jié)果顯示陽(yáng)山金礦帶巖漿巖侵位于晚三疊世(215Ma)(Yang et al.,2015b)。
圖1 文縣弧形構(gòu)造(a,據(jù)杜子圖,1997)和陽(yáng)山金礦帶地質(zhì)圖(b,據(jù)趙成海,2009 修改)Fig.1 Geological sketch map of the Wenxian arc structure (a,after Du,1997)and the Yangshan gold belt (b,modified after Zhao,2009)
圖2 安壩金礦床不同類型熱液蝕變顯微鏡下照片(a)石英脈中有黃鐵礦發(fā)育(-);(b)千枚巖發(fā)育絹云母化和黃鐵礦化(+);(c)絹云母被黃鐵礦包裹(+);(d)石英顆粒內(nèi)發(fā)育黃鐵礦顆粒;(e)方解石呈顆粒狀分布于巖石中(+);(f)斜長(zhǎng)花崗斑巖中鱗片狀絹云母和粒狀石英(+);(g)蒙脫石脈切穿石英顆粒(+);(h)斜長(zhǎng)石蝕變?yōu)榻佋颇?+);(i)石英-方解石脈(+). Py-黃鐵礦;Q-石英;Ser-絹云母;Mnt-蒙脫石;Cal-方解石;Pl-斜長(zhǎng)石;Asp-毒砂Fig.2 Micrographs of the different altered rock samples from the Anba gold deposit(a)pyrite in the quartz vein (-);(b)sericitization and pyrite develop in the phyllite (+);(c)pyrite includes sericite (+);(d)quartz grain includes pyrite grain;(e)the calcite grains in the rock (+);(f)scaly sericite and granular quartz in the plagioclase granite porphyry (+);(g)montmorillonite vein cuts across silica grains (+);(h)plagioclase was altered to sericite (+);(i)quartz-calcite vein (+). Py-pyrite;Q-quartz;Ser-sericite;Mnt-montmorillonite;Cal-calcite;Pl-plagioclase;Asp-arsenopyrite
陽(yáng)山金礦帶的控礦構(gòu)造為安昌河-觀音壩斷裂帶,該斷裂帶是由多條次級(jí)斷裂分支復(fù)合而成的。這些次級(jí)斷裂發(fā)育于礦區(qū)內(nèi)的葛條灣-草坪梁復(fù)背斜兩翼中,礦體就產(chǎn)在復(fù)背斜兩翼的次級(jí)層間斷裂中。
安壩金礦床位于陽(yáng)山金礦帶中部,為礦帶主要礦化集中區(qū)。礦床東至草坪梁,西至三角地,共發(fā)現(xiàn)31 條礦脈,礦脈長(zhǎng)200 ~2200m,厚0.75 ~7.42m,延深>1000m,品位1.15 ~6.55g/t。礦脈由南向北分為305#、306#和311#3 個(gè)脈群。由314#、305#、360#和311#4 條主礦脈組成,呈NE-NEE 向平行展布,累計(jì)探獲(332 +333 +334)資源量281454kg,占金總資源量的91.36%(閻鳳增等,2010)。安壩金礦床的礦石為原生礦石,其Au 含量與原生礦石中硫化物含量有密切關(guān)系。金礦床圍巖巖性有砂巖、灰?guī)r、千枚巖和斜長(zhǎng)花崗斑巖,礦石以蝕變千枚巖和蝕變斜長(zhǎng)花崗斑巖礦石為主。礦石一般均較為松散破碎。礦石結(jié)構(gòu)主要有自形粒狀結(jié)構(gòu)、他形粒狀結(jié)構(gòu)、環(huán)帶及環(huán)邊結(jié)構(gòu)、放射狀結(jié)構(gòu)、包含結(jié)構(gòu)、交代殘余結(jié)構(gòu)、草莓狀結(jié)構(gòu)、壓碎結(jié)構(gòu)等。礦石構(gòu)造主要有稀疏浸染狀,稠密浸染狀,脈狀和團(tuán)塊狀構(gòu)造等。
圖3 安壩金礦床4 號(hào)硐CM19 剖面不同蝕變礦物的體積百分含量變化Fig.3 Volume percentage change of different altered minerals in the CM19 profile of the 4th adit in the Anba deposit
安壩金礦床的地層和巖漿巖普遍發(fā)育多種蝕變作用(圖2),各種蝕變?cè)诳臻g上沒(méi)有明顯的分帶性,通過(guò)系統(tǒng)的觀察總結(jié)后發(fā)現(xiàn)蝕變與斷裂、巖漿巖在空間分布上具有一定關(guān)系(圖3)。硅化在礦區(qū)內(nèi)普遍發(fā)育,尤其在斷裂附近發(fā)育程度較強(qiáng);絹云母化在斜長(zhǎng)花崗斑巖及其附近的千枚巖中發(fā)育程度較強(qiáng);粘土化發(fā)育于斷裂帶附近;綠泥石化-綠簾石化主要發(fā)育于斜長(zhǎng)花崗斑巖和砂巖中;碳酸鹽化主要呈面狀發(fā)育于斜長(zhǎng)花崗斑巖中,或在千枚巖和斜長(zhǎng)花崗斑巖中以脈狀產(chǎn)出,并與石英礦物伴生。各種蝕變類型的特征如下:
硅化是發(fā)育最為廣泛的蝕變,見(jiàn)于不同巖性的巖石中。硅化在空間上未見(jiàn)到明顯的分帶,但一般靠近斷裂帶的地方發(fā)育程度強(qiáng),主要形成于成礦前、成礦期和成礦后。硅化表現(xiàn)為脈狀和面狀硅化。脈狀硅化以石英脈的形式出現(xiàn),石英脈寬幾厘米到十幾厘米,脈體主要為中粗粒石英,呈乳白色,有時(shí)含少量金屬硫化物(圖2a),主要為成礦期和成礦后的產(chǎn)物。面狀硅化表現(xiàn)為斜長(zhǎng)花崗斑巖或地層(千枚巖、灰?guī)r)中的石英呈極細(xì)粒的他形粒狀。蝕變斜長(zhǎng)花崗斑巖中的石英通常呈他形粒狀與絹云母伴生,多以基質(zhì)的形式出現(xiàn),反映了較為快速的結(jié)晶過(guò)程(圖2f)。
絹云母化主要發(fā)育在斜長(zhǎng)花崗斑巖及其附近的千枚巖中,主要形成于成礦前和成礦期。斜長(zhǎng)花崗斑巖中的斜長(zhǎng)石蝕變形成鱗片狀的絹云母和細(xì)粒石英(圖2f)。此外,千枚巖中的絹云母一般為鱗片狀,順千枚理定向排列,有些絹云母與黃鐵礦和毒砂共生(圖2b),可見(jiàn)其為成礦期的產(chǎn)物;此外,還有部分絹云母被黃鐵礦包裹(圖2c),該絹云母為成礦前的產(chǎn)物。
綠泥石-綠簾石化僅見(jiàn)于斜長(zhǎng)花崗斑巖脈和部分砂巖中,且兩種蝕變經(jīng)常共生。常呈鱗片浸染狀、粒狀集合體或微細(xì)脈產(chǎn)出。
碳酸鹽化主要為成礦晚階段和成礦后的產(chǎn)物。一般有兩種表現(xiàn)形式,一種是面狀的碳酸鹽化,其中方解石礦物均勻地分布在巖石中(圖2e);另一種呈方解石-石英脈產(chǎn)出。后一種形式的碳酸鹽化出現(xiàn)在成礦后,切穿了早期的礦化(圖2i)。
粘土化主要表現(xiàn)為高嶺土化和蒙脫石化,常見(jiàn)于斷裂帶附近,主要形成于成礦后。粘土化蝕變有兩種形式,一種是粘土礦物以微細(xì)浸染狀存在于礦物表面,另一種是粘土礦物呈脈狀切穿石英脈(圖2g)。
通過(guò)對(duì)西秦嶺安壩金礦床蝕變礦物和金屬礦物的觀察,并結(jié)合李楠等(2012)、李楠(2013)和Li et al. (2014)對(duì)陽(yáng)山金礦帶的成礦期次和階段的劃分,對(duì)西秦嶺安壩金礦床的蝕變礦物和金屬礦物生成順序進(jìn)行了重新劃分(表1)。
樣品主要采自陽(yáng)山金礦帶安壩金礦床4 號(hào)平硐,共19件巖礦石樣品(圖3)。其中16 件采自平硐CM19 巷道的千枚巖,3 件采自CM19 巷道的斜長(zhǎng)花崗斑巖。從千枚巖中選取了2 件新鮮的樣品作為原巖,2 件硅化樣品,以及3 件絹云母化樣品。在平硐內(nèi)對(duì)距離斷裂帶不同遠(yuǎn)近、不同巖性及不同蝕變類型的樣品均進(jìn)行了系統(tǒng)的采集。
全巖粉末樣處理工作在河北廊坊市地源礦物測(cè)試分選技術(shù)服務(wù)有限公司進(jìn)行。首先選取一小塊巖石磨制探針片后,剩余巖石樣粉碎至200 目,用于主微量元素分析測(cè)試。
表1 安壩金礦床熱液礦物成順序與成礦期次劃分Table 1 The paragenetic sequences of hydrothermal minerals in the Anba deposit
主量和微量元素分析工作在中國(guó)核工業(yè)集團(tuán)核工業(yè)北京地質(zhì)研究所完成。其中,主量元素采用X 射線熒光光譜儀(XRF)完成,稀土元素及微量元素采用等離子體質(zhì)譜儀(ICP-MS)測(cè)試完成。主元素的分析精度優(yōu)于1%,微量元素分析精度優(yōu)于5%。其主微量、稀土元素分析結(jié)果如表2。
質(zhì)量平衡方法主要研究各種地質(zhì)體系中組分遷移和質(zhì)量變化,Gresens(1967)率先以實(shí)際巖石化學(xué)分析研究巖石質(zhì)量平衡,并導(dǎo)出了著名的Gresens 方程;Grant(1986)對(duì)該方程進(jìn)行了有效的簡(jiǎn)化,得到“等濃度方程”;Brimhall et al.(1988)和Brimhall and Dietrich(1987)等從簡(jiǎn)單直觀的質(zhì)量平衡出發(fā),導(dǎo)出了以不活動(dòng)元素為參考物種的質(zhì)量變化和體積變化表達(dá)式。鄧海琳等(1999)對(duì)前人關(guān)于質(zhì)量平衡法的主要研究成果進(jìn)行分析比較,指出前人研究中存在的問(wèn)題和不足,并提出了相應(yīng)的改進(jìn)方法,推導(dǎo)出新的質(zhì)量平衡方程。上述各種方法提出后被廣泛地應(yīng)用于相關(guān)的研究中,對(duì)人們深入理解各種地質(zhì)作用過(guò)程中巖石體系元素活動(dòng)及質(zhì)量遷移起到了至關(guān)重要的作用。
在熱液蝕變過(guò)程中,常量元素Al 和Ti 通常被認(rèn)為是不活動(dòng)的(Ague,1991;Condie and Sinha,1996;Klammer,1997),但Al 在變形變質(zhì)作用過(guò)程中仍有一定的活動(dòng)性(Ague,1991,1997;唐紅峰等,2000),尤其是長(zhǎng)石絹云母化過(guò)程中有部分析出(O’Hara,1988;O’Hara and Blavkburn,1989),硅化、絹云母化蝕變的發(fā)育導(dǎo)致Al 并不適合作為不活動(dòng)組分來(lái)研究安壩金礦床熱液蝕變過(guò)程元素遷移情況。Ti 在巖石中活動(dòng)性最小,在流體滲濾過(guò)程中是相對(duì)穩(wěn)定的,在巖石變形變質(zhì)過(guò)程中的活動(dòng)性相當(dāng)有限,是一個(gè)理想的參照元素(Ague,1991,1997;O’Hara,1988;郭順等,2013;劉德良等,1996;鐘增球和游振東,1995;張可清和楊勇,2002)。通過(guò)以上分析,本文選定TiO2作為不活動(dòng)組分。通過(guò)ΔCi=CiA/k-Cio(Cio、CiA為原巖、蝕變巖中第i 種元素的含量;k =Mo/MA=CA/Co,Co、CA為原巖和蝕變巖中不活動(dòng)元素的質(zhì)量;Mo、MA分別為原巖和蝕變巖的質(zhì)量)計(jì)算安壩金礦床蝕變過(guò)程中主量元素和部分微量元素的得失變化(表3、圖4)。由于碳酸鹽化、粘土化和綠泥石-綠簾石化樣品中蝕變疊加嚴(yán)重,沒(méi)有只發(fā)育其中一種蝕變的樣品,因此只對(duì)與成礦有關(guān)的硅化和絹云母蝕變進(jìn)行了質(zhì)量平衡計(jì)算。
從表3 和圖4 中可知,在硅化蝕變過(guò)程中,明顯帶入的組分有SiO2、Fe2O3、FeO、MgO、CaO、C、S、Au、As、Hg、Pb、Zn;Rb 和Ba 元素被明顯帶出。在絹云母化蝕變過(guò)程中明顯帶入的組分為SiO2、Fe2O3、CaO、C、S、Au、As、Hg、Pb、Zn、Rb 和Ba;帶出組分為Na2O。
圖4 安壩金礦床不同蝕變過(guò)程中的元素得失圖Fig.4 Gain-loss diagram for elements in the different alteration processes in the Anba deposit
表3 安壩金礦床蝕變過(guò)程中主微量元素平均得失量Table 3 Average gain or loss contents of major and trace elements during alteration processes of the Anba gold deposit
表4 安壩金礦床不同類型蝕變巖石稀土元素分析數(shù)據(jù)(×10 -6)及部分計(jì)算參數(shù)值Table 4 The date analysis (×10 -6)and related calculated parameters of rare earth elements of altered rocks in the Anba gold deposit
研究區(qū)內(nèi)可見(jiàn)硅化石英、絹云母和黃鐵礦共生,表明研究區(qū)普遍發(fā)育含硫量較高的酸性含礦流體(Parsapoor et al.,2009),此外,礦區(qū)內(nèi)硅質(zhì)巖發(fā)育,說(shuō)明含礦流體中Si 的含量很高(戢興忠等,2014)。這些酸性的流體淋濾原巖時(shí)產(chǎn)生硅化(Stoffregen,1987)。硅化蝕變與礦化關(guān)系密切,隨著SiO2的帶入,中低溫成礦元素(Au、As、Hg、Pb 和Zn)也被帶入到系統(tǒng)中,成礦元素組成配合物與硅元素組成的配合物具有相似的穩(wěn)定性,它們?cè)跓嵋褐幸煌\(yùn)移、析出(孟良義,1998)。蝕變過(guò)程中有C 元素的帶入,說(shuō)明了含礦流體中含有CO2,該結(jié)果與李晶等(2007)通過(guò)對(duì)石英脈中流體包裹體的研究結(jié)果一致。Fe2O3、FeO 和S 的帶入,與礦區(qū)內(nèi)黃鐵礦化有關(guān)。此外,含礦流體從圍巖帶走了大量的Rb、Ba 元素,這是由于Rb、Ba 的不相容性及其在含礦流體中的高遷移性所致(Helba et al.,2001)。
絹云母化蝕變過(guò)程中發(fā)生反應(yīng)為:
3NaAlSi3O8(斜長(zhǎng)石)+ 2H++ K+= KAl2[AlSi3O10](OH)2(絹云母)+6SiO2+3Na+
在該過(guò)程中,K+可能來(lái)自于外界流體,也可能來(lái)自于鉀長(zhǎng)石的蝕變所釋放出的K+,反應(yīng)后表現(xiàn)為K+的帶入和Na+的帶出。在斜長(zhǎng)石蝕變?yōu)榻佋颇?圖2h)過(guò)程中,斜長(zhǎng)石是很重要的Eu 來(lái)源,但此時(shí)的流體環(huán)境造成了一小部分的Eu進(jìn)入云母中,大部分的Eu 則被流體帶走,而Eu 與Ca2+是替代關(guān)系(Budzinski and Tischendorf,1989),由此造成了CaO的帶入。雖然從上述反應(yīng)中可以看出有SiO2的形成,但并未被流體帶走,而是與圍巖反應(yīng)形成含硅礦物或是以石英脈的形式產(chǎn)出于千枚巖中,導(dǎo)致SiO2的富集,在絹母化蝕變的過(guò)程中,一定會(huì)伴隨著輕微硅化蝕變過(guò)程的發(fā)生。絹云母化蝕變與礦化關(guān)系密切。隨著蝕變過(guò)程的進(jìn)行,中低溫成礦元素(Au、As、Hg、Pb 和Zn)也帶入到系統(tǒng)中。蝕變過(guò)程中有C元素的帶入,說(shuō)明了含礦流體中含有CO2。Rb 主要賦存于含K 的礦物中,在千枚巖中含K 的礦物主要為絹云母,因此,在絹云母化蝕變的過(guò)程中有Rb 的明顯帶入(凌其聰和劉從強(qiáng),2002)。此外,在絹云母化蝕變過(guò)程中有Ba 的大量帶入,李裕能(1986)對(duì)陽(yáng)山金礦帶內(nèi)的重晶石進(jìn)行了研究,Ba的大量帶入與本區(qū)出現(xiàn)的重晶石有關(guān)(凌其聰和劉從強(qiáng),2002)。Fe2O3和S 的帶入,與礦區(qū)內(nèi)黃鐵礦化和毒砂化有關(guān)(盧煥章等,2013)。
圖5 蝕變圍巖與原巖的稀土元素配分模式圖Fig.5 Chondrite-normalized REE patterns of the altered rock and the original rock
對(duì)不同蝕變過(guò)程的稀土元素投蛛網(wǎng)圖(圖5),并對(duì)稀土元素的一些參數(shù)進(jìn)行了計(jì)算(表4),從圖表中可以看出蝕變巖與原巖的REE 球粒隕石標(biāo)準(zhǔn)化配分模式曲線變化趨勢(shì)相似,曲線為右傾型,有明顯的Eu 負(fù)異常,并且δEu 值介于0.70 ~0.76 之間,原巖的Eu 負(fù)異常值要比蝕變巖值低,凌其聰和劉從強(qiáng)(2002)認(rèn)為是熱液蝕變作用造成了Eu 活化遷出,從而導(dǎo)致了蝕變圍巖的Eu 含量的降低和Eu 負(fù)異常擴(kuò)大的現(xiàn)象。δCe 的值在1 左右,未發(fā)現(xiàn)Ce 異常。千枚巖原巖與蝕變千枚巖均富集輕稀土,而不富集重稀土,說(shuō)明在蝕變過(guò)程中有流體REE 的加入(凌其聰和劉從強(qiáng),2002)。此外,千枚巖原巖的稀土含量要比硅化和絹云母化千枚巖中的稀土含量要高,說(shuō)明了在蝕變過(guò)程中伴隨著稀土元素的流失。
在絹云母化蝕變過(guò)程中,可以看出LREE 的減少和K2O的增加,該現(xiàn)象表明了斜長(zhǎng)石蝕變?yōu)榻佋颇傅倪^(guò)程伴隨著REE 加入到流體中(Genna et al.,2014)。此外,斜長(zhǎng)石是Eu 的一個(gè)非常重要的來(lái)源(Budzinski and Tischendorf,1989),然而,斜長(zhǎng)石蝕變?yōu)榻佋颇傅倪^(guò)程中只有很少一部分Eu 能夠進(jìn)入到絹云母中(Alderton et al.,1980)。絹云母形成時(shí)流體的溫度<250℃,此時(shí)Eu 容易被流體帶走,進(jìn)而造成該區(qū)域Eu 的負(fù)異常(Genna et al.,2014)。
圖6 安壩金礦床4 號(hào)硐CM19 剖面元素含量變化Fig.6 Elements content variation in the CM19 profile of the 4th adit in the Anba deposit
對(duì)安壩金礦床4 號(hào)硐CM19 剖面上樣品的主微量數(shù)據(jù)進(jìn)行了相應(yīng)的投圖(圖6)。圖中CO2/(Fe+Mg+Ca)摩爾質(zhì)量比代表了碳酸鹽化程度(Chinnasamy and Mishra,2013;McCuaig and Kerrich,1998),從圖中可以看出,在靠近斷裂帶的地方碳酸鹽化程度較高,說(shuō)明了碳酸鹽化在安壩金礦床內(nèi)受斷裂帶控制。(3K+Na)/Al 摩爾質(zhì)量比代表堿金屬濃度集中程度,即代表含有堿金屬的云母礦物含量(Chinnasamy and Mishra,2013;McCuaig and Kerrich,1998),在安壩金礦床主要以絹云母為主。在巖漿巖中或距離巖漿巖較近的千枚巖中往往絹云母化蝕變的程度較高,可見(jiàn)絹云母化蝕變的空間分布受巖漿巖的控制。在陽(yáng)山金礦帶內(nèi),巖漿巖的空間分布在區(qū)域上明顯受斷裂帶的控制(王宏偉,2012;華北,2013),因此,絹云母化在空間分布上受斷裂帶的控制。SiO2含量在一定程度上代表硅化的程度,從圖中可知,在斷裂帶發(fā)育的地方硅化程度強(qiáng)。在野外常??梢?jiàn)在斷裂帶附近往往石英脈較發(fā)育,含礦流體一般都是沿?cái)嗔褞н\(yùn)移的,并在斷裂帶附近的圍巖中形成石英脈;此外,圍巖與含礦流體也更容易接觸發(fā)生交代反應(yīng)而形成含SiO2的礦物。以上兩種原因致使斷裂帶附近的圍巖硅化程度較高。粘土化發(fā)育于斷裂帶附近,而且越靠近斷裂帶的地方蝕變程度越高。
對(duì)安壩金礦床4 號(hào)硐CM19 剖面上Au、S、FeO、As 和Fe2O3的含量進(jìn)行了投圖(圖6)。結(jié)合圖3 發(fā)現(xiàn),在剖面上(3K+Na)/Al 摩爾比曲線在樣品3B-6、3B-9、3B-13、3B-16、3B-17、3B-19、3B-26、3B-27 處出現(xiàn)峰值;金含量曲線顯示在樣品3B-6、3B-9、3B-11、3B-16、3B-18、3B-27 處出現(xiàn)峰值;而觀察SiO2含量曲線可以發(fā)現(xiàn)在樣品3B-7、3B-11、3B-15、3B-17、3B-18、3B-20、3B-27 處硅化程度較高。樣品3B-6 發(fā)育絹云母化、粘土化和輕微的硅化,鏡下可見(jiàn)該樣品的硅化、粘土化蝕變與礦化沒(méi)有關(guān)系,而絹云母化伴隨有黃鐵礦化發(fā)育(圖2b),表明樣品3B-6 金含量高與絹云母化蝕變有關(guān)。樣品3B-9 僅發(fā)育絹云母化蝕變,并且鏡下可見(jiàn)絹云母化伴隨黃鐵礦化,說(shuō)明了該樣品中礦化與絹云母化關(guān)系密切。樣品3B-11 發(fā)育硅化,鏡下見(jiàn)硅化伴有黃鐵礦化(圖2d)。樣品3B-16、3B-27 發(fā)育硅化和絹云母化,樣品3B-18 發(fā)育硅化、絹云母化和碳酸鹽化,鏡下可見(jiàn)硅化和絹云母化伴隨黃鐵礦化,這三個(gè)樣品中礦化與硅化、絹云母化有關(guān)。樣品3B-7、3B-15、3B-17、3B-20 鏡下可見(jiàn)硅化,且硅化與礦化無(wú)關(guān)。樣品3B-13、3B-17、3B-19、3B-26 鏡下可見(jiàn)絹云母化,且絹云母化與礦化無(wú)關(guān),該絹云母應(yīng)該為成礦前的產(chǎn)物。
此外,在剖面上還發(fā)現(xiàn)S 百分含量呈現(xiàn)出6 個(gè)峰,這6個(gè)峰與Au 的含量呈現(xiàn)出的6 個(gè)峰位置相同,并且二者有相同的變化趨勢(shì),主要是因?yàn)樵诎矇谓鸬V床內(nèi)金主要賦存于金屬硫化物(黃鐵礦和毒砂)中。FeO 在剖面上的變化與Au 的變化趨勢(shì)僅局部變化一致,這是因?yàn)镕e2+主要賦存于黃鐵礦中(FeS),金不僅賦存于黃鐵礦中,還有部分金賦存于毒砂中。而在毒砂中Fe 以二價(jià)和三價(jià)的形式存在,并與As 和S結(jié)合。在剖面上25m 處的Au 含量特別高,此時(shí)Fe2+、Fe3+、As、S 的含量也很高,主要是因?yàn)檫@四種元素形成了大量的毒砂和黃鐵礦,Au 同時(shí)也發(fā)生了沉淀,并賦存于黃鐵礦和毒砂中(Fleet et al.,1993;Reich et al.,2005;Deditius et al.,2008;Zhang et al.,2013)。
硅化蝕變過(guò)程,含礦流體沿?cái)嗔褞蛏线\(yùn)移,在運(yùn)移時(shí)溫度、壓力逐漸下降,氧逸度升高。當(dāng)氧逸度升高時(shí),含礦流體呈弱酸性,而弱酸性、溫度壓力降低、氧逸度升高的條件促使SiO2沉淀,產(chǎn)生硅化(申婉妮,2010),并且硅化蝕變過(guò)程伴隨著黃鐵礦和毒砂的形成。安壩金礦床內(nèi)Au 以配離子[AuS]-的形式存在(謝廣東,1994;李楠,2013;朱光儒等,2014;Wang et al.,2015)。硅化蝕變過(guò)程中黃鐵礦和毒砂的沉淀,引起含礦流體中還原硫活度降低,從而導(dǎo)致金沉淀(李楠,2013)。
在絹云母化蝕變過(guò)程中能夠改變含礦流體的pH 值,而含礦流體的pH 值反過(guò)來(lái)影響金屬礦物的溶解度(Guilbert and Park,1986)。流體與圍巖反應(yīng)過(guò)程中消耗H+,并使溶液pH 值增大顯弱堿性(Helba et al.,2001;李晶等,2007)。含礦流體中含有豐富的Fe 和S 元素。
從上述反應(yīng)可以看出,絹云母化蝕變過(guò)程中有大量硫化物的形成。此外,K+和H+的減少和CO2的增加,可以降低Au 的溶解度(Kishida and Kerrich,1987;Gao and Kwak,1997)。所以,隨著Fe 含量的增加,含Au 的硫化物開(kāi)始沉淀(Helba et al.,2001)。
(1)安壩金礦床發(fā)育的蝕變有硅化、絹云母化、碳酸鹽化、綠泥石化、綠簾石化和粘土化,其中與成礦有關(guān)系的蝕變?yōu)楣杌徒佋颇富?。在時(shí)間上,硅化蝕變貫穿發(fā)育于成礦前、成礦期和成礦后,絹云母化蝕變?yōu)槌傻V前和成礦期的產(chǎn)物,碳酸鹽化蝕變主要發(fā)育于成礦晚階段和成礦后,而粘土化蝕變?yōu)槌傻V后的產(chǎn)物。在空間上,不同類型的蝕變均受礦區(qū)內(nèi)斷裂帶的控制。
(2)在硅化蝕變過(guò)程中,明顯帶入的組分有SiO2、Fe2O3、FeO、MgO、CaO、C、S、Au、As、Hg、Pb、Zn;Rb 和Ba 元素被明顯帶出。在絹云母化蝕變過(guò)程中明顯帶入的組分為SiO2、Fe2O3、CaO、C、S、Au、As、Hg、Pb、Zn、Rb 和Ba;帶出組分為Na2O。絹云母化過(guò)程中絹云母是由斜長(zhǎng)石蝕變而形成的。
(3)在稀土元素方面,表現(xiàn)為明顯的Eu 負(fù)異常、無(wú)Ce 異常。原巖的δEu=0.70,δCe =0.95;硅化巖石的δEu =0.72,δCe=1.00;絹云母化巖石的δEu=0.76,δCe=0.95。稀土元素的配分模式曲線變化趨勢(shì)相似,為右傾型曲線,并且富集輕稀土,而不富集重稀土。稀土元素的變化揭示了蝕變過(guò)程中有流體REE 的加入和稀土元素的流失。
(4)在硅化過(guò)程中,由于含礦流體溫度、壓力和氧逸度的變化,并伴隨著黃鐵礦和毒砂的形成,引起含礦流體中還原硫活度降低而導(dǎo)致金沉淀。在絹云母化過(guò)程中,含礦流體的pH 增大及K+和H+的減少和CO2的增加導(dǎo)致了Au 溶解度的降低,最終致使黃鐵礦和Au 沉淀。
致謝 野外工作得到了中國(guó)黃金集團(tuán)陽(yáng)山金礦有限公司工作人員、武警黃金部隊(duì)十二支隊(duì)官兵的幫助與支持;巖石主微量元素測(cè)試工作得到了核工業(yè)北京地質(zhì)研究院地質(zhì)分析測(cè)試研究中心相關(guān)人員的協(xié)助;論文成文過(guò)程中得到了中國(guó)地質(zhì)大學(xué)(北京)楊立強(qiáng)教授的悉心指導(dǎo),同時(shí)也得到了邱昆峰博士、李瑞紅博士和劉向東碩士的幫助;審稿人對(duì)本文提出了寶貴修改意見(jiàn);在此對(duì)他們表示最誠(chéng)摯的謝意。
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