黔中白云岩风化剖面淋溶实验及其元素地球化学特征

本文通过化学淋溶方法对分布在黔中白云岩风化剖面——平坝剖面进行研究，较系统地分析了原样、酸溶（AS）和酸不溶相（AI）中主量、微量和稀土元素（REE）的地球化学过程和分布分配特征。结果显示：主量元素在酸不溶相中其化学成分和原样非常接近，只是相对含量有所变化；微量元素在酸溶相（AS）中的分配率差别很大,在0～73.22%之间波动，其中Ga、Y、Ba、Pb、U的分配率均在30%以上；尤其值得我们注意的是Y和Zr的淋失量分别达到了59.64%和0.34%，这与传统所认为的Y和Zr为稳定元素不一致，可能对我们重新认识表生过程中化学元素的活动性及分配分布情况具有重要的指导意义；剖面稀土元素超常富集层的形成主要是由于对白云岩残积的继承和磷酸盐矿物的存在，这与先前所得出的结论基本一致。酸淋溶试验同时也反映出研究区的风化作用实质上是一种天然的酸淋溶作用。最后笔者等对酸溶相（AS）中REE和Sr的主要储库进行了讨论，推测磷酸盐是平坝剖面基岩和土层中酸溶相（AS）中REE的主要储库，而Sr的存在形式是碳酸盐矿物本身。     

白云岩风化剖面元素地球化学特征:对黔中九架炉组“三稀金属”富集机制的启示

黔中早石炭世九架炉组铝土矿含矿岩系富集Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th和稀土(REEs)等"三稀金属",具有成为独立矿床或伴生资源的潜力。这些元素大部分与九架炉组共有同一母岩,且富集程度受母岩的成分和风化作用控制。本研究选取九架炉组母岩乌当娄山关群白云岩和纳雍牛蹄塘组泥质白云岩的现代风化剖面为研究对象,研究元素在风化作用过程中的迁移特征及分布规律,进而为九架炉组微量元素的富集机制提供启示。研究获得以下认识:1)依据剖面结构、ZrHf、Nb-Ta、Y-Ho二元图特征及REE配分曲线和Eu/Eu*值的相似性表明研究区土层主要来源于基底或母岩的风化; 2)白云岩风化成土过程中Si、Fe、Cr、As、Sb、Ti、Nb、Ta、Zr、Hf、Th、REEs等元素化学性质相对稳定,富集程度较高,而Ca、Mg、Na、K、Sr、P、Mo、Cd等元素化学性质活泼,容易淋失亏损; 3)纳雍剖面REEs~(3+)和Ca~(2+)半径差与REEs富集系数相关性良好,表明碳酸盐岩风化过程中,含钙矿物磷灰石是稀土元素分配的重要控制因素; 4)九架炉组的母岩也是Ti、Li、Sc、V、Ga、Nb、Ta、Zr、Hf、Th等微量元素的主要物质来源,母岩风化过程中,这些微量元素首先在副矿物、黏土矿物、铝矿物及磷灰石等矿物相中初步富集,之后随风化碎屑物一起沉积形成微量元素超常富集地层; 5)纳雍剖面地表和地下水提供了部分P、Be、Zn、Sb、Pb、Y及REEs来源,指示水体迁入作用也是九架炉组REEs富集的重要原因。研究表明黔中九架炉组微量元素的来源较复杂,风化-沉积过程中,化学性质稳定的元素残留在风化碎屑物中并被搬运-沉积在负地形中,而化学性质活泼的元素首先被带入水体,在沉积-成岩过程中特定条件下发生二次富集作用(例如次生矿物的形成及吸附)形成微量元素富集的地层。     

碳酸盐岩风化剖面U和Th的富集特征 及淋溶实验的指示

通过对贵州岩溶区12条风化剖面U、Th的分布情况、岩-土界面岩粉层动态淋溶残余物的元素变化特征以及元素质量平衡的研究,初步揭示了碳酸盐岩风化剖面U、Th的富集特征.①在碳酸盐岩风化体系中,U呈现出明显的活性,而Th既有惰性的一面,又表现出活性的一面.②碳酸盐岩风化过程中,岩-土界面是U、Th产生突变性富集的重要地球化学场所,而剖面进一步发育演化中U、Th的变化是一个长期而缓慢的过程.岩-土界面反应中,由于风化残余物体积的巨大缩小,U呈现出低背景、强亏损、高富集的地球化学特征.当Th呈现活性态时,与U表现出相似的地球化学特征;当Th表现为惰性态时,其在剖面中的富集主要源于易溶组分溶蚀后的绝对残余.③碳酸盐岩风化剖面U、Th的富集系数与基岩酸不溶物含量存在明显的负相关,说明碳酸盐岩酸不溶物含量愈低,碳酸盐溶蚀的体量愈大,风化溶液带出的活性U或Th也愈多,风化残余物的体积缩小变化程度也愈强,因此残余U或Th的相对富集程度也愈高.     

二连盆地卫镜岩体风化作用地球化学特征研究

二连盆地的卫镜岩体被认为是二连盆地努和廷铀矿床的重要铀源,文章对卫镜岩体在风化条件下元素的活动性进行了分析,结果表明:风化样品的化学风化指数CIA值介于58.67～60.07,反映寒冷、干燥气候条件下低等化学风化程度。在半风化过程中,斜长石最先风化分解,Ca、 Na流失,钾长石相对稳定;在地表强风化条件下,钾长石风化分解明显,且原生含磷矿物分解释放P而淋失;黏土矿物的吸附作用导致Mg、 Ca在地表强风化条件下富集;Fe_2O_3~T、 FeO含量降低明显,更可能与磁铁矿和黄铁矿的氧化淋滤有关。H、 LOI、 S和C在强风化样品中含量明显降低,暗示风化条件为干燥氧化气候条件,卫镜岩体花岗岩风化过程中Ca、 K、 Mg、 Fe、 C、 S等元素容易迁移,P、 Mn、Na次之,而Ti、 Al属于稳定元素。铁族元素Cr、 Ni、 Ti及REE等微量元素保持稳定,Nb、 Ta、 Zr、Hf、 Th、 Y等高场强元素以及部分大离子亲石元素Pb、 Rb、 Be、 Li、 Sb一定程度富集,U、 V、 Sr明显迁出,且Zr/Hf、 Nb/Ta、 Th/Sc、 Zr/Nb等元素比值均发生变化,主要受风化条件下原生矿物分解释放和黏土矿物吸附相互制约的过程共同控制;不同样品稀土配分模式一致,但Y/Ho值明显高于新鲜岩石的值,可能主要与地表HCO_3~-含量丰富有关。在干旱氧化、富集HCO_3~-的化学风化条件下更容易导致U的淋滤迁出,为二连盆地铀成矿提供重要铀源。     

粤北碳酸盐岩化学风化过程中的元素地球化学行为

碳酸盐岩化学风化对于大型水系以及海水的化学组成具有重要的影响。然而,当前对碳酸盐岩化学风化过程中元素的迁移特征及其控制机制的认识尚存一些争议。本文通过报道粤北地区的一个典型碳酸盐岩风化剖面的矿物组成和主元素、微量元素含量的变化特征,试图探讨碳酸盐岩化学风化过程的元素地球化学行为。结果显示,碱土金属Ca、Sr大量迁出剖面,这与碳酸钙的溶解直接相关;而其他碱金属-碱土金属元素则发生了不同程度的富集,可能归因于黏土矿物对这些元素的吸附;过渡金属元素也存在明显的富集现象,可能与Fe、Al的氧化物/氢氧化物对其的吸附有关。平均上地壳(UCC)标准化的稀土元素(REE)图解显示,相对新鲜的母岩,风化产物中的稀土元素发生了显著的富集与分异,同时伴随着Ce的显著负异常(δCe=0.30~0.84)。本剖面上REE的迁移和再分配主要受控于介质p H值的变化:在近中性的条件下,碳酸根离子可以和REE形成稳定的络合物,显著提高了REE迁移能力,并在碱性较强的层位之上富集和再分配。然而,由于重稀土元素(HREE)的原子半径小于轻稀土元素(LREE),造成HREE与碳酸根络合物的稳定性显著大于LREE,最终导致碳酸盐岩风化过程中HREE的富集程度明显超过LREE。     

湘西下寒武统黑色页岩风化元素活动规律

为探讨黑色页岩风化过程中的元素活动规律,采集了湘西东坪、柑子坪下寒武统黑色页岩风化-成土剖面的样品进行了主、微量元素地球化学分析。结果表明,两剖面风化层有不同的主量元素组成,但其土壤层的主量元素组成相对均一。主量元素Si、K、Na、P等在风化过程中活泼而被淋滤释出;而Al、Fe、Mg等元素既可被淋滤释出,又可产生次生富集。而成土过程中,所有主量元素都表现被淋出的特征。元素Mn的次生富集明显;重金属V、Ni、Cu、Cr、Co、Zn、Pb等在风化-成土过程中的化学活性与Al、Fe等主量元素相似;亲石元素Sc、Rb、Sr、Cs、Ba、Th、U、Ga、Ge等在风化-成土过程中的活性较强,趋于被淋出,且其淋滤释出率随风化程度增强而升高;高强场元素Zr、Hf、Nb、Ta等的化学活性相对稳定。     

长白山区暗棕壤成土作用地球化学特征

以代表性暗棕壤垂直剖面土壤地球化学数据为依据,研究了长白山区特定的森林景观条件下成土过程中元素的分异与富集特征。研究结果表明,在岩石风化过程中主要以CaO、Na2O、Sr淋溶为主,有机酸淋溶过程中SiO2、Al2O3、K2O部分被淋溶,部分游离铁下渗到土体中下部氧化成铁锰胶膜;微量元素在风化过程中被次生黏土矿物吸附,不同程度地富集,在腐殖质积累过程中Cd、Zn、Pb、Mo、Hg、Co、Mn、Cr等亲生物元素进一步富集于表层土壤,Ce、Ni、Sb、Ti、V、Y、Zr在表生环境中地球化学性质稳定,残留富集于土壤表层。母质层继承和保留了基岩元素地球化学分布的基本特征。     

碳酸盐岩风化过程中高场强元素的地球化学行为研究——来自碳酸盐岩淋溶实验的证据

选择黔中地区的一条白云岩原位风化剖面（平坝剖面）作为研究对象,通过对岩-土界面之下的岩粉层（砂状碳酸盐岩）动态淋溶过程中高场强元素（HFSE）地球化学行为的研究,并结合其在风化壳剖面的分布特征,获得了以下主要认识:（1）碳酸盐岩风化过程中,HFSE间存在明显的分馏,而且元素分馏主要出现在岩-土界面作用过程中,即碳酸盐岩溶蚀形成残积土阶段;元素的地球化学惰性由强到弱的顺序依次为Zr>Hf>Nb>Sc>Th>Ta>Ti>Y,其中,Zr是最稳定的元素,Hf仅次于Zr,Nb和Sc也相对较为惰性,而Th、Ta、Ti、Y呈现出明显的活性;（2）对于碳酸盐岩风化剖面的质量平衡计算,Zr是理想的参比元素（即惰性元素）;（3）由基岩酸不溶物至风化壳剖面,元素对Nb-Ta、Zr-Hf显示出较好的协变性,没有明显分馏,因此,在利用这类元素对岩溶区风化壳的物源进行示踪时,碳酸盐岩作为潜在母岩,宜采用其酸不溶物作为参比对象;（4）碳酸盐岩风化过程中,虽然Sc也是一个较为稳定的HFSE,但在风化母岩中分布不均匀,不宜用于岩溶区风化壳的物源示踪。      

地壳风化速率研究综述

地壳风化速率研究的理论基础是质量守恒原理和溶液与矿物反应动力学法则。元素在风化过程中的行为受多种因素控制，主要包括基岩风化量、大气沉降量、径流量、生物的输出数量和人为输入量（如施肥）。硅酸盐矿物化学风化过程中，矿物与溶液之间总的化学反应速率是单个反应速率之和，其中涉及到 3个关键参数，即：酸中和能力（ANC）、基本阳离子/无机铝（BC/Al无机）比值和临界负荷（CL）。风化速率的研究主要采用四种方法，即PROFILE模型、基本阳离子损耗、元素输入-输出指数和Sr同位素比值等。PROFILE模型是一个稳定态的综合土壤化学模型，矿物的分解速率、矿物的暴露表面积、土壤水饱和度和土壤层厚度决定着该矿物的风化速率，总的风化速率为各种矿物的风化速率之和。元素损耗，主要是基本阳离子（Ca、Na、K和Mg）的损耗，假设Ti、 Zr和Nb在成土过程中含量稳定并不参与风化反应，那么对于给定的土壤层，化学风化损耗的基本阳离子可以通过比较土层与成土母质之间元素组成的差异来计算。输入-输出指数的假设前提是研究的流域处于稳定状态，一般认为输入指数是大气沉降，输出指数是河流搬运溶解部分、悬浮的非岩屑成因部分和生物营养净吸收部分。Sr同位素在生物和化学作用过程中并不分馏，不同生态系统阳离子场中Sr同位素组成是大气和矿物风化来源的Sr的混合物。     

中山市神湾镇晚中生代花岗岩风化壳剖面元素地球化学特征

选择珠三角沿海地区有代表性的中山市神湾镇三个晚中生代花岗岩风化壳剖面进行系统采样和主量、微量元素分析,研究了花岗岩风化壳剖面元素地球化学特征.花岗岩风化壳剖面自上而下可划分为淋溶层(E)、淀积层(B)、半风化层(C)和基岩层(R),不同层位的Si、Al、K、Rb、U、Nb、Ta、Hf、Th、Se含量均高于大陆上地壳相应元素的丰度平均值,Na、Ca、Mg、Mn、Ti、P、Sr、Cu、Cr、Ni、Zr含量则低于大陆上地壳相应元素的丰度平均值.剖面从母岩向上到表土层,化学风化程度逐渐增强,元素含量除继承母岩特征外,还发生了分异,其中Na、Ca、K、Mg、Rb、Sr、U等元素含量随风化程度的加深而降低,表现出在风化过程中淋失亏损的特征;Ti、P、Ta、Hf、Se、Nb、Th、Zr等元素含量随风化程度的加深而增高,表现出在风化过程中富集的特征.风化作用导致了研究区上层土壤中养分元素K、Ca、Mg淋失缺乏,硒在表层土壤中富集.     

Mineralogical and geochemical evolution of the Bidgol bauxite deposit,Zagros Mountain Belt,Iran: Implications for ore genesis,rare earth elements fractionation and parental affinity

The present study focuses on the Late Cretaceous Bidgol bauxite deposit in the Zagros Simply Fold Belt, SW Iran. The orebody is located in the eroded major NW–SE trending Koh-e-Hosseyn anticline and hosted as discontinuous stratified layers and lenses within the upper member of the Cenomanian–Turonian Sarvak Formation. Detailed mineralogical analysis reveals that diaspore, hematite, goethite, anatase, clinochlore, chamosite, and calcite are the major mineral components accompanied by minor amounts of detrital and REE-bearing minerals such as rutile, zircon and parisite. The ore texture suggest that the bauxite material has an authigenic origin but in some parts it has been transported short distances from a primary in situ environment and redeposited in karstic depressions. The spheroidal pisolites of the Bidgol bauxite formed under conditions of low water activity, favouring the formation of large diaspore cores and a single dry-to-wet climatic fluctuation. The mass change calculations relative to the immobile element Ti show that elements such as Si, Fe, Mg, K, Na and Sr are leached out of the weathered system; Al, Ni, Zr, Ga, Cr and Ba are concentrated in the residual system; and Hf, Ta, Co, Rb, Cs, Be, and U are relatively immobile during the bauxitisation processes. The Nb, Th, Y, V, Sc, Sn and ΣREE are relatively immobile in the initial stage of bauxitisation processes in the bauxite ores, but were slightly mobile at the later stage of bauxitisation. Geochemical data reveal progressive enrichment of the REE and intense LREE/HREE fractionation toward the lower parts of the bauxite profile. Cerium behaves differently from the other REEs (especially LREE) and show positive anomalies in the upper horizons that gradually become negative in the deeper parts of the profile. The distribution and fractionation of trace elements and REEs during the bauxitisation process in the Bidgol deposit are mainly controlled by the presence of REE-bearing minerals, fluctuations in soil solution pH, REE ionization potential and the presence of bicarbonates or organic matter. Geochemical analyses confirm a protolith contribution from the bedrock argillaceous limestone and suggest that the source material for the Bidgol bauxite was provided from a siliciclastic material derived from a continental margin. The mid-Turonian uplift led to the formation of karstic topography, rubbly breccia and a layer of ferruginous–argillaceous debris that was affected by lateritic weathering under humid tropical climate. Subsequently, mobile elements are removed from the profiles, while Al, Fe and Ti are enriched, resulting in the formation of the pristine bauxite materials. When the platform subsided into the water again, the pristine bauxitic materials were partly converted to bauxite. During the exposure of bauxite orebodies on the limbs and crests of anticlines and subsequent eroding and accumulation in the karstic depressions during folding and faulting in Oligocene–Miocene, important factors such as intensity of the weathering, drainage and floating flow may have improved the qualities of the bauxite ores.     

Genesis of the Guangou karstic bauxite deposit in western Henan,China

The Guangou bauxite deposit in western Henan, China, is located in the North China Block and to the north of the North Qinling orogenic belt. The orebody is hosted within the lower member of the Carboniferous Benxi Formation, which overlies unconformably upon the Ordovician Majiagou Formation. In the lower member of the Benxi Formation, the bauxite orebody (with a diaspore–illite–anatase mineral assemblage) is sandwiched between underlying ferric clay (illite–hematite–goethite) and overlying top clay (kaolinite–quartz–goethite). According to field observations and geochemical evidence including trace- and rare-earth-element (REE) compositions, especially Zr/Hf ratios, the ferric clays were weathered from the underlying argillaceous limestones in the Majiagou Formation. During this weathering process, trace elements S, Zn, Ni, Cr, V, Sc, F, Ba, and Be are depleted; Li, Rb, and B are enriched; and Zr, Hf, Bi, Ta, Ga, Nb, and Th are relatively immobile. REEs exhibit evident differentiation with enrichment of La, Ce, Pr, and Nd and depletion of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The bauxite formed in weak reducing, slightly basic water conditions according to the geneses of coexisting diaspore and anatase, and it was altered during the epigenetic and second exposure periods, forming kaolinite and goethite, respectively. Interelemental relationship analyses of the ores suggest that the elemental behaviors of trace elements and REEs in the bauxitization process are mainly controlled by the mineral compositions in bauxite ore and chemical properties of the elements. For instance, zircon, rutile, and anatase contain Zr, Hf, Nb, Ta, W, and U. Based on geochemical evidence, together with age data and chemical compositions of the detrital minerals, both distant igneous rocks in the plate margin and Paleozoic carbonates and Precambrian rocks inside North China Block provide the miscellaneous material for the bauxite ore and the top clay.     

NS935钻孔沉积物不活泼微量元素记录与陆源输入变化探讨

探讨了NS93－5钻孔沉积物的部分高场强元素和大离子亲石元素的含量变化，结果表明，Ti、Rb、Ga、Y、Zr、Nb、Cs、Hf、Ta、Th和稀土元素（REE）相互间含量变化具有很好的相关关系，反映这些元素均基本来自碎屑组分。经Ti和Sc标准化后这些元素含量的变化，以及Zr/Y等特征元素比值和Ge异常指数Ce/Ce、Eu异常指数Eu/Eu的变化，均反映出碎屑输入的通量或者组成的变化，例如火山灰的富集。其中一些变化与气候变化有关，可能反映周边陆壳的风化强度的波动。NS93－5钻孔沉积物的不活泼元素记录，可提供反映输入陆壳物源区的环境演变证据。     

Mineralogical and geochemical characteristics of hydrothermal alteration and episyenitization in the Königshain granites, northern Bohemian Massif, Germany

The late-Hercynian granites of Königshain underwent multistage hydrothermal processes. Extensive high-temperature late-magmatic alteration is, for example, indicated by low Zr/Hf and an REE pattern displaying the tetrad effect. Intensive post-magmatic alteration of the granite occurred along brittle structures. At least two main stages of post-magmatic hydrothermal alteration are involved. The first high-temperature stage, which is characterized by albitization and/or quartz leaching (episyenitization), resulted from fluid–rock interaction with late-magmatic fluids that very probably mixed with external low-salinity fluids. Quartz dissolution was triggered by vapour condensation and/or the cooling of these fluids (below 450??°C) along brittle structures. The high porosity resulting from quartz leaching during stage 1 assisted subsequent circulation of low-temperature fluids at stage 2; the latter is characterized by the chloritization and illitization of episyenites. Almost all major and trace elements were enriched or depleted during one of the main alteration stages. However, Zr, Hf, Th, and Ti were immobile during post-magmatic alteration. The significant depletion of LREE and the enrichment of HREE in albitized samples is controlled by the dissolution of monazite and the new formation of HREE-rich polycrase-(Y) or aeschynite-(Y) during post-magmatic stage 1. Negative Ce anomalies of episyenites are associated with illitization and suggest oxidizing conditions during stage 2.     

Extreme enrichment of Sb, Tl and other trace elements in altered MORB

We have analyzed 25 trace elements (e.g., Sb, Tl, Sn, rare earth elements (REE), Th, U, Nb, Pb, Zr, Hf, and Y) in altered mid-ocean ridge basalts (MORB) from locations near the mouth of the Gulf of California. Our results imply that the heavy REE and Y are not seriously affected by seawater alteration, in agreement with previous studies. The elements Zr, Hf, Nb, light REE and Sr are enriched up to a factor of 2 in some extremely altered samples. However, element ratios between Zr, Hf, and Nb (e.g., Zr/Hf, and Zr/Nb) are not greatly affected, presumably due to the chemical similarity of these elements during any exchange process. The enrichment of Th and Sn is even higher. Antimony, Tl, Cs, Rb, Rb, and Ba are most easily altered by water-rock interaction and are therefore the best indicators for seawater alteration. The enrichment factor of the most mobile element Sb is up to 2000.

There is a weak correlation between the concentration in seawater and the enrichment factors. On the other hand, the worldwide pelagic clay pattern matches the enrichment pattern much more closely, and the limited data available for local oceanic sediments give an even better correlation. A plausible model to explain the enrichment pattern may be an elemental exchange between basalt and seawater that had interacted earlier with overlying sediments.     

黔中红粘土的物质来源与成因研究——以平坝剖面为例

以黔中平坝剖面为具体对象,从矿物、元素地球化学、元素质量平衡等多方面对黔中白云岩上覆红粘土剖面进行了详细研究。结果显示该剖面是下伏基岩白云岩风化成土并累积的结果,无其他外来物源,是原位风化壳;成土过程具有两阶段模式特征,即白云石、方解石的溶蚀-酸不溶物累积和酸不溶物进一步风化两个阶段;长时期的构造稳定和白云岩整体溶蚀作用是黔中地区白云岩风化壳土层厚度大、分布连续的主要制约因素。     

黑色页岩风化过程中元素的活动性及参照系的选取初探--以湖南省麻田、桃花江剖面为例

系统考察了湖南省麻田和桃花江两个不同发育程度的下寒武统黑色页岩风化剖面,并提出了元素在理想剖面中的分布模式(概念模型);通过对比分析这两个剖面中元素的分布特征与理想分布模式的关系,并结合元素相关性研究、等质量图解的判别分析、微量元素的赋存状态及地球化学性质的探讨,认为在黑色页岩风化过程中,Ti为不活动元素,可作为参照系来计算其它元素的相对迁移性,Nb、Ta的活动性较小,Zr与Hf之间存在着共迁移现象;研究表明化学风化程度是影响元素活动性的重要因素.     

REE fractionation and Ce anomalies in weathered Karoo dolerite

Analyses of samples from a weathering profile on Karoo dolerite allow elements to be divided into three groups depending on their behaviour. Si, K, Na, Mg, Ca, Sr, Ba and V are mobilized and removed from weathered products. Fe, Al. Ti, Zr, Hf, Zn, Cu, Sc, Co and Ni are immobile. REE, Y, and to a lesser extent Cr, are mobile and redistributed within the profile without a net loss of these elements from the profile. Large positive Ce anomalies are developed in oxidized weathered products by preferential leaching of the other REE's. Negative Ce anomalies and REE enrichment is a feature of less altered dolerite.