An experimental study on felsic rock–artificial seawater interaction: implications for hydrothermal alteration and sulfate formation in the Kuroko mining area of Japan

Experimental studies on the interactions between artificial seawater (ASW) and fresh rhyolite, perlite and weakly altered dacitic tuff containing a small amount of smectite suggest changing cation transfer during smectite-forming processes. Initially, dissolution of K from the rocks accompanies incorporation of Mg and Ca from ASW during both earlier (devitrification stage) and later smectite formation, whereas Ca incorporated with early smectite formation redissolves with progressive reaction. Barium mobility increases toward the later smectite-forming reactions. Therefore, the large amounts of barite, anhydrite and gypsum in Kuroko ore deposits are considered to have precipitated from hydrothermal solutions derived from the interaction with previously altered felsic rocks during late smectite formation, rather than by the reaction with fresh felsic rocks.Editorial handling: D. Lentz     

Mechanisms for anhydrite and gypsum formation in the Kuroko massive sulfide–sulfate deposits,north Japan

The Sr, Ba, and rare earth elements (REEs) concentrations and Sr isotopic composition of anhydrite and gypsum have been determined for samples from the Matsumine, Shakanai, and Hanaoka Kuroko-type massive sulfide–sulfate deposits of northern Japan to evaluate the mechanisms of sekko (anhydrite and gypsum) ore formation. The Sr isotopic compositions of the samples fall in the range of 0.7077–0.7087, intermediate between that for middle Miocene (13–15 Ma) seawater (0.7088) (Peterman et al., Geochim Cosmochim Acta, 34:105–120, 1970) and that for country rocks (e.g., 0.7030–0.7050) (Shuto, Assn Geol Collab Japan Monograph 18:91–105, 1974). The Kuroko anhydrite samples exhibit two types of chondrite-normalized REE patterns: one with a decrease from light REEs (LREEs) to heavy REEs (HREEs) (type I), and another with a LREE-depleted pattern (type II). Based on the Sr content and isotopic ratio (assuming an Sr/Ca (mM/M) of 8.7 for seawater), anhydrite is considered to have formed by mixing of preheated seawater with a hydrothermal solution of Sr/Ca (mM/M) = ca. 0.59–1.36 under the condition in which the partition coefficient (Kd) ranges between ca. 0.5 and 0.7. This results in the formation of anhydrite with higher Sr content with an Sr isotopic value close to that of seawater under seawater-dominant conditions. Larger crystals of type II anhydrite are partly replaced by smaller ones, indicating that anhydrite dissolution and recrystallization occurred after or during the formation of sekko ore. Gypsum, which partially replaces anhydrite in the Kuroko deposits, also exhibits two distinct chondrite-normalized REE patterns. Because LREEs are likely to be more readily mobilized during dissolution and recrystallization, it is hypothesized that LREEs are leached from type I anhydrite, resulting in the formation of type II anhydrite with LREE-depleted profiles.     

Concentrations of rare earth elements in topsoil from East China

Fifty topsoil samples collected from 12 different regions of East China have been analyzed for rare earth elements (REEs). The average REE concentrations of the 50 topsoil samples are much higher than world average and are characterized by LREE-enrichment, HREE-depletion, Eu-depletion and Ce-enrichment. However, the REE concentration is not strongly affected by the climate of the sampling site; it is controlled mainly by parent materials. The plot of Ce/Eu against Eu/Sm is proved to be useful to distinguish different parent materials of topsoil. Each element in the 50 topsoil has a good correlation with its neighboring element. Seven of the 13 values are above 0.987.     

Exploration Indices and Mineral Potential Map of the Kuroko Deposits in Northeast Japan

Abstract. Recent discoveries of seafloor hydrothermal mineralization in submarine volcanic centers of felsic magma in western Pacific island arcs are regarded as modern analogues of Kuroko type deposits. Studies of these deposits and their surrounding geology raised question whether the exploration activity for the Kuroko deposits on land which peaked in the 1960's was adequate or not. However, such an evaluation is not easy because the exploration data are about to be lost as a result of the closure of all the Kuroko mines in the area since 1994.
The Metal Mining Agency of Japan (MMAJ), therefore, decided to compile existing data on about 180 Kuroko deposits and related mineral occurrences in northeast Japan as a new Kuroko database.
This study extends a concept called "exploration indices" which was developed based on a case study of the thoroughly surveyed Hokuroku district to draw a potential map of the Kuroko occurrences for the entire northeast Japan quantitatively with a Geographical Information System (GIS). Effective exploration indices include: 1) distribution of dacitic-rhy-olitic submarine volcanic rocks of the Nishikurosawa and Onnagawa stages, 2) distribution of intrusive rocks of pre- and post-Kuroko horizon, 3) low aeromagnetic anomaly caused by hydrothermal alteration of magnetite, 4) low gravity anomaly which suggests depressions in the basement rocks such as a tectonic basin and/or caldera, and 5) nearby existence of vein type deposits. It is concluded that about 33 % of known Kuroko deposits fall within the high potential zone (score=4 and 5) that occupies only 4 % of the entire northeast Japan arc. The Kuroko potential map is, therefore, useful for limiting the target area for Kuroko type deposits in an island arc setting.     

粉煤灰——稀土元素的潜在来源

稀土是在地壳发现的一系列化学元素,由于其独特的化学性质,稀土元素广泛应用于包括电子产品、计算机、通信系统、交通、医疗、国防等多个领域。随着稀土资源的持续开采、高昂的环境代价,以及新兴领域对稀土需求的日益增长提出对回收稀土加强研究,利用经济可行的方法,寻找更多来源的要求。     

Geochemistry of rare earth elements in a marine influenced coal and its organic solvent extracts from the Antaibao mining district, Shanxi, China

Twenty-six samples including roof, bottom and coal plies of a marine influenced coal bed were collected from the Antaibao mining district, Shanxi, China. The rare earth elements (REEs) were determined in solids and organic solvent extracts. The distribution pattern showed three distinct patterns: shale-like, LREE-rich and HREE-rich. This is attributed to the variable microenvironment of peat-forming swamp, the degree of marine influences and different REE sources. REEs in the coal are mainly controlled by detrital minerals but also affected by seawater. The chondrite-normalized REE patterns of the organic solvent extracts are distinctly different from those of corresponding original coal samples, which show a negative Eu anomaly, a depletion of middle REEs and an enrichment of HREEs. The LREEs in coal extracts are likely adsorbed by hydrogen-containing functional groups, and HREEs are likely bonded to carbon atoms.     

相山铀矿田成矿流体特征:来自微量、稀土元素地球化学证据

相山铀矿田的成矿流体性质和来源存在争议,为进一步探讨相山铀矿田成矿流体的性质和来源,本文对相山铀矿田西部的居隆庵铀矿床和北部的沙洲铀矿床中的新鲜围岩、蚀变围岩及矿石的微量、稀土元素含量及其变化进行了研究。结果显示:在含较多热液成因萤石的居隆庵铀矿床中,从新鲜围岩到蚀变围岩到矿石,Zr、Hf含量先降低再升高;而在含少量热液萤石的沙洲铀矿床中,新鲜围岩、蚀变围岩和矿石的Zr、Hf含量基本一致。鉴于富F流体易汲取岩石中的Zr、Hf,因此,这两个矿床中不同类型样品Zr、Hf含量的不同变化趋势,可能与居隆庵铀矿床的成矿流体富F、而沙洲铀矿床的成矿流体相对贫F有关。这两个铀矿床中矿石的稀土配分曲线与其各自的新鲜及蚀变围岩的稀土配分曲线形态相似但又存在差异,说明每个矿床的新鲜围岩、蚀变围岩和矿石之间的稀土元素既具有继承性、又受到不同性质的流体的影响。居隆庵铀矿床中矿石显示Eu负异常,可能主要是继承了围岩的Eu负异常;沙洲铀矿床中矿石Eu显示弱负异常至弱正异常的特征,可能与围岩中斜长石因热液蚀变作用而释放出的Eu的进入流体有关。基于新鲜围岩、蚀变围岩及矿石的U和REE研究,推断居隆庵铀矿床成矿流体中U和REE均以F的络合物形式迁移;但沙洲铀矿床中铀矿石品位较低,可能是与流体中相对贫F有关。     

巢湖的稀土元素地球化学特征

采用液-液萃取法和ICP-MS测试技术对巢湖的溶解态稀土元素进行了分析。结果表明,巢湖的溶解态稀土的含量与世界淡水相当,丰水期的样品含量高于其他季节。pH值和悬浮物、胶体是控制巢湖水体中溶解态稀土含量的主要因素。巢湖的溶解态稀土的分布模式以平坦型为主,少数呈现重稀土富集。丰水期和枯水期的溶解态稀土的(La/Yb)N值从西半湖区到东半湖区呈现有规律性的逐渐增大,并且丰水期的(La/Yb)N值低于枯水期。在富营养化湖泊中,胶体和水生生物可能是造成这一现象的主要原因。     

稀土元素在热液中的迁移与沉淀

近年来,高新技术产业的不断发展使得全球稀土资源需求不断上涨,此外稀土元素作为研究地球起源与演化等有关地球科学问题的重要工具也深受地球科学界的重视。而热水溶液体系中稀土元素迁移、富集、沉淀及分馏机制等相关理论知识的不断完善对于理解稀土成矿作用、稀土地球化学特征以及微量元素示踪等方面均具有重要意义。本文总结了近年来有关稀土元素在热液体系中迁移、沉淀以及轻、重稀土分馏的最新研究进展,对不同稀土络合物的稳定性、溶解度以及搬运稀土元素的能干性进行了阐述,最后展望了"稀土元素在热液中迁移与沉淀"研究中仍需完善及拓展的方向。     

Geochemistry of dissolved rare earth elements in the Equatorial Pacific Ocean

Seawater samples were collected from four locations in the Equatorial Pacific Ocean during the MR02-K06 cruise of the R/V Mirai and analyzed for dissolved rare earth elements (REEs) using inductively coupled plasma mass spectrometry. According to variations of REE concentrations and Yb/La ratios, the results show that the river input of the Papua New Guinea islands may affect the compositions of REEs in the Equatorial Pacific surface water. The Yb/La values and the REE concentrations in the waters deeper than 3,000 m in the western South Pacific and the Equatorial Pacific Oceans, which represent the characteristics of Antarctic Bottom Water (AABW), demonstrate similar variation trend with depth. This result also indicates that the REEs which originated from the South Pacific Ocean have entered the North Pacific Ocean across the equator with AABW intrusion.     

长江沉积物稀土元素的粒度效应研究

依据Stokes定律,将小于63μm的长江沉积物分成小于2、2～4、4～8、8～16、16～32、32～63μm6个粒级,采用ICP-MS法分别测试了分粒级沉积物的REE含量,结果显示:长江沉积物REE的丰度遵循元素的"粒度控制律",即随粒度变细,∑REE含量依次增高;北美页岩标准化分布曲线均呈右倾的近"W"型,轻、重稀土分馏明显,相对富集LREE,明显的Ce负异常和弱Eu亏损。对长江沉积物不同粒级样品进行X射线衍射分析和体视镜下观测,结果表明:长江沉积物随粒度增大石英和长石含量逐步增加,碳酸盐和重矿物在各个粒级中含量甚微并且随粒级变化不大;长江沉积物REE随粒度变细逐渐增加的特征主要受控于沉积物随粒度变化而变化的矿物成分,黏土粒级及细粉砂中较高的∑REE主要是黏土矿物吸附作用的结果,粗粉砂中较低的∑REE主要为长石和石英的稀释作用结果,而碳酸盐和重矿物因其较低的含量对稀土元素含量影响较小。     

Mineralogical and Genetical Aspects of the Doyashiki Kuroko Deposits, Hokuroku Basin, Japan

Abstract. A detail investigation of ore and gangue minerals was performed on the Doyashiki Kuroko deposits, Hokuroku basin, Japan for the first time. Main ore minerals are sphalerite, galena, pyrite, chalcopyrite, tetrahedrite-tennantite and digen-ite. Small amounts of enargite, wittichenite, electrum, covellite, bornite, marcasite and hematite are also observed. Quartz, barite and gypsum are common gangue minerals. Homogenization temperatures and salinities of fluid inclusions in quartz, sphalerite and barite range from 190 to 240C and 3.0 to 5.5 wt% NaCl equivalent, respectively. The FeS contents of sphalerite and Ag contents of electrum were 0.12 to 0.18 mol %, 39.0 to 39.6 atom %, respectively. The chemical composition of digenite as a primary mineral shows high sulfur contents.
These data indicate that ore fluid responsible for digenite and associated ore minerals was characterized by a range of high sulfur fugacity with a moderate formation temperature. This is concordant with the mineral assemblage of bornite-pyrite and chalcopyrite, which shows high sulfur fugacity conditions. It seems that the mineralization closely associated with acidic volcanism has occurred around 13 Ma of Middle Miocene on the seafloor at the depth of about 1500 m.     

川西呷村超大黑矿型矿床成矿流体烯土元素组成

本文用ＩＣＰ－ＭＳ首次测定了呷村银多金属黑矿型矿床矿石流体包裹体中的稀土元素含量,研究表明,主成矿期流体稀土元素配分模式均为轻稀土富集,Ｅｕ具明显正异常,通过初步对比,本区主成矿期流体与东太平洋脊、大西洋脊等现代高温酸性地热系统热液具有相似的稀土模式,反映了它们物化条件的相似性;但前者∑ＰＥＥ高于后者,且两者Ｅｕ／Ｅｕ＾＊值不同,经过分析,本区成矿流体Ｅｕ正异常主要为Ｔ、ｐＨ、ｆｏ２控制,另外,围     

新疆且日克其菱铁矿床稀土元素地球化学特征

新疆且日克其菱铁矿床赋存于下志留统温泉沟群中低级变质岩系中,由三个矿段组成,总体呈层状、似层状、透镜状.矿石稀土含量较高(∑REE=740.97 ×10-6～820.21×10-6),轻稀土富集(LREE/HREE=13.17～14.74)的特征暗示了矿床形成于弱-中碱性的含矿溶液;明显的Ce正异常(δCe=3.25～...     

Rare earth elements in modern coral sands: an environmental proxy

The concentration rare earth elements and Yttrium (REE + Y) were determined in coral sands from Kavaratti Island, Arabian Sea, India. Chondrite-normalized REE + Y patterns show: (1) high REE concentration particularly light REE (LREE) enrichment; (2) consistent negative Ce anomaly; (3) nearly chondritic Y/Ho ratios. All these features are consistent with the geochemistry of well oxygenated seawater with significant terrestrial contribution. The seawater composition of Nd/Yb ratio inferred from the coral record point to the dominance of LREE more than the heavy REE (HREE). The high terrestrial input rich in LREE and property of adsorption/scavenging processes of LREE than that of HREE may be the cause. Terrigenous contributions were detected on the basis of co-occurring trace element concentrations (Sc, Hf and Th) and Y/Ho ratio. Except for La, the REE distribution coefficients, KD(REE)s, are between 100 and 300. KDs are high comparing to the other elements in biogenic calcite which is attributed to detrital contamination during elemental incorporation. This study may not reflect original seawater chemistry but it can be a good proxy to indicate proximity of corals to terrigenous input sources.     

巴尔哲超大型稀有稀土矿床成矿机制研究

巴尔哲矿床中的矿化和非矿化碱性花岗岩主要造岩矿物均为微斜长石、石英、钠闪石和钠长石,但其相对含量及颗粒大小明显不同,且两类岩石中包裹体的组成特征及锆石的结晶习性也有显著差异.主量元素分析显示,矿化与非矿化碱性花岗岩均以富硅、富碱、贫镁和钙为特征,为较典型的非造山A型花岗岩.尽管矿化碱性花岗岩中K_2O和Na_2O的含量均没有明显的增加,但其Na+K/Al、Na_2O+K_2O/CaO、FeO~*/MgO及K_2O/MgO等岩石化学参数与非矿化碱性花岗岩明显不同.在矿化碱性花岗岩中除了矿化的稀土元素及Nb、Zr强烈富集外,U、Th及Y也明显富集,而Ba、Sr、P、Eu和Ti表现为强烈的亏损.在非矿化碱性花岗岩中除了大离子亲石元素Rb略有富集外,稀土元素、Nb、Zr、U、Th、Ta及Y并无明显富集,虽然Sr、P、Eu和Ti也表现为亏损,但与矿化碱性花岗岩相比其亏损程度明显降低.岩相学、岩石化学及微量元素地球化学特征显示,矿化碱性花岗岩不可能是非矿化碱性花岗岩硅化和钠长石化作用的产物,二者应是同一岩浆体系不同演化阶段熔体固结的产物.K/Rb、Rb/Sr及δEu等地球化学参数显示,矿化碱性花岗岩是高演化A型花岗质熔体固结的产物;而岩石学、包裹体及地球化学特征则显示,这种高演化的A型花岗质熔体已经进入了岩浆一热液过渡阶段.巴尔哲矿床稀有稀土元素的超常富集和成矿与A型花岗岩的高演化过程密切相关.     

新疆金矿火山岩微量及稀土元素地球化学特征

金矿火山岩微量元素以Th和Zr的明显正异常及Nb和Ti的明显负异常为特征。微量元素比值蛛网图模式曲线均呈微向左倾斜的多峰多谷曲线。过渡元素以Cr和Ni的明显负异常及Sc,Co,Cu明显正常为特征。过渡元素球粒陨石标准化曲线，也均呈微向右倾斜的W形曲线。稀土元素以稀土总量偏低，轻稀土富集，重稀土亏损，Eu具微弱异常至微弱正常为特征。稀土元素配分模式均呈微向右倾斜和近于水平的平滑曲线，陆相火山作用两类成矿岩浆建造－陆相火山岩与潜火山杂岩具有基本一致的微量元素和稀土元素地球化学特征。     

低级变质岩在热液蚀变过程中的微量元素地球化学行为——以赣东北银山地区双桥山群为例

对江西银山地区双桥山群绢云母千枚岩及其原岩的稀土及微量元素的研究表明，热液蚀变过程中它们的地球化学行为十分复杂：热兴蚀变作用并不使REE淋滤降低，反而导致∑REE较其原岩普遍升高，但岩体接触带附近蚀为围岩的∑REE则低于原岩。蚀变岩出现Eu亏损，∑LREE／∑HREE值降低。定量计算显示，∑REE总升幅中有29％－45％是由围岩质量迁移引起的表观浓缩效应，而另外的55％－71％则是流体带入了REE；在绢云母千格岩中娟云母可能是REE的主要寄主矿物相，REE主要以吸附作用的形式固有在矿物的表面或含有可交换电价的晶体结构层（四面体层和八面体层）的层面上；参与蚀为变作用的热液∑LREE／∑HREE值低、Eu强正异常。流体REE的带入可能是造成蚀为围岩较原岩轻重稀土比值降低的主要因素。热液蚀变作用使岩石的Eu被还原成更易活动的Eu^2 而活化迁出，导致蚀变岩的Eu负异常更显著；围岩蚀变作用凌其聪等：低级变质岩在热液蚀为过程中的微量元素地球化学行为－－以赣 东银山地区双桥山群为例。     

Heavy metals and rare earth elements (REEs) in soil from the Nam Co Basin,Tibetan Plateau

Twenty-eight soil samples collected from the Nam Co Basin, Tibetan Plateau, have been analyzed for heavy metals (Cd, Cr, Ni, Cu, Zn, Pb and Mn), arsenic (As) and rare earth elements (REEs). In addition, for establishing the basic physio-chemical characteristics of the soil, pH, total organic concentration, electrical conductivity, and effective cation exchange capacity were measured. The results indicate that soil in the Nam Co Basin is still at an early alkaline weathering stage (pH = 7.94). Mean concentrations of heavy metals and As decreased as follows: Mn > Cr > Zn > Pb > Ni > Cu > As > Cd. The values of Cd, Cr, As, Pb and REEs in soil from the Nam Co Basin are higher relative to averaged background values over China. The chondrite-normalized diagrams of REEs suggest high REE(ΣLa → Eu)—enrichment, HREE(ΣGd → Lu)—depletion and Eu—depletion. Vertical profiles indicate that both heavy metals (except As) and REEs primarily exist in the surface soil. However, heavy metals and REEs vary in the surface soil between the southern and the northern bank of Nam Co. These differences are controlled mainly by parent materials.     

Jusa and Barsuchi Log Volcanogenic Massive Sulfide Deposits from the Southern Urals of Russia: Devonian Analogs of the Kuroko Deposits of NE Honshu, Japan

Chemical analysis of 60 samples from the Jusa and Barsuchi Log volcanogenic massive sulfide (VMS) deposits by inductively coupled plasma–mass spectrometry shows that, on average, the Jusa deposit is more enriched in the chalcophilic elements than the Barsuchi Log deposit, whereas the Barsuchi Log deposit is more enriched in the lithogenous elements and Te. In addition, the yellow ores in these deposits are more enriched on average in Cu, As and Mo and the black ores more enriched in Zn, Ga, Cd, Sb, Ba , Hg and Pb relative to each other. Both these deposits are similar in composition to the Kuroko deposits of NE Honshu and may be considered to be analogs of these deposits. The Kuroko deposits, however, contain much higher concentrations of As, Ag, Sb, Ba, Hg and lower contents of Te on average than the Jusa and Barsuchi Log deposits. Based on the higher contents of Te in the Barsuchi Log deposit compared to the Jusa deposit, as well as on textural considerations, it is concluded that the Barsuchi Log deposit is intermediate between the Urals- and Kuroko-type deposits, whereas the Jusa deposit is more analogous to the Kuroko-type deposits. Based on the compositional data presented here, the Jusa and Barsuchi Log deposits may be described as Zn-Pb-Cu-Ba deposits rather than as Zn-Cu-Ba deposits, as the Baimak-type deposits of the west Magnitogrosk zone have previously been described.