太平洋调查区多金属结核的地球化学特征和成因

东太结核主要为半埋藏和埋藏型,发育于以黏土和硅质组分为主的沉积环境。东太结核的锰相矿物主要有水羟锰矿和钡镁锰矿,具有较高的REY、Cu、Ni含量和Mn/Fe比值,显示遭受间隙水的影响,落入水成成因和成岩成因两个区间范围。西太结核主体暴露在海水中,周围沉积物主要由深海黏土组成。西太结核的锰相矿物几乎只有水羟锰矿,具有较高的REY、Co含量和低Mn/Fe比值,属于典型的水成成因型。两个区域的多金属结核的稀土北美页岩标准化模式均显示Ce正异常、Y负异常和无或弱Eu异常,与海水稀土特征构成良好的耦合关系,是多金属结核对海水稀土选择性富集的结果。西太结核相对东太结核具有更高的Ce含量和δCe,Co、Ti与Ce具有良好的正相关关系。研究认为海水中溶解氧并不一定是控制结核Ce正异常程度的关键因素,Co、Ti等元素及其相关组分能够引起Ce与其他稀土元素的强烈分馏,也可能是影响多金属结核Ce正异常程度的控制因素。研究区多金属结核和富钴结壳表层样的ε_Nd范围为-6.6~-2.5,是全球最富放射性成因Nd的海洋铁锰壳层。结合稀土模式以及Eu异常特征,本研究认为多金属结核的稀土主要来自ε_Nd相对较高的周围陆壳,可以通过河流或者大气沉降等方式输送到大洋,而研究区广泛分布的海山玄武岩释放的放射性成因Nd同位素对海水的影响微弱。     

中国富钴结壳合同区海水的稀土元素特征及其意义

通过对西太平洋34件海水样品的稀土元素（REY:REE+Y）测试及其与研究区富钴结壳稀土耦合特征分析,揭示了海水稀土特征及其成因.海水的稀土含量随水深呈现逐渐增加的趋势,∑ REY范围为14.0×10-12~65.5×10-12,平均值为31.9×10-12,其中Y的绝对值（均值为6.0×10-12~24.1×10-12）和相对值（（Y/Ho）_N均值为1.98）均较高,La含量次之（均值为1.8×10-12~11.6×10-12）,Ce含量相对较低（均值为2.4×10-12~8.8×10-12）,δCe范围为0.33~1.03（均值为0.66）,（La/Yb）_N平均值为0.71.海水稀土元素北美页岩标准化后显示左倾模式,具有显著的Ce负异常、Y正异常和无明显的Eu异常特征.研究区普遍发育水成成因的富钴结壳,即其稀土元素和其他组分均源自海水.富钴结壳的稀土含量相对海水富集6~7个数量级,其Ce正异常和Y负异常的稀土模式与海水构成良好的耦合关系,指示富钴结壳类组分对海水稀土清扫具有选择性,是造成海水稀土模式的重要因素.海山上发育的磷块岩以及周围盆地深海泥中的磷酸盐组分,它们具有较高的稀土含量和类似于海水的稀土模式,指示海洋磷酸盐消耗稀土时并未分馏而是继承海水模式.海水独特的稀土模式特征是补给与消耗平衡作用的结果,铁锰氧化物和海洋磷酸盐是两种典型的海洋自生组分,它们对海水稀土特征的形成至关重要.      

西太平洋海山富钴结壳的稀土和铂族元素特征及其意义

为了探讨富钴结壳的稀土和铂族元素是否有相似的形成机制,对西太平洋海山富钴结壳稀土和铂族元素进行了类比研究.结果表明:富钴结壳的∑REY范围为1 433.7×10-6~2 888.0×10-6,其中Ce占到近50%,北美页岩标准化后显示较平坦的稀土模式和显著的Ce正异常特征.根据稀土配分模式及已有的Nd同位素结果,富钴结壳具有亲陆壳属性.富钴结壳具有极高的Pt (115.5×10-9~1 132.0×10-9)、(Pt/Pd)_N和 (Pt/Os)_N值,Ir与Pt及Rh与Pt显示良好相关性.经球粒陨石标准化后显示较一致PGE (platinum-group elements) 配分模式,从Os到Pt逐渐富集,Pd元素强烈亏损.已有的Os同位素研究结果显示物源在地质历史时期从幔源属性向陆源属性变化,但富钴结壳PGE元素内部相对含量仍在一定程度上保持稳定.研究认为:富钴结壳对海水中的稀土清扫具有选择性,Ce的正异常恰恰是结壳对海水稀土中Ce的优先选择造成的,从而导致海水亏损Ce.然而海水中Ce的亏损并未改变新形成富钴结壳的稀土模式,原因是在海洋中存在适量的具有亏损Ce特征的磷酸盐等组分,理论上只需要氧化物类稀土与磷酸盐类稀土消耗的稀土与海水中的补给平衡即可.只是在相关过程中,海洋中氧化物类对稀土的选择更具有主动性,而磷酸盐类表现更多的继承关系.尽管Os同位素显示物源供给发生变化,然而富钴结壳PGE模式相对稳定.因此富钴结壳PGE模式同样可以用富钴结壳对PGE的选择性吸收解释,因富钴结壳优先选择Pt与Ir以及相对排斥Pd和Os,形成了现有独特的PGE模式.      

Rare Earth Elements and Yttrium (REY) Geochemistry of Reefal Limestones in the Ordovician,Tarim Basin,NW China and their Paleoenvironment Implications

This study examines the rare earth elements and yttrium (REY) concentrations of twenty-five samples from the reef outcrop exposed along the Lianglitage Mountain in the Ordovician, Tarim Basin in China. The concentration analysis provides constraints on the paleoenvironment during reef deposition. Based on the detailed sedimentology and petrographic work, we divide the reef facies into four sub-facies: the base facies, reef-core facies, reef-flank facies, and sealing facies. The geochemical data (such as major and trace elements, carbon and oxygen isotopes, and REYs) are further used to study the coeval seawater characteristics as well as potential diagenesis overprints. The result indicated that the diagenesis has little effect on the REY patterns of the reefal limestones. The REY concentrations of the reefal limestones are overall low (ranging from 3.69 to 19.60 ppm, arithmetic mean=10.22 ppm, SD=5.4). The PAAS-normalized REY patterns are consistently flat compared to the typical well-oxidized, shallow marine water patterns. However, the light REE (LREE) depletions, positive La anomalies, negative Ce anomalies and positive Y anomalies, suggest that these reefal limestones are likely an indicative of contemporaneous seawater REY signals. The seawater-like Y/Ho ratios (average at 37.51) further support that REY signals in these limestones are likely a reflection of seawater with little diagenetic modifications. The low Y/Ho ratios presented only in the reef-flank facies and sealing facies are likely a suggestion of detrital contamination. Hence, this study confirms that REY patterns of the limestones at the base facies and reef-core facies can record ancient seawater information, and reefs can be used as a potential geochemical proxy for paleoenvironment studies throughout the Earth’s history.     

渭北煤田下峪口矿二叠纪煤中稀土元素地球化学研究

运用电感耦合等离子体质谱（ICP MS）对渭北煤田韩城下峪口矿二叠纪主采煤层及其顶底板中的稀土元素进行了测定。在此基础上,全面分析了稀土元素的含量特征和分布模式,探讨渭北煤田二叠纪煤中稀土元素的主要来源及赋存状态。结果表明：与华北和中国煤均值相比,本区煤层中稀土元素相对不富集,∑REY平均含量为87.70 μg/g;剖面上,2号煤中稀土含量稍高于3号煤,3号煤层中自上而下,稀土元素含量呈降低的趋势,在顶底板中出现富集。研究区煤层中轻稀土元素相对于重稀土元素明显富集,Ce呈微弱正异常,成煤沼泽受海水的影响程度较小。Eu明显负异常,且∑REY含量与CaO含量呈负相关关系,说明当时的成煤环境为酸性还原环境。煤层与其顶底板样品中稀土元素分布模式相似,成煤期间物质来源基本一致,陆源物质供应相对稳定。煤中稀土元素含量与灰分呈不太显著的正相关关系（R=0.216）,表明煤中稀土元素可能以无机态和有机吸附态共存。     

Comparison between Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on rare earth elements

Datangpo-type sedimentary manganese deposits, which are located in northeastern Guizhou province and its adjacent areas, are Mn carbonate-type deposits hosted in black carbonaceous shale that represent a series of medium to large deposits containing a huge tonnage of reserves. PAAS-normalized rare earth element distribution patterns of manganese ores record “hat-shaped” REY (REE + Y) plots characterized by pronounced middle rare earth element enrichment, evident positive Ce anomalies, weak to strong positive Eu anomalies and negligible negative Y anomalies. These REY geochemical characteristics are different from those of country rocks and record the processes and features of sedimentation and diagenesis. Manganese was precipitated as Mn-oxyhydroxide particles in oxidized water columns with the sorption of a certain amount of rare earth elements, subsequently transforming from Mn-oxyhydroxides to rhodochrosite and redistributing REY in reducing alkaline pore-water during early diagenesis. A number of similarities can be observed through a comparison of Datangpo-type manganese ores and modern marine ferromanganese oxyhydroxide precipitates based on their rare earth elements. The precipitation of Datangpo-type manganese ores is similar to that of hydrogenetic crusts and nodules based on their positive Ce anomalies and relatively higher total REY concentrations. However, several differences also exist. Compared to hydrogenetic crusts and nodules, Datangpo-type manganese ores record smaller positive Ce anomalies, lower total REY concentrations, unobvious fractionation between Y and Ho, and weak to strong positive Eu anomalies. These were caused by quicker sedimentary rates in the oxic water columns of the shallower basin, after which pore water became strongly reducing and alkaline due to the degradation of organic matter in the early diagenetic stage. In addition, compared to typical deposits in the world, Datangpo-type manganese ores are similar to hydrogenetic deposits and different than hydrothermal deposits. All of these characteristics of manganese ores indicate that Datangpo-type manganese ores, the principal metallogenic factors of which include oxidation conditions during deposition and reducing conditions during early diagenetic stages, represent hydrogenetic deposits.     

Noble Gas Isotopic Compositions of Cobalt-rich Ferromanganese Crusts from the Western Pacific Ocean and Their Geological Implications

1 Introduction Submarine metallic mineral resources consist mainly of polymetallic nodules and cobalt-rich ferromanganese crusts. Despite being discovered much later than the former, the latter are becoming one of the most important submarine polymetallic ore resources, because they containmany valuable metallic elements such as Co, platinum group elements (PGE), rare earth elements (REE), Ni and Cu, besides high contents of Fe and Mn (He et al., 2001). The Co-rich crusts are widely distr…     

Rare Earth Elements Composition and Constraint on the Genesis of the Polymetallic Crusts and Nodules in the South China Sea

The rare earth elements(REE) composition of the polymetallic crusts and nodules obtained from the South China Sea(SCS) were analyzed through inductively coupled plasma mass spectrometry.Results revealed great differences in the REE abundances(∑REE) of the SCS polymetallic crusts and nodules; the crusts show the highest ∑REE, whereas the nodules exhibit the lowest ∑REE. The similarity in their NASC-normalized patterns, the enriched light REE(LREE), the markedly positive Ce anomaly(δCe), and the non-or weakly positive Eu anomaly(δEu), suggest that the polymetallic crusts and nodules are of hydrogenetic origin. Moreover, the REE contents and their relevant parameters are quite different among the various layers of the crusts and nodules, which probably results from the different marginal sea environments and mineral assemblages of the samples. The growth profiles of the SCS polymetallic crusts and nodules reveal the tendency ∑REE and δCe to slightly increase from the outer to the inner layers, suggesting that the growth environments of these samples changed smoothly from an oxidizing to a relatively reducing environment; in addition, the crust ST1 may have experienced a regressive event(sea-level change) during its growth, although the REE composition of the seawater remained relatively stable. On the basis of the regional ∑REE distribution in the SCS crusts and nodules,the samples collected near the northern margin were influenced by terrigenous material more strongly compared with the other samples, and the REE contents are relatively low. Therefore, the special geotectonic environment is a significant factor influencing the abundance of elements, including REE and other trace elements. Compared with the oceanic seamount crusts and deep-sea nodules from other oceans,the SCS polymetallic crusts and nodules exhibit special REE compositions and shale-normalized patterns, implying that the samples are of marginal sea-type Fe-Mn sedimentary deposits, which are strongly affected by the epicontinental environment, and that they grew in a more oxidative seawater environment. This analysis indicates that the oxidized seawater environment and the special nano property of their Fe-Mn minerals enrich the REE adsorption.     

Incorporation of Transition and Platinum Group Elements (PGE) in Co-rich Mn Crusts at Afanasiy-Nikitin Seamount (AFS) in the Equatorial S Indian Ocean

Of the 12 elements enriched in Co-rich Mn crusts from the Afanasiy-Nikitin Seamount in the Equatorial S Indian Ocean, Mn, Fe and Co are enriched by a factor of ~10⁹ compared to their concentrations in seawater whereas Ni and Cu are enriched by a factor of ~10⁷ and the PGE and Au by a factor of ~10⁵ to 10⁷ compared to their concentrations in seawater. The relatively high concentration of Pt in the crusts reflects its occurrence as fine-grained particles in the crusts rather than adsorption of the elements from seawater.     

Role of Hydrology in the Formation of Co-rich Mn Crusts from the Equatorial N Pacific,Equatorial S Indian Ocean and the NE Atlantic Ocean

Co-rich Mn crusts from four different locations of the world ocean have been studied to understand the role of dissolved oxygen of the ambient seawater in the formation of Co-rich Mn crusts. WOCE (World Ocean Circulation Experiment) oxygen profiles of modern seawater in the Equatorial North Pacific Ocean, Equatorial South Indian Ocean and the North East Atlantic Ocean have been evaluated with respect to the occurrence of Co-rich Mn crusts at depths ranging from 1500 to 3200 m. The oxygen content at these depths varied from ∼90–240 µmol/kg. The oxygen minimum zone (OMZ), with oxygen contents in the range ∼45–100 µmol/kg, is located in the depth range 800–900 m in these regions. The age of the ocean crust on which seamounts formed is in the range 80.3–180 Ma. Profiles of the oxygen contents of seawater with depth in the oceans are shown to be extremely useful in establishing the optimum conditions for the formation of Co-rich Mn crusts. The use of WOCE oxygen profiles to study geochemical processes in the oceans is highly recommended.     

辽东辽河群大石桥组碳酸盐岩稀土元素地球化学及其对Lomagundi事件的指示

2.33～2.06Ga期间发生了全球性大气圈充氧作用及其相关的占δ~(13)C_(carb)正异常,被称为Lomagundi事件.2.2～2.174Ga的辽河群大石桥菱镁矿及其围岩显示了δ~(13)C_(carb)正异常,是运用REY(REE+Y)指纹技术研究Lomagundi事件的良好对象.本文研究表明,6件白云岩围岩样品∑REE为0.988×10-6～2.744×10-6;Y/Ho比值为37.9～49.4(平均42.5±4.7);(La/La~*)_(SN)为1.075±0.317,(Gd/Gd~*)_(SN)为1.390±0.166,均为正异常;HREE富集(Nd_(SN)/Yb(_SN)=0.38～0.78).所有上述特征与现代海水REY配分模式一致,表明这些样品记录了Lomagundi时期海水的REY特征.6件菱镁矿样品∑REE为4.549±2.239,高于围岩白云岩;HREE弱亏损(Nd_(SN)/Yb_(SN)=1.141±0.265),Y/Ho平均值为40.2±3.2;(La/La~*)_(SN)为0.657～1.149(平均0.919±0.203),(Gd/Gd~*)_(SN)=1.036±0.081,正异常程度弱于白云岩,但仍显示以海水来源为主.矿体顶板滑石白云岩∑REE含量最高(10.758);页岩标准化稀土配分模式为平坦型,(Eu/Eu~*)_(SN)正异常高达1.97,Gd和Y正异常最小,Y/Ho比值最低(31.3),(Nd/Yb)_(SN)为0.89,显示受后期热流体交代影响.菱镁矿(Sm/Yb)_(CN)值(2.61±0.45)高于白云岩(1.19±0.27),指示海水由深变浅,大石桥菱镁矿及其围岩白云岩REY主要来自陆源溶解物,洋底热液贡献微弱,制约REY特征的主导因素为大气圈-水圈的性质,如fO_2,pCO-2等.白云岩和菱镁矿(Ce/Ce~*)_(SN)值平均分别为1.11±0.13和1.04±0.08,表明2.2～2.174Ga期间大陆风化作用加剧,海水呈碱性,pH值＞8.2.2.33Ga前的化学沉积物(Eu/Eu~*)_(SN)＞1.53,2.06Ga后的化学沉积物(Eu/Eu~*)_(SN)＜1.53,大石桥组白云岩和菱镁矿(Eu/Eu~*)_(SN)均值分别为1.44±0.11和1.58±0.20.表明2.2～2.174Ga时海相沉积物(Eu/Eu~*)_(SN)≈1.53,2.33～2.06Ga是地球水圈-气圈系统由还原向氧化转变的关键时期.     

深海沉积物中的稀土矿产资源研究进展

近年发现,太平洋和印度洋的深海盆地中存在大量富含稀土的深海沉积物。主要类型为多金属软泥、沸石黏土和远洋黏土,其中的全稀土含量(∑REY,∑REE+Y)为400×10-6~2000×10-6,最高可达6600×10-6,重稀土含量(HREE)已达到或超过中国南方离子吸附型矿床的重稀土品位两倍以上,是潜在的新型稀土资源,具有重要的经济价值。目前不少学者对富稀土的深海沉积物进行了大量地球化学及部分矿物学的工作,认为多金属软泥中的稀土元素多赋存于与海底热液作用有关的铁锰氧化物和氢氧化物中,而沸石黏土和远洋黏土中稀土元素的富集则与磷酸盐的混入密切相关,其稀土元素主要存在于与磷灰石成分相当的生物鱼骨屑中。深海黏土的北美页岩标准化稀土配分模式与海水相似,表明其中的稀土元素主要来自于海水,REY富集成矿可能主要受控于磷灰石早期成岩阶段,期间稀土元素未发生分异。尽管近些年对深海沉积物中的稀土元素研究取得了不少成果,但是,对于沉积物中的稀土富集机制及影响因素等问题仍然需要更加深入的研究。作为稀土资源大国,为了争取我国在国际海底稀土资源竞争中的话语权,维护中国的稀土利益,中国应加紧开展相关的稀土资源勘查和潜力评价。     

太平洋多金属结核和富钴结壳稀土元素地球化学对比及其地质意义

多金属结核和富钴结壳是大洋两类典型的铁锰产物。为探讨不同海区多金属结核和富钴结壳之间稀土元素特点及其揭示的地质意义,利用近年中国在太平洋获取的样品进行对比,采用ICP-AES对稀土元素测试。结果表明,结壳具有正Ce异常明显、LREE富集、∑REE高的特点,而结核表现为HREE相对富集、∑REE相对较低,因成因类型不同,Ce异常或表现为正异常、负异常或异常不明显。结核形成后受到成岩作用的影响,而结壳则为水成作用形成;结核和结壳中REE的存在形式比较复杂,不同海区各不相同,中太平洋东部产出的结壳和位于东太平洋的结核中REE可能主要赋存于铁矿物相,而西太平洋结壳REE可能主要赋存于锰矿物相;结核和结壳REE可能分别来自海水和海山蚀变玄武岩,热液作用影响有限。     

Geochemistry of hydrothermal Mn-oxide deposits from the S.W. Pacific island arc

Hydrothermal Mn-oxide crusts have been removed from the Tonga-Kermadec Ridge, the first such hydrothermal deposits to be reported in the S.W. Pacific island arc. In several respects the deposits are similar to hydrothermal Mn-crusts from oceanic spreading centre settings. They are limited in areal extent, comprise well-crystalline birnessite and generally display extreme fractionation of Mn from Fe. They are strongly depleted in many elements compared to hydrogenous Mn deposits but are comparatively enriched in Li, Zn, Mo and Cd. The Group IA and Group IIA metals show strong intercorrelations and the behaviour of Mg in the purest samples may indicate the extent to which normal seawater has influenced the composition of the deposits.Certain aspects of the deposits are not typical of hydrothermal Mn deposits. In particular at least some of the crusts have developed on a sediment or unconsolidated talus substrate. Some crusts, or specific layers within some crusts, display a chemical composition which suggests a significant input from normal seawater.     

Chemical evolution of seawater in the Transvaal Ocean between 2426 Ma (Ongeluk Large Igneous Province) and 2413 Ma ago (Kalahari Manganese Field)

Drill core and outcrop samples of pure marine chemical sediments (banded iron formation (BIF), manganese formation (MnF), jaspilites, lutites, and cherts) from the transition of the ~2426 Ma old Ongeluk Formation into the 2413 Ma old Hotazel Formation, Transvaal Supergroup, South Africa, reveal remarkable changes of seawater chemistry in the Transvaal Ocean. Similar to pre-Ongeluk chemical sediments, the shale-normalized rare earths and yttrium (REY_SN) patterns of jaspilites intercalated with the volcanic rocks of the Ongeluk large igneous province and directly overlying cherts do not show positive Eu_SN anomalies, indicating that high-temperature (>250 °C) hydrothermal fluids did not contribute significantly to the REY budget of ambient waters. However, a 10 cm drill core section in the lower Hotazel Formation is characterized by conspicuous positive Eu_SN anomalies, revealing temporary inflow of water masses strongly affected by high-temperature hydrothermal fluids. After this short episode, the REY_SN pattern of Transvaal seawater returned to that of pre-Ongeluk times, showing heavy REY_SN enrichment, positive La_SN, Gd_SN and Y_SN anomalies, but no Ce_SN or Eu_SN anomalies. Higher up in the stratigraphy, the Hotazel Formation shows negative Ce_SN anomalies in some of the lutites, BIFs and MnFs, reflecting Ce depletion in ambient seawater. All Hotazel lutite, BIF, and MnF samples studied show unradiogenic εNd_(t) values (−0.5 ± 0.2 to −2.4 ± 0.2), indicating a mostly continental REY source. The REY distribution and Nd isotope data combined suggest that oxidative terrestrial weathering of this continental crustal source supplied most of the dissolved REY to local “Transvaal seawater”. Precipitation of the Hotazel lutites, BIFs and MnFs with negative Ce_SN anomalies, therefore, suggests that oxic conditions prevailed on the Kaapvaal Craton and in Hotazel seawater already at ~2.413 Ga, i.e. 80 m.y. before the disappearance of mass-independent sulfur isotope fractionation (MIF-S) that defines the Great Oxidation Event at ~2.33 Ga.     

Controls on the distribution of rare earth elements in deep-sea sediments in the North Atlantic Ocean

Deep-sea sediments can contain relatively high concentrations of rare earth elements and yttrium (REY), with a growing interest in their exploitation as an alternative to land-based REY resources. To understand the processes that lead to enrichment of the REY in deep-sea sediments, we have undertaken a detailed geochemical study of sediments recovered from the Atlantic Ocean, on a transect along ~ 24°N that includes the deep Nares Abyssal Plain and the Canary and North America Basins.Total REY concentrations (ΣREY) range from 7.99 to 513 ppm, and total concentrations of the heavy REY (Eu - Lu) range from 0.993 to 56.3 ppm. REY concentrations are highest in slowly accumulating pelagic red clays, especially in samples that contain ferromanganese micronodules. Factor analysis reveals that hydrogenous Fe- and Mn-(oxyhydr)oxides are the primary REY carrier phase in the red clays. In situ analysis of individual micronodules confirms that they have high ΣREY (up to 3620 ppm). REY concentrations are higher in micronodules that have a hydrogenous source, characterised by higher Fe/Mn, compared to micronodules that have a diagenetic source.The ΣREY content of North Atlantic deep-sea sediments is ~ 4 times lower than in Pacific deep-sea sediments. We calculate that the area of seafloor required to extract ~ 10% of the global annual REY demand is ~ 100 km², assuming removal of the upper 1 m of sediment.     

Strategic and rare elements in Cretaceous-Cenozoic cobalt-rich ferromanganese crusts from seamounts in the Canary Island Seamount Province (northeastern tropical Atlantic)

Thick ferromanganese (Fe-Mn) crusts from four Cretaceous seamounts (The Paps, Tropic, Echo and Drago) at the southern Canary Island Seamount Province (CISP) in the northeastern tropical Atlantic were recovered along the flanks and summits from 1700 to 3000 m water depths. CISP is composed of > 100 seamounts and submarine hills, is likely the oldest hotspot track in the Atlantic Ocean, and is the most long-lived of known hotspots globally. The Fe-Mn crusts grow on basalt-sedimentary rock substrates below the northeastern tropical Atlantic core of the oxygen minimum zone (OMZ) with a maximum thickness of 250 mm at a water depth of 2400 m. The mineralogical and chemical composition of these Fe-Mn crusts indicate a hydrogenetic origin. The main Mn minerals are vernadite with minor interlayered todorokite and asbolane-buserite. Fe oxides are essentially ferroxyhyte and goethite. The Fe-Mn crusts show high average contents in Fe (23.5 wt%), Mn (16.1 wt%), and trace elements like Co (4700 μg/g), Ni (2800 μg/g), V (2400 μg/g) and Pb (1600 μg/g). Rare earth elements plus yttrium (REY) averages 2800 μg/g with high proportions of Ce (1600 μg/g). Total platinum group elements (PGEs) average 230 ng/g, with average Pt of 182 ng/g. Two main types of growth layers form the crusts: 1) a dense laminae of oxides with high contents in Mn, Co and Ni associated with vernadite and Cu, Ni, and Zn associated with todorokite; 2) botryoidal layers with high contents in Fe, Ti, V and REY associated with goethite. The Fe-Mn crusts from the CISP region show higher contents in Fe, V, Pb and REY but lower Mn, Co, Ni and PGEs contents than Pacific or Indian ocean seamount crusts. The oldest maximum age of initiation of crust growth was at 76 Ma (Campanian, Late Cretaceous). Using a combination of high resolution Co-chronometer and geochemical data along an Electron Probe Micro Analysis (EPMA) transect, four stages in morphology, chemical contents and growth rates can be differentiated in the the Cenozoic crusts since 28 Ma, which we interpret as due to changes in the ventilation of the North Atlantic OMZ and to the increase of Saharian dust inputs. An earliest growth period, characterized by similar contents of Fe and Mn in the interval 27.8–24.45 Ma (late Oligocene-early Miocene) reflects slow precipitation related to a thick OMZ. An intermediate laminated zone with higher contents of Fe, Si and P, high growth rates reaching 4.5 mm/Ma, and precipitation of Fe-Mn oxides during the interval 24.5–16 Ma is related to periods of ventilation of the OMZ by intrusion of deep upwelling currents. Significant increase in Fe contents at ca. 16 Ma correlates with the onset of incursions of Northern Component Waters into the North Atlantic. Finally, since 12 Ma, the very low growth rates (< 0.5 mm/Ma) of the crust are related to a thick North Atlantic OMZ, an increase in Sahara dust input and a stable thermohaline circulation.     

西太平洋富钴结壳生长与富集特征

通过对西太平洋麦哲伦海山区富钴结壳的大尺度细致研究 ,笔者较为深入地探讨了该区结壳的生长与富集特征。研究表明 ,该区结壳自古近纪开始生长 ,生长速率变化范围为 1.5～ 12 .3mm/Ma,速率相差近一个数量级 ,平均生长速率为 3.81m m/Ma;生长过程中成矿元素的地球化学行为呈现明显差异 ;环境发生“骤变”的 O/M界面 ,可能是结壳生长过程中其构造和色泽发生“突变”的一个重要年代 ;成矿元素成分的时序演化主要受控于海水化学和各种不同地质作用的综合影响 ,成矿与非成矿地质作用在生长过程中呈现为互为消长的特征。研究发现 ,该区结壳和太平洋深海粘土元素的分配系数间存在着显著的线性相关关系 ,相关系数为 0 .89,显示它们有相近的元素富集机理。此外 ,笔者还从元素的滞留时间、阳离子的电子键能及其在海水中的水解行为与结壳富集特征间的关系进行了探讨。     

Thermal waters in the Lower Yarmouk Gorge and their relation to surrounding aquifers

Sources and mineralization of groundwaters from Cretaceous A7/B2 and B4 limestone aquifers in the Golan and Ajloun Heights are derived from conjoint discussion of stable isotopes of water and sulphate, major ion chemistry, rare earth distribution patterns and the (hydro)geological setting. Isotope fractionation of precipitation was used to derive elevation and continental influence of recharge areas. Positive shift of δ¹⁸O and δ²H occur due to evaporation before replenishment and the interaction with basalts. Major infiltration areas for Golan Heights are the limy foothills of the Mt. Hermon and for the Ajloun Heights the Plateau itself. To a less degree, precipitation infiltrates also the basaltic catchments. Groundwaters are mineralized by water/rock (i) variably altered limestones by diagenesis, (ii) evaporates and seawater brines enclosed in limestone matrix and (iii) locally occurring basaltic intrusiva. In the Yarmouk Gorge, a deep-seated brine of the Ha’on type ascends and mixes with the fresh shallow groundwater.Contrasting the macro chemical composition, REY distribution patterns indicate the lithology of the recharge areas. Infiltration over basalts results in REY patterns distinctly different to those derived from limy catchments.REY and isotope fingerprints prove that water from the Syrian Hauran Plateau is recharging springs and wells in the lowermost Yamouk gorge. The basaltic cover of the Golan Heights is of minor importance for recharge of the underlying A7/B2 aquifer, which becomes recharged at the foothills of Mt. Hermon and gets confined southwards. Even the wells in the basaltic cover receive water from the underlying limestone aquifer.Anomalous heat flux near the Yarmouk gorge and locally in the western escarpment of the Ajloun may be produced by ascending fluids from greater depth and/or by basaltic intrusions.     

Geochemistry and mineralogy of REY-rich mud in the eastern Indian Ocean

Deep-sea sediments in parts of the Pacific Ocean were recently found to contain remarkably high concentrations of rare-earth elements and yttrium (REY) of possible economic significance. Here we report similar REY-rich mud in a core section from Deep Sea Drilling Project Site 213 in the eastern Indian Ocean. The sediments consist mainly of siliceous ooze, with subordinate zeolitic clay that contains relatively high REY concentrations. The maximum and average total REY (ΣREY) contents of this material are 1113 and 629 ppm, respectively, which are comparable to those reported from the Pacific Ocean. The REY-rich mud at Site 213 shows enrichment in heavy rare-earth elements, negative Ce anomalies, and relatively low Fe₂O₃/ΣREY ratios, similar to those in the Pacific Ocean. In addition, the major-element composition of the Indian Ocean REY-rich mud indicates slight enrichment in lithogenic components, which probably reflects a contribution from southern African eolian dust. A volcaniclastic component from neighboring mid-ocean ridges or intraplate volcanoes is also apparent. Elemental compositions and X-ray diffraction patterns for bulk sediment, and microscopic observation and elemental mapping of a polished thin section, demonstrate the presence of phillipsite and biogenic apatite, such as fish debris, in the REY-rich mud. The strong correlation between total REY content and apatite abundance implies that apatite plays an important role as a host phase of REY in the present deep-sea sediment column. However, positive correlations between ΣREY and elements not present in apatite (e.g., Fe₂O₃, MnO, and TiO₂) imply that the REY-rich mud is not formed by a simple mixture of REY-enriched apatite and other components.