Rare earth elements and yttrium in ferromanganese deposits from the South China Sea: distribution, composition and resource considerations

Ferromanganese nodules and crusts contain relatively high concentration of rare earth elements(REE) and yttrium(REY),with a growing interest in exploitation as an alternative to land-based REY resources.On the basis of comprehensive geochemical approach,the abundance and distribution of REY in the ferromanganese nodules from the South China Sea are analyzed.The results indicate that the REY contents in ferromanganese deposits show a clear geographic regularity.Total REY contents range from 69.1×10~(–6) to 2 919.4×10~(–6),with an average value of 1 459.5×10~(–6).Especially,the enrichment rate of Ce content is high,accounting for almost 60% of the total REY.This REE enrichment is controlled mainly by the sorption of ferromanganese oxides and clay minerals in the nodules and crusts.Moreover,the total REY are higher in ferromanganese deposits of hydrogenous origin than of diagenetic origin.Finally,Light REE(LREE) and heavy REE(HREE) oxides of the ferromanganese deposits in the study area can be classified into four grades: non-enriched type,weakly enriched type,enriched type,and extremely enriched type.According to the classification criteria of rare earth resources,the Xisha and Zhongsha platform-central deep basin areas show a great potential for these rare earth metals.     

70年来中国化学海洋学研究的主要进展

我国的海洋化学工作者通过70年来,特别是近30年来的化学海洋学研究,实现了我国与世界先进水平进入同步发展的快车道,其显著的特点是:(1)化学海洋学研究从元素地球化学分布系统转向了以揭示深层次海洋生物地球化学过程为核心的研究;(2)化学海洋学研究实现了多领域、多视点的综合交叉研究;(3)更加关注了人为影响与自然变化共同作用下的海洋生态环境变化研究,对近海和海岸带而言,更加注重从海陆统筹一体化角度探析化学物质的分布迁移特征。本文从生源要素的海洋生物地球化学过程、微/痕量元素与同位素的海洋化学研究、生物过程作用下的化学海洋学过程等角度,重点总结归纳和分析了30年来我国海洋化学研究的重要进展和发展状况,以期对化学海洋学的进一步研究提供借鉴和启迪。     

Origin of the Breno and Esino dolomites in the western Southern Alps (Italy): Implications for a volcanic influence

The Esino Limestone of the western Southern Alps represents a differentiated Ladinian-Lower Carnian (?) carbonate platform comprised of margin, slope and peritidal inner platform facies up to 1000 m thick. A major regional subaerial exposure event lead to coverage by another peritidal Lower Carnian carbonate platform (Breno Formation). Multiphase dolomitization affected the carbonate sediments. Petrographic examinations identified at least three main generations of dolomites (D1, D2, and D3) that occur as both replacement and fracture-filling cements. These phases have crystal-size ranges of 3–35 μm (dolomicrite D1), 40–600 μm (eu-to subhedral crystals D2), and 200 μm to 5 mm (cavity- and fracture-filling anhedral to subhedral saddle dolomite D3), respectively.The fabric retentive near-micritic grain size coupled with low mean Sr concentration (76 ± 37 ppm) and estimated δ¹⁸O of the parent dolomitizing fluids of D1 suggest formation in shallow burial setting at temperature ∼ 45–50 °C with possible contributions from volcanic-related fluids (basinal fluids circulated in volcaniclastics or related to volcanic activity), which is consistent with its abnormally high Fe (4438 ± 4393 ppm) and Mn (1219 ± 1418 ppm) contents. The larger crystal sizes, homogenization temperatures (D2, 108 ± 9 °C; D3, 111 ± 14 °C) of primary two-phase fluid inclusions, and calculated salinity estimates (D2, 23 ± 2 eq wt% NaCl; D3, 20 ± 4 eq wt% NaCl) of D2 and D3 suggest that they formed at later stages under mid-to deeper burial settings at higher temperatures from dolomitizing fluids of higher salinity, which is supported by higher estimated δ¹⁸O values of their parent dolomitizing fluids. This is also consistent with their high Fe (4462 ± 4888 ppm; and 1091 ± 1183 ppm, respectively) and Mn (556 ± 289 ppm and 1091 ± 1183 ppm) contents, and low Sr concentrations (53 ± 31 ppm and 57 ± 24 ppm, respectively).The similarity in shale-normalized (SN) REE patterns and Ce (Ce/Ce*)_SN and La (Pr/Pr*)_SN anomalies of the investigated carbonates support the genetic relationship between the dolomite generations and their calcite precursor. Positive Eu anomalies, coupled with fluid-inclusion gas ratios (N₂/Ar, CO₂/CH₄, Ar/He), high F⁻ concentration, high F/Cl and high Cl/Br molar ratios suggest an origin from diagenetic fluids circulated through volcanic rocks, which is consistent with the co-occurrence of volcaniclastic lenses in the investigated sequence.     

胶州湾海水中悬浮颗粒对溶解态微量元素的影响

运用离子色谱离线螯合结合ICP-MS的方法,对胶州湾海水中的微量元素(V,Co,Ni,Cu,Mo,Cd,Pb,U,REEs)进行了精确的定量分析。在测试前对在同一站位不同层位采集的平行海水样品进行了两种不同的酸化处理:一份采取先过滤后酸化的方式,以获得海水中溶解态微量元素的含量;另一份采取直接酸化后分析的方式,以评估悬浮颗粒中的可交换态微量元素对溶解态微量元素测定结果可能造成的影响。通过对比研究发现,不同处理方法得到的V、Ni、Cu、Co、Pb以及稀土元素(REEs)的质量浓度存在很大差异,说明悬浮颗粒物质可能对海水中相应元素的测定产生较大的影响。各种微量元素之间的差异和相应离子或离子团的电荷性质、在海水中的配位作用以及悬浮颗粒物质的表面电荷性质有关。初步研究结果表明,在类似于胶州湾这样的近海海域,悬浮颗粒物质是控制微量元素分布特征的一个重要因素。     

Diagnosis of trace metal contamination in sediments: the example of Ensenada and El Sauzal, two harbors in Baja California, Mexico

Total metal concentrations in sediments from within Ensenada and El Sauzal Harbors are generally higher than at the mouths. Grain-size analyses suggested that this enrichment could be due to the presence of fine-grained sediments in the inner part of the harbors rather than to anthropogenic perturbations. The (Me/Al)(sample) ratios for Pb, Co, Ni and Fe were significantly higher for Ensenada Harbor relative to El Sauzal Harbor, whereas the ratios for Cd, Mn, Zn and Cu were statistically equivalent for both harbors. Calculated enrichment factors [EF(Me)=(Me/Al)(sample)/(Me/Al)(shale)] indicated that the metals showing slight enrichment were those associated with anthropogenic contamination (Pb, Zn), or probably related to primary productivity in the water column (Cd, Co). The levels of most of the metals were not greatly enriched, a consideration that is of the utmost importance when contamination issues are at stake.     

离线固相萃取螯合富集分离-ICP-MS测定海水中的稀土元素

通过测定条件优化、方法比对等实验建立了一种固相萃取小柱离线螯合富集分离电感耦合等离子体质谱仪测定海水中稀土元素的方法。海水样品通过调节p H后,进入VAC ELUT SPS24 Agilent圆形固相萃取装置,其主要基体物质的去除率高于97%;萃取富集的优化条件是海水样品p H 4.0~7.0,海水进入萃取柱速率2 m L/min,硝酸洗脱液浓度为1 mol/L;方法对稀土元素的加标回收率为83%~108%,14种稀土元素的检出限为0.057~0.613 ng/L,RSD10%;该方法与氢氧化铁共沉淀法富集稀土元素比对测定结果一致,方法具有准确度与精密度高、操作简便快速等优点,可用于海水样品中稀土元素的定量精确测量。     

18.5 ka以来冲绳海槽中部沉积物碎屑态来源和古环境变化的常量元素记录

为进一步了解冲绳海槽中部18.5 ka以来柱状沉积物碎屑态的常量元素组成特征及其古环境指示意义,对KX12-3孔进行了151个样品中碎屑态的提取及其常量元素和粒度综合分析。结果表明：主要常量元素含量表现出明显的两段式垂向变化特征,底部的Z1阶段(492~96 cm)形成于末次冰消期及早全新世(18.5~9.6 ka),中国大陆河流(长江、黄河)物质输入是沉积物中陆源碎屑物质的主要来源;而顶部的Z2阶段(96~0 cm)则形成于早全新世以来(＜9.6 ka),沉积物中的陆源碎屑物质仍以中国大陆来源为主,台湾物质输入也有一定贡献。此外,岩心中还记录到了7.3 ka时发生的K-Ah火山事件。常量元素相关性、R型因子及典型常量元素比值分析均表明主要氧化物含量在垂向上的变化主要受控于附近的陆源碎屑物质输入,热液活动和火山物质的影响较小。不同时期陆源碎屑物质对研究区的影响表现出明显的变化规律,并与海平面波动及黑潮的演化具有很好的耦合关系。此外,在5~3.5 ka期间,KX12-3孔的Fe2O3、MgO、Fe/Ti、Mg/Ti值及粒度减小,这应该是由当时黑潮的减弱或“摆动”出冲绳海槽引起的。     

Rare Earth and Metal Geochemistry of Land and Submarine Phosphorites in the Baja California Peninsula,Mexico

The geochemical composition of phosphorites and phosphatic sediments in the Baja California peninsula is studied and used to assess the environment in which phosphogenesis took place. The deposits are classified in three groups: (1) stratified phosphorites, (2) phosphatic sandy sediments from beaches and dunes, and (3) submarine sediments. Some of the elements that might have substituted Ca and PO₄ during francolite mineralization were studied by means of ICP-AES. Significant differences are seen in the concentration of these metals (e.g., Cr = 72-406 μg g^?1 and V = 17-198 μg g^?1), indicating that their concentration is not only controlled by the P₂O₅ concentration, but also by paleo-environmental conditions existing during francolite precipitation. Shale normalized REE patterns suggest two main environments of formation: (1) a strong negative Ce anomaly (< ? 0.3) and La enrichment (La/Nd ≥ 1) enrichment, suggesting well oxygenated shelf environments and probably lower light REE weathering, and (2) a weak negative Ce anomaly (> ? 0.3) and La depletion (La/Nd ≤ 1) suggesting shallower waters or restricted circulation and probably LREE weathering.     

东海盆地某油气田A井P层沉积体系研究

东海盆地某油气田A井钻遇古近系平湖组P层为一套灰绿色含砾细砂岩.对此层中的微量元素、古生物资料、粒度特征以及测井资料的分析表明：沉积物中的硼元素含量较低,Sr/Ba比值小于1,Fe/Mn比值远大于5,这些指标反映沉积水体为淡水;同时,Ni/Co比值大多数介于2.5～5之间,而V/Ni比值大于1,指示研究层位沉积于还原环境中.该层沉积物中,蕨类孢子含量极高,花粉组合以阔叶类木本为主,且含较多喜暖湿针叶类花粉,说明当时盆地周边区域气候大致相当于现代亚热带气候,较温暖且偏湿润.A井P层中,砾石具近源快速堆积特征,泥岩属较深水沉积,岩层粒度具浊积岩特征;结合空间岩性展布状况可以判断,P层沉积相属于温暖湿润气候下的淡水近岸水下扇相.     

复合加载模式作用下地基承载性能数值分析

确定竖向荷载(V)、水平荷载(H)和力矩(M)共同作用下建筑物地基的破坏模式及在荷载空间(H,V,M)中的破坏包络面是地基设计中的关键问题。为提高Swipe试验方法计算精度,提出了改进方案,进而利用有限元方法分析了复合加载模式作用下均质粘性土地基上条形基础的破坏包络面。计算表明,基于改进Swipe试验方法的数值模拟结果明显好于常规Swipe试验方法。针对海洋工程中实际复合加载模式的特点,探讨了竖向荷载分量V对地基破坏模式和H-M荷载平面上的破坏包络线的影响,结果表明竖向荷载分量显著地改变了地基的破坏模式及包络线的形状。