马里亚纳海槽扩张轴(中心)玄武岩铂族元素特征

马里亚纳海槽扩张轴中心玄武岩铂族元素(PGE)总量变化范围为0.418×10-9~1.022×10-9,其原始地幔标准化配分模式呈正倾斜型,表现出PPGE(包括Pt,Pd,Rh)和金的相对富集.与其他幔源岩石相比,该区玄武岩PGE总量较低,(Pd/Ir)N,(Pd/Pt)N,(Pd/Ru)N变化较大,表现出铂、铱的相对亏损和明显的铂负异常(Pt/Pt*=0.01~0.15).PGE的分布特征一方面反映了该区地幔熔融度不高,另一方面,大离子亲石元素LILE(铷、锶、钾等)、铅和轻稀土LREE略富集,暗示扩张中心之下的软流圈地幔源受到了岛弧地幔的混染.上述特征反映了马里亚纳海槽玄武岩是MORB型与岛弧型地幔源不同程度混合后部分融熔的产物.     

西太平洋Kocebu海山铁锰结壳稀土元素地球化学特征

西太平洋麦哲伦海山区是全球重要的铁锰结壳资源分布区,具有丰富的稀土元素资源潜力。本文对采自麦哲伦海山区Kocebu海山的11个铁锰结壳表层样（＜1 mm）进行稀土元素地球化学研究,探讨其含量特征、成因和影响稀土元素富集的环境因素。结果表明：Kocebu海山铁锰结壳表层样品ΣREY（Rare earth elements and yttrium）平均含量为1 366 mg/kg,低于前人在麦哲伦海山区其他海山以及邻近的马尔库斯–威克海山区的分析结果;样品轻稀土富集和Ce正异常（平均值为1.45）特征以及稀土元素成因图解、配分曲线和分配系数曲线等均表明该海山结壳属于水成成因;海水中稀土元素含量和溶解氧含量是控制结壳生长的关键环境参数,二者在Kocebu海山所在海区的浅水环境中含量较低;结壳ΣREY含量偏低与采样点水深较浅导致的海水稀土元素含量和溶解氧含量较低密切相关,受碎屑矿物的稀释作用影响较小。在开展铁锰结壳地球化学特征研究和资源勘探评价时应充分考虑采样水深的分布范围,局部水深样品的分析结果可能导致研究结果出现较大偏差。     

Improved understanding of petroleum migration history in the Hongche fault zone,northwestern Junggar Basin (northwest China): Constrained by vein-calcite fluid inclusions and trace elements

Calcite veins and cements occur widely in Carboniferous and Permian reservoirs of the Hongche fault zone, northwestern Junggar Basin in northwest China. The calcites were investigated by fluid inclusion and trace-element analyses, providing an improved understanding of the petroleum migration history. It is indicated that the Hongche fault behaved as a migration pathway before the Early Cretaceous, allowing two oil charges to migrate into the hanging-wall, fault-core and footwall reservoirs across the fault. Since the Late Cretaceous, the Hongche fault has been sealed. As a consequence, meteoric water flowed down only into the hanging-wall and fault-core reservoirs. The meteoric-water incursion is likely an important cause for degradation of reservoir oils. In contrast, the footwall reservoirs received gas charge (the third hydrocarbon event) following the Late Cretaceous. This helps explain the distribution of petroleum across the fault. This study provides an example of how a fault may evolve as pathway and seal over time, and how reservoir diagenetic minerals can provide clues to complex petroleum migration histories.     

Distribution of major and trace elements in surface sediments of Hangzhou Bay in China

The Inductively Coupled Plasma Optical Emission Spectrometer was used to analyze sediment samples collected from the Hangzhou Bay to determine major and trace elemental concentrations. Based on these concentrations, the study area can be classified into three geochemical provinces. Province I covers the northern Hangzhou Bay area and contains high concentrations of Al₂ O₃ , Fe₂ O₃ , MgO, Na₂ O, K₂ O, MnO, Cr, Cu, Ni, Pb, V, Co and Zn. Province III is located in the western Hangzhou Bay, near the Qiantang River mouth, and contains high concentrations of SiO₂ , Na₂ O, P₂ O₅ , TiO₂ , Cr, Sr, Zr. Province II is located in the middle and eastern Hangzhou Bay, with the medium concentrations of major and trace elements. The results also demonstrate that the grain size is the dominating factor controlling the spatial variations of elemental concentrations, and the Changjiang River （Yangtze River） and Qiantang River sediments play an important role in the distribution of these elements. Anthropogenic impact on heavy metal concentrations （especially Cr, Sr and Zr） can be detected in the surface sediments near the Qiantang River mouth.     

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。